Platinum-alkali/alkaline-earth catalyst formulations for hydrogen generation

Abstract
A method and catalysts and fuel processing apparatus for producing a hydrogen-rich gas, such as a hydrogen-rich syngas are disclosed. According to the method a CO-containing gas, such as a syngas, contacts a water gas shift catalyst in the presence of water, preferably at a temperature of less than about 450° C. to produce a hydrogen-rich gas, such as a hydrogen-rich syngas. Also disclosed is a water gas shift catalyst comprising:
Description


BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention


[0003] This invention relates to methods and catalysts to generate a hydrogen-rich gas from gas mixtures containing carbon monoxide and water, such as water-containing syngas mixtures. More particularly, the invention includes methods using platinum-based catalysts which contain alkali or alkaline-earth metals. The catalysts may be supported on a variety of catalyst support materials. Catalysts of the invention exhibit both high activity and selectivity to hydrogen generation and carbon monoxide oxidation.


[0004] 2. Discussion of the Related Art


[0005] Numerous chemical and energy-producing processes require a hydrogen-rich composition (e.g. feed stream.) A hydrogen-rich feed stream is typically combined with other reactants to carry out various processes. Nitrogen fixation processes, for example, produce ammonia by reacting feed streams containing hydrogen and nitrogen under high pressures and temperatures in the presence of a catalyst. In other processes, the hydrogen-rich feed stream should not contain components detrimental to the process. Fuel cells such as polymer electrode membrane (PEM) fuel cells, produce energy from a hydrogen-rich feed stream. PEM fuel cells typically operate with a feed stream gas inlet temperature of less than 450° C. Carbon monoxide is excluded from the feed stream to the extent possible to prevent poisoning of the electrode catalyst, which is typically a platinum-containing catalyst. See U.S. Pat. No. 6,299,995.


[0006] One route for producing a hydrogen-rich gas is hydrocarbon steam reforming. In a hydrocarbon steam reforming process steam is reacted with a hydrocarbon fuel, such as methane, iso-octane, toluene, etc., to produce hydrogen gas and carbon dioxide. The reaction, shown below with methane (CH4), is strongly endothermic; it requires a significant amount of heat.


CH4+2H2O→4H2+CO2


[0007] In the petrochemical industry, hydrocarbon steam reforming of natural gas is typically performed at temperatures in excess of 900° C. Even for catalyst assisted hydrocarbon steam reforming the temperature requirement is often still above 700° C. See, for example, U.S. Pat. No. 6,303,098. Steam reforming of hydrocarbons, such as methane, using nickel- and gold-containing catalysts and temperatures greater than 450° C. is described in U.S. Pat. No. 5,997,835. The catalyzed process forms a hydrogen-rich gas, with depressed carbon formation.


[0008] One example of effective hydrocarbon steam reforming catalysts is the Sinfelt compositions which are composed of Pt, a Group 11 metal, and a Group 8-10 metal. Group 111 metals include Cu, Ag and Au while Group 8-10 metals include the other noble metals. These catalyst formulations are well known in the promotion of hydrogenation, hydrogenolysis, hydrocracking, dealkylation of aromatics, and naphtha reforming processes. See, for example, U.S. Pat. Nos. 3,567,625 and 3,953,368. The application of catalysts based on the Sinfelt model to the water gas shift (“WGS”) reaction, in particular at conditions suitable for lower temperature WGS applications such as PEM fuel cells, has not been previously reported.


[0009] Purified hydrogen-containing feed streams have also been produced by filtering the gas mixture produced by hydrocarbon steam reformation through hydrogen-permeable and hydrogen-selective membranes. See, for example, U.S. Pat. No. 6,221,117. Such approaches suffer from drawbacks due to the complexity of the system and slow flow rates through the membranes.


[0010] Another method of producing a hydrogen-rich gas such as a feed stream starts with a gas mixture containing hydrogen and carbon monoxide and with the absence of any substantial amount of water. For instance, this may be the product of reforming a hydrocarbon or an alcohol, and selectively removes the carbon monoxide from that gas mixture. The carbon monoxide can be removed by absorption of the carbon monoxide and/or by its oxidation to carbon dioxide. Such a process utilizing a ruthenium based catalyst to remove and oxidize the carbon monoxide is disclosed in U.S. Pat. No. 6,190,430.


[0011] The WGS reaction is another mechanism for producing a hydrogen-rich gas but from water (steam) and carbon monoxide. An equilibrium process, the water gas shift reaction, shown below, converts water and carbon monoxide to hydrogen and carbon dioxide, and vice versa.


H2O+COH2+CO2


[0012] Various catalysts have been developed to catalyze the WGS reaction. These catalysts are typically intended for use at temperatures greater than 450° C. and/or pressures above 1 bar. For instance, U.S. Pat. No. 5,030,440 relates to a palladium and platinum-containing catalyst formulation for catalyzing the shift reaction at 550° C. to 650° C. See also U.S. Pat. No. 5,830,425 for an iron/copper based catalyst formulation.


[0013] Catalytic conversion of water and carbon monoxide under water gas shift reaction conditions has been used to produce hydrogen-rich and carbon monoxide-poor gas mixtures. Existing WGS catalysts, however, do not exhibit sufficient activity at a given temperature to reach or even closely approach thermodynamic equilibrium concentrations of hydrogen and carbon monoxide such that the product gas may subsequently be used as a hydrogen feed stream. Specifically, existing catalyst formulations are not sufficiently active at low temperatures, that is, below about 450° C. See U.S. Pat. No. 5,030,440.


[0014] Platinum (Pt) is a well-known catalyst for both hydrocarbon steam reforming and water gas shift reactions. Under typical hydrocarbon steam reforming conditions, high temperature (above 850° C.) and high pressure (greater than 10 bar), the WGS reaction may occur post-reforming over the hydrocarbon steam reforming catalyst due to the high temperature and generally unselective catalyst compositions. See, for instance, U.S. Pat. Nos. 6,254,807; 5,368,835; 5,134,109 and 5,030,440 for a variety of catalyst compositions and reaction conditions under which the water gas shift reaction may occur post-reforming.


[0015] Metals such as cobalt (Co), ruthenium (Ru), palladium (Pd), rhodium (Rh) and nickel (Ni) have also been used as WGS catalysts but are normally too active for the selective WGS reaction and cause methanation of CO to CH4 under typical reaction conditions. In other words, the hydrogen produced by the water gas shift reaction is consumed as it reacts with the CO present in the presence of such catalysts to yield methane. This methanation reaction activity has limited the utility of metals such as Co, Ru, Pd, Rh and Ni as water gas shift catalysts.


[0016] A need exists, therefore, for a method to produce a hydrogen-rich syngas, and catalysts which are highly active and highly selective for both hydrogen generation and carbon monoxide oxidation at moderate temperatures (e.g. below about 450° C.) to provide a hydrogen-rich syngas from a gas mixture containing hydrogen and carbon monoxide.



SUMMARY OF THE INVENTION

[0017] The invention meets the need for highly active and selective catalysts for the generation of hydrogen and the oxidation of carbon monoxide and to thereby provide a hydrogen-rich gas, such as a hydrogen-rich syngas, from a gas mixture of at least carbon monoxide and water. Accordingly, the invention provides methods and catalysts for producing a hydrogen-rich gas.


[0018] The invention is, in a first general embodiment, a method for producing a hydrogen- rich gas (e.g., syngas) by contacting a CO-containing gas, such as a syngas mixture, with a water gas shift catalyst in the presence of water at a temperature of not more than 450° C. In the first general embodiment, the water gas shift catalyst comprises a) Pt, its oxides or mixtures thereof, b) at least one of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, their oxides and mixtures thereof, and c) at least one of Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Pd, Rh, La, Ce, Pr, Nd, Sm, Eu, their oxides and mixtures thereof. In another method of the first general embodiment, the water gas shift catalyst comprises Pt, its oxides or mixtures thereof, at least one of V, Zr, their oxides and mixtures thereof, and at least one of Ti, Mo, Co, their oxides and mixtures thereof. The catalyst may be supported on a carrier, for example, at least one member selected from the group consisting of alumina, zirconia, titania, ceria, magnesia, lanthania, niobia, zeolite, perovskite, silica clay, yttria, iron oxide and mixtures thereof. The method of the invention may be conducted at a temperature ranging from about 150° C. to about 450° C.


[0019] In a second general embodiment, the invention relates to the water gas shift catalysts themselves—both supported and unsupported catalysts. The inventive water gas shift catalyst comprises a) Pt, its oxides or mixtures thereof, b) at least one of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, their oxides and mixtures thereof, and c) at least one of Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Pd, Rh, La, Ce, Pr, Nd, Sm, Eu, their oxides and mixtures thereof. In another catalyst of the second general embodiment, the water gas shift catalyst comprises Pt, its oxides or mixtures thereof, at least one of V, Zr, their oxides and mixtures thereof, and at least one of Ti, Mo, Co, their oxides and mixtures thereof. The catalysts may be supported on a carrier comprising at least one member selected from the group consisting of alumina, zirconia, titania, ceria, magnesia, lanthania, niobia, yttria, iron oxide and mixtures thereof.


[0020] In a third general embodiment, the invention is directed to the aforementioned water gas shift catalysts of the second general embodiment in an apparatus for generating a hydrogen gas containing stream from a hydrocarbon or substituted hydrocarbon feed stream. The apparatus further comprises, in addition to the WGS catalyst, a fuel reformer, a water gas shift reactor, and a temperature controller.







BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.


[0022] The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate preferred embodiments of the invention and together with the detailed description serve to explain the principles of the invention. In the drawings:


[0023]
FIGS. 1A-1C illustrate the process of producing a library test wafer;


[0024]
FIGS. 2A-2C illustrate the process of producing a library test wafer;


[0025]
FIGS. 3A-3I, illustrate the process of producing a library test wafer;


[0026]
FIGS. 3J-3K, illustrate SpotFire plots of the CO conversion versus CO2 production for the wafer under WGS conditions at various temperatures. The legend for FIG. 3A also applies to FIGS. 3B-3I exclusively;


[0027]
FIGS. 4A-4C illustrate the process of producing a library test wafer;


[0028]
FIGS. 5A-5C illustrate the process of producing a library test wafer;


[0029]
FIGS. 5D-5H illustrate SpotFire plots of the CO conversion versus CO2 production for the wafer under WGS conditions. The legend for FIG. 5A also applies to FIGS. 5B and 5C exclusively;


[0030]
FIGS. 6A-6F, illustrate the process of producing a library test wafer;


[0031]
FIGS. 6G, 6H, and 6I, illustrate SpotFire plots of the CO conversion versus CO2 production for the wafer under WGS conditions at various temperatures. The legend for FIG. 6A also applies to FIGS. 6B-6F exclusively;


[0032]
FIG. 7 illustrates plots of CO concentration versus temperature for scaled-up catalyst samples under WGS conditions;


[0033]
FIG. 8 illustrates plots of CO concentration versus temperature for scaled-up catalyst samples under WGS conditions;


[0034]
FIG. 9 illustrates plots of CO concentration versus temperature for scaled-up catalyst samples under WGS conditions;


[0035]
FIGS. 10A-10F, illustrate the compositional make-up of various exemplary library test wafers. The legend for FIGS. 10A-10C applies only to FIGS. 10A-10C. The legend for FIGS. 10D-10F applies only to FIGS. 10D-10F;


[0036]
FIG. 11A illustrates a representative plot of CO conversion versus CO2 production for a prototypical library test wafer at various temperatures;


[0037]
FIG. 1I B illustrates the effect of catalyst selectivity and activity versus the WGS mass balance;


[0038]
FIG. 11C illustrates the effect of temperature on catalyst performance under WGS conditions; and


[0039]
FIG. 12 illustrates plots of CO concentration versus temperature for scaled-up catalyst samples under WGS conditions.







DETAILED DESCRIPTION OF THE INVENTION

[0040] The invention relates to a method for producing a hydrogen-rich gas, such as a hydrogen-rich syngas. According to the method, a CO-containing gas, such as a syngas, contacts a water gas shift catalyst, in the presence of water, preferably a stoichiometric excess of water, preferably at a reaction temperature of less than about 450° C. to produce a hydrogen-rich gas, such as a hydrogen-rich syngas. The reaction pressure is preferably not more than about 10 bar. The invention also relates to a water gas shift catalyst itself and to apparatus such as water gas shift reactors and fuel processing apparatus comprising such WGS catalysts.


[0041] A water gas shift catalyst according to the invention comprises a platinum-based catalyst containing at least one alkali or alkaline-earth metal and at least a third metal. The presence of the alkali or alkaline-earth metal enhances the activity of the water gas shift catalyst at low temperature reaction conditions. Water gas shift catalysts of the invention comprise:


[0042] a) Pt, its oxides or mixtures thereof;


[0043] b) at least one of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, their oxides and mixtures thereof; and


[0044] c) at least one of Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Pd, Rh, La, Ce, Pr, Nd, Sm, Eu, their oxides and mixtures thereof.


[0045] The WGS catalysts of the invention comprise combinations of at least three metals or metalloids, selected from at least three groups a), b) and c) indicated above, in each and every possible permutation and combination, except as specifically and expressly excluded. Although particular subgroupings of preferred combinations of metals or metalloids are also presented, the present invention is not limited to the particularly recited subgroupings.


[0046] In one particularly preferred subgrouping which incorporates additional metals not listed in the above groups a), b) and c), a water gas shift catalyst according to the invention comprises Pt, its oxides or mixtures thereof; at least one of V, Zr, their oxides and mixtures thereof; and at least one of Ti, Mo, Co, their oxides and mixtures thereof. This subgrouping comprises combinations of at least three metals or metalloids, selected from the three groups described immediately above, in each and every possible permutation and combination, except as specifically and expressly excluded.


[0047] Discussion regarding the particular function of various components of catalysts and catalyst systems is provided herein solely to explain the advantage of the invention, and is not limiting as to the scope of the invention or the intended use, function, or mechanism of the various components and/or compositions disclosed and claimed. As such, any discussion of component and/or compositional function is made, without being bound by theory and by current understanding, unless and except such requirements are expressly recited in the claims. Generally, for example, and without being bound by theory, Pt, component a), has activity as a WGS catalyst. The alkali and alkaline-earth metals enhance the low temperature activity of the catalyst and provide basic sites for the adsorption of water by the catalyst. The metals of component c) may or may not themselves have activity as WGS catalysts but function in combination with Pt and the alkali and/or alkaline-earth metals to impart beneficial properties to the catalyst of the invention.


[0048] Catalysts of the invention can catalyze the WGS reaction at varying temperatures, avoid or attenuate unwanted side reactions such as methanation reactions, as well as generate a hydrogen-rich gas, such as a hydrogen-rich syngas. The composition of the WGS catalysts of the invention and their use in WGS reactions are discussed below.


[0049] 1. Definitions


[0050] Water gas shift (“WGS”) reaction: Reaction which produces hydrogen and carbon dioxide from water and carbon monoxide, and vice versa:


H2O+COH2+CO2


[0051] Generally, and unless explicitly stated to the contrary, each of the WGS catalysts of the invention can be advantageously applied both in connection with the forward reaction as shown above (i.e., for the production of H2), or alternatively, in connection with the reverse reaction as shown above (i.e., for the production of CO). As such, the various catalysts disclosed herein can be used to specifically control the ratio of H2 to CO in a gas stream.


[0052] Methanation reaction: Reaction which produces methane and water from a carbon source, such as carbon monoxide or carbon dioxide, and hydrogen:


CO+3H2→CH4+H2O


CO2+4H2→CH4+2H2O


[0053] “Syngas” (also called synthesis gas): Gaseous mixture comprising hydrogen (H2) and carbon monoxide (CO) which may also contain other gas components such as carbon dioxide (CO2), water (H2O), methane (CH4) and nitrogen (N2).


[0054] LTS: Refers to “low temperature shift” reaction conditions where the reaction temperature is less than about 250° C., preferably ranging from about 150° C. to about 250° C.


[0055] MTS: Refers to “medium temperature shift” reaction conditions where the reaction temperature ranges from about 250° C. to about 350° C.


[0056] HTS: Refers to “high temperature shift” reaction conditions where the reaction temperature is more than about 350° C. and up to about 450° C.


[0057] Hydrocarbon: Compound containing hydrogen, carbon, and optionally, oxygen.


[0058] The Periodic Table of the Elements is based on the present TUPAC convention, thus, for example, Group 1 contains the alkali metals Li, Na, K, Rb, and Cs. (See http://www.iupac.org dated May 30, 2002.) As discussed herein, the catalyst composition nomenclature uses a dash (i.e., “-”) to separate catalyst component groups where a catalyst may contain one or more of the catalyst components listed for each component group, brackets (i.e., “{ }”) are used to enclose the members of a catalyst component group, “{two of . . . }” is used if two or more members of a catalyst component group are required to be present in a catalyst composition, “blank” is used within the “{ }” to indicate the possible choice that no additional element is added, and a slash (i.e., “/”) is used to separate supported catalyst components from their support material, if any. Additionally, the elements within catalyst composition formulations include all possible oxidation states, including oxides, or salts, or mixtures thereof.


[0059] Using this shorthand nomenclature, for example, “Pt-{Rh, Ni}-{Na, K, Fe, Os}/ZrO2” would represent catalyst compositions containing Pt, one or more of Rh and Ni, and one or more of Na, K, Fe, and Os supported on ZrO2; all of the catalyst elements may be in any possible oxidation state, unless explicitly indicated otherwise. “Pt-Rh-Ni-{two of Na, K, Fe, Os}” would represent a supported or unsupported catalyst composition containing Pt, Rh, and Ni, and two or more of Na, K, Fe, and Os. “Rh-{Cu, Ag, Au}-{Na, K, blank}/TiO2” would represent catalyst compositions containing Rh, one or more of Cu, Ag, and Au, and optionally, one of Na or K supported on TiO2.


[0060] 2. WGS Catalyst


[0061] A water gas shift catalyst of the invention comprises:


[0062] a) Pt, its oxides or mixtures thereof,


[0063] b) at least one of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, their oxides and mixtures thereof; and


[0064] c) at least one of Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Pd, Rh, La, Ce, Pr, Nd, Sm, Eu, their oxides and mixtures thereof.


[0065] Another water gas shift catalyst according to the invention comprises Pt, its oxides or mixtures thereof; at least one of V, Zr, their oxides and mixtures thereof; and at least one of Ti, Mo, Co, their oxides and mixtures thereof.


[0066] Suitable carriers for supported catalysts are discussed below.


[0067] The catalyst components are typically present in a mixture of the reduced or oxide forms; typically, one of the forms will predominate in the mixture. A WGS catalyst of the invention may be prepared by mixing the metals and/or metalloids in their elemental forms or as oxides or salts to form a catalyst precursor. This catalyst precursor mixture generally undergoes a calcination and/or reductive treatment, which may be in-situ (within the reactor), prior to use as a WGS catalyst. Without being bound by theory, the catalytically active species are generally understood to be species which are in the reduced elemental state or in other possible higher oxidation states. The catalyst precursor species are believed to be substantially completely converted to the catalytically active species by the pre-use treatment. Nonetheless, the catalyst component species present after calcination and/or reduction may be a mixture of catalytically active species such as the reduced metal or other possible higher oxidation states and uncalcined or unreduced species depending on the efficiency of the calcination and/or reduction conditions.


[0068] A. Catalyst Compositions


[0069] As discussed above, one embodiment of the invention is a catalyst for catalyzing the water gas shift reaction (or its reverse reaction). According to the invention, a WGS catalyst may have the following composition:


[0070] a) Pt, its oxides or mixtures thereof;


[0071] b) at least one of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, their oxides and mixtures thereof; and


[0072] c) at least one of Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Pd, Rh, La, Ce, Pr, Nd, Sm, Eu, their oxides and mixtures thereof.


[0073] Water gas shift catalysts where component b) is at least one of Li, Na, K, their oxides, and mixtures thereof represent a preferred group of catalysts. Another preferred group of catalysts are those where component c) is Fe, its oxides or a mixture thereof. Particularly preferred catalysts are those where component b) is at least one of Li, Na, K, their oxides, and mixtures thereof, and component c) is Fe, its oxides or a mixture thereof. Specific water gas shift catalysts of the invention, using the shorthand notation discussed above, include but are not limited to:


[0074] Pt-Li-{Fe, Co, Ce};


[0075] Pt-Na-{Zr, La, Y, Ce, Mo, Fe, Co, Mn};


[0076] Pt-Na-Zr-Co;


[0077] Pt-K-{Ce, Fe, Co}/ZrO2; and


[0078] Pt-K-Ce/ZrO2.


[0079] A discussion of each of the catalyst components a), b) and c) follows.


[0080] Another water gas shift catalyst according to the invention comprises Pt, its oxides or mixtures thereof, at least one of V, Zr, their oxides and mixtures thereof, and at least one of Ti, Mo, Co, their oxides and mixtures thereof.


[0081] The amount of a given metal present in a WGS catalyst of to the invention varies depending on the water gas shift reaction conditions under which the catalyst is to operate. The amount of each metal present depends on the total weight of the catalyst component in its final state in the catalyst composition after the final catalyst preparation step (i.e., the resulting oxidation state or states) with respect to the total weight of all catalyst components plus the support material, if any. Generally, a Group 8, 9, or 10 metal may be present in an amount ranging from about 0.01 wt. % to about 10 wt. %, preferably about 0.01 wt. % to about 2 wt. %, and more preferably about 0.05 wt. % to about 0.5 wt. %. The lanthanide elements and transition metals may be present, typically, in amounts ranging from about 0.01 wt. % to about 40 wt. %, preferably about 0.1 wt. % to about 30 wt. %. The main group elements, including the alkali and alkaline-earth metals, and the metalloid elements may be present in amounts ranging, generally, from about 0.02 wt. % to about 30 wt. %, preferably about 0.04 wt. % to about 20 wt. %. The presence of a given catalyst component in the support material and the extent and type of its interaction with other catalyst components may effect the amount of a component needed to achieve the desired performance effect.


[0082] B. Catalyst Component a): Pt


[0083] A first component in a catalyst of the invention is Pt, component a). Platinum may be present in its reduced form, as an oxide, or a combination of those forms. As discussed in the Background of the Invention, Pt itself is well known to catalyze the WGS reaction.


[0084] C. Catalyst Component b): Alkali/Alkaline-earth Metals


[0085] The catalysts of the invention, containing at least one alkali (Group 1) metals and/or alkaline-earth (Group 2) metals, are not only active WGS catalysts over a broad range of temperatures, but are particularly active under LTS water gas shift conditions. The presence of the alkali and/or alkaline-earth metal basic sites within the catalyst which are believed to adsorb and activate water in the WGS reaction, resulting in better WGS performance. Particularly preferred alkali and alkaline-earth metals include Li, Na and K, with Na and K being most preferred for use in WGS catalysts of the invention. In general, Na-containing catalysts show greater activity than K-containing catalysts at LTS water gas shift conditions. Under HTS water gas shift conditions the presence of an alkali and/or alkaline-earth metal may act to moderate or slightly deactivate the catalyst. It is preferred and in fact advantageous, then, to use the catalysts of the invention under LTS and MTS water gas shift reaction conditions.


[0086] D. Catalyst Component c): “Functional” Metals or Metalloids


[0087] The WGS catalysts of the invention contain at least three metals or metalloids. In addition to components a) and b), discussed above, a WGS catalyst contains metals or metalloids which, when used in combination with Pt and an alkali and/or alkaline-earth metal, function to impart beneficial properties to the catalyst of the invention. A catalyst of the invention, then, further comprises at least one of Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Pd, Rh, La, Ce, Pr, Nd, Sm, Eu, their oxides and mixtures thereof, component c).


[0088] In a preferred embodiment of the invention, component c) of the WGS catalyst is Fe. WGS catalysts according to the invention which contain Fe have high activity under MTS conditions. Fe has an affinity for CO which enhances CO absorption by the catalyst and the catalyst's activity.


[0089] E. Functional Classification of Catalyst Components


[0090] Without limiting the scope of the invention, a discussion of the functions of the various catalyst components is offered, along with a template for composing catalyst compositions according to the invention. The following classification of catalyst components will direct one of skill in the art in the selection of various catalyst components to formulate WGS catalyst compositions according to the present invention and depending on the reaction conditions of interest.


[0091] Furthermore, according to the invention, there are several classes of catalyst components and metals which may be incorporated into a water gas shift catalyst. Hence, the various elements recited as components in any of the described embodiments (e.g., as component (c)), may be included in any various combination and permutation to achieve a catalyst composition that is coarsely or finely tuned for a specific application (e.g. including for a specific set of conditions, such as, temperature, pressure, space velocity, catalyst precursor, catalyst loading, catalyst surface area/presentation, reactant flow rates, reactant ratios, etc.). In some cases, the effect of a given component may vary with the operating temperature for the catalyst. These catalyst components may function as, for instance, activators or moderators depending upon their effect on the performance characteristics of the catalyst. For example, if greater activity is desired, an activator may be incorporated into a catalyst, or a moderator may be replaced by at least one activator or, alternatively, by at least one moderator one step further up the “activity ladder.” An “activity ladder” ranks secondary or added catalyst components, such as activators or moderators, in order of the magnitude of their respective effect on the performance of a principal catalyst constituent. Conversely, if WGS selectivity of a catalyst needs to be increased (e.g., decrease the occurrence of the competing methanation reaction), then either an activator may be removed from the catalyst or, alternatively, the current moderator may be replaced by at least one moderator one step down the “activity ladder.” The function of these catalyst components may be further described as “hard” or “soft” depending on the relative effect obtained by incorporating a given component into a catalyst. The catalyst components may be metals, metalloids, or non-metals.


[0092] For instance, typically, a WGS catalyst according to the invention suitable for use under LTS conditions employs activators and may only be minimally moderated, if at all, because activation is generally the important parameter to be considered under LTS conditions. Such LTS catalysts also may preferably employ high surface area carriers to enhance catalyst activity. Conversely, WGS catalysts used in HTS conditions may benefit from the catalyst being moderated because selectivity and methanation are parameters to be considered. Such HTS catalysts may use, for example, low surface area carriers. Accordingly, operating temperature may be considered in selecting a WGS catalyst according to the present invention for a particular operating environment.


[0093] Activators used in catalysts according to the invention, such as for example Co, are active and selective WGS-promoting metals. Pd is an example of a metal that is moderately active but not very selective and also promotes methanation. Ir has also been observed to have a slight moderating or activating function, depending on the presence of other counter metals. Other activators may include, but are not limited to, Ti, Zr, V, Mo, La, Ce, Pr and Eu. Ce may be the most active rare earth metal for activating the WGS reaction. La, Pr, Sm and Eu may also be active, particularly at lower temperatures. For HTS, Pr and Sm are preferred soft moderators enhancing selectivity without sacrificing much activity. For LTS, La and Eu may be useful activators. In general, all lanthanides, other than Ce, show comparable performance and tend to moderate rather than activate noble metal containing catalyst systems. Y is a highly selective moderator for HTS systems whereas La and Eu are active and comparable to Ce for LTS. La is only slightly moderating when doping Ce, and may therefore be used to adjust the selectivity of Ce containing catalysts.


[0094] Catalyst components that are slightly moderating and highly selective over a relatively broad temperature range (e.g., a temperature range of at least about 50° C., preferably at least about 75° C., and most preferably a temperature range of at least about 100° C.), where such temperature range is included within the overall preferred temperature ranges of up to about 450° C., include Y, Mo, Fe, Pr and Sm; these tend to be selective but not very active at low temperatures, about 250° C. The redox dopants Mo, Fe, Pr and Sm generally lose activity with increasing pre-reduction temperatures while Fe becomes moderately active on its own at high WGS reaction temperatures.


[0095] F. Supports


[0096] The support or carrier may be any support or carrier used with the catalyst which allows the water gas shift reaction to proceed. The support or carrier may be a porous, adsorptive, high surface area support with a surface area of about 25 to about 500 m2/g. The porous carrier material may be relatively inert to the conditions utilized in the WGS process, and may include carrier materials that have traditionally be utilized in hydrocarbon steam reforming processes, such as, (1) activated carbon, coke, or charcoal; (2) silica or silica gel, silicon carbide, clays, and silicates including those synthetically prepared and naturally occurring, for example, china clay, diatomaceous earth, fuller's earth, kaolin, etc.; (3) ceramics, porcelain, bauxite; (4) refractory inorganic oxides such as alumina, titanium dioxide, zirconium oxide, magnesia, etc.; (5) crystalline and amorphous aluminosilicates such as naturally occurring or synthetically prepared mordenite and/or faujasite; and, (6) combinations of these groups.


[0097] When a WGS catalyst of the invention is a supported catalyst, the support utilized may contain one or more of the metals (or metalloids) of the catalyst. The support may contain sufficient or excess amounts of the metal for the catalyst such that the catalyst may be formed by combining the other components with the support. Examples of such supports include ceria which can contribute cerium, Ce, (component c)) to a catalyst, or iron oxide which can contribute iron, Fe, (component c)). When such supports are used the amount of the catalyst component in the support typically may be far in excess of the amount of the catalyst component needed for the catalyst. Thus the support may act as both an active catalyst component and a support material for the catalyst. Alternatively, the support may have only minor amounts of a metal making up the WGS catalyst such that the catalyst may be formed by combining all desired components on the support.


[0098] Carrier screening with catalysts containing Pt as the only active noble metal revealed that a water gas shift catalyst may also be supported on a carrier comprising alumina, zirconia, titania, ceria, magnesia, lanthania, niobia, yttria and iron oxide. Perovskite, supported on the above listed carriers or unsupported, may also be utilized as a support for the inventive catalyst formulations.


[0099] Zirconia, titania and ceria may be supports for the present invention and provide high activity for the WGS reaction. Preferably, zirconia is in the monoclinic phase. Highly pure ceria was found to activate Pt in LTS conditions more than cerias doped with additives. Niobia, yttria and iron oxide carriers provide high selectivity but are also less active which is believed to be due to a lack of surface area. In addition to their use as carriers, iron, yttrium, and magnesium oxides may be utilized as primary layers on carriers such as zirconia to provide both higher surface area and low moderator concentration. Pt on magnesia carriers formulated to have high surface areas (approximately 100 m2/g) exhibit high selectivity but also exhibit activity which decreases rapidly with falling reaction temperature.


[0100] In general, alumina has been found to be an active but unselective carrier for Pt only containing WGS catalysts. However, the selectivity of gamma alumina may be improved by doping with Zr, Co, or one of the rare earth elements, such as, for example, La and Ce alone or in combination. This doping may be accomplished by addition of the oxides or other salts such as nitrates, in either liquid or solid form, to the alumina. Other possible dopants to increase the selectivity include redox dopants, such as for instance, Mo, Fe and basic dopants. Preferred is an embodiment of gamma alumina combined with Zr and/or Co which exhibits both high activity and selectivity over a broad temperature range.


[0101] High surface area aluminas, such as gamma-, delta-, or theta-alumina are preferred alumina carriers. Other alumina carriers, such as mixed silica alumina, sol-gel alumina, as well as sol-gel or co-precipitated alumina-zirconia carriers may be used. Alumina typically has a higher surface area and a higher pore volume than carriers such as zirconia and offers a price advantage over other more expensive carriers.


[0102] Examples of a WGS catalyst of the invention supported on a carrier, using the shorthand notation discussed above, include:


[0103] Pt-Na-{Zr, La, Y, Ce, Mo, Fe, Co, Mn}/Al2O3;


[0104] Pt-Na-Zr-Co/Al2O3;


[0105] Pt-Na-{Fe, Co, Ce}/ZrO2;


[0106] Pt-K-{Fe, Co, Ce}/ZrO2; and


[0107] Pt-Li-{Fe, Co, Ce}/ZrO2.


[0108] For the alumina supported catalysts, gamma alumina (γ-Al2O3) is preferred.


[0109] G. Methods of Making a WGS Catalyst


[0110] As set forth above, a WGS catalyst of the invention may be prepared by mixing the metals and/or metalloids in their elemental forms or as oxides or salts to form a catalyst precursor, which generally undergoes a calcination and/or reductive treatment. Without being bound by theory, the catalytically active species are generally understood to be species which are in the reduced elemental state or in other possible higher oxidation states.


[0111] The WGS catalysts of the invention may be prepared by any well known catalyst synthesis processes. See, for example, U.S. Pat. Nos. 6,299,995 and 6,293,979. Spray drying, precipitation, impregnation, incipient wetness, ion exchange, fluid bed coating, physical or chemical vapor deposition are just examples of several methods that may be utilized to make the present WGS catalysts. Preferred approaches, include, for instance, impregnation or incipient wetness. The catalyst may be in any suitable form, such as, pellets, granular, bed, or monolith. See also co-pending U.S. patent application Ser. No. ______, entitled “Methods For The Preparation Of Catalysts For Hydrogen Generation” to Hagemeyer et al. (Attorney Docket No. 7080-011-01), filed on the same date as the present application, for further details on methods of catalyst preparation and catalyst precursors.


[0112] The WGS catalyst of the invention may be prepared on a solid support or carrier material. Preferably, the support or carrier is, or is coated with, a high surface area material onto which the precursors of the catalyst are added by any of several different possible techniques, as set forth above and as known in the art. The catalyst of the invention may be employed in the form of pellets, or on a support, preferably a monolith, for instance a honeycomb monolith.


[0113] One preferred method of preparing the catalysts involves depositing or impregnating catalyst components onto the catalyst in a sequence such that the catalyst components are deposited onto the substrate in the order of decreasing calcination temperature, with a calcination step following each deposition step, and with Pt typically impregnated and calcined last. One exception to this preparation procedure concerns catalyst formulations which contain both Pt and an alkali metal, like Na; in such a case the Pt is impregnated and calcined next to last, with the alkali metal then added and calcined at a calcination temperature of less than about 300° C., preferably about 200° C., or more preferably about the reaction temperature of the intended function of the catalyst. Pre-reduction under, for example, H2 of the calcined Pt-containing catalyst formulation may also be beneficial to catalyst performance. High temperature, greater than about 300° C. tends to be deleterious to the performance of Na containing formulations. This procedure appears to be especially beneficial to catalysts formulated to operate at LTS and/or MTS operating conditions.


[0114] Catalyst precursor solutions are preferably composed of easily decomposable forms of the catalyst component in a sufficiently high enough concentration to permit convenient preparation. Examples of easily decomposable precursor forms include the nitrate, amine, and oxalate salts. Typically, chlorine containing precursors are avoided to prevent chlorine poisoning of the catalyst. Solutions can be aqueous or non-aqueous solutions. Exemplary non-aqueous solvents can include polar solvents, aprotic solvents, alcohols, and crown ethers, for example, tetrahydrofuran and ethanol. Concentration of the precursor solutions generally may be up to the solubility limitations of the preparation technique with consideration given to such parameters as, for example, porosity of the support, number of impregnation steps, pH of the precursor solutions, and so forth. The appropriate catalyst component precursor concentration can be readily determined by one of ordinary skill in the art of catalyst preparation.


[0115] Li—The acetate, hydroxide, nitrate and formate salts are both possible catalyst precursors for lithium.


[0116] Na—Sodium acetate, alkoxides including methoxide, propoxide, and ethoxide, bicarbonate, carbonate, citrate, formate, hydroxide, nitrate, nitrite and oxalate may be used to prepare WGS catalysts of the invention.


[0117] Mg—Water soluble magnesium precursors include the nitrate, acetate, lactate and formate salts.


[0118] K—Potassium nitrate, acetate, carbonate, hydroxide and formate are possible potassium catalyst precursors. The KOAc salt is volatile with possible potassium losses when heating up to calcination temperature.


[0119] Ca—The nitrate, acetate and hydroxide salts, preferable salts highly soluble in water, may be used to prepare catalysts of the invention.


[0120] Sc—The nitrate salt, Sc(NO3)3 may be a precursor for scandium.


[0121] Ti—Titanium precursors which may be utilized in the present invention include ammonium titanyl oxalate, (NH4)2TiO(C2O4)2, available from Aldrich, and titanium(IV) bis(ammonium lactato)dihydroxide, 50 wt % solution in water, [CH3CH(O—)CO2NH4]2Ti(OH)2, available from Aldrich. Other titanium containing precursors include Ti oxalate prepared by dissolving a Ti(IV) alkoxide, such as Ti(IV) propoxide, Ti(OCH2CH2CH3)4, (Aldrich) in 1M aqueous oxalic acid at 60° C. and stirring for a couple of hours, to produce a 0.72M clear colorless solution; TiO(acac)oxalate prepared by dissolving Ti(IV) oxide acetylacetonate, TiO(acac)2, (Aldrich) in 1.5M aqueous oxalic acid at 60° C. with stirring for a couple of hours, following by cooling to room temperature overnight to produce 1M clear yellow-brown solution; TiO(acac)2, may also be dissolved in dilute acetic acid (50:50 HOAc:H2O) at room temperature to produce a 1M clear yellow solution of TiO acac. Preferably, titanium dioxide in the anatase form is utilized as a catalyst precursor material.


[0122] V—Vanadium (IV) oxalate, a vanadium precursor, may be prepared from V2O5, (Aldrich), which is slurried in 1.5M aqueous oxalic acid on hot plate for 1 hour until it turns dark blue due to V(V) reduction to V(IV) by oxalic acid. Ammonium metavanadate(V), (NH4)VO3, (Cerac, Alfa) may be used as a precursor by dissolving it in water, preferably hot, about 80° C. water. Various polycarboxylic organic acid vanadium precursors can be prepared and used as catalyst precursors, for example, citric, maleic, malonic, and tartatic. Vanadium citrate can be prepared by reacting V2O5 with citric acid and heating to about 80° C. Ammonium vanadium(V) oxalate may be prepared by reacting (NH4)VO3 and NH4OH in room temperature water, increasing temperature to 90° C., stirring to dissolve all solids, cooling to room temperature and adding oxalic acid; this produces a clear orange solution, which is stable for about 2 days. Ammonium vanadium(V) citrate and ammonium vanadium(V) lactate are both prepared by shaking NH4VO3 in, respectively, aqueous citric acid or aqueous lactic acid, at room temperature. Diammonium vanadium(V) citrate may be prepared by dissolving, for instance, 0.25M NH4VO3 in citric acid diammonium salt (Alfa) at room temperature. An exemplary method of preparing ammonium vanadium(V) formate is to dissolve NH4VO3 (0.25M) in water at 95° C., react with 98% formic acid and NH4OH to produce the desired ammonium vanadium(V) formate.


[0123] Cr—Both the nitrate and acetate hydroxides are possible catalyst precursors for chromium.


[0124] Mn—Manganese nitrate, manganese acetate (Aldrich) and manganese formate (Alfa) are all possible catalyst precursors for manganese.


[0125] Fe—Iron (III) nitrate, Fe(NO3)3, iron(III) ammonium oxalate, (NH4)3 Fe(C2O4)3, iron(III) oxalate, Fe2(C2O4)3, and iron(II) acetate, Fe(OAc)2, are all water soluble; although the iron(III)oxalate undergoes thermal decomposition at only 100° C. Potassium iron(III) oxalate, iron(III) formate and iron(III) citrate are additional iron precursors.


[0126] Co—Both cobalt nitrate and acetate are water soluble precursor solutions. The cobalt (II) formate, Co(OOCH)2, has low solubility in cold water of about 5 g/100 ml, while cobalt (II) oxalate is soluble in aqueous NH4OH. Another possible precursor is sodium hexanitrocobaltate(III), Na3Co(NO2)6 which is water soluble, with gradual decomposition of aqueous solutions slowed by addition of small amounts of acetic acid. Hexaammine Co(III) nitrate is also soluble in hot (65° C.) water and NMe4OH. Cobalt citrate, prepared by dissolving Co(OH)2 in aqueous citric acid at 80° C. for 1 to 2 hours, is another suitable cobalt precursor.


[0127] Ni—Nickel nitrate, Ni(NO3)2, and nickel formate are both possible nickel precursors. The nickel formate may be prepared by dissolving Ni(HCO2)2 in water and adding formic acid, or by dissolving in dilute formic acid, to produce clear greenish solutions.


[0128] Cu—Copper precursors include nitrate, Cu(NO3)2, acetate, Cu(OAc)2, and formate, Cu(OOCH)2, which are increasingly less water soluble in the order presented. Ammonium hydroxide is used to solublize oxalate, Cu(C2O4)2, and Cu(NH3)4(OH)2 which is soluble in aqueous 5N NH4OH. Copper citrate and copper amine carbonate may be prepared from Cu(OH)2.


[0129] Zn—Zinc nitrate, acetate and formate are all water soluble and possible catalyst precursors. Ammonium zinc carbonate, (NH4)2Zn(OH)2CO3, prepared by reacting zinc hydroxide and ammonium carbonate for a week at room temperature, is another possible precursor for zinc.


[0130] Ge—Germanium oxalate may be prepared from amorphous Ge(IV) oxide, glycol-soluble GeO2, (Aldrich) by reaction with 1M aqueous oxalic acid at room temperature. H2GeO3 may be prepared by dissolving GeO2 in water at 80° C. and adding 3 drops of NH4OH (25%) to produce a clear, colorless H2GeO3 solution. (NMe4)2GeO3 may be prepared by dissolving 0.25 M GeO2 in 0.1 M NMe4OH. (NH4)2GeO3 may be prepared by dissolving 0.25 M GeO2 in 0.25M NH4OH.


[0131] Rb—The nitrate, acetate, carbonate and hydroxide salts may be used as catalyst precursors to prepare the WGS catalyst of the invention. Preferred are water soluble salts.


[0132] Sr—The acetate is soluble in cold water to produce a clear colorless solution.


[0133] Y—Yttrium nitrate and acetate are both possible catalyst precursors.


[0134] Zr—Zirconyl nitrate and acetate, commercially available from Aldrich, and ammonium Zr carbonate and zirconia, available from MEI, are possible precursors for zirconium in either or both the support or catalyst formulation itself.


[0135] Nb—Niobium oxalate prepared by dissolving niobium (V) ethoxide in aqueous oxalic acid at 60° C. for 12 hours is a possible catalyst precursor. Another preparative route to the oxalate is dissolving niobic acid or niobic oxide (Nb2O5) in oxalic acid at 65° C. Ammonium Nb oxalate is also a possible catalyst precursor for niobium. Dissolving niobic oxide (0.10 M Nb) in NMe4OH (0.25 M) and stirring overnight at 65° C. will produce (NMe4)2NbO6.


[0136] Mo—Molybdenum containing precursor solutions may be derived from ammonium molybdate (NH4)2MoO4 (Aldrich) dissolved in room temperature water; Mo oxalate prepared by dissolving MoO3 (Aldrich) in 1.5M aqueous oxalic acid at 60° C. overnight; and ammonium Mo oxalate prepared from (NH4)6Mo7O244H2O (Strem) dissolved in 1M aqueous oxalic acid at room temperature. (NH4)6Mo7O24.4H2O (Strem) may also be dissolved in water at room temperature to produce a stable solution of ammonium paramolybdate tetrahydrate. Molybdic acid, H2MoO4, (Alfa Aesar or Aldrich) may each be dissolved in room temperature water to produce 1M Mo containing solutions.


[0137] Ru—Ru nitrosyl nitrate, Ru(NO)(NO3)3 (Aldrich), potassium ruthenium oxide, K2RuO4.H2O, potassium perruthenate, KRuO4, ruthenium nitrosyl acetate, Ru(NO)(OAc)3, and tetrabutylammonium perruthenate, NBu4RuO4, are all possible ruthenium metal catalyst precursors. NMe4Ru(NO)(OH)4 solution can be prepared by dissolving Ru(NO)(OH)3 (0.1 M) (H. C. Starck) in NMe4OH (0.12M) at 80° C. produces a clear dark red-brown 0.1M Ru solution useful as a catalyst precursor solution.


[0138] Rh—A suitable rhodium catalyst precursor is Rh nitrate (Aldrich or Strem).


[0139] Pd—Catalyst compositions containing Pd can be prepared by using precursors like Pd nitrate, typically stabilized by dilute HNO3, and available as a 10 wt. % solution from Aldrich, or Pd(NH3)2(NO2)2 available as a 5 wt. % Pd commercial solution, stabilized by dilute NH4OH. Pd(NH3)4(NO3)2 and Pd(NH3)4(0H)2 are also available commercially.


[0140] Ag—Silver nitrate, silver nitrite, silver diammine nitrite, and silver acetate are possible silver catalyst precursors.


[0141] Cd—Cadmium nitrate is water soluble and a suitable catalyst precursor.


[0142] In—Indium formate and indium nitrate are preferred precursors for indium.


[0143] Sn—Tin oxalate produced by reacting the acetate with oxalic acid may be used as a catalyst precursor. Tin tartrate, 5 nC4H4O6, in NMe4OH at about 0.25 M Sn concentration, and tin acetate, also dissolved in NMe4OH at about 0.25 M Sn concentration, may be used as catalyst precursors.


[0144] Sb—Ammonium antimony oxalate produced by reacting the acetate with oxalic acid and ammonia is a suitable antimony precursor. Antimony oxalate, Sb2(C2O4)3, available from Pfaltz & Bauer, is a water soluble precursor. Potassium antimony oxide, KSbO3, and antimony citrate, prepared by stirring antimony(II) acetate in 1 M citric acid at room temperature, are both possible catalyst precursors.


[0145] Te—Telluric acid, Te(OH)6, may be used as a precursor for tellurium.


[0146] Cs—Cs salts including the nitrate, acetate, carbonate, and hydroxide are soluble in water and possible catalyst precursors.


[0147] Ba—Barium acetate and barium nitrate are both suitable precursors for barium catalyst components.


[0148] La—Lanthanum precursors include nitrate, La(NO3)3, acetate, La(OAc)3, and perchlorate, La(ClO4)3, all of which may be prepared as aqueous solutions.


[0149] Ce—Ce(III) and Ce(IV) solutions may be prepared from Ce(III) nitrate hexahydrate, Ce(NO3)3.6H2O, (Aldrich) and ammonium cerium(IV) nitrate, (NH4)2Ce(NO3)6, (Aldrich), respectively, by dissolution in room temperature water. Nitric acid, 5 vol. %, may be added to the Ce(III) salt to increase solubility and stability. Ce(OAc)3 (Alfa) or Ce(NO3)4 (Alfa) may also be utilized as a catalyst precursor.


[0150] Pr, Nd, Sm and Eu—The nitrate, Ln(NO3)3, or acetate, Ln(O2CCH3)3, are possible catalyst precursors for these lanthanides.


[0151] Hf—Hafnoyl chloride and nitrate are both possible precursors. Preparing the hafnoyl nitrate by dissolving Hf(acac)4 in dilute HNO3 at low heat provides a clear stable solution of hafnoyl nitrate.


[0152] Ta—Tantalum oxalate solution, Ta2O(C2O4)4, available from H. C. Starck, or prepared by dissolving Ta(OEt)5 in aqueous oxalic acid at 60° C. for 12 hours, is a possible catalyst precursor.


[0153] W—Ammonium metatungstate hydrate, (NH4)6W12O39, is water soluble and a possible tungsten catalyst precursor. H2WO4 is reacted with NH4OH and NMe4OH, respectively, to prepare (NH4)2WO4 and (NMe4)2WO4 which are both possible precursors.


[0154] Re—Rhenium oxide in H2O2, perrhenic acid, (HReO4), NaReO4 and NH4ReO4 are suitable rhenium precursors.


[0155] Ir—Hexachloroiridate acid, H2IrCl6, potassium hexacyanoiridate and potassium hexanitroiridate are all possible catalyst precursors for iridium.


[0156] Pt—Platinum containing catalyst compositions may be prepared by using any one of a number of precursor solutions, such as, Pt(NH3)4(NO3)2 (Aldrich, Alfa, Heraeus, or Strem), Pt(NH3)2(NO2)2 in nitric acid, Pt(NH3)4(OH)2 (Alfa), K2Pt(NO2)4, Pt(NO3)2, PtCl4 and H2PtCl6 (chloroplatinic acid). Pt(NH3)4(HCO3)2, Pt(NH3)4(HPO4), (NMe4)2Pt(OH)6, H2Pt(OH)6, K2Pt(OH)6, Na2Pt(OH)6 and K2Pt(CN)6 are also possible choices along with Pt oxalate salts, such as K2Pt(C2O4)2. The Pt oxalate salts may be prepared from Pt(NH3)4(OH)2 which is reacted with 1M oxalic acid solution to produce a clear, colorless solution of the desired Pt oxalate salts.


[0157] Au—Auric acid, HAuCl4, in dilute HCl at about 5% Au may be a gold precursor. Gold nitrate in 0.1 M concentration may be prepared by dissolving HAu(NO3)4 (Alfa) in concentrated nitric acid, followed by stirring at room temperature for 1 week in the dark, then diluting 1:1 with water to produce a yellow solution. It should be noted that further dilution may result in Au precipitation. More concentrated, 0.25M, for example, gold nitrate may be prepared by starting with Au(OH)3 (Alfa). NaAu(OH)4, KAu(OH)4, and NMe4Au(OH)4 may each be prepared from Au(OH)3 dissolved in bases NaOH, KOH, or NMe4OH, respectively, in base concentrations ranging from, for instance, 0.25 M or higher.


[0158] 3. Producing a Hydrogen-rich Gas, such as a Hydrogen-Rich Syngas


[0159] The invention also relates to a method for producing a hydrogen-rich gas, such as a hydrogen-rich syngas. An additional embodiment of the invention may be directed to a method of producing a CO depleted gas, such as a CO-depleted syngas.


[0160] A CO-containing gas, such as a syngas contacts a water gas shift catalyst in the presence of water according to the method of the invention. The reaction preferably may occur at a temperature of less than 450° C. to produce a hydrogen-rich gas such as a hydrogen-rich syngas.


[0161] A method of the invention may be utilized over a broad range of reaction conditions. Preferably, the method is conducted at a pressure of no more than about 75 bar, preferably at a pressure of no more than about 50 bar to produce a hydrogen-rich syngas. Even more preferred is to have the reaction occur at a pressure of no more than about 25 bar, or even no more than about 15 bar, or not more than about 10 bar. Especially preferred is to have the reaction occur at, or about atmospheric pressure. Depending on the formulation of the catalyst according to the present invention, the present method may be conducted at reactant gas temperatures ranging from less than about 250° C. to up to about 450° C. Preferably, the reaction occurs at a temperature selected from one or more temperature subranges of LTS, MTS and/or HTS as described above. Space velocities may range from about 1 hr−1 up to about 1,000,000 hr−1. Feed ratios, temperature, pressure and the desired product ratio are factors that would normally be considered by one of skill in the art to determine a desired optimum space velocity for a particular catalyst formulation.


[0162] 4. Fuel Processor Apparatus


[0163] The invention further relates to a fuel processing system for generation of a hydrogen-rich gas from a hydrocarbon or substituted hydrocarbon fuel. Such a fuel processing system would comprise, for example, a fuel reformer, a water gas shift reactor and a temperature controller.


[0164] The fuel reformer would convert a fuel reactant stream comprising a hydrocarbon or a substituted hydrocarbon fuel to a reformed product stream comprising carbon monoxide and water. The fuel reformer may typically have an inlet for receiving the reactant stream, a reaction chamber for converting the reactant stream to the product stream, and an outlet for discharging the product stream.


[0165] The fuel processor system would also comprise a water gas shift reactor for effecting a water gas shift reaction at a temperature of less than about 450° C. This water gas shift reactor may comprise an inlet for receiving a water gas shift feed stream comprising carbon monoxide and water from the product stream of the fuel reformer, a reaction chamber having a water gas shift catalyst as described herein located therein, and an outlet for discharging the resulting hydrogen-rich gas. The water gas shift catalyst would preferable be effective for generating hydrogen and carbon dioxide from the water gas shift feed stream.


[0166] The temperature controller may be adapted to maintain the temperature of the reaction chamber of the water gas shift reactor at a temperature of less than about 450° C.


[0167] 5. Industrial Applications


[0168] Syngas is used as a reactant feed in number of industrial applications, including for example, methanol synthesis, ammonia synthesis, oxoaldehyde synthesis from olefins (typically in combination with a subsequent hydrogenation to form the corresponding oxoalcohol), hydrogenations and carbonylations. Each of these various industrial applications preferably includes a certain ratio of H2 to CO in the syngas reactant stream. For methanol synthesis the ratio of H2:CO is preferably about 2:1. For oxosynthesis of oxoaldehydes from olefins, the ratio of H2:CO is preferably about 1:1. For ammonia synthesis, the ratio of H2 to N2 (e.g., supplied from air) is preferably about 3:1. For hydrogenations, syngas feed streams that have higher ratios of H2:CO are preferred (e.g., feed streams that are H2 enriched, and that are preferably substantially H2 pure feed streams). Carbonylation reactions are preferably effected using feed streams that have lower ratios of H2:CO (e.g., feed streams that are CO enriched, and that are preferably substantially CO pure feed streams).


[0169] The WGS catalysts of the present invention, and the methods disclosed herein that employ such WGS catalysts, can be applied industrially to adjust or control the relative ratio H2:CO in a feed stream for a synthesis reaction, such as methanol synthesis, ammonia synthesis, oxoaldehyde synthesis, hydrogenation reactions and carbonylation reactions. In one embodiment, for example, a syngas product stream comprising CO and H2 can be produced from a hydrocarbon by a reforming reaction in a reformer (e.g., by steam reforming of a hydrocarbon such as methanol or naphtha). The syngas product stream can then be fed (directly or indirectly after further downstream processing) as the feed stream to a WGS reactor, preferably having a temperature controller adapted to maintain the temperature of the WGS reactor at a temperature of about 450° C. or less during the WGS reaction (or at lower temperatures or temperature ranges as described herein in connection with the catalysts of the present invention). The WGS catalyst(s) employed in the WGS reactor are preferably selected from one or more of the catalysts and/or methods of the invention. The feed stream to the WGS reactor is contacted with the WGS catalyst(s) under reaction conditions effective for controlling the ratio of H2:CO in the product stream from the WGS reactor (i.e., the “shifted product stream”) to the desired ratio for the downstream reaction of interest (e.g., methanol synthesis), including to ratios described above in connection with the various reactions of industrial significance. As a non-limiting example, a syngas product stream from a methane steam reformer will typically have a H2:CO ratio of about 6:1. The WGS catalyst(s) of the present invention can be employed in a WGS reaction (in the forward direction as shown above) to further enhance the amount of H2 relative to CO, for example to more than about 10:1, for a downstream hydrogenation reaction. As another example, the ratio of H2:CO in such a syngas product stream can be reduced by using a WGS catalyst(s) of the present invention in a WGS reaction (in the reverse direction as shown above) to achieve or approach the desired 2:1 ratio for methanol synthesis. Other examples will be known to a person of skill in the art in view of the teachings of the present invention.


[0170] 6. Preparative Method for Li- and Fe-Containing Catalyst Formulations


[0171] The invention further provides a method of producing a water gas shift catalyst comprising Pt, Li and Fe, their oxides or mixtures thereof. The preparative method comprises the steps of depositing Li and Fe onto a surface, preferably a catalyst support, calcining at a calcination temperature from about 600° C. to about 900° C. and then depositing Pt onto the Li and Fe containing catalyst. More preferably the calcination temperature is from about 650° C. to about 800° C., and most preferably at a temperature of about 700° C. A further embodiment of this invention includes a step of depositing Na onto the catalyst after the calcination of Li and Fe. The Na deposition may occur simultaneous with the Pt deposition.


[0172] A person of skill in the art will understand and appreciate that with respect to each of the preferred catalyst embodiments as described in the preceding paragraphs, the particular components of each embodiment can be present in their elemental state, or in one or more oxide states, or mixtures thereof.


[0173] Although the foregoing description is directed to the preferred embodiments of the invention, it is noted that other variations and modifications will be apparent to those skilled in the art, and which may be made without departing from the spirit or scope of the invention.



EXAMPLES

[0174] General


[0175] Small quantity catalyst composition samples are generally prepared by automated liquid dispensing robots (Cavro Scientific Instruments) on flat quartz test wafers.


[0176] Generally, supported catalysts are prepared by providing a catalyst support (e.g. alumina, silica, titania, etc.) to the wafer substrate, typically as a slurry composition using a liquid-handling robot to individual regions or locations on the substrate or by wash-coating a surface of the substrate using techniques known to those of skill in the art, and drying to form dried solid support material on the substrate. Discrete regions of the support-containing substrate are then impregnated with specified compositions intended to operate as catalysts or catalyst precursors, with the compositions comprising metals (e.g. various combinations of transition metal salts). In some circumstances the compositions are delivered to the region as a mixture of different metal-containing components and in some circumstances (additionally or alternatively) repeated or repetitive impregnation steps are performed using different metal-containing precursors. The compositions are dried to form supported catalyst precursors. The supported catalyst precursors are treated by calcining and/or reducing to form active supported catalytic materials at discrete regions on the wafer substrate.


[0177] Bulk catalysts may also be prepared on the substrate. Such multi-component bulk catalysts are purchased from a commercial source and/or are prepared by precipitation or co-precipitation protocols, and then optionally treated—including mechanical pretreatment (grinding, sieving, pressing). The bulk catalysts are placed on the substrate, typically by slurry dispensing and drying, and then optionally further doped with additional metal-containing components (e.g. metal salt precursors) by impregnation and/or incipient wetness techniques to form bulk catalyst precursors, with such techniques being generally known to those of skill in the art. The bulk catalyst precursors are treated by calcining and/or reducing to form active bulk catalytic materials at discrete regions on the wafer substrate.


[0178] The catalytic materials (e.g., supported or bulk) on the substrate are tested for activity and selectivity for the WGS reaction using a scanning mass spectrometer (SMS) comprising a scanning/sniffing probe and a mass spectrometer. More details on the scanning mass spectrometer instrument and screening procedure are set forth in U.S. Pat. No. 6,248,540, in European Patent No. EP 1019947, and in European Patent Application No. EP 1186892 and corresponding U.S. application Ser. No. 09/652,489 filed Aug. 31, 2000 by Wang et al., the complete disclosure of each of which is incorporated herein in its entirety. Generally, the reaction conditions (e.g. contact time and/or space velocities, temperature, pressure, etc.) associated with the scanning mass spectrometer catalyst screening reactor are controlled such that partial conversions (i.e., non-equilibrium conversions, e.g., ranging from about 10% to about 40% conversion) are obtained in the scanning mass spectrometer, for discrimination and ranking of catalyst activities for the various catalytic materials being screened. Additionally, the reaction conditions and catalyst loadings are established such that the results scale appropriately with the reaction conditions and catalyst loadings of larger scale laboratory research reactors for WGS reactions. A limited set of tie-point experiments are performed to demonstrate the scalability of results determined using the scanning mass spectrometer to those using larger scale laboratory research reactors for WGS reactions. See, for example, Example 12 of U.S. Provisional Patent Application Serial No. 60/434,708 entitled “Platinum-Ruthenium Containing Catalyst Formulations for Hydrogen Generation” filed by Hagemeyer et al. on Dec. 20, 2002.


[0179] Preparative and Testing Procedures


[0180] The catalysts and compositions of the present invention were identified using high- throughput experimental technology, with the catalysts being prepared and tested in library format, as described generally above, and in more detail below. Specifically, such techniques were used for identifying catalyst compositions that were active and selective as WGS catalysts. As used in these examples, a “catalyst library” refers to an associated collection of candidate WGS catalysts arrayed on a wafer substrate, and having at least two, and typically three or more common metal components (including metals in the fully reduced state, or in a partially or fully oxidized state, such as metal salts), but differing from each other with respect to relative stoichiometry of the common metal components.


[0181] Depending on the library design and the scope of the investigation with respect to a particular library, multiple (i.e., two or more) libraries were typically formed on each wafer substrate. A first group of test wafers each comprised about 100 different catalyst compositions formed on a three-inch wafer substrate, typically with most catalysts being formed using at least three different metals. A second group of test wafers each comprised about 225 different catalyst compositions on a four-inch wafer substrate, again typically with most catalysts being formed using at least three different metals. Each test wafer itself typically comprised multiple libraries. Each library typically comprised binary, ternary or higher-order compositions—that is, for example, as ternary compositions that comprised at least three components (e.g., A, B, C) combined in various relative ratios to form catalytic materials having a molar stoichiometry covering a range of interest (e.g., typically ranging from about 20% to about 80% or more (e.g. to about 100% in some cases) of each component). For supported catalysts, in addition to varying component stoichiometry for the ternary compositions, relative total metal loadings were also investigated.


[0182] Typical libraries formed on the first group of (three-inch) test wafers included, for example, “five-point libraries” (e.g., twenty libraries, each having five different associated catalyst compositions), or “ten-point” libraries (e.g., ten libraries, each having ten different associated catalyst compositions), or “fifteen-point libraries” (e.g., six libraries, each having fifteen different associated catalyst compositions) or “twenty-point libraries” (e.g., five libraries, each having twenty different associated catalyst compositions). Typical libraries formed on the second group of (four-inch) test wafers included, for example, “nine-point libraries” (e.g., twenty-five libraries, each having nine different associated catalyst compositions), or “twenty-five point” libraries (e.g., nine libraries, each having twenty-five different associated catalyst compositions). Larger compositional investigations, including “fifty-point libraries” (e.g., two or more libraries on a test wafer, each having fifty associated catalyst compositions), were also investigated. Typically, the stoichiometric increments of candidate catalyst library members ranged from about 1.5% (e.g. for a “fifty-five point ternary”) to about 15% (e.g., for a “five- point” ternary). See, generally, for example, WO 00/17413 for a more detailed discussion of library design and array organization. FIGS. 10A-10F show library designs for libraries prepared on a common test wafer, as graphically represented using Library Studios (Symyx Technologies, Inc., Santa Clara, Calif.), where the libraries may vary with respect to both stoichiometry and catalyst loading. Libraries of catalytic materials that vary with respect to relative stoichiometry and/or relative catalyst loading can also be represented in a compositional table, such as is shown in the several examples of this application.


[0183] Referring to FIG. 10A, for example, the test wafer includes nine libraries, where each of the nine libraries comprise nine different ternary compositions of the same three-component system. In the nomenclature of the following examples, such a test wafer is said to include nine, nine-point-ternary (“9PT”) libraries. The library depicted in the upper right hand corner of this test wafer includes catalyst compositions comprising components A, B and XI in 9 different stoichiometries. As another example, with reference to FIG. 10B, a partial test wafer is depicted that includes a fifteen-point-ternary (“15PT”) library having catalyst compositions of Pt, Pd and Cu in fifteen various stoichiometries. Generally, the composition of each catalyst included within a library is graphically represented by an association between the relative amount (e.g., moles or weight) of individual components of the composition and the relative area shown as corresponding to that component. Hence, referring again to the fifteen different catalyst compositions depicted on the partial test wafer represented in FIG. 10B, it can be seen that each composition includes Pt (red), Pd (green) and Cu (blue), with the relative amount of Pt increasing from column 1 to column 5 (but being the same as compared between rows within a given column), with the relative amount of Pd decreasing from row 1 to row 5 (but being the same as compared between columns within a given row), and with the relative amount of Cu decreasing from a maximum value at row 5, column 1 to a minimum at, for example, row 1, column 1. FIG. 10C shows a test wafer that includes a fifty-point-ternary (“50PT”) library having catalyst compositions of Pt, Pd and Cu in fifty various stoichiometries. This test library could also include another fifty-point ternary library (not shown), for example with three different components of interest.


[0184]
FIGS. 10D-10F are graphical representations of two fifty-point ternary libraries (“bis 50PT libraries”) at various stages of preparation—including a Pt-Au-Ag/CeO2 library (shown as the upper right ternary library of FIG. 10E) and a Pt-Au-Ce/ZrO2 library (shown as the lower left ternary library of FIG. 1E). Note that the Pt-Au-Ag/CeO2 library also includes binary- impregnated compositions—Pt-Au/CeO2 binary catalysts (row 2) and Pt-Ag/CeO2 (column 10). Likewise, the Pt-Au-Ce/ZrO2 library includes binary-impregnated compositions—Pt-Ce/ZrO2 (row 11) and Au-Ce/ZrO2 (column 1). Briefly, the bis 50PT libraries were prepared by depositing CeO2 and ZrO2 supports onto respective portions of the test wafer as represented graphically in FIG. 10D. The supports were deposited onto the test wafer as a slurry in a liquid media using a liquid handling robot, and the test wafer was subsequently dried to form dried supports. Thereafter, salts of Pt, Au and Ag were impregnated onto the regions of the test wafer containing the CeO2 supports in the various relative stoichiometries as represented in FIG. 10E (upper-right-hand library). Likewise, salts of Pt, Au and Ce were impregnated onto the regions of the test wafer containing the ZrO2 supports in the various relative stoichiometries as represented in FIG. 10E (lower-left-hand library). FIG. 10F is a graphical representation of the composite library design, including the relative amount of catalyst support.


[0185] Specific compositions of tested catalytic materials of the invention are detailed in the following examples for selected libraries.


[0186] Performance benchmarks and reference experiments (e.g., blanks) were also provided on each quartz catalyst test wafer as a basis for comparing the catalyst compositions of the libraries on the test wafer. The benchmark catalytic material formulations included a Pt/zirconia catalyst standard with about 3% Pt catalyst loading (by weight, relative to total weight of catalyst and support). The Pt/zirconia standard was typically synthesized by impregnating 3 μL of, for example, 1.0% or 2.5% by weight, Pt stock solution onto zirconia supports on the wafer prior to calcination and reduction pretreatment.


[0187] Typically wafers were calcined in air at a temperature ranging from 300° C. to 500° C. and/or reduced under a continuous flow of 5% hydrogen at a temperature ranging from about 200° C. to about 500° C. (e.g., 450° C.). Specific treatment protocols are described below with respect to each of the libraries of the examples.


[0188] For testing using the scanning mass spectrometer, the catalyst wafers were mounted on a wafer holder which provided movement in an XY plane. The sniffing/scanning probe of the scanning mass spectrometer moved in the Z direction (a direction normal to the XY plane of movement for the wafer holder), and approached in close proximity to the wafer to surround each independent catalyst element, deliver the feed gas and transmit the product gas stream from the catalyst surface to the quadrupole mass spectrometer. Each element was heated locally from the backside using a CO2 laser, allowing for an accessible temperature range of about 200° C. to about 600° C. The mass spectrometer monitored seven masses for hydrogen, methane, water, carbon monoxide, argon, carbon dioxide and krypton: 2, 16, 18, 28, 40, 44 and 84, respectively.


[0189] Catalyst compositions were tested at various reaction temperatures, typically including for example at about 300° C., 350° C. and/or 400° C. and additionally, usually for more active formulations, at 250° C. Particularly for LTS formulations, testing of catalyst activity at reaction temperatures starting as low as 200° C. may occur. The feed gas typically consisted of 51.6% H2, 7.4% Kr, 7.4% CO, 7.4% CO2 and 26.2% H2O. The H2, CO, CO2 and Kr internal standard are premixed in a single gas cylinder and then combined with the water feed. Treated water (18.1 mega-ohms-cm at 27.5° C.) produced by a Barnstead Nano Pure Ultra Water system was used, without degassing.


[0190] Data Processing and Analysis


[0191] Data analysis was based on mass balance plots where CO conversion was plotted versus CO2 production. The mass spectrometer signals were uncalibrated for CO and CO2 but were based on Kr-normalized mass spectrometer signals. The software package SpotFire™ (sold by SpotFire, Inc. of Somerville, Mass.) was used for data visualization.


[0192] A representative plot of CO conversion versus CO2 production for a WGS reaction is shown in FIG. 11A involving, for discussion purposes, two ternary catalyst systems—a Pt-Au- Ag/CeO2 catalyst library and a Pt-Au-Ce/ZrO2 catalyst library—as described above in connection with FIGS. 10D-10F. The catalyst compositions of these libraries were screened at four temperatures: 250° C., 300° C., 350° C. and 400° C. With reference to the schematic diagram shown in FIG. 1I B, active and highly selective WGS catalysts (e.g., Line I of FIG. 11B) will approach a line defined by the mass balance for the water-gas-shift reaction (the “WGS diagonal”) with minimal deviation, even at relatively high conversions (i.e., at CO conversions approaching the thermodynamic equilibrium conversion (point “TE” on FIG. 11B)). Highly active catalysts may begin to deviate from the WGS diagonal due to cross-over to the competing methanation reaction (point “M” on FIG. 11C). Catalyst compositions that exhibit such deviation may still, however, be useful WGS catalysts depending on the conversion level at which such deviation occurs. For example, catalysts that first deviate from the WGS diagonal at higher conversion levels (e.g., Line II of FIG. 11B) can be employed as effective WGS catalysts by reducing the overall conversion (e.g., by lowering catalyst loading or by increasing space velocity) to the operational point near the WGS diagonal. In contrast, catalysts that deviate from the WGS diagonal at low conversion levels (e.g., Line III of FIG. 11B) will be relatively less effective as WGS catalysts, since they are unselective for the WGS reaction even at low conversions. Temperature affects the thermodynamic maximum CO conversion, and can affect the point of deviation from the mass-balance WGS diagonal as well as the overall shape of the deviating trajectory, since lower temperatures will generally reduce catalytic activity. For some compositions, lower temperatures will result in a more selective catalyst, demonstrated by a WGS trajectory that more closely approximates the WGS mass-balance diagonal. (See FIG. 11C). Referring again to FIG. 11A, it can be seen that the Pt-Au-Ag/CeO2 and the Pt-Au-Ce/ZrO2 catalyst compositions are active and selective WGS catalysts at each of the screened temperatures, and particularly at lower temperatures.


[0193] Generally, the compositions on a given wafer substrate were tested together in a common experimental run using the scanning mass spectrometer and the results were considered together. In this application, candidate catalyst compositions of a particular library on the substrate (e.g., ternary or higher-order catalysts comprising three or more metal components) were considered as promising candidates for an active and selective commercial catalyst for the WGS reaction based on a comparison to the Pt/ZrO2 standard composition included on that wafer. Specifically, libraries of catalytic materials were deemed to be particularly preferred WGS catalysts if the results demonstrated that a meaningful number of catalyst compositions in that library compared favorably to the Pt/ZrO2 standard composition included on the wafer substrate with respect to catalytic performance. In this context, a meaningful number of compositions was generally considered to be at least three of the tested compositions of a given library. Also in this context, favorable comparison means that the compositions had catalytic performance that was as good as or better than the standard on that wafer, considering factors such as conversion, selectivity and catalyst loading. All catalyst compositions of a given library were in many cases positively identified as active and selective WGS catalysts even in situations where only some of the library members compared favorably to the Pt/ZrO2 standard, and other compositions within that library compared less than favorably to the Pt/ZrO2 standard. In such situations, the basis for also including members of the library that compared somewhat less favorably to the standard is that these members in fact positively catalyzed the WGS reaction (i.e., were effective as catalysts for this reaction). Additionally, it is noted that such compositions may be synthesized and/or tested under more optimally tuned conditions (e.g., synthesis conditions, treatment conditions and/or testing conditions (e.g., temperature)) than occurred during actual testing in the library format, and significantly, that the optimal conditions for the particular catalytic materials being tested may differ from the optimal conditions for the Pt/ZrO2 standard—such that the actual test conditions may have been closer to the optimal conditions for the standard than for some of the particular members. Therefore, it was specifically contemplated that optimization of synthesis, treatment and/or screening conditions, within the generally defined ranges of the invention as set forth herein, would result in even more active and selective WGS catalysts than what was demonstrated in the experiments supporting this invention. Hence, in view of the foregoing discussion, the entire range of compositions defined by each of the claimed compositions (e.g., each three-component catalytic material, or each four-component catalytic material) was demonstrated as being effective for catalyzing the WGS reaction. Further optimization is considered, with various specific advantages associated with various specific catalyst compositions, depending on the desired or required commercial application of interest. Such optimization can be achieved, for example, using techniques and instruments such as those described in U.S. Pat. No. 6,149,882, or those described in WO 01/66245 and its corresponding U.S. applications, U.S. Ser. No. 09/801,390, entitled “Parallel Flow Process Optimization Reactor” filed Mar. 7, 2001 by Bergh et al., and U.S. Ser. No. 09/801,389, entitled “Parallel Flow Reactor Having Variable Feed Composition” filed Mar. 7, 2001 by Bergh et al., each of which are incorporated herein by reference for all purposes.


[0194] Additionally, based on the results of screening of initial libraries, selective additional “focus” libraries were selectively prepared and tested to confirm the results of the initial library screening, and to further identify better performing compositions, in some cases under the same and/or different conditions. The test wafers for the focus libraries typically comprised about 225 different candidate catalyst compositions formed on a four-inch wafer substrate, with one or more libraries (e.g. associated ternary compositions A, B, C) formed on each test wafer. Again, the metal-containing components of a given library were typically combined in various relative ratios to form catalysts having stoichiometry ranging from about 0% to about 100% of each component, and for example, having stoichiometric increments of about 10% or less, typically about 2% or less (e.g., for a “fifty-six point ternary”). Focus libraries are more generally discussed, for example, in WO 00/17413. Such focus libraries were evaluated according to the protocols described above for the initial libraries.


[0195] The raw residual gas analyzer (“rga”) signal values generated by the mass spectrometer for the individual gases are uncalibrated and therefore different gases may not be directly compared. Methane data (mass 16) was also collected as a control. The signals are typically standardized by using the raw rga signal for krypton (mass 84) to remove the effect of gas flow rate variations. Thus, for each library element, the standardized signal is determined as, for example, sH2O=raw H2O/raw Kr; sCO=raw CO/raw Kr; sCO2=raw CO2/raw Kr and so forth.


[0196] Blank or inlet concentrations are determined from the average of the standardized signals for all blank library elements, i.e. library elements for which the composition contains at most only support. For example, bavg H2O=average sH2O for all blank elements in the library; bavg CO=average sCO for all blank elements in the library; and so forth.


[0197] Conversion percentages are calculated using the blank averages to estimate the input level (e.g., bavg CO) and the standardized signal (e.g., sCO) as the output for each library element of interest. Thus, for each library element, COconversion=100×(bavg CO−sCO)/bavg CO and H2Oconversion=100×(bavg H2O−sH2O)/bavg H2O.


[0198] The carbon monoxide (CO) to carbon dioxide (CO2) selectivity is estimated by dividing the amount of CO2 produced (sCO2−bavg CO2) by the amount of CO consumed (bavg CO−sCO). The CO2 and CO signals are not directly comparable because the rga signals are uncalibrated. However, an empirical conversion constant (0.6 CO2 units=1 CO unit) has been derived, based on the behavior of highly selective standard catalyst compositions. The selectivity of the highly selective standard catalyst compositions approach 100% selectivity at low conversion rates. Therefore, for each library element, estimated CO to CO2 selectivity=100×0.6×(sCO2−bavg CO2)/(bavg CO−sCO). Low CO consumption rates can produce highly variable results, and thus the reproducibility of CO2 selectivity values is maintained by artificially limiting the CO2 selectivity to a range of 0 to 140%.


[0199] The complete disclosure of all references cited herein are incorporated herein in their entireties for all purposes.


[0200] The following examples are representative of the screening of libraries that lead to identification of the particularly claimed inventions herein.



Example 1

[0201] A 4″ quartz wafer was precoated with a γ-Al2O3 (Catalox Sba-150) carrier by slurry dispensing 3 μL (1 g of γ-Al2O3 in 4 mL of ethylene glycol (“EG”)/H2O, 50:50) to each element of a 15×15 square on the wafer. The wafer was then oven-dried at 70° C. for 12 minutes.


[0202] Six internal standards were synthesized by Cavro spotting 3 μL of a Pt(NH3)2(NO2)2 (2.5% Pt) stock solution into the corresponding first row/last column positions. The wafer was impregnated with a uniform Pt layer by dispensing into columns C1 to C5 (2.5 μL per well) a stock solution of Na2Pt(OH)6 (from powder, 1% Pt) to the wafer.


[0203] Columns C6 to C15 of the wafer were then impregnated with the following ten metal-gradients respectively from top to bottom: ZrO(NO3)2, La(NO3)3, Y(NO3)3, Ce(NO3)3, H2MoO4, Fe(NO3)3, Co(NO3)2, ZrO(OAc)2, Mn(NO3)2 and KRuO4 by Cavro dispensing from the respective stock solution vials to a microtiter plate and diluted with distilled water. A replica transfer of the microtiter plate pattern to the wafer followed (2.5 μL dispense volume per well), resulting in a 10×15 point rectangle on the wafer (10 columns with metal gradients).


[0204] The wafer was dried for 3.5 hours at room temperature and then coated with base gradients (0.5M, opposing gradients) including CsOH—NaOH, LiOH—NaOH, RbOH—NaOH and KOH—NaOH separately in each of the first four columns, respectively, and NaOH in columns 5 to 15 (1M base with a gradient from bottom to top) by Cavro dispensing from the corresponding stock solution vials to the microtiter plate and diluting with distilled water. A replica transfer of the microtiter plate pattern to the wafer followed (2.5 μL dispense volume per well), resulting in a 15×15 point rectangle on the wafer (15 columns with base gradients). The wafer was dried overnight at room temperature and oven-dried for 2 minutes.


[0205] The final impregnation was a uniform dispensing (2.5 μL dispense volume per well, resulting a 10×15 point square) from a stock solution vial of Na2Pt(OH)6 (from powder, 1% Pt) to the wafer (C6-C15.) as a ternary layer.


[0206] The wafer was dried at room temperature for 4 hours and then calcined in air at 450° C. for 2 hours followed by reduction with 5% H2/N2 at 250° C. for 2 hours. Commercial catalyst was slurried into 5 positions of the first row and last column as an external standard (3 μL). See FIGS. 1A-1C.


[0207] The library was screened in a scanning mass spectrometer (“SMS”) for WGS activity with a H2/CO/CO2/H2O mixed feed at 200° C., 230° C. and 260° C.


[0208] This experiment demonstrated active and selective WGS catalyst formulations of various alkali and Pt containing formulations on the wafer.



Example 2

[0209] A 4″ 16×16 quartz wafer was pre-coated with ZrO2 (Norton ZrO2 XZ16052) carrier by slurry dispensing 3 μL (1.5 g of ZrO2 in 4 mL of EG/H2O/MEO, 32.5:30:37.5) to each element of a 15×15 square on the wafer. The wafer was then oven-dried at 70° C. for 12 minutes.


[0210] The zirconia carrier pre-coated wafer was impregnated with a 8-point Ce(NO3)3 concentration gradient (0.25M Ce stock solution) and a 7-point Fe(NO3)3 concentration gradient (0.5M Fe stock solution) by Cavro dispensing from the Ce- and Fe-nitrate stock solution vials to a microtiter plate and diluting with distilled water. A replica transfer of the microtiter plate pattern to the wafer followed (2.5 μL dispense volume per well).


[0211] The wafer was dried for 4 hours at room temperature and then coated with Na- and K-hydroxide gradients by Cavro dispensing from NaOH (1M) and KOH (1M) stock solution vials to the microtiter plate and diluting with distilled water (sodium onto the upper and potassium onto the lower part of the wafer). A replica transfer of the microtiter plate pattern to the wafer followed (2.5 μL dispense volume per well, 7 replicas of the 8-point gradient and 8 replicas of the 7-point gradient, 7×8=56 point ternaries). The wafer was dried at room temperature overnight and oven-dried for 2 minutes.


[0212] The final impregnation was a uniform dispensing (2.5 μl dispense volume per well, resulting in a 15×15 point square) from a stock solution vial of Pt(NH3)2(NO2)2 (1% Pt) to the wafer. Six internal standards were synthesized by spotting 3 μL of Pt(NH3)2(NO2)2 stock solution (2.5% Pt) into the corresponding first row/last column positions.


[0213] The wafer was dried at room temperature for 2 hours and then calcined in air at 450° C. for 2 hours followed by reduction with 5% H2/N2 at 200° C. for 2 hours. Commercial catalyst was slurried into 5 positions of the first row and last column as an external standard (3 μL). See FIGS. 2A-AC.


[0214] The library was then screened in SMS for WGS activity with a H2/CO/CO2/H2O mixed feed at 200° C., 230° C. and 260° C.


[0215] This experiment demonstrated active and selective WGS catalyst formulations of Pt, alkali and Fe or Ce containing formulations on the wafer.



Example 3

[0216] A 4″ quartz wafer was pre-coated with a ZrO2 (Norton XZ16052) carrier by slurry dispensing 3 μL (1.5 g of ZrO2 in 4 mL of EG/H2O/MEO, 32.5:30:37.5) to each element of a 15×15 square on the wafer. The wafer was then oven-dried at 70° C. for 12 minutes.


[0217] Nine internal standards were synthesized by Cavro spotting 2.5 μL of a Pt(NH3)2(NO2)2 (1% Pt) stock solution into the corresponding first row/last column positions. The wafer was impregnated with 3 metal gradients (5-point gradients) from top to bottom as follows: rows 2 through 6 with Co(NO3)2 (0.25M), rows 7 through 11 with Ru(NO)(NO3)3 (0.05M) and rows 12-16 with H2MoO4 (0.25M) by Cavro dispensing from the corresponding stock solution vials to a microtiter plate and diluted with distilled water. A replica transfer of the microtiter plate pattern to the wafer followed (2.5 μL dispense volume per well), resulting in three 5×15 point rectangles on the wafer.


[0218] The wafer was dried for 4 hours at room temperature and then coated with the following metal gradients (reverse gradients) from bottom to top to produce 5 point dopant binaries at various column/row positions on the wafer: (NH4)2Ce(NO3)6, Co(NO3)2, Ru(NO)(NO3)3, H2MoO4, Co(OAc)2, Na3Co(NO3)6, KRuO4, Ru(NO)(OAc)3, La(NO3)3, Cd(NO3)3, ZrO(NO3)2, ZrO(OAc)2, Cu(NO3)2, NH4ReO4 and Ge(OX)2 by Cavro dispensing from the respective stock solution vials to the microtiter plate and diluted with distilled water. A replica transfer of the microtiter plate to the wafer followed (2.5 μL dispense volume per well), resulting in three 5×15 point rectangles on the wafer.


[0219] The wafer was dried for 4 hours at room temperature and then coated with a uniform top layer (2.5 μL dispense volume per well) from the corresponding stock solution vials to the wafer consisting of Pt(NH3)2(NO2)2 (1% Pt) as a third layer.


[0220] The wafer was dried overnight at room temperature and then calcined in air at 350° C. for 2 hours followed by reduction with 5% H2/N2 at 300° C. for 2 hours. See FIGS. 3A-31.


[0221] The library was then screened in SMS for WGS activity with a H2/CO/CO2/H2O mixed feed at 250° C. Detailed test results, such as CO conversion, CO2 production and CH4 production at 250° C. for each of the 225 individual catalyst wells are presented in Table 1.


[0222] This experiment demonstrated that Pt—Co—Na where both Na and Co were derived from Na3Co(NO2)6 exhibited WGS activity superior to the Pt/ZrO2 standards. See FIGS. 3J-3K.



Example 4

[0223] A 4″ quartz wafer was precoated with 7 different carriers by slurry dispensing an amount of 3 μL to vertical 15 point columns on the wafer. The carrier deposition was carried out with the following carriers: CeO2, 99.5% (Alfa, 0.75 g in 4 mL of EG/H2O, 50:50); La2O3, 99.9% (Gernch, 1.5 g in 4 mL of EG/H2O/MEO, 40:30:30); ZrVOx (1 g in 4 mL of EG/H2O, 50:50); ZrO2 FZO 923 (MEI 1.5 g in 4 mL of EG/H2O/MEO, 32.5:30:37.5); TiO2 (Aerolyst 7708, P25, Degussa, 1 g in 4 mL of EG/H2O/MEO, 32.5:30:37.5); TiO2 VKR611 (BASF, 1 g in 4 mL of EG/H2O/MEO, 32.5.5:30:37.5); TiO2 XT25384 (Norton, 1 g in 4 mL of EG/H2O/MEO, 32.5.5:30:37.5) and ZrO2 XZ16052 (Norton, 1.5 g in 4 mL of EG/H2O/MEO, 32.5.5:30:37.5). After dispensing, the samples were oven-dried at 70° C. for 12 minutes, except for the dispensed ceria from Alfa which was oven-dried for 24 minutes at 70° C.


[0224] Selected carrier pre-coated columns were impregnated by Cavro with 6 metal gradients from top to bottom: Co(NO3)2, Fe(NO3)3, Ce(NO3)3, (NH4)2MoO4, Pd(NH3)2(NO2)2 and La(NO3)3 by Cavro dispensing from the corresponding stock solution vials to microtiter plate and diluting with distilled water. A replica transfer of the microtiter plate to the wafer followed (2.5 μL dispense volume per well), resulting in a 6×15 point rectangle on the wafer.


[0225] Six internal standards were synthesized by Cavro spotting of 3 μL of a Pt(NH3)2(NO2)2 (2.5% Pt) stock solution into the corresponding first row/last column positions and then the last column was coated with a uniform layer of HAu(NO3)4 (0.1M) by dispensing of 2 μL by pipette.


[0226] The non-impregnated columns were coated with 2 platinum gradients from bottom to top consisting of Pt(NH3)2(NO2)2 (1% Pt) by Cavro dispensing from the respective stock solution vials to the microtiter plate and diluting with distilled water. A replica transfer of the microtiter plate to the wafer followed (2.5 μL dispense volume per well), resulting in a 8×15 point rectangle on the wafer and dispensing 2.5 μl dispense volume per well.


[0227] The wafer was dried overnight at room temperature and then coated with a uniform layer of sodium hydroxide (NaOH, 1M) by Cavro dispensing (2.5 μL dispense volume per well) from the respective stock solution vial to water resulting in a 7×15 point rectangle on the lower part of the wafer.


[0228] The wafer was dried for 2 hours at room temperature and oven-dried for 2 minutes at 70° C. The last impregnation was a dispensing of the ternary layer to the columns with 2 Pt- gradients from bottom to top consisting of Pt(NH3)2(NO2)2 (1% Pt) by Cavro dispensing from the corresponding stock solution vial to the microtiter plate and diluting with distilled water. A replica transfer of the microtiter plate to the wafer followed (2.5 μL dispense volume per well), resulting in a 7×15 point rectangle on the wafer.


[0229] The wafer was dried at room temperature for 4 hours and then calcined in air at 500° C. for 2 hours followed by reduction with 5% H2/N2 at 500° C. for 2 hours. See FIGS. 4A-4C.


[0230] The library was then screened in SMS for WGS activity with a H2/CO/CO2/H2O mixed feed at 230° C. and 260° C. More detailed test results, such as CO conversion, CO2 production and CH4 production at 200° C. for each of the 225 individual catalyst wells are presented in Table 2.


[0231] This experiment demonstrated active and selective WGS catalyst formulations of Pt and alkali metal containing compositions on the wafer. Also the positive effect of Na post-impregnation is observed.



Example 5

[0232] A 3″ quartz wafer was coated with niobia, ceria and magnesia carriers by slurry- dispensing aqueous carrier slurries onto the wafer (4 μl slurry/well, 1 g of carrier powder slurried in 2 ml H2O for niobia and ceria; 500 mg of carrier powder slurried in 2 ml H2O for magnesia). Niobia carriers were produced by Norton, product numbers 2001250214, 2000250356, 2000250355, 2000250354 and 2000250351. Cerias came from Norton (product numbers 2001080053, 2001080052 and 2001080051) and Aldrich (product number 21,157-50. Magnesia was obtained from Aldrich (product number 24,338-8).


[0233] The carrier precoated wafer was then loaded with the same Pt gradient for each carrier in a single impregnation step by liquid dispensing 3 μl Pt(NH3)2(NO2)2 solution (5% Pt) from microtiter plate to wafer. The wafer was dried and then reduced in 5% H2/Ar at 450° C. for 2 hours. See FIGS. 5A-5C.


[0234] The reduced library was then screened in SMS for WGS activity with a H2/CO/CO2/H2O mixed feed at 250° C., 300° C., 350° C., and 400° C. Results at 250° C., 300° C., 350° C., and 400° C. are presented in FIGS. 5D-5H. This set of experiments demonstrated active and selective WGS catalyst formulations of various Pt on one of Nb oxide, Ce oxide or Mg oxide formulations on the wafer. Various Norton niobia carriers were found to be very active and selective over a broad temperature range. Norton ceria 2001080051 was found to be very selective at higher temperatures. Magnesia was less active than either of niobia or ceria but did exhibit highly selective WGS performance.



Example 6

[0235] A 4″ quartz wafer was coated with fourteen different catalyst carriers by slurry- dispensing the carrier slurries onto the wafer. The carriers were slurried in a mixture of EG/H2O/MEO at a ratio of 40:30:30. Each wafer column was coated with a different carrier, except for columns 14 and 15 which were both coated with gamma-alumina, described below:


[0236] 1) Ceria, 99.5% purity; 9 to 15 nm particle size; BET (m2/g): 55-95; Alfa 43136; dispensed onto the wafer from a slurry of 0.75 g powder slurried in 4 mL EG/H2O/MEO.


[0237] 2) Ceria, produced by the low temperature calcination of precipitated Ce hydroxide; dispensed onto the wafer from a slurry of 1.5 g powder slurried in 4 mL EG/H2O/MEO.


[0238] 3) Zirconia; 99.8% purity; BET (m2/g): greater than 90; Norton XZ16052; dispensed onto the wafer from a slurry of 1.5 g powder slurried in 4 mL EG/H2O/MEO.


[0239] 4) Zirconia; 99.8% purity; BET (m2/g): 269; Norton XZ16154; dispensed onto the wafer from a slurry of 1.5 g powder slurried in 4 mL EG/H2O/MEO.


[0240] 5) Titania; BET (m2/g): 45; Degussa Aerolyst 7708; dispensed onto the wafer from a slurry of 1.0 g powder slurried in 4 mL EG/H2O/MEO.


[0241] 6) Titania; 99% purity; BET (m2/g): 37; Norton XT25384; dispensed onto the wafer from a slurry of 1.0 g powder slurried in 4 mL EG/H2O/MEO.


[0242] 7) Niobia; 97% purity; BET (m2/g): 27; Norton 2000250355; dispensed onto the wafer from a slurry of 1.0 g powder slurried in 4 mL EG/H2O/MEO.


[0243] 8) Lanthania; 99.999% purity; Gemre-5N from Gemch Co., Ltd. (Shanghai, China); dispensed onto the wafer from a slurry of 1.5 g powder slurried in 4 mL EG/H2O/MEO.


[0244] 9) Mixed Fe—Ce—O; coprecipitated Fe and Ce oxalate; calcined at 360° C.; dispensed onto the wafer from a slurry of 1.0 g powder slurried in 4 mL EG/H2O/MEO.


[0245] 10) Mixed La—Ce—O; coprecipitated La and Ce oxalate; calcined at 760° C.; dispensed onto the wafer from a slurry of 1.0 g powder slurried in 4 mL EG/H2O/MEO.


[0246] 11) Mixed Sb3O4—SnO2 carrier from Alfa; 99.5% purity; BET (m2/g): 30-80; Sb3O4:SnO2 ratio is 10:90 by weight; dispensed onto the wafer from a slurry of 1.0 g powder slurried in 4 mL EG/H2O/MEO.


[0247] 12) Mixed Fe—Cr—Al—O; commercially available high temperature water gas shift catalyst; dispensed onto the wafer from a slurry of 1.0 powder slurried in 4 mL. EG/H2O/MEO.


[0248] 13) Fe2O3/FeOOH; BET (m2/g): 14; 50:50 physical mixture of commercial powders (Bayferrox 720N: Bayoxide E3920 from Bayer); dispensed onto the wafer from a slurry of 1.0 g powder slurried in 4 mL EG/H2O/MEO.


[0249] 14 and 15) Gamma-Al2O3; BET (m2/g): 150; Condea Catalox Sbal50; dispensed onto the wafer from a slurry of 1.0 g powder slurried in 4 mL EG/H2O/MEO.


[0250] In all cases, except for carrier 1, the slurries were applied in 3 μl/well; carrier 1 was deposited as two aliquots of 3 μl/well. The wafer was then dried at 70° C. for 10 minutes.


[0251] Columns 14 and 15 were coated with 2.5 μl/well of zirconyl nitrate (0.25 M) and lanthanum nitrate (0.25 M), respectively, then dried for 10 minutes at 70° C. The first 13 columns of the carrier coated wafer were then loaded with a 15 point Pt gradient by liquid dispensing of 3 μl Pt(NH3)2(NO2)2 solution (1% Pt) from microtiter plate to wafer. The wafer was dried at 70° C. for 10 minutes. Columns 14 and 15 were then loaded with a 15 point Pt gradient by liquid dispensing of 3 μl Pt(NH3)2(NO2)2 solution (1% Pt) from microtiter plate to wafer. The wafer was dried at 70° C. for 10 minutes, calcined in air at 350° C. for 2 hours, then reduced in 5% H2/Ar at 450° C. for 2 hours. Six internal standards were synthesized by spotting 3 μl Pt(NH3)2(NO2)2 solution (1.0% Pt) into the corresponding first row/last column positions. See FIGS. 6A-6F.


[0252] The reduced library was then screened in SMS for WGS activity with a H2/CO/CO2/H2O mixed feed at 250° C. and 300° C. The CO conversion versus CO2 production results at 250° C. and 300° C. are presented in FIGS. 6G, 6H, and 61. More detailed test results, such as, CO conversion, CO2 production and CH4 production at 250° C. and 300° C. for each of the 225 individual catalyst wells on the test wafer are presented in Table 3.


[0253] This set of experiments demonstrated active and selective WGS catalyst formulations of various Pt on various of the oxide carrier formulations on the wafer.



Example 7

[0254] Scale-up catalyst samples were prepared by using incipient wetness impregnation of 0.75 grams of ZrO2 support (Norton, 80-120 mesh) which had been weighed into a 10-dram vial. Aqueous metal precursor salt solutions were then added in the order: Co, Mo, or V, Pt, and then K. The precursor salt solutions were tetraammineplatinum (II) hydroxide (9.09% Pt (w/w)), cobalt (II) nitrate (11.0M), molydbic acid (1.0M), vanadium citrate (1.0M), and potassium hydroxide (13.92% K). All reagents were nominally research grade from Aldrich, Strem, or Alfa. Following each metal addition, the catalysts were dried at 80° C. overnight and then calcined in air as follows:
1After Pt addition300° C. for 3 hoursAfter Co addition450° C. for 3 hoursAfter Mo or V addition350° C. for 3 hours


[0255] Following K addition, the catalysts were calcined at 300° C. for 3 hours, then the catalysts were reduced in-situ at 300° C. for 3 hours in a 10% H2/N2 feed.


[0256] Catalyst Testing Conditions


[0257] Catalysts were tested in a fixed bed reactor. Approximately 0.15 g of catalyst was weighed and mixed with an equivalent mass of SiC. The mixture was loaded into a reactor and heated to reaction temperature. Reaction gases were delivered via mass flow controllers (Brooks) with water introduced with a metering pump (Quizix). The composition of the reaction mixture was as follows: H2 50%, CO 10%, CO2 10%, and H2O 30%. The reactant mixture was passed through a pre-heater before contacting the catalyst bed. Following reaction, the product gases were analyzed using a micro gas chromatograph (Varian Instruments, or Shimadzu). Compositional data on the performance diagram (FIG. 7) is on a dry basis with water removed. Testing Results


[0258]
FIG. 7 shows the CO composition in the product stream following the scale-up testing at a gas hour space velocity of 50,000 h−1.
2TABLE 4Catalyst Compositions (mass ratio)RowColZrO2CoWaterPtKMoV110.910.00500.060.02500120.8850.00500.060.0500130.91000.060.0250.0050140.885000.060.050.0050150.905000.060.02500.01160.88000.060.0500.01210.9050.0100.060.02500220.880.0100.060.0500230.905000.060.0250.010240.88000.060.050.010250.895000.060.02500.02260.87000.060.0500.02310.90.01500.060.02500320.8750.01500.060.0500330.9000.060.0250.0150340.875000.060.050.0150350.885000.060.02500.03360.86000.060.0500.03410.8950.0200.060.02500420.870.0200.060.0500430.895000.060.0250.020440.87000.060.050.020450.875000.060.02500.04460.85000.060.0500.04



Example 8

[0259] Scale-up catalyst samples were prepared by using incipient wetness impregnation of 0.75 grams of ZrO2 support (Norton, 80-120 mesh) which had been weighed into a 10-dram vial. Aqueous metal precursor salt solutions were then added in the order: Co, Mo, or V, Pt, and then Li. The precursor salt solutions were tetraammineplatinum (II) hydroxide (9.09% Pt (w/w)), cobalt (II) nitrate (1.0M), molydbic acid (1.0M), vanadium citrate (1.0M), and lithium hydroxide monohydrate (2.5M). All reagents were nominally research grade from Aldrich, Strem, or Alfa. Following each metal addition, the catalysts were dried at 80° C. overnight and then calcined in air as follows:
3After Pt addition300° C. for 3 hoursAfter Co addition450° C. for 3 hoursAfter Mo, or V addition350° C. for 3 hoursAfter Li addition300° C. for 3 hours.


[0260] Following final addition, the catalysts were reduced in-situ at 300° C. for 3 hours in a 10% H2/N2 feed.


[0261] Catalyst Testing Conditions


[0262] Catalysts were tested in a fixed bed reactor. Approximately 0.15 g of catalyst was weighed and mixed with an equivalent mass of SiC. The mixture was loaded into a reactor and heated to reaction temperature. Reaction gases were delivered via mass flow controllers (Brooks) with water introduced with a metering pump (Quizix). The composition of the reaction mixture was as follows: H2 50%, CO 10%, CO2 10%, and H2O 30%. The reactant mixture was passed through a pre-heater before contacting the catalyst bed. Following reaction, the product gases were analyzed using a micro gas chromatograph (Varian Instruments, or Shimadzu). Compositional data on the performance diagram (FIG. 8) is on a dry basis with water removed.


[0263] Testing Results


[0264]
FIG. 8 shows the CO composition in the product stream following the scale-up testing at a gas hour space velocity of 50,000 h−1.
4TABLE 5Catalyst Compositions (mass ratio)RowColZrO2CoWaterPtLiMoVA10.910.00500.060.02500A20.910.00500.060.02500A30.91000.060.0250.0050A40.91000.060.0250.0050A50.905000.060.02500.01A60.905000.060.02500.01B10.9050.0100.060.02500B20.9050.0100.060.02500B30.905000.060.0250.010B40.905000.060.0250.010B50.895000.060.02500.02B60.895000.060.02500.02C10.90.01500.060.02500C20.90.01500.060.02500C30.9000.060.0250.0150C40.9000.060.0250.0150C50.885000.060.02500.03C60.885000.060.02500.03D10.8950.0200.060.02500D20.8950.0200.060.02500D30.895000.060.0250.020D40.895000.060.0250.020D50.875000.060.02500.04D60.875000.060.02500.04



Example 9

[0265] Scale-up catalyst samples were prepared by using incipient wetness impregnation of 0.75 grams of ZrO2 support (Norton, 80-120 mesh) which had been weighed into a 10-dram vial. Aqueous metal precursor salt solutions were then added in the order: La, Ce, one of Co, Mo, or V, Pt, and finally Na. The precursor salt solutions were tetraammineplatinum (II) hydroxide (9.09% Pt (w/w)), lanthanum (III) nitrate (1.0M), cerium (IV) nitrate (1.0N), cobalt (II) nitrate (11.0M), molydbic acid (1.0M), vanadium citrate (1.0M), and sodium hydroxide (3.0N). All reagents were nominally research grade from Aldrich, Strem, or Alfa. Following each metal addition, the catalysts were dried at 80° C. overnight and then calcined in air as follows:
5After Pt addition300° C. for 3 hoursAfter La or Ce addition450° C. for 3 hoursAfter Co, Mo, or V addition350° C. for 3 hours.


[0266] Following Na addition, the catalysts were calcined at 300° C. for 3 hours, then the catalysts were reduced in-situ at 300° C. for 3 hours in a 10% H2/N2 feed.


[0267] Catalyst Testing Conditions


[0268] Catalysts were tested in a fixed bed reactor. Approximately 0.15 g of catalyst was weighed and mixed with an equivalent mass of SiC. The mixture was loaded into a reactor and heated to reaction temperature. Reaction gases were delivered via mass flow controllers (Brooks) with water introduced with a metering pump (Quizix). The composition of the reaction mixture was as follows: H2 50%, CO 10%, CO2 10%, and H2O 30%. The reactant mixture was passed through a pre-heater before contacting the catalyst bed. Following reaction, the product gases were analyzed using a micro gas chromatograph (Varian Instruments, or Shimadzu). Compositional data on the performance diagram (FIG. 9) is on a dry basis with water removed.


[0269] Testing Results


[0270]
FIG. 9 shows the CO composition in the product stream following the scale-up testing at a gas hour space velocity of 50,000 h−1.
6TABLE 6Catalyst Compositions (mass ratio)RowColSupportCoPtLaNaCeMoVA10.8850.0050.060.0250.025000A20.8850.0050.0600.0250.02500A30.88500.060.0250.02500.0050A40.88500.0600.0250.0250.0050A50.8800.060.0250.025000.01A60.8800.0600.0250.02500.01B10.860.0050.060.050.025000B20.860.0050.0600.0250.0500B30.8600.060.050.02500.0050B40.8600.0600.0250.050.0050B50.85500.060.050.025000.01B60.85500.0600.0250.0500.01C10.880.010.060.0250.025000C20.880.010.0600.0250.02500C30.8800.060.0250.02500.010C40.8800.0600.0250.0250.010C50.8700.060.0250.025000.02C60.8700.0600.0250.02500.02D10.8550.010.060.050.025000D20.8550.010.0600.0250.0500D30.85500.060.050.02500.010D40.85500.0600.0250.050.010D50.84500.060.050.025000.02D60.84500.0600.0250.0500.02



Example 10

[0271] Scale-up catalyst samples were prepared by using incipient wetness impregnation of 0.75 grams of ZrO2 support (Norton, 80-120 mesh) which had been weighed into a 10-dram vial. Aqueous metal precursor salt solutions were then added in the order: V, Pt, and finally Na. The precursor salt solutions were tetraammineplatinum (II) hydroxide solution (9.09% Pt (w/w)), vanadium citrate (1.0M), and sodium hydroxide (3.0 N). All starting reagents were nominally research grade from Aldrich, Strem, or Alfa. Following each metal addition, the catalysts were dried at 80° C. overnight and then calcined in air as follows:
7After Pt addition300° C. for 3 hoursAfter V addition350° C. for 3 hours.


[0272] Following Na addition, the catalysts were calcined at 300° C. for 3 hours, then the catalysts were reduced in-situ at 300° C. for 3 hours in a 10% H2/N2 feed.


[0273] Catalyst Testing Conditions


[0274] Catalysts were tested in a fixed bed reactor. Approximately 0.15 g of catalyst was weighed and mixed with an equivalent mass of SiC. The mixture was loaded into a reactor and heated to reaction temperature. Reaction gases were delivered via mass flow controllers (Brooks) with water introduced with a metering pump (Quizix). The composition of the reaction mixture was as follows: H2 50%, CO 10%, CO2 10%, and H2O 30%. The reactant mixture was passed through a pre-heater before contacting the catalyst bed. Following reaction, the product gases were analyzed using a micro gas chromatograph (Varian Instruments, or Shimadzu). Compositional data on the performance diagram (FIG. 12) is on a dry basis with water removed.


[0275] Testing Results


[0276]
FIG. 12 shows the CO composition in the product stream following the scale-up testing at a gas hour space velocity of 50,000 h−1.
8TABLE 7Catalyst Compositions (mass ratio)RowColSupportPtNaVA194.002.002.501.5A291.502.005.001.5A392.004.002.501.5A489.504.005.001.5A590.006.002.501.5A687.506.005.001.5B192.502.002.503.0B290.002.005.003.0B390.504.002.503.0B488.004.005.003.0B588.506.002.503.0B686.006.005.003.0C191.002.002.504.5C288.502.005.004.5C389.004.002.504.5C486.504.005.004.5C587.006.002.504.5C684.506.005.004.5D189.502.002.506.0D287.002.005.006.0D387.504.002.506.0D485.004.005.006.0D585.506.002.506.0D683.006.005.006.0


[0277]

9















TABLE I

















Pt1.0%/





R
C
COCONV
H2OCONV
CO2PROD
CO2PERPROD
CH4PROD
ZrO2_std
CeNO33
NH42CeNO36
CoNO32


real
real
real
real
real
real
real
real
real
real
real





Temperature


250 C


1
1
29.8402
21.1977
1.0839
39.7897
0.1693
0.1275
0
0
0


1
2
−0.8066
−0.3468
0.0199
0.7318
0.015
0
0
0
0


1
3
−1.342
−0.8883
−0.0103
−0.3788
0.0069
0
0
0
0


1
4
−0.4471
−0.8737
−0.0209
−0.7679
0.0045
0
0
0
0


1
5
0.2051
−0.7078
0.0201
0.7386
0.0086
0
0
0
0


1
6
−0.2701
−1.1286
−0.0074
−0.273
0.0008
0
0
0
0


1
7
28.4296
17.0396
0.9422
34.5858
0.1303
0.1275
0
0
0


1
8
0.3481
−0.0616
−0.0199
−0.7298
−0.0025
0
0
0
0


1
9
−0.1214
−1.3018
−0.0217
−0.7951
0.001
0
0
0
0


1
10
1.2904
−0.1752
−0.0251
−0.9203
−0.0045
0
0
0
0


1
11
−0.1983
−0.4964
−0.0223
−0.8192
0.0005
0
0
0
0


1
12
−0.0741
−1.2392
−0.019
−0.6989
0.0004
0
0
0
0


1
13
27.9999
15.9352
0.9526
34.9687
0.128
0.1275
0
0
0


1
14
0.6232
−0.3023
0.0112
0.4122
0.0003
0
0
0
0


1
15
−0.1018
0.0336
−0.0235
−0.8632
−0.0047
0
0
0
0


1
16
27.2351
16.5803
0.888
32.5966
0.1185
0.1275
0
0
0


2
1
25.6429
17.9695
0.8313
30.5152
0.0986
0
0
0
0.125


2
2
29.4104
18.6834
0.9576
35.1519
0.1186
0
0
0.5
0.125


2
3
22.3392
8.9723
0.6239
22.9019
0.1378
0
0
0
0.125


2
4
0.8395
0.2708
0.0014
0.0528
−0.0013
0
0
0
0.125


2
5
22.4525
13.4385
0.672
24.6699
0.1033
0
0
0
0.125


2
6
30.6495
18.9614
1.028
37.7387
0.136
0
0
0
0.125


2
7
22.8992
14.6855
0.7054
25.8949
0.0994
0
0
0
0.125


2
8
16.4705
11.3025
0.4957
18.197
0.0643
0
0
0
0.125


2
9
25.2898
17.1191
0.8418
30.903
0.1018
0
0
0
0.125


2
10
27.7651
17.855
0.9307
34.1645
0.1134
0
0.5
0
0.125


2
11
15.2353
10.1525
0.5062
18.5825
0.0625
0
0
0
0.125


2
12
6.6516
3.7768
0.2027
7.4414
0.0231
0
0
0
0.125


2
13
5.6662
4.3865
0.1536
5.6377
0.0183
0
0
0
0.125


2
14
20.5443
12.549
0.6838
25.1023
0.0868
0
0
0
0.125


2
15
2.2164
0.1212
0.0573
2.1049
0.0061
0
0
0
0.125


2
16
0.393
1.3011
−0.0224
−0.821
−0.0062
0
0
0
0


3
1
22.2454
15.3754
0.7105
26.0826
0.0816
0
0
0
0.2188


3
2
28.0083
19.5547
0.885
32.4878
0.1083
0
0
0.4063
0.2188


3
3
23.6895
14.2896
0.6787
24.9136
0.1246
0
0
0
0.2188


3
4
0.9693
2.2659
−0.0302
−1.1081
−0.0146
0
0
0
0.2188


3
5
28.2742
16.4476
0.8881
32.6016
0.1315
0
0
0
0.2188


3
6
40.4567
21.9704
1.2225
44.8759
0.2055
0
0
0
0.2188


3
7
25.2346
17.7275
0.8079
29.6585
0.1051
0
0
0
0.2188


3
8
23.7508
16.0999
0.736
27.0183
0.1041
0
0
0
0.2188


3
9
26.3184
19.4909
0.8642
31.7233
0.098
0
0
0
0.2188


3
10
26.3066
17.5553
0.8712
31.9817
0.1009
0
0.4063
0
0.2188


3
11
16.5069
12.0298
0.525
19.2728
0.0577
0
0
0
0.2188


3
12
15.7501
11.8225
0.4936
18.1205
0.0521
0
0
0
0.2188


3
13
6.2855
5.3787
0.1728
6.3432
0.01
0
0
0
0.2188


3
14
18.4215
14.2445
0.619
22.7235
0.0672
0
0
0
0.2188


3
15
1.6097
3.5749
0.0233
0.8544
−0.0089
0
0
0
0.2188


3
16
1.3509
0.7363
0.0005
0.0168
−0.0077
0
0
0
0


4
1
23.1744
16.9866
0.7784
28.5757
0.0904
0
0
0
0.3125


4
2
28.5323
20.2685
0.9161
33.6276
0.112
0
0
0.3125
0.3125


4
3
24.9023
16.5852
0.7687
28.2199
0.1184
0
0
0
0.3125


4
4
8.3484
7.4139
0.2462
9.0365
0.0236
0
0
0
0.3125


4
5
28.2314
16.652
0.814
29.8824
0.1533
0
0
0
0.3125


4
6
39.4798
24.09
1.1719
43.0211
0.2026
0
0
0
0.3125


4
7
25.0657
17.1429
0.7976
29.2776
0.105
0
0
0
0.3125


4
8
20.8684
14.4244
0.6484
23.8022
0.0887
0
0
0
0.3125


4
9
26.476
18.4214
0.8784
32.2449
0.1005
0
0
0
0.3125


4
10
25.3804
18.1039
0.8522
31.2829
0.0975
0
0.3125
0
0.3125


4
11
13.9181
9.2274
0.4588
16.8412
0.0498
0
0
0
0.3125


4
12
13.6987
10.4619
0.434
15.9319
0.0459
0
0
0
0.3125


4
13
8.069
7.5589
0.2327
8.5431
0.0185
0
0
0
0.3125


4
14
21.7048
15.5036
0.7237
26.5651
0.0794
0
0
0
0.3125


4
15
7.1383
7.611
0.2204
8.0914
0.0168
0
0
0
0.3125


4
16
28.2274
18.5972
0.9383
34.4443
0.1182
0.1275
0
0
0


5
1
25.0356
17.8739
0.8182
30.0351
0.0996
0
0
0
0.4063


5
2
29.5211
21.5832
0.9284
34.0807
0.1135
0
0
0.2188
0.4063


5
3
25.5889
17.3611
0.7957
29.211
0.1149
0
0
0
0.4063


5
4
11.1187
9.9822
0.3389
12.4417
0.0338
0
0
0
0.4063


5
5
27.9457
16.713
0.8317
30.5293
0.1491
0
0
0
0.4063


5
6
38.1172
21.2674
1.1043
40.539
0.2047
0
0
0
0.4063


5
7
24.6847
17.5415
0.8004
29.3828
0.098
0
0
0
0.4063


5
8
24.8369
17.0456
0.7916
29.0571
0.1039
0
0
0
0.4063


5
9
25.2684
19.1268
0.8271
30.3624
0.0942
0
0
0
0.4063


5
10
25.9949
19.5089
0.8585
31.5149
0.0991
0
0.2188
0
0.4063


5
11
17.6559
13.8567
0.5775
21.1997
0.0635
0
0
0
0.4063


5
12
19.56
14.366
0.6131
22.5058
0.0705
0
0
0
0.4063


5
13
7.807
6.7271
0.2181
8.005
0.021
0
0
0
0.4063


5
14
22.2026
14.967
0.748
27.4571
0.0898
0
0
0
0.4063


5
15
11.4161
8.8494
0.3588
13.173
0.0373
0
0
0
0.4063


5
16
0.0343
0.2746
−0.0017
−0.0622
−0.007
0
0
0
0


6
1
28.3635
19.4266
0.9197
33.7623
0.1222
0
0
0
0.5


6
2
30.4663
20.8458
0.9865
36.2151
0.1288
0
0
0.125
0.5


6
3
24.5123
16.1173
0.794
29.1455
0.1075
0
0
0
0.5


6
4
20.2767
14.6918
0.6733
24.7161
0.0801
0
0
0
0.5


6
5
33.2496
16.76
0.9351
34.3274
0.2217
0
0
0
0.5


6
6
38.5058
19.2941
1.0938
40.154
0.2327
0
0
0
0.5


6
7
24.1336
17.4112
0.7994
29.3455
0.1052
0
0
0
0.5


6
8
22.6528
14.9365
0.7653
28.0945
0.0974
0
0
0
0.5


6
9
26.9144
19.6802
0.8845
32.4702
0.1055
0
0
0
0.5


6
10
26.6038
18.7414
0.9208
33.8001
0.11
0
0.125
0
0.5


6
11
22.4349
14.9258
0.7817
28.6959
0.0944
0
0
0
0.5


6
12
20.9112
14.2122
0.6922
25.4099
0.0817
0
0
0
0.5


6
13
11.904
7.5826
0.4014
14.7338
0.0486
0
0
0
0.5


6
14
23.5252
16.7311
0.7707
28.2915
0.0917
0
0
0
0.5


6
15
17.2103
10.833
0.5735
21.0513
0.067
0
0
0
0.5


6
16
1.0088
−0.1805
0.0177
0.6503
−0.0041
0
0
0
0


7
1
29.1091
18.3888
0.9377
34.4238
0.1288
0
0
0
0


7
2
23.4675
15.9929
0.7993
29.3427
0.1033
0
0
0
0.5


7
3
24.4
17.9806
0.8052
29.5583
0.0931
0
0
0.5
0


7
4
23.9259
17.6284
0.8206
30.1251
0.0928
0
0
0
0


7
5
21.9374
15.2657
0.7495
27.5124
0.0915
0
0
0
0


7
6
34.6888
23.3528
1.131
41.5182
0.1544
0
0
0
0


7
7
23.0341
16.9495
0.7009
25.7276
0.099
0
0
0
0


7
8
28.7153
15.6433
0.8015
29.4221
0.1671
0
0
0
0


7
9
21.8886
15.6142
0.7632
28.0152
0.0898
0
0
0
0


7
10
21.9107
15.6183
0.7745
28.4325
0.0907
0
0.5
0
0


7
11
18.5907
14.206
0.615
22.5768
0.0714
0
0
0
0


7
12
24.8013
17.9553
0.8391
30.8011
0.1049
0
0
0
0


7
13
4.148
4.5963
0.1558
5.7193
0.01
0
0
0
0


7
14
25.1707
16.9965
0.8683
31.875
0.1033
0
0
0
0


7
15
10.053
7.9852
0.3638
13.3549
0.0383
0
0
0
0


7
16
27.3338
18.6129
0.9314
34.1925
0.1154
0.1275
0
0
0


8
1
27.8709
16.8374
0.9039
33.1799
0.1419
0
0
0
0


8
2
25.0239
16.3557
0.8605
31.5885
0.1186
0
0
0
0.4063


8
3
23.3124
16.5445
0.7803
28.6442
0.1016
0
0
0.4063
0


8
4
30.4167
20.755
1.0121
37.1518
0.1278
0
0
0
0


8
5
22.4729
15.5952
0.7556
27.7364
0.0987
0
0
0
0


8
6
33.8859
22.7736
1.1246
41.2829
0.1534
0
0
0
0


8
7
23.0982
15.007
0.72
26.4315
0.1098
0
0
0
0


8
8
27.9822
13.7786
0.811
29.7729
0.1778
0
0
0
0


8
9
23.7305
17.1175
0.8213
30.1477
0.1059
0
0
0
0


8
10
24.1435
16.057
0.8058
29.5803
0.1029
0
0.4063
0
0


8
11
22.7845
15.9341
0.7662
28.126
0.1051
0
0
0
0


8
12
22.5472
14.8209
0.7762
28.4929
0.1038
0
0
0
0


8
13
4.6
5.0283
0.1611
5.9139
0.0164
0
0
0
0


8
14
26.3117
17.5568
0.8937
32.8057
0.1158
0
0
0
0


8
15
19.2935
13.6483
0.7008
25.725
0.0827
0
0
0
0


8
16
0.3501
2.3807
0.0044
0.1601
−0.0072
0
0
0
0


9
1
30.2669
17.4031
0.9382
34.439
0.1638
0
0
0
0


9
2
24.7831
15.5168
0.8133
29.856
0.1193
0
0
0
0.3125


9
3
24.8843
16.3799
0.8144
29.8952
0.1144
0
0
0.3125
0


9
4
27.7158
18.3043
0.9486
34.8222
0.1209
0
0
0
0


9
5
22.301
14.7031
0.7678
28.1862
0.1077
0
0
0
0


9
6
31.7529
21.8186
1.0511
38.5834
0.1407
0
0
0
0


9
7
22.4223
13.2509
0.6914
25.3794
0.1125
0
0
0
0


9
8
26.7272
10.823
0.7966
29.2411
0.1718
0
0
0
0


9
9
18.6358
11.9972
0.6423
23.5776
0.0893
0
0
0
0


9
10
21.5732
13.0857
0.7295
26.7785
0.0998
0
0.3125
0
0


9
11
21.8603
13.7562
0.7383
27.1031
0.1087
0
0
0
0


9
12
23.2584
14.2339
0.7779
28.5546
0.1092
0
0
0
0


9
13
6.1089
5.8813
0.2145
7.8737
0.0226
0
0
0
0


9
14
21.796
14.0238
0.7518
27.5966
0.1012
0
0
0
0


9
15
14.7758
10.7605
0.524
19.2341
0.0608
0
0
0
0


9
16
0.0047
0.3621
0.0345
1.268
0.0006
0
0
0
0


10 
1
32.2957
12.969
0.8786
32.253
0.2259
0
0
0
0


10 
2
22.9073
13.5906
0.7444
27.3268
0.1229
0
0
0
0.2188


10 
3
24.02
14.4655
0.7658
28.1101
0.1285
0
0
0.2188
0


10 
4
27.4735
18.2379
0.9287
34.0901
0.1247
0
0
0
0


10 
5
25.7888
14.3222
0.7908
29.0301
0.1508
0
0
0
0


10 
6
28.2681
18.4984
0.959
35.2041
0.1403
0
0
0
0


10 
7
26.3335
13.7746
0.7698
28.257
0.1587
0
0
0
0


10 
8
27.2793
11.6159
0.7715
28.3222
0.181
0
0
0
0


10 
9
23.7532
13.9992
0.7647
28.0727
0.1187
0
0
0
0


10 
10
23.0104
12.8612
0.7501
27.5368
0.1242
0
0.2188
0
0


10 
11
24.3958
13.8516
0.7821
28.7085
0.1283
0
0
0
0


10 
12
24.7178
14.4298
0.7945
29.1648
0.1251
0
0
0
0


10 
13
6.2103
5.4757
0.2329
8.5508
0.0276
0
0
0
0


10 
14
20.3259
13.0573
0.6932
25.4467
0.0987
0
0
0
0


10 
15
18.1743
12.8071
0.6685
24.5392
0.0818
0
0
0
0


10 
16
25.148
16.3311
0.9105
33.4226
0.1159
0.1275
0
0
0


11 
1
33.2657
13.7869
0.9096
33.389
0.2236
0
0
0
0


11 
2
26.3629
12.996
0.8123
29.819
0.1618
0
0
0
0.125


11 
3
24.9661
13.9343
0.8015
29.4223
0.135
0
0
0.125
0


11 
4
25.749
14.2206
0.8562
31.4286
0.1402
0
0
0
0


11 
5
23.3622
11.0514
0.726
26.6504
0.1408
0
0
0
0


11 
6
25.4002
15.3152
0.8622
31.652
0.1297
0
0
0
0


11 
7
23.7527
11.0405
0.7081
25.9945
0.1474
0
0
0
0


11 
8
25.2713
10.4518
0.7606
27.9193
0.1663
0
0
0
0


11 
9
22.1004
12.2049
0.7055
25.8981
0.1177
0
0
0
0


11 
10
21.8975
12.2273
0.7148
26.2406
0.1184
0
0.125
0
0


11 
11
22.2123
12.4559
0.7208
26.4587
0.1235
0
0
0
0


11 
12
22.4272
13.3655
0.7375
27.0716
0.1141
0
0
0
0


11 
13
10.6819
7.0626
0.3567
13.095
0.0525
0
0
0
0


11 
14
22.4528
12.9362
0.7568
27.7801
0.1206
0
0
0
0


11 
15
19.7448
13.9333
0.6951
25.5175
0.0875
0
0
0
0


11 
16
−0.1972
1.471
0.0237
0.8717
0.0002
0
0
0
0


12 
1
31.5656
21.6797
1.0782
39.5788
0.1397
0
0
0
0


12 
2
19.6043
13.572
0.6955
25.5322
0.089
0
0
0
0.5


12 
3
28.1666
17.3647
0.9244
33.9334
0.1488
0
0
0
0


12 
4
31.3253
21.7961
1.0594
38.89
0.1349
0
0
0.5
0


12 
5
17.3834
14.0571
0.6238
22.8995
0.0749
0
0
0
0


12 
6
35.3057
24.5521
1.1878
43.6046
0.1566
0
0
0
0


12 
7
23.1431
16.6639
0.8015
29.4211
0.1066
0
0
0
0


12 
8
26.6065
17.7981
0.9318
34.2045
0.1338
0
0
0
0


12 
9
31.073
22.4346
1.0697
39.269
0.1354
0
0
0
0


12 
10
29.9328
22.2939
1.0514
38.5962
0.1273
0
0.5
0
0


12 
11
28.5736
20.9007
1.0125
37.1693
0.1236
0
0
0
0


12 
12
28.8195
19.4676
1.0399
38.1729
0.1274
0
0
0
0


12 
13
2.9218
3.3576
0.0985
3.6155
0.0097
0
0
0
0


12 
14
25.7013
17.9671
0.9023
33.1211
0.1147
0
0
0
0


12 
15
8.492
5.9126
0.3308
12.1433
0.0423
0
0
0
0


12 
16
−0.1015
0.1618
0.0165
0.6066
0.0023
0
0
0
0


13 
1
32.929
23.1662
1.1398
41.8401
0.1451
0
0
0
0


13 
2
12.9188
10.5882
0.449
16.481
0.0547
0
0
0
0.4063


13 
3
28.0856
18.7043
0.9401
34.5103
0.126
0
0
0
0


13 
4
31.7131
22.9009
1.054
38.6919
0.1335
0
0
0.4063
0


13 
5
10.3872
8.6629
0.3924
14.405
0.0454
0
0
0
0


13 
6
32.6469
22.0266
1.0976
40.2904
0.1422
0
0
0
0


13 
7
26.7979
19.1216
0.9313
34.1868
0.1168
0
0
0
0


13 
8
27.1205
19.4829
0.9549
35.0517
0.1223
0
0
0
0


13 
9
29.5931
21.5231
1.038
38.1041
0.1264
0
0
0
0


13 
10
28.868
20.7843
1.0163
37.3068
0.1254
0
0.4063
0
0


13 
11
19.8455
15.1061
0.6906
25.353
0.0865
0
0
0
0


13 
12
28.8191
20.6337
1.0134
37.1994
0.1238
0
0
0
0


13 
13
2.6024
3.2972
0.0961
3.526
0.0071
0
0
0
0


13 
14
25.0501
16.2104
0.9126
33.5022
0.1159
0
0
0
0


13 
15
6.4246
5.1337
0.2835
10.4071
0.0349
0
0
0
0


13 
16
24.6043
16.341
0.9005
33.0556
0.1142
0.1275
0
0
0


14 
1
31.1905
22.5852
1.0761
39.5045
0.1379
0
0
0
0


14 
2
15.3686
12.5627
0.5534
20.3138
0.0672
0
0
0
0.3125


14 
3
28.5902
21.079
0.9573
35.1415
0.1252
0
0
0
0


14 
4
30.8225
21.6996
1.0648
39.0881
0.1372
0
0
0.3125
0


14 
5
10.1619
9.3091
0.3843
14.1078
0.0446
0
0
0
0


14 
6
25.9037
19.3547
0.9378
34.425
0.1151
0
0
0
0


14 
7
28.9615
21.1086
0.9966
36.5847
0.129
0
0
0
0


14 
8
25.3268
19.6253
0.9096
33.392
0.1117
0
0
0
0


14 
9
30.5368
22.8098
1.0517
38.6072
0.1317
0
0
0
0


14 
10
30.4639
21.8604
1.0468
38.4279
0.1319
0
0.3125
0
0


14 
11
28.5368
20.5826
1.0152
37.2667
0.1262
0
0
0
0


14 
12
28.9878
20.031
1.0283
37.748
0.1277
0
0
0
0


14 
13
1.9405
3.4997
0.1021
3.7493
0.0083
0
0
0
0


14 
14
26.2698
18.1259
0.9407
34.5326
0.1172
0
0
0
0


14 
15
3.5222
3.4456
0.1728
6.345
0.0193
0
0
0
0


14 
16
−1.2721
0.2876
0.0152
0.5574
0
0
0
0
0


15 
1
21.9285
16.5533
0.7944
29.1616
0.0981
0
0
0
0


15 
2
8.5556
7.9322
0.3176
11.6581
0.0386
0
0
0
0.2188


15 
3
28.9139
19.3873
1.0115
37.1305
0.1329
0
0
0
0


15 
4
29.4947
20.5675
1.0129
37.1816
0.1319
0
0
0.2188
0


15 
5
10.3199
7.8183
0.3758
13.7939
0.0488
0
0
0
0


15 
6
19.07
12.9719
0.6822
25.0424
0.0872
0
0
0
0


15 
7
24.4592
16.5438
0.8787
32.2577
0.1122
0
0
0
0


15 
8
26.1966
19.0364
0.9283
34.0753
0.1149
0
0
0
0


15 
9
28.805
20.399
1.0007
36.7353
0.1231
0
0
0
0


15 
10
27.8671
19.9279
0.9883
36.2797
0.1237
0
0.2188
0
0


15 
11
25.9077
18.1393
0.9238
33.9133
0.1174
0
0
0
0


15 
12
26.8168
19.5131
0.9364
34.3739
0.1198
0
0
0
0


15 
13
3.1831
4.1719
0.1255
4.6087
0.0135
0
0
0
0


15 
14
25.6485
17.9831
0.9073
33.3061
0.1142
0
0
0
0


15 
15
3.4019
2.8501
0.1862
6.8334
0.0252
0
0
0
0


15 
16
−0.6764
0.6935
0.0304
1.1161
0.0028
0
0
0
0


16 
1
27.2358
17.9797
0.9948
36.5199
0.1324
0
0
0
0


16 
2
20.4235
13.9408
0.7544
27.693
0.0997
0
0
0
0.125


16 
3
22.1148
16.7994
0.7919
29.0693
0.101
0
0
0
0


16 
4
27.8457
18.1657
0.9706
35.6285
0.1316
0
0
0.125
0


16 
5
16.0515
10.9271
0.6032
22.1443
0.0766
0
0
0
0


16 
6
21.5319
16.4412
0.8048
29.5417
0.101
0
0
0
0


16 
7
28.6538
19.2213
1.0145
37.243
0.1346
0
0
0
0


16 
8
27.0582
20.0777
0.9481
34.8038
0.1218
0
0
0
0


16 
9
28.251
19.2368
1.0097
37.0662
0.132
0
0
0
0


16 
10
28.3144
19.6597
0.9907
36.3661
0.1282
0
0.125
0
0


16 
11
25.2372
17.9227
0.9037
33.1748
0.1146
0
0
0
0


16 
12
27.1113
19.9798
0.984
36.1202
0.1221
0
0
0
0


16 
13
7.0222
6.86
0.2888
10.6009
0.0359
0
0
0
0


16 
14
24.3113
16.5973
0.9032
33.1567
0.1156
0
0
0
0


16 
15
11.0117
7.8026
0.4408
16.1825
0.0553
0
0
0
0


16 
16
24.9744
15.3136
0.9047
33.2092
0.1182
0.1275
0
0
0





















R
CoOAc2
Na3CoNO36
CuNO32
GeOX2
H2MoO4
KRuO4
RuNONO33
RuNOOAc3
LaNO33
NH4ReO4
PtNH32NO22


real
real
real
real
real
real
real
real
real
real
real
real





Temper-


ature:


250 C.


1
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0


2
0
0
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0.0989
0
0
0
0.1275


2
0
0
0
0
0.5
0
0
0
0
0
0.1275


2
0.5
0
0
0
0
0
0
0
0
0
0.1275


2
0
0.5
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0.098
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0.098
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.5
0
0.1275


2
0
0
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0
0
0.1275


2
0
0
0.5
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0
0.1074
0.1275


2
0
0
0
0.2
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0
0
0


3
0
0
0
0
0
0
0
0
0
0
0.1275


3
0
0
0
0
0
0
0
0
0
0
0.1275


3
0
0
0
0
0
0
0.0804
0
0
0
0.1275


3
0
0
0
0
0.4063
0
0
0
0
0
0.1275


3
0.4063
0
0
0
0
0
0
0
0
0
0.1275


3
0
0.4063
0
0
0
0
0
0
0
0
0.1275


3
0
0
0
0
0
0
0
0
0
0
0.1275


3
0
0
0
0
0
0
0
0.0796
0
0
0.1275


3
0
0
0
0
0
0
0
0
0.4063
0
0.1275


3
0
0
0
0
0
0
0
0
0
0
0.1275


3
0
0
0
0
0
0
0
0
0
0
0.1275


3
0
0
0
0
0
0
0
0
0
0
0.1275


3
0
0
0.4063
0
0
0
0
0
0
0
0.1275


3
0
0
0
0
0
0
0
0
0
0.0873
0.1275


3
0
0
0
0.1625
0
0
0
0
0
0
0.1275


3
0
0
0
0
0
0
0
0
0
0
0


4
0
0
0
0
0
0
0
0
0
0
0.1275


4
0
0
0
0
0
0
0
0
0
0
0.1275


4
0
0
0
0
0
0
0.0618
0
0
0
0.1275


4
0
0
0
0
0.3125
0
0
0
0
0
0.1275


4
0.3125
0
0
0
0
0
0
0
0
0
0.1275


4
0
0.3125
0
0
0
0
0
0
0
0
0.1275


4
0
0
0
0
0
0.0613
0
0
0
0
0.1275


4
0
0
0
0
0
0
0
0.0613
0
0
0.1275


4
0
0
0
0
0
0
0
0
0.3125
0
0.1275


4
0
0
0
0
0
0
0
0
0
0
0.1275


4
0
0
0
0
0
0
0
0
0
0
0.1275


4
0
0
0
0
0
0
0
0
0
0
0.1275


4
0
0
0.3125
0
0
0
0
0
0
0
0.1275


4
0
0
0
0
0
0
0
0
0
0.0671
0.1275


4
0
0
0
0.125
0
0
0
0
0
0
0.1275


4
0
0
0
0
0
0
0
0
0
0
0


5
0
0
0
0
0
0
0
0
0
0
0.1275


5
0
0
0
0
0
0
0
0
0
0
0.1275


5
0
0
0
0
0
0
0.0433
0
0
0
0.1275


5
0
0
0
0
0.2188
0
0
0
0
0
0.1275


5
0.2188
0
0
0
0
0
0
0
0
0
0.1275


5
0
0.2188
0
0
0
0
0
0
0
0
0.1275


5
0
0
0
0
0
0.0429
0
0
0
0
0.1275


5
0
0
0
0
0
0
0
0.0429
0
0
0.1275


5
0
0
0
0
0
0
0
0
0.2188
0
0.1275


5
0
0
0
0
0
0
0
0
0
0
0.1275


5
0
0
0
0
0
0
0
0
0
0
0.1275


5
0
0
0
0
0
0
0
0
0
0
0.1275


5
0
0
0.2188
0
0
0
0
0
0
0
0.1275


5
0
0
0
0
0
0
0
0
0
0.047
0.1275


5
0
0
0
0.0875
0
0
0
0
0
0
0.1275


5
0
0
0
0
0
0
0
0
0
0
0


6
0
0
0
0
0
0
0
0
0
0
0.1275


6
0
0
0
0
0
0
0
0
0
0
0.1275


6
0
0
0
0
0
0
0.0247
0
0
0
0.1275


6
0
0
0
0
0.125
0
0
0
0
0
0.1275


6
0.125
0
0
0
0
0
0
0
0
0
0.1275


6
0
0.125
0
0
0
0
0
0
0
0
0.1275


6
0
0
0
0
0
0.0245
0
0
0
0
0.1275


6
0
0
0
0
0
0
0
0.0245
0
0
0.1275


6
0
0
0
0
0
0
0
0
0.125
0
0.1275


6
0
0
0
0
0
0
0
0
0
0
0.1275


6
0
0
0
0
0
0
0
0
0
0
0.1275


6
0
0
0
0
0
0
0
0
0
0
0.1275


6
0
0
0.125
0
0
0
0
0
0
0
0.1275


6
0
0
0
0
0
0
0
0
0
0.0269
0.1275


6
0
0
0
0.05
0
0
0
0
0
0
0.1275


6
0
0
0
0
0
0
0
0
0
0
0


7
0
0
0
0
0
0
0.0247
0
0
0
0.1275


7
0
0
0
0
0
0
0.0247
0
0
0
0.1275


7
0
0
0
0
0
0
0.0247
0
0
0
0.1275


7
0
0
0
0
0.5
0
0.0247
0
0
0
0.1275


7
0.5
0
0
0
0
0
0.0247
0
0
0
0.1275


7
0
0.5
0
0
0
0
0.0247
0
0
0
0.1275


7
0
0
0
0
0
0.098
0.0247
0
0
0
0.1275


7
0
0
0
0
0
0
0.0247
0.098
0
0
0.1275


7
0
0
0
0
0
0
0.0247
0
0.5
0
0.1275


7
0
0
0
0
0
0
0.0247
0
0
0
0.1275


7
0
0
0
0
0
0
0.0247
0
0
0
0.1275


7
0
0
0
0
0
0
0.0247
0
0
0
0.1275


7
0
0
0.5
0
0
0
0.0247
0
0
0
0.1275


7
0
0
0
0
0
0
0.0247
0
0
0.1074
0.1275


7
0
0
0
0.2
0
0
0.0247
0
0
0
0.1275


7
0
0
0
0
0
0
0
0
0
0
0


8
0
0
0
0
0
0
0.0433
0
0
0
0.1275


8
0
0
0
0
0
0
0.0433
0
0
0
0.1275


8
0
0
0
0
0
0
0.0433
0
0
0
0.1275


8
0
0
0
0
0.4063
0
0.0433
0
0
0
0.1275


8
0.4063
0
0
0
0
0
0.0433
0
0
0
0.1275


8
0
0.4063
0
0
0
0
0.0433
0
0
0
0.1275


8
0
0
0
0
0
0.0796
0.0433
0
0
0
0.1275


8
0
0
0
0
0
0
0.0433
0.0796
0
0
0.1275


8
0
0
0
0
0
0
0.0433
0
0.4063
0
0.1275


8
0
0
0
0
0
0
0.0433
0
0
0
0.1275


8
0
0
0
0
0
0
0.0433
0
0
0
0.1275


8
0
0
0
0
0
0
0.0433
0
0
0
0.1275


8
0
0
0.4063
0
0
0
0.0433
0
0
0
0.1275


8
0
0
0
0
0
0
0.0433
0
0
0.0873
0.1275


8
0
0
0
0.1625
0
0
0.0433
0
0
0
0.1275


8
0
0
0
0
0
0
0
0
0
0
0


9
0
0
0
0
0
0
0.0618
0
0
0
0.1275


9
0
0
0
0
0
0
0.0618
0
0
0
0.1275


9
0
0
0
0
0
0
0.0618
0
0
0
0.1275


9
0
0
0
0
0.3125
0
0.0618
0
0
0
0.1275


9
0.3125
0
0
0
0
0
0.0618
0
0
0
0.1275


9
0
0.3125
0
0
0
0
0.0618
0
0
0
0.1275


9
0
0
0
0
0
0.0613
0.0618
0
0
0
0.1275


9
0
0
0
0
0
0
0.0618
0.0613
0
0
0.1275


9
0
0
0
0
0
0
0.0618
0
0.3125
0
0.1275


9
0
0
0
0
0
0
0.0618
0
0
0
0.1275


9
0
0
0
0
0
0
0.0618
0
0
0
0.1275


9
0
0
0
0
0
0
0.0618
0
0
0
0.1275


9
0
0
0.3125
0
0
0
0.0618
0
0
0
0.1275


9
0
0
0
0
0
0
0.0618
0
0
0.0671
0.1275


9
0
0
0
0.125
0
0
0.0618
0
0
0
0.1275


9
0
0
0
0
0
0
0
0
0
0
0


10 
0
0
0
0
0
0
0.0804
0
0
0
0.1275


10 
0
0
0
0
0
0
0.0804
0
0
0
0.1275


10 
0
0
0
0
0
0
0.0804
0
0
0
0.1275


10 
0
0
0
0
0.2188
0
0.0804
0
0
0
0.1275


10 
0.2188
0
0
0
0
0
0.0804
0
0
0
0.1275


10 
0
0.2188
0
0
0
0
0.0804
0
0
0
0.1275


10 
0
0
0
0
0
0.0429
0.0804
0
0
0
0.1275


10 
0
0
0
0
0
0
0.0804
0.0429
0
0
0.1275


10 
0
0
0
0
0
0
0.0804
0
0.2188
0
0.1275


10 
0
0
0
0
0
0
0.0804
0
0
0
0.1275


10 
0
0
0
0
0
0
0.0804
0
0
0
0.1275


10 
0
0
0
0
0
0
0.0804
0
0
0
0.1275


10 
0
0
0.2188
0
0
0
0.0804
0
0
0
0.1275


10 
0
0
0
0
0
0
0.0804
0
0
0.047
0.1275


10 
0
0
0
0.0875
0
0
0.0804
0
0
0
0.1275


10 
0
0
0
0
0
0
0
0
0
0
0


11 
0
0
0
0
0
0
0.0989
0
0
0
0.1275


11 
0
0
0
0
0
0
0.0989
0
0
0
0.1275


11 
0
0
0
0
0
0
0.0989
0
0
0
0.1275


11 
0
0
0
0
0.125
0
0.0989
0
0
0
0.1275


11 
0.125
0
0
0
0
0
0.0989
0
0
0
0.1275


11 
0
0.125
0
0
0
0
0.0989
0
0
0
0.1275


11 
0
0
0
0
0
0.0245
0.0989
0
0
0
0.1275


11 
0
0
0
0
0
0
0.0989
0.0245
0
0
0.1275


11 
0
0
0
0
0
0
0.0989
0
0.125
0
0.1275


11 
0
0
0
0
0
0
0.0989
0
0
0
0.1275


11 
0
0
0
0
0
0
0.0989
0
0
0
0.1275


11 
0
0
0
0
0
0
0.0989
0
0
0
0.1275


11 
0
0
0.125
0
0
0
0.0989
0
0
0
0.1275


11 
0
0
0
0
0
0
0.0989
0
0
0.0269
0.1275


11 
0
0
0
0.05
0
0
0.0989
0
0
0
0.1275


11 
0
0
0
0
0
0
0
0
0
0
0


12 
0
0
0
0
0.125
0
0
0
0
0
0.1275


12 
0
0
0
0
0.125
0
0
0
0
0
0.1275


12 
0
0
0
0
0.125
0
0.0989
0
0
0
0.1275


12 
0
0
0
0
0.125
0
0
0
0
0
0.1275


12 
0.5
0
0
0
0.125
0
0
0
0
0
0.1275


12 
0
0.5
0
0
0.125
0
0
0
0
0
0.1275


12 
0
0
0
0
0.125
0.098
0
0
0
0
0.1275


12 
0
0
0
0
0.125
0
0
0.098
0
0
0.1275


12 
0
0
0
0
0.125
0
0
0
0.5
0
0.1275


12 
0
0
0
0
0.125
0
0
0
0
0
0.1275


12 
0
0
0
0
0.125
0
0
0
0
0
0.1275


12 
0
0
0
0
0.125
0
0
0
0
0
0.1275


12 
0
0
0.5
0
0.125
0
0
0
0
0
0.1275


12 
0
0
0
0
0.125
0
0
0
0
0.1074
0.1275


12 
0
0
0
0.2
0.125
0
0
0
0
0
0.1275


12 
0
0
0
0
0
0
0
0
0
0
0


13 
0
0
0
0
0.2188
0
0
0
0
0
0.1275


13 
0
0
0
0
0.2188
0
0
0
0
0
0.1275


13 
0
0
0
0
0.2188
0
0.0804
0
0
0
0.1275


13 
0
0
0
0
0.2188
0
0
0
0
0
0.1275


13 
0.4063
0
0
0
0.2188
0
0
0
0
0
0.1275


13 
0
0.4063
0
0
0.2188
0
0
0
0
0
0.1275


13 
0
0
0
0
0.2188
0.0796
0
0
0
0
0.1275


13 
0
0
0
0
0.2188
0
0
0.0796
0
0
0.1275


13 
0
0
0
0
0.2188
0
0
0
0.4063
0
0.1275


13 
0
0
0
0
0.2188
0
0
0
0
0
0.1275


13 
0
0
0
0
0.2188
0
0
0
0
0
0.1275


13 
0
0
0
0
0.2188
0
0
0
0
0
0.1275


13 
0
0
0.4063
0
0.2188
0
0
0
0
0
0.1275


13 
0
0
0
0
0.2188
0
0
0
0
0.0873
0.1275


13 
0
0
0
0.1625
0.2188
0
0
0
0
0
0.1275


13 
0
0
0
0
0
0
0
0
0
0
0


14 
0
0
0
0
0.3125
0
0
0
0
0
0.1275


14 
0
0
0
0
0.3125
0
0
0
0
0
0.1275


14 
0
0
0
0
0.3125
0
0.0618
0
0
0
0.1275


14 
0
0
0
0
0.3125
0
0
0
0
0
0.1275


14 
0.3125
0
0
0
0.3125
0
0
0
0
0
0.1275


14 
0
0.3125
0
0
0.3125
0
0
0
0
0
0.1275


14 
0
0
0
0
0.3125
0.0613
0
0
0
0
0.1275


14 
0
0
0
0
0.3125
0
0
0.0613
0
0
0.1275


14 
0
0
0
0
0.3125
0
0
0
0.3125
0
0.1275


14 
0
0
0
0
0.3125
0
0
0
0
0
0.1275


14 
0
0
0
0
0.3125
0
0
0
0
0
0.1275


14 
0
0
0
0
0.3125
0
0
0
0
0
0.1275


14 
0
0
0.3125
0
0.3125
0
0
0
0
0
0.1275


14 
0
0
0
0
0.3125
0
0
0
0
0.0671
0.1275


14 
0
0
0
0.125
0.3125
0
0
0
0
0
0.1275


14 
0
0
0
0
0
0
0
0
0
0
0


15 
0
0
0
0
0.4063
0
0
0
0
0
0.1275


15 
0
0
0
0
0.4063
0
0
0
0
0
0.1275


15 
0
0
0
0
0.4063
0
0.0433
0
0
0
0.1275


15 
0
0
0
0
0.4063
0
0
0
0
0
0.1275


15 
0.2188
0
0
0
0.4063
0
0
0
0
0
0.1275


15 
0
0.2188
0
0
0.4063
0
0
0
0
0
0.1275


15 
0
0
0
0
0.4063
0.0429
0
0
0
0
0.1275


15 
0
0
0
0
0.4063
0
0
0.0429
0
0
0.1275


15 
0
0
0
0
0.4063
0
0
0
0.2188
0
0.1275


15 
0
0
0
0
0.4063
0
0
0
0
0
0.1275


15 
0
0
0
0
0.4063
0
0
0
0
0
0.1275


15 
0
0
0
0
0.4063
0
0
0
0
0
0.1275


15 
0
0
0.2188
0
0.4063
0
0
0
0
0
0.1275


15 
0
0
0
0
0.4063
0
0
0
0
0.047
0.1275


15 
0
0
0
0.0875
0.4063
0
0
0
0
0
0.1275


15 
0
0
0
0
0
0
0
0
0
0
0


16 
0
0
0
0
0.5
0
0
0
0
0
0.1275


16 
0
0
0
0
0.5
0
0
0
0
0
0.1275


16 
0
0
0
0
0.5
0
0.0247
0
0
0
0.1275


16 
0
0
0
0
0.5
0
0
0
0
0
0.1275


16 
0.125
0
0
0
0.5
0
0
0
0
0
0.1275


16 
0
0.125
0
0
0.5
0
0
0
0
0
0.1275


16 
0
0
0
0
0.5
0.0245
0
0
0
0
0.1275


16 
0
0
0
0
0.5
0
0
0.0245
0
0
0.1275


16 
0
0
0
0
0.5
0
0
0
0.125
0
0.1275


16 
0
0
0
0
0.5
0
0
0
0
0
0.1275


16 
0
0
0
0
0.5
0
0
0
0
0
0.1275


16 
0
0
0
0
0.5
0
0
0
0
0
0.1275


16 
0
0
0.125
0
0.5
0
0
0
0
0
0.1275


16 
0
0
0
0
0.5
0
0
0
0
0.0269
0.1275


16 
0
0
0
0.05
0.5
0
0
0
0
0
0.1275


16 
0
0
0
0
0
0
0
0
0
0
0























R
ZrONO32
ZrOOAc2
SUM
mol %
mol %
mol %
mol %
mol %
mol %
mol %
mol %
mol %
mol %


real
real
real
micromols
Ce
Co
Cu
Ge
Mo
Ru
La
Re
Pt
Zr





Temperature:


250 C


1
0
0
0.1275
0
0
0
0
0
0
0
0
100
0


1
0
0
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0.1275
0
0
0
0
0
0
0
0
100
0


1
0
0
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0.1275
0
0
0
0
0
0
0
0
100
0


1
0
0
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0
0
0
0


1
0
0
0.1275
0
0
0
0
0
0
0
0
100
0


2
0
0
0.2525
0
49.5
0
0
0
0
0
0
50.5
0


2
0
0
0.7525
66.45
16.61
0
0
0
0
0
0
16.94
0


2
0
0
0.3514
0
35.57
0
0
0
28.14
0
0
36.28
0


2
0
0
0.7525
0
16.61
0
0
66.45
0
0
0
16.94
0


2
0
0
0.7525
0
83.06
0
0
0
0
0
0
16.94
0


2
0
0
0.7525
0
83.06
0
0
0
0
0
0
16.94
0


2
0
0
0.3505
0
35.66
0
0
0
27.96
0
0
36.38
0


2
0
0
0.3505
0
35.66
0
0
0
27.96
0
0
36.38
0


2
0
0
0.7525
0
16.61
0
0
0
0
66.45
0
16.94
0


2
0
0
0.7525
66.45
16.61
0
0
0
0
0
0
16.94
0


2
0.5
0
0.7525
0
16.61
0
0
0
0
0
0
16.94
66.45


2
0
0.5
0.7525
0
16.61
0
0
0
0
0
0
16.94
66.45


2
0
0
0.7525
0
16.61
66.45
0
0
0
0
0
16.94
0


2
0
0
0.3599
0
34.73
0
0
0
0
0
29.84
35.43
0


2
0
0
0.4525
0
27.62
0
44.2
0
0
0
0
28.18
0


2
0
0
0
0
0
0
0
0
0
0
0
0
0


3
0
0
0.3463
0
63.18
0
0
0
0
0
0
36.82
0


3
0
0
0.7525
53.99
29.07
0
0
0
0
0
0
16.94
0


3
0
0
0.4266
0
51.28
0
0
0
18.84
0
0
29.89
0


3
0
0
0.7525
0
29.07
0
0
53.99
0
0
0
16.94
0


3
0
0
0.7525
0
83.06
0
0
0
0
0
0
16.94
0


3
0
0
0.7525
0
83.06
0
0
0
0
0
0
16.94
0


3
0
0
0.4259
0
51.36
0
0
0
18.7
0
0
29.94
0


3
0
0
0.4259
0
51.36
0
0
0
18.7
0
0
29.94
0


3
0
0
0.7525
0
29.07
0
0
0
0
53.99
0
16.94
0


3
0
0
0.7525
53.99
29.07
0
0
0
0
0
0
16.94
0


3
0.4063
0
0.7525
0
29.07
0
0
0
0
0
0
16.94
53.99


3
0
0.4063
0.7525
0
29.07
0
0
0
0
0
0
16.94
53.99


3
0
0
0.7525
0
29.07
53.99
0
0
0
0
0
16.94
0


3
0
0
0.4335
0
50.46
0
0
0
0
0
20.13
29.41
0


3
0
0
0.5088
0
43
0
31.94
0
0
0
0
25.06
0


3
0
0
0
0
0
0
0
0
0
0
0
0
0


4
0
0
0.44
0
71.02
0
0
0
0
0
0
28.98
0


4
0
0
0.7525
41.53
41.53
0
0
0
0
0
0
16.94
0


4
0
0
0.5018
0
62.27
0
0
0
12.32
0
0
25.41
0


4
0
0
0.7525
0
41.53
0
0
41.23
0
0
0
16.94
0


4
0
0
0.7525
0
83.06
0
0
0
0
0
0
16.94
0


4
0
0
0.7525
0
83.06
0
0
0
0
0
0
16.94
0


4
0
0
0.5013
0
62.34
0
0
0
12.22
0
0
25.44
0


4
0
0
0.5013
0
62.34
0
0
0
12.22
0
0
25.44
0


4
0
0
0.7525
0
41.53
0
0
0
0
41.53
0
16.94
0


4
0
0
0.7525
0
41.53
0
0
0
0
0
0
16.94
0


4
0.3125
0
0.7525
41.53
41.53
0
0
0
0
0
0
16.94
41.53


4
0
0.3125
0.7525
0
41.53
0
0
0
0
0
0
16.94
41.53


4
0
0
0.7525
0
41.53
41.53
0
0
0
0
0
16.94
0


4
0
0
0.5071
0
61.62
0
0
0
0
0
13.24
25.14
0


4
0
0
0.565
0
55.31
0
22.12
0
0
0
0
22.57
0


4
0
0
0.1275
0
0
0
0
0
0
0
0
100
0


5
0
0
0.5338
0
76.11
0
0
0
0
0
0
23.89
0


5
0
0
0.7525
29.07
53.99
0
0
0
0
0
0
16.94
0


5
0
0
0.577
0
70.4
0
0
0
7.5
0
0
22.1
0


5
0
0
0.7525
0
53.99
0
0
29.07
0
0
0
16.94
0


5
0
0
0.7525
0
83.06
0
0
0
0
0
0
16.94
0


5
0
0
0.7525
0
83.06
0
0
0
0
0
0
16.94
0


5
0
0
0.5766
0
70.45
0
0
0
7.44
0
0
22.11
0


5
0
0
0.5766
0
70.45
0
0
0
7.44
0
0
22.11
0


5
0
0
0.7525
0
53.99
0
0
0
0
29.07
0
16.94
0


5
0
0
0.7525
29.07
53.99
0
0
0
0
0
0
16.94
0


5
0.2188
0
0.7525
0
53.99
0
0
0
0
0
0
16.94
29.07


5
0
0.2188
0.7525
0
53.99
0
0
0
0
0
0
16.94
29.07


5
0
0
0.7525
0
53.99
29.07
0
0
0
0
0
16.94
0


5
0
0
0.5807
0
69.95
0
0
0
0
0
8.09
21.95
0


5
0
0
0.6213
0
65.39
0
14.08
0
0
0
0
20.52
0


5
0
0
0
0
0
0
0
0
0
0
0
0
0


6
0
0
0.6275
0
79.68
0
0
0
0
0
0
20.32
0


6
0
0
0.7525
16.61
66.45
0
0
0
0
0
0
16.94
0


6
0
0
0.6522
0
76.66
0
0
0
3.79
0
0
19.55
0


6
0
0
0.7525
0
66.45
0
0
16.61
0
0
0
16.94
0


6
0
0
0.7525
0
83.06
0
0
0
0
0
0
16.94
0


6
0
0
0.7525
0
83.06
0
0
0
0
0
0
16.94
0


6
0
0
0.652
0
76.69
0
0
0
3.76
0
0
19.56
0


6
0
0
0.652
0
76.69
0
0
0
3.76
0
0
19.56
0


6
0
0
0.7525
0
66.45
0
0
0
0
16.61
0
16.94
0


6
0
0
0.7525
16.61
66.45
0
0
0
0
0
0
16.94
0


6
0.125
0
0.7525
0
66.45
0
0
0
0
0
0
16.94
16.61


6
0
0.125
0.7525
0
66.45
0
0
0
0
0
0
16.94
16.61


6
0
0
0.7525
0
66.45
16.61
0
0
0
0
0
16.94
0


6
0
0
0.6544
0
76.41
0
0
0
0
0
4.1
19.48
0


6
0
0
0.6775
0
73.8
0
7.38
0
0
0
0
18.82
0


6
0
0
0
0
0
0
0
0
0
0
0
0
0


7
0
0
0.1522
0
0
0
0
0
16.24
0
0
83.76
0


7
0
0
0.6522
0
76.66
0
0
0
3.79
0
0
19.55
0


7
0
0
0.6522
76.66
0
0
0
0
3.79
0
0
19.55
0


7
0
0
0.6522
0
0
0
0
76.66
3.79
0
0
19.55
0


7
0
0
0.6522
0
76.66
0
0
0
3.79
0
0
19.55
0


7
0
0
0.6522
0
76.66
0
0
0
3.79
0
0
19.55
0


7
0
0
0.2502
0
0
0
0
0
49.05
0
0
50.95
0


7
0
0
0.2502
0
0
0
0
0
49.05
0
0
50.95
0


7
0
0
0.6522
0
0
0
0
0
3.79
76.66
0
19.55
0


7
0
0
0.6522
76.66
0
0
0
0
3.79
0
0
19.55
0


7
0.5
0
0.6522
0
0
0
0
0
3.79
0
0
19.55
76.66


7
0
0.5
0.6522
0
0
0
0
0
3.79
0
0
19.55
76.66


7
0
0
0.6522
0
0
76.66
0
0
3.79
0
0
19.55
0


7
0
0
0.2596
0
0
0
0
0
9.52
0
41.37
49.11
0


7
0
0
0.3522
0
0
0
56.78
0
7.02
0
0
36.2
0


7
0
0
0.1275
0
0
0
0
0
0
0
0
100
0


8
0
0
0.1708
0
0
0
0
0
25.34
0
0
74.66
0


8
0
0
0.577
0
70.4
0
0
0
7.5
0
0
22.1
0


8
0
0
0.577
70.4
0
0
0
0
7.5
0
0
22.1
0


8
0
0
0.577
0
0
0
0
70.4
7.5
0
0
22.1
0


8
0
0
0.577
0
70.4
0
0
0
7.5
0
0
22.1
0


8
0
0
0.577
0
70.4
0
0
0
7.5
0
0
22.1
0


8
0
0
0.2504
0
0
0
0
0
49.08
0
0
50.92
0


8
0
0
0.2504
0
0
0
0
0
49.08
0
0
50.92
0


8
0
0
0.577
0
0
0
0
0
7.5
70.4
0
22.1
0


8
0
0
0.577
70.4
0
0
0
0
7.5
0
0
22.1
0


8
0.4063
0
0.577
0
0
0
0
0
7.5
0
0
22.1
70.4


8
0
0.4063
0.577
0
0
0
0
0
7.5
0
0
22.1
70.4


8
0
0
0.577
0
0
70.4
0
0
7.5
0
0
22.1
0


8
0
0
0.258
0
0
0
0
0
16.77
0
33.82
49.41
0


8
0
0
0.333
0
0
0
48.76
0
12.98
0
0
38.26
0


8
0
0
0
0
0
0
0
0
0
0
0
0
0


9
0
0
0.1893
0
0
0
0
0
32.65
0
0
67.35
0


9
0
0
0.5018
0
62.27
0
0
0
12.32
0
0
25.41
0


9
0
0
0.5018
62.27
0
0
0
0
12.32
0
0
25.41
0


9
0
0
0.5018
0
0
0
0
62.27
12.32
0
0
25.41
0


9
0
0
0.5018
0
62.27
0
0
0
12.32
0
0
25.41
0


9
0
0
0.5018
0
62.27
0
0
0
12.32
0
0
25.41
0


9
0
0
0.2506
0
0
0
0
0
49.11
0
0
50.89
0


9
0
0
0.2506
0
0
0
0
0
49.11
0
0
50.89
0


9
0
0
0.5018
0
0
0
0
0
12.32
62.27
0
25.41
0


9
0
0
0.5018
62.27
0
0
0
0
12.32
0
0
25.41
0


9
0.3125
0
0.5018
0
0
0
0
0
12.32
0
0
25.41
62.27


9
0
0.3125
0.5018
0
0
0
0
0
12.32
0
0
25.41
62.27


9
0
0
0.5018
0
0
62.27
0
0
12.32
0
0
25.41
0


9
0
0
0.2564
0
0
0
0
0
24.1
0
26.18
49.72
0


9
0
0
0.3143
0
0
0
39.77
0
19.67
0
0
40.56
0


9
0
0
0
0
0
0
0
0
0
0
0
0
0


10 
0
0
0.2079
0
0
0
0
0
38.66
0
0
61.34
0


10 
0
0
0.4266
0
51.28
0
0
0
18.84
0
0
29.89
0


10 
0
0
0.4266
51.28
0
0
0
0
18.84
0
0
29.89
0


10 
0
0
0.4266
0
0
0
0
51.28
18.84
0
0
29.89
0


10 
0
0
0.4266
0
51.28
0
0
0
18.84
0
0
29.89
0


10 
0
0
0.4266
0
51.28
0
0
0
18.84
0
0
29.89
0


10 
0
0
0.2507
0
0
0
0
0
49.15
0
0
50.85
0


10 
0
0
0.2507
0
0
0
0
0
49.15
0
0
50.85
0


10 
0
0
0.4266
0
0
0
0
0
18.84
51.28
0
29.89
0


10 
0
0
0.4266
51.28
0
0
0
0
18.84
0
0
29.89
0


10 
0.2188
0
0.4266
0
0
0
0
0
18.84
0
0
29.89
51.28


10 
0
0.2188
0.4266
0
0
0
0
0
18.84
0
0
29.89
51.28


10 
0
0
0.4266
0
0
51.28
0
0
18.84
0
0
29.89
0


10 
0
0
0.2548
0
0
0
0
0
31.53
0
18.44
50.03
0


10 
0
0
0.2954
0
0
0
29.63
0
27.21
0
0
43.17
0


10 
0
0
0.1275
0
0
0
0
0
0
0
0
100
0


11 
0
0
0.2264
0
0
0
0
0
43.68
0
0
56.32
0


11 
0
0
0.3514
0
35.57
0
0
0
28.14
0
0
36.28
0


11 
0
0
0.3514
35.57
0
0
0
0
28.14
0
0
36.28
0


11 
0
0
0.3514
0
0
0
0
35.57
28.14
0
0
36.28
0


11 
0
0
0.3514
0
35.57
0
0
0
28.14
0
0
36.28
0


11 
0
0
0.3514
0
35.57
0
0
0
28.14
0
0
36.28
0


11 
0
0
0.2509
0
0
0
0
0
49.18
0
0
50.82
0


11 
0
0
0.2509
0
0
0
0
0
49.18
0
0
50.82
0


11 
0
0
0.3514
0
0
0
0
0
28.14
35.57
0
36.28
0


11 
0
0
0.3514
35.57
0
0
0
0
28.14
0
0
36.28
0


11 
0.125
0
0.3514
0
0
0
0
0
28.14
0
0
36.28
35.57


11 
0
0.125
0.3514
0
0
0
0
0
28.14
0
0
36.28
35.57


11 
0
0
0.3514
0
0
35.57
0
0
28.14
0
0
36.28
0


11 
0
0
0.2533
0
0
0
0
0
39.05
0
10.6
50.35
0


11 
0
0
0.2764
0
0
0
18.09
0
35.78
0
0
46.13
0


11 
0
0
0
0
0
0
0
0
0
0
0
0
0


12 
0
0
0.2525
0
0
0
0
49.5
0
0
0
50.5
0


12 
0
0
0.7525
0
66.45
0
0
16.61
0
0
0
16.94
0


12 
0
0
0.3514
0
0
0
0
35.57
28.14
0
0
36.28
0


12 
0
0
0.7525
66.45
0
0
0
16.61
0
0
0
16.94
0


12 
0
0
0.7525
0
66.45
0
0
16.61
0
0
0
16.94
0


12 
0
0
0.7525
0
66.45
0
0
16.61
0
0
0
16.94
0


12 
0
0
0.3505
0
0
0
0
35.66
27.96
0
0
36.38
0


12 
0
0
0.3505
0
0
0
0
35.66
27.96
0
0
36.38
0


12 
0
0
0.7525
0
0
0
0
16.61
0
66.45
0
16.94
0


12 
0
0
0.7525
66.45
0
0
0
16.61
0
0
0
16.94
0


12 
0.5
0
0.7525
0
0
0
0
16.61
0
0
0
16.94
66.45


12 
0
0.5
0.7525
0
0
0
0
16.61
0
0
0
16.94
66.45


12 
0
0
0.7525
0
0
66.45
0
16.61
5
0
0
16.94
0


12 
0
0
0.3599
0
0
0
0
34.73
0
0
29.84
35.43
0


12 
0
0
0.4525
0
0
0
44.2
27.62
0
0
0
28.18
0


12 
0
0
0
0
0
0
0
0
0
0
0
0
0


13 
0
0
0.3463
0
0
0
0
63.18
0
0
0
36.82
0


13 
0
0
0.7525
0
53.99
0
0
29.07
0
0
0
16.94
0


13 
0
0
0.4266
0
0
0
0
51.28
18.84
0
0
29.89
0


13 
0
0
0.7525
53.99
0
0
0
29.07
0
0
0
16.94
0


13 
0
0
0.7525
0
53.99
0
0
29.07
0
0
0
16.94
0


13 
0
0
0.7525
0
53.99
0
0
29.07
0
0
0
16.94
0


13 
0
0
0.4259
0
0
0
0
51.36
18.7
0
0
29.94
0


13 
0
0
0.4259
0
0
0
0
51.36
18.7
0
0
29.94
0


13 
0
0
0.7525
0
0
0
0
29.07
0
53.99
0
16.94
0


13 
0
0
0.7525
53.99
0
0
0
29.07
0
0
0
16.94
0


13 
0.4063
0
0.7525
0
0
0
0
29.07
0
0
0
16.94
53.99


13 
0
0.4063
0.7525
0
0
0
0
29.07
0
0
0
16.94
53.99


13 
0
0
0.7525
0
0
53.99
0
29.07
0
0
0
16.94
0


13 
0
0
0.4335
0
0
0
0
50.46
0
0
20.13
29.41
0


13 
0
0
0.5088
0
0
0
31.94
43
0
0
0
25.06
0


13 
0
0
0.1275
0
0
0
0
0
0
0
0
100
0


14 
0
0
0.44
0
0
0
0
71.02
0
0
0
28.98
0


14 
0
0
0.7525
0
41.53
0
0
41.53
0
0
0
16.94
0


14 
0
0
0.5018
0
0
0
0
62.27
12.32
0
0
25.41
0


14 
0
0
0.7525
41.53
0
0
0
41.53
0
0
0
16.94
0


14 
0
0
0.7525
0
41.53
0
0
41.53
0
0
0
16.94
0


14 
0
0
0.7525
0
41.53
0
0
41.53
0
0
0
16.94
0


14 
0
0
0.5013
0
0
0
0
62.34
12.22
0
0
25.44
0


14 
0
0
0.5013
0
0
0
0
62.34
12.22
0
0
25.44
0


14 
0
0
0.7525
0
0
0
0
41.53
0
41.53
0
16.94
0


14 
0
0
0.7525
41.53
0
0
0
41.53
0
0
0
16.94
0


14 
0.3125
0
0.7525
0
0
0
0
41.53
0
0
0
16.94
41.53


14 
0
0.3125
0.7525
0
0
0
0
41.53
0
0
0
16.94
41.53


14 
0
0
0.7525
0
0
41.53
0
41.53
0
0
0
16.94
0


14 
0
0
0.5071
0
0
0
0
61.62
0
0
13.24
25.14
0


14 
0
0
0.565
0
0
0
22.12
55.31
0
0
0
22.57
0


14 
0
0
0
0
0
0
0
0
0
0
0
0
0


15 
0
0
0.5338
0
0
0
0
76.11
0
0
0
23.89
0


15 
0
0
0.7525
0
29.07
0
0
53.99
0
0
0
16.94
0


15 
0
0
0.577
0
0
0
0
70.4
7.5
0
0
22.1
0


15 
0
0
0.7525
29.07
0
0
0
53.99
0
0
0
16.94
0


15 
0
0
0.7525
0
29.07
0
0
53.99
0
0
0
16.94
0


15 
0
0
0.7525
0
29.07
0
0
53.99
0
0
0
16.94
0


15 
0
0
0.5766
0
0
0
0
70.45
7.44
0
0
22.11
0


15 
0
0
0.5766
0
0
0
0
70.45
7.44
0
0
22.11
0


15 
0
0
0.7525
0
0
0
0
53.99
0
29.07
0
16.94
0


15 
0
0
0.7525
29.07
0
0
0
53.99
0
0
0
16.94
0


15 
0.2188
0
0.7525
0
0
0
0
53.99
0
0
0
16.94
29.07


15 
0
0.2188
0.7525
0
0
0
0
53.99
0
0
0
16.94
29.07


15 
0
0
0.7525
0
0
29.07
0
53.99
0
0
0
16.94
0


15 
0
0
0.5807
0
0
0
0
69.95
0
0
8.09
21.95
0


15 
0
0
0.6213
0
0
0
14.08
65.39
0
0
0
20.52
0


15 
0
0
0
0
0
0
0
0
0
0
0
0
0


16 
0
0
0.6275
0
0
0
0
79.68
0
0
0
20.32
0


16 
0
0
0.7525
0
16.61
0
0
66.45
0
0
0
16.94
0


16 
0
0
0.6522
0
0
0
0
76.66
3.79
0
0
19.55
0


16 
0
0
0.7525
16.61
0
0
0
66.45
0
0
0
16.94
0


16 
0
0
0.7525
0
16.61
0
0
66.45
0
0
0
16.94
0


16 
0
0
0.7525
0
16.61
0
0
66.45
0
0
0
16.94
0


16 
0
0
0.652
0
0
0
0
76.69
3.76
0
0
19.56
0


16 
0
0
0.652
0
0
0
0
76.69
3.76
0
0
19.56
0


16 
0
0
0.7525
0
0
0
0
66.45
0
16.61
0
16.94
0


16 
0
0
0.7525
16.61
0
0
0
66.45
0
0
0
16.94
0


16 
0.125
0
0.7525
0
0
0
0
66.45
0
0
0
16.94
16.61


16 
0
0.125
0.7525
0
0
0
0
66.45
0
0
0
16.94
16.61


16 
0
0
0.7525
0
0
16.61
0
66.45
0
0
0
16.94
0


16 
0
0
0.6544
0
0
0
0
76.41
0
0
4.1
19.48
0


16 
0
0
0.6775
0
0
0
7.38
73.8
0
0
0
18.82
0


16 
0
0
0.1275
0
0
0
0
0
0
0
0
100
0










[0278]

10














TABLE II

















Pt2.5%/

shift2


R
C
COCONV
H2OCONV
CO2PROD
CO2PERPROD
CH4PROD
ZrO2_std
PtNH32NO22
std


real
real
real
real
real
real
real
real
real
real





Temperature:


200 C.


1
1
5.8854
7.1324
0.334
12.4611
0.0591
0.384
0
0


1
2
−0.6933
1.7113
0.0121
0.4524
0.0112
0
0
0


1
3
−1.0879
−0.033
0.0156
0.5835
0.0099
0
0
0


1
4
8.4959
6.4002
0.3047
11.3709
0.0443
0
0
0.768


1
5
−0.2835
0.6389
0.0083
0.3103
0.0042
0
0
0


1
6
−0.0255
1.131
−0.0073
−0.2728
0.0001
0
0
0


1
7
16.8595
11.8588
0.5807
21.6685
0.0759
0.384
0
0


1
8
0.5792
1.6555
−0.0166
−0.6207
−0.0015
0
0
0


1
9
0.5058
−0.1249
−0.0251
−0.9379
−0.0006
0
0
0


1
10
2.462
0.2771
0.0413
1.541
0.0092
0
0
0.768


1
11
0.0019
−1.3951
−0.0192
−0.7182
0.0002
0
0
0


1
12
0.2469
−0.1814
−0.0266
−0.9942
−0.0021
0
0
0


1
13
11.9953
8.0254
0.352
13.1329
0.044
0.384
0
0


1
14
−0.2562
−2.7011
−0.0114
−0.4265
0.0037
0
0
0


1
15
0.6886
−0.0929
−0.0235
−0.8767
−0.0026
0
0
0


1
16
2.2755
−0.5365
0.0631
2.3544
0.0118
0
0
0.768


2
1
1.6292
1.7918
0.0235
0.8778
0.0007
0
0.1275
0


2
2
1.0595
0.9687
−0.0202
−0.752
−0.0051
0
0.1275
0


2
3
3.1871
2.0235
0.0769
2.8696
0.0072
0
0.1275
0


2
4
11.3379
8.344
0.3126
11.6649
0.0345
0
0.1275
0


2
5
7.334
4.6193
0.1933
7.2111
0.0233
0
0.1275
0


2
6
16.1807
10.5884
0.5103
19.0429
0.0638
0
0.1275
0


2
7
13.3218
8.6946
0.3821
14.2574
0.0468
0
0.1275
0


2
8
13.8451
8.4363
0.4407
16.4438
0.0555
0
0.1275
0


2
9
3.7336
1.8779
0.076
2.8349
0.0082
0
0.1275
0


2
10
3.7611
2.5358
0.0642
2.3968
0.0066
0
0.1275
0


2
11
9.6508
6.4773
0.2773
10.347
0.035
0
0.1275
0


2
12
9.1424
6.1475
0.2521
9.4059
0.0294
0
0.1275
0


2
13
5.5133
3.6401
0.155
5.7829
0.0203
0
0.1275
0


2
14
4.9192
2.3616
0.1071
3.9974
0.014
0
0.1275
0


2
15
3.2245
1.7666
0.0897
3.3488
0.0134
0
0.1275
0


2
16
0.0898
−0.5096
−0.0063
−0.2341
0.001
0
0
0


3
1
6.9984
4.7277
0.1921
7.1687
0.0208
0
0.1148
0


3
2
1.7067
0.9785
0.0029
0.108
−0.0017
0
0.1148
0


3
3
2.6544
1.9617
0.0481
1.7934
0.0045
0
0.1148
0


3
4
12.8291
8.3823
0.3884
14.4943
0.0479
0
0.1148
0


3
5
7.3563
5.392
0.2102
7.8432
0.025
0
0.1148
0


3
6
16.2779
11.5339
0.4914
18.3342
0.0591
0
0.1148
0


3
7
14.8045
9.8506
0.4449
16.6026
0.0553
0
0.1148
0


3
8
11.2329
7.7728
0.3309
12.3461
0.0385
0
0.1148
0


3
9
2.866
2.3243
0.048
1.7899
0.0045
0
0.1148
0


3
10
4.7888
4.0416
0.0856
3.1937
0.0072
0
0.1148
0


3
11
7.5704
6.3606
0.2386
8.9027
0.0272
0
0.1148
0


3
12
8.8338
8.1131
0.241
8.9937
0.0242
0
0.1148
0


3
13
5.5254
3.9512
0.1376
5.1339
0.0154
0
0.1148
0


3
14
6.1987
4.2911
0.1741
6.4953
0.0195
0
0.1148
0


3
15
3.654
2.1732
0.0701
2.6141
0.0056
0
0.1148
0


3
16
0.3139
−0.4382
−0.0103
−0.3839
−0.002
0
0
0


4
1
8.1372
6.051
0.2684
10.0162
0.0285
0
0.102
0


4
2
1.4135
−1.0921
−0.0019
−0.0694
0.0006
0
0.102
0


4
3
2.3694
2.3665
0.05
1.8672
0.0016
0
0.102
0


4
4
12.8778
10.2102
0.3982
14.858
0.0416
0
0.102
0


4
5
6.8789
5.4193
0.218
8.1354
0.0221
0
0.102
0


4
6
17.1121
11.1844
0.5742
21.4257
0.0656
0
0.102
0


4
7
15.2253
7.4374
0.5006
18.6802
0.0634
0
0.102
0


4
8
12.1072
6.9574
0.3621
13.5097
0.0421
0
0.102
0


4
9
3.0168
2.3445
0.0559
2.0868
0.0029
0
0.102
0


4
10
3.4366
2.6695
0.0827
3.0869
0.0059
0
0.102
0


4
11
9.3273
8.1068
0.2694
10.0512
0.0274
0
0.102
0


4
12
8.2623
5.7824
0.2401
8.9601
0.0264
0
0.102
0


4
13
6.4459
5.7408
0.1696
6.3286
0.0159
0
0.102
0


4
14
7.5269
4.4391
0.2096
7.8207
0.0229
0
0.102
0


4
15
2.3665
3.2131
0.1135
4.2368
0.0107
0
0.102
0


4
16
14.955
9.0888
0.4741
17.6909
0.0576
0.384
0
0


5
1
7.255
5.6173
0.2393
8.929
0.0219
0
0.0893
0


5
2
1.2894
1.2279
−0.0083
−0.3084
−0.0072
0
0.0893
0


5
3
2.7038
3.3448
0.0437
1.6316
−0.0003
0
0.0893
0


5
4
11.707
8.2569
0.3623
13.517
0.0367
0
0.0893
0


5
5
7.6925
6.1121
0.2125
7.9274
0.0185
0
0.0893
0


5
6
17.0142
12.7392
0.5131
19.1465
0.0602
0
0.0893
0


5
7
14.8949
11.3697
0.4646
17.3347
0.0527
0
0.0893
0


5
8
9.7274
5.9642
0.3049
11.3767
0.0342
0
0.0893
0


5
9
3.4389
3.1002
0.0582
2.1723
0.0038
0
0.0893
0


5
10
3.1194
2.1123
0.0777
2.8988
0.007
0
0.0893
0


5
11
9.8621
7.5832
0.2728
10.1805
0.0278
0
0.0893
0


5
12
7.0266
5.2932
0.1915
7.1464
0.0207
0
0.0893
0


5
13
5.7354
4.6583
0.155
5.7842
0.0157
0
0.0893
0


5
14
5.5119
4.962
0.1327
4.952
0.0106
0
0.0893
0


5
15
2.8173
1.2279
0.0802
2.993
0.004
0
0.0893
0


5
16
0.8239
1.9962
0.0239
0.8909
−0.0001
0
0
0


6
1
4.7196
3.0755
0.1686
6.2918
0.018
0
0.0765
0


6
2
0.6723
0.5379
0.0114
0.4248
−0.001
0
0.0765
0


6
3
1.5179
1.911
0.0258
0.9622
−0.0024
0
0.0765
0


6
4
11.4899
6.8245
0.3774
14.0835
0.0427
0
0.0765
0


6
5
7.2343
5.5992
0.2075
7.7439
0.0214
0
0.0765
0


6
6
16.1946
11.0902
0.5277
19.6917
0.062
0
0.0765
0


6
7
14.3055
10.2177
0.4469
16.6766
0.0505
0
0.0765
0


6
8
8.3454
6.6475
0.2423
9.0418
0.0238
0
0.0765
0


6
9
4.5897
2.8387
0.0804
3.0009
0.0145
0
0.0765
0


6
10
3.5258
2.9589
0.0899
3.3528
0.0069
0
0.0765
0


6
11
9.6292
7.4338
0.3058
11.4104
0.0348
0
0.0765
0


6
12
5.4461
4.774
0.14
5.2242
0.0095
0
0.0765
0


6
13
5.2789
3.9957
0.1742
6.4996
0.0198
0
0.0765
0


6
14
6.0234
3.1388
0.208
7.7595
0.023
0
0.0765
0


6
15
2.7153
2.6186
0.0572
2.1344
0.0026
0
0.0765
0


6
16
0.6172
0.881
−0.0048
−0.1782
−0.006
0
0
0


7
1
3.6058
2.8177
0.1122
4.1848
0.0114
0
0.0638
0


7
2
1.5457
1.1415
−0.0046
−0.1727
−0.0077
0
0.0638
0


7
3
1.1265
1.8421
0.0513
1.9154
0.0017
0
0.0638
0


7
4
10.9458
6.7214
0.3327
12.4157
0.0389
0
0.0638
0


7
5
7.3704
6.6413
0.2192
8.18
0.0202
0
0.0638
0


7
6
16.5168
12.5524
0.5112
19.0738
0.0567
0
0.0638
0


7
7
14.124
9.8009
0.4529
16.8982
0.0533
0
0.0638
0


7
8
8.0466
6.418
0.2665
9.9439
0.0279
0
0.0638
0


7
9
4.9159
1.9763
0.102
3.8056
0.021
0
0.0638
0


7
10
3.921
1.5095
0.0817
3.0486
0.0055
0
0.0638
0


7
11
9.7833
6.8289
0.3095
11.5499
0.0353
0
0.0638
0


7
12
5.7437
4.0574
0.1866
6.9609
0.0216
0
0.0638
0


7
13
5.4086
4.6319
0.1686
6.2897
0.0153
0
0.0638
0


7
14
4.7264
2.9579
0.1463
5.4578
0.0098
0
0.0638
0


7
15
2.2359
1.425
0.0541
2.0176
0.003
0
0.0638
0


7
16
1.905
−0.5369
0.0559
2.0863
0.0028
0
0
0.768


8
1
1.8516
1.7327
0.0497
1.8541
−0.001
0
0.051
0


8
2
0.7246
−0.2854
0.0085
0.3172
−0.0044
0
0.051
0


8
3
2.2172
1.0419
0.0055
0.2056
−0.0051
0
0.051
0


8
4
8.5881
6.1691
0.2633
9.8264
0.031
0
0.051
0


8
5
6.9155
5.1078
0.1919
7.1608
0.0186
0
0.051
0


8
6
13.6231
8.8606
0.4319
16.1142
0.0489
0
0.051
0


8
7
12.7013
7.6084
0.3755
14.013
0.0421
0
0.051
0


8
8
5.7321
3.3144
0.1554
5.7994
0.0148
0
0.051
0


8
9
6.1461
1.113
0.0847
3.1618
0.0264
0
0.051
0


8
10
3.0168
1.2432
0.0668
2.491
0.003
0
0.051
0


8
11
7.9516
3.9932
0.2353
8.7787
0.0247
0
0.051
0


8
12
4.5547
2.22
0.1059
3.9517
0.0094
0
0.051
0


8
13
5.4421
2.2227
0.1712
6.3866
0.0179
0
0.051
0


8
14
2.9709
1.2529
0.0884
3.2997
0.0058
0
0.051
0


8
15
2.0502
0.6577
0.053
1.9778
0.0016
0
0.051
0


8
16
1.0942
−0.5602
−0.0087
−0.3263
−0.0082
0
0
0


9
1
3.6525
0.857
0.0654
2.4413
0.0008
0
0.0383
0


9
2
0.9979
0.3153
0.0037
0.1389
−0.0052
0
0.0383
0


9
3
1.7466
−0.0553
0.0132
0.492
−0.004
0
0.0383
0


9
4
8.1388
6.6606
0.2396
8.9397
0.0239
0
0.0383
0


9
5
6.3048
3.5229
0.1519
5.6663
0.0115
0
0.0383
0


9
6
11.8358
7.3317
0.3738
13.9486
0.044
0
0.0383
0


9
7
12.0946
6.9223
0.3836
14.3153
0.0431
0
0.0383
0


9
8
4.5013
2.4933
0.127
4.7393
0.0114
0
0.0383
0


9
9
5.5653
−1.5672
0.0994
3.7081
0.0371
0
0.0383
0


9
10
2.0973
−0.2551
0.0556
2.0746
0.0051
0
0.0383
0


9
11
6.2072
3.3304
0.1879
7.0119
0.0196
0
0.0383
0


9
12
3.6564
2.9811
0.0776
2.8969
0.004
0
0.0383
0


9
13
5.2299
1.9964
0.1531
5.7131
0.0156
0
0.0383
0


9
14
1.9393
0.5427
0.0483
1.8011
0.0018
0
0.0383
0


9
15
1.6602
0.2685
0.0303
1.1291
0.0009
0
0.0383
0


9
16
−0.3094
−1.3702
0.0051
0.1919
−0.0023
0
0
0


10 
1
1.2902
−0.2919
−0.0046
−0.1733
−0.005
0
0.1275
0


10 
2
0.5013
−0.0646
0.0015
0.055
−0.0023
0
0.1275
0


10 
3
6.4947
3.5233
0.2062
7.6942
0.0238
0
0.1275
0


10 
4
4.8095
1.6288
0.1367
5.0991
0.0131
0
0.1275
0


10 
5
11.2766
6.8521
0.3728
13.9092
0.04
0
0.1275
0


10 
6
6.4291
3.2734
0.2109
7.8701
0.0235
0
0.1275
0


10 
7
5.8614
3.204
0.1874
6.9938
0.0213
0
0.1275
0


10 
8
3.9022
−0.0952
0.1469
5.4801
0.0167
0
0.1275
0


10 
9
5.9845
3.8381
0.1724
6.4326
0.0186
0
0.1275
0


10 
10
6.3544
3.1325
0.1996
7.4459
0.0201
0
0.1275
0


10 
11
4.2593
1.9552
0.1068
3.9844
0.009
0
0.1275
0


10 
12
11.8549
4.3493
0.4371
16.3114
0.0553
0
0.1275
0


10 
13
3.4944
1.347
0.0565
2.1073
0.0007
0
0.1275
0


10 
14
1.6799
−1.1032
0.0339
1.2643
0.0015
0
0.1275
0


10 
15
1.2201
0.118
0.0146
0.5448
−0.0033
0
0.1275
0


10 
16
13.1891
7.744
0.4607
17.19
0.0567
0.384
0
0


11 
1
0.4697
−0.9386
0.0209
0.7815
−0.0002
0
0.1126
0


11 
2
0.3137
−0.3079
0.0152
0.5655
−0.0038
0
0.1126
0


11 
3
3.7312
3.0925
0.1295
4.8339
0.0116
0
0.1126
0


11 
4
4.2947
4.1725
0.1258
4.6927
0.0118
0
0.1126
0


11 
5
8.2513
4.6606
0.2639
9.848
0.0294
0
0.1126
0


11 
6
7.7794
6.0534
0.2575
9.6078
0.0255
0
0.1126
0


11 
7
7.1211
4.9645
0.2168
8.0891
0.0217
0
0.1126
0


11 
8
6.6894
3.5982
0.2513
9.3781
0.0253
0
0.1126
0


11 
9
5.7623
1.227
0.1774
6.6189
0.0215
0
0.1126
0


11 
10
3.9535
3.5594
0.1199
4.4725
0.0085
0
0.1126
0


11 
11
2.9585
1.468
0.1075
4.0128
0.0071
0
0.1126
0


11 
12
10.8769
7.5198
0.371
13.8434
0.0424
0
0.1126
0


11 
13
2.5558
1.6142
0.0798
2.9792
0.0034
0
0.1126
0


11 
14
0.9894
0.2057
0.0325
1.2133
0.0006
0
0.1126
0


11 
15
−0.1651
−0.5824
0.0225
0.8396
0.0003
0
0.1126
0


11 
16
0.2312
−0.1398
0.0419
1.5619
0.0035
0
0
0


12 
1
0.1745
−0.7789
0.0282
1.0504
−0.0007
0
0.0978
0


12 
2
0.1358
−0.938
0.0123
0.4577
−0.0028
0
0.0978
0


12 
3
2.687
2.3049
0.1171
4.3697
0.0094
0
0.0978
0


12 
4
2.7011
2.3219
0.0919
3.43
0.0055
0
0.0978
0


12 
5
7.2214
3.1868
0.2524
9.4194
0.0269
0
0.0978
0


12 
6
5.2931
1.7052
0.2034
7.5887
0.0227
0
0.0978
0


12 
7
5.7915
3.2059
0.1832
6.8371
0.015
0
0.0978
0


12 
8
1.223
−0.5999
0.053
1.9777
0.0048
0
0.0978
0


12 
9
4.3277
1.446
0.1789
6.6748
0.0204
0
0.0978
0


12 
10
2.3611
−1.6069
0.0943
3.5182
0.0118
0
0.0978
0


12 
11
1.217
1.2973
0.0636
2.3728
0.0026
0
0.0978
0


12 
12
9.4921
6.357
0.3144
11.7329
0.0336
0
0.0978
0


12 
13
1.1195
−0.1983
0.051
1.9028
0.0019
0
0.0978
0


12 
14
−0.4284
−1.8025
0.0316
1.1789
0.004
0
0.0978
0


12 
15
−0.3772
−1.2476
0.0263
0.9816
−0.0008
0
0.0978
0


12 
16
−0.6263
−0.7525
0.0219
0.8183
−0.0027
0
0
0


13 
1
−0.2044
−0.3108
0.0233
0.869
−0.001
0
0.0829
0


13 
2
−0.0357
−1.5987
0.0196
0.731
−0.0015
0
0.0829
0


13 
3
2.5404
2.3681
0.0759
2.8308
0.0035
0
0.0829
0


13 
4
2.9681
1.1781
0.1095
4.0842
0.009
0
0.0829
0


13 
5
4.7412
2.8854
0.1519
5.6697
0.0123
0
0.0829
0


13 
6
4.056
3.1404
0.1425
5.3155
0.0122
0
0.0829
0


13 
7
3.445
3.976
0.1125
4.1961
0.0064
0
0.0829
0


13 
8
2.1923
2.6039
0.0689
2.5713
0.0029
0
0.0829
0


13 
9
3.6921
2.839
0.1493
5.5723
0.0156
0
0.0829
0


13 
10
1.9985
1.0455
0.0943
3.5184
0.0065
0
0.0829
0


13 
11
1.8485
1.7993
0.0648
2.4165
0.001
0
0.0829
0


13 
12
7.3772
4.858
0.2612
9.7459
0.0272
0
0.0829
0


13 
13
0.67
−0.7364
0.0509
1.8995
0.0036
0
0.0829
0


13 
14
−0.1545
−0.1684
0.04
1.4918
0.0027
0
0.0829
0


13 
15
−0.2342
−1.9441
0.0301
1.1244
0.0022
0
0.0829
0


13 
16
1.0182
−0.222
0.0635
2.3688
0.0043
0
0
0.768


14 
1
0.0925
0.2319
0.0233
0.8681
−0.0031
0
0.068
0


14 
2
−0.3296
1.4585
0.019
0.7088
−0.0031
0
0.068
0


14 
3
1.1002
0.2941
0.0694
2.5909
0.0068
0
0.068
0


14 
4
0.2831
0.151
0.054
2.0157
0.0033
0
0.068
0


14 
5
3.0444
2.2158
0.1301
4.8563
0.0105
0
0.068
0


14 
6
0.0907
−1.4912
0.0607
2.2642
0.0081
0
0.068
0


14 
7
1.4092
0.7998
0.0648
2.4188
0.0046
0
0.068
0


14 
8
0.6786
0.7924
0.041
1.5316
0.0021
0
0.068
0


14 
9
2.5503
0.8249
0.1115
4.1607
0.0105
0
0.068
0


14 
10
0.8956
−0.2159
0.066
2.4626
0.0059
0
0.068
0


14 
11
0.524
0.8305
0.0497
1.8557
0.0015
0
0.068
0


14 
12
2.3834
0.0805
0.1461
5.4498
0.0132
0
0.068
0


14 
13
0.7037
−0.6285
0.0416
1.5519
0.0023
0
0.068
0


14 
14
−0.8416
−2.9099
0.0431
1.6083
0.0049
0
0.068
0


14 
15
−0.5009
−2.4335
0.0188
0.7005
0.0002
0
0.068
0


14 
16
−0.5344
1.0228
0.0124
0.4625
−0.0053
0
0
0


15 
1
−0.7531
−0.171
0.0264
0.9837
0.0003
0
0.0531
0


15 
2
−0.0408
0.6254
0.0184
0.6852
−0.0028
0
0.0531
0


15 
3
0.8082
0.4025
0.0618
2.3061
0.0107
0
0.0531
0


15 
4
1.2594
1.0454
0.0358
1.3359
−0.001
0
0.0531
0


15 
5
2.5885
0.4231
0.0623
2.3251
0.0048
0
0.0531
0


15 
6
2.0805
1.313
0.0715
2.6661
0.0026
0
0.0531
0


15 
7
1.2853
−0.982
0.0166
0.619
−0.0002
0
0.0531
0


15 
8
1.379
0.7764
0.051
1.9016
−0.0004
0
0.0531
0


15 
9
2.5418
1.2534
0.1081
4.0346
0.0103
0
0.0531
0


15 
10
1.0685
−0.8601
0.0743
2.7741
0.0064
0
0.0531
0


15 
11
1.164
−0.8841
0.0493
1.838
0.0024
0
0.0531
0


15 
12
3.2541
0.4687
0.0978
3.6488
0.0107
0
0.0531
0


15 
13
0.7229
−1.7297
0.0427
1.5935
0.0043
0
0.0531
0


15 
14
−0.147
−2.0863
0.0308
1.1508
0.0011
0
0.0531
0


15 
15
−0.4081
−1.1644
0.0228
0.8506
−0.0018
0
0.0531
0


15 
16
−1.3762
−0.7377
0.0187
0.6978
−0.0005
0
0
0


16 
1
−0.3238
−1.8866
0.0223
0.8307
0.0022
0
0.0383
0


16 
2
−0.737
−2.0712
0.0255
0.9531
0.0029
0
0.0383
0


16 
3
0.5162
−0.8854
0.0618
2.3044
0.0068
0
0.0383
0


16 
4
−0.2988
−2.786
0.0518
1.9344
0.0068
0
0.0383
0


16 
5
0.2181
−2.0545
0.046
1.7167
0.0031
0
0.0383
0


16 
6
1.0602
−0.8314
0.0728
2.7146
0.0079
0
0.0383
0


16 
7
0.0957
−0.6392
0.0297
1.1082
0
0
0.0383
0


16 
8
0.0204
1.6265
0.035
1.3063
0.0005
0
0.0383
0


16 
9
1.0716
−0.778
0.1026
3.827
0.012
0
0.0383
0


16 
10
0.8362
−0.3843
0.0627
2.3403
0.0051
0
0.0383
0


16 
11
−0.1288
−1.9691
0.0497
1.8532
0.002
0
0.0383
0


16 
12
0.1343
−1.5044
0.055
2.0541
0.0049
0
0.0383
0


16 
13
0.429
−2.01
0.0785
2.9277
0.0085
0
0.0383
0


16 
14
−1.0174
−1.6418
0.0537
2.005
0.0049
0
0.0383
0


16 
15
1.8432
0.7481
0.122
4.5536
0.0109
0
0.0383
0


16 
16
2.6729
0.281
0.1635
6.1005
0.0213
0.384
0
0


Temperature:


230 C.


1
1
20.5122
11.752
0.7383
27.1989
0.0999
0.384
0
0


1
2
−0.5534
−1.2706
0.0115
0.4228
0.0074
0
0
0


1
3
−0.3862
−1.1153
−0.0091
−0.3362
0.0007
0
0
0


1
4
20.3694
11.7741
0.7182
26.4567
0.0968
0
0
0.768


1
5
0.5126
0.9775
0.0005
0.0193
−0.0007
0
0
0


1
6
0.538
−0.273
−0.0138
−0.5092
−0.002
0
0
0


1
7
30.5533
19.0026
1.0333
38.0659
0.1385
0.384
0
0


1
8
−0.0401
−0.0595
0.0032
0.1164
0.0012
0
0
0


1
9
−0.1373
−0.8776
−0.024
−0.8845
−0.001
0
0
0


1
10
6.5067
3.4452
0.1909
7.0333
0.0238
0
0
0.768


1
11
0.077
−0.4121
−0.0292
−1.0749
−0.0048
0
0
0


1
12
−0.3715
−0.8872
−0.0219
−0.8077
−0.004
0
0
0


1
13
26.1724
16.1062
0.8511
31.3551
0.1126
0.384
0
0


1
14
0.0813
0.1564
−0.0053
−0.1965
0.0013
0
0
0


1
15
−0.6823
0.1234
−0.0145
−0.5342
−0.0002
0
0
0


1
16
6.0422
3.4535
0.1841
6.7836
0.0224
0
0
0.768


2
1
3.4848
2.1816
0.1088
4.009
0.0136
0
0.1275
0


2
2
0.5403
2.0682
0.0138
0.507
−0.0002
0
0.1275
0


2
3
10.2899
7.8458
0.3465
12.7641
0.0425
0
0.1275
0


2
4
21.3326
14.5433
0.7146
26.3272
0.0931
0
0.1275
0


2
5
13.0906
9.73
0.4281
15.7709
0.0531
0
0.1275
0


2
6
25.9089
17.7979
0.8414
30.9982
0.1067
0
0.1275
0


2
7
19.5485
14.2096
0.6102
22.4782
0.08
0
0.1275
0


2
8
27.4426
18.9183
0.8632
31.7987
0.1139
0
0.1275
0


2
9
11.071
7.6374
0.3388
12.4807
0.0416
0
0.1275
0


2
10
7.8063
6.711
0.2101
7.7386
0.0232
0
0.1275
0


2
11
21.9836
15.8925
0.7133
26.2767
0.0923
0
0.1275
0


2
12
21.4248
14.9353
0.6819
25.1197
0.088
0
0.1275
0


2
13
13.9332
10.1621
0.4422
16.2904
0.0516
0
0.1275
0


2
14
12.1357
9.0183
0.403
14.8477
0.0497
0
0.1275
0


2
15
10.1205
7.3514
0.3359
12.3746
0.0422
0
0.1275
0


2
16
−0.1813
−0.1996
−0.0083
−0.3052
−0.0008
0
0
0


3
1
14.6192
9.6539
0.477
17.5727
0.0598
0
0.1148
0


3
2
3.5237
1.6063
0.1056
3.8917
0.0137
0
0.1148
0


3
3
7.5414
5.7472
0.2505
9.2275
0.0293
0
0.1148
0


3
4
25.6608
16.2436
0.8269
30.4612
0.1087
0
0.1148
0


3
5
13.2052
9.4936
0.4538
16.7197
0.0568
0
0.1148
0


3
6
25.3315
16.7131
0.8179
30.1312
0.1061
0
0.1148
0


3
7
21.3268
13.9191
0.682
25.1235
0.0887
0
0.1148
0


3
8
24.7757
17.4515
0.7954
29.301
0.1012
0
0.1148
0


3
9
8.4714
6.7116
0.2707
9.9741
0.032
0
0.1148
0


3
10
11.8838
8.5049
0.3571
13.1539
0.0407
0
0.1148
0


3
11
20.031
14.4004
0.6352
23.402
0.0805
0
0.1148
0


3
12
19.8788
14.2811
0.6381
23.5091
0.0788
0
0.1148
0


3
13
12.9699
9.8171
0.4046
14.9042
0.0477
0
0.1148
0


3
14
17.4726
12.8596
0.582
21.4404
0.0711
0
0.1148
0


3
15
9.2964
6.3491
0.287
10.574
0.0339
0
0.1148
0


3
16
0.0039
0.2785
−0.0092
−0.3384
−0.0048
0
0
0


4
1
17.3609
12.5782
0.6049
22.2858
0.072
0
0.102
0


4
2
3.8887
3.9128
0.0902
3.3222
0.0077
0
0.102
0


4
3
7.8741
7.2509
0.2413
8.8886
0.0267
0
0.102
0


4
4
24.9061
17.8056
0.7889
29.0621
0.0992
0
0.102
0


4
5
13.5943
11.0916
0.4332
15.9588
0.05
0
0.102
0


4
6
25.7929
19.6971
0.8186
30.1556
0.1001
0
0.102
0


4
7
21.072
14.4215
0.6748
24.8609
0.0869
0
0.102
0


4
8
26.0921
18.743
0.8103
29.8516
0.1023
0
0.102
0


4
9
9.0667
6.8545
0.3023
11.1355
0.0361
0
0.102
0


4
10
9.9682
9.0867
0.3095
11.4025
0.0375
0
0.102
0


4
11
22.5703
17.6942
0.7028
25.892
0.0881
0
0.102
0


4
12
17.6725
13.6191
0.5819
21.4383
0.072
0
0.102
0


4
13
13.3204
11.7478
0.4371
16.1046
0.0501
0
0.102
0


4
14
18.8588
14.1349
0.626
23.0617
0.0749
0
0.102
0


4
15
10.9773
9.4417
0.3661
13.4881
0.0434
0
0.102
0


4
16
25.5043
16.3074
0.8602
31.6906
0.1124
0.384
0
0


5
1
15.726
10.879
0.5349
19.706
0.0654
0
0.0893
0


5
2
1.2361
2.1554
0.0379
1.395
0.0012
0
0.0893
0


5
3
8.2732
7.1702
0.2632
9.6977
0.0305
0
0.0893
0


5
4
23.479
17.3054
0.7815
28.7895
0.0978
0
0.0893
0


5
5
13.4611
8.7548
0.4398
16.2013
0.0532
0
0.0893
0


5
6
24.6516
18.1881
0.8117
29.9015
0.1024
0
0.0893
0


5
7
20.6256
15.1295
0.6933
25.5417
0.0834
0
0.0893
0


5
8
22.0706
16.9093
0.728
26.8185
0.0934
0
0.0893
0


5
9
9.5062
8.3409
0.2942
10.8373
0.036
0
0.0893
0


5
10
9.7534
6.8249
0.3242
11.9447
0.0406
0
0.0893
0


5
11
23.0838
17.321
0.7228
26.6283
0.0902
0
0.0893
0


5
12
13.0683
10.718
0.4431
16.3235
0.0529
0
0.0893
0


5
13
12.4403
9.1189
0.408
15.0297
0.0501
0
0.0893
0


5
14
15.6144
11.8708
0.5015
18.4747
0.0598
0
0.0893
0


5
15
8.013
6.9957
0.2667
9.8269
0.0321
0
0.0893
0


5
16
1.5841
3.1393
0.0592
2.1826
0.0038
0
0
0


6
1
11.9181
7.529
0.4121
15.1809
0.0515
0
0.0765
0


6
2
2.6337
2.1059
0.0447
1.6457
0.0033
0
0.0765
0


6
3
5.4951
5.1434
0.1607
5.9193
0.0161
0
0.0765
0


6
4
23.8763
15.5411
0.7888
29.0607
0.0966
0
0.0765
0


6
5
12.93
10.1219
0.3818
14.0649
0.045
0
0.0765
0


6
6
23.5796
15.9125
0.7649
28.1784
0.0973
0
0.0765
0


6
7
18.9005
15.2143
0.6468
23.829
0.077
0
0.0765
0


6
8
20.3497
13.5583
0.6825
25.1424
0.0825
0
0.0765
0


6
9
11.2224
6.8155
0.3486
12.8407
0.0488
0
0.0765
0


6
10
10.2035
7.9968
0.3412
12.5707
0.0409
0
0.0765
0


6
11
23.4001
17.0529
0.7491
27.5961
0.0963
0
0.0765
0


6
12
9.7991
8.2616
0.3252
11.9814
0.0374
0
0.0765
0


6
13
11.7581
8.3105
0.4047
14.9078
0.0515
0
0.0765
0


6
14
18.0336
13.0945
0.6005
22.1227
0.0726
0
0.0765
0


6
15
7.911
4.3785
0.2682
9.8789
0.0312
0
0.0765
0


6
16
−0.6688
1.4355
−0.0035
−0.1305
−0.0019
0
0
0


7
1
8.2588
5.3884
0.2833
10.4355
0.0335
0
0.0638
0


7
2
0.8857
1.2193
0.0252
0.9302
0.0016
0
0.0638
0


7
3
6.6639
4.2553
0.2108
7.7677
0.0263
0
0.0638
0


7
4
22.5348
14.4689
0.7837
28.8734
0.0978
0
0.0638
0


7
5
12.3747
10.2625
0.4082
15.037
0.0518
0
0.0638
0


7
6
24.0886
16.8609
0.7789
28.6964
0.0959
0
0.0638
0


7
7
19.4243
13.7709
0.6285
23.1531
0.076
0
0.0638
0


7
8
20.9167
14.354
0.6951
25.6082
0.0874
0
0.0638
0


7
9
11.0085
7.0474
0.3181
11.7196
0.0506
0
0.0638
0


7
10
9.8927
8.1601
0.2841
10.4662
0.0307
0
0.0638
0


7
11
22.9498
15.5482
0.7494
27.6082
0.0971
0
0.0638
0


7
12
10.8518
7.6716
0.3566
13.1386
0.0428
0
0.0638
0


7
13
11.1438
7.8195
0.3629
13.3706
0.0434
0
0.0638
0


7
14
13.8746
9.9693
0.4684
17.2575
0.0579
0
0.0638
0


7
15
6.983
6.1175
0.2213
8.1545
0.0244
0
0.0638
0


7
16
5.3562
3.5355
0.2036
7.5023
0.025
0
0
0.768


8
1
5.1472
4.2085
0.1241
4.5708
0.0114
0
0.051
0


8
2
2.6812
0.6825
0.0185
0.6825
−0.0028
0
0.051
0


8
3
4.8568
3.4396
0.1483
5.4617
0.0157
0
0.051
0


8
4
19.2612
15.3513
0.6197
22.8294
0.0741
0
0.051
0


8
5
11.2913
10.0059
0.3626
13.3581
0.0399
0
0.051
0


8
6
20.5183
14.6059
0.6588
24.2717
0.0798
0
0.051
0


8
7
16.4533
12.6987
0.5352
19.7185
0.0653
0
0.051
0


8
8
15.0048
11.2762
0.4823
17.7662
0.0569
0
0.051
0


8
9
13.9254
8.7784
0.3288
12.1131
0.0683
0
0.051
0


8
10
7.8726
7.4388
0.2396
8.8259
0.0244
0
0.051
0


8
11
19.82
15.1827
0.6372
23.4739
0.0765
0
0.051
0


8
12
7.605
6.8751
0.2285
8.4184
0.0281
0
0.051
0


8
13
10.7449
8.7771
0.3532
13.0108
0.0437
0
0.051
0


8
14
9.4537
7.0641
0.335
12.3405
0.0432
0
0.051
0


8
15
4.9948
4.1176
0.165
6.0799
0.0191
0
0.051
0


8
16
0.039
1.3054
0.0022
0.0814
−0.0018
0
0
0


9
1
5.4948
5.2568
0.1619
5.9632
0.0172
0
0.0383
0


9
2
1.2957
1.792
0.0246
0.9071
0.0007
0
0.0383
0


9
3
4.561
3.4219
0.1167
4.3001
0.0112
0
0.0383
0


9
4
18.1494
12.2628
0.6027
22.2032
0.0759
0
0.0383
0


9
5
9.3792
7.0297
0.3096
11.4063
0.0375
0
0.0383
0


9
6
18.4118
12.8378
0.6302
23.2159
0.0763
0
0.0383
0


9
7
16.3053
13.3828
0.5228
19.2604
0.0596
0
0.0383
0


9
8
11.9275
10.3345
0.3942
14.5228
0.0464
0
0.0383
0


9
9
13.8245
7.7844
0.3136
11.5513
0.0738
0
0.0383
0


9
10
5.9945
6.2382
0.161
5.9323
0.0148
0
0.0383
0


9
11
16.467
12.1554
0.5233
19.2796
0.0638
0
0.0383
0


9
12
4.8586
6.0202
0.1535
5.6534
0.0137
0
0.0383
0


9
13
8.9256
6.8906
0.3084
11.3617
0.0373
0
0.0383
0


9
14
6.5689
5.4424
0.1857
6.8397
0.02
0
0.0383
0


9
15
4.0595
3.9488
0.1149
4.2325
0.012
0
0.0383
0


9
16
0.1737
−0.0654
−0.0123
−0.4528
−0.0033
0
0
0


10 
1
1.5477
2.4162
0.0571
2.1025
0.0057
0
0.1275
0


10 
2
0.7481
0.278
0.0266
0.9802
0.0042
0
0.1275
0


10 
3
17.9789
12.2101
0.6266
23.0845
0.0773
0
0.1275
0


10 
4
15.7177
12.2677
0.4832
17.8
0.0563
0
0.1275
0


10 
5
23.4232
17.8043
0.7802
28.7411
0.0932
0
0.1275
0


10 
6
18.8559
14.0032
0.644
23.7233
0.0803
0
0.1275
0


10 
7
16.6936
12.534
0.5444
20.0565
0.0655
0
0.1275
0


10 
8
15.7358
12.1987
0.5156
18.9943
0.0626
0
0.1275
0


10 
9
19.5604
13.1002
0.7006
25.8091
0.0879
0
0.1275
0


10 
10
18.0579
13.0064
0.5957
21.9464
0.074
0
0.1275
0


10 
11
14.3925
10.1347
0.4699
17.3093
0.0581
0
0.1275
0


10 
12
23.9347
15.9894
0.8104
29.854
0.1014
0
0.1275
0


10 
13
9.5428
6.0585
0.3205
11.8074
0.0415
0
0.1275
0


10 
14
6.0412
4.3478
0.216
7.9578
0.0244
0
0.1275
0


10 
15
2.0188
2.7553
0.0713
2.6262
0.0092
0
0.1275
0


10 
16
23.9818
15.3099
0.8173
30.1102
0.1051
0.384
0
0


11 
1
1.6265
−0.4393
0.0572
2.1077
0.0082
0
0.1126
0


11 
2
0.7512
0.0655
0.0158
0.5811
−0.0006
0
0.1126
0


11 
3
11.6267
7.1062
0.4011
14.7754
0.0508
0
0.1126
0


11 
4
14.9632
10.2139
0.512
18.8615
0.0629
0
0.1126
0


11 
5
20.7287
14.0712
0.6984
25.728
0.0888
0
0.1126
0


11 
6
22.2788
15.4473
0.7325
26.9837
0.0899
0
0.1126
0


11 
7
18.3124
13.0396
0.6421
23.6548
0.0789
0
0.1126
0


11 
8
22.0934
15.6671
0.7274
26.7979
0.0885
0
0.1126
0


11 
9
22.0321
14.1023
0.7675
28.2737
0.1001
0
0.1126
0


11 
10
13.3746
7.6722
0.473
17.424
0.0603
0
0.1126
0


11 
11
11.8485
8.1997
0.4037
14.8713
0.0501
0
0.1126
0


11 
12
21.6762
14.7974
0.7674
28.2709
0.095
0
0.1126
0


11 
13
9.6066
6.771
0.3198
11.7825
0.041
0
0.1126
0


11 
14
5.2261
3.1774
0.1451
5.3441
0.0182
0
0.1126
0


11 
15
1.1397
1.4718
0.029
1.068
0.0045
0
0.1126
0


11 
16
1.7146
−0.1881
0.06
2.2093
0.007
0
0
0


12 
1
0.7424
−0.8795
0.0693
2.5545
0.0111
0
0.0978
0


12 
2
0.3751
0.6279
0.0316
1.1642
0.0022
0
0.0978
0


12 
3
10.7908
6.692
0.3558
13.1083
0.0449
0
0.0978
0


12 
4
9.0282
8.0275
0.3374
12.4281
0.0429
0
0.0978
0


12 
5
17.5272
11.6688
0.6128
22.5774
0.0768
0
0.0978
0


12 
6
16.7422
11.3782
0.5685
20.9454
0.0738
0
0.0978
0


12 
7
15.061
11.2786
0.5101
18.7911
0.0642
0
0.0978
0


12 
8
7.3694
5.1322
0.2558
9.4242
0.0332
0
0.0978
0


12 
9
21.793
14.3754
0.7334
27.018
0.0954
0
0.0978
0


12 
10
8.735
5.3347
0.3294
12.1334
0.0442
0
0.0978
0


12 
11
6.8362
3.8479
0.2586
9.5255
0.0346
0
0.0978
0


12 
12
19.758
12.0896
0.6949
25.5986
0.0882
0
0.0978
0


12 
13
4.91
2.0226
0.1761
6.4864
0.0235
0
0.0978
0


12 
14
2.3397
1.3074
0.074
2.7266
0.0117
0
0.0978
0


12 
15
−0.0988
−1.055
0.028
1.0331
0.0057
0
0.0978
0


12 
16
−0.6493
−1.8142
0.0031
0.1125
0.0042
0
0
0


13 
1
0.4429
0.1915
0.0431
1.5867
0.0084
0
0.0829
0


13 
2
0.7285
−0.4527
0.0242
0.8909
0.0045
0
0.0829
0


13 
3
7.4333
3.9871
0.2548
9.3868
0.0323
0
0.0829
0


13 
4
10.9401
6.7321
0.404
14.883
0.0536
0
0.0829
0


13 
5
14.4732
9.4042
0.4872
17.9486
0.0633
0
0.0829
0


13 
6
14.7593
9.7152
0.4959
18.27
0.0626
0
0.0829
0


13 
7
11.6134
5.9928
0.4019
14.8073
0.0498
0
0.0829
0


13 
8
9.8226
7.3952
0.3336
12.2913
0.0402
0
0.0829
0


13 
9
19.1421
12.2144
0.6691
24.6503
0.0908
0
0.0829
0


13 
10
8.7276
5.9972
0.2896
10.6673
0.0366
0
0.0829
0


13 
11
6.8431
3.0277
0.2592
9.5503
0.0335
0
0.0829
0


13 
12
16.1712
11.1574
0.5535
20.3907
0.0686
0
0.0829
0


13 
13
4.6027
2.533
0.1557
5.7347
0.0213
0
0.0829
0


13 
14
2.6175
2.1368
0.109
4.0151
0.0134
0
0.0829
0


13 
15
0.1712
0.1937
0.0256
0.9427
0.0015
0
0.0829
0


13 
16
5.2254
3.6667
0.2167
7.9825
0.026
0
0
0.768


14 
1
−0.6129
−0.7022
0.0256
0.943
0.0061
0
0.068
0


14 
2
−0.0825
0.1999
0.017
0.6261
0.0049
0
0.068
0


14 
3
5.4052
6.7553
0.1725
6.3547
0.0192
0
0.068
0


14 
4
4.5583
2.1299
0.158
5.8214
0.0202
0
0.068
0


14 
5
10.1192
7.5886
0.3644
13.4249
0.0467
0
0.068
0


14 
6
4.2773
4.269
0.1697
6.2535
0.0232
0
0.068
0


14 
7
5.8243
4.2454
0.206
7.5899
0.0279
0
0.068
0


14 
8
4.5156
3.7194
0.166
6.1153
0.0207
0
0.068
0


14 
9
15.8111
11.2165
0.5256
19.3644
0.0737
0
0.068
0


14 
10
5.4062
3.196
0.1896
6.985
0.0244
0
0.068
0


14 
11
3.7866
1.825
0.1438
5.2965
0.0222
0
0.068
0


14 
12
7.7545
4.1296
0.2784
10.2559
0.0368
0
0.068
0


14 
13
2.8508
2.631
0.1214
4.4727
0.0154
0
0.068
0


14 
14
0.5309
−1.0896
0.0675
2.4849
0.0099
0
0.068
0


14 
15
0.1398
−1.9674
0.0158
0.5813
0.0012
0
0.068
0


14 
16
−0.3316
0.0358
0.01
0.3687
0.0004
0
0
0


15 
1
−0.1148
0.1922
0.0092
0.3376
0.0008
0
0.0531
0


15 
2
0.1079
0.1039
0.0042
0.1541
0.0032
0
0.0531
0


15 
3
3.5717
2.2496
0.1406
5.1802
0.0221
0
0.0531
0


15 
4
4.6567
1.8374
0.1474
5.4311
0.0196
0
0.0531
0


15 
5
6.8308
3.9469
0.2744
10.1092
0.0376
0
0.0531
0


15 
6
7.5086
3.6352
0.2419
8.911
0.0314
0
0.0531
0


15 
7
3.6177
2.7378
0.0881
3.2446
0.0122
0
0.0531
0


15 
8
6.3617
3.1726
0.1952
7.1899
0.0269
0
0.0531
0


15 
9
13.9802
8.5923
0.4839
17.826
0.0689
0
0.0531
0


15 
10
4.8923
3.9039
0.1737
6.4005
0.023
0
0.0531
0


15 
11
5.59
3.4292
0.1956
7.2047
0.0283
0
0.0531
0


15 
12
6.8024
5.5785
0.2192
8.0763
0.0294
0
0.0531
0


15 
13
3.7607
2.3756
0.121
4.4593
0.0166
0
0.0531
0


15 
14
0.937
1.5442
0.0699
2.5762
0.0097
0
0.0531
0


15 
15
0.2832
0.3246
0.02
0.7379
0.0033
0
0.0531
0


15 
16
−0.7225
−0.2893
0.0016
0.0571
−0.0006
0
0
0


16 
1
−0.0142
−1.1024
0.0215
0.7913
0.0057
0
0.0383
0


16 
2
0.4952
−0.4098
0.0194
0.7148
0.0058
0
0.0383
0


16 
3
3.2579
1.3122
0.1477
5.4418
0.0221
0
0.0383
0


16 
4
1.625
−0.1101
0.1214
4.4707
0.0211
0
0.0383
0


16 
5
1.8652
0.6067
0.0939
3.4593
0.0153
0
0.0383
0


16 
6
4.8965
3.555
0.1734
6.3862
0.0233
0
0.0383
0


16 
7
0.5706
−0.0127
0.0426
1.5679
0.0079
0
0.0383
0


16 
8
1.5788
1.8244
0.0682
2.5118
0.0091
0
0.0383
0


16 
9
7.3237
3.5992
0.2614
9.63
0.0399
0
0.0383
0


16 
10
3.4023
0.894
0.1499
5.5241
0.0224
0
0.0383
0


16 
11
1.8143
−0.758
0.0668
2.4619
0.0101
0
0.0383
0


16 
12
0.8507
0.6985
0.052
1.9172
0.0098
0
0.0383
0


16 
13
3.0836
3.6579
0.1369
5.0426
0.0179
0
0.0383
0


16 
14
0.8053
−0.2459
0.0311
1.1471
0.0073
0
0.0383
0


16 
15
5.3415
3.7713
0.2488
9.1666
0.0341
0
0.0383
0


16 
16
9.4755
5.5863
0.3659
13.4784
0.0487
0.384
0
0


Temperature:


260 C.


1
1
23.9548
12.5586
0.792
28.945
0.1185
0.384
0
0


1
2
−0.1251
−1.1682
0.0079
0.2905
0.0029
0
0
0


1
3
−0.2445
−1.2984
−0.0091
−0.3313
0.0016
0
0
0


1
4
26.223
16.8044
0.8614
31.4805
0.1117
0
0
0.768


1
5
0.5935
1.5609
0.0111
0.4048
0.0008
0
0
0


1
6
0.3452
−0.5656
−0.0202
−0.7401
−0.002
0
0
0


1
7
33.6381
20.613
1.115
40.751
0.161
0.384
0
0


1
8
0.3663
0.721
0.0118
0.4304
0.0043
0
0
0


1
9
−0.3414
0.3286
−0.0389
−1.4226
−0.0089
0
0
0


1
10
16.1672
9.9936
0.5479
20.0238
0.0714
0
0
0.768


1
11
−0.1542
−0.1519
−0.03
−1.095
−0.0036
0
0
0


1
12
−0.706
−0.9411
−0.0392
−1.4334
−0.0032
0
0
0


1
13
31.908
19.6537
1.0424
38.0961
0.1437
0.384
0
0


1
14
0.5711
−0.2625
−0.0125
−0.4566
−0.0012
0
0
0


1
15
−0.5994
−1.1609
−0.025
−0.9131
−0.0045
0
0
0


1
16
13.0157
7.0184
0.4715
17.2323
0.0599
0
0
0.768


2
1
7.6165
4.4571
0.249
9.0986
0.0316
0
0.1275
0


2
2
2.04
1.7045
0.0513
1.8735
0.0074
0
0.1275
0


2
3
19.8301
14.357
0.6798
24.8446
0.0858
0
0.1275
0


2
4
25.5767
16.9766
0.8497
31.0534
0.1122
0
0.1275
0


2
5
19.6461
12.5711
0.6752
24.6783
0.0908
0
0.1275
0


2
6
29.3737
20.6255
0.9524
34.8088
0.1251
0
0.1275
0


2
7
25.3081
17.3872
0.7934
28.9974
0.1065
0
0.1275
0


2
8
31.2784
20.4979
0.9823
35.9021
0.1389
0
0.1275
0


2
9
19.8631
13.7444
0.6352
23.2152
0.0763
0
0.1275
0


2
10
10.4121
7.8726
0.3241
11.845
0.0384
0
0.1275
0


2
11
28.2753
19.8643
0.8954
32.7261
0.116
0
0.1275
0


2
12
28.388
19.6094
0.888
32.4551
0.1133
0
0.1275
0


2
13
21.9441
15.5641
0.6867
25.0976
0.0849
0
0.1275
0


2
14
21.0969
15.4875
0.6762
24.712
0.0815
0
0.1275
0


2
15
17.2387
11.7114
0.5678
20.7519
0.0707
0
0.1275
0


2
16
0.3495
−0.3711
0.005
0.1841
0.0007
0
0
0


3
1
20.2367
13.2497
0.6915
25.2741
0.0869
0
0.1148
0


3
2
8.9669
5.9386
0.2877
10.5137
0.0347
0
0.1148
0


3
3
16.7768
10.897
0.565
20.6503
0.0706
0
0.1148
0


3
4
27.777
18.2759
0.9351
34.1766
0.1287
0
0.1148
0


3
5
20.3263
13.9316
0.6648
24.2965
0.0839
0
0.1148
0


3
6
28.7316
18.8028
0.9427
34.4528
0.1245
0
0.1148
0


3
7
25.4654
18.4277
0.8264
30.2015
0.1095
0
0.1148
0


3
8
29.6117
21.6329
0.9545
34.8833
0.126
0
0.1148
0


3
9
17.2418
12.6896
0.5857
21.4042
0.0712
0
0.1148
0


3
10
19.8929
14.3675
0.6554
23.9547
0.081
0
0.1148
0


3
11
28.1629
17.7133
0.9147
33.4316
0.1189
0
0.1148
0


3
12
25.2171
16.6791
0.7977
29.1554
0.102
0
0.1148
0


3
13
19.4575
14.7466
0.6586
24.0702
0.0828
0
0.1148
0


3
14
26.4424
17.3168
0.8888
32.4841
0.1138
0
0.1148
0


3
15
16.101
11.3039
0.5812
21.2404
0.0742
0
0.1148
0


3
16
−0.023
1.4313
−0.0247
−0.9042
−0.0064
0
0
0


4
1
21.7975
15.4921
0.7711
28.1812
0.0932
0
0.102
0


4
2
10.7163
8.3886
0.3262
11.9235
0.0386
0
0.102
0


4
3
17.1487
14.3548
0.5793
21.1714
0.07
0
0.102
0


4
4
27.6901
18.0677
0.9147
33.4286
0.1231
0
0.102
0


4
5
19.834
14.4675
0.6659
24.3388
0.0858
0
0.102
0


4
6
28.4061
20.4494
0.9351
34.1766
0.1216
0
0.102
0


4
7
25.0251
19.0757
0.8051
29.4259
0.1044
0
0.102
0


4
8
30.1323
21.8658
0.9545
34.8849
0.1285
0
0.102
0


4
9
17.4353
13.7445
0.5888
21.5204
0.0724
0
0.102
0


4
10
18.5879
14.8039
0.6274
22.9309
0.0756
0
0.102
0


4
11
28.8642
21.4484
0.9293
33.9638
0.122
0
0.102
0


4
12
21.4072
15.6073
0.7437
27.1816
0.0938
0
0.102
0


4
13
20.4004
15.2176
0.6641
24.2712
0.084
0
0.102
0


4
14
26.9082
18.8
0.8724
31.8854
0.1143
0
0.102
0


4
15
19.1005
13.9277
0.6384
23.3336
0.0811
0
0.102
0


4
16
29.0091
17.9895
0.9619
35.1545
0.142
0.384
0
0


5
1
19.6008
14.7724
0.6977
25.4997
0.0863
0
0.0893
0


5
2
4.4591
5.8398
0.1267
4.6297
0.0115
0
0.0893
0


5
3
17.4615
13.2093
0.5716
20.8904
0.0684
0
0.0893
0


5
4
27.191
17.9075
0.9098
33.2513
0.121
0
0.0893
0


5
5
19.0595
15.5605
0.6287
22.9776
0.0753
0
0.0893
0


5
6
27.8708
19.2272
0.8978
32.8131
0.1167
0
0.0893
0


5
7
24.4016
19.1467
0.8152
29.7949
0.1021
0
0.0893
0


5
8
27.9965
21.5105
0.9029
32.9989
0.1173
0
0.0893
0


5
9
17.2513
13.7436
0.5629
20.5717
0.0705
0
0.0893
0


5
10
18.4671
13.4843
0.6255
22.8613
0.0758
0
0.0893
0


5
11
29.3804
21.3425
0.9532
34.8381
0.1229
0
0.0893
0


5
12
16.4671
14.1712
0.5223
19.0903
0.0603
0
0.0893
0


5
13
18.5408
14.4036
0.6009
21.9625
0.074
0
0.0893
0


5
14
25.0803
18.6587
0.8426
30.7933
0.1019
0
0.0893
0


5
15
16.054
10.8572
0.5467
19.9812
0.0675
0
0.0893
0


5
16
2.21
2.6719
0.0893
3.2654
0.0093
0
0
0


6
1
17.2143
10.5925
0.5785
21.1428
0.0704
0
0.0765
0


6
2
6.5615
3.8939
0.2245
8.204
0.0283
0
0.0765
0


6
3
14.665
10.1505
0.4705
17.1975
0.0571
0
0.0765
0


6
4
26.914
18.4424
0.9031
33.008
0.1147
0
0.0765
0


6
5
18.3107
13.344
0.6235
22.7882
0.0779
0
0.0765
0


6
6
26.6766
18.1581
0.9136
33.3883
0.1139
0
0.0765
0


6
7
23.7003
15.7944
0.8064
29.4712
0.1026
0
0.0765
0


6
8
26.7761
17.0647
0.8747
31.9669
0.1173
0
0.0765
0


6
9
16.1131
11.9414
0.5207
19.0297
0.0642
0
0.0765
0


6
10
18.9129
14.7068
0.6221
22.7361
0.0735
0
0.0765
0


6
11
29.0675
19.5103
0.9635
35.2139
0.129
0
0.0765
0


6
12
11.7426
10.2734
0.3717
13.5833
0.0422
0
0.0765
0


6
13
16.8626
11.5965
0.5855
21.3985
0.0773
0
0.0765
0


6
14
26.4065
19.0014
0.8963
32.7585
0.1118
0
0.0765
0


6
15
14.603
10.4082
0.4617
16.8728
0.0553
0
0.0765
0


6
16
−0.7718
−0.9228
−0.0099
−0.3607
0.0007
0
0
0


7
1
13.0412
9.5302
0.4162
15.2125
0.0503
0
0.0638
0


7
2
3.8611
2.4286
0.0928
3.392
0.0105
0
0.0638
0


7
3
15.3005
10.0224
0.5176
18.9172
0.0635
0
0.0638
0


7
4
25.9965
17.958
0.8622
31.5124
0.1085
0
0.0638
0


7
5
18.203
14.3266
0.6071
22.1899
0.0739
0
0.0638
0


7
6
26.4572
19.5242
0.898
32.8198
0.1116
0
0.0638
0


7
7
22.8328
16.0377
0.7813
28.5553
0.0978
0
0.0638
0


7
8
26.6147
20.0129
0.8716
31.8557
0.1132
0
0.0638
0


7
9
14.1961
12.1463
0.4578
16.7301
0.0582
0
0.0638
0


7
10
17.8887
13.1344
0.6076
22.2047
0.0718
0
0.0638
0


7
11
29.3
20.7004
0.9421
34.4302
0.1256
0
0.0638
0


7
12
12.7912
9.683
0.3949
14.434
0.0473
0
0.0638
0


7
13
16.1059
10.337
0.5525
20.1938
0.0715
0
0.0638
0


7
14
23.9848
17.1651
0.7971
29.1323
0.0995
0
0.0638
0


7
15
10.2355
6.3735
0.355
12.9727
0.0462
0
0.0638
0


7
16
13.7951
9.0124
0.478
17.4709
0.0607
0
0
0.768


8
1
8.7108
7.6478
0.278
10.1604
0.0318
0
0.051
0


8
2
5.6619
3.0544
0.1607
5.8731
0.0182
0
0.051
0


8
3
12.7243
8.2404
0.4297
15.7034
0.0548
0
0.051
0


8
4
23.1824
15.3102
0.7818
28.5718
0.1032
0
0.051
0


8
5
16.8934
12.5464
0.5477
20.0177
0.0693
0
0.051
0


8
6
23.0844
16.8013
0.786
28.7276
0.0972
0
0.051
0


8
7
21.1268
13.7292
0.7006
25.6053
0.0886
0
0.051
0


8
8
21.8373
14.2275
0.7572
27.6751
0.096
0
0.051
0


8
9
13.5928
9.6006
0.4328
15.8191
0.058
0
0.051
0


8
10
14.5523
10.281
0.4839
17.6837
0.0618
0
0.051
0


8
11
26.6525
18.3392
0.9016
32.9501
0.1139
0
0.051
0


8
12
8.5309
7.1825
0.2649
9.683
0.0303
0
0.051
0


8
13
15.3085
10.76
0.5211
19.0435
0.0676
0
0.051
0


8
14
18.6343
14.2101
0.616
22.5118
0.0767
0
0.051
0


8
15
8.4219
5.8283
0.2782
10.1692
0.0344
0
0.051
0


8
16
−0.0515
0.4898
0.0128
0.4665
0.0006
0
0
0


9
1
7.3166
5.319
0.2691
9.8339
0.0316
0
0.0383
0


9
2
4.4987
1.546
0.1044
3.8148
0.0146
0
0.0383
0


9
3
10.2033
7.0123
0.3423
12.51
0.0448
0
0.0383
0


9
4
21.9197
15.8941
0.7279
26.6038
0.0945
0
0.0383
0


9
5
13.7404
10.7958
0.4389
16.0401
0.0523
0
0.0383
0


9
6
22.0391
16.325
0.7157
26.1572
0.0859
0
0.0383
0


9
7
19.6992
14.7156
0.6399
23.3875
0.0796
0
0.0383
0


9
8
18.8782
13.41
0.6389
23.3487
0.0825
0
0.0383
0


9
9
11.5326
8.0541
0.3741
13.6723
0.0512
0
0.0383
0


9
10
11.4588
7.9653
0.3912
14.2987
0.0499
0
0.0383
0


9
11
24.0261
16.4691
0.8098
29.5975
0.1024
0
0.0383
0


9
12
5.2417
5.2691
0.138
5.0443
0.0148
0
0.0383
0


9
13
13.6632
9.0008
0.4457
16.2885
0.0596
0
0.0383
0


9
14
13.958
10.1125
0.4726
17.2727
0.0588
0
0.0383
0


9
15
7.3577
5.1203
0.2531
9.2493
0.0314
0
0.0383
0


9
16
−0.6656
−0.3365
−0.0192
−0.7029
−0.0013
0
0
0


10 
1
4.1613
3.3032
0.1544
5.6446
0.0193
0
0.1275
0


10 
2
2.503
1.9852
0.0794
2.9011
0.0086
0
0.1275
0


10 
3
22.5185
16.2252
0.777
28.3968
0.0938
0
0.1275
0


10 
4
21.9249
17.4869
0.7138
26.0883
0.0819
0
0.1275
0


10 
5
25.2635
18.8907
0.8754
31.9941
0.1044
0
0.1275
0


10 
6
25.3786
19.7077
0.8305
30.3522
0.0992
0
0.1275
0


10 
7
23.279
18.1733
0.7584
27.7191
0.0891
0
0.1275
0


10 
8
23.9911
18.2144
0.795
29.0572
0.0985
0
0.1275
0


10 
9
27.1738
19.0835
0.9247
33.7964
0.1169
0
0.1275
0


10 
10
24.9585
18.3458
0.8669
31.6823
0.1061
0
0.1275
0


10 
11
23.4382
17.1163
0.7984
29.1814
0.1007
0
0.1275
0


10 
12
27.0826
19.1195
0.8924
32.6135
0.1125
0
0.1275
0


10 
13
18.4256
12.7535
0.6262
22.8872
0.0811
0
0.1275
0


10 
14
15.4756
10.6861
0.5085
18.5857
0.0641
0
0.1275
0


10 
15
5.8605
5.3508
0.2013
7.3589
0.0255
0
0.1275
0


10 
16
26.4434
15.6699
0.9053
33.0873
0.1296
0.384
0
0


11 
1
3.3631
2.4086
0.1301
4.755
0.0163
0
0.1126
0


11 
2
1.1385
1.5047
0.0639
2.3355
0.0058
0
0.1126
0


11 
3
18.1923
12.056
0.6322
23.1046
0.0768
0
0.1126
0


11 
4
20.8536
14.0326
0.7301
26.6842
0.0894
0
0.1126
0


11 
5
25.2787
19.0321
0.8169
29.8542
0.0984
0
0.1126
0


11 
6
26.5724
19.0476
0.8949
32.7054
0.1104
0
0.1126
0


11 
7
23.8679
17.1511
0.8261
30.1927
0.1024
0
0.1126
0


11 
8
27.0578
20.7184
0.9008
32.9204
0.1104
0
0.1126
0


11 
9
28.3897
19.3393
0.9733
35.5716
0.1218
0
0.1126
0


11 
10
21.8095
15.8474
0.7866
28.7469
0.0975
0
0.1126
0


11 
11
21.1677
16.0245
0.7546
27.5785
0.0913
0
0.1126
0


11 
12
26.6583
19.4333
0.9012
32.9382
0.1129
0
0.1126
0


11 
13
19.2461
13.9305
0.6446
23.5598
0.0791
0
0.1126
0


11 
14
13.3117
9.1142
0.4767
17.4229
0.0596
0
0.1126
0


11 
15
3.338
4.4882
0.1241
4.5368
0.0112
0
0.1126
0


11 
16
1.6855
2.0504
0.0688
2.5135
0.006
0
0
0


12 
1
2.9708
2.5243
0.1413
5.1644
0.0173
0
0.0978
0


12 
2
2.1159
3.2147
0.0729
2.6644
0.006
0
0.0978
0


12 
3
16.9197
12.3294
0.5601
20.4707
0.0661
0
0.0978
0


12 
4
16.8097
12.7361
0.5719
20.901
0.0701
0
0.0978
0


12 
5
20.7869
17.0843
0.7264
26.5499
0.0844
0
0.0978
0


12 
6
22.5089
17.2645
0.7643
27.9321
0.0911
0
0.0978
0


12 
7
20.3063
13.5884
0.7135
26.0775
0.0877
0
0.0978
0


12 
8
16.2687
11.1505
0.5577
20.3839
0.0703
0
0.0978
0


12 
9
26.0301
16.9468
0.8731
31.9104
0.1108
0
0.0978
0


12 
10
17.4285
11.5132
0.607
22.186
0.0766
0
0.0978
0


12 
11
15.8306
10.5339
0.5491
20.0671
0.069
0
0.0978
0


12 
12
22.7247
14.7061
0.7955
29.074
0.0971
0
0.0978
0


12 
13
11.2534
7.305
0.4058
14.8324
0.051
0
0.0978
0


12 
14
7.4166
3.4671
0.2736
9.9978
0.0337
0
0.0978
0


12 
15
1.307
0.3938
0.0689
2.5194
0.0082
0
0.0978
0


12 
16
−1.2094
−1.9329
−0.0041
−0.1501
−0.0003
0
0
0


13 
1
2.9967
3.7384
0.0553
2.0203
0.0022
0
0.0829
0


13 
2
1.7052
1.3563
0.0398
1.4543
0.0027
0
0.0829
0


13 
3
13.0887
9.6959
0.4612
16.8547
0.0549
0
0.0829
0


13 
4
17.0868
13.3998
0.5915
21.6191
0.0696
0
0.0829
0


13 
5
19.7818
15.0495
0.6769
24.7406
0.0833
0
0.0829
0


13 
6
21.0147
15.0505
0.716
26.168
0.0861
0
0.0829
0


13 
7
18.0319
14.6478
0.6107
22.3182
0.0712
0
0.0829
0


13 
8
18.7202
14.921
0.6192
22.63
0.0741
0
0.0829
0


13 
9
24.5564
17.2349
0.8727
31.8947
0.1135
0
0.0829
0


13 
10
16.4168
13.0312
0.5761
21.0552
0.068
0
0.0829
0


13 
11
16.6658
11.451
0.5704
20.8485
0.0687
0
0.0829
0


13 
12
19.9683
13.87
0.7112
25.9917
0.0867
0
0.0829
0


13 
13
10.9425
8.5671
0.4247
15.5217
0.0556
0
0.0829
0


13 
14
9.7737
8.0718
0.3096
11.3139
0.036
0
0.0829
0


13 
15
1.7288
1.0718
0.0759
2.7725
0.0082
0
0.0829
0


13 
16
10.952
6.7668
0.393
14.3637
0.0488
0
0
0.768


14 
1
0.859
0.8081
0.0661
2.4145
0.0076
0
0.068
0


14 
2
1.2176
2.4624
0.0396
1.4476
0.0025
0
0.068
0


14 
3
10.267
8.591
0.3654
13.3559
0.0408
0
0.068
0


14 
4
10.9361
8.2471
0.3609
13.1888
0.0394
0
0.068
0


14 
5
15.763
12.2528
0.5463
19.9672
0.0631
0
0.068
0


14 
6
12.2511
9.7701
0.4074
14.8894
0.0458
0
0.068
0


14 
7
12.7569
8.9769
0.4403
16.0909
0.0523
0
0.068
0


14 
8
11.771
10.0769
0.4011
14.6594
0.0473
0
0.068
0


14 
9
20.4667
13.9256
0.7145
26.1126
0.0934
0
0.068
0


14 
10
11.2785
7.3023
0.4152
15.1763
0.0536
0
0.068
0


14 
11
10.3127
6.1338
0.3609
13.1915
0.0461
0
0.068
0


14 
12
10.1414
8.3737
0.3548
12.9684
0.0414
0
0.068
0


14 
13
7.4485
5.7711
0.2732
9.9858
0.0317
0
0.068
0


14 
14
4.6897
3.6728
0.1896
6.9291
0.0206
0
0.068
0


14 
15
0.4469
0.4157
0.0425
1.5524
0.0066
0
0.068
0


14 
16
0.0205
0.2191
0.0325
1.1895
0.0045
0
0
0


15 
1
0.1326
1.2014
0.0213
0.7772
−0.0014
0
0.0531
0


15 
2
0.5446
2.0595
0.029
1.0596
−0.0016
0
0.0531
0


15 
3
6.4394
4.0672
0.2646
9.6705
0.0317
0
0.0531
0


15 
4
8.7498
6.8198
0.3376
12.3395
0.0412
0
0.0531
0


15 
5
12.8715
8.7415
0.4617
16.8745
0.0557
0
0.0531
0


15 
6
13.4066
9.3322
0.4526
16.5409
0.0568
0
0.0531
0


15 
7
8.1085
6.4379
0.237
8.6612
0.0266
0
0.0531
0


15 
8
12.9214
9.0713
0.4624
16.9008
0.0559
0
0.0531
0


15 
9
19.1264
13.1011
0.6567
23.9995
0.0828
0
0.0531
0


15 
10
10.2178
8.3832
0.3465
12.6635
0.0409
0
0.0531
0


15 
11
12.0399
9.5234
0.4507
16.4738
0.0536
0
0.0531
0


15 
12
9.1992
6.9676
0.3338
12.1989
0.0394
0
0.0531
0


15 
13
7.5413
6.3157
0.2885
10.544
0.0368
0
0.0531
0


15 
14
4.7466
3.9707
0.2032
7.4265
0.0238
0
0.0531
0


15 
15
1.2498
1.3505
0.0593
2.1676
0.0065
0
0.0531
0


15 
16
−1.2496
−0.3611
−0.0064
−0.2348
0.0003
0
0
0


16 
1
0.2469
0.431
0.0311
1.1382
0.0048
0
0.0383
0


16 
2
1.1204
2.4401
0.0624
2.2793
0.0026
0
0.0383
0


16 
3
5.6729
3.8623
0.2177
7.9579
0.0269
0
0.0383
0


16 
4
5.1165
3.5211
0.2607
9.5268
0.0327
0
0.0383
0


16 
5
6.9249
4.6954
0.2462
8.9973
0.0286
0
0.0383
0


16 
6
9.5123
6.7076
0.3377
12.3415
0.0392
0
0.0383
0


16 
7
3.3103
3.062
0.1141
4.169
0.015
0
0.0383
0


16 
8
5.5678
4.0843
0.2158
7.8876
0.0249
0
0.0383
0


16 
9
13.2231
9.6653
0.4812
17.5857
0.0603
0
0.0383
0


16 
10
6.6341
4.1143
0.2436
8.9035
0.029
0
0.0383
0


16 
11
4.5017
2.0396
0.1675
6.1202
0.0201
0
0.0383
0


16 
12
0.5165
1.8075
0.0714
2.6096
0.0084
0
0.0383
0


16 
13
5.834
2.5756
0.2576
9.4154
0.0338
0
0.0383
0


16 
14
1.9456
0.638
0.1291
4.7172
0.0188
0
0.0383
0


16 
15
8.6195
6.634
0.3572
13.0562
0.0472
0
0.0383
0


16 
16
14.4734
8.8212
0.5143
18.7981
0.0652
0.384
0
0




















CeNO33
CoNO32
FeNO33
HAuNO34
LaNO33
NH42MoO4
NaOH
PdNH32NO22
SUM-


R
real
real
real
real
real
real
real
real
micromols





Temperature


200 C.


1
0
0
0
0
0
0
0
0
0.384


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0.768


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0.384


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0.768


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0.384


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0.768


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0.125
0
0
0
0
0
0
0.2525


2
0
0
0.125
0
0
0
0
0
0.2525


2
0.125
0
0
0
0
0
0
0
0.2525


2
0
0
0
0
0
0.125
0
0
0.2525


2
0
0
0
0
0
0
0
0.0235
0.151


2
0
0
0
0
0.125
0
0
0
0.2525


2
0
0
0
0.2
0
0
0
0
0.3275


2
0
0
0
0
0
0
0
0
0


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0.1964
0
0
0
0
0
0
0.3112


3
0
0
0.1964
0
0
0
0
0
0.3112


3
0.1964
0
0
0
0
0
0
0
0.3112


3
0
0
0
0
0
0.1964
0
0
0.3112


3
0
0
0
0
0
0
0
0.0369
0.1517


3
0
0
0
0
0.1964
0
0
0
0.3112


3
0
0
0
0.2
0
0
0
0
0.3148


3
0
0
0
0
0
0
0
0
0


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0.2679
0
0
0
0
0
0
0.3699


4
0
0
0.2679
0
0
0
0
0
0.3699


4
0.2679
0
0
0
0
0
0
0
0.3699


4
0
0
0
0
0
0.2679
0
0
0.3699


4
0
0
0
0
0
0
0
0.0504
0.1524


4
0
0
0
0
0.2679
0
0
0
0.3699


4
0
0
0
0.2
0
0
0
0
0.302


4
0
0
0
0
0
0
0
0
0.384


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0.3393
0
0
0
0
0
0
0.4285


5
0
0
0.3393
0
0
0
0
0
0.4285


5
0.3393
0
0
0
0
0
0
0
0.4285


5
0
0
0
0
0
0.3393
0
0
0.4285


5
0
0
0
0
0
0
0
0.0638
0.153


5
0
0
0
0
0.3393
0
0
0
0.4285


5
0
0
0
0.2
0
0
0
0
0.2893


5
0
0
0
0
0
0
0
0
0


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0.4107
0
0
0
0
0
0
0.4872


6
0
0
0.4107
0
0
0
0
0
0.4872


6
0.4107
0
0
0
0
0
0
0
0.4872


6
0
0
0
0
0
0.4107
0
0
0.4872


6
0
0
0
0
0
0
0
0.0772
0.1537


6
0
0
0
0
0.4107
0
0
0
0.4872


6
0
0
0
0.2
0
0
0
0
0.2765


6
0
0
0
0
0
0
0
0
0


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0.4821
0
0
0
0
0
0
0.5459


7
0
0
0.4821
0
0
0
0
0
0.5459


7
0.4821
0
0
0
0
0
0
0
0.5459


7
0
0
0
0
0
0.4821
0
0
0.5459


7
0
0
0
0
0
0
0
0.0906
0.1544


7
0
0
0
0
0.4821
0
0
0
0.5459


7
0
0
0
0.2
0
0
0
0
0.2638


7
0
0
0
0
0
0
0
0
0.768


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0.5536
0
0
0
0
0
0
0.6046


8
0
0
0.5536
0
0
0
0
0
0.6046


8
0.5536
0
0
0
0
0
0
0
0.6046


8
0
0
0
0
0
0.5536
0
0
0.6046


8
0
0
0
0
0
0
0
0.1041
0.1551


8
0
0
0
0
0.5536
0
0
0
0.6046


8
0
0
0
0.2
0
0
0
0
0.251


8
0
0
0
0
0
0
0
0
0


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0.625
0
0
0
0
0
0
0.6633


9
0
0
0.625
0
0
0
0
0
0.6633


9
0.625
0
0
0
0
0
0
0
0.6633


9
0
0
0
0
0
0.625
0
0
0.6633


9
0
0
0
0
0
0
0
0.1175
0.1558


9
0
0
0
0
0.625
0
0
0
0.6633


9
0
0
0
0.2
0
0
0
0
0.2383


9
0
0
0
0
0
0
0
0
0


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0.125
0
0
0
0
1.25
0
1.5025


10 
0
0
0.125
0
0
0
1.25
0
1.5025


10 
0.125
0
0
0
0
0
1.25
0
1.5025


10 
0
0
0
0
0
0.125
1.25
0
1.5025


10 
0
0
0
0
0
0
1.25
0.0235
1.401


10 
0
0
0
0
0.125
0
1.25
0
1.5025


10 
0
0
0
0.2
0
0
1.25
0
1.5775


10 
0
0
0
0
0
0
0
0
0.384


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0.2083
0
0
0
0
1.25
0
1.571


11 
0
0
0.2083
0
0
0
1.25
0
1.571


11 
0.2083
0
0
0
0
0
1.25
0
1.571


11 
0
0
0
0
0
0.2083
1.25
0
1.571


11 
0
0
0
0
0
0
1.25
0.0392
1.4018


11 
0
0
0
0
0.2083
0
1.25
0
1.571


11 
0
0
0
0.2
0
0
1.25
0
1.5626


11 
0
0
0
0
0
0
0
0
0


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0.2917
0
0
0
0
1.25
0
1.6394


12 
0
0
0.2917
0
0
0
1.25
0
1.6394


12 
0.2917
0
0
0
0
0
1.25
0
1.6394


12 
0
0
0
0
0
0.2917
1.25
0
1.6394


12 
0
0
0
0
0
0
1.25
0.0548
1.4026


12 
0
0
0
0
0.2917
0
1.25
0
1.6394


12 
0
0
0
0.2
0
0
1.25
0
1.5478


12 
0
0
0
0
0
0
0
0
0


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0.375
0
0
0
0
1.25
0
1.7079


13 
0
0
0.375
0
0
0
1.25
0
1.7079


13 
0.375
0
0
0
0
0
1.25
0
1.7079


13 
0
0
0
0
0
0.375
1.25
0
1.7079


13 
0
0
0
0
0
0
1.25
0.0705
1.4034


13 
0
0
0
0
0.375
0
1.25
0
1.7079


13 
0
0
0
0.2
0
0
1.25
0
1.5329


13 
0
0
0
0
0
0
0
0
0.768


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0.4583
0
0
0
0
1.25
0
1.7763


14 
0
0
0.4583
0
0
0
1.25
0
1.7763


14 
0.4583
0
0
0
0
0
1.25
0
1.7763


14 
0
0
0
0
0
0.4583
1.25
0
1.7763


14 
0
0
0
0
0
0
1.25
0.0862
1.4042


14 
0
0
0
0
0.4583
0
1.25
0
1.7763


14 
0
0
0
0.2
0
0
1.25
0
1.518


14 
0
0
0
0
0
0
0
0
0


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0.5417
0
0
0
0
1.25
0
1.8448


15 
0
0
0.5417
0
0
0
1.25
0
1.8448


15 
0.5417
0
0
0
0
0
1.25
0
1.8448


15 
0
0
0
0
0
0.5417
1.25
0
1.8448


15 
0
0
0
0
0
0
1.25
0.1018
1.405


15 
0
0
0
0
0.5417
0
1.25
0
1.8448


15 
0
0
0
0.2
0
0
1.25
0
1.5031


15 
0
0
0
0
0
0
0
0
0


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0.625
0
0
0
0
1.25
0
1.9133


16 
0
0
0.625
0
0
0
1.25
0
1.9133


16 
0.625
0
0
0
0
0
1.25
0
1.9133


16 
0
0
0
0
0
0.625
1.25
0
1.9133


16 
0
0
0
0
0
0
1.25
0.1175
1.4058


16 
0
0
0
0
0.625
0
1.25
0
1.9133


16 
0
0
0
0.2
0
0
1.25
0
1.4883


16 
0
0
0
0
0
0
0
0
0.384


Temperature


230 C.


1
0
0
0
0
0
0
0
0
0.384


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0.768


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0.384


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0.768


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0.384


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0.768


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0.125
0
0
0
0
0
0
0.2525


2
0
0
0.125
0
0
0
0
0
0.2525


2
0.125
0
0
0
0
0
0
0
0.2525


2
0
0
0
0
0
0.125
0
0
0.2525


2
0
0
0
0
0
0
0
0.0235
0.151


2
0
0
0
0
0.125
0
0
0
0.2525


2
0
0
0
0.2
0
0
0
0
0.3275


2
0
0
0
0
0
0
0
0
0


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0.1964
0
0
0
0
0
0
0.3112


3
0
0
0.1964
0
0
0
0
0
0.3112


3
0.1964
0
0
0
0
0
0
0
0.3112


3
0
0
0
0
0
0.1964
0
0
0.3112


3
0
0
0
0
0
0
0
0.0369
0.1517


3
0
0
0
0
0.1964
0
0
0
0.3112


3
0
0
0
0.2
0
0
0
0
0.3148


3
0
0
0
0
0
0
0
0
0


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0.2679
0
0
0
0
0
0
0.3699


4
0
0
0.2679
0
0
0
0
0
0.3699


4
0.2679
0
0
0
0
0
0
0
0.3699


4
0
0
0
0
0
0.2679
0
0
0.3699


4
0
0
0
0
0
0
0
0.0504
0.1524


4
0
0
0
0
0.2679
0
0
0
0.3699


4
0
0
0
0.2
0
0
0
0
0.302


4
0
0
0
0
0
0
0
0
0.384


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0.3393
0
0
0
0
0
0
0.4285


5
0
0
0.3393
0
0
0
0
0
0.4285


5
0.3393
0
0
0
0
0
0
0
0.4285


5
0
0
0
0
0
0.3393
0
0
0.4285


5
0
0
0
0
0
0
0
0.0638
0.153


5
0
0
0
0
0.3393
0
0
0
0.4285


5
0
0
0
0.2
0
0
0
0
0.2893


5
0
0
0
0
0
0
0
0
0


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0.4107
0
0
0
0
0
0
0.4872


6
0
0
0.4107
0
0
0
0
0
0.4872


6
0.4107
0
0
0
0
0
0
0
0.4872


6
0
0
0
0
0
0.4107
0
0
0.4872


6
0
0
0
0
0
0
0
0.0772
0.1537


6
0
0
0
0
0.4107
0
0
0
0.4872


6
0
0
0
0.2
0
0
0
0
0.2765


6
0
0
0
0
0
0
0
0
0


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0.4821
0
0
0
0
0
0
0.5459


7
0
0
0.4821
0
0
0
0
0
0.5459


7
0.4821
0
0
0
0
0
0
0
0.5459


7
0
0
0
0
0
0.4821
0
0
0.5459


7
0
0
0
0
0
0
0
0.0906
0.1544


7
0
0
0
0
0.4821
0
0
0
0.5459


7
0
0
0
0.2
0
0
0
0
0.2638


7
0
0
0
0
0
0
0
0
0.768


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0.5536
0
0
0
0
0
0
0.6046


8
0
0
0.5536
0
0
0
0
0
0.6046


8
0.5536
0
0
0
0
0
0
0
0.6046


8
0
0
0
0
0
0.5536
0
0
0.6046


8
0
0
0
0
0
0
0
0.1041
0.1551


8
0
0
0
0
0.5536
0
0
0
0.6046


8
0
0
0
0.2
0
0
0
0
0.251


8
0
0
0
0
0
0
0
0
0


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0.625
0
0
0
0
0
0
0.6633


9
0
0
0.625
0
0
0
0
0
0.6633


9
0.625
0
0
0
0
0
0
0
0.6633


9
0
0
0
0
0
0.625
0
0
0.6633


9
0
0
0
0
0
0
0
0.1175
0.1558


9
0
0
0
0
0.625
0
0
0
0.6633


9
0
0
0
0.2
0
0
0
0
0.2383


9
0
0
0
0
0
0
0
0
0


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0.125
0
0
0
0
1.25
0
1.5025


10 
0
0
0.125
0
0
0
1.25
0
1.5025


10 
0.125
0
0
0
0
0
1.25
0
1.5025


10 
0
0
0
0
0
0.125
1.25
0
1.5025


10 
0
0
0
0
0
0
1.25
0.0235
1.401


10 
0
0
0
0
0.125
0
1.25
0
1.5025


10 
0
0
0
0.2
0
0
1.25
0
1.5775


10 
0
0
0
0
0
0
0
0
0.384


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0.2083
0
0
0
0
1.25
0
1.571


11 
0
0
0.2083
0
0
0
1.25
0
1.571


11 
0.2083
0
0
0
0
0
1.25
0
1.571


11 
0
0
0
0
0
0.2083
1.25
0
1.571


11 
0
0
0
0
0
0
1.25
0.0392
1.4018


11 
0
0
0
0
0.2083
0
1.25
0
1.571


11 
0
0
0
0.2
0
0
1.25
0
1.5626


11 
0
0
0
0
0
0
0
0
0


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0.2917
0
0
0
0
1.25
0
1.6394


12 
0
0
0.2917
0
0
0
1.25
0
1.6394


12 
0.2917
0
0
0
0
0
1.25
0
1.6394


12 
0
0
0
0
0
0.2917
1.25
0
1.6394


12 
0
0
0
0
0
0
1.25
0.0548
1.4026


12 
0
0
0
0
0.2917
0
1.25
0
1.6394


12 
0
0
0
0.2
0
0
1.25
0
1.5478


12 
0
0
0
0
0
0
0
0
0


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0.375
0
0
0
0
1.25
0
1.7079


13 
0
0
0.375
0
0
0
1.25
0
1.7079


13 
0.375
0
0
0
0
0
1.25
0
1.7079


13 
0
0
0
0
0
0.375
1.25
0
1.7079


13 
0
0
0
0
0
0
1.25
0.0705
1.4034


13 
0
0
0
0
0.375
0
1.25
0
1.7079


13 
0
0
0
0.2
0
0
1.25
0
1.5329


13 
0
0
0
0
0
0
0
0
0.768


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0.4583
0
0
0
0
1.25
0
1.7763


14 
0
0
0.4583
0
0
0
1.25
0
1.7763


14 
0.4583
0
0
0
0
0
1.25
0
1.7763


14 
0
0
0
0
0
0.4583
1.25
0
1.7763


14 
0
0
0
0
0
0
1.25
0.0862
1.4042


14 
0
0
0
0
0.4583
0
1.25
0
1.7763


14 
0
0
0
0.2
0
0
1.25
0
1.518


14 
0
0
0
0
0
0
0
0
0


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0.5417
0
0
0
0
1.25
0
1.8448


15 
0
0
0.5417
0
0
0
1.25
0
1.8448


15 
0.5417
0
0
0
0
0
1.25
0
1.8448


15 
0
0
0
0
0
0.5417
1.25
0
1.8448


15 
0
0
0
0
0
0
1.25
0.1018
1.405


15 
0
0
0
0
0.5417
0
1.25
0
1.8448


15 
0
0
0
0.2
0
0
1.25
0
1.5031


15 
0
0
0
0
0
0
0
0
0


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0.625
0
0
0
0
1.25
0
1.9133


16 
0
0
0.625
0
0
0
1.25
0
1.9133


16 
0.625
0
0
0
0
0
1.25
0
1.9133


16 
0
0
0
0
0
0.625
1.25
0
1.9133


16 
0
0
0
0
0
0
1.25
0.1175
1.4058


16 
0
0
0
0
0.625
0
1.25
0
1.9133


16 
0
0
0
0.2
0
0
1.25
0
1.4883


16 
0
0
0
0
0
0
0
0
0.384


Temperature


260 C.


1
0
0
0
0
0
0
0
0
0.384


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0.768


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0.384


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0.768


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0.384


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0.768


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0
0
0
0
0
0
0
0.1275


2
0
0.125
0
0
0
0
0
0
0.2525


2
0
0
0.125
0
0
0
0
0
0.2525


2
0.125
0
0
0
0
0
0
0
0.2525


2
0
0
0
0
0
0.125
0
0
0.2525


2
0
0
0
0
0
0
0
0.0235
0.151


2
0
0
0
0
0.125
0
0
0
0.2525


2
0
0
0
0.2
0
0
0
0
0.3275


2
0
0
0
0
0
0
0
0
0


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0
0
0
0
0
0
0
0.1148


3
0
0.1964
0
0
0
0
0
0
0.3112


3
0
0
0.1964
0
0
0
0
0
0.3112


3
0.1964
0
0
0
0
0
0
0
0.3112


3
0
0
0
0
0
0.1964
0
0
0.3112


3
0
0
0
0
0
0
0
0.0369
0.1517


3
0
0
0
0
0.1964
0
0
0
0.3112


3
0
0
0
0.2
0
0
0
0
0.3148


3
0
0
0
0
0
0
0
0
0


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0
0
0
0
0
0
0
0.102


4
0
0.2679
0
0
0
0
0
0
0.3699


4
0
0
0.2679
0
0
0
0
0
0.3699


4
0.2679
0
0
0
0
0
0
0
0.3699


4
0
0
0
0
0
0.2679
0
0
0.3699


4
0
0
0
0
0
0
0
0.0504
0.1524


4
0
0
0
0
0.2679
0
0
0
0.3699


4
0
0
0
0.2
0
0
0
0
0.302


4
0
0
0
0
0
0
0
0
0.384


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0
0
0
0
0
0
0
0.0893


5
0
0.3393
0
0
0
0
0
0
0.4285


5
0
0
0.3393
0
0
0
0
0
0.4285


5
0.3393
0
0
0
0
0
0
0
0.4285


5
0
0
0
0
0
0.3393
0
0
0.4285


5
0
0
0
0
0
0
0
0.0638
0.153


5
0
0
0
0
0.3393
0
0
0
0.4285


5
0
0
0
0.2
0
0
0
0
0.2893


5
0
0
0
0
0
0
0
0
0


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0
0
0
0
0
0
0
0.0765


6
0
0.4107
0
0
0
0
0
0
0.4872


6
0
0
0.4107
0
0
0
0
0
0.4872


6
0.4107
0
0
0
0
0
0
0
0.4872


6
0
0
0
0
0
0.4107
0
0
0.4872


6
0
0
0
0
0
0
0
0.0772
0.1537


6
0
0
0
0
0.4107
0
0
0
0.4872


6
0
0
0
0.2
0
0
0
0
0.2765


6
0
0
0
0
0
0
0
0
0


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0
0
0
0
0
0
0
0.0638


7
0
0.4821
0
0
0
0
0
0
0.5459


7
0
0
0.4821
0
0
0
0
0
0.5459


7
0.4821
0
0
0
0
0
0
0
0.5459


7
0
0
0
0
0
0.4821
0
0
0.5459


7
0
0
0
0
0
0
0
0.0906
0.1544


7
0
0
0
0
0.4821
0
0
0
0.5459


7
0
0
0
0.2
0
0
0
0
0.2638


7
0
0
0
0
0
0
0
0
0.768


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0
0
0
0
0
0
0
0.051


8
0
0.5536
0
0
0
0
0
0
0.6046


8
0
0
0.5536
0
0
0
0
0
0.6046


8
0.5536
0
0
0
0
0
0
0
0.6046


8
0
0
0
0
0
0.5536
0
0
0.6046


8
0
0
0
0
0
0
0
0.1041
0.1551


8
0
0
0
0
0.5536
0
0
0
0.6046


8
0
0
0
0.2
0
0
0
0
0.251


8
0
0
0
0
0
0
0
0
0


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0
0
0
0
0
0
0
0.0383


9
0
0.625
0
0
0
0
0
0
0.6633


9
0
0
0.625
0
0
0
0
0
0.6633


9
0.625
0
0
0
0
0
0
0
0.6633


9
0
0
0
0
0
0.625
0
0
0.6633


9
0
0
0
0
0
0
0
0.1175
0.1558


9
0
0
0
0
0.625
0
0
0
0.6633


9
0
0
0
0.2
0
0
0
0
0.2383


9
0
0
0
0
0
0
0
0
0


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0
0
0
0
0
1.25
0
1.3775


10 
0
0.125
0
0
0
0
1.25
0
1.5025


10 
0
0
0.125
0
0
0
1.25
0
1.5025


10 
0.125
0
0
0
0
0
1.25
0
1.5025


10 
0
0
0
0
0
0.125
1.25
0
1.5025


10 
0
0
0
0
0
0
1.25
0.0235
1.401


10 
0
0
0
0
0.125
0
1.25
0
1.5025


10 
0
0
0
0.2
0
0
1.25
0
1.5775


10 
0
0
0
0
0
0
0
0
0.384


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0
0
0
0
0
1.25
0
1.3626


11 
0
0.2083
0
0
0
0
1.25
0
1.571


11 
0
0
0.2083
0
0
0
1.25
0
1.571


11 
0.2083
0
0
0
0
0
1.25
0
1.571


11 
0
0
0
0
0
0.2083
1.25
0
1.571


11 
0
0
0
0
0
0
1.25
0.0392
1.4018


11 
0
0
0
0
0.2083
0
1.25
0
1.571


11 
0
0
0
0.2
0
0
1.25
0
1.5626


11 
0
0
0
0
0
0
0
0
0


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0
0
0
0
0
1.25
0
1.3478


12 
0
0.2917
0
0
0
0
1.25
0
1.6394


12 
0
0
0.2917
0
0
0
1.25
0
1.6394


12 
0.2917
0
0
0
0
0
1.25
0
1.6394


12 
0
0
0
0
0
0.2917
1.25
0
1.6394


12 
0
0
0
0
0
0
1.25
0.0548
1.4026


12 
0
0
0
0
0.2917
0
1.25
0
1.6394


12 
0
0
0
0.2
0
0
1.25
0
1.5478


12 
0
0
0
0
0
0
0
0
0


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0
0
0
0
0
1.25
0
1.3329


13 
0
0.375
0
0
0
0
1.25
0
1.7079


13 
0
0
0.375
0
0
0
1.25
0
1.7079


13 
0.375
0
0
0
0
0
1.25
0
1.7079


13 
0
0
0
0
0
0.375
1.25
0
1.7079


13 
0
0
0
0
0
0
1.25
0.0705
1.4034


13 
0
0
0
0
0.375
0
1.25
0
1.7079


13 
0
0
0
0.2
0
0
1.25
0
1.5329


13 
0
0
0
0
0
0
0
0
0.768


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0
0
0
0
0
1.25
0
1.318


14 
0
0.4583
0
0
0
0
1.25
0
1.7763


14 
0
0
0.4583
0
0
0
1.25
0
1.7763


14 
0.4583
0
0
0
0
0
1.25
0
1.7763


14 
0
0
0
0
0
0.4583
1.25
0
1.7763


14 
0
0
0
0
0
0
1.25
0.0862
1.4042


14 
0
0
0
0
0.4583
0
1.25
0
1.7763


14 
0
0
0
0.2
0
0
1.25
0
1.518


14 
0
0
0
0
0
0
0
0
0


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0
0
0
0
0
1.25
0
1.3031


15 
0
0.5417
0
0
0
0
1.25
0
1.8448


15 
0
0
0.5417
0
0
0
1.25
0
1.8448


15 
0.5417
0
0
0
0
0
1.25
0
1.8448


15 
0
0
0
0
0
0.5417
1.25
0
1.8448


15 
0
0
0
0
0
0
1.25
0.1018
1.405


15 
0
0
0
0
0.5417
0
1.25
0
1.8448


15 
0
0
0
0.2
0
0
1.25
0
1.5031


15 
0
0
0
0
0
0
0
0
0


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0
0
0
0
0
1.25
0
1.2883


16 
0
0.625
0
0
0
0
1.25
0
1.9133


16 
0
0
0.625
0
0
0
1.25
0
1.9133


16 
0.625
0
0
0
0
0
1.25
0
1.9133


16 
0
0
0
0
0
0.625
1.25
0
1.9133


16 
0
0
0
0
0
0
1.25
0.1175
1.4058


16 
0
0
0
0
0.625
0
1.25
0
1.9133


16 
0
0
0
0.2
0
0
1.25
0
1.4883


16 
0
0
0
0
0
0
0
0
0.384





















mol %
mol %
mol %
mol %
mol %
mol %
mol %
mol %
mol %
mol %


R
Pt
shift
Ce
Co
Fe
Au
La
Mo
Na
Pd





Temperature


200 C.


1
100
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
100
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
100
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
100
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
100
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
100
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
50.5
0
0
49.5
0
0
0
0
0
0


2
50.5
0
0
0
49.5
0
0
0
0
0


2
50.5
0
49.5
0
0
0
0
0
0
0


2
50.5
0
0
0
0
0
0
49.5
0
0


2
84.44
0
0
0
0
0
0
0
0
15.56


2
50.5
0
0
0
0
0
49.5
0
0
0


2
38.93
0
0
0
0
61.07
0
0
0
0


2
0
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
36.88
0
0
63.12
0
0
0
0
0
0


3
36.88
0
0
0
63.12
0
0
0
0
0


3
36.88
0
63.12
0
0
0
0
0
0
0


3
36.88
0
0
0
0
0
0
63.12
0
0


3
75.65
0
0
0
0
0
0
0
0
24.35


3
36.88
0
0
0
0
0
63.12
0
0
0


3
36.46
0
0
0
0
63.54
0
0
0
0


3
0
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
27.58
0
0
72.42
0
0
0
0
0
0


4
27.58
0
0
0
72.42
0
0
0
0
0


4
27.58
0
72.42
0
0
0
0
0
0
0


4
27.58
0
0
0
0
0
0
72.42
0
0


4
66.95
0
0
0
0
0
0
0
0
33.05


4
27.58
0
0
0
0
0
72.42
0
0
0


4
33.77
0
0
0
0
66.23
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
20.83
0
0
79.17
0
0
0
0
0
0


5
20.83
0
0
0
79.17
0
0
0
0
0


5
20.83
0
79.17
0
0
0
0
0
0
0


5
20.83
0
0
0
0
0
0
79.17
0
0


5
58.32
0
0
0
0
0
0
0
0
41.68


5
20.83
0
0
0
0
0
79.17
0
0
0


5
30.86
0
0
0
0
69.14
0
0
0
0


5
0
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
15.7
0
0
84.3
0
0
0
0
0
0


6
15.7
0
0
0
84.3
0
0
0
0
0


6
15.7
0
84.3
0
0
0
0
0
0
0


6
15.7
0
0
0
0
0
0
84.3
0
0


6
49.77
0
0
0
0
0
0
0
0
50.23


6
15.7
0
0
0
0
0
84.3
0
0
0


6
27.67
0
0
0
0
72.33
0
0
0
0


6
0
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
11.68
0
0
88.32
0
0
0
0
0
0


7
11.68
0
0
0
88.32
0
0
0
0
0


7
11.68
0
88.32
0
0
0
0
0
0
0


7
11.68
0
0
0
0
0
0
88.32
0
0


7
41.29
0
0
0
0
0
0
0
0
58.71


7
11.68
0
0
0
0
0
88.32
0
0
0


7
24.17
0
0
0
0
75.83
0
0
0
0


7
0
100
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
8.44
0
0
91.56
0
0
0
0
0
0


8
8.44
0
0
0
91.56
0
0
0
0
0


8
8.44
0
91.56
0
0
0
0
0
0
0


8
8.44
0
0
0
0
0
0
91.56
0
0


8
32.89
0
0
0
0
0
0
0
0
67.11


8
8.44
0
0
0
0
0
91.56
0
0
0


8
20.32
0
0
0
0
79.68
0
0
0
0


8
0
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
5.77
0
0
94.23
0
0
0
0
0
0


9
5.77
0
0
0
94.23
0
0
0
0
0


9
5.77
0
94.23
0
0
0
0
0
0
0


9
5.77
0
0
0
0
0
0
94.23
0
0


9
24.56
0
0
0
0
0
0
0
0
75.44


9
5.77
0
0
0
0
0
94.23
0
0
0


9
16.05
0
0
0
0
83.95
0
0
0
0


9
0
0
0
0
0
0
0
0
0
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
8.49
0
0
8.32
0
0
0
0
83.19
0


10 
8.49
0
0
0
8.32
0
0
0
83.19
0


10 
8.49
0
8.32
0
0
0
0
0
83.19
0


10 
8.49
0
0
0
0
0
0
8.32
83.19
0


10 
9.1
0
0
0
0
0
0
0
89.22
1.68


10 
8.49
0
0
0
0
0
8.32
0
83.19
0


10 
8.08
0
0
0
0
12.68
0
0
79.24
0


10 
100
0
0
0
0
0
0
0
0
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
7.17
0
0
13.26
0
0
0
0
79.57
0


11 
7.17
0
0
0
13.26
0
0
0
79.57
0


11 
7.17
0
13.26
0
0
0
0
0
79.57
0


11 
7.17
0
0
0
0
0
0
13.26
79.57
0


11 
8.03
0
0
0
0
0
0
0
89.17
2.79


11 
7.17
0
0
0
0
0
13.26
0
79.57
0


11 
7.21
0
0
0
0
12.8
0
0
79.99
0


11 
0
0
0
0
0
0
0
0
0
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
5.96
0
0
17.79
0
0
0
0
76.25
0


12 
5.96
0
0
0
17.79
0
0
0
76.25
0


12 
5.96
0
17.79
0
0
0
0
0
76.25
0


12 
5.96
0
0
0
0
0
0
17.79
76.25
0


12 
6.97
0
0
0
0
0
0
0
89.12
3.91


12 
5.96
0
0
0
0
0
17.79
0
76.25
0


12 
6.32
0
0
0
0
12.92
0
0
80.76
0


12 
0
0
0
0
0
0
0
0
0
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
4.85
0
0
21.96
0
0
0
0
73.19
0


13 
4.85
0
0
0
21.96
0
0
0
73.19
0


13 
4.85
0
21.96
0
0
0
0
0
73.19
0


13 
4.85
0
0
0
0
0
0
21.96
73.19
0


13 
5.91
0
0
0
0
0
0
0
89.07
5.02


13 
4.85
0
0
0
0
0
21.96
0
73.19
0


13 
5.41
0
0
0
0
13.05
0
0
81.55
0


13 
0
100
0
0
0
0
0
0
0
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
3.83
0
0
25.8
0
0
0
0
70.37
0


14 
3.83
0
0
0
25.8
0
0
0
70.37
0


14 
3.83
0
25.8
0
0
0
0
0
70.37
0


14 
3.83
0
0
0
0
0
0
25.8
70.37
0


14 
4.84
0
0
0
0
0
0
0
89.02
6.14


14 
3.83
0
0
0
0
0
25.8
0
70.37
0


14 
4.48
0
0
0
0
13.18
0
0
82.35
0


14 
0
0
0
0
0
0
0
0
0
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
2.88
0
0
29.36
0
0
0
0
67.76
0


15 
2.88
0
0
0
29.36
0
0
0
67.76
0


15 
2.88
0
29.36
0
0
0
0
0
67.76
0


15 
2.88
0
0
0
0
0
0
29.36
67.76
0


15 
3.78
0
0
0
0
0
0
0
88.97
7.25


15 
2.88
0
0
0
0
0
29.36
0
67.76
0


15 
3.53
0
0
0
0
13.31
0
0
83.16
0


15 
0
0
0
0
0
0
0
0
0
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2
0
0
32.67
0
0
0
0
65.33
0


16 
2
0
0
0
32.67
0
0
0
65.33
0


16 
2
0
32.67
0
0
0
0
0
65.33
0


16 
2
0
0
0
0
0
0
32.67
65.33
0


16 
2.72
0
0
0
0
0
0
0
88.92
8.36


16 
2
0
0
0
0
0
32.67
0
65.33
0


16 
2.57
0
0
0
0
13.44
0
0
83.99
0


16 
100
0
0
0
0
0
0
0
0
0


Temperature


230 C.


1
100
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
100
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
100
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
100
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
100
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
100
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
50.5
0
0
49.5
0
0
0
0
0
0


2
50.5
0
0
0
49.5
0
0
0
0
0


2
50.5
0
49.5
0
0
0
0
0
0
0


2
50.5
0
0
0
0
0
0
49.5
0
0


2
84.44
0
0
0
0
0
0
0
0
15.56


2
50.5
0
0
0
0
0
49.5
0
0
0


2
38.93
0
0
0
0
61.07
0
0
0
0


2
0
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
36.88
0
0
63.12
0
0
0
0
0
0


3
36.88
0
0
0
63.12
0
0
0
0
0


3
36.88
0
63.12
0
0
0
0
0
0
0


3
36.88
0
0
0
0
0
0
63.12
0
0


3
75.65
0
0
0
0
0
0
0
0
24.35


3
36.88
0
0
0
0
0
63.12
0
0
0


3
36.46
0
0
0
0
63.54
0
0
0
0


3
0
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
27.58
0
0
72.42
0
0
0
0
0
0


4
27.58
0
0
0
72.42
0
0
0
0
0


4
27.58
0
72.42
0
0
0
0
0
0
0


4
27.58
0
0
0
0
0
0
72.42
0
0


4
66.95
0
0
0
0
0
0
0
0
33.05


4
27.58
0
0
0
0
0
72.42
0
0
0


4
33.77
0
0
0
0
66.23
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
20.83
0
0
79.17
0
0
0
0
0
0


5
20.83
0
0
0
79.17
0
0
0
0
0


5
20.83
0
79.17
0
0
0
0
0
0
0


5
20.83
0
0
0
0
0
0
79.17
0
0


5
58.32
0
0
0
0
0
0
0
0
41.68


5
20.83
0
0
0
0
0
79.17
0
0
0


5
30.86
0
0
0
0
69.14
0
0
0
0


5
0
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
15.7
0
0
84.3
0
0
0
0
0
0


6
15.7
0
0
0
84.3
0
0
0
0
0


6
15.7
0
84.3
0
0
0
0
0
0
0


6
15.7
0
0
0
0
0
0
84.3
0
0


6
49.77
0
0
0
0
0
0
0
0
50.23


6
15.7
0
0
0
0
0
84.3
0
0
0


6
27.67
0
0
0
0
72.33
0
0
0
0


6
0
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
11.68
0
0
88.32
0
0
0
0
0
0


7
11.68
0
0
0
88.32
0
0
0
0
0


7
11.68
0
88.32
0
0
0
0
0
0
0


7
11.68
0
0
0
0
0
0
88.32
0
0


7
41.29
0
0
0
0
0
0
0
0
58.71


7
11.68
0
0
0
0
0
88.32
0
0
0


7
24.17
0
0
0
0
75.83
0
0
0
0


7
0
100
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
8.44
0
0
91.56
0
0
0
0
0
0


8
8.44
0
0
0
91.56
0
0
0
0
0


8
8.44
0
91.56
0
0
0
0
0
0
0


8
8.44
0
0
0
0
0
0
91.56
0
0


8
32.89
0
0
0
0
0
0
0
0
67.11


8
8.44
0
0
0
0
0
91.56
0
0
0


8
20.32
0
0
0
0
79.68
0
0
0
0


8
0
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
5.77
0
0
94.23
0
0
0
0
0
0


9
5.77
0
0
0
94.23
0
0
0
0
0


9
5.77
0
94.23
0
0
0
0
0
0
0


9
5.77
0
0
0
0
0
0
94.23
0
0


9
24.56
0
0
0
0
0
0
0
0
75.44


9
5.77
0
0
0
0
0
94.23
0
0
0


9
16.05
0
0
0
0
83.95
0
0
0
0


9
0
0
0
0
0
0
0
0
0
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
8.49
0
0
8.32
0
0
0
0
83.19
0


10 
8.49
0
0
0
8.32
0
0
0
83.19
0


10 
8.49
0
8.32
0
0
0
0
0
83.19
0


10 
8.49
0
0
0
0
0
0
8.32
83.19
0


10 
9.1
0
0
0
0
0
0
0
89.22
1.68


10 
8.49
0
0
0
0
0
8.32
0
83.19
0


10 
8.08
0
0
0
0
12.68
0
0
79.24
0


10 
100
0
0
0
0
0
0
0
0
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
7.17
0
0
13.26
0
0
0
0
79.57
0


11 
7.17
0
0
0
13.26
0
0
0
79.57
0


11 
7.17
0
13.26
0
0
0
0
0
79.57
0


11 
7.17
0
0
0
0
0
0
13.26
79.57
0


11 
8.03
0
0
0
0
0
0
0
89.17
2.79


11 
7.17
0
0
0
0
0
13.26
0
79.57
0


11 
7.21
0
0
0
0
12.8
0
0
79.99
0


11 
0
0
0
0
0
0
0
0
0
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
5.96
0
0
17.79
0
0
0
0
76.25
0


12 
5.96
0
0
0
17.79
0
0
0
76.25
0


12 
5.96
0
17.79
0
0
0
0
0
76.25
0


12 
5.96
0
0
0
0
0
0
17.79
76.25
0


12 
6.97
0
0
0
0
0
0
0
89.12
3.91


12 
5.96
0
0
0
0
0
17.79
0
76.25
0


12 
6.32
0
0
0
0
12.92
0
0
80.76
0


12 
0
0
0
0
0
0
0
0
0
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
4.85
0
0
21.96
0
0
0
0
73.19
0


13 
4.85
0
0
0
21.96
0
0
0
73.19
0


13 
4.85
0
21.96
0
0
0
0
0
73.19
0


13 
4.85
0
0
0
0
0
0
21.96
73.19
0


13 
5.91
0
0
0
0
0
0
0
89.07
5.02


13 
4.85
0
0
0
0
0
21.96
0
73.19
0


13 
5.41
0
0
0
0
13.05
0
0
81.55
0


13 
0
100
0
0
0
0
0
0
0
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
3.83
0
0
25.8
0
0
0
0
70.37
0


14 
3.83
0
0
0
25.8
0
0
0
70.37
0


14 
3.83
0
25.8
0
0
0
0
0
70.37
0


14 
3.83
0
0
0
0
0
0
25.8
70.37
0


14 
4.84
0
0
0
0
0
0
0
89.02
6.14


14 
3.83
0
0
0
0
0
25.8
0
70.37
0


14 
4.48
0
0
0
0
13.18
0
0
82.35
0


14 
0
0
0
0
0
0
0
0
0
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
2.88
0
0
29.36
0
0
0
0
67.76
0


15 
2.88
0
0
0
29.36
0
0
0
67.76
0


15 
2.88
0
29.36
0
0
0
0
0
67.76
0


15 
2.88
0
0
0
0
0
0
29.36
67.76
0


15 
3.78
0
0
0
0
0
0
0
88.97
7.25


15 
2.88
0
0
0
0
0
29.36
0
67.76
0


15 
3.53
0
0
0
0
13.31
0
0
83.16
0


15 
0
0
0
0
0
0
0
0
0
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2
0
0
32.67
0
0
0
0
65.33
0


16 
2
0
0
0
32.67
0
0
0
65.33
0


16 
2
0
32.67
0
0
0
0
0
65.33
0


16 
2
0
0
0
0
0
0
32.67
65.33
0


16 
2.72
0
0
0
0
0
0
0
88.92
8.36


16 
2
0
0
0
0
0
32.67
0
65.33
0


16 
2.57
0
0
0
0
13.44
0
0
83.99
0


16 
100
0
0
0
0
0
0
0
0
0


Temperature


260 C.


1
100
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
100
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
100
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
100
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
100
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
0
0
0
0
0
0
0
0
0


1
0
100
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
100
0
0
0
0
0
0
0
0
0


2
50.5
0
0
49.5
0
0
0
0
0
0


2
50.5
0
0
0
49.5
0
0
0
0
0


2
50.5
0
49.5
0
0
0
0
0
0
0


2
50.5
0
0
0
0
0
0
49.5
0
0


2
84.44
0
0
0
0
0
0
0
0
15.56


2
50.5
0
0
0
0
0
49.5
0
0
0


2
38.93
0
0
0
0
61.07
0
0
0
0


2
0
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
100
0
0
0
0
0
0
0
0
0


3
36.88
0
0
63.12
0
0
0
0
0
0


3
36.88
0
0
0
63.12
0
0
0
0
0


3
36.88
0
63.12
0
0
0
0
0
0
0


3
36.88
0
0
0
0
0
0
63.12
0
0


3
75.65
0
0
0
0
0
0
0
0
24.35


3
36.88
0
0
0
0
0
63.12
0
0
0


3
36.46
0
0
0
0
63.54
0
0
0
0


3
0
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


4
27.58
0
0
72.42
0
0
0
0
0
0


4
27.58
0
0
0
72.42
0
0
0
0
0


4
27.58
0
72.42
0
0
0
0
0
0
0


4
27.58
0
0
0
0
0
0
72.42
0
0


4
66.95
0
0
0
0
0
0
0
0
33.05


4
27.58
0
0
0
0
0
72.42
0
0
0


4
33.77
0
0
0
0
66.23
0
0
0
0


4
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
100
0
0
0
0
0
0
0
0
0


5
20.83
0
0
79.17
0
0
0
0
0
0


5
20.83
0
0
0
79.17
0
0
0
0
0


5
20.83
0
79.17
0
0
0
0
0
0
0


5
20.83
0
0
0
0
0
0
79.17
0
0


5
58.32
0
0
0
0
0
0
0
0
41.68


5
20.83
0
0
0
0
0
79.17
0
0
0


5
30.86
0
0
0
0
69.14
0
0
0
0


5
0
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
100
0
0
0
0
0
0
0
0
0


6
15.7
0
0
84.3
0
0
0
0
0
0


6
15.7
0
0
0
84.3
0
0
0
0
0


6
15.7
0
84.3
0
0
0
0
0
0
0


6
15.7
0
0
0
0
0
0
84.3
0
0


6
49.77
0
0
0
0
0
0
0
0
50.23


6
15.7
0
0
0
0
0
84.3
0
0
0


6
27.67
0
0
0
0
72.33
0
0
0
0


6
0
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
100
0
0
0
0
0
0
0
0
0


7
11.68
0
0
88.32
0
0
0
0
0
0


7
11.68
0
0
0
88.32
0
0
0
0
0


7
11.68
0
88.32
0
0
0
0
0
0
0


7
11.68
0
0
0
0
0
0
88.32
0
0


7
41.29
0
0
0
0
0
0
0
0
58.71


7
11.68
0
0
0
0
0
88.32
0
0
0


7
24.17
0
0
0
0
75.83
0
0
0
0


7
0
100
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
100
0
0
0
0
0
0
0
0
0


8
8.44
0
0
91.56
0
0
0
0
0
0


8
8.44
0
0
0
91.56
0
0
0
0
0


8
8.44
0
91.56
0
0
0
0
0
0
0


8
8.44
0
0
0
0
0
0
91.56
0
0


8
32.89
0
0
0
0
0
0
0
0
67.11


8
8.44
0
0
0
0
0
91.56
0
0
0


8
20.32
0
0
0
0
79.68
0
0
0
0


8
0
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
100
0
0
0
0
0
0
0
0
0


9
5.77
0
0
94.23
0
0
0
0
0
0


9
5.77
0
0
0
94.23
0
0
0
0
0


9
5.77
0
94.23
0
0
0
0
0
0
0


9
5.77
0
0
0
0
0
0
94.23
0
0


9
24.56
0
0
0
0
0
0
0
0
75.44


9
5.77
0
0
0
0
0
94.23
0
0
0


9
16.05
0
0
0
0
83.95
0
0
0
0


9
0
0
0
0
0
0
0
0
0
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
9.26
0
0
0
0
0
0
0
90.74
0


10 
8.49
0
0
8.32
0
0
0
0
83.19
0


10 
8.49
0
0
0
8.32
0
0
0
83.19
0


10 
8.49
0
8.32
0
0
0
0
0
83.19
0


10 
8.49
0
0
0
0
0
0
8.32
83.19
0


10 
9.1
0
0
0
0
0
0
0
89.22
1.68


10 
8.49
0
0
0
0
0
8.32
0
83.19
0


10 
8.08
0
0
0
0
12.68
0
0
79.24
0


10 
100
0
0
0
0
0
0
0
0
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
8.27
0
0
0
0
0
0
0
91.73
0


11 
7.17
0
0
13.26
0
0
0
0
79.57
0


11 
7.17
0
0
0
13.26
0
0
0
79.57
0


11 
7.17
0
13.26
0
0
0
0
0
79.57
0


11 
7.17
0
0
0
0
0
0
13.26
79.57
0


11 
8.03
0
0
0
0
0
0
0
89.17
2.79


11 
7.17
0
0
0
0
0
13.26
0
79.57
0


11 
7.21
0
0
0
0
12.8
0
0
79.99
0


11 
0
0
0
0
0
0
0
0
0
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
7.25
0
0
0
0
0
0
0
92.75
0


12 
5.96
0
0
17.79
0
0
0
0
76.25
0


12 
5.96
0
0
0
17.79
0
0
0
76.25
0


12 
5.96
0
17.79
0
0
0
0
0
76.25
0


12 
5.96
0
0
0
0
0
0
17.79
76.25
0


12 
6.97
0
0
0
0
0
0
0
89.12
3.91


12 
5.96
0
0
0
0
0
17.79
0
76.25
0


12 
6.32
0
0
0
0
12.92
0
0
80.76
0


12 
0
0
0
0
0
0
0
0
0
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
6.22
0
0
0
0
0
0
0
93.78
0


13 
4.85
0
0
21.96
0
0
0
0
73.19
0


13 
4.85
0
0
0
21.96
0
0
0
73.19
0


13 
4.85
0
21.96
0
0
0
0
0
73.19
0


13 
4.85
0
0
0
0
0
0
21.96
73.19
0


13 
5.91
0
0
0
0
0
0
0
89.07
5.02


13 
4.85
0
0
0
0
0
21.96
0
73.19
0


13 
5.41
0
0
0
0
13.05
0
0
81.55
0


13 
0
100
0
0
0
0
0
0
0
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
5.16
0
0
0
0
0
0
0
94.84
0


14 
3.83
0
0
25.8
0
0
0
0
70.37
0


14 
3.83
0
0
0
25.8
0
0
0
70.37
0


14 
3.83
0
25.8
0
0
0
0
0
70.37
0


14 
3.83
0
0
0
0
0
0
25.8
70.37
0


14 
4.84
0
0
0
0
0
0
0
89.02
6.14


14 
3.83
0
0
0
0
0
25.8
0
70.37
0


14 
4.48
0
0
0
0
13.18
0
0
82.35
0


14 
0
0
0
0
0
0
0
0
0
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
4.08
0
0
0
0
0
0
0
95.92
0


15 
2.88
0
0
29.36
0
0
0
0
67.76
0


15 
2.88
0
0
0
29.36
0
0
0
67.76
0


15 
2.88
0
29.36
0
0
0
0
0
67.76
0


15 
2.88
0
0
0
0
0
0
29.36
67.76
0


15 
3.78
0
0
0
0
0
0
0
88.97
7.25


15 
2.88
0
0
0
0
0
29.36
0
67.76
0


15 
3.53
0
0
0
0
13.31
0
0
83.16
0


15 
0
0
0
0
0
0
0
0
0
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2.97
0
0
0
0
0
0
0
97.03
0


16 
2
0
0
32.67
0
0
0
0
65.33
0


16 
2
0
0
0
32.67
0
0
0
65.33
0


16 
2
0
32.67
0
0
0
0
0
65.33
0


16 
2
0
0
0
0
0
0
32.67
65.33
0


16 
2.72
0
0
0
0
0
0
0
88.92
8.36


16 
2
0
0
0
0
0
32.67
0
65.33
0


16 
2.57
0
0
0
0
13.44
0
0
83.99
0


16 
100
0
0
0
0
0
0
0
0
0










[0279]

11



















TABLE III















Pt1.0%/ZrO2









R
C
COCONV
H2OCONV
CO2PROD
CO2PERPROD
CH4PROD
std
LaNO33
PtNH32NO22
ZrONO32


mol %


real
real
real
real
real
real
real
real
real
real
real
SUM_micromols
mol % La
Pt
mol % Zr





























Temperature:
















250 C.


1
1
24.0554
20.3567
1.0059
36.8713
0.1785
0.1275
0
0
0
0.1275
0
100
0


1
2
−1.7201
3.3539
0.049
1.7972
0.0067
0
0
0
0
0
0
0
0


1
3
−1.3278
2.2499
0.0009
0.0315
−0.0026
0
0
0
0
0
0
0
0


1
4
−1.208
2.4958
0.005
0.1823
−0.0038
0
0
0
0
0
0
0
0


1
5
−1.3966
−0.6647
0.0138
0.5067
−0.0024
0
0
0
0
0
0
0
0


1
6
−0.857
−0.806
0.0089
0.3249
−0.0058
0
0
0
0
0
0
0
0


1
7
26.8747
16.7142
0.9416
34.513
0.151
0.1275
0
0
0
0.1275
0
100
0


1
8
−0.1762
0.0001
0.0106
0.3868
−0.0076
0
0
0
0
0
0
0
0


1
9
−0.605
−1.4054
0.0016
0.0598
−0.0081
0
0
0
0
0
0
0
0


1
10
−0.1705
5.1803
−0.0005
−0.0171
−0.0108
0
0
0
0
0
0
0
0


1
11
0.0287
−2.3403
−0.0261
−0.9568
−0.0134
0
0
0
0
0
0
0
0


1
12
−0.3619
−2.3753
−0.0191
−0.6997
−0.0107
0
0
0
0
0
0
0
0


1
13
26.9134
15.6985
0.9206
33.7449
0.1456
0.1275
0
0
0
0.1275
0
100
0


1
14
0.2866
−1.4436
0.0104
0.3794
−0.0009
0
0
0
0
0
0
0
0


1
15
−0.2691
−2.5021
−0.0098
−0.3592
−0.0125
0
0
0
0
0
0
0
0


1
16
26.3015
15.0776
0.9071
33.2485
0.1422
0.1275
0
0
0
0.1275
0
100
0


2
1
10.3797
7.5635
0.2714
9.9469
0.0465
0
0
0.0319
0
0.0319
0
100
0


2
2
22.2742
13.6256
0.7038
25.7961
0.1014
0
0
0.0319
0
0.0319
0
100
0


2
3
20.1518
11.8043
0.6181
22.6557
0.0925
0
0
0.0319
0
0.0319
0
100
0


2
4
14.7068
7.5278
0.4396
16.1127
0.074
0
0
0.0319
0
0.0319
0
100
0


2
5
12.5748
6.9812
0.3538
12.9691
0.0619
0
0
0.0319
0
0.0319
0
100
0


2
6
12.5733
7.5902
0.3721
13.6375
0.065
0
0
0.0319
0
0.0319
0
100
0


2
7
3.9682
1.1157
0.1053
3.861
0.0291
0
0
0.0319
0
0.0319
0
100
0


2
8
4.2902
1.5276
0.1017
3.728
0.0316
0
0
0.0319
0
0.0319
0
100
0


2
9
17.5859
9.8527
0.5611
20.5685
0.0868
0
0
0.0319
0
0.0319
0
100
0


2
10
4.0056
0.7967
0.1073
3.9343
0.0337
0
0
0.0319
0
0.0319
0
100
0


2
11
0.4511
−1.4852
−0.0262
−0.9611
0.0142
0
0
0.0319
0
0.0319
0
100
0


2
12
8.7515
3.1358
0.2704
9.9096
0.0534
0
0
0.0319
0
0.0319
0
100
0


2
13
1.1667
−0.4291
0.0028
0.1022
0.0172
0
0
0.0319
0
0.0319
0
100
0


2
14
5.3788
3.039
0.1661
6.0891
0.0402
0
0
0.0319
0.625
0.6569
0
4.85
95.15


2
15
13.8175
7.9862
0.4538
16.6329
0.0753
0
0.625
0.0319
0
0.6569
95.15
4.85
0


2
16
0.5892
0.0397
−0.0171
−0.6274
−0.0021
0
0
0
0
0
0
0
0


3
1
23.0341
14.9411
0.7335
26.8867
0.1082
0
0
0.0387
0
0.0387
0
100
0


3
2
24.8268
16.0912
0.7611
27.8973
0.108
0
0
0.0387
0
0.0387
0
100
0


3
3
21.0312
12.2163
0.6617
24.2545
0.0974
0
0
0.0387
0
0.0387
0
100
0


3
4
15.3062
8.5994
0.4563
16.7247
0.0714
0
0
0.0387
0
0.0387
0
100
0


3
5
13.1818
6.4699
0.3775
13.8381
0.0651
0
0
0.0387
0
0.0387
0
100
0


3
6
14.4778
9.2713
0.4241
15.5437
0.0643
0
0
0.0387
0
0.0387
0
100
0


3
7
5.5717
3.3425
0.1029
3.772
0.0251
0
0
0.0387
0
0.0387
0
100
0


3
8
6.8228
1.6923
0.1521
5.5733
0.0283
0
0
0.0387
0
0.0387
0
100
0


3
9
18.2423
12.1678
0.5606
20.5468
0.0831
0
0
0.0387
0
0.0387
0
100
0


3
10
6.7011
5.5857
0.1612
5.907
0.033
0
0
0.0387
0
0.0387
0
100
0


3
11
1.3529
1.3312
−0.0328
−1.2024
0.0065
0
0
0.0387
0
0.0387
0
100
0


3
12
8.988
6.9454
0.2544
9.3233
0.0421
0
0
0.0387
0
0.0387
0
100
0


3
13
1.9882
1.6201
−0.0124
−0.4561
0.0102
0
0
0.0387
0
0.0387
0
100
0


3
14
6.7207
4.8802
0.1283
4.7036
0.0288
0
0
0.0387
0.625
0.6637
0
5.83
94.17


3
15
13.1254
7.8413
0.4144
15.1912
0.0623
0
0.625
0.0387
0
0.6637
94.17
5.83
0


3
16
1.6968
−0.6116
−0.0065
−0.238
0.007
0
0
0
0
0
0
0
0


4
1
25.6701
19.5197
0.7514
27.5411
0.0986
0
0
0.0455
0
0.0455
0
100
0


4
2
23.653
16.9227
0.7928
29.0607
0.0984
0
0
0.0455
0
0.0455
0
100
0


4
3
22.8118
16.1844
0.6593
24.168
0.0919
0
0
0.0455
0
0.0455
0
100
0


4
4
16.4182
10.7873
0.4837
17.731
0.0754
0
0
0.0455
0
0.0455
0
100
0


4
5
14.5564
7.5137
0.4146
15.1965
0.0579
0
0
0.0455
0
0.0455
0
100
0


4
6
15.7933
9.8273
0.453
16.6027
0.0657
0
0
0.0455
0
0.0455
0
100
0


4
7
6.1716
5.3192
0.1362
4.9935
0.0244
0
0
0.0455
0
0.0455
0
100
0


4
8
7.1386
3.6867
0.1822
6.6787
0.0338
0
0
0.0455
0
0.0455
0
100
0


4
9
20.7303
13.3734
0.6248
22.9033
0.0886
0
0
0.0455
0
0.0455
0
100
0


4
10
8.9131
3.194
0.1982
7.2642
0.0334
0
0
0.0455
0
0.0455
0
100
0


4
11
1.6189
1.2404
−0.0525
−1.926
−0.0002
0
0
0.0455
0
0.0455
0
100
0


4
12
10.7432
5.782
0.2838
10.4022
0.045
0
0
0.0455
0
0.0455
0
100
0


4
13
1.5884
0.8166
−0.0105
−0.3833
0.0101
0
0
0.0455
0
0.0455
0
100
0


4
14
6.4031
3.2336
0.1734
6.3554
0.0362
0
0
0.0455
0.625
0.6705
0
6.79
93.21


4
15
15.6125
10.3811
0.4713
17.2763
0.0703
0
0.625
0.0455
0
0.6705
93.21
6.79
0


4
16
27.9195
15.9998
0.8541
31.3081
0.1277
0.1275
0
0
0
0.1275
0
100
0


5
1
23.5648
16.7387
0.7605
27.8743
0.1008
0
0
0.0524
0
0.0524
0
100
0


5
2
24.3053
17.3486
0.7802
28.5962
0.1046
0
0
0.0524
0
0.0524
0
100
0


5
3
22.341
15.7024
0.7107
26.0515
0.1019
0
0
0.0524
0
0.0524
0
100
0


5
4
17.6158
11.8733
0.5469
20.0479
0.0791
0
0
0.0524
0
0.0524
0
100
0


5
5
14.2387
10.1452
0.4049
14.8406
0.0574
0
0
0.0524
0
0.0524
0
100
0


5
6
15.1152
10.7747
0.4328
15.8622
0.0615
0
0
0.0524
0
0.0524
0
100
0


5
7
6.2094
5.1538
0.1363
4.9969
0.0249
0
0
0.0524
0
0.0524
0
100
0


5
8
7.6993
4.4249
0.2079
7.6192
0.0348
0
0
0.0524
0
0.0524
0
100
0


5
9
20.3032
12.9878
0.6687
24.5092
0.091
0
0
0.0524
0
0.0524
0
100
0


5
10
10.467
7.0359
0.2642
9.6824
0.0427
0
0
0.0524
0
0.0524
0
100
0


5
11
2.8488
0.9928
−0.0496
−1.8191
−0.0034
0
0
0.0524
0
0.0524
0
100
0


5
12
8.6081
4.7427
0.2975
10.9032
0.0379
0
0
0.0524
0
0.0524
0
100
0


5
13
2.4786
0.2441
−0.0353
−1.2925
0.0105
0
0
0.0524
0
0.0524
0
100
0


5
14
5.1083
3.0311
0.1416
5.192
0.0285
0
0
0.0524
0.625
0.6774
0
7.73
92.27


5
15
11.8585
7.5495
0.3716
13.62
0.0576
0
0.625
0.0524
0
0.6774
92.27
7.73
0


5
16
0.172
0.0674
−0.0092
−0.3389
0.01
0
0
0
0
0
0
0
0


6
1
22.8548
15.2481
0.7655
28.0601
0.1096
0
0
0.0592
0
0.0592
0
100
0


6
2
25.4205
16.425
0.8006
29.3446
0.11
0
0
0.0592
0
0.0592
0
100
0


6
3
25.0359
16.7118
0.7742
28.379
0.1081
0
0
0.0592
0
0.0592
0
100
0


6
4
19.8242
13.56
0.6037
22.1285
0.0864
0
0
0.0592
0
0.0592
0
100
0


6
5
15.5667
10.9252
0.4506
16.5181
0.0668
0
0
0.0592
0
0.0592
0
100
0


6
6
14.9248
9.1668
0.4848
17.7684
0.0716
0
0
0.0592
0
0.0592
0
100
0


6
7
6.2748
4.0969
0.1824
6.6868
0.0317
0
0
0.0592
0
0.0592
0
100
0


6
8
8.4858
5.8883
0.251
9.2019
0.0404
0
0
0.0592
0
0.0592
0
100
0


6
9
21.0027
12.7923
0.7581
27.7862
0.1015
0
0
0.0592
0
0.0592
0
100
0


6
10
4.1864
1.0991
0.2231
8.177
0.044
0
0
0.0592
0
0.0592
0
100
0


6
11
−1.2373
−1.4393
0.0135
0.4931
0.0092
0
0
0.0592
0
0.0592
0
100
0


6
12
10.6286
6.8786
0.3149
11.5433
0.0492
0
0
0.0592
0
0.0592
0
100
0


6
13
1.0716
0.1767
0.0081
0.2959
0.0131
0
0
0.0592
0
0.0592
0
100
0


6
14
6.6959
4.4786
0.1742
6.3849
0.0291
0
0
0.0592
0.625
0.6842
0
8.65
91.35


6
15
14.9263
8.9373
0.4504
16.5076
0.0691
0
0.625
0.0592
0
0.6842
91.35
8.65
0


6
16
0.9734
0.524
−0.0068
−0.2476
0.0095
0
0
0
0
0
0
0
0


7
1
22.5418
15.4759
0.726
26.6121
0.0978
0
0
0.066
0
0.066
0
100
0


7
2
25.3352
17.1813
0.8109
29.7233
0.1123
0
0
0.066
0
0.066
0
100
0


7
3
25.4575
17.3091
0.7912
29.0012
0.1094
0
0
0.066
0
0.066
0
100
0


7
4
20.6572
14.3391
0.6313
23.1392
0.0896
0
0
0.066
0
0.066
0
100
0


7
5
15.932
11.3449
0.4504
16.51
0.0654
0
0
0.066
0
0.066
0
100
0


7
6
15.7862
11.3444
0.4701
17.2316
0.0672
0
0
0.066
0
0.066
0
100
0


7
7
6.5518
5.4328
0.1609
5.8983
0.0264
0
0
0.066
0
0.066
0
100
0


7
8
8.798
5.7477
0.2274
8.3369
0.0394
0
0
0.066
0
0.066
0
100
0


7
9
23.0075
15.3925
0.6659
24.4074
0.0863
0
0
0.066
0
0.066
0
100
0


7
10
9.2334
7.3996
0.2983
10.934
0.0356
0
0
0.066
0
0.066
0
100
0


7
11
0.7033
0.897
−0.0323
−1.1825
0.0007
0
0
0.066
0
0.066
0
100
0


7
12
9.8812
6.9932
0.3106
11.3832
0.047
0
0
0.066
0
0.066
0
100
0


7
13
1.8315
1.5281
−0.0004
−0.0142
0.0064
0
0
0.066
0
0.066
0
100
0


7
14
5.9233
4.0164
0.1346
4.9347
0.024
0
0
0.066
0.625
0.691
0
9.55
90.45


7
15
11.3981
7.0352
0.3499
12.8255
0.0508
0
0.625
0.066
0
0.691
90.45
9.55
0


7
16
26.5669
16.7815
0.8474
31.0624
0.1182
0.1275
0
0
0
0.1275
0
100
0


8
1
22.7201
15.0948
0.694
25.4388
0.0942
0
0
0.0729
0
0.0729
0
100
0


8
2
25.5968
16.5345
0.8165
29.9286
0.1106
0
0
0.0729
0
0.0729
0
100
0


8
3
26.9015
16.5093
0.8118
29.7556
0.1132
0
0
0.0729
0
0.0729
0
100
0


8
4
22.6912
14.399
0.6735
24.6849
0.0922
0
0
0.0729
0
0.0729
0
100
0


8
5
16.1513
10.0868
0.4873
17.8622
0.0711
0
0
0.0729
0
0.0729
0
100
0


8
6
14.9604
9.3549
0.5104
18.7093
0.0788
0
0
0.0729
0
0.0729
0
100
0


8
7
9.1106
4.8845
0.1351
4.9537
0.0227
0
0
0.0729
0
0.0729
0
100
0


8
8
11.6445
4.2759
0.265
9.7129
0.0431
0
0
0.0729
0
0.0729
0
100
0


8
9
22.1496
13.0101
0.7517
27.5537
0.103
0
0
0.0729
0
0.0729
0
100
0


8
10
10.7574
7.0805
0.323
11.8395
0.0477
0
0
0.0729
0
0.0729
0
100
0


8
11
3.6004
0.9577
0.0383
1.4029
0.0094
0
0
0.0729
0
0.0729
0
100
0


8
12
11.534
7.8883
0.3533
12.9484
0.0508
0
0
0.0729
0
0.0729
0
100
0


8
13
1.3464
0.5169
−0.0012
−0.0457
0.0054
0
0
0.0729
0
0.0729
0
100
0


8
14
6.4094
3.371
0.1695
6.2144
0.0276
0
0
0.0729
0.625
0.6979
0
10.44
89.56


8
15
12.8137
8.3353
0.3838
14.067
0.054
0
0.625
0.0729
0
0.6979
89.56
10.44
0


8
16
0.6005
0.7618
−0.0245
−0.8983
0.0023
0
0
0
0
0
0
0
0


9
1
22.4957
14.7378
0.6826
25.0193
0.0926
0
0
0.0797
0
0.0797
0
100
0


9
2
25.986
17.2218
0.8042
29.4787
0.1075
0
0
0.0797
0
0.0797
0
100
0


9
3
26.7278
17.0659
0.8299
30.4191
0.1155
0
0
0.0797
0
0.0797
0
100
0


9
4
21.7825
14.3953
0.6911
25.3306
0.0965
0
0
0.0797
0
0.0797
0
100
0


9
5
17.2508
11.3087
0.5012
18.3711
0.0717
0
0
0.0797
0
0.0797
0
100
0


9
6
16.9581
10.5872
0.4639
17.0022
0.0651
0
0
0.0797
0
0.0797
0
100
0


9
7
6.3335
4.0566
0.1665
6.1027
0.0326
0
0
0.0797
0
0.0797
0
100
0


9
8
11.9448
6.8015
0.2794
10.2426
0.0347
0
0
0.0797
0
0.0797
0
100
0


9
9
22.3682
14.3068
0.6953
25.4874
0.0927
0
0
0.0797
0
0.0797
0
100
0


9
10
10.6395
6.5727
0.3015
11.0498
0.0426
0
0
0.0797
0
0.0797
0
100
0


9
11
0.7463
−0.5268
−0.0297
−1.0885
0.0037
0
0
0.0797
0
0.0797
0
100
0


9
12
11.6436
6.9032
0.3308
12.1271
0.0465
0
0
0.0797
0
0.0797
0
100
0


9
13
2.2734
1.3731
−0.0036
−0.1307
0.0063
0
0
0.0797
0
0.0797
0
100
0


9
14
5.2473
2.3383
0.133
4.8766
0.0256
0
0
0.0797
0.625
0.7047
0
11.31
88.69


9
15
14.1744
8.1484
0.4386
16.0753
0.0629
0
0.625
0.0797
0
0.7047
88.69
11.31
0


9
16
1.1167
0.6406
−0.0074
−0.2708
0.0074
0
0
0
0
0
0
0
0


10
1
21.0706
14.7112
0.6846
25.0928
0.0968
0
0
0.0865
0
0.0865
0
100
0


10
2
26.8869
17.9825
0.8859
32.4724
0.1184
0
0
0.0865
0
0.0865
0
100
0


10
3
26.6813
16.9521
0.9023
33.0744
0.1263
0
0
0.0865
0
0.0865
0
100
0


10
4
22.8526
14.0275
0.7543
27.65
0.106
0
0
0.0865
0
0.0865
0
100
0


10
5
16.4643
9.638
0.5121
18.772
0.0768
0
0
0.0865
0
0.0865
0
100
0


10
6
16.974
10.2305
0.4989
18.2853
0.0738
0
0
0.0865
0
0.0865
0
100
0


10
7
7.0764
3.7892
0.217
7.954
0.0367
0
0
0.0865
0
0.0865
0
100
0


10
8
10.3301
7.0156
0.3079
11.2846
0.0444
0
0
0.0865
0
0.0865
0
100
0


10
9
22.9265
14.8712
0.7519
27.5603
0.1024
0
0
0.0865
0
0.0865
0
100
0


10
10
12.4677
6.9963
0.3574
13.1014
0.0529
0
0
0.0865
0
0.0865
0
100
0


10
11
0.5969
−0.5299
−0.0215
−0.7876
0.0033
0
0
0.0865
0
0.0865
0
100
0


10
12
13.3324
8.0107
0.3981
14.593
0.0579
0
0
0.0865
0
0.0865
0
100
0


10
13
1.9031
0.5698
0.0129
0.4715
0.0076
0
0
0.0865
0
0.0865
0
100
0


10
14
6.4847
3.7801
0.156
5.7172
0.0292
0
0
0.0865
0.625
0.7115
0
12.16
87.84


10
15
13.3979
8.7146
0.4385
16.0738
0.0621
0
0.625
0.0865
0
0.7115
87.84
12.16
0


10
16
25.4495
16.0477
0.8342
30.5766
0.1176
0.1275
0
0
0
0.1275
0
100
0


11
1
20.1375
13.3902
0.695
25.4752
0.0941
0
0
0.0933
0
0.0933
0
100
0


11
2
27.139
17.1786
0.8841
32.4048
0.1236
0
0
0.0933
0
0.0933
0
100
0


11
3
26.9388
16.683
0.9125
33.4483
0.127
0
0
0.0933
0
0.0933
0
100
0


11
4
24.5762
15.8875
0.789
28.9207
0.1089
0
0
0.0933
0
0.0933
0
100
0


11
5
15.1923
9.882
0.4773
17.4944
0.0718
0
0
0.0933
0
0.0933
0
100
0


11
6
15.7362
10.517
0.4959
18.1782
0.0704
0
0
0.0933
0
0.0933
0
100
0


11
7
6.9524
4.547
0.2149
7.8771
0.0338
0
0
0.0933
0
0.0933
0
100
0


11
8
10.7228
5.8543
0.3063
11.2265
0.0473
0
0
0.0933
0
0.0933
0
100
0


11
9
21.6871
13.7234
0.7381
27.0563
0.1017
0
0
0.0933
0
0.0933
0
100
0


11
10
10.2552
6.749
0.3273
11.9961
0.0462
0
0
0.0933
0
0.0933
0
100
0


11
11
0.1751
−0.8137
−0.0162
−0.5948
0.0093
0
0
0.0933
0
0.0933
0
100
0


11
12
12.9233
7.3461
0.3959
14.5118
0.058
0
0
0.0933
0
0.0933
0
100
0


11
13
2.1161
−0.0461
0.0196
0.7173
0.0121
0
0
0.0933
0
0.0933
0
100
0


11
14
5.318
2.5839
0.1421
5.2076
0.028
0
0
0.0933
0.625
0.7183
0
12.99
87.01


11
15
12.7569
6.3017
0.3941
14.4456
0.0579
0
0.625
0.0933
0
0.7183
87.01
12.99
0


11
16
0.8455
−1.3583
0.0027
0.0985
0.0084
0
0
0
0
0
0
0
0


12
1
15.9884
10.3576
0.5209
19.0939
0.0763
0
0
0.1002
0
0.1002
0
100
0


12
2
27.3984
16.7714
0.9241
33.8719
0.128
0
0
0.1002
0
0.1002
0
100
0


12
3
28.1625
17.4315
0.9325
34.1804
0.1313
0
0
0.1002
0
0.1002
0
100
0


12
4
24.8213
15.2594
0.851
31.1941
0.1246
0
0
0.1002
0
0.1002
0
100
0


12
5
16.5105
9.4519
0.5715
20.9463
0.089
0
0
0.1002
0
0.1002
0
100
0


12
6
16.2367
8.6629
0.5246
19.229
0.0791
0
0
0.1002
0
0.1002
0
100
0


12
7
7.0822
2.7268
0.2494
9.143
0.0433
0
0
0.1002
0
0.1002
0
100
0


12
8
11.1025
6.1665
0.3763
13.7941
0.056
0
0
0.1002
0
0.1002
0
100
0


12
9
23.5429
14.4559
0.8026
29.419
0.1129
0
0
0.1002
0
0.1002
0
100
0


12
10
12.4169
7.2141
0.384
14.0754
0.0576
0
0
0.1002
0
0.1002
0
100
0


12
11
−0.2192
−1.5288
−0.0114
−0.4195
0.0063
0
0
0.1002
0
0.1002
0
100
0


12
12
13.2567
7.0496
0.4182
15.3281
0.0611
0
0
0.1002
0
0.1002
0
100
0


12
13
1.2187
−0.6308
0.0286
1.0496
0.0116
0
0
0.1002
0
0.1002
0
100
0


12
14
5.5276
1.9229
0.1649
6.0426
0.0328
0
0
0.1002
0.625
0.7252
0
13.81
86.19


12
15
13.3469
6.2659
0.4232
15.5137
0.0634
0
0.625
0.1002
0
0.7252
86.19
13.81
0


12
16
1.0083
−0.586
0.011
0.4039
0.0096
0
0
0
0
0
0
0
0


13
1
18.6644
11.2964
0.6506
23.8458
0.0932
0
0
0.107
0
0.107
0
100
0


13
2
27.845
15.9413
0.9392
34.4261
0.1308
0
0
0.107
0
0.107
0
100
0


13
3
27.3697
17.3186
0.9442
34.6097
0.1337
0
0
0.107
0
0.107
0
100
0


13
4
25.678
15.9207
0.8401
30.7915
0.1183
0
0
0.107
0
0.107
0
100
0


13
5
15.7945
10.0005
0.5228
19.164
0.0793
0
0
0.107
0
0.107
0
100
0


13
6
15.3463
9.2398
0.5087
18.6471
0.0765
0
0
0.107
0
0.107
0
100
0


13
7
6.7754
3.6609
0.2308
8.459
0.0396
0
0
0.107
0
0.107
0
100
0


13
8
11.692
6.4553
0.3752
13.7513
0.0561
0
0
0.107
0
0.107
0
100
0


13
9
23.2809
13.521
0.8112
29.7353
0.1124
0
0
0.107
0
0.107
0
100
0


13
10
13.5562
7.5286
0.4302
15.7676
0.0624
0
0
0.107
0
0.107
0
100
0


13
11
1.1357
−1.0497
−0.0258
−0.9457
0.0072
0
0
0.107
0
0.107
0
100
0


13
12
14.0892
7.0847
0.4404
16.1411
0.0683
0
0
0.107
0
0.107
0
100
0


13
13
1.2307
−0.0972
0.0411
1.5048
0.0161
0
0
0.107
0
0.107
0
100
0


13
14
5.0473
1.1814
0.1519
5.5685
0.0306
0
0
0.107
0.625
0.732
0
14.62
85.38


13
15
12.8894
6.9657
0.3932
14.413
0.0574
0
0.625
0.107
0
0.732
85.38
14.62
0


13
16
27.0196
15.8321
0.9126
33.449
0.1349
0.1275
0
0
0
0.1275
0
100
0


14
1
21.6824
14.5808
0.7642
28.0108
0.1054
0
0
0.1138
0
0.1138
0
100
0


14
2
27.9534
18.5673
0.9122
33.4357
0.1269
0
0
0.1138
0
0.1138
0
100
0


14
3
28.3871
17.6025
0.9506
34.8433
0.1361
0
0
0.1138
0
0.1138
0
100
0


14
4
26.5322
15.1329
0.8627
31.6204
0.1283
0
0
0.1138
0
0.1138
0
100
0


14
5
17.27
10.4633
0.5486
20.1091
0.0846
0
0
0.1138
0
0.1138
0
100
0


14
6
16.6826
9.6418
0.5721
20.9704
0.0848
0
0
0.1138
0
0.1138
0
100
0


14
7
7.7667
4.5307
0.2694
9.8752
0.0433
0
0
0.1138
0
0.1138
0
100
0


14
8
13.2575
8.5866
0.4374
16.0317
0.064
0
0
0.1138
0
0.1138
0
100
0


14
9
24.5972
16.2327
0.8255
30.2566
0.1118
0
0
0.1138
0
0.1138
0
100
0


14
10
14.1237
8.1483
0.478
17.5191
0.0713
0
0
0.1138
0
0.1138
0
100
0


14
11
−0.172
−1.5106
−0.0204
−0.7482
0.0089
0
0
0.1138
0
0.1138
0
100
0


14
12
15.8277
8.9664
0.5076
18.6043
0.0706
0
0
0.1138
0
0.1138
0
100
0


14
13
1.0637
−1.0104
0.0444
1.6268
0.0139
0
0
0.1138
0
0.1138
0
100
0


14
14
4.6635
2.3532
0.1677
6.1462
0.0296
0
0
0.1138
0.625
0.7388
0
15.41
84.59


14
15
12.9488
7.3298
0.4296
15.7453
0.0651
0
0.625
0.1138
0
0.7388
84.59
15.41
0


14
16
0.3061
−0.5069
−0.0065
−0.2391
0.0099
0
0
0
0
0
0
0
0


15
1
17.1998
12.0104
0.5755
21.0955
0.0799
0
0
0.1207
0
0.1207
0
100
0


15
2
27.4482
17.526
0.933
34.1967
0.1316
0
0
0.1207
0
0.1207
0
100
0


15
3
28.1178
18.8556
0.9242
33.8763
0.1324
0
0
0.1207
0
0.1207
0
100
0


15
4
26.8701
17.1463
0.856
31.3778
0.1258
0
0
0.1207
0
0.1207
0
100
0


15
5
17.6631
10.9667
0.5845
21.4248
0.0858
0
0
0.1207
0
0.1207
0
100
0


15
6
17.1402
10.8854
0.5425
19.8853
0.0798
0
0
0.1207
0
0.1207
0
100
0


15
7
8.2663
5.3027
0.2441
8.9487
0.0387
0
0
0.1207
0
0.1207
0
100
0


15
8
11.9892
6.7241
0.3904
14.3081
0.0566
0
0
0.1207
0
0.1207
0
100
0


15
9
24.1606
15.639
0.8291
30.3902
0.1118
0
0
0.1207
0
0.1207
0
100
0


15
10
15.0377
10.3936
0.4614
16.9136
0.0638
0
0
0.1207
0
0.1207
0
100
0


15
11
0.2191
−0.9933
−0.0152
−0.558
0.0074
0
0
0.1207
0
0.1207
0
100
0


15
12
16.1138
9.1228
0.5094
18.6707
0.0732
0
0
0.1207
0
0.1207
0
100
0


15
13
2.4821
0.3422
0.0309
1.1317
0.0144
0
0
0.1207
0
0.1207
0
100
0


15
14
5.4454
0.6463
0.189
6.9276
0.035
0
0
0.1207
0.625
0.7457
0
16.18
83.82


15
15
14.0229
7.8558
0.4492
16.4654
0.0681
0
0.625
0.1207
0
0.7457
83.82
16.18
0


15
16
0.4686
−0.7131
0.0197
0.7216
0.01
0
0
0
0
0
0
0
0


16
1
7.4861
4.4402
0.2493
9.1386
0.0401
0
0
0.1275
0
0.1275
0
100
0


16
2
29.0506
17.8613
0.9483
34.7579
0.1412
0
0
0.1275
0
0.1275
0
100
0


16
3
29.4694
17.4993
0.9236
33.8554
0.1479
0
0
0.1275
0
0.1275
0
100
0


16
4
28.4749
16.4322
0.9104
33.3693
0.1531
0
0
0.1275
0
0.1275
0
100
0


16
5
22.0326
12.6858
0.7055
25.8606
0.1115
0
0
0.1275
0
0.1275
0
100
0


16
6
20.0805
12.1402
0.6291
23.0594
0.0943
0
0
0.1275
0
0.1275
0
100
0


16
7
9.0587
5.2161
0.2666
9.7703
0.0461
0
0
0.1275
0
0.1275
0
100
0


16
8
13.983
9.3075
0.4391
16.0948
0.0636
0
0
0.1275
0
0.1275
0
100
0


16
9
26.9905
17.0719
0.877
32.1456
0.1198
0
0
0.1275
0
0.1275
0
100
0


16
10
14.704
8.6762
0.4886
17.9102
0.073
0
0
0.1275
0
0.1275
0
100
0


16
11
0.7191
−1.4742
−0.0041
−0.1519
0.0077
0
0
0.1275
0
0.1275
0
100
0


16
12
19.314
11.1355
0.6495
23.808
0.0899
0
0
0.1275
0
0.1275
0
100
0


16
13
2.4636
0.033
0.0679
2.4886
0.0206
0
0
0.1275
0
0.1275
0
100
0


16
14
11.4461
6.8975
0.3856
14.134
0.0639
0
0
0.1275
0.625
0.7525
0
16.94
83.06


16
15
20.8264
13.1623
0.7
25.6595
0.0961
0
0.625
0.1275
0
0.7525
83.06
16.94
0


16
16
26.7851
15.9945
0.9048
33.1661
0.1319
0.1275
0
0
0
0.1275
0
100
0


Temperature:


300 C.


1
1
26.0412
13.6761
0.7608
27.4327
0.1592
0.1275
0
0
0
0.1275
0
100
0


1
2
1.9716
2.4686
0.0066
0.2386
0.0092
0
0
0
0
0
0
0
0


1
3
0.3229
0.3952
−0.0391
−1.4081
0.0062
0
0
0
0
0
0
0
0


1
4
0.6417
0.8578
−0.0504
−1.8187
−0.0005
0
0
0
0
0
0
0
0


1
5
0.173
0.5233
−0.0449
−1.6183
0.0024
0
0
0
0
0
0
0
0


1
6
0.3624
0.0747
−0.0376
−1.3546
−0.0039
0
0
0
0
0
0
0
0


1
7
26.157
12.3934
0.797
28.7383
0.1699
0.1275
0
0
0
0.1275
0
100
0


1
8
3.5333
0.2801
−0.0585
−2.108
−0.0107
0
0
0
0
0
0
0
0


1
9
−1.8657
−3.8002
−0.0104
−0.375
0.0197
0
0
0
0
0
0
0
0


1
10
2.592
0.129
−0.014
−0.5051
−0.0253
0
0
0
0
0
0
0
0


1
11
−3.1613
−1.397
−0.0273
−0.9858
0.0043
0
0
0
0
0
0
0
0


1
12
−0.5382
−0.741
−0.0195
−0.7042
−0.0352
0
0
0
0
0
0
0
0


1
13
25.293
12.9331
0.8097
29.194
0.1597
0.1275
0
0
0
0.1275
0
100
0


1
14
0.8774
0.3654
−0.018
−0.648
0.0052
0
0
0
0
0
0
0
0


1
15
−1.2793
0.1383
−0.0181
−0.6543
0.0027
0
0
0
0
0
0
0
0


1
16
25.6735
12.143
0.7277
26.2368
0.1566
0.1275
0
0
0
0.1275
0
100
0


2
1
14.8766
10.2106
0.3917
14.1217
0.0524
0
0
0.0319
0
0.0319
0
100
0


2
2
20.4545
14.6181
0.746
26.8969
0.1088
0
0
0.0319
0
0.0319
0
100
0


2
3
19.9352
12.3858
0.6977
25.1579
0.1196
0
0
0.0319
0
0.0319
0
100
0


2
4
16.0396
10.1097
0.6511
23.4768
0.109
0
0
0.0319
0
0.0319
0
100
0


2
5
15.904
10.2101
0.4597
16.5765
0.0626
0
0
0.0319
0
0.0319
0
100
0


2
6
14.9915
9.8692
0.3995
14.4034
0.0662
0
0
0.0319
0
0.0319
0
100
0


2
7
6.2101
5.2473
0.1852
6.6763
0.0252
0
0
0.0319
0
0.0319
0
100
0


2
8
9.4972
5.8339
0.283
10.205
0.0496
0
0
0.0319
0
0.0319
0
100
0


2
9
21.1669
13.9111
0.6435
23.2016
0.0932
0
0
0.0319
0
0.0319
0
100
0


2
10
8.0932
5.8934
0.2958
10.6661
0.0493
0
0
0.0319
0
0.0319
0
100
0


2
11
0.4906
0.3109
−0.0754
−2.7173
0.0004
0
0
0.0319
0
0.0319
0
100
0


2
12
12.7979
8.96
0.445
16.0439
0.0703
0
0
0.0319
0
0.0319
0
100
0


2
13
1.7683
2.1621
0.0286
1.0326
0.0176
0
0
0.0319
0
0.0319
0
100
0


2
14
11.5049
8.9483
0.3603
12.9899
0.0656
0
0
0.0319
0.625
0.6569
0
4.85
95.15


2
15
19.2509
11.5249
0.6541
23.5849
0.0881
0
0.625
0.0319
0
0.6569
95.15
4.85
0


2
16
−2.2275
0.1022
0.0038
0.136
0.001
0
0
0
0
0
0
0
0


3
1
19.5625
13.7405
0.7553
27.2322
0.1169
0
0
0.0387
0
0.0387
0
100
0


3
2
23.3448
16.4986
0.7782
28.0599
0.1055
0
0
0.0387
0
0.0387
0
100
0


3
3
20.2746
14.4888
0.7447
26.8513
0.1236
0
0
0.0387
0
0.0387
0
100
0


3
4
21.042
14.6567
0.5975
21.5435
0.0868
0
0
0.0387
0
0.0387
0
100
0


3
5
15.227
11.3009
0.5184
18.6931
0.0896
0
0
0.0387
0
0.0387
0
100
0


3
6
16.2981
13.1574
0.4916
17.7266
0.0804
0
0
0.0387
0
0.0387
0
100
0


3
7
7.5318
7.7146
0.2177
7.8495
0.0364
0
0
0.0387
0
0.0387
0
100
0


3
8
14.1025
10.9954
0.419
15.1061
0.0628
0
0
0.0387
0
0.0387
0
100
0


3
9
20.9253
15.3432
0.7024
25.3266
0.1019
0
0
0.0387
0
0.0387
0
100
0


3
10
13.728
11.1605
0.4466
16.1033
0.0679
0
0
0.0387
0
0.0387
0
100
0


3
11
−1.0656
0.7638
−0.03
−1.0824
−0.001
0
0
0.0387
0
0.0387
0
100
0


3
12
12.0316
9.0087
0.4143
14.9372
0.064
0
0
0.0387
0
0.0387
0
100
0


3
13
2.3735
2.427
0.0472
1.7003
0.0158
0
0
0.0387
0
0.0387
0
100
0


3
14
10.011
6.6184
0.4321
15.5784
0.078
0
0
0.0387
0.625
0.6637
0
5.83
94.17


3
15
17.1288
11.9418
0.6936
25.0081
0.1016
0
0.625
0.0387
0
0.6637
94.17
5.83
0


3
16
−0.0207
−0.0056
0.0564
2.0341
−0.003
0
0
0
0
0
0
0
0


4
1
23.9972
15.9845
0.7717
27.8233
0.119
0
0
0.0455
0
0.0455
0
100
0


4
2
24.3635
16.2531
0.7072
25.5007
0.1199
0
0
0.0455
0
0.0455
0
100
0


4
3
21.4425
14.1432
0.7498
27.0362
0.1265
0
0
0.0455
0
0.0455
0
100
0


4
4
19.4479
12.996
0.6822
24.5996
0.107
0
0
0.0455
0
0.0455
0
100
0


4
5
16.0527
11.3163
0.5819
20.98
0.0935
0
0
0.0455
0
0.0455
0
100
0


4
6
17.5309
11.186
0.5671
20.447
0.0842
0
0
0.0455
0
0.0455
0
100
0


4
7
8.0993
5.7381
0.3374
12.166
0.0503
0
0
0.0455
0
0.0455
0
100
0


4
8
14.119
9.8107
0.5489
19.7929
0.0801
0
0
0.0455
0
0.0455
0
100
0


4
9
23.2762
14.9011
0.7786
28.0723
0.1033
0
0
0.0455
0
0.0455
0
100
0


4
10
14.7194
10.4363
0.5718
20.6185
0.08
0
0
0.0455
0
0.0455
0
100
0


4
11
1.1453
0.3882
−0.067
−2.4162
−0.0168
0
0
0.0455
0
0.0455
0
100
0


4
12
12.7656
8.8311
0.4759
17.1582
0.0689
0
0
0.0455
0
0.0455
0
100
0


4
13
4.4502
1.323
0.0072
0.2593
0.0135
0
0
0.0455
0
0.0455
0
100
0


4
14
13.3844
9.4729
0.4141
14.9311
0.0687
0
0
0.0455
0.625
0.6705
0
6.79
93.21


4
15
20.7018
14.4153
0.6795
24.5002
0.0932
0
0.625
0.0455
0
0.6705
93.21
6.79
0


4
16
26.3093
12.5646
0.7405
26.6988
0.1561
0.1275
0
0
0
0.1275
0
100
0


5
1
21.4105
14.4067
0.7125
25.6898
0.11
0
0
0.0524
0
0.0524
0
100
0


5
2
22.1022
14.8036
0.819
29.5304
0.1282
0
0
0.0524
0
0.0524
0
100
0


5
3
22.5933
14.8442
0.7244
26.1201
0.1233
0
0
0.0524
0
0.0524
0
100
0


5
4
21.0057
13.8057
0.6911
24.9201
0.1153
0
0
0.0524
0
0.0524
0
100
0


5
5
17.672
12.2393
0.5728
20.6522
0.0902
0
0
0.0524
0
0.0524
0
100
0


5
6
16.0245
11.7967
0.5902
21.2789
0.0941
0
0
0.0524
0
0.0524
0
100
0


5
7
8.682
6.8022
0.35
12.6185
0.0569
0
0
0.0524
0
0.0524
0
100
0


5
8
16.2047
10.7313
0.5656
20.3921
0.0857
0
0
0.0524
0
0.0524
0
100
0


5
9
21.0729
14.0649
0.7974
28.7515
0.124
0
0
0.0524
0
0.0524
0
100
0


5
10
18.1655
12.1093
0.6249
22.5323
0.094
0
0
0.0524
0
0.0524
0
100
0


5
11
−3.2789
−1.8833
0.0173
0.625
−0.017
0
0
0.0524
0
0.0524
0
100
0


5
12
12.1376
7.6528
0.5085
18.3339
0.0689
0
0
0.0524
0
0.0524
0
100
0


5
13
2.8719
1.6064
0.0398
1.4347
0.0232
0
0
0.0524
0
0.0524
0
100
0


5
14
11.6313
7.1984
0.3756
13.5442
0.064
0
0
0.0524
0.625
0.6774
0
7.73
92.27


5
15
18.7077
12.3422
0.6784
24.4596
0.1017
0
0.625
0.0524
0
0.6774
92.27
7.73
0


5
16
−0.923
0.6423
0.0024
0.0871
−0.0005
0
0
0
0
0
0
0
0


6
1
22.0063
14.1082
0.7772
28.0216
0.121
0
0
0.0592
0
0.0592
0
100
0


6
2
23.7522
14.4251
0.8181
29.4983
0.1363
0
0
0.0592
0
0.0592
0
100
0


6
3
23.7349
12.7968
0.778
28.0518
0.1487
0
0
0.0592
0
0.0592
0
100
0


6
4
21.7688
12.1769
0.7488
27.0006
0.1335
0
0
0.0592
0
0.0592
0
100
0


6
5
18.6185
12.368
0.6292
22.6862
0.1057
0
0
0.0592
0
0.0592
0
100
0


6
6
17.435
11.7025
0.6457
23.2833
0.0997
0
0
0.0592
0
0.0592
0
100
0


6
7
9.5496
7.4033
0.4005
14.4418
0.0656
0
0
0.0592
0
0.0592
0
100
0


6
8
18.8345
12.608
0.602
21.7077
0.0895
0
0
0.0592
0
0.0592
0
100
0


6
9
22.7783
14.5707
0.7858
28.3319
0.1268
0
0
0.0592
0
0.0592
0
100
0


6
10
14.2889
9.3319
0.4808
17.3344
0.0626
0
0
0.0592
0
0.0592
0
100
0


6
11
−1.4423
−3.1898
0.0072
0.2597
−0.0242
0
0
0.0592
0
0.0592
0
100
0


6
12
14.6391
9.1343
0.5169
18.6393
0.0784
0
0
0.0592
0
0.0592
0
100
0


6
13
1.3924
0.1849
0.1067
3.8458
0.0254
0
0
0.0592
0
0.0592
0
100
0


6
14
12.4467
7.9011
0.47
16.947
0.0796
0
0
0.0592
0.625
0.6842
0
8.65
91.35


6
15
20.5551
12.4877
0.7241
26.1085
0.1086
0
0.625
0.0592
0
0.6842
91.35
8.65
0


6
16
1.8224
1.9194
0.0293
1.0577
−0.001
0
0
0
0
0
0
0
0


7
1
20.1793
13.5157
0.7141
25.7483
0.1062
0
0
0.066
0
0.066
0
100
0


7
2
23.9199
15.0715
0.7923
28.5691
0.1334
0
0
0.066
0
0.066
0
100
0


7
3
24.0921
13.8724
0.7704
27.7794
0.1489
0
0
0.066
0
0.066
0
100
0


7
4
22.4883
13.3333
0.7472
26.9401
0.1331
0
0
0.066
0
0.066
0
100
0


7
5
18.3753
10.967
0.6933
24.9964
0.1147
0
0
0.066
0
0.066
0
100
0


7
6
19.1636
11.8882
0.594
21.4179
0.0973
0
0
0.066
0
0.066
0
100
0


7
7
11.6242
8.7829
0.358
12.9075
0.0589
0
0
0.066
0
0.066
0
100
0


7
8
18.9461
11.9304
0.6075
21.9057
0.0865
0
0
0.066
0
0.066
0
100
0


7
9
20.8727
13.268
0.8581
30.9391
0.1366
0
0
0.066
0
0.066
0
100
0


7
10
19.7469
12.533
0.627
22.6084
0.0889
0
0
0.066
0
0.066
0
100
0


7
11
0.2661
−1.0746
−0.0206
−0.7417
−0.0241
0
0
0.066
0
0.066
0
100
0


7
12
14.9635
8.7674
0.5117
18.4485
0.0776
0
0
0.066
0
0.066
0
100
0


7
13
2.473
1.1259
0.0915
3.3004
0.0134
0
0
0.066
0
0.066
0
100
0


7
14
10.4908
6.4436
0.4097
14.774
0.0771
0
0
0.066
0.625
0.691
0
9.55
90.45


7
15
17.9387
11.3159
0.7335
26.449
0.109
0
0.625
0.066
0
0.691
90.45
9.55
0


7
16
24.6649
12.1883
0.7892
28.4564
0.1735
0.1275
0
0
0
0.1275
0
100
0


8
1
20.4072
13.9072
0.7031
25.3521
0.1107
0
0
0.0729
0
0.0729
0
100
0


8
2
23.2299
15.5533
0.8078
29.1272
0.1368
0
0
0.0729
0
0.0729
0
100
0


8
3
24.3029
13.9797
0.7799
28.1203
0.1564
0
0
0.0729
0
0.0729
0
100
0


8
4
22.2113
14.5975
0.7495
27.0256
0.1425
0
0
0.0729
0
0.0729
0
100
0


8
5
18.1577
13.0692
0.6943
25.034
0.1167
0
0
0.0729
0
0.0729
0
100
0


8
6
16.4584
11.241
0.6799
24.5135
0.1128
0
0
0.0729
0
0.0729
0
100
0


8
7
11.3178
9.6452
0.4321
15.5795
0.0596
0
0
0.0729
0
0.0729
0
100
0


8
8
20.8336
14.4605
0.6457
23.2815
0.0922
0
0
0.0729
0
0.0729
0
100
0


8
9
23.346
15.3942
0.8346
30.0941
0.1169
0
0
0.0729
0
0.0729
0
100
0


8
10
20.3283
13.3467
0.6964
25.1102
0.1063
0
0
0.0729
0
0.0729
0
100
0


8
11
6.0017
3.7447
0.2344
8.4523
0.0402
0
0
0.0729
0
0.0729
0
100
0


8
12
14.0669
9.2173
0.572
20.6246
0.0862
0
0
0.0729
0
0.0729
0
100
0


8
13
0.4343
−0.3379
0.1029
3.7103
0.0224
0
0
0.0729
0
0.0729
0
100
0


8
14
12.9196
8.2041
0.4689
16.9054
0.0749
0
0
0.0729
0.625
0.6979
0
10.44
89.56


8
15
20.3025
12.6472
0.6618
23.8639
0.1
0
0.625
0.0729
0
0.6979
89.56
10.44
0


8
16
0.7273
0.7062
−0.0175
−0.63
−0.0087
0
0
0
0
0
0
0
0


9
1
19.0866
13.801
0.6956
25.0805
0.1067
0
0
0.0797
0
0.0797
0
100
0


9
2
23.4011
15.4022
0.8062
29.0677
0.1362
0
0
0.0797
0
0.0797
0
100
0


9
3
24.2636
14.0356
0.8069
29.094
0.1585
0
0
0.0797
0
0.0797
0
100
0


9
4
23.0618
13.7204
0.7603
27.4122
0.137
0
0
0.0797
0
0.0797
0
100
0


9
5
19.2953
12.3324
0.6838
24.6546
0.1191
0
0
0.0797
0
0.0797
0
100
0


9
6
16.4524
11.6941
0.5833
21.033
0.0966
0
0
0.0797
0
0.0797
0
100
0


9
7
8.8155
6.193
0.4081
14.7154
0.0678
0
0
0.0797
0
0.0797
0
100
0


9
8
18.3421
12.4823
0.6492
23.4094
0.095
0
0
0.0797
0
0.0797
0
100
0


9
9
22.5571
15.4221
0.8241
29.7153
0.1201
0
0
0.0797
0
0.0797
0
100
0


9
10
18.2863
13.1397
0.6724
24.2444
0.0988
0
0
0.0797
0
0.0797
0
100
0


9
11
−1.5339
−0.5868
−0.0006
−0.0218
−0.0198
0
0
0.0797
0
0.0797
0
100
0


9
12
13.9602
9.1693
0.5547
20.0022
0.0819
0
0
0.0797
0
0.0797
0
100
0


9
13
1.1827
1.2849
0.1107
3.9916
0.0024
0
0
0.0797
0
0.0797
0
100
0


9
14
10.2757
6.1288
0.3969
14.3106
0.0711
0
0
0.0797
0.625
0.7047
0
11.31
88.69


9
15
19.4095
11.4849
0.732
26.3918
0.1116
0
0.625
0.0797
0
0.7047
88.69
11.31
0


9
16
−0.4746
0.3
0.0649
2.3389
0.0106
0
0
0
0
0
0
0
0


10
1
19.6155
13.2592
0.7151
25.784
0.1137
0
0
0.0865
0
0.0865
0
100
0


10
2
24.4255
14.2114
0.8452
30.474
0.1541
0
0
0.0865
0
0.0865
0
100
0


10
3
25.1167
12.0723
0.8229
29.6706
0.1783
0
0
0.0865
0
0.0865
0
100
0


10
4
23.9367
12.0867
0.8302
29.934
0.1595
0
0
0.0865
0
0.0865
0
100
0


10
5
20.499
11.2772
0.6949
25.0561
0.1257
0
0
0.0865
0
0.0865
0
100
0


10
6
18.4277
10.342
0.652
23.5077
0.1136
0
0
0.0865
0
0.0865
0
100
0


10
7
10.6829
8.2331
0.4943
17.8212
0.0797
0
0
0.0865
0
0.0865
0
100
0


10
8
21.0351
13.5697
0.6934
25.0025
0.1016
0
0
0.0865
0
0.0865
0
100
0


10
9
23.3546
15.5724
0.8319
29.9961
0.1265
0
0
0.0865
0
0.0865
0
100
0


10
10
20.2733
13.206
0.7226
26.0547
0.1094
0
0
0.0865
0
0.0865
0
100
0


10
11
−2.2709
−1.6818
−0.003
−0.1081
−0.0191
0
0
0.0865
0
0.0865
0
100
0


10
12
15.5394
9.154
0.5767
20.7948
0.0875
0
0
0.0865
0
0.0865
0
100
0


10
13
2.338
0.6958
0.1166
4.204
0.0286
0
0
0.0865
0
0.0865
0
100
0


10
14
11.8371
7.0502
0.4485
16.1702
0.0781
0
0
0.0865
0.625
0.7115
0
12.16
87.84


10
15
18.9643
11.9052
0.7159
25.8125
0.1082
0
0.625
0.0865
0
0.7115
87.84
12.16
0


10
16
23.3683
12.0328
0.7792
28.0962
0.1577
0.1275
0
0
0
0.1275
0
100
0


11
1
18.6802
11.5742
0.6796
24.5045
0.1057
0
0
0.0933
0
0.0933
0
100
0


11
2
25.0222
13.9863
0.8039
28.9852
0.1512
0
0
0.0933
0
0.0933
0
100
0


11
3
25.6394
13.1215
0.8122
29.2838
0.1687
0
0
0.0933
0
0.0933
0
100
0


11
4
24.6744
14.5183
0.7802
28.132
0.1536
0
0
0.0933
0
0.0933
0
100
0


11
5
19.3295
12.6135
0.685
24.6995
0.1225
0
0
0.0933
0
0.0933
0
100
0


11
6
18.7665
11.7823
0.6491
23.4044
0.1112
0
0
0.0933
0
0.0933
0
100
0


11
7
12.0459
8.262
0.4669
16.8355
0.0746
0
0
0.0933
0
0.0933
0
100
0


11
8
19.7356
12.2924
0.7225
26.0526
0.1072
0
0
0.0933
0
0.0933
0
100
0


11
9
23.3494
14.4131
0.8518
30.7139
0.1298
0
0
0.0933
0
0.0933
0
100
0


11
10
19.1323
12.6849
0.7094
25.5779
0.105
0
0
0.0933
0
0.0933
0
100
0


11
11
−0.9895
−0.2695
−0.004
−0.1435
−0.0127
0
0
0.0933
0
0.0933
0
100
0


11
12
14.8304
10.1963
0.582
20.9867
0.0899
0
0
0.0933
0
0.0933
0
100
0


11
13
2.208
2.5587
0.1029
3.7107
0.0204
0
0
0.0933
0
0.0933
0
100
0


11
14
10.9763
6.4266
0.3918
14.1258
0.0707
0
0
0.0933
0.625
0.7183
0
12.99
87.01


11
15
18.1906
10.6621
0.698
25.1685
0.106
0
0.625
0.0933
0
0.7183
87.01
12.99
0


11
16
−0.9643
−0.7161
0.0392
1.4143
−0.0048
0
0
0
0
0
0
0
0


12
1
15.4588
10.1833
0.5953
21.4632
0.1001
0
0
0.1002
0
0.1002
0
100
0


12
2
24.7319
13.6012
0.8478
30.5688
0.161
0
0
0.1002
0
0.1002
0
100
0


12
3
26.8912
12.8758
0.8008
28.8754
0.1851
0
0
0.1002
0
0.1002
0
100
0


12
4
24.6558
12.9216
0.8196
29.5504
0.1758
0
0
0.1002
0
0.1002
0
100
0


12
5
20.5267
12.1018
0.7215
26.0139
0.1329
0
0
0.1002
0
0.1002
0
100
0


12
6
18.4287
11.4481
0.6811
24.5589
0.1172
0
0
0.1002
0
0.1002
0
100
0


12
7
13.4393
9.372
0.4909
17.6995
0.0793
0
0
0.1002
0
0.1002
0
100
0


12
8
21.0809
13.9911
0.7512
27.0875
0.111
0
0
0.1002
0
0.1002
0
100
0


12
9
23.772
15.0448
0.8517
30.7084
0.1339
0
0
0.1002
0
0.1002
0
100
0


12
10
19.8095
12.8912
0.7381
26.6137
0.1093
0
0
0.1002
0
0.1002
0
100
0


12
11
−1.4941
−1.399
−0.0134
−0.4846
−0.018
0
0
0.1002
0
0.1002
0
100
0


12
12
16.0743
10.6539
0.5977
21.5507
0.092
0
0
0.1002
0
0.1002
0
100
0


12
13
2.0581
1.6359
0.1105
3.986
0.0298
0
0
0.1002
0
0.1002
0
100
0


12
14
10.744
6.4761
0.4184
15.0852
0.076
0
0
0.1002
0.625
0.7252
0
13.81
86.19


12
15
18.2843
10.3265
0.6975
25.1492
0.112
0
0.625
0.1002
0
0.7252
86.19
13.81
0


12
16
−0.4083
−1.1083
0.0632
2.2805
0.02
0
0
0
0
0
0
0
0


13
1
17.3784
11.3659
0.6531
23.5471
0.1026
0
0
0.107
0
0.107
0
100
0


13
2
24.8735
13.9698
0.8645
31.1714
0.1634
0
0
0.107
0
0.107
0
100
0


13
3
26.731
13.2379
0.8304
29.9397
0.1799
0
0
0.107
0
0.107
0
100
0


13
4
25.0125
13.3208
0.8199
29.5626
0.1706
0
0
0.107
0
0.107
0
100
0


13
5
20.9959
12.5637
0.7
25.2389
0.1263
0
0
0.107
0
0.107
0
100
0


13
6
19.7859
13.0643
0.6384
23.0182
0.1112
0
0
0.107
0
0.107
0
100
0


13
7
12.7701
8.6484
0.4737
17.0786
0.0821
0
0
0.107
0
0.107
0
100
0


13
8
19.9798
12.3643
0.7421
26.7561
0.1113
0
0
0.107
0
0.107
0
100
0


13
9
23.9004
15.4262
0.8368
30.1725
0.1326
0
0
0.107
0
0.107
0
100
0


13
10
20.1688
14.395
0.7685
27.7093
0.1134
0
0
0.107
0
0.107
0
100
0


13
11
−1.5531
−0.2131
0.0003
0.0093
−0.0139
0
0
0.107
0
0.107
0
100
0


13
12
16.261
10.9519
0.6007
21.66
0.0928
0
0
0.107
0
0.107
0
100
0


13
13
2.1579
1.7026
0.1307
4.7131
0.0287
0
0
0.107
0
0.107
0
100
0


13
14
10.3449
7.0881
0.4013
14.4697
0.0725
0
0
0.107
0.625
0.732
0
14.62
85.38


13
15
17.9906
12.3676
0.6892
24.8485
0.1057
0
0.625
0.107
0
0.732
85.38
14.62
0


13
16
24.9296
12.3107
0.7853
28.3135
0.1895
0.1275
0
0
0
0.1275
0
100
0


14
1
19.7006
13.895
0.7196
25.9447
0.1225
0
0
0.1138
0
0.1138
0
100
0


14
2
24.628
13.7864
0.8645
31.1715
0.1715
0
0
0.1138
0
0.1138
0
100
0


14
3
27.0603
12.7211
0.8226
29.6605
0.2007
0
0
0.1138
0
0.1138
0
100
0


14
4
24.9719
12.0514
0.83
29.9259
0.1896
0
0
0.1138
0
0.1138
0
100
0


14
5
20.0669
11.3486
0.7334
26.4431
0.1416
0
0
0.1138
0
0.1138
0
100
0


14
6
19.3148
11.3116
0.7073
25.5033
0.128
0
0
0.1138
0
0.1138
0
100
0


14
7
13.0698
9.2496
0.5178
18.6703
0.0862
0
0
0.1138
0
0.1138
0
100
0


14
8
21.4825
14.0766
0.7634
27.5263
0.1153
0
0
0.1138
0
0.1138
0
100
0


14
9
23.8379
15.3459
0.8607
31.0347
0.1367
0
0
0.1138
0
0.1138
0
100
0


14
10
21.5278
13.8928
0.7851
28.3081
0.1137
0
0
0.1138
0
0.1138
0
100
0


14
11
−2.1621
−1.2165
−0.0091
−0.3271
−0.0078
0
0
0.1138
0
0.1138
0
100
0


14
12
17.3041
11.5725
0.646
23.2923
0.0958
0
0
0.1138
0
0.1138
0
100
0


14
13
1.949
2.0565
0.0896
3.2302
0.028
0
0
0.1138
0
0.1138
0
100
0


14
14
9.3689
6.5087
0.3449
12.4353
0.0636
0
0
0.1138
0.625
0.7388
0
15.41
84.59


14
15
18.4324
12.0276
0.6914
24.9297
0.1067
0
0.625
0.1138
0
0.7388
84.59
15.41
0


14
16
−0.7558
−0.6898
0.0165
0.5934
0.0011
0
0
0
0
0
0
0
0


15
1
18.1472
11.9418
0.6987
25.1939
0.1082
0
0
0.1207
0
0.1207
0
100
0


15
2
24.7631
13.6604
0.8641
31.1563
0.1697
0
0
0.1207
0
0.1207
0
100
0


15
3
26.1211
11.8227
0.834
30.0705
0.2037
0
0
0.1207
0
0.1207
0
100
0


15
4
24.5677
11.9552
0.7923
28.5692
0.1875
0
0
0.1207
0
0.1207
0
100
0


15
5
20.0898
11.474
0.7193
25.9371
0.144
0
0
0.1207
0
0.1207
0
100
0


15
6
19.3675
11.6613
0.6822
24.5972
0.1254
0
0
0.1207
0
0.1207
0
100
0


15
7
12.9911
8.3415
0.5124
18.477
0.0905
0
0
0.1207
0
0.1207
0
100
0


15
8
19.4851
12.9013
0.711
25.6353
0.1146
0
0
0.1207
0
0.1207
0
100
0


15
9
23.6077
14.5462
0.8618
31.074
0.1436
0
0
0.1207
0
0.1207
0
100
0


15
10
21.2589
13.7735
0.7922
28.5624
0.1207
0
0
0.1207
0
0.1207
0
100
0


15
11
−1.3789
−1.3203
0.0019
0.0686
−0.0106
0
0
0.1207
0
0.1207
0
100
0


15
12
16.8366
10.3498
0.6489
23.3953
0.1014
0
0
0.1207
0
0.1207
0
100
0


15
13
2.5374
0.8067
0.138
4.9742
0.0357
0
0
0.1207
0
0.1207
0
100
0


15
14
11.1396
7.0915
0.4088
14.741
0.0773
0
0
0.1207
0.625
0.7457
0
16.18
83.82


15
15
17.5426
10.4944
0.7045
25.4019
0.1136
0
0.625
0.1207
0
0.7457
83.82
16.18
0


15
16
−0.4051
−0.4444
0.0729
2.6294
0.0112
0
0
0
0
0
0
0
0


16
1
15.0725
8.0994
0.5869
21.1613
0.0985
0
0
0.1275
0
0.1275
0
100
0


16
2
24.67
8.6858
0.7009
25.2716
0.2051
0
0
0.1275
0
0.1275
0
100
0


16
3
27.4278
6.3099
0.707
25.4923
0.2645
0
0
0.1275
0
0.1275
0
100
0


16
4
24.8032
6.1186
0.6967
25.1217
0.2372
0
0
0.1275
0
0.1275
0
100
0


16
5
20.9479
7.854
0.6707
24.1843
0.1784
0
0
0.1275
0
0.1275
0
100
0


16
6
19.4346
9.972
0.6893
24.8548
0.1408
0
0
0.1275
0
0.1275
0
100
0


16
7
14.3144
8.9315
0.5183
18.6864
0.0889
0
0
0.1275
0
0.1275
0
100
0


16
8
20.6449
13.6205
0.7023
25.3217
0.1142
0
0
0.1275
0
0.1275
0
100
0


16
9
24.2561
14.785
0.854
30.7919
0.1506
0
0
0.1275
0
0.1275
0
100
0


16
10
21.0486
14.0733
0.6995
25.2209
0.1084
0
0
0.1275
0
0.1275
0
100
0


16
11
−2.2759
−0.0846
0.0413
1.4879
0.024
0
0
0.1275
0
0.1275
0
100
0


16
12
17.1423
10.7518
0.5869
21.1613
0.0898
0
0
0.1275
0
0.1275
0
100
0


16
13
3.0092
2.0883
0.2069
7.4586
0.0432
0
0
0.1275
0
0.1275
0
100
0


16
14
12.8714
7.6083
0.5142
18.5415
0.1069
0
0
0.1275
0.625
0.7525
0
16.94
83.06


16
15
17.5841
9.9481
0.6294
22.6946
0.129
0
0.625
0.1275
0
0.7525
83.06
16.94
0


16
16
25.0686
11.1805
0.8288
29.884
0.1822
0.1275
0
0
0
0.1275
0
100
0










Claims
  • 1. A method for producing a hydrogen-rich gas which comprises: contacting a CO-containing gas with a water gas shift catalyst in the presence of water at a temperature of not more than about 450° C., wherein the water gas shift catalyst comprises: a) Pt, its oxides or mixtures thereof, b) at least one of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, their oxides and mixtures thereof, and c) at least one of Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Pd, La, Ce, Pr, Nd, Sm, Eu, their oxides and mixtures thereof.
  • 2. The method according to claim 1, wherein the CO-containing gas is a syngas.
  • 3. The method according to claim 1, wherein the water gas shift catalyst comprises at least one of Li, Na, K, their oxides and mixtures thereof.
  • 4. The method according to claim 3, wherein the water gas shift catalyst comprises Fe, its oxides or mixtures thereof.
  • 5. The method according to claim 3, wherein the water gas shift catalyst is selected from the group consisting of Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Zr, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and La, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Y, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Mo, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Mn, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, Zr, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof; and Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof.
  • 6. The method according to claim 1, wherein the water gas shift catalyst is supported in a carrier selected from alumina, zirconia, titania, ceria, magnesia, lanthania, niobia, zeolite, perovskite, silica clay, yttria, iron oxide or mixtures thereof.
  • 7. The method according to claim 6, wherein the water gas shift catalyst comprises at least one of Li, Na, K, their oxides or mixtures thereof.
  • 8. The method according to claim 7, wherein the water gas shift catalyst comprises Fe, its oxides or mixtures thereof.
  • 9. The method according to claim 7, wherein the supported water gas shift catalyst is selected from: Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof and Zr, its oxides or mixtures thereof on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and La, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Y, its oxides or mixtures thereof on Al2O3; Pt, its oxides or mixtures thereof. Na, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof and Mo, its oxides or mixtures thereof on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof. Na, its oxides or mixtures thereof and Co, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof and Mn, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, Zr, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on ZrO2; and Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof, on ZrO2.
  • 10. The method according to claim 9, wherein the Al2O3 is γ-Al2O3.
  • 11. The method according to claim 6, wherein the carrier comprises at least one member selected from the group consisting of iron oxide zirconia, titania and ceria.
  • 12. The method according to claim 11, wherein the carrier comprises zirconia.
  • 13. The method according to claim 1, wherein the CO-containing gas is contacted with the water gas shift catalyst at a temperature ranging from about 150° C. to about 450° C.
  • 14. The method according to claim 13, wherein the CO-containing gas is contacted with a water gas shift catalyst at a temperature ranging from more than about 350° C. to up to about 450° C.
  • 15. The method according to claim 13, wherein the CO-containing gas is contacted with a water gas shift catalyst at a temperature ranging from about 250° C. to up to about 350° C.
  • 16. The method according to claim 13, wherein the CO-containing gas is contacted with a water gas shift catalyst at a temperature ranging from about 150° C. to up to about 250° C.
  • 17. The method according to claim 1, wherein the CO-containing gas is contacted with the water gas shift catalyst at a pressure of no more than about 75 bar.
  • 18. The method according to claim 17, wherein the CO-containing gas is contacted with the water gas shift catalyst at a pressure of no more than about 50 bar.
  • 19. The method according to claim 17, wherein the CO-containing gas is contacted with the water gas shift catalyst at a pressure of no more than about 15 bar.
  • 20. The method according to claim 17, wherein the CO-containing gas is contacted with the water gas shift catalyst at a pressure of no more than about 1 bar.
  • 21. The method according to claim 1, wherein the water gas shift catalyst comprises about 0.01 wt. % to about 10 wt. %, with respect to the total weight of all catalyst components plus the support material, of each Group 8, 9 or 10 element present in the water gas shift catalyst.
  • 22. The method according to claim 21, wherein the water gas shift catalyst comprises about 0.01 wt. % to about 2 wt. % of each Group 8, 9 or 10 element present in the water gas shift catalyst.
  • 23. The method according to claim 22, wherein the water gas shift catalyst comprises about 0.05 wt. % to about 0.5 wt. % of each Group 8, 9 or 10 element present in the water gas shift catalyst.
  • 24. The method according to claim 1, wherein the water gas shift catalyst comprises about 0.05 wt. % to about 20 wt. %, with respect to the total weight of all catalyst components plus the support material, of each lanthanide element present in the water gas shift catalyst.
  • 25. A catalyst for catalyzing the water gas shift reaction comprising: a) Pt, its oxides or mixtures thereof, b) at least one of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, their oxides and mixtures thereof, and c) at least one of Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Pd, La, Ce, Pr, Nd, Sm, Eu, their oxides and mixtures thereof.
  • 26. The catalyst according to claim 25, wherein the catalyst comprises at least one of Li, Na, K, their oxides and mixtures thereof.
  • 27. The catalyst according to claim 26, wherein the catalyst comprises Fe, its oxides or mixtures thereof.
  • 28. The catalyst according to claim 26, wherein the catalyst is selected from the group consisting of: Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Zr, its oxides or mixtures thereof, Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and La, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Y, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Mo, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Mn, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, Zr, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof; Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof; and Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof.
  • 29. The catalyst according to claim 25, further comprising a support selected from alumina, zirconia, titania, ceria, magnesia, lanthania, niobia, zeolite, perovskite, silica clay, yttria, iron oxide or mixtures thereof.
  • 30. The catalyst according to claim 29, wherein the catalyst comprises at least one of Li, Na, K, their oxides and mixtures thereof.
  • 31. The catalyst according to claim 29, wherein the catalyst comprises Fe, its oxides, or mixtures thereof.
  • 32. The catalyst according to claim 30, wherein the supported catalyst is selected from: Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Li, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Zr, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and La, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Y, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Mo, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Mn, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, Zr, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on Al2O3; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, Na, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Fe, its oxides or mixtures thereof, on ZrO2; Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Co, its oxides or mixtures thereof, on ZrO2; and Pt, its oxides or mixtures thereof, K, its oxides or mixtures thereof, and Ce, its oxides or mixtures thereof, on ZrO2.
  • 33. The catalyst according to claim 32, wherein the Al2O3 is γ-Al2O3.
  • 34. The catalyst according to claim 25, wherein the catalyst comprises about 0.01 wt. % to about 10 wt. %, with respect to the total weight of all catalyst components plus the support material, of each Group 8, 9 or 10 element present in the catalyst.
  • 35. The catalyst according to claim 34, wherein the catalyst comprises about 0.01 wt. % to about 2 wt. % of each Group 8, 9 or 10 element present in the catalyst.
  • 36. The catalyst according to claim 35, wherein the catalyst comprises about 0.05 wt. % to about 0.5 wt. % of each Group 8, 9 or 10 element present in the catalyst.
  • 37. The catalyst according to claim 25, wherein the catalyst comprises about 0.05 wt. % to about 20 wt. %, with respect to the total weight of all catalyst components plus the support material, of each lanthanide element present in the catalyst.
  • 38. A catalyst for catalyzing the water gas shift reaction comprising: a) Pt, its oxides or mixtures thereof; b) at least one of V, Zr, their oxides and mixtures thereof; and c) at least one of Ti, Mo, Co, their oxides and mixtures thereof.
  • 39. The catalyst according to claim 38, wherein the catalyst further comprises Na, its oxides or mixtures thereof.
  • 40. A method for producing a hydrogen-rich syngas which comprises: contacting a CO-containing gas with a water gas shift catalyst in the presence of water at a temperature of not more than about 450° C., wherein the water gas shift catalyst comprises: a) Pt, its oxides or mixtures thereof; b) at least one of V, Zr, their oxides and mixtures thereof, and c) at least one of Ti, Mo, Co, their oxides and mixtures thereof.
  • 41. The method according to claim 40, wherein the water gas shift catalyst further comprises Na, its oxides or mixtures thereof.
  • 42. A method of preparing a catalyst comprising the steps of applying Li and Fe containing precursors to a surface; calcining the Li and Fe containing surface to a temperature of between about 600° C. and about 900° C. to form a treated surface; applying a Pt containing precursor to the treated surface.
  • 43. A method according to claim 42, wherein Na is impregnated onto the treated surface after the calcination step.
  • 44. A method according to claim 42, wherein the temperature is about 700° C.
  • 45. A fuel processing system for generation of a hydrogen-rich gas from a hydrocarbon or substituted hydrocarbon fuel, the fuel processing system comprising: a fuel reformer for converting a fuel reactant stream comprising a hydrocarbon or a substituted hydrocarbon fuel to a reformed product stream comprising carbon monoxide and water, the fuel reformer having an inlet for receiving the reactant stream, a reaction chamber for converting the reactant stream to the product stream and an outlet for discharging the product stream; a water gas shift reactor for effecting a water gas shift reaction at a temperature of less than about 450° C., the water gas shift reactor comprising an inlet for receiving a water gas shift feed stream comprising carbon monoxide and water from the product stream of the fuel reformer, a reaction chamber comprising the water gas shift catalyst of claim 25, the water gas shift catalyst being effective for generating hydrogen and carbon dioxide from the water gas shift feed stream and an outlet for discharging the resulting hydrogen-rich gas; and a temperature controller adapted for maintaining the temperature of the reaction chamber of the water gas shift reactor at a temperature of less than about 450° C.
CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims benefit from earlier filed U.S. Provisional Application No. 60/434,682, filed Dec. 20, 2002, which is incorporated herein in its entirety by reference for all purposes. The present application also incorporates by reference PCT International Patent Application No. ______ entitled “Platinum-Alkali/Alkaline-Earth Catalyst Formulations For Hydrogen Generation” naming as inventors Hagemeyer et al. (Attorney Docket No. 708000601PCT) filed on the same date as the present application.

Provisional Applications (1)
Number Date Country
60434682 Dec 2002 US