RUTHENIUM-COPPER CHROMITE HYDROGENATION CATALYSTS

FIELD OF THE INVENTION

This invention pertains to hydrogenation catalysts comprising copper chromite having ruthenium and one or more promoters deposited thereon. More specifically, this invention pertains to hydrogenation catalysts comprising copper chromite having ruthenium, and at least one promoter selected from alkali metals, alkaline earth metals, rare earth metals, and manganese, deposited thereon. This invention further pertains to processes for the preparation of methanol by hydrogenation of carbon monoxide and of alcohols by the hydrogenation of carbonyl compounds using the above hydrogenation catalysts.

DETAILED DESCRIPTION

The synthesis of methanol from mixtures of carbon monoxide, carbon dioxide, and hydrogen (referred to herein as “syngas”) is an equilibrium reaction that favors high conversion to methanol at low operating temperatures. An increase in conversion of methanol at low temperature reduces the production cost of methanol by lowering the requirement for recycle of unreacted syngas and the attendant compression and capital costs. Moreover, operation at lower temperatures extends the life of methanol catalysts by retarding the rate of sintering. Sintering leads to gradual catalyst deactivation by reducing active catalyst surface area. The syngas feedstock typically used for the production of methanol also can contain high levels of carbon dioxide, which can inhibit the activity of the methanol catalysts. Methanol catalysts are needed, therefore, which have high activity under mild operating conditions and which can tolerate carbon dioxide well.

The preparation of alcohols by hydrogenation of carbonyl compounds such as, for example, aldehydes, ketones, and carboxylic acid esters, is an important commercial process. In particular, the hydrogenation of carboxylic acid esters is used for the production of detergent alcohols and polymer intermediates. Typically, the hydrogenation of esters requires aggressive process conditions and some catalysts used in these processes can present disposal problems. For example, when used in fixed bed reactors, the existing catalysts are used as shaped bodies which can have limited mechanical stability under the mechanical stresses occurring there. In addition, the hydrogenation activity of these catalysts such as, for example, in the production polyhydric alcohols by hydrogenation of polybasic acid esters, can be insufficient for the achievement of high space-time yields. New catalysts that exhibit high activities, long lifetimes, and good mechanical stabilities are needed.

We have discovered novel compositions that are useful as catalysts for the preparation of methanol by hydrogenation of carbon monoxide and for the preparation of alcohols by the hydrogenation of carbonyl compounds. In one embodiment, therefore, our invention provides a hydrogenation catalyst, comprising: copper chromite, ruthenium, and at least one promoter selected from alkali metals, alkaline earth metals, rare earth metals, and manganese, wherein the ruthenium and the at least one promoter are deposited on the copper chromite. Our novel hydrogenation catalysts exhibit high catalytic activities and selectivities for methanol using feedstocks that contain both low and high concentrations of carbon dioxide. Our catalysts can show significant enhancement in CO hydrogenation activity over traditional copper chromite catalysts. Furthermore, the ruthenium-containing catalysts of the invention show low or no hydrocarbon products, although ruthenium catalysts are known to be active for the production of hydrocarbons from synthesis gas.

Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, each numerical parameter should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Further, the ranges stated in this disclosure and the claims are intended to include the entire range specifically and not just the endpoint(s). For example, a range stated to be 0 to 10 is intended to disclose all whole numbers between 0 and 10 such as, for example 1, 2, 3, 4, etc., all fractional numbers between 0 and 10, for example 1.5, 2.3, 4.57, 6.1113, etc., and the endpoints 0 and 10. Also, a range associated with chemical substituent groups such as, for example, “C₁to C₅hydrocarbons”, is intended to specifically include and disclose C₁and C₅hydrocarbons as well as C₂, C₃, and C₄hydrocarbons.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

As used in the specification and the claims, the singular forms “a,” “an” and “the” include their plural referents unless the context clearly dictates otherwise. For example, references to a “promoter,” or a “reactor” is intended to include the one or more promoters or reactors. References to a composition or process containing or including “an” ingredient or “a” step is intended to include other ingredients or other steps, respectively, in addition to the one named.

The terms “containing” or “including”, are synonymous with the term “comprising”, and is intended to mean that at least the named compound, element, particle, or method step, etc., is present in the composition or article or method, but does not exclude the presence of other compounds, catalysts, materials, particles, method steps, etc, even if the other such compounds, material, particles, method steps, etc., have the same function as what is named, unless expressly excluded in the claims.

It is also to be understood that the mention of one or more method steps does not preclude the presence of additional method steps before or after the combined recited steps or intervening method steps between those steps expressly identified. Moreover, the lettering of process steps or ingredients is a convenient means for identifying discrete activities or ingredients and the recited lettering can be arranged in any sequence, unless otherwise indicated.

The catalysts of the invention are hydrogenation catalysts. The term “hydrogenation catalyst”, as used herein, is intended to have its commonly accepted meaning as would be understood by persons having ordinary skill in the art, that is, a substance that increases the rate of a hydrogenation reaction, without itself being consumed. The term “hydrogenation”, as used herein, is also intended to have its commonly accepted meaning, that is, the reaction of hydrogen with an organic compound. For the purposes of the present invention, “hydrogenation” is understood to mean the addition of hydrogen to the double bonds or triple bonds of an unsaturated molecule such as, for example, carbon monoxide or a carbonyl compound, to produce a molecule having a higher degree of saturation such as, for example, methanol or an alcohol corresponding to the carbonyl compound. Also for the present invention, the term “hydrogenation” is intended to include “hydrogenolysis” in which the addition of hydrogen causes the rupture of bonds with the subsequent reaction of hydrogen with the molecular fragments. For example, the hydrogenation of esters can be occur by the rupture of a carbon oxygen bond to form alcohol and aldehyde fragments, followed by hydrogenation of the aldehyde fragment to form a second alcohol corresponding to the aldehyde fragment. Thus, according to the present invention, the phrase “hydrogenation of an aldehyde or ketone”, is understood to mean addition of hydrogen to the carbon-oxygen double bond to produce an alcohol corresponding to the aldehyde or ketone. Similarly, “hydrogenation of a carboxylic acid ester”, is understood to mean the hydrogenolysis of the ester to produce an alcohol corresponding to the acid residue of the ester.

The catalysts of the invention comprise copper chromite. The term “copper chromite”, as used herein, is intended have its commonly understood meaning in the art and includes copper chromite itself as represented by the general formula, CuCr₂O_x, non-stoichiometric mixed copper-chromium oxides, prepared by coprecipitation, and the various mixtures of copper chromite with copper metal, copper oxides, and chromium oxides that may be formed during the catalyst manufacturing process and its subsequent use as a hydrogenation catalyst. For example, the copper chromite, as prepared, may comprise one or more of: copper(II) oxide, copper chromite (CuCr₂O₄), chromium trioxide (CrO₃), or chromic oxide (Cr₂O₃). In one embodiment of the invention, for example, the copper chromite may comprise about 24-26 weight % copper(II) oxide, about 65-67 weight % copper chromite, about 1 weight % chromium trioxide, about 1 weight % chromic oxide, and about 0-4 weight % graphite. During the hydrogenation process, a portion of the copper oxide may be reduced to copper metal. Thus, under hydrogenation conditions, the copper chromite of the invention can comprise mixtures of copper chromite, copper oxides, chromium oxides, and copper metal in various proportions. The copper chromite component of the catalysts can be prepared using conventional coprecipitation techniques well known in the art. In addition, the copper chromite may be further compounded with binders to aid in pellet formation or supported on additional support materials such as, for example, alumina, titania, carbon, graphite, zirconia, silica, and the like.

Typically, copper chromite having various molar ratios of copper to chromium may be conveniently prepared by coprecipitation of an aqueous solution of soluble copper and chromium compounds at a pH of 7 or above. The precipitate, typically, is filtered, washed with water, dried, and calcined in air to give the final catalyst. One example of the preparation of a copper chromite that can be used in the present invention is provided by Conner et al., J. Amer. Chem. Soc., 53, 1091(1931). In another example, copper chromite may be prepared in the following manner: Copper sulfate, CuSO₄.5H₂O, and sodium dichromate, Na₂Cr₂O₇.2H₂O, can be combined with ammonium hydroxide to form a complex from which copper chromite may be prepared. The copper sulfate and sodium dichromate are dissolved in water to form a solution. To this solution ammonium hydroxide is added until the pH reaches 7.0 to 7.5. A precipitate is formed which is a complex and is believed to have the formula Cu(OH)NH₄CrO₄. This complex can be filtered, washed with water, dried, and calcined in air to give a copper chromite.

In another example, copper chromite catalyst can prepared by mixing respective solutions of copper nitrate (Cu(NO₃)₂) or another soluble copper (II) salt and a stoichiometric excess of a solution of ammonium chromate ((NH₄)₂CrO₄) with at least a 3:1 weight ratio of ammonium chromate to copper nitrate. If desired, ammonium hydroxide or an equivalent soluble ammonium salt can be partially substituted for ammonium chromate. Precipitation of the copper-ammonium-chromate precipitate is effected by mixing of the two (i.e., copper nitrate and ammonium chromate) solutions. If ammonium hydroxide is to be present, it can be mixed with the ammonium chromate solution prior to mixing with the copper nitrate solution. The precipitate is separated from the mixture and dried by any suitable nondegradative means (e.g. by filtering and vacuum drying) to produce a product which is typically brown in color.

The copper chromite can have a wide range of copper and chromium content. For example, in one embodiment, the copper chromite can have copper content of about 15 to about 60 weight percent and a chromium content of about 15 to 60 weight percent, based on the total weight of the copper chromite. In another example, the copper chromite can have a copper content of about 30 to about 50 weight percent and a chromium content of about 30 to about 50 weight percent. Typically, the gram-atom ratio of copper to chromium can be about 1:10 to about 10:1. Additional examples of gram-atom ratios of copper to chromium are about 1:5 to about 5:1 and about 1:2 to about 2:1.

The catalyst also comprises ruthenium and at least one promoter selected from alkali metals, alkaline earth metals, rare earth metals, and manganese, deposited on the copper chromite. The term “promoter”, as used herein, is understood to mean as substance that, when added in relatively small quantities to a catalyst, increases its activity. By the term “deposited on”, as used herein, it is understood that the ruthenium and other metals are placed on the surface of the copper chromite using conventional techniques, well-known in the art. A physical mixture of ruthenium and copper chromite, for example, would not have ruthenium deposited on the copper chromite. The ruthenium and other metals may be deposited on the copper chromite by contacting the copper chromite with an aqueous solution of compounds of ruthenium and the other promoter metals followed by filtering and drying the copper chromite at a temperature of about 40 to about 150° C. Typically, the ruthenium and the other metals are dissolved in aqueous solution as various water-soluble salts such as, for example, as their nitrates, carbonates, oxides, hydroxides, bicarbonates, formates, chromates, sulfates, acetates, benzoates, and the like. The dried copper chromite may then be calcined by heating at a temperature of about 350 to about 600° C. in the presence of air or an inert gas such as, for example, nitrogen or argon. The terms “calcined”, “calcination”, and “calcining”, as used herein, are intended to have their commonly understood meanings in the art, that is, heating the catalyst composition or catalyst precursor composition to a temperature below its melting point to bring about a state of thermal decomposition or a phase transition of some or all of its components other than melting. During calcining, for example, organic compounds and ammonium salts can be decomposed and water of hydration can be expelled. In a variant of the above impregnation process, the solution of ruthenium and other promoters may be deposited on the copper chromite by incipient wetness methods well-known to persons skilled in the art. The ruthenium and promoter may be deposited on the copper chromite at the same time or sequentially in any order. For example, the copper chromite can be impregnated first with a solution of a water soluble ruthenium compound. After filtering, drying, and calcining the ruthenium-impregnated copper chromite as described above, the copper chromite can be further impregnated with a aqueous solution of one or more alkali metals, alkaline earth metals, rare earth metals, or manganese. The impregnated copper chromite can be dried and calcined as described previously.

The catalyst, in addition to ruthenium, comprises about 100 to about 5000 parts per million, based on the total weight of the catalyst, of at least one promoter selected from alkali metals, alkaline earth metals, rare earth metals, and manganese. Other examples of concentrations of these metals other than ruthenium are about 1000 to about 3000 parts per million and about 1000 to about 2000 part per million. For example, in addition to ruthenium, the catalyst can comprise at least one promoter selected from sodium, potassium, calcium, barium, magnesium, manganese, and lanthanum. In another example, the promoter can be selected from lanthanum, calcium, barium, and potassium.

In one embodiment of the invention, for example, the catalyst comprises copper chromite having a gram-atom ratio of copper to chromium of about 1:2 to 2:1, and on which is deposited about 0.5 to about 5 weight percent ruthenium and about 100 to about 5000 parts per million of at least one promoter selected from lanthanum, sodium, magnesium, potassium, manganese, calcium and barium. As described previously, the above weight percent and parts per million are based on the total weight of the catalyst. Further, the above embodiment can include the various, other embodiments of copper chromite, ruthenium, other metals, and catalyst preparation conditions described hereinabove and in any combination.

For example, the copper chromite can have a gram-atom ratio of copper to chromium of about 1:1. In another example, catalyst can comprise about 1 weight percent ruthenium. In still another example, the catalyst can comprise about 1000 parts per million, based on the total weight of the catalyst, of at least one promoter in addition to ruthenium. As described above, representative examples of promoters include sodium, calcium, barium, manganese, and lanthanum.

In yet another example, the catalyst of the invention comprises: copper chromite having a gram-atom ratio of copper to chromium of about 1:1, about 1 weight percent ruthenium and about 1000 parts per million of at least one promoter selected from lanthanum, manganese, sodium, potassium, calcium, magnesium, and barium; wherein the ruthenium and promoter are deposited on the copper chromite and the weight percent and parts per million are based on the total weight of the catalyst. The various embodiments of copper chromite, ruthenium, promoters, and catalyst preparation conditions are described hereinabove and can be used in any combination.

Our invention also provides a catalyst consisting essentially of: copper chromite having a gram-atom ratio of copper to chromium of about 1:2 to 2:1, about 0.5 to about 5 weight percent ruthenium and about 100 to about 5000 parts per million of at least one promoter selected from lanthanum, sodium, magnesium, potassium, manganese, calcium and barium, wherein the ruthenium and the at least one promoter are deposited on the copper chromite and the weight percent and parts per million are based on the total weight of the catalyst. Other embodiments of copper chromite, ruthenium, promoters, and catalyst preparation conditions described hereinabove may be included in any combination.

The phrase “consisting essentially of”, as used herein, is intended to encompass a catalyst which comprises primarily copper chromite on which is deposited ruthenium and one or more promoter metals selected from lanthanum, sodium, magnesium, potassium, manganese, calcium and barium. It is understood to exclude any elements that would substantially alter the essential properties of the catalyst to which the phrase refers. Although the catalysts of the present invention are based predominantly on copper chromite, ruthenium, and the above listed promoter metals, it is understood that the catalyst can also comprise binders, support materials, and small amounts of other noble and non-noble metals, promoters, salts, deposited thereon, as long as the catalyst properties are not significantly affected. For example, the catalyst may contain additional metals or metal compounds, in small amounts, i.e., generally less than 1000 ppm, as long as the additional metal and/or metal compounds do not significantly affect the performance and properties of the catalyst. For example, the copper chromite catalyst containing the ruthenium and promoter metals deposited thereon, may be further compounded with binders to aid in pellet formation or supported on additional support materials such as, for example, alumina, titania, carbon, graphite, zirconia, silica, and the like. By contrast, catalyst compositions in which the ruthenium and promoter metals are not deposited on the copper chromite are intended to be excluded. For example, a physical mixture or blend of the copper chromite, ruthenium compounds, and promoter components are intended to be excluded from the invention because in such as mixture, the ruthenium and promoter metals would not be deposited on the copper chromite. The discussion herein provides examples of the kinds of modifications that may be employed, but those of skill in the art will readily recognize others.

For example, the catalyst may comprise copper chromite having a gram-atom ratio of copper to chromium of about 1:1, about 1 weight percent ruthenium and about 1000 parts per million of at least one promoter. The promoters may be selected from lanthanum, manganese, sodium, potassium, calcium, magnesium, and barium. As noted above, the ruthenium and promoter are deposited on the copper chromite and the weight percent and parts per million are based on the total weight of the catalyst.

Our invention also include a process for the preparation of a catalyst, comprising: contacting copper chromite with a solution of a ruthenium compound and a solution of at least one promoter selected from compounds of lanthanum, sodium, potassium, magnesium, calcium and barium; drying the copper chromite, and calcining the dried copper chromite. The copper chromite may be contacted with an aqueous solution of compounds of ruthenium and the other promoter metals followed by filtering and drying the copper chromite at a temperature of about 40 to about 150° C., as described above. Typically, the ruthenium and the other metals are dissolved in aqueous solution as their various water-soluble salts such as, for example, as their nitrates, carbonates, oxides, hydroxides, bicarbonates, formates, chromates, sulfates, acetates, benzoates, and the like. The dried copper chromite may then be calcined by heating at a temperature of about 350 to about 600° C. in the presence of air or an inert gas such as, for example, nitrogen or argon.

The ruthenium and one or more promoters may be contacted with or deposited on the copper chromite at the same time or sequentially in any order. For example, the copper chromite can be impregnated first with a solution of a water soluble ruthenium compound. After filtering, drying, and calcining the ruthenium-impregnated copper chromite as described above, the ruthenium-modified copper chromite can be further impregnated with a aqueous solution of one or more alkali metals, alkaline earth metals, rare earth metals, or manganese. The impregnated copper chromite can be dried and calcined as described previously. Thus, the above process may further comprise (i) contacting copper chromite with a solution of a ruthenium compound; (ii) drying the copper chromite; (iii) calcining the dried copper chromite from step (ii); (iv) contacting the calcined copper chromite from step (iii) with a solution of at least one compound selected from lanthanum, sodium, magnesium, potassium, calcium, manganese, and barium; (v) drying the copper chromite from step (iv); and (vi) calcining the dried copper chromite from step (v). The drying steps (ii) and (v) independently can be carried out at a temperature of about 40 to about 150° C. and the calcination steps (iii) and (vi) independently can be carried out at a temperature of about 400 to about 600° C.

The catalyst prepared by the process of the invention is understood to include the various embodiments of copper chromite, ruthenium, and promoters as described above and in any combination. For example, the catalyst can comprise about 0.1 to about 10 weight percent ruthenium and about 100 to about 5000 parts per million of at least one promoter selected from lanthanum, sodium, manganese, potassium, magnesium, calcium, and barium. In another example, the catalyst can comprise about 0.5 to about 2 weight percent ruthenium and about 1000 to about 2000 parts per million of at least one promoter selected from lanthanum, sodium, calcium, barium, and manganese.

Our catalysts are useful for the hydrogenation of carbon monoxide and/or carbon dioxide to methanol. Our invention, therefore, includes a process for the preparation of methanol, comprising: contacting a gaseous feed comprising hydrogen, carbon monoxide, and optionally carbon dioxide, with a catalyst comprising copper chromite, ruthenium and at least one promoter selected from alkali metals, alkaline earth metals, rare earth metals, and manganese; wherein the ruthenium and the at least one promoter are deposited on the copper chromite. The catalyst is understood to include the various embodiments of copper chromite, ruthenium, and promoters as described above and in any combination. In one example, the catalyst can comprise about 0.1 to about 10 weight percent ruthenium based on the total weight of the catalyst. Other examples of ruthenium weight percentage ranges for the catalyst are about 0.5 to about 5 weight percent and about 0.5 to about 2 weight percent.

As described previously, the catalyst also may comprise about 100 to about 5000 parts per million, based on the total weight of the catalyst, of at least one promoter selected from alkali metals, alkaline earth metals, rare earth metals, and manganese. Additional representative ranges of promoters include about 1000 to about 3000 parts per million and about 1000 to about 2000 parts per million. Typical promoters can be selected from sodium, potassium, calcium, barium, lanthanum, and combinations of these promoters.

The catalyst typically will comprise greater than 50 weight percent copper chromite, based on the total weight of the catalyst. Other examples of copper chromite levels within the catalysts of the invention, are at least 60 weight percent, at least 70 weight percent, at least 80 weight percent, and at least 90 weight percent. In one example, the catalyst comprises about 85 to about 99.89 weight percent of copper chromite. In another embodiment, the copper chromite can have a copper content of about 15 to about 60 weight percent and a chromium content of about 15 to about 60 weight percent, based on the total weight of the copper chromite. In yet another example, the copper chromite can have a copper content of about 30 to about 50 weight percent and a chromium content of about 30 to about 50 weight percent. Typically, the gram-atom ratio of copper to chromium will be about 1:10 to about 10:1. Additional examples of gram-atom ratios of copper to chromium are about 1:5 to about 5:1 and about 1:2 to about 2:1. In still another embodiment of our hydrogenation process, the catalyst can comprise copper chromite having a gram-atom ratio of copper to chromium of about 1:2 to 2:1, about 0.5 to about 5 weight percent ruthenium and about 100 to about 5000 parts per million of at least one promoter selected from lanthanum, sodium, potassium, manganese, calcium, magnesium, and barium, the weight percent and parts per million being based on the total weight of the catalyst.

The catalyst is contacted with a gaseous feed comprising hydrogen, carbon monoxide, and optionally, carbon dioxide. Such mixtures are commonly referred to as “syngas” and can be produced by blending the individual gases or by any of a number of methods known in the art including steam or carbon dioxide reforming of carbonaceous materials such as natural gas or petroleum derivatives; and the partial oxidation or gasification of carbonaceous materials, such as petroleum residuum, bituminous, subbituminous, and anthracitic coals and cokes, lignite, oil shale, oil sands, peat, biomass, petroleum refining residues or cokes, and the like.

The hydrogen, carbon monoxide, and/or carbon dioxide content of the syngas may be adjusted for efficiency of conversion. For example, the gaseous feed to the catalyst can have a molar ratio of hydrogen to carbon oxides (CO+CO₂) in the range of from about 0.5:1 to about 20:1, preferably in the range of from about 2:1 to about 10:1. In another embodiment, the gaseous feed can have a molar ratio of hydrogen (H₂) to carbon monoxide (CO) of at least 2:1.

Carbon dioxide may be optionally present in an amount of not greater than 50% by weight, based on total volume of the gaseous feed. Additional examples of carbon dioxide levels in the gaseous feed include, but are not limited to about 1 to about 25 weight percent carbon dioxide, about 1 to about 5 weight percent carbon dioxide, and about 10 to about 20 weight percent carbon dioxide.

The CO₂content, relative to that of CO, in the gaseous feed can be high enough so as to maintain an appropriately high reaction temperature and to minimize the amount of undesirable by-products such as, for example, paraffins. At the same time, the relative CO₂content should not be too high so as to reduce methanol yield. Typically, the gaseous feed will contain CO₂and CO at a molar ratio of from about 0.5 to about 1.2 or, in another example, from about 0.6 to about 1.0.

The process of the invention may be carried out over a range of temperatures. The gaseous mixture of carbon monoxide, hydrogen, and optionally, carbon dioxide typically is contacted with the catalyst at a temperature of about 150 to about 350° C. and at a pressure of about 10 to about 100 bara. In another example, the gaseous mixture may be contacted with the catalyst at temperature of about 180 to about 250° C. and at a pressure of about 30 to about 70 bara.

The methanol process can be carried out in any type of methanol synthesis plant known to persons skilled in the art and many of which are widely practiced on a commercial basis. Examples of such processes include batch processes and continuous processes. Tubular bed processes and fluidized bed processes are examples of types of continuous processes. A number of different process technologies are known for synthesizing methanol such as, for example, the ICI (Imperial Chemical Industries) or Haldor Topsoe processes, the Lurgi process, and the Mitsubishi process. Liquid phase processes are also well known in the art. For example, the gaseous feed and catalyst of the process according to the present invention may be contacted in a fixed bed or liquid slurry phase reactor.

The syngas stream is typically supplied to a methanol reactor at the pressure of about 25 to about 140 bara, depending upon the process employed. The syngas then reacts over a catalyst to form methanol. The reaction is exothermic; therefore, heat removal is ordinarily required. The raw or impure methanol is then condensed and may be purified to remove impurities such as higher alcohols including ethanol, propanol, and the like, or used without further purification. The uncondensed vapor phase comprising unreacted syngas feedstock typically is recycled to the methanol process feed.

The hydrogenation process may be conducted at various gas hourly space velocities depending upon the type of process that is used. In one embodiment, for example, the gas hourly space velocity of flow of gas through the catalyst bed is in the range of from about 50 hr⁻¹to about 50,000 hr⁻¹. In other examples, the gas hourly space velocity of flow of gas through the catalyst bed is about 250 hr⁻¹to about 25,000 hr⁻¹, or about 500 hr⁻¹to about 15,000 hr⁻¹.

Our invention also may be used for the preparation of alcohols from organic carbonyl compounds such as, for example, an aliphatic, cycloaliphatic and aromatic carbonyl compound by hydrogenation in the presence of the catalysts described hereinabove. Thus, another aspect of the invention is a process for hydrogenating a carbonyl compound to an alcohol, comprising contacting at least one carbonyl compound with hydrogen in the presence of a catalyst comprising copper chromite, ruthenium and at least one promoter selected from alkali metals, alkaline earth metals, rare earth metals, and manganese; wherein the ruthenium and at least one promoter are deposited on the copper chromite.

The catalyst is understood to include the various embodiments of copper chromite, ruthenium, and promoters as described above and in any combination. For example, the catalyst can comprise about 0.1 to about 10 weight percent ruthenium based on the total weight of the catalyst. Other examples of ruthenium weight percentage ranges for the catalyst are about 0.5 to about 5 weight percent and about 0.5 to about 2 weight percent.

The catalyst also can comprise about 100 to about 5000 parts per million, based on the total weight of the catalyst, of at least one promoter selected from alkali metals, alkaline earth metals, rare earth metals, and manganese. Additional representative ranges of promoters include about 1000 to about 3000 parts per million and about 1000 to about 2000 parts per million. Typical promoters can be selected from sodium, potassium, calcium, barium, lanthanum, and combinations of these promoters.

The carbonyl compound can comprise an aldehyde, ketone, carboxylic acid ester, or a combination thereof. Examples of the carbonyl compounds which can be hydrogenated include aliphatic, cycloaliphatic and aromatic aldehydes, esters and ketones containing up to about 50 carbon atoms. Acetophenone, benzophenone, acetone, methyl butyl ketone, benzaldehyde, crotonaldehyde, acetaldehyde, and butyraldehyde are typical ketones and aldehydes which may be converted to alcohols according to the present invention. Thus, one aspect of the novel hydrogenation process provides a process for the preparation of an alcohol by the hydrogenation of an aliphatic, cycloaliphatic or aromatic aldehyde, carboxylic acid ester, or ketone in the presence of one of the catalysts described hereinabove under hydrogenation conditions of temperature and pressure.

In one embodiment of the invention, for example, the carbonyl compound employed in the hydrogenation process can be an aliphatic, cycloaliphatic, or araliphatic ester of an aliphatic or cycloaliphatic mono- or polycarboxylic acid. As another example, the carbonyl compound can comprise an alkyl carboxylate comprising residues of at least one hydroxy compound containing from 1 to about 40 carbon atoms. Representative examples of hydroxy compounds are methanol, ethanol, propanol, 1-butanol, 2-butanol, isobutanol, 2-ethylhexanol, 2,2-dimethyl-1,3-propanediol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, cyclohexanol, 4-methylcyclohexanemethanol, diethylene glycol, glycerin, trimethylolpropane, and combinations thereof.

The carboxylic acid residue of the alkyl carboxylate is not important to our process provided that each oxycarbonyl group hydrogenated is bonded to an aliphatic, aralkyl, aryl, or cycloaliphatic carbon atom. The alkyl carboxylate, for example, may comprise residues of at least one aliphatic, cycloaliphatic, aryl, or aralkyl carboxylic acid having from 1 to 40 carbon atoms. In another example, the alkyl carboxylate can comprise the residues of an aliphatic or cycloaliphatic carboxylic acid. Typical examples of cycloaliphatic carboxylic acids are 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and combinations thereof. The aliphatic acid residues may be straight- or branched-chain, saturated or unsaturated and unsubstituted or substituted, for example, with a wide variety of substituents such as halogen, hydroxy, alkoxy, amino, substituted amino, acylamido, aryl, cycloalkyl, etc. The main chain of the aliphatic acid residues also may contain hetero atoms such as oxygen, sulfur and nitrogen atoms. In another embodiment of the present invention, esters of arylcarboxylic acids such as alkyl benzoates are excluded from the term “alkyl carboxylate”, whereas esters of aralkylcarboxylic acids, such as alkyl phenylacetates are included within the meaning of alkyl carboxylates.

Additional representative examples of aliphatic and cycloaliphatic acids include, but are not limited to, formic, acetic, propionic, glycolic, butyric, valeric, hexanoic, heptanoic, octanoic, nonanoic, decanoic, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, heptadecanoic, stearic, oleic, linoleic, linolenic, nonadecanoic, eicosanoic, arachidonic, heneicosanoic, docosanoic, tetracosanoic, octacosanoic, triacontanoic, dotriacontanoic, acrylic, methacrylic, crotonic, 3-butenoic, cyclobutanecarboxylic, 2-norbornane-carboxylic, malonic, succinic, glutamic, maleic, glutaconic, adipic, pimelic, suberic, azelaic, sebacic, 1,2,4-hexanetricarboxylic, 1,2-, 1,3-, and 1,4-cyclohexanedicarboxylic, 2,6- and 2,7-octahydronaphthalenedicarboxylic, 3-1(2-carboxyethyl)thiolbutyric, and the line. Typical examples of esters useful in the invention process, based on the combination of the hydroxy compounds and carboxylic acids described hereinabove, include, but are not limited to, methyl acetate, methyl formate, methyl glycolate, ethyl acetate, methyl n-octa-decanoate, isobutyl decanoate, t-butylnonoate, phenyl acetate, 2-naphthyl propionate, dimethyl oxalate, diethyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate, dimethyl adipate, diethyl adipate, methyl cyclohexylcarboxylate, dimethyl 1,4-cyclohexaned icarboxylate, ethyl cyclohexylacetate, isopropyl acetate, and sec-butyl propionate. The catalysts of the invention can be used, for example, to hydrogenate an alkyl glycolate, such as methyl glycolate, to ethylene glycol.

The amount of catalyst required can be varied substantially depending on a number of factors such as, for example, the physical form of the catalyst, the hydrogenation conditions, and mode of operation. The hydrogenation conditions of pressure and temperature also can be varied depending not only on one another but also on the activity of the catalyst, the mode of operation, selectivity considerations and the desired rate of conversion. Carbonyl compounds may be hydrogenated to their corresponding alcohols according to the invention using temperatures in the range of about 150° C. to about 350° C. and hydrogen pressures in the range of about 40 to 450 bars absolute (“bara”). However, since hydrogenation rates generally increase with temperature, it may desirable to operate in the range of about 180 to about 300° C. and at a pressure of about 200 to about 350 bara to maximize both conversion rates and utilization of the commercial hydrogenation facility. While rates and conversions generally also increase with increasing pressure, the energy costs for compression of hydrogen, as well as the increased cost of high-pressure equipment render the use of the lowest pressure practical desirable.

The hydrogen gas used in the process may comprise fresh gas or a mixture of fresh gas and recycle gas. The hydrogen gas can be a mixture of hydrogen, optional minor amounts of components such as CO and CO₂, and inert gases, such as argon, nitrogen, or methane, containing at least about 70 mole % of hydrogen. For example, the hydrogen gas may contain at least 90 mole % or, in another example, at least 97 mole %, of hydrogen. The hydrogen gas may be obtained from any of the common sources well known in the art such as, for example, by partial oxidation or steam reforming of natural gas. Pressure swing absorption can be used if a high purity hydrogen gas is desired. If gas recycle is utilized in the process, then the recycle gas will normally contain minor amounts of one or more products of the hydrogenation reaction which have not been fully condensed in the product recovery stage downstream from the hydrogenation zone. Thus, when using gas recycle in the process of the invention, the gas recycle stream will typically contain a minor amount of an alkanol, e.g., methanol.

The ester hydrogenation process of this invention may be carried out in the absence or presence of an inert solvent, i.e., a solvent for the ester being hydrogenated which does not affect significantly the activity of the catalyst and does not react with the hydrogenation product or products. Examples of such solvents include alcohols such as ethanol and lauryl alcohol; glycols such as mono-, di- and tri-ethylene glycol; hydrocarbons such as hexane, cyclohexane, octane and decane; and aromatic ethers such as diphenyl ether, etc.

The hydrogenation process may be carried out as a batch, semi-continuous or continuous process. Examples of suitable reactor types include, but are not limited to, stirred tank, continuous stirred tank, trickle bed, tower, slurry, and tubular reactors. The catalyst should be dispersed throughout the reaction media to effectively assist contact of reactants and catalyst. For example, the catalyst may be introduced as small particles that can be slurried or suspended in an agitated reaction mixture. Typically, the catalyst is used in the form of a fixed bed or in slurry form through which reactants are continuously circulated in the liquid or gas phase.

In batch operation, a slurry of the catalyst in the reactant and/or an inert solvent in which the reactant has been dissolved is fed to a pressure vessel equipped with means for agitation. The pressure vessel is then pressurized with hydrogen to a predetermined pressure followed by heating to bring the reaction mixture to the desired temperature. After the hydrogenation is complete, the reaction mixture is removed from the pressure vessel, the catalyst is separated by filtration and the product is isolated, for example, in a distillation train.

Continuous operation can utilize a fixed bed using a larger particle size of catalyst, e.g., catalyst pellets. The catalyst bed may be fixed in a tubular or columnar, high pressure reactor and the liquid reactant, dissolved in an inert solvent if necessary or desired, slowly fed continuously above the bed at elevated pressure and temperature and crude product removed from the base of the reactor. Another mode of continuous operation utilizes a slurry of the catalyst in an agitated pressure vessel which is equipped with a filter leg to permit continuous removal of a solution of product in unreacted ester and/or an inert solvent. In this manner, a liquid reactant or reactant solution can be continuously fed to and product solution continuously removed from an agitated pressure vessel containing an agitated slurry of the catalyst.

The hydrogenation process provided by the invention can be used for converting dialkyl cyclohexanedicarboxylic acid esters to cyclohexanedimethanols. Our invention, therefore, also provides a process for the preparation of a cyclohexanedimethanol comprising contacting at least one dialkyl cyclohexanedicarboxylate with hydrogen in the presence of a catalyst comprising copper chromite, ruthenium and at least one promoter selected from alkali metals, alkaline earth metals, rare earth metals, and manganese; wherein the ruthenium and the at least one promoter are deposited on the copper chromite. The term “cyclohexanedimethanol”, as used herein, means one or more compounds having a cyclohexane ring bearing 2 hydroxymethyl substituents. Examples of cyclohexanedimethanols include 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and 1,1-cyclohexane-dimethanol. The cyclohexanedicarboxylate ester reactant may be any ester of a cyclohexanedicarboxylic acid. For example, the cyclohexanedimethanol may be 1,4-cyclohexanedimethanol and the cyclohexanedicarboxylate ester is a dialkyl 1,4-cyclohexanedicarboxylate comprising one or more residues of a hydroxy compound containing from 1 to about 20 carbon atoms. Examples of hydroxy compound residues are any mono- or polyhydroxy compound such as methanol, ethanol, butanol, 2-butanol, 2-ethylhexanol, 2,2-dimethyl-1,3-propanediol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, cyclohexanol, benzyl alcohol, diethylene glycol, glycerin, trimethylolpropane, and combinations thereof.

Dialkyl cyclohexanedicarboxylates may be obtained commercially as a mixture of cis and trans isomers or as purified cis or trans isomers. Dimethyl 1,4-cyclohexanedicarboxylate, for example, may be used as a mixture of cis and trans isomers, although pure cis and trans grades of dimethyl 1,4-cyclohexane-dicarboxylate may be used if desired. For example, in one embodiment, the alkyl carboxylate comprises dimethyl 1,4-cyclohexanedicarboxylate having a cis:trans molar ratio of about 1:1 to about 2:1. In a typical bulk sample of commercially available dimethyl 1,4-cyclohexanedicarboxylate, the molar cis:trans isomer ratio is about 2:1 to about 1.7:1. The 1,4-cyclohexanedimethanol product, in turn, can have a cis:trans molar ratio of about 0.7:1 to about 2:1.

The hydrogenation conditions of pressure and temperature may be varied depending not only on one another but also on the activity of the catalyst, the mode of operation, selectivity considerations, and the desired rate of conversion. The process, typically, can be conducted at temperatures in the range of about 150° C. to about 350° C. and pressures in the range of about 40 to about 450 bars absolute (abbreviated herein as “bara”). Further examples of temperatures and pressures at which the process of the invention may be operated are about 175° C. to about 300° C. at about 200 to about 380 bara, and about 200° C. to about 250° C. at about 300 to about 350 bara. While rates and conversions generally also increase with increasing pressure, the energy costs for compression of hydrogen, as well as the increased cost of high-pressure equipment generally make the use of the lowest pressure practical desirable.

The process of the invention may be carried out in the absence or presence of an inert solvent, i.e., a solvent for the cyclohexanedicarboxylate ester being hydrogenated which does not affect significantly the activity of the catalyst and does not react with the hydrogenation product or products. Examples of such solvents include alcohols such as ethanol and lauryl alcohol; glycols such as mono-, di- and tri-ethylene glycol; hydrocarbons such as hexane, cyclohexane, octane and decane; and aromatic ethers such as diphenyl ether, etc. It is often economically desirable, however, to conduct the process in the absence of solvent and use the neat, molten cyclohexanedicarboxylate ester alone or as a mixture with the cyclohexanedimethanol and other hydrogenation products as the feed to the process.

The process may be carried out as a batch, semi-continuous or continuous process and may utilize a variety of reactor types. Examples of suitable reactor types include, but are not limited to, stirred tank, continuous stirred tank, slurry, tubular, fixed bed, and trickle bed. The term “continuous” as used herein means a process wherein reactants are introduced and products withdrawn simultaneously in an uninterrupted manner. By “continuous” it is meant that the process is substantially or completely continuous in operation in contrast to a “batch” process. “Continuous” is not meant in any way to prohibit normal interruptions in the continuity of the process due to, for example, start-up, reactor maintenance, or scheduled shut down periods. The term “batch” process as used herein means a process wherein all the reactants are added to the reactor and then processed according to a predetermined course of reaction during which no material is fed or removed into the reactor. For example, in a batch operation, a slurry of the catalyst in the cyclohexanedicarboxylate ester and/or an inert solvent in which the cyclohexanedicarboxylate ester has been dissolved is fed to a pressure vessel equipped with means for agitation. The pressure vessel is then pressurized with hydrogen to a predetermined pressure followed by heating to bring the reaction mixture to the desired temperature. After the hydrogenation is complete, the reaction mixture is removed from the pressure vessel, the catalyst is separated by filtration and the cyclohexanedimethanol product is isolated, for example, in a distillation train. The term “semicontinuous” means a process where some of the reactants are charged at the beginning of the process and the remaining reactants are fed continuously as the reaction progresses. Alternatively, a semicontinuous process may also include a process similar to a batch process in which all the reactants are added at the beginning of the process except that one or more of the products are removed continuously as the reaction progresses.

For economic and operability reasons, the process may be operated as a continuous process which comprises contacting the hydrogen the catalyst in a fixed bed or a liquid slurry phase reactor. Continuous operation may utilize a fixed bed with a larger particle size of catalyst such as, for example, granules, pellets, various multilobal shaped pellets, rings, or saddles that are well known to skilled persons in the art.

As an example of a continuous process, the catalyst bed may be fixed in a high pressure, tubular or columnar reactor and the liquid cyclohexanedicarboxylate ester, dissolved in an inert solvent if necessary or desired, fed continuously into the top of the bed at elevated pressure and temperature, and the crude hydrogenation product removed from the base of the reactor. Alternatively, it is possible to feed the cyclohexanedicarboxylate ester into the bottom of the bed and remove the crude product from the top of the reactor. It is also possible to use 2 or more catalyst beds or hydrogenation zones connected in parallel or in series to improve conversion, to reduce the quantity of catalyst, or to by-pass a catalyst bed for periodic maintenance or catalyst removal. Another mode of continuous operation utilizes a slurry of the catalyst in an agitated pressure vessel which is equipped with a filter leg to permit continuous removal of a solution of product in unreacted ester and/or an inert solvent. In this manner a liquid reactant or reactant solution can be continuously fed to and product solution continuously removed from an agitated pressure vessel containing an agitated slurry of the catalyst.

The process may be conducted in the liquid phase, the vapor phase, or as combination of the liquid and vapor phase. For example, the process may be carried in the vapor phase as described, for example, in U.S. Pat. No. 5,395,987. In one example of a vapor phase operation, the process of the invention may be operated using vaporous feed conditions by feeding the cyclohexanedicarboxylate ester in essentially liquid free, vaporous form to a hydrogenation zone comprising the catalyst of the invention. Hence, the feed stream is introduced into the hydrogenation zone at a temperature which is above the dew point of the mixture. The process may be operated such that vapor phase conditions will exist throughout the hydrogenation zone. Such a vapor phase process often has the advantage of lower operating pressures in comparison to liquid phase process which can reduce the construction and operating costs of a commercial plant.

In a vapor phase process, it is desirable but not essential to avoid contact of the cyclohexanedicarboxylate ester liquid with the catalyst to prevent localized overheating of and damage to the catalyst from the exothermic nature of the hydrogenation reaction. In conventional liquid phase hydrogenation processes, this danger is lessened by the greater heat capacity of the liquids surrounding the catalyst. It is desirable, therefore, that the vaporous feed stream is maintained above its dew point so that the cyclohexanedicarboxylate ester is present in the vapor phase at the inlet end of the catalyst. This means that the composition of the vaporous feed mixture must be controlled so that, under the selected operating conditions, the temperature of the mixture at the inlet end of the catalyst bed is always above its dew point at the operating pressure. The term “dew point”, as used herein, means that temperature at which a gas or a mixture of gases is saturated with respect to a condensable component. This dew point liquid will normally contain all the condensable components of the vapor phase, as well as dissolved gases, in concentrations that satisfy vapor/liquid equilibrium conditions. Typically the feed temperature of the vaporous feed mixture to the hydrogenation zone is from about 5° C. to about 10° C. or more above its dew point at the operating pressure.

A convenient method of forming a vaporous mixture for use in a vapor phase process is to spray liquid cyclohexanedicarboxylate ester or a cyclohexanedicarboxylate ester solution into a stream of hot hydrogen-containing gas to form a saturated or partially saturated vaporous mixture. Alternatively, such a vapor mixture can be obtained by bubbling a hot hydrogen-containing gas through a body of the liquid 1,4-cyclohexane-dicarboxylate ester or cyclohexanedicarboxylate ester solution. If a saturated vapor mixture is formed it should then be heated further or diluted with more hot gas so as to produce a partially saturated vaporous mixture prior to contact with the catalyst. To maintain the vaporous feed stream above its dew point at the inlet end of a catalyst bed at the operating pressure, the hydrogen-containing gas:cyclohexanedicarboxylate ester molar ratio is desirably about 10:1 to about 8000:1 or about 200:1 to about 1000:1.

For a vapor phase process, the cyclohexanedicarboxylate ester, typically, is fed to the catalyst bed at a liquid hourly space velocity of about 0.05 to about 4.0 h⁻¹. Liquid hourly space velocity, as used herein, is defined as the liquid volume of the hydrogenatable material fed to the vaporization zone per volume of catalyst per unit time (typically hours). Thus, for the above liquid hourly space velocity, the cyclohexanedicarboxylate ester is fed to the vaporisation zone at a rate which is equivalent to, per unit volume of catalyst, from about 0.05 to about 4.0 unit volumes of cyclohexanedicarboxylate ester per hour (i.e. about 0.05 to about 4.0 m³h⁻¹per m³of catalyst). In another example, the liquid hourly space velocity is from about 0.1 h⁻¹to about 1.0 h⁻¹.

EXAMPLES

The invention is further illustrated by the following examples. The ruthenium copper chromite catalysts that are the subject of this invention were prepared by wet impregnation of commercial E403TU copper chromite obtained from BASF Corporation (Lot 68D-10E). The copper chromite had a surface area of 30 m²/g, and contained approximately 24-26 weight % copper(II) oxide, 65-67 weight % copper chromite, 1 weight % chromium trioxide, 1 weight % chromic oxide, and 0-4 weight % graphite. The copper content was about 37 weight % copper and the chromium content about 31 weight %. The gram-atom ratio of copper to chromium was approximately 1:1. Impregnation was done with a solution of Ru(NO)(NO₃)₃obtained from Chempur (13.9 weight percent Ru). The catalyst was slowly dried at 50° C. for about 60 hours, then dried at 110° C. for 4 hours, and finally calcined at 500° C. for 2 hours. The calcination heating rate was 2° C./min. This treatment gave a modified copper chromite catalyst containing 1 weight percent ruthenium metal. The ruthenium modified copper chromite catalyst was further impregnated with a solution of the desired alkali, alkaline earth, or rare earth metal salt to a target level of either 1000 ppm or 5000 ppm by agitating the catalyst and salt solution for 2 hours. This treatment was followed by heating at 60° C. until dryness, after which the catalysts were further dried at 110° C. for 4 hours, and finally calcined at 500° C. for 2 hours.

Catalyst activity was measured using a system of parallel, fixed-bed, quartz microreactors with a 2-mm inside diameter. These reactors are suitable for testing from 25 to 250 mg of catalyst. Each reactor was charged with 25 microliters of catalyst for these experiments. Catalysts were reduced by heating the reactors at a rate of 5° C./min to 220° C. in a flow of 80 volume %/20 volume % nitrogen and hydrogen. The reactors were pressurized to 3.45 MPa at 0.5 MPa/min and then pure hydrogen feed was started. The reactors were maintained under these conditions for four hours.

Methanol synthesis was conducted at temperatures ranging from 180° C. to 240° C. at a pressure of 5.5 MPa. Two synthesis gas feed compositions were employed for these tests. The lean CO₂gas mixture contained 68 weight % hydrogen, 29.3 weight % CO, and 2.7 weight % CO₂. The CO₂rich gas stream contained 73.5 weight % hydrogen, 6.7 weight % CO, and 19.8 weight % CO₂. Both gas streams approximate an equivalent stoichiometric ratio of H₂/CO of 2.0 after adjusting for the influence of the water gas shift reaction. A gas feed rate (GHSV) of 12000 hr −1 was selected to keep conversion with the most active catalysts below 50% and avoid thermodynamic equilibrium effects.

Products were analyzed by on-line gas chromatography using a Varian 4900 Micro-GC equipped with a thermal conductivity detector. A 5 A molecular sieve was used with He carrier in one channel to separate CH₄, CO₂, ethane, water, propane, dimethyl ether (DME), and methanol. Another channel employed PPQ and a nitrogen carrier to separate H₂, O₂, CH₄and CO from the He internal standard. The product from every reactor was sampled twice at each temperature with the time interval between analyses being approximately three to four hours. The results of these experiments are shown in Tables 1-8. The temperatures shown in Tables 1-8 represent the temperatures of the catalyst bed which, under the conditions of the experiments, was approximately isothermal. The quantities of hydrogen, carbon monoxide, carbon dioxide, dimethyl ether, and methanol are provided in Tables 1-8 as weight percentages of the reactor effluent.

The relative activity of the subject catalysts was determined by comparing the amount of methanol in the reactor product, and the total conversion of CO and CO₂achieved in the reaction. A comparison of the activity of various promoted ruthenium copper chromite catalysts for methanol production is shown in Table 1, which is sorted in order of activity for both high and low CO₂syngas. The best activity is obtained in low CO₂syngas at about 240° C. The reactor product contains as much as 20 weight % methanol with several different promoters (see, for example, Table 1, Examples 125-132, 134-136, and 138-147). As shown in Table 2, this level of activity is comparable to the activity obtained with two commercial copper zinc methanol catalysts under the same conditions (see, for example, Table 2, Comparative Examples 5-16 and 56-65).

Methanol production is cut in half when the syngas contains a high level of CO₂, but significant methanol production activity remains. In fact, Table 3 shows that the activity of the two commercial copper zinc reference catalysts (Ref A and B) can be lower than the copper chromite based catalyst in the high CO₂syngas feed at about 240° C. (see, for example, Table 3, Comparative Examples 96-103 and 131-137 versus Table 1, Example 1-4 and 10-19). Whereas the two commercial catalysts were about equivalent in activity in the low CO₂syngas, in a high CO₂environment, one of the commercial copper zinc catalysts appears to be much less active than the other catalyst, and lower in activity than the promoted ruthenium copper chromite catalyst.

The high activity of promoted ruthenium copper chromite catalysts for methanol synthesis is unexpected in view of the fact that copper chromite alone has a low activity for methanol synthesis, and addition of either ruthenium or various promoters to the copper chromite does not give a meaningful improvement in the activity of the base catalyst. The activities of these comparison catalysts is shown in Tables 4, 5, and 6. The activity of promoted copper zinc catalysts is shown in Table 4. Unmodified copper chromite, shown in Table 5, gave a maximum methanol concentration in the product of 1.5 weight % at 240° C. (see, for example, Comparative Example 445) when feeding the low CO₂syngas. This is an order of magnitude lower than the activity obtained with the promoted ruthenium catalysts prepared from this base catalyst (see, for example, Example 125). Results in the high CO₂syngas again were about half the values obtained with the low CO₂feed.

Impregnation of the base copper chromite catalyst with 1% ruthenium actually reduced the activity of the resulting catalyst for methanol synthesis. As shown in Table 6, less than 0.5 weight % methanol was produced in either the low or high CO₂syngas at 240° C. The addition of promoters shown in Table 7, but not ruthenium, to the base copper chromite had a generally negative impact on the activity of the catalyst. However, the addition of 1000 ppm rubidium to the copper chromite catalyst (see, for example, Comparative Examples 544 and 545) improved the activity under high CO₂conditions, producing more methanol at 240° C. than the unpromoted catalyst achieved in the low CO₂syngas (see, for example, Comparative Examples 445-447).

The influence of ruthenium and promoter metals on activity of copper chromite catalysts was examined for copper zinc catalysts. The activity of the commercial copper zinc catalyst designated Reference A was tested after impregnation with either 1% ruthenium or 5% ruthenium, and a variety of the same promoters that were found to be effective with copper chromite. The results from these tests are shown in Table 8. The highest activity at 240° C. was with the 1% ruthenium copper zinc catalyst promoted with 1000 ppm lanthanum, but only 2.2 weight % methanol was produced by this catalyst (see, for example, Comparative Example 630). The higher levels of promoters and ruthenium produced catalysts that were essentially inactive for methanol production.

TABLE 1

Activity of Promoted 1% Ruthenium on Copper Chromite Catalysts for Methanol Production

CO₂

Promoter

DME

CO & CO₂

Ex. No
Level
Promoter
(ppm)
Temp (° C.)
H₂wt %
CO wt %
CO₂wt %
% wt
MeOH wt %
conv %

1
High
La
1000
238.5
65.81
1.44
19.72
0.00
11.01
34.66

2
High
La
1000
238.7
65.84
1.48
19.69
0.00
10.96
34.53

3
High
K
1000
238.5
66.11
1.68
19.69
0.00
10.50
33.31

4
High
K
1000
238.3
66.00
1.66
19.74
0.00
10.60
33.25

5
High
La
1000
228.5
66.75
2.00
19.79
0.00
9.49
30.84

6
High
La
1000
228.5
66.59
2.26
19.77
0.00
9.42
29.74

7
High
Mn
1000
238.5
66.87
2.68
19.52
0.00
8.97
29.16

8
High
K
1000
228.6
66.86
2.33
19.77
0.00
9.09
28.97

9
High
K
1000
228.6
66.87
2.36
19.84
0.00
8.97
28.62

10
High
Na
1000
239.7
66.91
2.70
19.58
0.00
8.85
28.51

11
High
Mn
1000
238.5
66.63
2.69
19.67
0.00
9.05
28.48

12
High
Na
1000
239.6
66.79
2.72
19.58
0.00
8.96
28.43

13
High
Na
1000
240.0
66.71
2.76
19.72
0.00
8.87
27.71

14
High
Mg
1000
239.9
67.49
3.14
19.54
0.00
7.92
25.91

15
High
Mg
1000
240.0
67.48
3.29
19.44
0.00
7.87
25.67

16
High
Mg
1000
239.9
67.35
3.13
19.64
0.00
7.96
25.61

17
High
Ca
5000
238.4
67.85
3.84
19.09
0.00
7.30
24.99

18
High
Ba
1000
240.0
67.58
3.45
19.44
0.00
7.63
24.94

19
High
Ba
1000
239.9
67.55
3.51
19.41
0.00
7.63
24.84

20
High
Na
1000
230.1
68.02
3.51
19.39
0.00
7.19
24.24

21
High
Ba
1000
239.9
67.38
3.57
19.50
0.00
7.64
24.21

22
High
Ca
5000
238.4
67.68
3.88
19.21
0.00
7.32
24.13

23
High
Mn
1000
228.6
67.89
3.60
19.44
0.00
7.17
23.85

24
High
Na
1000
229.9
68.04
3.57
19.42
0.00
7.08
23.79

25
High
Na
1000
230.2
67.96
3.65
19.40
0.00
7.10
23.64

26
High
Mn
1000
228.3
67.71
3.70
19.48
0.00
7.22
23.48

27
High
Mg
1000
228.3
68.84
4.26
19.25
0.00
5.80
20.39

28
High
Mg
1000
228.3
68.83
4.31
19.27
0.00
5.74
19.74

29
High
Mg
1000
228.3
68.69
4.27
19.38
0.00
5.82
19.57

30
High
Ca
5000
228.5
68.99
4.95
18.94
0.00
5.28
18.77

31
High
Ba
1000
228.3
68.95
4.73
19.11
0.00
5.38
18.54

32
High
Ca
5000
228.2
68.89
5.00
18.99
0.00
5.28
18.44

33
High
Ba
1000
228.5
68.86
4.70
19.25
0.00
5.36
18.05

34
High
Ba
1000
228.3
68.84
4.77
19.25
0.00
5.32
17.64

35
High
La
1000
198.7
70.94
5.97
18.70
0.00
2.65
11.18

36
High
K
1000
198.6
71.03
5.97
18.69
0.00
2.57
11.05

37
High
La
1000
198.7
70.85
6.04
18.70
0.00
2.67
10.85

38
High
K
1000
198.7
70.90
5.99
18.80
0.00
2.57
10.33

39
High
Na
1000
200.3
71.51
6.33
18.45
0.00
1.99
9.99

40
High
Na
1000
200.0
71.52
6.29
18.48
0.00
1.99
9.97

41
High
Na
1000
199.8
71.46
6.33
18.48
0.00
2.01
9.75

42
High
Ca
1000
238.4
72.15
7.44
17.99
0.00
0.66
9.54

43
High
Mg
1000
199.8
71.56
6.42
18.55
0.00
1.75
8.73

44
High
Ca
1000
228.3
72.11
7.39
18.22
0.00
0.52
8.64

45
High
Mn
1000
198.7
71.03
6.56
18.66
0.00
2.02
8.41

46
High
Mg
1000
199.8
71.53
6.38
18.65
0.00
1.73
8.32

47
High
Mn
1000
198.7
71.03
6.56
18.67
0.00
2.02
8.20

48
High
Mg
1000
199.6
71.51
6.50
18.54
0.00
1.74
8.18

49
High
Ca
1000
228.3
72.25
7.34
18.15
0.00
0.52
8.11

50
High
Ba
1000
199.6
71.51
6.52
18.64
0.00
1.63
7.84

51
High
Ba
1000
200.0
71.51
6.60
18.58
0.00
1.61
7.48

52
High
Ca
5000
198.7
71.32
6.81
18.59
0.00
1.56
7.23

53
High
Ba
1000
199.8
71.40
6.59
18.71
0.00
1.61
7.18

54
High
Ca
5000
198.9
71.23
6.88
18.60
0.00
1.57
6.88

55
High
Na
1000
180.2
72.20
6.57
18.62
0.00
0.92
6.45

56
High
La
1000
178.9
72.03
6.44
18.74
0.00
1.11
6.35

57
High
K
1000
179.1
72.08
6.38
18.78
0.00
1.08
6.32

58
High
K
1000
178.9
71.95
6.54
18.77
0.00
1.06
5.58

59
High
Na
1000
179.9
72.13
6.47
18.82
0.00
0.90
5.57

60
High
La
1000
179.1
71.89
6.63
18.70
0.00
1.10
5.47

61
High
Mn
1000
178.9
72.00
6.41
18.97
0.00
0.93
5.37

62
High
Ca
1000
178.3
72.07
7.08
19.01
0.00
0.12
4.99

63
High
Mg
1000
179.9
72.05
6.68
18.75
0.00
0.84
4.92

64
High
La
5000
238.5
72.46
6.43
18.94
0.00
0.50
4.91

65
High
Na
5000
240.1
72.45
6.65
18.75
0.00
0.47
4.63

66
High
Mn
1000
178.9
71.86
6.84
18.72
0.00
0.90
4.58

67
High
Na
1000
180.0
71.92
6.71
18.79
0.00
0.90
4.50

68
High
La
5000
238.5
72.38
6.55
18.91
0.00
0.49
4.36

69
High
La
5000
228.5
72.51
6.48
18.95
0.00
0.39
4.30

70
High
Ca
5000
179.2
71.85
6.99
18.72
0.00
0.76
4.27

71
High
La
5000
228.3
72.58
6.44
18.95
0.00
0.37
4.23

72
High
Mg
1000
179.9
72.01
6.58
18.93
0.00
0.81
4.19

73
High
Na
5000
240.0
72.38
6.75
18.70
0.00
0.50
4.17

74
High
Ba
1000
179.9
72.00
6.60
18.95
0.00
0.78
4.11

75
High
K
5000
238.5
72.18
6.99
18.61
0.00
0.54
4.11

76
High
Mg
1000
180.2
72.01
6.51
19.02
0.00
0.79
3.95

77
High
Ca
5000
179.2
71.78
7.03
18.76
0.00
0.75
3.91

78
High
K
5000
238.4
72.08
6.84
18.84
0.00
0.56
3.73

79
High
Na
5000
240.0
72.31
6.77
18.77
0.00
0.49
3.68

80
High
Na
5000
229.8
72.48
6.70
18.77
0.00
0.39
3.56

81
High
Ba
1000
180.0
71.82
6.70
19.04
0.00
0.77
3.50

82
High
Na
5000
229.9
72.42
6.68
18.82
0.00
0.42
3.45

83
High
Ba
1000
179.7
71.83
6.76
18.98
0.00
0.76
3.33

84
High
Na
5000
230.1
72.45
6.64
18.89
0.00
0.37
3.29

85
High
K
5000
215.5
72.16
6.90
18.82
0.00
0.46
2.98

86
High
Na
5000
199.8
72.75
6.46
19.01
0.00
0.15
2.82

87
High
K
5000
228.2
72.16
6.97
18.80
0.00
0.41
2.79

88
High
Na
5000
199.5
72.69
6.53
18.99
0.00
0.15
2.52

89
High
Mn
5000
238.4
72.29
7.14
18.76
0.00
0.15
2.38

90
High
Na
5000
199.6
72.61
6.58
19.01
0.00
0.17
2.26

91
High
Ca
1000
238.3
71.43
7.44
18.79
0.00
0.66
2.07

92
High
La
5000
198.6
72.50
6.42
19.29
0.00
0.15
2.02

93
High
K
5000
178.9
72.65
6.10
19.52
0.00
0.09
2.00

94
High
Na
5000
179.9
72.72
6.37
19.19
0.00
0.08
1.98

95
High
La
5000
179.2
72.62
6.40
19.28
0.00
0.07
1.94

96
High
Ca
1000
198.6
71.65
7.14
19.28
0.00
0.24
1.83

97
High
Mg
5000
228.3
72.26
6.74
19.18
0.00
0.16
1.74

98
High
Na
5000
180.0
72.66
6.46
19.17
0.00
0.07
1.56

99
High
Na
5000
179.9
72.65
6.34
19.30
0.00
0.08
1.55

100
High
La
5000
179.1
72.60
6.54
19.15
0.00
0.07
1.52

101
High
La
5000
198.7
72.44
6.43
19.35
0.00
0.14
1.49

102
High
Mn
5000
228.3
72.21
7.05
18.96
0.00
0.12
1.49

103
High
Mg
5000
239.9
72.11
6.88
19.12
0.00
0.24
1.48

104
High
Mg
5000
240.0
72.10
6.87
19.15
0.00
0.22
1.42

105
High
Mn
5000
238.3
72.13
7.13
18.94
0.00
0.14
1.32

106
High
Mn
5000
228.3
72.20
7.02
19.01
0.00
0.11
1.26

107
High
Mg
5000
228.5
72.21
6.79
19.18
0.00
0.17
1.23

108
High
K
5000
196.0
72.24
6.75
19.19
0.00
0.18
1.14

109
High
Mg
5000
199.6
72.38
6.64
19.27
0.00
0.07
1.13

110
High
K
5000
179.2
72.43
6.64
19.22
0.00
0.08
0.91

111
High
Mg
5000
240.0
72.02
6.93
19.16
0.00
0.24
0.88

112
High
K
5000
198.9
72.21
6.78
19.21
0.00
0.16
0.82

113
High
Mg
5000
179.9
72.35
6.65
19.32
0.00
0.04
0.80

114
High
Mg
5000
199.8
72.31
6.66
19.31
0.00
0.08
0.72

115
High
Mn
5000
178.3
72.36
6.85
19.14
0.00
0.02
0.71

116
High
Mg
5000
228.3
72.10
6.76
19.31
0.00
0.19
0.69

117
High
Mn
5000
178.5
72.29
6.80
19.26
0.00
0.01
0.64

118
High
Ca
1000
178.5
71.85
7.05
19.32
0.00
0.12
0.50

119
High
Mg
5000
199.6
72.31
6.73
19.26
0.00
0.06
0.45

120
High
Mn
5000
198.4
72.17
6.95
19.20
0.00
0.04
0.34

121
High
Mg
5000
180.2
72.28
6.61
19.44
0.00
0.03
0.29

122
High
Mg
5000
179.9
72.29
6.60
19.44
0.00
0.03
0.15

123
High
Mn
5000
198.6
72.18
6.87
19.27
0.00
0.04
0.13

124
High
Ca
1000
198.4
71.50
7.14
19.47
0.00
0.24
−1.37

125
Low
La
1000
240.1
51.55
21.45
3.77
0.01
20.97
42.03

126
Low
La
1000
239.9
51.19
21.70
3.79
0.01
21.04
41.79

127
Low
Ca
5000
239.6
52.17
21.80
3.67
0.01
20.12
40.80

128
Low
Ca
5000
239.6
52.21
21.90
3.67
0.01
19.99
40.43

129
Low
Ba
1000
239.7
52.1
21.9
3.7
0.01
20.08
40.36

130
Low
Ba
1000
239.9
52.19
21.88
3.67
0.01
20.03
40.35

131
Low
Ca
5000
240.1
52.18
21.85
3.69
0.01
20.06
40.30

132
Low
Ca
5000
240.3
51.76
22.11
3.72
0.01
20.16
40.07

133
Low
Ca
5000
274.7
53.78
21.40
4.34
0.06
18.20
39.92

134
Low
La
1000
238.5
53.23
22.24
3.34
0.00
18.99
39.78

135
Low
La
1000
238.3
53.16
22.24
3.34
0.00
19.06
39.74

136
Low
Na
1000
240.1
52.77
22.17
3.67
0.00
19.17
39.39

137
Low
Ca
1000
274.6
54.03
21.82
4.21
0.04
17.70
38.87

138
Low
Na
1000
239.7
52.44
22.45
3.67
0.00
19.21
38.87

139
Low
Ca
1000
239.7
53.45
22.37
3.58
0.01
18.41
38.66

140
Low
Ca
1000
240.0
53.40
22.45
3.56
0.00
18.40
38.33

141
Low
Ca
1000
238.5
53.31
22.81
3.55
0.01
18.16
36.92

142
Low
Ca
1000
238.3
53.4
22.9
3.5
0.01
17.99
36.57

143
Low
Na
1000
238.4
53.8
23.0
3.5
0.00
17.55
36.10

144
Low
Mn
1000
238.5
54.47
22.95
3.48
0.00
16.97
35.88

145
Low
Na
1000
238.8
53.86
23.18
3.49
0.00
17.33
35.44

146
Low
Mn
1000
238.5
54.42
23.09
3.48
0.00
16.88
35.36

147
Low
Mn
1000
238.5
54.4
23.1
3.5
0.00
16.88
35.36

148
Low
La
1000
229.8
54.60
23.24
3.48
0.00
16.56
34.80

149
Low
La
1000
229.7
54.58
23.34
3.47
0.00
16.49
34.55

150
Low
Ca
5000
230.2
55.92
23.39
3.37
0.00
15.24
33.69

151
Low
Ca
5000
230.1
55.26
23.50
3.42
0.00
15.71
33.64

152
Low
Ca
5000
229.9
55.72
23.54
3.35
0.00
15.30
33.10

153
Low
Ba
1000
228.3
55.77
23.58
3.37
0.00
15.20
32.98

154
Low
Ca
5000
230.1
55.19
23.70
3.42
0.00
15.59
32.95

155
Low
Ba
1000
229.9
56.03
23.73
3.36
0.00
14.82
32.07

156
Low
Na
1000
230.2
55.84
24.01
3.38
0.00
14.70
31.49

157
Low
La
1000
228.3
56.78
24.02
3.06
0.00
14.09
31.48

158
Low
La
1000
228.6
57.10
24.12
3.05
0.00
13.69
31.07

159
Low
K
1000
240.0
56.37
24.07
3.30
0.00
14.20
31.07

160
Low
Na
1000
230.1
56.06
24.09
3.35
0.00
14.44
30.93

161
Low
Ca
5000
291.9
57.49
23.24
4.52
0.09
12.59
30.62

162
Low
Ca
1000
229.8
56.83
24.11
3.28
0.00
13.74
30.36

163
Low
Ca
1000
228.6
56.76
24.20
3.27
0.00
13.73
30.31

164
Low
Ca
1000
229.7
56.86
24.18
3.28
0.00
13.65
30.26

165
Low
K
1000
239.6
56.39
24.28
3.29
0.00
13.99
30.07

166
Low
Ca
1000
295.2
58.78
23.20
4.49
0.06
11.41
30.01

167
Low
Mg
1000
238.3
56.24
24.44
3.29
0.00
13.98
29.90

168
Low
Mg
1000
238.4
56.26
24.46
3.29
0.00
13.96
29.71

169
Low
Na
1000
228.5
57.17
24.40
3.23
0.00
13.17
29.35

170
Low
Ca
5000
238.3
56.96
24.21
3.20
0.00
13.62
29.10

171
Low
Ca
1000
228.6
56.81
24.39
3.25
0.00
13.54
28.96

172
Low
Ca
1000
239.9
57.22
24.56
3.28
0.00
12.93
28.66

173
Low
Ca
5000
238.5
57.30
24.30
3.18
0.01
13.22
28.51

174
Low
Ca
1000
240.0
57.00
24.71
3.29
0.00
12.98
28.33

175
Low
Na
1000
228.2
57.51
24.45
3.22
0.00
12.82
28.25

176
Low
Mn
1000
228.3
57.73
24.67
3.21
0.00
12.39
27.59

177
Low
Mn
1000
228.5
58.02
24.59
3.22
0.00
12.19
27.51

178
Low
K
1000
229.8
59.08
25.25
3.09
0.00
10.63
24.57

179
Low
K
1000
229.9
59.05
25.49
3.08
0.00
10.44
24.09

180
Low
Ca
5000
316.8
62.80
23.86
4.97
0.13
6.30
22.78

181
Low
Ca
1000
316.8
62.82
24.15
4.81
0.09
6.21
22.04

182
Low
Mg
1000
228.5
59.54
25.87
3.03
0.00
9.64
22.03

183
Low
Mg
1000
228.3
59.99
25.79
3.00
0.00
9.35
20.60

184
Low
Ca
1000
230.1
60.13
26.13
3.04
0.00
8.80
20.39

185
Low
Ca
1000
229.9
60.09
26.18
3.04
0.00
8.80
20.26

186
Low
Ca
5000
228.3
61.02
26.16
2.91
0.00
8.06
18.64

187
Low
Ca
5000
228.6
61.36
26.40
2.88
0.00
7.53
17.34

188
Low
Ca
5000
200.1
66.05
28.14
2.60
0.00
1.53
5.66

189
Low
Ca
5000
200.1
65.95
28.21
2.60
0.00
1.56
5.39

190
Low
La
1000
198.4
66.26
28.37
2.42
0.00
1.28
5.32

191
Low
La
1000
198.7
66.39
28.28
2.41
0.00
1.25
5.21

192
Low
Ca
1000
200.0
66.26
28.30
2.59
0.00
1.18
4.88

193
Low
Ba
1000
200.1
66.13
28.24
2.60
0.00
1.35
4.73

194
Low
Ca
1000
199.6
66.24
28.32
2.58
0.00
1.18
4.68

195
Low
La
1000
200.0
65.69
28.45
2.64
0.00
1.53
4.55

196
Low
Ba
1000
199.8
66.07
28.32
2.60
0.00
1.33
4.40

197
Low
Na
1000
199.0
66.03
28.46
2.57
0.00
1.27
4.27

198
Low
Mn
1000
198.6
66.28
28.34
2.60
0.00
1.11
4.17

199
Low
Na
1000
198.6
66.01
28.46
2.57
0.00
1.29
4.12

200
Low
Ca
5000
199.8
65.70
28.53
2.62
0.00
1.47
4.09

201
Low
La
1000
200.0
65.54
28.58
2.63
0.00
1.56
3.99

202
Low
K
1000
200.0
66.20
28.47
2.56
0.00
1.10
3.81

203
Low
Ca
1000
198.6
66.11
28.51
2.56
0.00
1.14
3.77

204
Low
Mn
1000
198.6
66.21
28.42
2.60
0.00
1.10
3.70

205
Low
Ca
5000
199.6
65.53
28.68
2.62
0.00
1.49
3.58

206
Low
K
5000
238.4
67.19
28.23
2.50
0.00
0.42
3.58

207
Low
K
5000
228.3
67.30
28.26
2.50
0.00
0.29
3.44

208
Low
Na
1000
200.1
65.63
28.69
2.63
0.00
1.37
3.42

209
Low
Ca
5000
198.6
66.46
28.55
2.55
0.00
0.76
3.32

210
Low
Ca
1000
198.9
66.13
28.54
2.56
0.00
1.11
3.27

211
Low
K
1000
200.0
66.13
28.59
2.56
0.00
1.05
3.23

212
Low
Mg
1000
198.3
66.03
28.77
2.55
0.00
0.97
3.10

213
Low
K
5000
238.8
67.08
28.37
2.50
0.00
0.40
3.01

214
Low
Na
1000
199.8
65.57
28.79
2.62
0.00
1.34
2.94

215
Low
La
1000
178.6
66.92
28.68
2.40
0.00
0.35
2.69

216
Low
Mg
1000
198.6
66.06
28.78
2.55
0.00
0.95
2.64

217
Low
La
5000
239.9
66.99
28.33
2.68
0.00
0.35
2.58

218
Low
Ca
5000
198.4
66.38
28.64
2.55
0.00
0.77
2.54

219
Low
K
5000
228.5
67.07
28.48
2.49
0.00
0.32
2.45

220
Low
La
1000
178.8
66.86
28.74
2.40
0.00
0.35
2.44

221
Low
K
5000
198.6
67.38
28.40
2.50
0.00
0.09
2.22

222
Low
K
1000
180.0
66.84
28.65
2.55
0.00
0.32
2.19

223
Low
Ca
5000
179.9
66.74
28.63
2.55
0.00
0.43
2.13

224
Low
Ca
1000
199.8
66.00
28.90
2.59
0.00
0.84
2.06

225
Low
La
5000
240.1
66.97
28.39
2.67
0.00
0.33
1.99

226
Low
Na
1000
178.8
66.71
28.72
2.54
0.00
0.39
1.97

227
Low
Ca
1000
179.6
66.76
28.69
2.56
0.00
0.33
1.96

228
Low
La
5000
229.9
67.01
28.40
2.68
0.00
0.28
1.95

229
Low
K
1000
179.9
66.74
28.71
2.54
0.00
0.36
1.95

230
Low
Ba
1000
180.0
66.84
28.57
2.58
0.00
0.36
1.92

231
Low
Na
5000
238.1
66.87
28.93
2.43
0.00
0.12
1.85

232
Low
K
5000
178.5
67.24
28.57
2.51
0.00
0.05
1.84

233
Low
Na
1000
179.1
66.72
28.73
2.54
0.00
0.36
1.80

234
Low
Ca
1000
179.7
66.69
28.75
2.56
0.00
0.34
1.79

235
Low
Na
5000
228.3
66.88
28.94
2.44
0.00
0.08
1.79

236
Low
K
5000
178.6
67.23
28.58
2.51
0.00
0.04
1.78

237
Low
Ba
1000
180.0
66.83
28.56
2.57
0.00
0.39
1.77

238
Low
Ca
1000
178.5
66.75
28.73
2.54
0.00
0.33
1.72

239
Low
Ca
1000
200.3
65.95
28.96
2.59
0.00
0.84
1.69

240
Low
Na
5000
238.4
66.89
28.91
2.44
0.00
0.11
1.69

241
Low
Ca
1000
178.8
66.80
28.70
2.55
0.00
0.31
1.66

242
Low
Ca
5000
178.9
66.74
28.77
2.57
0.00
0.27
1.63

243
Low
Mg
5000
198.6
67.15
28.46
2.66
0.00
0.09
1.62

244
Low
La
5000
228.5
66.94
28.51
2.67
0.00
0.25
1.56

245
Low
Na
5000
228.5
66.84
28.99
2.44
0.00
0.09
1.51

246
Low
Mg
5000
179.1
67.17
28.49
2.66
0.00
0.03
1.49

247
Low
K
5000
198.7
67.14
28.63
2.49
0.00
0.10
1.48

248
Low
Ca
5000
178.5
66.69
28.84
2.57
0.00
0.26
1.43

249
Low
Mn
1000
179.2
66.74
28.71
2.59
0.00
0.32
1.39

250
Low
Na
5000
178.5
66.80
29.06
2.47
0.00
0.01
1.34

251
Low
Mn
1000
179.1
66.75
28.70
2.59
0.00
0.31
1.33

252
Low
La
5000
200.0
67.10
28.50
2.68
0.00
0.08
1.29

253
Low
Na
5000
198.3
66.78
29.08
2.46
0.00
0.03
1.24

254
Low
Na
5000
198.4
66.91
28.97
2.45
0.00
0.03
1.24

255
Low
Mg
5000
228.5
66.84
28.58
2.66
0.00
0.28
1.20

256
Low
Mg
1000
178.3
66.54
28.97
2.54
0.00
0.30
1.18

257
Low
La
5000
199.8
67.08
28.52
2.68
0.00
0.09
1.17

258
Low
La
1000
179.7
66.47
28.88
2.60
0.00
0.40
1.16

259
Low
La
1000
179.9
66.46
28.89
2.60
0.00
0.40
1.14

260
Low
Na
5000
178.3
66.73
29.13
2.47
0.00
0.01
1.07

261
Low
La
5000
180.0
67.13
28.51
2.69
0.00
0.04
0.99

262
Low
Mg
1000
178.5
66.59
28.91
2.53
0.00
0.32
0.94

263
Low
Mn
5000
178.6
67.00
28.67
2.68
0.00
0.02
0.93

264
Low
Ca
5000
180.0
66.41
28.95
2.59
0.00
0.40
0.93

265
Low
Na
1000
179.9
66.37
28.99
2.60
0.00
0.38
0.87

266
Low
Mn
5000
228.8
66.80
28.73
2.68
0.00
0.15
0.87

267
Low
Mg
5000
228.5
66.78
28.67
2.66
0.00
0.25
0.85

268
Low
La
5000
180.0
67.15
28.49
2.68
0.00
0.05
0.80

269
Low
Ca
5000
179.9
66.54
28.81
2.56
0.00
0.45
0.79

270
Low
Mg
5000
238.7
66.58
28.76
2.68
0.00
0.35
0.73

271
Low
Mg
5000
238.7
66.54
28.78
2.67
0.00
0.37
0.72

272
Low
Ca
1000
179.9
66.43
29.04
2.59
0.00
0.29
0.72

273
Low
Na
1000
179.9
66.40
28.98
2.60
0.00
0.38
0.70

274
Low
Mg
5000
178.9
67.09
28.58
2.66
0.00
0.04
0.65

275
Low
Mn
5000
198.9
66.96
28.68
2.68
0.00
0.04
0.63

276
Low
Mn
5000
228.5
66.87
28.66
2.68
0.00
0.16
0.62

277
Low
Mn
5000
178.8
66.92
28.74
2.68
0.00
0.02
0.56

278
Low
Ca
1000
179.9
66.40
29.06
2.59
0.00
0.30
0.51

279
Low
Mg
5000
198.7
66.96
28.68
2.66
0.00
0.08
0.47

280
Low
Ca
5000
179.9
66.31
29.07
2.58
0.00
0.40
0.45

281
Low
Mn
5000
238.4
66.61
28.85
2.68
0.00
0.22
0.30

282
Low
Mn
5000
198.4
66.95
28.70
2.68
0.00
0.04
0.12

283
Low
Mn
5000
238.7
66.47
29.00
2.68
0.00
0.21
−0.44

TABLE 2

Activity of Reference Copper Zinc Catalysts for Methanol Production in Low CO₂Syngas.

Comp.

CO & CO₂

Ex. No
CO₂
Cat
Temp (° C.)
H₂wt %
CO wt %
CO₂wt %
DME % wt
MeOH wt %
conv %

1
Low
CuZnO Ref A
316.8
62.46
24.47
4.87
0.07
6.20
20.78

2
Low
CuZnO Ref A
297.7
59.30
25.34
3.67
0.03
9.71
22.43

3
Low
CuZnO Ref A
294.8
58.69
23.10
4.50
0.05
11.59
30.69

4
Low
CuZnO Ref A
274.7
53.58
21.85
4.22
0.03
18.11
39.01

5
Low
CuZnO Ref A
240.3
51.15
21.60
3.73
0.00
21.26
42.22

6
Low
CuZnO Ref A
240.1
51.20
21.69
3.71
0.00
21.13
41.86

7
Low
CuZnO Ref A
240.1
56.20
23.60
3.12
0.00
15.01
33.52

8
Low
CuZnO Ref A
240.0
53.25
22.90
3.60
0.00
18.06
37.10

9
Low
CuZnO Ref A
240.0
56.69
23.93
3.07
0.00
14.25
32.07

10
Low
CuZnO Ref A
240.0
58.47
25.18
3.22
0.00
11.18
24.60

11
Low
CuZnO Ref A
239.7
53.32
22.64
3.60
0.00
18.26
37.57

12
Low
CuZnO Ref A
239.6
59.42
25.41
3.17
0.00
10.09
22.98

13
Low
CuZnO Ref A
238.7
51.43
21.58
3.70
0.00
21.02
42.00

14
Low
CuZnO Ref A
238.4
56.35
24.71
3.27
0.00
13.64
28.86

15
Low
CuZnO Ref A
238.3
51.26
21.50
3.73
0.00
21.26
42.17

16
Low
CuZnO Ref A
238.3
56.20
24.47
3.29
0.00
14.00
29.87

17
Low
CuZnO Ref A
230.2
58.46
24.73
2.94
0.00
11.89
27.78

18
Low
CuZnO Ref A
230.1
59.79
25.61
3.14
0.00
9.55
21.85

19
Low
CuZnO Ref A
230.1
57.70
24.39
3.00
0.00
12.89
29.60

20
Low
CuZnO Ref A
230.1
55.59
24.02
3.38
0.00
14.93
31.62

21
Low
CuZnO Ref A
229.9
55.45
23.88
3.39
0.00
15.18
32.32

22
Low
CuZnO Ref A
229.9
60.33
25.88
3.09
0.00
8.82
20.42

23
Low
CuZnO Ref A
229.8
53.64
22.97
3.48
0.00
17.75
36.55

24
Low
CuZnO Ref A
229.7
53.71
22.91
3.49
0.00
17.74
36.65

25
Low
CuZnO Ref A
228.8
53.87
22.82
3.49
0.00
17.67
36.68

26
Low
CuZnO Ref A
228.5
54.11
22.87
3.47
0.00
17.40
36.32

27
Low
CuZnO Ref A
228.5
58.91
25.61
3.07
0.00
10.48
23.46

28
Low
CuZnO Ref A
228.2
59.04
25.43
3.08
0.00
10.51
23.90

29
Low
CuZnO Ref A
200.4
65.53
28.37
2.71
0.00
1.71
4.55

30
Low
CuZnO Ref A
200.3
65.53
28.11
2.46
0.00
2.19
7.38

31
Low
CuZnO Ref A
200.1
64.93
28.41
2.68
0.00
2.28
5.66

32
Low
CuZnO Ref A
200.1
64.71
28.01
2.68
0.00
2.87
7.90

33
Low
CuZnO Ref A
199.8
65.95
27.97
2.44
0.00
1.94
7.19

34
Low
CuZnO Ref A
199.6
65.01
28.32
2.68
0.00
2.28
6.00

35
Low
CuZnO Ref A
199.6
65.73
28.52
2.69
0.00
1.38
3.39

36
Low
CuZnO Ref A
199.5
64.81
27.88
2.69
0.00
2.89
8.45

37
Low
CuZnO Ref A
198.7
65.03
27.90
2.68
0.00
2.67
7.56

38
Low
CuZnO Ref A
198.6
65.53
28.71
2.57
0.00
1.50
4.07

39
Low
CuZnO Ref A
198.6
65.13
27.81
2.68
0.00
2.67
8.03

40
Low
CuZnO Ref A
198.4
65.60
28.70
2.57
0.00
1.44
4.01

41
Low
CuZnO Ref A
180.3
66.41
28.66
2.66
0.00
0.62
2.14

42
Low
CuZnO Ref A
180.2
66.23
28.87
2.59
0.00
0.65
1.83

43
Low
CuZnO Ref A
180.0
66.78
28.59
2.38
0.00
0.59
3.40

44
Low
CuZnO Ref A
180.0
66.46
28.72
2.66
0.00
0.51
1.71

45
Low
CuZnO Ref A
180.0
66.66
28.64
2.38
0.00
0.66
3.47

46
Low
CuZnO Ref A
179.9
66.42
28.65
2.56
0.00
0.71
2.96

47
Low
CuZnO Ref A
179.9
66.17
28.95
2.59
0.00
0.63
1.53

48
Low
CuZnO Ref A
179.7
66.19
28.88
2.55
0.00
0.71
2.16

49
Low
CuZnO Ref A
179.2
66.56
28.56
2.56
0.00
0.68
2.47

50
Low
CuZnO Ref A
179.2
66.51
28.61
2.56
0.00
0.66
2.31

51
Low
CuZnO Ref A
178.5
66.39
28.95
2.52
0.00
0.48
1.93

52
Low
CuZnO Ref A
178.5
66.36
29.02
2.52
0.00
0.44
1.21

53
Low
CuZnO Ref B
316.8
62.70
24.36
4.79
0.15
6.08
21.27

54
Low
CuZnO Ref B
292.6
58.33
23.04
4.39
0.08
12.09
31.27

55
Low
CuZnO Ref B
275.0
53.94
21.97
4.18
0.05
17.66
38.35

56
Low
CuZnO Ref B
240.1
52.10
21.74
3.69
0.01
20.22
41.32

57
Low
CuZnO Ref B
240.1
53.25
23.06
3.59
0.01
17.92
36.36

58
Low
CuZnO Ref B
240.0
52.14
21.81
3.68
0.01
20.13
40.94

59
Low
CuZnO Ref B
240.0
57.31
24.66
3.23
0.00
12.80
28.08

60
Low
CuZnO Ref B
240.0
57.52
25.05
3.20
0.00
12.24
26.55

61
Low
CuZnO Ref B
239.9
53.56
22.76
3.57
0.01
17.94
36.65

62
Low
CuZnO Ref B
238.4
53.68
22.49
3.31
0.01
18.34
38.64

63
Low
CuZnO Ref B
238.4
53.77
22.52
3.30
0.01
18.22
38.53

64
Low
CuZnO Ref B
238.4
56.43
24.29
3.31
0.00
13.93
30.09

65
Low
CuZnO Ref B
238.4
56.59
24.24
3.30
0.00
13.83
30.29

66
Low
CuZnO Ref B
230.1
54.55
23.19
3.44
0.00
16.68
35.25

67
Low
CuZnO Ref B
229.9
55.96
24.46
3.34
0.00
14.18
29.96

68
Low
CuZnO Ref B
229.9
56.15
24.46
3.32
0.00
14.03
29.55

69
Low
CuZnO Ref B
229.9
59.82
25.93
3.01
0.00
9.32
21.57

70
Low
CuZnO Ref B
229.8
59.76
25.64
3.04
0.00
9.65
22.53

71
Low
CuZnO Ref B
229.5
54.39
22.99
3.46
0.00
17.02
35.86

72
Low
CuZnO Ref B
228.3
56.88
24.13
3.05
0.00
13.90
31.01

73
Low
CuZnO Ref B
228.3
59.55
25.71
3.07
0.00
9.76
22.45

74
Low
CuZnO Ref B
228.3
59.64
25.72
3.06
0.00
9.67
22.22

75
Low
CuZnO Ref B
228.2
56.74
24.14
3.05
0.00
14.03
31.06

76
Low
CuZnO Ref B
200.1
65.01
28.73
2.66
0.00
1.91
4.16

77
Low
CuZnO Ref B
200.0
64.96
28.80
2.65
0.00
1.90
3.99

78
Low
CuZnO Ref B
199.8
65.16
27.90
2.67
0.00
2.55
7.96

79
Low
CuZnO Ref B
199.8
65.82
28.56
2.57
0.00
1.36
4.27

80
Low
CuZnO Ref B
199.8
65.87
28.61
2.56
0.00
1.28
3.43

81
Low
CuZnO Ref B
199.5
65.11
27.97
2.66
0.00
2.54
7.73

82
Low
CuZnO Ref B
198.7
65.84
28.20
2.43
0.00
1.83
6.21

83
Low
CuZnO Ref B
198.6
65.90
28.07
2.45
0.00
1.88
7.04

84
Low
CuZnO Ref B
198.6
65.84
28.66
2.59
0.00
1.24
3.09

85
Low
CuZnO Ref B
198.6
65.84
28.68
2.59
0.00
1.21
3.25

86
Low
CuZnO Ref B
180.3
66.64
28.75
2.54
0.00
0.42
2.19

87
Low
CuZnO Ref B
180.0
66.26
28.84
2.58
0.00
0.66
1.69

88
Low
CuZnO Ref B
180.0
65.97
29.26
2.59
0.00
0.53
0.51

89
Low
CuZnO Ref B
180.0
66.46
28.89
2.53
0.00
0.47
1.93

90
Low
CuZnO Ref B
179.9
65.98
29.25
2.59
0.00
0.53
0.55

91
Low
CuZnO Ref B
179.6
66.47
28.65
2.57
0.00
0.65
2.91

92
Low
CuZnO Ref B
178.9
66.75
28.66
2.40
0.00
0.53
3.26

93
Low
CuZnO Ref B
178.8
66.78
28.65
2.40
0.00
0.52
3.19

94
Low
CuZnO Ref B
178.5
66.49
28.92
2.57
0.00
0.37
0.92

95
Low
CuZnO Ref B
178.3
66.56
28.84
2.57
0.00
0.39
1.12

TABLE 3

Activity of Copper Zinc Reference Catalysts for Methanol Production in High CO₂Syngas

Comp.

Ex. No.
CO₂
Cat
Temp (° C.)
H₂wt %
CO wt %
CO₂wt %
DME % wt
MeOH wt %
CO & CO₂conv %

96
High
CuZnO Ref A
238.5
66.53
2.15
19.61
0.00
9.72
31.34

97
High
CuZnO Ref A
238.4
66.49
2.29
19.57
0.00
9.66
30.77

98
High
CuZnO Ref A
238.3
66.54
2.60
19.59
0.00
9.30
29.55

99
High
CuZnO Ref A
238.5
66.66
2.68
19.47
0.00
9.22
29.54

100
High
CuZnO Ref A
238.4
66.95
2.50
19.57
0.00
9.02
29.41

101
High
CuZnO Ref A
239.6
66.70
2.75
19.62
0.00
8.97
28.33

102
High
CuZnO Ref A
238.4
66.79
2.63
19.67
0.00
8.94
28.83

103
High
CuZnO Ref A
240.1
66.84
2.83
19.48
0.00
8.89
28.58

104
High
CuZnO Ref A
228.3
67.46
2.98
19.50
0.00
8.13
26.87

105
High
CuZnO Ref A
228.5
67.32
3.08
19.64
0.00
8.04
25.80

106
High
CuZnO Ref A
228.3
67.45
3.31
19.55
0.00
7.78
25.12

107
High
CuZnO Ref A
228.3
67.50
3.42
19.50
0.00
7.67
24.70

108
High
CuZnO Ref A
229.9
67.80
3.41
19.38
0.00
7.49
25.29

109
High
CuZnO Ref A
229.8
67.73
3.45
19.50
0.00
7.41
24.45

110
High
CuZnO Ref A
229.8
67.79
3.53
19.44
0.00
7.34
24.12

111
High
CuZnO Ref A
228.5
67.91
3.42
19.53
0.00
7.23
24.27

112
High
CuZnO Ref A
228.9
67.93
3.46
19.58
0.00
7.14
23.85

113
High
CuZnO Ref A
198.6
71.03
6.22
18.63
0.00
2.39
10.15

114
High
CuZnO Ref A
198.4
70.82
6.32
18.75
0.00
2.37
9.06

115
High
CuZnO Ref A
198.7
70.93
6.37
18.66
0.00
2.30
9.49

116
High
CuZnO Ref A
198.4
70.99
6.35
18.64
0.00
2.28
9.68

117
High
CuZnO Ref A
199.6
71.29
6.24
18.49
0.00
2.24
10.76

118
High
CuZnO Ref A
200.0
71.35
6.25
18.45
0.00
2.22
10.64

119
High
CuZnO Ref A
200.1
71.17
6.27
18.62
0.00
2.20
10.00

120
High
CuZnO Ref A
198.6
71.11
6.25
18.75
0.00
2.16
9.75

121
High
CuZnO Ref A
198.9
71.09
6.13
18.88
0.00
2.15
9.86

122
High
CuZnO Ref A
179.2
72.10
6.30
18.88
0.00
1.03
6.47

123
High
CuZnO Ref A
179.1
72.03
6.52
18.74
0.00
1.03
6.04

124
High
CuZnO Ref A
178.9
71.85
6.65
18.81
0.00
1.01
4.91

125
High
CuZnO Ref A
179.4
71.91
6.73
18.67
0.00
1.00
5.55

126
High
CuZnO Ref A
180.2
72.01
6.67
18.64
0.00
0.99
5.86

127
High
CuZnO Ref A
180.0
71.90
6.52
18.92
0.00
0.98
5.06

128
High
CuZnO Ref A
180.2
72.02
6.71
18.60
0.00
0.97
5.87

129
High
CuZnO Ref A
178.9
71.89
6.69
18.78
0.00
0.96
5.21

130
High
CuZnO Ref A
178.9
71.95
6.65
18.76
0.00
0.96
5.63

131
High
CuZnO Ref B
240.0
67.92
3.55
19.32
0.00
7.31
24.62

132
High
CuZnO Ref B
239.9
67.95
3.59
19.38
0.00
7.17
24.34

133
High
CuZnO Ref B
239.7
67.85
3.66
19.39
0.00
7.21
23.57

134
High
CuZnO Ref B
238.4
68.53
4.66
19.19
0.00
5.77
19.36

135
High
CuZnO Ref B
238.4
68.62
4.77
19.09
0.00
5.68
19.14

136
High
CuZnO Ref B
238.4
70.01
3.96
18.48
0.00
5.66
25.96

137
High
CuZnO Ref B
238.1
69.99
3.84
18.54
0.00
5.74
26.08

138
High
CuZnO Ref B
230.1
68.88
4.44
19.10
0.00
5.73
20.13

139
High
CuZnO Ref B
230.1
68.90
4.57
19.18
0.00
5.50
19.01

140
High
CuZnO Ref B
229.7
68.92
4.48
19.13
0.00
5.63
19.62

141
High
CuZnO Ref B
228.3
69.41
5.52
18.99
0.00
4.29
14.89

142
High
CuZnO Ref B
228.3
70.71
4.67
18.50
0.00
4.28
21.17

143
High
CuZnO Ref B
228.3
69.51
5.57
18.94
0.00
4.19
14.66

144
High
CuZnO Ref B
228.2
70.89
5.05
18.12
0.00
4.10
21.24

145
High
CuZnO Ref B
200.3
71.48
6.49
18.49
0.00
1.83
8.88

146
High
CuZnO Ref B
200.1
71.63
6.44
18.43
0.00
1.78
9.31

147
High
CuZnO Ref B
199.6
71.57
6.33
18.58
0.00
1.81
9.16

148
High
CuZnO Ref B
198.6
71.30
6.84
18.67
0.00
1.48
6.61

149
High
CuZnO Ref B
198.6
71.15
6.92
18.77
0.00
1.45
5.48

150
High
CuZnO Ref B
198.6
72.87
5.99
17.97
0.00
1.42
13.89

151
High
CuZnO Ref B
198.4
72.51
6.30
18.01
0.00
1.44
12.21

152
High
CuZnO Ref B
180.0
72.07
6.55
18.82
0.00
0.88
5.36

153
High
CuZnO Ref B
179.7
72.05
6.63
18.74
0.00
0.90
5.32

154
High
CuZnO Ref B
179.7
72.03
6.59
18.84
0.00
0.87
4.93

155
High
CuZnO Ref B
178.9
71.99
6.65
18.95
0.00
0.73
4.60

156
High
CuZnO Ref B
178.9
71.82
6.86
18.93
0.00
0.72
3.77

157
High
CuZnO Ref B
178.5
73.29
6.15
18.16
0.00
0.71
10.32

158
High
CuZnO Ref B
178.2
73.21
6.20
18.20
0.00
0.70
10.02

TABLE 4

Activity of Promoted Copper Zinc Oxide Catalysts for Methanol Production

Comp.
CO₂

Promoter

DME
MeOH
CO & CO₂

Ex. No.
Level
Support
Promoter
(ppm)
Temp (° C.)
H₂wt %
CO wt %
CO₂wt %
% wt
wt %
conv %

159
Low
CuZnO Ref A
Ga
5000
316.9
62.53
24.47
4.66
0.09
6.34
21.35

160
Low
CuZnO Ref A
K
5000
316.8
62.67
24.19
4.87
0.05
6.28
21.94

161
Low
CuZnO Ref A
K
5000
293.3
58.13
23.04
4.45
0.04
12.28
31.35

162
Low
CuZnO Ref A
Ga
5000
292.3
57.97
23.08
4.31
0.06
12.51
31.43

163
Low
CuZnO Ref A
K
5000
274.7
53.69
21.56
4.24
0.02
18.27
39.84

164
Low
CuZnO Ref A
Ga
5000
274.7
54.05
21.91
4.13
0.04
17.68
38.40

165
Low
CuZnO Ref A
Rb
5000
240.1
54.07
23.26
3.51
0.00
17.03
35.04

166
Low
CuZnO Ref A
La
5000
240.1
55.61
23.88
3.37
0.01
15.07
31.73

167
Low
CuZnO Ref A
Ga
5000
240.0
53.86
22.90
3.51
0.00
17.58
36.46

168
Low
CuZnO Ref A
Sr
1000
240.0
66.57
28.66
2.65
0.00
0.47
1.56

169
Low
CuZnO Ref A
K
1000
240.0
67.03
28.58
2.48
0.00
0.26
2.35

170
Low
CuZnO Ref A
Ga
5000
239.9
53.86
22.67
3.53
0.00
17.78
37.23

171
Low
CuZnO Ref A
La
5000
239.9
55.57
23.75
3.39
0.01
15.20
32.56

172
Low
CuZnO Ref A
Rb
1000
239.9
66.38
28.82
2.70
0.00
0.44
0.85

173
Low
CuZnO Ref A
Rb
1000
239.9
66.22
28.99
2.71
0.00
0.44
0.60

174
Low
CuZnO Ref A
K
5000
239.7
52.32
21.91
3.67
0.00
19.88
40.53

175
Low
CuZnO Ref A
Rb
5000
239.7
54.22
22.95
3.51
0.00
17.18
35.89

176
Low
CuZnO Ref A
Sr
1000
239.7
66.35
28.91
2.65
0.00
0.45
0.20

177
Low
CuZnO Ref A
K
1000
239.7
67.09
28.53
2.49
0.00
0.25
2.62

178
Low
CuZnO Ref A
K
5000
239.6
52.32
21.94
3.66
0.00
19.86
40.46

179
Low
CuZnO Ref A
Ba
1000
238.7
66.44
28.48
2.83
0.00
0.61
0.82

180
Low
CuZnO Ref A
Sr
5000
238.7
66.43
28.98
2.66
0.00
0.29
0.09

181
Low
CuZnO Ref A
K
5000
238.5
50.30
20.80
3.56
0.00
23.04
45.46

182
Low
CuZnO Ref A
K
5000
238.5
50.53
20.95
3.53
0.00
22.69
44.95

183
Low
CuZnO Ref A
Na
5000
238.5
54.22
22.71
3.51
0.00
17.42
36.63

184
Low
CuZnO Ref A
Na
5000
238.5
54.28
22.81
3.49
0.00
17.28
36.34

185
Low
CuZnO Ref A
Li
5000
238.5
66.59
28.31
2.71
0.00
0.72
3.25

186
Low
CuZnO Ref A
Na
1000
238.5
66.12
28.91
2.83
0.00
0.51
−0.99

187
Low
CuZnO Ref A
Li
5000
238.4
66.60
28.31
2.72
0.00
0.72
3.31

188
Low
CuZnO Ref A
Ba
1000
238.4
66.48
28.40
2.84
0.00
0.64
1.14

189
Low
CuZnO Ref A
Na
1000
238.4
66.06
28.95
2.83
0.00
0.54
−1.13

190
Low
CuZnO Ref A
Li
1000
238.4
67.20
28.17
2.50
0.00
0.47
3.95

191
Low
CuZnO Ref A
La
1000
238.4
66.72
28.69
2.65
0.00
0.30
1.10

192
Low
CuZnO Ref A
La
1000
238.4
66.70
28.72
2.65
0.00
0.29
1.25

193
Low
CuZnO Ref A
Sr
5000
238.4
66.43
29.00
2.66
0.00
0.27
0.17

194
Low
CuZnO Ref A
Li
1000
238.3
67.23
28.11
2.51
0.00
0.50
4.16

195
Low
CuZnO Ref A
Ga
5000
230.1
57.25
24.21
3.26
0.00
13.24
30.01

196
Low
CuZnO Ref A
K
1000
230.1
67.09
28.57
2.49
0.00
0.20
2.46

197
Low
CuZnO Ref A
Rb
5000
229.9
56.73
24.49
3.30
0.00
13.45
28.99

198
Low
CuZnO Ref A
Ga
5000
229.9
57.23
24.22
3.26
0.00
13.27
29.87

199
Low
CuZnO Ref A
La
5000
229.9
58.79
25.13
3.12
0.00
11.01
25.26

200
Low
CuZnO Ref A
Sr
1000
229.9
66.70
28.65
2.65
0.00
0.36
1.58

201
Low
CuZnO Ref A
Rb
1000
229.9
66.44
28.87
2.70
0.00
0.34
0.81

202
Low
CuZnO Ref A
K
5000
229.8
55.29
23.51
3.38
0.00
15.71
33.64

203
Low
CuZnO Ref A
Rb
5000
229.8
56.43
24.41
3.34
0.00
13.78
29.72

204
Low
CuZnO Ref A
La
5000
229.8
58.83
25.13
3.12
0.00
10.97
25.29

205
Low
CuZnO Ref A
Rb
1000
229.8
66.39
28.94
2.70
0.00
0.33
0.36

206
Low
CuZnO Ref A
K
1000
229.8
67.16
28.52
2.49
0.00
0.18
2.62

207
Low
CuZnO Ref A
K
5000
229.7
55.35
23.57
3.39
0.00
15.59
33.30

208
Low
CuZnO Ref A
Sr
1000
229.7
66.82
28.55
2.65
0.00
0.32
2.23

209
Low
CuZnO Ref A
Sr
5000
228.8
66.62
28.87
2.65
0.00
0.20
0.77

210
Low
CuZnO Ref A
Ba
1000
228.6
66.50
28.56
2.83
0.00
0.48
0.07

211
Low
CuZnO Ref A
Na
1000
228.6
66.40
28.73
2.82
0.00
0.43
−0.56

212
Low
CuZnO Ref A
Li
1000
228.6
67.24
28.28
2.49
0.00
0.34
2.97

213
Low
CuZnO Ref A
Sr
5000
228.6
66.66
28.82
2.65
0.00
0.22
0.48

214
Low
CuZnO Ref A
K
5000
228.5
53.41
22.26
3.30
0.00
18.84
39.32

215
Low
CuZnO Ref A
Na
5000
228.5
57.23
24.18
3.28
0.00
13.30
29.47

216
Low
CuZnO Ref A
Na
1000
228.5
66.41
28.74
2.83
0.00
0.39
−0.47

217
Low
CuZnO Ref A
La
1000
228.5
66.76
28.71
2.66
0.00
0.24
1.05

218
Low
CuZnO Ref A
K
5000
228.3
53.11
22.21
3.32
0.00
19.16
39.80

219
Low
CuZnO Ref A
Na
5000
228.3
57.49
24.19
3.25
0.00
13.05
29.45

220
Low
CuZnO Ref A
Li
5000
228.3
66.73
28.45
2.72
0.00
0.46
1.99

221
Low
CuZnO Ref A
Li
5000
228.3
66.82
28.38
2.71
0.00
0.44
2.30

222
Low
CuZnO Ref A
Li
1000
228.3
67.16
28.31
2.49
0.00
0.38
3.15

223
Low
CuZnO Ref A
La
1000
228.3
66.72
28.78
2.65
0.00
0.21
0.65

224
Low
CuZnO Ref A
Ba
1000
228.2
66.55
28.47
2.83
0.00
0.51
0.66

225
Low
CuZnO Ref A
Rb
5000
200.3
65.08
28.44
2.71
0.00
2.07
5.12

226
Low
CuZnO Ref A
K
5000
200.1
65.71
28.17
2.65
0.00
1.78
5.89

227
Low
CuZnO Ref A
K
5000
200.1
65.66
28.23
2.65
0.00
1.76
5.64

228
Low
CuZnO Ref A
La
5000
200.1
66.20
28.64
2.55
0.00
0.94
3.09

229
Low
CuZnO Ref A
K
1000
200.1
67.00
28.79
2.50
0.00
0.07
1.56

230
Low
CuZnO Ref A
K
1000
200.1
67.16
28.64
2.49
0.00
0.06
1.75

231
Low
CuZnO Ref A
Sr
1000
200.0
66.97
28.64
2.65
0.00
0.11
0.96

232
Low
CuZnO Ref A
Rb
1000
200.0
66.62
28.93
2.70
0.00
0.11
0.17

233
Low
CuZnO Ref A
Sr
1000
200.0
66.97
28.64
2.65
0.00
0.10
1.21

234
Low
CuZnO Ref A
Rb
5000
199.8
65.10
28.42
2.72
0.00
2.07
5.34

235
Low
CuZnO Ref A
La
5000
199.8
66.14
28.64
2.55
0.00
1.00
3.29

236
Low
CuZnO Ref A
Ga
5000
199.6
65.87
28.36
2.60
0.00
1.48
4.90

237
Low
CuZnO Ref A
Rb
1000
199.6
66.58
28.98
2.70
0.00
0.10
−0.15

238
Low
CuZnO Ref A
Ga
5000
199.5
65.91
28.30
2.60
0.00
1.50
5.30

239
Low
CuZnO Ref A
K
5000
198.7
65.43
27.86
2.50
0.00
2.49
8.34

240
Low
CuZnO Ref A
Li
5000
198.7
66.95
28.57
2.72
0.00
0.12
0.82

241
Low
CuZnO Ref A
Li
1000
198.7
67.33
28.42
2.50
0.00
0.12
2.13

242
Low
CuZnO Ref A
Sr
5000
198.7
66.81
28.82
2.66
0.00
0.08
0.82

243
Low
CuZnO Ref A
Na
5000
198.6
66.16
28.19
2.63
0.00
1.34
4.56

244
Low
CuZnO Ref A
Na
5000
198.6
66.22
28.13
2.63
0.00
1.34
4.79

245
Low
CuZnO Ref A
Ba
1000
198.6
66.76
28.65
2.84
0.00
0.14
−0.74

246
Low
CuZnO Ref A
Na
1000
198.6
66.62
28.81
2.82
0.00
0.13
−1.31

247
Low
CuZnO Ref A
Na
1000
198.6
66.63
28.80
2.83
0.00
0.12
−0.85

248
Low
CuZnO Ref A
Li
1000
198.6
67.42
28.35
2.49
0.00
0.11
2.44

249
Low
CuZnO Ref A
Li
5000
198.6
67.01
28.52
2.73
0.00
0.11
1.06

250
Low
CuZnO Ref A
Sr
5000
198.6
66.87
28.75
2.66
0.00
0.07
1.10

251
Low
CuZnO Ref A
K
5000
198.4
65.54
27.71
2.50
0.00
2.53
8.59

252
Low
CuZnO Ref A
Ba
1000
198.4
66.79
28.60
2.84
0.00
0.15
−0.41

253
Low
CuZnO Ref A
La
1000
198.4
66.79
28.84
2.66
0.00
0.08
0.05

254
Low
CuZnO Ref A
La
1000
198.4
66.83
28.80
2.66
0.00
0.07
0.27

255
Low
CuZnO Ref A
K
5000
180.2
66.55
28.79
2.60
0.00
0.41
1.57

256
Low
CuZnO Ref A
K
5000
180.2
66.65
28.70
2.59
0.00
0.40
2.01

257
Low
CuZnO Ref A
Ga
5000
180.0
66.30
29.04
2.57
0.00
0.44
0.21

258
Low
CuZnO Ref A
Rb
5000
180.0
66.29
29.00
2.63
0.00
0.43
0.70

259
Low
CuZnO Ref A
Rb
5000
180.0
66.26
29.03
2.63
0.00
0.43
0.67

260
Low
CuZnO Ref A
La
5000
180.0
66.61
28.83
2.53
0.00
0.38
1.52

261
Low
CuZnO Ref A
Rb
1000
180.0
66.63
28.97
2.71
0.00
0.05
−0.19

262
Low
CuZnO Ref A
Sr
1000
180.0
67.06
28.61
2.66
0.00
0.05
0.84

263
Low
CuZnO Ref A
La
5000
179.9
66.80
28.69
2.55
0.00
0.32
1.79

264
Low
CuZnO Ref A
Sr
1000
179.9
67.08
28.58
2.65
0.00
0.06
0.99

265
Low
CuZnO Ref A
Rb
1000
179.9
66.60
29.01
2.70
0.00
0.05
−0.49

266
Low
CuZnO Ref A
K
1000
179.9
67.02
28.79
2.50
0.00
0.03
1.67

267
Low
CuZnO Ref A
K
1000
179.9
67.07
28.75
2.51
0.00
0.03
1.78

268
Low
CuZnO Ref A
Ga
5000
179.6
66.60
28.75
2.57
0.00
0.43
1.99

269
Low
CuZnO Ref A
Li
5000
179.6
66.97
28.63
2.73
0.00
0.05
0.16

270
Low
CuZnO Ref A
Na
1000
179.4
66.71
28.79
2.83
0.00
0.06
−0.83

271
Low
CuZnO Ref A
Na
1000
179.1
66.75
28.73
2.82
0.00
0.06
−0.50

272
Low
CuZnO Ref A
K
5000
178.9
66.90
28.55
2.42
0.00
0.48
2.99

273
Low
CuZnO Ref A
Na
5000
178.9
66.88
28.58
2.60
0.00
0.30
1.41

274
Low
CuZnO Ref A
Ba
1000
178.9
66.83
28.64
2.85
0.00
0.06
−0.72

275
Low
CuZnO Ref A
Li
5000
178.9
67.04
28.54
2.73
0.00
0.05
0.74

276
Low
CuZnO Ref A
Sr
5000
178.9
66.93
28.74
2.66
0.00
0.04
0.79

277
Low
CuZnO Ref A
Sr
5000
178.9
66.90
28.77
2.66
0.00
0.03
0.47

278
Low
CuZnO Ref A
K
5000
178.8
66.97
28.49
2.42
0.00
0.47
3.28

279
Low
CuZnO Ref A
Ba
1000
178.8
66.82
28.66
2.85
0.00
0.06
−0.83

280
Low
CuZnO Ref A
Na
5000
178.6
66.90
28.54
2.60
0.00
0.31
1.66

281
Low
CuZnO Ref A
Li
1000
178.6
67.42
28.38
2.51
0.00
0.05
2.68

282
Low
CuZnO Ref A
Li
1000
178.6
67.25
28.57
2.50
0.00
0.05
1.85

283
Low
CuZnO Ref A
La
1000
178.5
66.89
28.78
2.66
0.00
0.04
0.17

284
Low
CuZnO Ref A
La
1000
178.5
66.85
28.83
2.66
0.00
0.03
0.07

285
Low
CuZnO Ref B
Ga
5000
316.9
62.50
24.65
4.51
0.33
6.11
20.88

286
Low
CuZnO Ref B
Ga
5000
295.9
58.95
23.70
4.22
0.20
10.91
28.46

287
Low
CuZnO Ref B
Ga
5000
275.0
54.98
22.52
3.97
0.09
16.29
36.10

288
Low
CuZnO Ref B
Ga
5000
240.0
56.41
23.86
3.34
0.01
14.32
31.79

289
Low
CuZnO Ref B
Ga
5000
239.9
56.36
23.79
3.34
0.01
14.43
31.88

290
Low
CuZnO Ref B
K
5000
239.9
58.79
25.38
3.17
0.00
10.71
24.35

291
Low
CuZnO Ref B
K
5000
239.7
58.78
25.42
3.16
0.00
10.69
24.25

292
Low
CuZnO Ref B
Ga
5000
230.1
59.75
25.62
3.06
0.00
9.65
22.79

293
Low
CuZnO Ref B
K
5000
229.9
61.38
26.71
2.96
0.00
7.09
16.97

294
Low
CuZnO Ref B
K
5000
229.9
61.44
26.65
2.97
0.00
7.09
16.92

295
Low
CuZnO Ref B
Ga
5000
229.5
59.85
25.59
3.06
0.00
9.57
22.86

296
Low
CuZnO Ref B
K
5000
200.3
66.22
28.74
2.63
0.00
0.74
2.32

297
Low
CuZnO Ref B
Ga
5000
199.8
66.23
28.51
2.58
0.00
1.01
3.88

298
Low
CuZnO Ref B
Ga
5000
199.8
66.16
28.59
2.58
0.00
1.00
3.45

299
Low
CuZnO Ref B
K
5000
199.8
66.16
28.80
2.62
0.00
0.75
2.20

300
Low
CuZnO Ref B
K
5000
180.2
66.55
28.94
2.63
0.00
0.23
0.56

301
Low
CuZnO Ref B
K
5000
180.0
66.59
28.90
2.63
0.00
0.23
0.76

302
Low
CuZnO Ref B
Ga
5000
179.9
66.67
28.77
2.58
0.00
0.32
1.83

303
Low
CuZnO Ref B
Ga
5000
179.7
66.67
28.79
2.58
0.00
0.32
1.52

304
High
CuZnO Ref A
La
1000
240.1
72.29
6.78
18.78
0.00
0.49
3.80

305
High
CuZnO Ref A
K
5000
240.0
67.72
3.73
19.59
0.00
7.08
22.48

306
High
CuZnO Ref A
Rb
5000
240.0
68.43
4.10
19.42
0.00
6.19
20.83

307
High
CuZnO Ref A
Li
1000
240.0
72.39
6.70
18.79
0.00
0.45
3.93

308
High
CuZnO Ref A
La
5000
239.9
67.81
3.55
19.30
0.00
7.44
24.83

309
High
CuZnO Ref A
K
5000
239.9
67.79
3.74
19.58
0.00
7.02
22.30

310
High
CuZnO Ref A
Li
1000
239.9
72.44
6.66
18.76
0.00
0.48
4.22

311
High
CuZnO Ref A
Rb
1000
239.9
72.41
6.70
18.79
0.00
0.43
4.66

312
High
CuZnO Ref A
Rb
1000
239.9
72.23
6.77
18.92
0.00
0.41
3.26

313
High
CuZnO Ref A
La
5000
239.7
67.83
3.43
19.35
0.00
7.48
25.12

314
High
CuZnO Ref A
La
5000
239.7
67.86
3.59
19.26
0.00
7.39
24.96

315
High
CuZnO Ref A
K
5000
239.7
67.66
3.69
19.57
0.00
7.19
22.92

316
High
CuZnO Ref A
La
1000
239.7
72.24
6.82
18.81
0.00
0.47
3.43

317
High
CuZnO Ref A
Li
1000
239.7
72.28
6.88
18.72
0.00
0.47
3.24

318
High
CuZnO Ref A
K
1000
239.7
72.31
6.72
18.95
0.00
0.35
3.58

319
High
CuZnO Ref A
K
1000
239.7
72.35
6.70
18.94
0.00
0.34
3.71

320
High
CuZnO Ref A
Rb
5000
239.6
68.56
4.08
19.44
0.00
6.08
20.60

321
High
CuZnO Ref A
Na
1000
238.7
72.10
7.05
18.67
0.00
0.51
3.41

322
High
CuZnO Ref A
Sr
1000
238.7
72.19
6.51
19.14
0.00
0.48
4.04

323
High
CuZnO Ref A
Sr
5000
238.7
71.84
7.34
18.81
0.00
0.35
1.23

324
High
CuZnO Ref A
Ga
5000
238.5
67.28
3.30
19.73
0.00
7.78
24.59

325
High
CuZnO Ref A
Na
5000
238.5
68.09
4.28
19.39
0.00
6.37
20.52

326
High
CuZnO Ref A
Na
5000
238.5
68.34
4.37
19.14
0.00
6.28
21.49

327
High
CuZnO Ref A
Sr
1000
238.5
72.21
6.62
19.04
0.00
0.46
3.95

328
High
CuZnO Ref A
Ga
5000
238.4
67.25
3.35
19.71
0.00
7.79
24.23

329
High
CuZnO Ref A
Na
1000
238.4
72.15
6.97
18.72
0.00
0.49
3.49

330
High
CuZnO Ref A
Ba
1000
238.4
71.94
7.21
18.93
0.00
0.26
1.06

331
High
CuZnO Ref A
Ba
1000
238.4
71.96
7.11
19.03
0.00
0.25
1.19

332
High
CuZnO Ref A
Li
5000
238.3
72.03
6.98
18.78
0.00
0.53
3.93

333
High
CuZnO Ref A
Li
5000
238.3
71.81
7.04
18.96
0.00
0.52
2.58

334
High
CuZnO Ref A
Sr
5000
238.3
71.92
7.34
18.75
0.00
0.33
1.77

335
High
CuZnO Ref A
La
5000
230.1
68.78
4.64
19.42
0.00
5.35
17.06

336
High
CuZnO Ref A
Rb
5000
230.1
69.48
4.64
19.17
0.00
4.89
18.12

337
High
CuZnO Ref A
Rb
5000
230.1
69.39
4.74
19.29
0.00
4.76
16.78

338
High
CuZnO Ref A
Rb
5000
230.1
69.41
4.77
19.36
0.00
4.65
16.32

339
High
CuZnO Ref A
Li
1000
230.1
72.44
6.67
18.87
0.00
0.37
3.42

340
High
CuZnO Ref A
La
1000
230.1
72.39
6.69
18.90
0.00
0.36
3.29

341
High
CuZnO Ref A
Rb
1000
229.9
72.46
6.60
18.95
0.00
0.32
3.95

342
High
CuZnO Ref A
K
1000
229.9
72.30
6.75
19.00
0.00
0.29
2.86

343
High
CuZnO Ref A
K
1000
229.9
72.32
6.68
19.08
0.00
0.26
2.55

344
High
CuZnO Ref A
La
5000
229.8
69.17
4.76
18.94
0.00
5.29
19.07

345
High
CuZnO Ref A
La
5000
229.8
69.36
4.82
18.97
0.00
5.02
18.37

346
High
CuZnO Ref A
La
1000
229.8
72.31
6.76
18.87
0.00
0.40
3.04

347
High
CuZnO Ref A
Li
1000
229.8
72.42
6.74
18.79
0.00
0.39
3.27

348
High
CuZnO Ref A
La
1000
229.8
72.26
6.80
18.91
0.00
0.37
2.80

349
High
CuZnO Ref A
Li
1000
229.8
72.45
6.71
18.83
0.00
0.36
3.49

350
High
CuZnO Ref A
Rb
1000
229.7
72.31
6.74
18.94
0.00
0.36
3.16

351
High
CuZnO Ref A
Na
1000
228.6
72.29
6.83
18.80
0.00
0.41
3.51

352
High
CuZnO Ref A
Ga
5000
228.5
68.64
4.31
19.45
0.00
5.75
19.48

353
High
CuZnO Ref A
K
5000
228.5
68.97
4.87
19.29
0.00
5.06
16.76

354
High
CuZnO Ref A
Sr
1000
228.5
72.11
6.59
19.24
0.00
0.39
2.75

355
High
CuZnO Ref A
Na
1000
228.5
72.05
6.96
18.95
0.00
0.38
1.97

356
High
CuZnO Ref A
Sr
1000
228.5
72.09
6.53
19.36
0.00
0.36
2.27

357
High
CuZnO Ref A
Sr
5000
228.5
71.86
7.29
18.92
0.00
0.28
0.73

358
High
CuZnO Ref A
Sr
5000
228.5
71.86
7.26
18.97
0.00
0.26
0.33

359
High
CuZnO Ref A
Ba
1000
228.5
71.94
7.11
19.10
0.00
0.21
0.43

360
High
CuZnO Ref A
Ga
5000
228.3
68.64
4.38
19.36
0.00
5.77
19.61

361
High
CuZnO Ref A
K
5000
228.3
69.05
4.75
19.28
0.00
5.11
17.32

362
High
CuZnO Ref A
Na
5000
228.3
69.20
5.10
19.06
0.00
4.82
17.00

363
High
CuZnO Ref A
Na
5000
228.3
69.27
5.08
19.12
0.00
4.71
16.58

364
High
CuZnO Ref A
Li
5000
228.3
71.83
6.95
19.18
0.00
0.37
1.41

365
High
CuZnO Ref A
Ba
1000
228.3
71.82
7.11
19.24
0.00
0.19
−0.25

366
High
CuZnO Ref A
K
5000
228.2
68.99
4.82
19.40
0.00
4.98
16.44

367
High
CuZnO Ref A
Li
5000
228.2
71.89
6.99
19.07
0.00
0.39
2.02

368
High
CuZnO Ref A
La
1000
200.3
72.65
6.56
19.00
0.00
0.15
2.73

369
High
CuZnO Ref A
K
5000
200.1
71.41
6.53
18.81
0.00
1.55
7.00

370
High
CuZnO Ref A
K
1000
200.1
72.26
6.67
19.32
0.00
0.11
1.15

371
High
CuZnO Ref A
K
5000
200.0
71.44
6.58
18.72
0.00
1.55
7.07

372
High
CuZnO Ref A
Rb
5000
200.0
71.70
6.45
18.70
0.00
1.44
7.35

373
High
CuZnO Ref A
Rb
5000
200.0
71.69
6.47
18.73
0.00
1.41
7.13

374
High
CuZnO Ref A
La
5000
200.0
71.83
6.64
18.49
0.00
1.33
7.09

375
High
CuZnO Ref A
Li
1000
200.0
72.61
6.52
19.06
0.00
0.16
2.21

376
High
CuZnO Ref A
La
1000
200.0
72.62
6.57
19.01
0.00
0.15
2.78

377
High
CuZnO Ref A
La
5000
199.8
71.53
6.47
18.90
0.00
1.41
6.03

378
High
CuZnO Ref A
La
5000
199.8
71.87
6.54
18.52
0.00
1.36
7.73

379
High
CuZnO Ref A
Li
1000
199.8
72.69
6.47
19.05
0.00
0.15
2.69

380
High
CuZnO Ref A
Li
1000
199.8
72.65
6.52
19.05
0.00
0.14
2.39

381
High
CuZnO Ref A
Rb
1000
199.8
72.47
6.58
19.16
0.00
0.14
2.25

382
High
CuZnO Ref A
La
1000
199.8
72.47
6.62
19.13
0.00
0.14
1.66

383
High
CuZnO Ref A
K
5000
199.6
71.47
6.57
18.72
0.00
1.54
7.25

384
High
CuZnO Ref A
Rb
5000
199.6
71.71
6.49
18.68
0.00
1.42
7.21

385
High
CuZnO Ref A
Rb
1000
199.6
72.40
6.57
19.24
0.00
0.13
1.77

386
High
CuZnO Ref A
K
1000
199.6
72.50
6.63
19.11
0.00
0.11
2.25

387
High
CuZnO Ref A
Na
5000
199.0
71.24
6.83
18.80
0.00
1.44
5.69

388
High
CuZnO Ref A
Ga
5000
198.7
70.96
6.69
18.98
0.00
1.66
5.80

389
High
CuZnO Ref A
Na
1000
198.7
72.37
6.69
19.14
0.00
0.16
1.45

390
High
CuZnO Ref A
Sr
1000
198.7
71.96
6.74
19.52
0.00
0.15
−0.33

391
High
CuZnO Ref A
Sr
5000
198.7
72.05
7.07
19.15
0.00
0.10
−0.18

392
High
CuZnO Ref A
Ba
1000
198.7
72.00
7.13
19.14
0.00
0.08
−0.02

393
High
CuZnO Ref A
Ba
1000
198.7
71.90
7.14
19.25
0.00
0.07
−0.89

394
High
CuZnO Ref A
Na
1000
198.6
72.15
6.86
19.20
0.00
0.15
0.30

395
High
CuZnO Ref A
Sr
1000
198.6
72.06
6.66
19.51
0.00
0.14
−0.02

396
High
CuZnO Ref A
Li
5000
198.6
72.01
6.75
19.46
0.00
0.12
0.63

397
High
CuZnO Ref A
Sr
5000
198.6
71.88
7.16
19.23
0.00
0.10
−0.98

398
High
CuZnO Ref A
Ga
5000
198.4
71.07
6.50
19.05
0.00
1.67
6.41

399
High
CuZnO Ref A
Na
5000
198.4
71.24
6.91
18.69
0.00
1.45
5.86

400
High
CuZnO Ref A
Li
5000
198.4
71.97
6.81
19.44
0.00
0.13
0.21

401
High
CuZnO Ref A
K
5000
180.0
71.82
6.81
18.99
0.00
0.71
3.19

402
High
CuZnO Ref A
Rb
5000
180.0
72.06
6.65
19.02
0.00
0.62
3.43

403
High
CuZnO Ref A
Rb
5000
180.0
72.04
6.59
19.10
0.00
0.61
3.25

404
High
CuZnO Ref A
Rb
5000
180.0
72.25
6.67
18.81
0.00
0.60
4.44

405
High
CuZnO Ref A
Li
1000
180.0
72.65
6.48
19.16
0.00
0.08
1.78

406
High
CuZnO Ref A
La
1000
180.0
72.57
6.45
19.27
0.00
0.08
1.53

407
High
CuZnO Ref A
Li
1000
180.0
72.46
6.42
19.42
0.00
0.08
0.72

408
High
CuZnO Ref A
Rb
1000
180.0
72.77
6.57
18.94
0.00
0.07
3.12

409
High
CuZnO Ref A
Rb
1000
180.0
72.54
6.51
19.25
0.00
0.06
1.78

410
High
CuZnO Ref A
K
1000
180.0
72.65
6.54
19.11
0.00
0.06
1.95

411
High
CuZnO Ref A
K
1000
180.0
72.42
6.66
19.23
0.00
0.05
1.27

412
High
CuZnO Ref A
K
5000
179.9
71.88
6.79
18.96
0.00
0.70
3.50

413
High
CuZnO Ref A
La
5000
179.9
72.25
6.61
18.81
0.00
0.66
4.66

414
High
CuZnO Ref A
La
5000
179.9
72.24
6.58
18.87
0.00
0.64
4.29

415
High
CuZnO Ref A
La
5000
179.9
72.24
6.66
18.80
0.00
0.64
4.42

416
High
CuZnO Ref A
La
1000
179.9
72.63
6.52
19.13
0.00
0.07
1.87

417
High
CuZnO Ref A
K
5000
179.7
72.00
6.64
18.97
0.00
0.72
4.06

418
High
CuZnO Ref A
La
1000
179.7
72.43
6.50
19.37
0.00
0.08
0.67

419
High
CuZnO Ref A
Li
1000
179.7
72.57
6.50
19.23
0.00
0.07
1.13

420
High
CuZnO Ref A
Na
1000
179.2
72.39
6.64
19.26
0.00
0.07
0.80

421
High
CuZnO Ref A
Sr
5000
179.2
72.21
6.81
19.28
0.00
0.04
0.52

422
High
CuZnO Ref A
Ga
5000
179.1
71.75
6.57
19.23
0.00
0.77
3.50

423
High
CuZnO Ref A
Na
5000
179.1
72.13
6.56
18.96
0.00
0.66
4.85

424
High
CuZnO Ref A
Ba
1000
179.1
72.18
6.89
19.25
0.00
0.03
0.32

425
High
CuZnO Ref A
Na
5000
178.9
71.93
6.93
18.81
0.00
0.66
3.83

426
High
CuZnO Ref A
Na
1000
178.9
72.52
6.53
19.24
0.00
0.08
1.38

427
High
CuZnO Ref A
Sr
1000
178.9
72.12
6.69
19.49
0.00
0.07
−0.39

428
High
CuZnO Ref A
Sr
1000
178.9
71.98
6.72
19.61
0.00
0.06
−1.08

429
High
CuZnO Ref A
Sr
5000
178.9
72.07
7.01
19.23
0.00
0.04
−0.36

430
High
CuZnO Ref A
Ba
1000
178.9
72.18
6.86
19.27
0.00
0.04
0.41

431
High
CuZnO Ref A
Ga
5000
178.8
71.70
6.68
19.17
0.00
0.77
3.37

432
High
CuZnO Ref A
Li
5000
178.5
72.18
6.76
19.36
0.00
0.06
0.44

433
High
CuZnO Ref A
Li
5000
178.5
72.19
6.79
19.31
0.00
0.05
0.74

434
High
CuZnO Ref B
Ga
5000
239.9
67.81
3.52
19.42
0.00
7.35
24.32

435
High
CuZnO Ref B
Ga
5000
239.9
67.75
3.44
19.57
0.00
7.34
24.16

436
High
CuZnO Ref B
Ga
5000
230.1
68.84
4.63
19.20
0.00
5.50
18.61

437
High
CuZnO Ref B
Ga
5000
229.9
69.01
4.57
19.17
0.00
5.41
19.20

438
High
CuZnO Ref B
Ga
5000
200.1
71.48
6.52
18.64
0.00
1.65
8.09

439
High
CuZnO Ref B
Ga
5000
199.8
71.41
6.40
18.84
0.00
1.63
7.79

440
High
CuZnO Ref B
Ga
5000
180.0
72.27
6.52
18.72
0.00
0.82
5.77

441
High
CuZnO Ref B
Ga
5000
180.0
72.07
6.56
18.91
0.00
0.78
4.93

TABLE 5

Activity of Unmodified Copper Chromite Catalyst for Methanol Production

Comp.

CO & CO₂

Ex. No.
CO₂
Cat
Temp (° C.)
H₂wt %
CO wt %
CO₂wt %
DME % wt
MeOH wt %
conv %

442
Low
CuCrOx
293.7
62.33
26.26
3.24
0.22
6.11
16.94

443
Low
CuCrOx
316.8
62.97
25.98
3.68
0.51
5.02
16.50

444
Low
CuCrOx
274.8
63.57
26.98
2.96
0.09
4.62
13.07

445
Low
CuCrOx
240.1
65.93
28.15
2.72
0.01
1.50
5.37

446
Low
CuCrOx
239.6
65.92
28.22
2.71
0.01
1.45
5.14

447
Low
CuCrOx
229.8
66.17
28.28
2.71
0.00
1.16
4.32

448
Low
CuCrOx
230.1
66.17
28.32
2.71
0.00
1.11
4.17

449
Low
CuCrOx
199.8
66.74
28.54
2.69
0.00
0.38
2.31

450
Low
CuCrOx
200.1
66.73
28.57
2.69
0.00
0.36
2.06

451
Low
CuCrOx
180.3
66.55
28.96
2.69
0.00
0.17
−0.05

452
Low
CuCrOx
179.7
66.87
28.64
2.68
0.00
0.16
1.56

453
High
CuCrOx
238.4
71.75
7.31
18.40
0.00
0.85
4.81

454
High
CuCrOx
238.4
71.72
7.28
18.47
0.00
0.83
4.85

455
High
CuCrOx
228.5
71.79
7.24
18.66
0.00
0.64
3.30

456
High
CuCrOx
228.3
71.78
7.22
18.70
0.00
0.61
3.26

457
High
CuCrOx
198.6
71.90
7.05
19.17
0.00
0.23
0.53

458
High
CuCrOx
198.4
71.97
7.09
19.08
0.00
0.22
0.60

459
High
CuCrOx
178.9
72.29
6.85
19.10
0.00
0.11
1.60

460
High
CuCrOx
179.1
72.13
6.93
19.19
0.00
0.11
0.51

TABLE 6

Activity of Unpromoted 1% Ruthenium Copper Chromite Catalyst for Methanol Production

Comp.

CO & CO₂

Ex. No.
CO₂
Cat
Promoter
Temp (° C.)
H₂wt %
CO wt %
CO₂wt %
DME % wt
MeOH wt %
conv %

461
Low
RuCuCrOx
None
239.9
67.0
28.4
2.5
0.00
0.46
3.15

462
Low
RuCuCrOx
None
240.1
67.1
28.3
2.5
0.00
0.44
3.89

463
Low
RuCuCrOx
None
229.8
67.2
28.4
2.5
0.00
0.34
3.20

464
Low
RuCuCrOx
None
229.9
67.1
28.5
2.5
0.00
0.31
2.52

465
Low
RuCuCrOx
None
199.8
67.2
28.5
2.5
0.00
0.10
2.23

466
Low
RuCuCrOx
None
200.1
67.2
28.6
2.5
0.00
0.09
2.27

467
Low
RuCuCrOx
None
180.0
67.3
28.5
2.5
0.00
0.04
2.32

468
Low
RuCuCrOx
None
179.9
67.3
28.6
2.5
0.00
0.04
2.05

469
High
RuCuCrOx
None
238.5
72.23
6.68
19.05
0.00
0.38
3.35

470
High
RuCuCrOx
None
238.4
72.23
6.69
19.05
0.00
0.36
3.21

471
High
RuCuCrOx
None
228.5
72.24
6.65
19.14
0.00
0.30
2.94

472
High
RuCuCrOx
None
228.6
72.37
6.65
19.04
0.00
0.28
2.99

473
High
RuCuCrOx
None
198.6
72.33
6.55
19.36
0.00
0.11
1.70

474
High
RuCuCrOx
None
198.6
72.31
6.56
19.38
0.00
0.10
1.10

475
High
RuCuCrOx
None
179.1
72.55
6.56
19.20
0.00
0.05
1.94

476
High
RuCuCrOx
None
179.2
72.32
6.66
19.33
0.00
0.05
0.92

TABLE 7

Activity of Promoted Copper Chromite Catalysts without Ru for Methanol Production

Comp.

Prom

CO & CO₂

Ex. No.
CO₂
Prom
ppm
Temp (° C.)
H₂wt %
CO wt %
CO₂wt %
DME % wt
MeOH wt %
conv %

477
Low
Ga
5000
294.1
63.22
26.79
2.99
0.06
5.14
14.34

478
Low
Ga
5000
316.9
63.12
26.52
3.27
0.18
5.10
15.09

479
Low
Ga
5000
275.1
64.32
27.81
2.80
0.02
3.32
8.55

480
Low
Ga
5000
239.7
66.39
28.28
2.69
0.00
0.97
4.13

481
Low
Ga
5000
239.7
66.40
28.28
2.69
0.00
0.96
3.95

482
Low
Li
1000
240.1
66.69
28.20
2.68
0.00
0.77
3.80

483
Low
Li
1000
240.1
66.77
28.15
2.68
0.00
0.74
3.56

484
Low
Ga
5000
229.5
66.58
28.35
2.68
0.00
0.72
3.29

485
Low
Ga
5000
229.8
66.64
28.32
2.69
0.00
0.69
3.35

486
Low
Sr
1000
239.9
66.59
28.44
2.67
0.00
0.65
2.61

487
Low
La
1000
238.4
66.40
28.74
2.57
0.00
0.63
2.01

488
Low
Sr
1000
239.6
66.71
28.33
2.67
0.00
0.63
3.44

489
Low
La
1000
238.5
66.09
29.08
2.57
0.00
0.61
0.96

490
Low
Ba
1000
240.0
66.92
28.34
2.48
0.00
0.60
3.70

491
Low
Ba
1000
239.7
66.89
28.39
2.48
0.00
0.59
3.54

492
Low
Na
1000
238.7
66.39
28.74
2.65
0.00
0.57
1.33

493
Low
Na
1000
238.5
66.39
28.76
2.65
0.00
0.55
1.25

494
Low
Li
1000
229.9
66.75
28.42
2.67
0.00
0.52
2.21

495
Low
K
1000
238.5
66.40
28.78
2.66
0.00
0.52
1.12

496
Low
K
1000
238.5
66.31
28.88
2.66
0.00
0.50
0.60

497
Low
Li
1000
229.9
66.85
28.36
2.67
0.00
0.49
2.32

498
Low
Sr
1000
229.9
66.84
28.40
2.67
0.00
0.43
2.29

499
Low
La
1000
228.3
67.64
27.84
2.43
0.00
0.42
6.00

500
Low
Sr
1000
229.8
66.78
28.50
2.67
0.00
0.41
1.82

501
Low
La
1000
228.2
66.32
29.04
2.59
0.00
0.41
0.39

502
Low
Ba
1000
229.9
66.94
28.53
2.48
0.00
0.40
2.64

503
Low
Na
1000
228.8
66.72
28.62
2.64
0.00
0.38
1.16

504
Low
Ba
1000
230.2
67.09
28.41
2.48
0.00
0.38
3.15

505
Low
Rb
1000
238.5
66.92
28.38
2.68
0.00
0.37
2.39

506
Low
Rb
1000
238.7
66.89
28.42
2.68
0.00
0.36
2.44

507
Low
Na
1000
228.3
66.71
28.64
2.65
0.00
0.36
1.50

508
Low
K
1000
228.6
66.62
28.75
2.65
0.00
0.34
1.09

509
Low
K
1000
228.3
66.80
28.58
2.65
0.00
0.32
1.85

510
Low
Rb
1000
228.5
66.86
28.57
2.68
0.00
0.25
1.16

511
Low
Rb
1000
228.3
66.99
28.45
2.68
0.00
0.24
1.74

512
Low
Ga
5000
200.1
66.98
28.47
2.68
0.00
0.23
2.05

513
Low
Ga
5000
199.6
67.01
28.44
2.68
0.00
0.22
2.26

514
Low
Li
1000
200.1
67.02
28.53
2.67
0.00
0.14
1.17

515
Low
Li
1000
200.3
67.09
28.47
2.67
0.00
0.13
1.33

516
Low
Sr
1000
200.0
66.96
28.61
2.67
0.00
0.12
1.03

517
Low
La
1000
198.4
67.38
28.36
2.48
0.00
0.12
3.61

518
Low
Ba
1000
199.8
67.11
28.63
2.49
0.00
0.12
2.11

519
Low
Na
1000
198.6
66.96
28.64
2.64
0.00
0.11
1.33

520
Low
Sr
1000
200.1
67.01
28.56
2.68
0.00
0.11
1.16

521
Low
La
1000
198.6
67.32
28.42
2.50
0.00
0.11
3.11

522
Low
Ba
1000
200.1
67.18
28.57
2.49
0.00
0.10
2.96

523
Low
Na
1000
198.9
66.96
28.66
2.65
0.00
0.10
0.95

524
Low
K
1000
198.6
66.92
28.70
2.65
0.00
0.10
1.00

525
Low
Ga
5000
180.3
66.87
28.70
2.69
0.00
0.10
0.93

526
Low
Ga
5000
179.6
67.09
28.49
2.68
0.00
0.09
1.80

527
Low
K
1000
198.6
67.09
28.52
2.66
0.00
0.09
1.52

528
Low
Rb
1000
198.6
66.98
28.63
2.68
0.00
0.08
0.65

529
Low
Li
1000
180.0
67.15
28.47
2.67
0.00
0.07
1.34

530
Low
Rb
1000
198.7
67.04
28.57
2.69
0.00
0.07
0.87

531
Low
Ba
1000
180.0
67.30
28.49
2.50
0.00
0.06
2.41

532
Low
Sr
1000
180.0
67.03
28.59
2.68
0.00
0.06
0.91

533
Low
La
1000
178.5
68.16
27.68
2.43
0.00
0.06
6.11

534
Low
Li
1000
180.0
67.08
28.56
2.67
0.00
0.06
0.75

535
Low
Na
1000
178.8
67.12
28.54
2.65
0.00
0.06
1.42

536
Low
Sr
1000
180.0
67.09
28.53
2.69
0.00
0.05
1.15

537
Low
La
1000
178.5
66.71
29.03
2.57
0.00
0.05
0.08

538
Low
Ba
1000
179.9
67.19
28.62
2.50
0.00
0.05
2.04

539
Low
Na
1000
178.8
67.00
28.67
2.65
0.00
0.05
0.65

540
Low
K
1000
179.2
67.16
28.50
2.66
0.00
0.05
1.29

541
Low
K
1000
178.9
67.14
28.53
2.66
0.00
0.04
1.32

542
Low
Rb
1000
179.2
66.99
28.65
2.69
0.00
0.04
0.29

543
Low
Rb
1000
179.2
67.07
28.58
2.69
0.00
0.03
0.70

544
High
Rb
1000
239.9
72.15
4.79
19.15
0.00
2.19
12.39

545
High
Rb
1000
240.0
71.98
5.03
19.13
0.00
2.16
10.99

546
High
Rb
1000
239.9
72.08
5.08
19.02
0.00
2.12
11.32

547
High
Rb
1000
228.3
72.54
5.30
19.11
0.00
1.37
8.64

548
High
Rb
1000
228.3
72.66
5.29
19.03
0.00
1.34
9.20

549
High
Rb
1000
228.3
72.53
5.38
19.12
0.00
1.29
8.17

550
High
Sr
1000
238.3
71.99
6.99
18.57
0.00
0.78
4.54

551
High
Sr
1000
238.4
72.06
7.12
18.37
0.00
0.77
4.95

552
High
Ba
1000
239.9
72.11
6.81
18.68
0.00
0.72
4.76

553
High
Ba
1000
239.9
72.02
6.82
18.78
0.00
0.71
4.21

554
High
Ba
1000
240.0
72.15
6.81
18.67
0.00
0.70
4.66

555
High
Na
1000
238.5
71.76
6.86
19.05
0.00
0.66
2.89

556
High
Na
1000
238.3
71.73
6.84
19.10
0.00
0.66
2.67

557
High
Li
1000
238.4
71.96
7.23
18.48
0.00
0.65
4.30

558
High
Li
1000
238.3
72.04
7.22
18.42
0.00
0.64
4.53

559
High
Ga
5000
238.4
71.95
6.98
18.75
0.00
0.64
4.11

560
High
Ga
5000
238.4
71.86
7.17
18.66
0.00
0.63
3.81

561
High
K
1000
238.7
72.29
6.78
18.70
0.00
0.56
4.24

562
High
Sr
1000
228.5
72.06
6.98
18.74
0.00
0.55
3.20

563
High
K
1000
238.4
72.13
6.88
18.77
0.00
0.55
3.64

564
High
Sr
1000
228.5
72.10
7.00
18.69
0.00
0.55
3.53

565
High
Ba
1000
229.9
72.31
6.77
18.74
0.00
0.52
4.15

566
High
La
1000
240.0
71.98
6.93
18.90
0.00
0.51
2.82

567
High
Ba
1000
229.7
72.18
6.82
18.83
0.00
0.51
3.45

568
High
Ba
1000
230.1
72.26
6.71
18.86
0.00
0.50
3.71

569
High
La
1000
239.7
72.05
6.81
18.97
0.00
0.50
2.98

570
High
La
1000
240.0
72.02
6.90
18.92
0.00
0.49
2.76

571
High
Na
1000
228.5
72.01
6.72
19.14
0.00
0.48
2.64

572
High
Ga
5000
228.2
71.91
7.16
18.80
0.00
0.47
2.54

573
High
Na
1000
228.5
72.00
6.74
19.12
0.00
0.47
2.74

574
High
Li
1000
228.3
71.86
7.15
18.86
0.00
0.47
1.96

575
High
Li
1000
228.5
71.87
7.18
18.83
0.00
0.46
1.86

576
High
Ga
5000
228.3
71.81
7.09
18.97
0.00
0.46
2.12

577
High
K
1000
228.2
72.19
6.71
19.04
0.00
0.40
3.14

578
High
K
1000
228.2
72.27
6.67
19.01
0.00
0.39
2.97

579
High
Rb
1000
199.6
73.36
5.48
19.15
0.00
0.37
5.58

580
High
Rb
1000
199.6
73.22
5.64
19.15
0.00
0.36
4.98

581
High
Rb
1000
199.6
73.29
5.59
19.14
0.00
0.35
5.09

582
High
La
1000
228.3
72.16
6.79
19.06
0.00
0.33
2.21

583
High
La
1000
228.5
72.12
6.80
19.09
0.00
0.33
1.88

584
High
La
1000
228.3
72.07
6.81
19.13
0.00
0.33
1.96

585
High
Sr
1000
198.3
72.28
6.70
19.19
0.00
0.19
1.30

586
High
Sr
1000
198.6
72.20
6.91
19.07
0.00
0.18
0.82

587
High
Ba
1000
200.0
72.45
6.58
19.17
0.00
0.17
1.78

588
High
Ba
1000
200.1
72.56
6.52
19.11
0.00
0.17
2.28

589
High
Ga
5000
198.6
72.06
6.91
19.21
0.00
0.17
1.01

590
High
Ba
1000
200.1
72.57
6.65
18.97
0.00
0.16
2.48

591
High
Ga
5000
198.4
72.02
6.90
19.27
0.00
0.16
0.68

592
High
Na
1000
198.4
71.96
6.59
19.64
0.00
0.16
−0.12

593
High
Li
1000
198.6
72.09
6.86
19.24
0.00
0.16
0.66

594
High
Li
1000
198.7
72.22
6.93
19.05
0.00
0.16
1.20

595
High
Na
1000
198.7
71.92
6.57
19.72
0.00
0.15
−0.61

596
High
Rb
1000
179.9
73.38
5.61
19.23
0.00
0.15
4.23

597
High
Rb
1000
180.2
73.10
5.69
19.45
0.00
0.14
2.52

598
High
Rb
1000
180.0
73.25
5.64
19.35
0.00
0.14
3.47

599
High
K
1000
198.9
72.31
6.68
19.24
0.00
0.13
1.18

600
High
K
1000
198.7
72.28
6.62
19.34
0.00
0.13
0.94

601
High
La
1000
199.8
72.32
6.73
19.19
0.00
0.11
1.22

602
High
La
1000
199.6
72.20
6.77
19.28
0.00
0.11
0.67

603
High
La
1000
199.6
72.32
6.77
19.16
0.00
0.11
1.11

604
High
Sr
1000
179.2
72.72
6.25
19.30
0.00
0.09
2.62

605
High
Ba
1000
180.0
72.58
6.60
19.10
0.00
0.08
1.68

606
High
Sr
1000
179.2
72.49
6.62
19.17
0.00
0.08
1.19

607
High
Ga
5000
178.3
72.24
6.83
19.21
0.00
0.08
0.81

608
High
Ga
5000
178.5
72.12
6.83
19.33
0.00
0.07
0.46

609
High
Ba
1000
180.0
72.49
6.61
19.19
0.00
0.07
1.16

610
High
Na
1000
179.4
72.12
6.55
19.62
0.00
0.07
−0.43

611
High
Ba
1000
180.0
72.48
6.55
19.27
0.00
0.07
1.02

612
High
Li
1000
179.1
72.36
6.77
19.16
0.00
0.07
1.21

613
High
Li
1000
179.1
72.20
6.87
19.22
0.00
0.07
0.24

614
High
Na
1000
179.1
72.12
6.58
19.59
0.00
0.07
−0.23

615
High
K
1000
178.8
72.46
6.64
19.21
0.00
0.06
0.95

616
High
La
1000
180.2
72.29
6.61
19.41
0.00
0.05
0.42

617
High
K
1000
179.2
72.47
6.61
19.23
0.00
0.05
1.20

618
High
La
1000
179.7
72.36
6.59
19.36
0.00
0.05
0.87

619
High
La
1000
180.0
72.16
6.72
19.44
0.00
0.05
−0.43

TABLE 8

Activity of Promoted Ruthenium on Copper Zinc Oxide Catalyst A

Comp.

H₂
CO
CO₂
DME
MeOH
CO & CO₂

Ex. No.
CO₂
Support
Ru wt %
Prom
Prom ppm
Temp (° C.)
wt %
wt %
wt %
% wt
wt %
% conv

620
Low
CuZnO Ref A
1
Mg
1000
299.8
65.45
28.64
2.69
0.01
1.53
3.68

621
Low
CuZnO Ref A
1
Na
1000
299.8
65.69
28.41
2.71
0.00
1.51
4.34

622
Low
CuZnO Ref A
1
Ca
1000
299.7
65.75
28.87
2.65
0.00
1.05
2.35

623
Low
CuZnO Ref A
1
K
1000
299.1
65.81
29.23
2.81
0.00
0.51
−1.11

624
Low
CuZnO Ref A
1
Mn
1000
299.0
65.23
28.37
2.77
0.01
1.93
4.72

625
Low
CuZnO Ref A
1
Ba
1000
297.7
65.33
28.86
2.82
0.01
1.33
1.10

626
Low
CuZnO Ref A
1
La
1000
297.6
65.84
29.32
2.66
0.00
0.53
0.12

627
Low
CuZnO Ref A
1
Mg
1000
240.1
66.87
28.65
2.64
0.00
0.19
1.34

628
Low
CuZnO Ref A
1
Ba
1000
240.1
66.61
28.77
2.82
0.00
0.17
−0.18

629
Low
CuZnO Ref A
1
Mg
1000
240.1
66.91
28.58
2.72
0.00
0.15
1.13

630
Low
CuZnO Ref A
1
La
1000
240.0
64.94
28.46
2.71
0.00
2.18
5.55

631
Low
CuZnO Ref A
1
Ba
1000
240.0
66.49
28.88
2.81
0.00
0.19
−0.70

632
Low
CuZnO Ref A
1
Na
1000
240.0
66.84
28.71
2.66
0.00
0.15
1.01

633
Low
CuZnO Ref A
1
Ca
1000
240.0
66.75
28.85
2.67
0.00
0.09
0.49

634
Low
CuZnO Ref A
1
La
1000
239.9
65.08
28.29
2.70
0.00
2.23
5.87

635
Low
CuZnO Ref A
1
Ca
1000
239.9
66.76
28.84
2.66
0.00
0.10
0.53

636
Low
CuZnO Ref A
1
Na
1000
239.7
66.85
28.59
2.64
0.00
0.26
1.71

637
Low
CuZnO Ref A
1
K
1000
239.4
66.62
28.87
2.83
0.00
0.05
−0.57

638
Low
CuZnO Ref A
1
Mn
1000
239.1
66.98
28.46
2.65
0.00
0.27
2.21

639
Low
CuZnO Ref A
1
K
1000
239.1
66.30
29.06
2.87
0.00
0.14
−1.01

640
Low
CuZnO Ref A
1
Mn
1000
239.0
66.95
28.55
2.66
0.00
0.19
1.57

641
Low
CuZnO Ref A
1
Mg
1000
230.1
66.75
28.60
2.62
0.00
0.39
1.72

642
Low
CuZnO Ref A
1
Na
1000
230.1
66.65
28.70
2.63
0.00
0.37
1.31

643
Low
CuZnO Ref A
1
La
1000
229.9
65.57
28.56
2.67
0.00
1.51
4.24

644
Low
CuZnO Ref A
1
La
1000
229.9
65.50
28.72
2.66
0.00
1.44
3.45

645
Low
CuZnO Ref A
1
Na
1000
229.9
66.75
28.71
2.63
0.00
0.26
1.43

646
Low
CuZnO Ref A
1
Mg
1000
229.9
66.78
28.73
2.62
0.00
0.23
1.05

647
Low
CuZnO Ref A
1
Ca
1000
229.9
66.65
28.95
2.66
0.00
0.11
−0.03

648
Low
CuZnO Ref A
1
Ba
1000
229.8
66.60
28.80
2.81
0.00
0.16
−0.33

649
Low
CuZnO Ref A
1
Ca
1000
229.8
66.88
28.73
2.67
0.00
0.07
1.21

650
Low
CuZnO Ref A
1
Ba
1000
229.7
66.47
28.86
2.79
0.00
0.25
−0.62

651
Low
CuZnO Ref A
1
K
1000
229.5
66.63
28.86
2.83
0.00
0.05
−0.59

652
Low
CuZnO Ref A
1
Mn
1000
229.4
66.70
28.60
2.63
0.00
0.43
1.75

653
Low
CuZnO Ref A
1
Mn
1000
229.4
66.79
28.66
2.63
0.00
0.28
1.44

654
Low
CuZnO Ref A
1
K
1000
229.2
66.55
28.94
2.83
0.00
0.05
−1.01

655
Low
CuZnO Ref A
1
Na
1000
200.1
66.96
28.64
2.64
0.00
0.12
1.15

656
Low
CuZnO Ref A
1
La
1000
200.0
66.35
29.02
2.62
0.00
0.36
0.79

657
Low
CuZnO Ref A
1
La
1000
200.0
66.29
29.09
2.62
0.00
0.35
0.34

658
Low
CuZnO Ref A
1
Mg
1000
200.0
66.98
28.49
2.69
0.00
0.20
1.67

659
Low
CuZnO Ref A
1
Ba
1000
200.0
66.50
28.94
2.78
0.00
0.14
−0.97

660
Low
CuZnO Ref A
1
Mg
1000
200.0
67.00
28.60
2.64
0.00
0.12
1.33

661
Low
CuZnO Ref A
1
Ca
1000
200.0
66.86
28.74
2.65
0.00
0.11
0.94

662
Low
CuZnO Ref A
1
Ca
1000
200.0
66.83
28.81
2.67
0.00
0.04
0.50

663
Low
CuZnO Ref A
1
Na
1000
199.8
66.90
28.66
2.62
0.00
0.18
1.40

664
Low
CuZnO Ref A
1
Ba
1000
199.8
66.58
28.90
2.80
0.00
0.09
−1.07

665
Low
CuZnO Ref A
1
Mn
1000
199.3
66.96
28.63
2.64
0.00
0.14
1.01

666
Low
CuZnO Ref A
1
Mn
1000
199.2
66.97
28.56
2.63
0.00
0.20
1.76

667
Low
CuZnO Ref A
1
K
1000
199.2
66.68
28.84
2.83
0.00
0.03
−0.61

668
Low
CuZnO Ref A
1
K
1000
199.2
66.72
28.78
2.84
0.00
0.02
−0.33

669
Low
CuZnO Ref A
1
Ba
1000
180.3
66.74
28.74
2.79
0.00
0.10
−0.08

670
Low
CuZnO Ref A
1
Mg
1000
180.2
67.09
28.50
2.62
0.00
0.15
1.96

671
Low
CuZnO Ref A
1
Na
1000
180.2
66.96
28.67
2.64
0.00
0.08
0.90

672
Low
CuZnO Ref A
1
La
1000
180.0
66.47
29.09
2.64
0.00
0.15
−0.18

673
Low
CuZnO Ref A
1
Ca
1000
180.0
66.94
28.67
2.64
0.00
0.11
1.34

674
Low
CuZnO Ref A
1
Mg
1000
180.0
67.01
28.62
2.64
0.00
0.10
1.19

675
Low
CuZnO Ref A
1
Ca
1000
180.0
66.93
28.70
2.66
0.00
0.06
1.16

676
Low
CuZnO Ref A
1
La
1000
179.9
66.42
29.15
2.64
0.00
0.16
−0.47

677
Low
CuZnO Ref A
1
Na
1000
179.9
67.14
28.47
2.62
0.00
0.13
1.45

678
Low
CuZnO Ref A
1
Ba
1000
179.7
66.72
28.77
2.80
0.00
0.07
−0.51

679
Low
CuZnO Ref A
1
K
1000
179.7
66.67
28.85
2.82
0.00
0.03
−0.58

680
Low
CuZnO Ref A
1
Mn
1000
179.4
67.12
28.50
2.65
0.00
0.09
1.69

681
Low
CuZnO Ref A
1
K
1000
179.4
66.64
28.89
2.83
0.00
0.02
−0.80

682
Low
CuZnO Ref A
1
Mn
1000
179.2
67.10
28.50
2.63
0.00
0.13
1.63

683
Low
CuZnO Ref A
1
Mn
5000
299.8
65.45
28.74
2.71
0.01
1.42
2.92

684
Low
CuZnO Ref A
1
Mg
5000
299.0
65.30
28.55
2.71
0.01
1.74
4.13

685
Low
CuZnO Ref A
1
K
5000
298.9
66.11
29.00
2.62
0.00
0.61
1.02

686
Low
CuZnO Ref A
1
Na
5000
297.9
66.26
28.74
2.63
0.00
0.70
2.09

687
Low
CuZnO Ref A
1
La
5000
297.7
65.38
28.74
2.66
0.01
1.53
3.03

688
Low
CuZnO Ref A
1
Mn
5000
240.1
66.75
28.79
2.66
0.00
0.15
0.63

689
Low
CuZnO Ref A
1
Ca
5000
239.9
65.60
28.15
2.69
0.00
1.87
5.19

690
Low
CuZnO Ref A
1
Ca
5000
239.9
65.48
28.32
2.70
0.00
1.81
5.02

691
Low
CuZnO Ref A
1
La
5000
239.9
66.75
28.78
2.65
0.00
0.18
0.80

692
Low
CuZnO Ref A
1
Mn
5000
239.9
66.78
28.79
2.66
0.00
0.13
0.63

693
Low
CuZnO Ref A
1
La
5000
239.7
66.77
28.74
2.65
0.00
0.20
1.02

694
Low
CuZnO Ref A
1
Na
5000
239.7
66.90
28.72
2.66
0.00
0.07
0.95

695
Low
CuZnO Ref A
1
Na
5000
239.7
66.79
28.85
2.67
0.00
0.05
0.46

696
Low
CuZnO Ref A
1
K
5000
239.3
66.77
28.88
2.67
0.00
0.05
0.16

697
Low
CuZnO Ref A
1
Mg
5000
239.1
66.75
28.77
2.64
0.00
0.21
0.96

698
Low
CuZnO Ref A
1
Mg
5000
239.0
66.74
28.80
2.64
0.00
0.18
0.59

699
Low
CuZnO Ref A
1
K
5000
239.0
66.81
28.84
2.67
0.00
0.04
0.41

700
Low
CuZnO Ref A
1
La
5000
230.2
66.76
28.75
2.63
0.00
0.21
0.99

701
Low
CuZnO Ref A
1
Na
5000
230.1
66.82
28.80
2.66
0.00
0.08
0.50

702
Low
CuZnO Ref A
1
Ca
5000
229.9
65.90
28.59
2.65
0.00
1.19
2.98

703
Low
CuZnO Ref A
1
Na
5000
229.9
66.77
28.88
2.66
0.00
0.05
0.18

704
Low
CuZnO Ref A
1
Ca
5000
229.8
65.76
28.64
2.66
0.00
1.27
3.26

705
Low
CuZnO Ref A
1
La
5000
229.8
66.63
28.78
2.61
0.00
0.33
1.12

706
Low
CuZnO Ref A
1
Mn
5000
229.8
66.77
28.76
2.64
0.00
0.18
1.02

707
Low
CuZnO Ref A
1
Mn
5000
229.7
66.59
28.82
2.63
0.00
0.32
0.90

708
Low
CuZnO Ref A
1
Mg
5000
229.4
66.68
28.76
2.61
0.00
0.30
1.32

709
Low
CuZnO Ref A
1
K
5000
229.4
66.81
28.83
2.67
0.00
0.05
0.55

710
Low
CuZnO Ref A
1
K
5000
229.4
66.80
28.86
2.68
0.00
0.03
0.26

711
Low
CuZnO Ref A
1
Mg
5000
229.2
66.80
28.73
2.63
0.00
0.20
1.02

712
Low
CuZnO Ref A
1
Mn
5000
200.1
66.71
28.83
2.62
0.00
0.20
0.73

713
Low
CuZnO Ref A
1
La
5000
200.1
66.86
28.75
2.64
0.00
0.11
0.49

714
Low
CuZnO Ref A
1
Ca
5000
200.0
66.54
28.89
2.63
0.00
0.30
0.77

715
Low
CuZnO Ref A
1
Mn
5000
200.0
66.80
28.80
2.64
0.00
0.12
0.57

716
Low
CuZnO Ref A
1
Na
5000
200.0
67.05
28.60
2.68
0.00
0.03
1.09

717
Low
CuZnO Ref A
1
La
5000
199.8
66.73
28.83
2.62
0.00
0.18
0.53

718
Low
CuZnO Ref A
1
Ca
5000
199.6
66.63
28.79
2.63
0.00
0.31
1.12

719
Low
CuZnO Ref A
1
Na
5000
199.6
66.98
28.64
2.66
0.00
0.07
1.16

720
Low
CuZnO Ref A
1
Mg
5000
199.3
66.82
28.76
2.61
0.00
0.17
0.64

721
Low
CuZnO Ref A
1
Mg
5000
199.3
66.85
28.78
2.63
0.00
0.11
0.50

722
Low
CuZnO Ref A
1
K
5000
199.3
66.81
28.86
2.68
0.00
0.02
0.12

723
Low
CuZnO Ref A
1
K
5000
199.3
66.87
28.80
2.68
0.00
0.01
0.49

724
Low
CuZnO Ref A
1
Mn
5000
180.2
66.98
28.60
2.62
0.00
0.17
1.37

725
Low
CuZnO Ref A
1
Ca
5000
180.2
66.74
28.83
2.66
0.00
0.13
0.67

726
Low
CuZnO Ref A
1
Na
5000
180.2
67.00
28.66
2.67
0.00
0.03
1.20

727
Low
CuZnO Ref A
1
La
5000
180.0
66.98
28.61
2.64
0.00
0.12
1.60

728
Low
CuZnO Ref A
1
Na
5000
180.0
67.05
28.58
2.67
0.00
0.05
1.47

729
Low
CuZnO Ref A
1
Ca
5000
179.9
66.66
28.92
2.65
0.00
0.13
0.25

730
Low
CuZnO Ref A
1
Mn
5000
179.9
66.90
28.72
2.64
0.00
0.10
0.92

731
Low
CuZnO Ref A
1
La
5000
179.7
67.05
28.57
2.65
0.00
0.09
1.36

732
Low
CuZnO Ref A
1
Mg
5000
179.6
67.00
28.62
2.63
0.00
0.11
1.19

733
Low
CuZnO Ref A
1
Mg
5000
179.6
66.98
28.66
2.64
0.00
0.08
1.22

734
Low
CuZnO Ref A
1
K
5000
179.6
66.90
28.77
2.68
0.00
0.01
0.47

735
Low
CuZnO Ref A
1
K
5000
179.6
66.89
28.79
2.69
0.00
0.00
0.35

736
Low
CuZnO Ref A
5
Mg
1000
300.0
66.17
29.23
2.75
0.00
0.19
−0.35

737
Low
CuZnO Ref A
5
Ca
1000
299.8
66.35
29.07
2.72
0.00
0.21
0.37

738
Low
CuZnO Ref A
5
Na
1000
299.8
66.85
28.83
2.69
0.00
0.00
0.09

739
Low
CuZnO Ref A
5
Mn
1000
298.9
66.07
29.29
2.82
0.00
0.16
−0.29

740
Low
CuZnO Ref A
5
La
1000
297.7
66.13
29.41
2.65
0.00
0.17
−0.89

741
Low
CuZnO Ref A
5
Ba
1000
297.7
66.04
29.45
2.70
0.00
0.17
−1.25

742
Low
CuZnO Ref A
5
K
1000
297.7
66.03
29.51
2.64
0.00
0.17
−1.21

743
Low
CuZnO Ref A
5
Ba
1000
240.3
66.61
29.05
2.70
0.00
0.02
−0.48

744
Low
CuZnO Ref A
5
Ca
1000
240.1
66.98
28.67
2.69
0.00
0.01
0.92

745
Low
CuZnO Ref A
5
Mg
1000
240.1
66.79
28.87
2.68
0.00
0.01
0.36

746
Low
CuZnO Ref A
5
Ca
1000
240.1
66.98
28.67
2.69
0.00
0.01
0.92

747
Low
CuZnO Ref A
5
Mg
1000
240.0
66.80
28.87
2.68
0.00
0.02
0.27

748
Low
CuZnO Ref A
5
Ba
1000
240.0
66.66
28.99
2.70
0.00
0.01
−0.34

749
Low
CuZnO Ref A
5
Ca
1000
239.9
66.88
28.78
2.69
0.00
0.02
0.39

750
Low
CuZnO Ref A
5
La
1000
239.9
66.61
29.07
2.67
0.00
0.01
−0.26

751
Low
CuZnO Ref A
5
Na
1000
239.7
67.01
28.66
2.70
0.00
0.00
0.93

752
Low
CuZnO Ref A
5
Na
1000
239.7
66.86
28.81
2.69
0.00
0.00
0.08

753
Low
CuZnO Ref A
5
K
1000
239.6
66.63
29.03
2.69
0.00
0.01
0.17

754
Low
CuZnO Ref A
5
La
1000
239.4
66.60
29.07
2.67
0.00
0.02
−0.23

755
Low
CuZnO Ref A
5
K
1000
239.4
66.57
29.09
2.68
0.00
0.01
−0.30

756
Low
CuZnO Ref A
5
Mn
1000
239.3
66.78
28.86
2.70
0.00
0.02
0.23

757
Low
CuZnO Ref A
5
Mn
1000
239.1
66.81
28.83
2.71
0.00
0.02
0.31

758
Low
CuZnO Ref A
5
Ca
1000
230.1
66.94
28.72
2.69
0.00
0.01
0.63

759
Low
CuZnO Ref A
5
Mg
1000
229.9
66.89
28.76
2.69
0.00
0.01
0.61

760
Low
CuZnO Ref A
5
Mg
1000
229.9
66.87
28.80
2.69
0.00
0.01
0.49

761
Low
CuZnO Ref A
5
Na
1000
229.9
66.92
28.76
2.69
0.00
0.00
0.20

762
Low
CuZnO Ref A
5
Ba
1000
229.8
66.72
28.94
2.70
0.00
0.01
−0.15

763
Low
CuZnO Ref A
5
Ca
1000
229.8
66.97
28.69
2.69
0.00
0.01
0.83

764
Low
CuZnO Ref A
5
Ba
1000
229.8
66.68
28.98
2.70
0.00
0.01
−0.20

765
Low
CuZnO Ref A
5
Na
1000
229.7
67.00
28.66
2.70
0.00
0.00
0.95

766
Low
CuZnO Ref A
5
Mn
1000
229.5
66.92
28.72
2.71
0.00
0.01
0.84

767
Low
CuZnO Ref A
5
Mn
1000
229.2
66.84
28.81
2.70
0.00
0.01
0.41

768
Low
CuZnO Ref A
5
K
1000
228.3
66.60
29.06
2.69
0.00
0.01
−0.21

769
Low
CuZnO Ref A
5
K
1000
228.3
66.61
29.05
2.68
0.00
0.01
−0.22

770
Low
CuZnO Ref A
5
La
1000
228.3
66.62
29.06
2.67
0.00
0.01
−0.29

771
Low
CuZnO Ref A
5
La
1000
228.2
66.67
29.00
2.68
0.00
0.01
0.09

772
Low
CuZnO Ref A
5
Ba
1000
200.3
66.72
28.95
2.70
0.00
0.00
−0.47

773
Low
CuZnO Ref A
5
Mg
1000
200.1
66.89
28.78
2.69
0.00
0.00
0.44

774
Low
CuZnO Ref A
5
Na
1000
200.1
66.90
28.76
2.71
0.00
0.00
0.18

775
Low
CuZnO Ref A
5
Na
1000
200.1
66.89
28.77
2.71
0.00
0.00
0.10

776
Low
CuZnO Ref A
5
Ca
1000
200.0
67.06
28.61
2.70
0.00
0.00
1.24

777
Low
CuZnO Ref A
5
Mg
1000
200.0
66.94
28.73
2.69
0.00
0.00
0.64

778
Low
CuZnO Ref A
5
Ca
1000
200.0
66.91
28.76
2.69
0.00
0.00
0.40

779
Low
CuZnO Ref A
5
La
1000
200.0
66.59
29.10
2.68
0.00
0.00
−0.61

780
Low
CuZnO Ref A
5
Ba
1000
199.8
66.83
28.83
2.70
0.00
0.00
0.09

781
Low
CuZnO Ref A
5
K
1000
199.8
66.60
29.07
2.69
0.00
0.00
−0.26

782
Low
CuZnO Ref A
5
K
1000
199.8
66.61
29.06
2.69
0.00
0.00
−0.29

783
Low
CuZnO Ref A
5
La
1000
199.8
66.74
28.94
2.68
0.00
0.00
−0.35

784
Low
CuZnO Ref A
5
Mn
1000
199.5
66.87
28.79
2.70
0.00
0.00
0.25

785
Low
CuZnO Ref A
5
Mn
1000
199.3
66.78
28.89
2.70
0.00
0.00
−0.24

786
Low
CuZnO Ref A
5
Mg
1000
180.2
67.15
28.52
2.69
0.00
0.00
1.54

787
Low
CuZnO Ref A
5
Na
1000
180.2
67.00
28.65
2.72
0.00
0.00
0.55

788
Low
CuZnO Ref A
5
Ba
1000
180.2
66.87
28.79
2.70
0.00
0.00
0.36

789
Low
CuZnO Ref A
5
K
1000
180.2
66.73
28.93
2.70
0.00
0.00
0.34

790
Low
CuZnO Ref A
5
Mg
1000
180.0
67.12
28.54
2.70
0.00
0.00
1.39

791
Low
CuZnO Ref A
5
Ca
1000
180.0
67.05
28.63
2.69
0.00
0.00
0.81

792
Low
CuZnO Ref A
5
Na
1000
179.9
67.12
28.53
2.72
0.00
0.00
1.06

793
Low
CuZnO Ref A
5
Ca
1000
179.9
67.02
28.65
2.69
0.00
0.00
0.83

794
Low
CuZnO Ref A
5
Ba
1000
179.9
66.79
28.87
2.70
0.00
0.00
0.12

795
Low
CuZnO Ref A
5
La
1000
179.9
66.77
28.91
2.68
0.00
0.00
0.08

796
Low
CuZnO Ref A
5
K
1000
179.9
66.63
29.04
2.69
0.00
0.00
−0.23

797
Low
CuZnO Ref A
5
La
1000
179.7
66.69
28.99
2.68
0.00
0.00
−0.17

798
Low
CuZnO Ref A
5
Mn
1000
179.6
67.02
28.64
2.71
0.00
0.00
0.93

799
Low
CuZnO Ref A
5
Mn
1000
179.4
66.93
28.72
2.71
0.00
0.00
0.52

800
Low
CuZnO Ref A
5
K
5000
300.0
66.37
29.13
2.70
0.00
0.16
−0.15

801
Low
CuZnO Ref A
5
Na
5000
298.0
66.51
29.03
2.69
0.00
0.13
−0.24

802
Low
CuZnO Ref A
5
Mg
5000
297.9
66.26
29.20
2.73
0.00
0.16
−0.57

803
Low
CuZnO Ref A
5
La
5000
297.7
66.19
29.39
2.62
0.00
0.15
−0.68

804
Low
CuZnO Ref A
5
Mn
5000
297.7
66.16
29.32
2.71
0.00
0.15
−0.44

805
Low
CuZnO Ref A
5
Ca
5000
297.7
66.72
28.95
2.58
0.00
0.10
1.08

806
Low
CuZnO Ref A
5
K
5000
240.0
66.87
28.79
2.69
0.00
0.01
0.53

807
Low
CuZnO Ref A
5
K
5000
240.0
66.82
28.84
2.69
0.00
0.01
0.39

808
Low
CuZnO Ref A
5
K
5000
240.0
66.87
28.79
2.69
0.00
0.01
0.53

809
Low
CuZnO Ref A
5
K
5000
240.0
66.82
28.84
2.69
0.00
0.01
0.39

810
Low
CuZnO Ref A
5
Mg
5000
239.9
66.94
28.73
2.68
0.00
0.01
0.61

811
Low
CuZnO Ref A
5
Mn
5000
239.9
66.80
28.86
2.69
0.00
0.01
0.36

812
Low
CuZnO Ref A
5
Mn
5000
239.9
66.77
28.89
2.69
0.00
0.01
0.25

813
Low
CuZnO Ref A
5
Na
5000
239.9
67.02
28.65
2.68
0.00
0.01
0.63

814
Low
CuZnO Ref A
5
Na
5000
239.9
66.98
28.69
2.69
0.00
0.01
0.41

815
Low
CuZnO Ref A
5
Mg
5000
239.9
66.94
28.73
2.68
0.00
0.01
0.61

816
Low
CuZnO Ref A
5
Na
5000
239.9
67.02
28.65
2.68
0.00
0.01
0.63

817
Low
CuZnO Ref A
5
Mn
5000
239.9
66.80
28.86
2.69
0.00
0.01
0.36

818
Low
CuZnO Ref A
5
Mn
5000
239.9
66.77
28.89
2.69
0.00
0.01
0.25

819
Low
CuZnO Ref A
5
Na
5000
239.9
66.98
28.69
2.69
0.00
0.01
0.41

820
Low
CuZnO Ref A
5
Ca
5000
239.9
67.25
28.55
2.56
0.00
0.00
1.93

821
Low
CuZnO Ref A
5
Ca
5000
239.9
67.25
28.55
2.56
0.00
0.00
1.93

822
Low
CuZnO Ref A
5
Mg
5000
239.7
66.85
28.82
2.68
0.00
0.02
0.17

823
Low
CuZnO Ref A
5
Mg
5000
239.7
66.85
28.82
2.68
0.00
0.02
0.17

824
Low
CuZnO Ref A
5
La
5000
239.7
66.58
29.10
2.66
0.00
0.01
−0.23

825
Low
CuZnO Ref A
5
La
5000
239.7
66.58
29.10
2.66
0.00
0.01
−0.23

826
Low
CuZnO Ref A
5
La
5000
239.3
66.67
29.01
2.67
0.00
0.01
0.21

827
Low
CuZnO Ref A
5
La
5000
239.3
66.67
29.01
2.67
0.00
0.01
0.21

828
Low
CuZnO Ref A
5
Ca
5000
239.3
67.33
28.46
2.56
0.00
0.00
2.40

829
Low
CuZnO Ref A
5
Ca
5000
239.3
67.33
28.46
2.56
0.00
0.00
2.40

830
Low
CuZnO Ref A
5
Mg
5000
230.1
66.98
28.69
2.68
0.00
0.01
0.68

831
Low
CuZnO Ref A
5
Mn
5000
230.1
66.74
28.93
2.68
0.00
0.01
0.02

832
Low
CuZnO Ref A
5
Na
5000
230.1
67.05
28.62
2.69
0.00
0.00
0.88

833
Low
CuZnO Ref A
5
Mg
5000
229.9
66.98
28.69
2.68
0.00
0.01
0.53

834
Low
CuZnO Ref A
5
Na
5000
229.9
67.12
28.55
2.69
0.00
0.01
0.96

835
Low
CuZnO Ref A
5
Mn
5000
229.9
66.87
28.79
2.69
0.00
0.01
0.67

836
Low
CuZnO Ref A
5
K
5000
229.8
66.86
28.81
2.69
0.00
0.00
0.26

837
Low
CuZnO Ref A
5
K
5000
229.8
66.84
28.84
2.69
0.00
0.00
0.15

838
Low
CuZnO Ref A
5
La
5000
228.3
66.69
28.99
2.67
0.00
0.01
−0.16

839
Low
CuZnO Ref A
5
La
5000
228.2
66.64
29.04
2.67
0.00
0.01
−0.14

840
Low
CuZnO Ref A
5
Ca
5000
228.2
67.55
28.23
2.57
0.00
0.00
3.20

841
Low
CuZnO Ref A
5
Ca
5000
228.2
67.35
28.45
2.56
0.00
0.00
2.18

842
Low
CuZnO Ref A
5
Mn
5000
200.3
66.79
28.88
2.69
0.00
0.00
0.25

843
Low
CuZnO Ref A
5
Na
5000
200.1
67.10
28.57
2.70
0.00
0.00
0.82

844
Low
CuZnO Ref A
5
Mn
5000
200.1
66.74
28.93
2.69
0.00
0.00
−0.06

845
Low
CuZnO Ref A
5
Ca
5000
200.0
67.45
28.33
2.57
0.00
0.00
2.65

846
Low
CuZnO Ref A
5
Mg
5000
200.0
67.06
28.62
2.69
0.00
0.00
0.66

847
Low
CuZnO Ref A
5
Na
5000
200.0
67.02
28.65
2.70
0.00
0.00
0.43

848
Low
CuZnO Ref A
5
K
5000
200.0
66.89
28.77
2.70
0.00
0.00
0.33

849
Low
CuZnO Ref A
5
La
5000
200.0
66.67
29.01
2.68
0.00
0.00
−0.21

850
Low
CuZnO Ref A
5
Ca
5000
199.8
67.51
28.28
2.57
0.00
0.00
2.57

851
Low
CuZnO Ref A
5
Mg
5000
199.8
67.03
28.65
2.69
0.00
0.00
0.55

852
Low
CuZnO Ref A
5
K
5000
199.8
66.90
28.77
2.70
0.00
0.00
0.36

853
Low
CuZnO Ref A
5
La
5000
199.8
66.72
28.96
2.68
0.00
0.00
0.28

854
Low
CuZnO Ref A
5
Ca
5000
180.2
67.59
28.18
2.58
0.00
0.00
3.42

855
Low
CuZnO Ref A
5
K
5000
180.2
67.01
28.65
2.70
0.00
0.00
0.88

856
Low
CuZnO Ref A
5
Ca
5000
180.0
67.53
28.25
2.58
0.00
0.00
3.03

857
Low
CuZnO Ref A
5
Mg
5000
180.0
67.13
28.54
2.69
0.00
0.00
1.05

858
Low
CuZnO Ref A
5
Mn
5000
180.0
66.80
28.87
2.70
0.00
0.00
0.09

859
Low
CuZnO Ref A
5
Mg
5000
179.9
67.13
28.54
2.69
0.00
0.00
1.13

860
Low
CuZnO Ref A
5
K
5000
179.9
66.99
28.68
2.70
0.00
0.00
0.90

861
Low
CuZnO Ref A
5
La
5000
179.9
66.81
28.87
2.68
0.00
0.00
0.84

862
Low
CuZnO Ref A
5
Na
5000
179.9
67.06
28.61
2.70
0.00
0.00
0.55

863
Low
CuZnO Ref A
5
La
5000
179.9
66.69
28.99
2.68
0.00
0.00
0.15

864
Low
CuZnO Ref A
5
Na
5000
179.7
67.07
28.60
2.70
0.00
0.00
0.66

865
Low
CuZnO Ref A
5
Mn
5000
179.7
66.92
28.75
2.70
0.00
0.00
0.62

866
Low
CuZnO Ref A
1
none

299.0
65.50
28.70
2.64
0.01
1.46
3.44

867
Low
CuZnO Ref A
1
none

239.3
66.75
28.80
2.64
0.00
0.17
1.04

868
Low
CuZnO Ref A
1
none

239.1
66.62
28.95
2.64
0.00
0.15
0.38

869
Low
CuZnO Ref A
1
none

229.5
66.75
28.81
2.63
0.00
0.17
0.86

870
Low
CuZnO Ref A
1
none

229.2
66.75
28.84
2.64
0.00
0.13
0.71

871
Low
CuZnO Ref A
1
none

199.3
66.87
28.74
2.63
0.00
0.11
1.13

872
Low
CuZnO Ref A
1
none

199.3
66.72
28.94
2.65
0.00
0.05
0.09

873
Low
CuZnO Ref A
1
none

179.6
66.86
28.78
2.63
0.00
0.09
0.88

874
Low
CuZnO Ref A
1
none

179.4
66.88
28.77
2.65
0.00
0.06
0.72

875
Low
CuZnO Ref A
5
none

300.0
66.37
29.11
2.64
0.00
0.23
0.26

876
Low
CuZnO Ref A
5
none

240.1
66.85
28.80
2.69
0.00
0.02
0.53

877
Low
CuZnO Ref A
5
none

240.0
66.91
28.75
2.68
0.00
0.02
0.82

878
Low
CuZnO Ref A
5
none

230.1
66.87
28.79
2.69
0.00
0.01
0.48

879
Low
CuZnO Ref A
5
none

229.7
66.89
28.78
2.69
0.00
0.01
0.55

880
Low
CuZnO Ref A
5
none

200.1
66.89
28.78
2.69
0.00
0.00
0.35

881
Low
CuZnO Ref A
5
none

199.8
66.93
28.74
2.70
0.00
0.00
0.60

882
Low
CuZnO Ref A
5
none

180.0
66.99
28.68
2.70
0.00
0.00
0.70

883
Low
CuZnO Ref A
5
none

179.9
67.07
28.60
2.70
0.00
0.00
0.96

RUTHENIUM-COPPER CHROMITE HYDROGENATION CATALYSTS

Information

Publication Number

Date Filed

Date Published

Inventors

Original Assignees

CPC

US Classifications

International Classifications

Abstract

Description

Claims