Patent Grant
7674941
This application is related to the following copending patent applications: U.S. patent application Ser. No. 11/778,479 filed on Jul. 16, 2007 and entitled “Process for Converting Gaseous Alkanes to Liquid Hydrocarbons”; and U.S. patent application Ser. No. 11/957,261 filed on Dec. 14, 2007 and entitled “Process for Converting Gaseous Alkanes to Liquid Hydrocarbons”.
The present invention relates to processes for converting lower molecular weight alkanes to olefins, higher molecular weight hydrocarbons, or mixtures thereof that may be useful as fuels or monomers and intermediates in the production of fuels or chemicals, such as lubricants and fuel additives, and more particularly, in one or more embodiments, to processes wherein a gas that comprises lower molecular weight alkanes is reacted with bromine to form alkyl bromides and hydrobromic acid in a manner to effectively reduce formation of multi-brominated species to a level that can be tolerated in subsequent process steps.
Natural gas which is primarily composed of methane and other light alkanes has been discovered in large quantities throughout the world. Many of the locales in which natural gas has been discovered are far from populated regions which have significant gas pipeline infrastructure or market demand for natural gas. Due to the low density of natural gas, transportation thereof in gaseous form, for example, by pipeline or as compressed gas in vessels, is expensive. Accordingly, practical and economic limits exist to the distance over which natural gas may be transported in its gaseous form. Cryogenic liquefaction of natural gas (often referred to as “LNG”) is often used to more economically transport natural gas over large distances. However, this LNG process is expensive and there are limited regasification facilities in only a few countries that are equipped to import LNG.
Another use of methane is as feed to processes for the production of methanol. Methanol can be made commercially via conversion of methane to synthesis gas (CO and H2) (often referred to as “syn-gas”) at high temperatures (e.g., approximately 1000° C.) followed by synthesis at high pressures (approximately 100 atmospheres). There are several types of technologies for the production of synthesis gas from methane. Among these are steam-methane reforming (SMR), partial oxidation (POX), autothermal reforming (ATR), gas-heated reforming (GHR), and various combinations thereof. There are advantages and disadvantages associated with each. For instance, SMR and GHR usually operate at high pressures and temperatures, generally in excess of 600° C., and require expensive furnaces or reactors containing special heat and corrosion-resistant alloy tubes filled with expensive reforming catalyst. POX and ATR processes usually operate at high pressures and even higher temperatures, generally in excess of 1000° C. As there are no known practical metals or alloys that can operate at these temperatures, complex and costly refractory-lined reactors and high-pressure waste-heat boilers to quench and cool the synthesis gas effluent are required. Also, significant capital cost and large amounts of power are required for compression of oxygen or air to these high-pressure processes. Thus, due to the high temperatures and pressures involved, synthesis gas technology is generally viewed as expensive, resulting in a high cost methanol product. This cost can limit higher-value uses of the methanol, such as for chemical feedstocks and solvents. Furthermore, it is generally thought that production of synthesis gas can be thermodynamically and chemically inefficient, in that it can produce large excesses of waste heat and unwanted carbon dioxide, which tends to lower the conversion efficiency of the overall process. Fischer-Tropsch Gas-to-Liquids (GTL) technology can also be used to convert synthesis gas to heavier liquid hydrocarbons, however investment cost for this process at this point in time are higher than other types of processes. In each case, the production of synthesis gas represents a large fraction of the capital costs for these methane conversion processes.
Numerous alternatives to the conventional production of synthesis gas as a route to methanol or higher molecular weight hydrocarbons have been proposed. However, to date, none of these alternatives has attained commercial status for various reasons. Some of the previous alternative prior-art methods are directed to reacting a lower alkane, such as methane, with a metal halide to form an alkyl halide and hydrohalic acid, which can be reacted with magnesium oxide to form corresponding alkanols. Halogenation of methane using chlorine as the halogen usually results in poor selectivity to the monomethyl halide (CH3Cl), but rather produces unwanted by-products such as CH2Cl2 and CHCl3. These are thought to be difficult to convert or require severe limitation of conversion per pass, and hence very high recycle rates.
Other existing processes propose the catalytic chlorination or bromination of methane as an alternative to generation of synthesis gas (CO and H2). To improve the selectivity of a methane halogenation step in an overall process for the production of methanol, one process teaches the use of bromine, generated by thermal decomposition of a metal bromide, to brominate alkanes in the presence of excess alkanes, which results in improved selectivity to mono-halogenated intermediates such as methyl bromide. To avoid the drawbacks of utilizing fluidized beds of moving solids, the process utilizes a circulating liquid mixture of metal chloride hydrates and metal bromides. Other processes are also capable of attaining higher selectivity to mono-halogenated intermediates by the use of bromination. The resulting alkyl bromides intermediates such as methyl bromide, are further converted to the corresponding alcohols and ethers, by reaction with metal oxides in circulating beds of moving solids. Another embodiment of such processes avoids the drawbacks of moving beds by utilizing a zoned reactor vessel containing a fixed bed of metal bromide/oxide solids that is operated cyclically in four steps. While certain ethers, such as dimethylether (DME) are a promising potential diesel engine fuel substitute, as of yet, there currently exists no substantial market for DME, and hence an expensive additional catalytic process conversion step would be required to convert DME into a currently marketable product. Other processes have been proposed which circumvent the need for production of synthesis gas, such as U.S. Pat. No. 4,467,130 to Olah in which methane is catalytically condensed into gasoline-range hydrocarbons via catalytic condensation using superacid catalysts. However, none of these earlier alternative approaches have resulted in commercial processes.
In some instances, substituted alkanes, in particular methanol, can be converted to olefins and gasoline boiling-range hydrocarbons over various forms of crystalline alumino-silicates also known as zeolites. In the Methanol to Gasoline (MTG) process, a shape selective zeolite catalyst, ZSM-5, is used to convert methanol to gasoline. Coal or methane gas can thus be converted to methanol using conventional technology and subsequently converted to gasoline. However due to the high cost of methanol production, and at current or projected prices for gasoline, the MTG process is not considered economically viable. Thus, a need exists for an economic process for the conversion of methane and other alkanes found in various gas feeds to olefins, higher molecular weight hydrocarbons or mixtures thereof which have an increased value and are more economically transported thereby significantly aiding development of remote natural gas reserves. A further need exists for an efficient manner of brominating alkanes present in various gas feeds, such as natural gas, to mono-brominated alkanes while minimizing the amount of undesirable multi-halogenated alkanes formed.
To achieve the foregoing and other objects, and in accordance with the purposes of the present invention, as embodied and broadly described herein, one characterization of the present invention is a process comprising contacting bromine with gaseous alkanes at a methane to bromine molar ratio of at least about 2.5:1 to form bromination products comprising alkyl bromides. The alkyl bromides are reacted with C2+ hydrocarbons in the presence of a catalyst to convert at least a portion of dibrominated alkanes and tribrominated alkanes present in the alkyl bromides to monobrominated alkanes.
In another characterization of the present invention, a process is provided for removing C2+ alkanes from lower molecular weight alkanes to obtain a feed gas comprising at least about 90 mol % methane; which is reacted with bromine at a methane to bromine molar ratio of at least about 2.5:1 to form bromination products comprising alkyl bromides. The alkyl bromides are reacted with C2+ hydrocarbons in the presence of a catalyst to convert at least a portion of dibrominated alkanes and tribrominated alkanes present in the alkyl bromides to monobrominated alkanes.
In still another characterization of the present invention, a process is provided for reacting bromine with gaseous alkanes in a first reactor and at a residence time of less than about 5 seconds to form bromination products comprising alkyl bromides and reacting the alkyl bromides with C2+ hydrocarbons in a second reactor and in the presence of a catalyst to convert at least a portion of dibrominated alkanes and tribrominated alkanes present in said alkyl bromides to monobrominated alkanes.
In a still further characterization of the present invention, a process is provided for removing lower molecular weight alkanes comprising at least 90 mol % methane from a hydrocarbon product and contacting the lower molecular weight alkanes with bromine at a methane to bromine molar ratio of at least about 2.5:1 to form bromination products comprising alkyl bromides. The alkyl bromides are reacted with C2+ hydrocarbons in the presence of a first catalyst to convert at least a portion of dibrominated alkanes and tribrominated alkanes present in the alkyl bromides to monobrominated alkanes and after reaction with the C2+ hydrocarbons, the alkyl bromides are reacted in the presence of a second catalyst to form the hydrocarbon product.
The accompanying drawings, which are incorporated in and form a part of the specification, illustrate the embodiments of the present invention and, together with the description, serve to explain the principles of the invention.
In the drawings:
The term “high molecular weight hydrocarbons” as used herein refers to hydrocarbons comprising C3 chains and longer hydrocarbon chains. In some embodiments, the higher molecular weight hydrocarbons may be used directly as a product (e.g., LPG, motor fuel, etc.). In other instances, the higher molecular weight hydrocarbon stream may be used as an intermediate product or as a feedstock for further processing. In other instances, the higher molecular weight hydrocarbons may be further processed, for example, to produce gasoline grade fuels, diesel grade fuels, and fuel additives. In some embodiments, the higher molecular weight hydrocarbons obtained by the processes of the present invention can be used directly as a motor gasoline fuel having a substantial aromatic content, as a fuel blending stock, or as feedstock for further processing such as an aromatic feed to a process producing aromatic polymers such as polystyrene or related polymers an olefin feed to a process for producing polyolefins. The term “olefins” as used herein refers to hydrocarbons that contain two to six carbon atoms and at least one carbon-carbon double bond. The olefins may be further processed if desired. For instance, in some instances, the olefins produced by the processes of the present invention may be further reacted in a polymerization reaction (for example, a reaction using a metallocene catalyst) to produce poly(olefins), which may be useful in many end products such as plastics or synthetic lubricants.
The end use of the high molecular weight hydrocarbons, the olefins or mixtures thereof may depend on the particular catalyst employed in the oligomerization portion of the methods discussed below, as well as the operating parameters employed in the process. Other uses will be evident to those skilled in the art with the benefit of this disclosure.
In some embodiments, the present invention comprises reacting a feed gas stream with bromine from a suitable bromine source to produce alkyl bromides. As used herein, the term “alkyl bromides” refers to mono, di, and tri-brominated alkanes, and combinations of these. These alkyl bromides may then be reacted over suitable catalysts so as to form olefins, higher molecular weight hydrocarbons or mixtures thereof.
Lower molecular weight alkanes may be used as a feed stock for the methods described herein. A suitable source of lower molecular weight alkanes may be natural gas. As utilized throughout this description, the term “lower molecular weight alkanes” refers to methane, ethane, propane, butane, pentane or mixtures of two or more of these individual alkanes. The lower molecular weight alkanes may be from any suitable source, for example, any source of gas that provides lower molecular weight alkanes, whether naturally occurring or synthetically produced. Examples of sources of lower molecular weight alkanes for use in the processes of the present invention include, but are not limited to, natural gas, coal-bed methane, regasified liquefied natural gas, gas derived from gas hydrates and/or chlathrates, gas derived from anerobic decomposition of organic matter or biomass, gas derived in the processing of tar sands, and synthetically produced natural gas or alkanes. Combinations of these may be suitable as well in some embodiments. In some embodiments, it may be desirable to treat the feed gas to remove undesirable compounds, such as sulfur compounds and carbon dioxide. In any event, it is important to note that small amounts of carbon dioxide, e.g., less than about 2 mol %, can be tolerated in the feed gas to the processes of the present invention.
Suitable sources of bromine that may be used in various embodiments of the present invention include, but are not limited to, elemental bromine, bromine salts, aqueous hydrobromic acid, metal bromide salts, and the like. Combinations may be suitable, but as recognized by those skilled in the art, using multiple sources may present additional complications. Certain embodiments of the methods of the invention are described below. Although major aspects of what is to believed to be the primary chemical reactions involved in the methods are discussed in detail as it is believed that they occur, it should be understood that side reactions may take place. One should not assume that the failure to discuss any particular side reaction herein means that that reaction does not occur. Conversely, those that are discussed should not be considered exhaustive or limiting. Additionally, although figures are provided that schematically show certain aspects of the methods of the present invention, these figures should not be viewed as limiting on any particular method of the invention.
A block flow diagram generally depicting the processes of the present invention is illustrated in
The feed gas, residual hydrocarbons and olefins, higher molecular weight hydrocarbons or mixtures thereof are conveyed to a dehydration and product recovery unit wherein water is removed from the remaining constituents. The feed gas and primarily methane and ethane hydrocarbons are then separated from the olefins, higher molecular weight hydrocarbons or mixtures thereof and conveyed to the alkane bromination stage of the present invention. The remaining olefins, higher molecular weight hydrocarbons or mixtures thereof are removed from the dehydration and product recovery stage for use as a fuel, a fuel blend or for further petrochemical or fuel processing.
As further generally illustrated in
Referring to
In first reactor 30, the lower molecular weight alkanes may be reacted exothermically with dry bromine vapor at a temperature in the range of about 250° C. to about 600° C., and at a pressure in the range of about 1 bar to about 80 bar, and more preferably about 1 bar to 30 bar, to produce gaseous alkyl bromides and hydrobromic acid vapors. As will be evident to a skilled artisan with the benefit of this disclosure, the bromination reaction in first reactor 30 may be an exothermic reaction or a catalytic reaction. Non-limiting examples of suitable catalysts that may be used in first reactor 30 include platinum, palladium, or supported non-stoichiometric metal oxy-halides, such as FeOxBry or FeOxCly or supported metal oxy-halides, such as TaOF3, NbOF3, ZrOF2, SbOF3 as described in Olah, et al, J. Am. Chem. Soc. 1985, 107, 7097-7105. It is believed that the upper limit of the operating temperature range may be greater than the upper limit of the reaction initiation temperature range to which the feed mixture is heated due to the exothermic nature of the bromination reaction. In the case of methane, it is believed that the formation of methyl bromide occurs in accordance with the following general overall reaction:
CH4(g)+Br2(g)→CH3Br(g)+HBr(g)
Due to the free-radical mechanism of the gas-phase bromination reaction, di-bromomethane and some tri-bromomethane and other alkyl bromides are also formed. However, this reaction in accordance with the processes of the present invention often occurs with a relatively high degree of selectivity to methyl bromide due to the alkane to bromine ratio employed in first reactor 30. For example, in the case of the bromination of methane, a methane to bromine ratio of about 6:1 is believed to increase the selectivity to mono-halogenated methyl bromide to average approximately 88%, depending on reaction conditions, such as residence time, temperature, and turbulent mixing. At these conditions, some dibromomethane and only extremely small amounts of tribromomethane approaching the detectable limits also may be formed in the bromination reaction. If a lower methane to bromine ratio of approximately 2.6 to 1 is utilized, selectivity to the mono-halogenated methyl bromide may fall to the range of approximately 65 to 75% depending on other reaction conditions. At a methane to bromine ratio significantly less than about 2.5 to 1, unacceptable low selectivities to methyl bromide occurs, and, moreover, significant formation of undesirable di-bromomethane, tri-bromomethane, and carbon soot is observed. The residence time of the reactants in first reactor 30 necessary to achieve such selectivity to mono-halogenated methyl bromide is relatively short and may be as little as 1-5 seconds under adiabatic reaction conditions. Higher alkanes, such as ethane, propane and butane, also may be brominated, resulting in mono and multiple brominated species such as ethyl bromides, propyl bromides and butyl bromides Further, in some embodiments, the dry bromine vapor that is feed into first reactor 30 may be substantially water-free. Applicant has discovered that, at least in some instances, this may be preferred because it appears that elimination of substantially all water vapor from the bromination step in first reactor 30 substantially eliminates the formation of unwanted carbon dioxide. This may increase the selectivity of alkane bromination to alkyl bromides, thus possibly eliminating the large amount of waste heat generated in the formation of carbon dioxide from alkanes.
An effluent that comprises alkyl bromides and hydrobromic acid may be withdrawn from the first reactor via line 31. This effluent may be partially cooled in heat exchanger 32 before flowing to a second reactor 34. The temperature to which the effluent is partially cooled in heat exchanger 34 is in the range of about 150° C. to about 390° C. when it is desired to convert the alkyl bromides to higher molecular weight hydrocarbons in second reactor 34, or to range of about 150° C. to about 450° C. when it is desired to convert the alkyl bromides to olefins a second reactor 34. Second reactor 34 is thought to oligomerize the alkyl units so as to form products that comprise olefins, higher molecular weight hydrocarbons or mixtures thereof. In second reactor 34, the alkyl bromides are reacted exothermically at a temperature range of from about 150° C. to about 450° C., and a pressure in the range of about 1 to 80 bar, over a suitable catalyst to produce desired products (e.g., olefins and higher molecular weight hydrocarbons).
The catalyst used in reactor 34 may be any of a variety of suitable materials for catalyzing the conversion of the brominated alkanes to product hydrocarbons. In certain embodiments, second reactor 34 may comprise a fixed bed 33 of the catalyst. A fluidized-bed of synthesis catalyst may also be used in certain circumstances, particularly in larger applications and may have certain advantages, such as constant removal of coke and a steady selectivity to product composition. Examples of suitable catalysts include a fairly wide range of materials that have the common functionality of being acidic ion-exchangers and which also contain a synthetic crystalline alumino-silicate oxide framework. In certain embodiments, a portion of the aluminum in the crystalline alumino-silicate oxide framework may be substituted with magnesium, boron, gallium and/or titanium. In certain embodiments, a portion of the silicon in the crystalline alumino-silicate oxide framework may be optionally substituted with phosphorus. The crystalline alumino-silicate catalyst generally may have a significant anionic charge within the crystalline alumino-silicate oxide framework structure which may be balanced, for example, by cations of elements selected from the group H, Li, Na, K or Cs or the group Mg, Ca, Sr or Ba. Although zeolitic catalysts may be commonly obtained in a sodium form, a protonic or hydrogen form (via ion-exchange with ammonium hydroxide, and subsequent calcining) is preferred, or a mixed protonic/sodium form may also be used. The zeolite may also be modified by ion exchange with other alkali metal cations, such as Li, K, or Cs, with alkali-earth metal cations, such as Mg, Ca, Sr, or Ba, or with transition metal cations, such as Ni, Mn, V, W. Such subsequent ion-exchange, may replace the charge-balancing counter-ions, but furthermore may also partially replace ions in the oxide framework resulting in a modification of the crystalline make-up and structure of the oxide framework. The crystalline alumino-silicate or substituted crystalline alumino-silicate may include a microporous or mesoporous crystalline aluminosilicate, but, in certain embodiments, may include a synthetic microporous crystalline zeolite, and, for example, being of the MFI structure such as ZSM-5. Moreover, the crystalline alumino-silicate or substituted crystalline alumino-silicate, in certain embodiments, may be subsequently impregnated with an aqueous solution of a Mg, Ca, Sr, or Ba salt. In certain embodiments, the salts may be a halide salt, such as a bromide salt, such as MgBr2. Optionally, the crystalline alumino-silicate or substituted crystalline alumino-silicate may also contain between about 0.1 to about 1 weight % Pt, about 0.1 to 5 weight % Pd, or about 0.1 to about 5 weight % Ni in the metallic state. Although, such materials are primarily initially crystalline, it should be noted that some crystalline catalysts may undergo some loss of crystallinity either due to initial ion-exchange or impregnation or due to operation at the reaction conditions or during regeneration and hence my also contain significant amorphous character, yet still retain significant, and in some cases improved activity.
The particular catalyst used in second reactor 34 will depend, for example, upon the particular product hydrocarbons that are desired. For example, when product hydrocarbons having primarily C3, C4 and C5+ gasoline-range aromatic compounds and heavier hydrocarbon fractions are desired, a ZSM-5 zeolite catalyst may be used. When it is desired to produce product hydrocarbons comprising a mixture of olefins and C5+ products, an X-type or Y-type zeolite catalyst or SAPO zeolite catalyst may be used. Examples of suitable zeolites include an X-type, such as 10-X, or Y-type zeolite, although other zeolites with differing pore sizes and acidities, may be used in embodiments of the present invention.
In addition to the catalyst, the temperature at which the second reactor 34 is operated is an important parameter in determining the selectivity and conversion of the reaction to the particular product desired. For example, when a X type or Y type zeolite catalyst is used and it is desired to produce olefins, it may be advisable to operate second reactor 34 at a temperature within the range of about 250° to 500° C. Alternatively, in an embodiment involving a ZSM-5 zeolite catalyst operating in a slightly lower temperature range of about 250° to 450° C., cyclization reactions in the second reactor occur such that the C7+ fractions contain primarily substituted aromatics and also light alkanes primarily in the C3 to C5+ range. Surprisingly, very little ethane or C2, —C3 olefin components are found in the products.
In the example of a gas mixture containing methyl bromide reacting over a ZSM-5 catalyst at a GHSV in the range of about 100 to 1000 hr−1, at increasing temperatures approaching 400° C., methyl bromide conversion increases towards 90% or greater, however selectivity towards C5+ hydrocarbons decreases and selectivity towards lighter products of the process, particularly increases. At temperatures exceeding 550° C., it is believed that a high conversion of methyl bromide to methane and carbonaceous, coke may occur. In the preferred operating temperature range of between about 350° C. and 450° C., as a byproduct of the reaction, a lesser amount of coke may build up on the catalyst over time during operation. Coke build-up may be problematic as it can lead to a decline in catalyst activity over a range of hours, up to hundreds of hours, depending on the reaction conditions and the composition of the feed gas. It is believed that higher reaction temperatures above about 400° C., associated with the formation of methane favor the thermal cracking of alkyl bromides and formation of carbon or coke, and hence, an increase in the rate of deactivation of the catalyst. Conversely, temperatures at the lower end of the range, particularly below about 350° C. may also contribute to deactivation due to a reduced rate of desorption of heavier products from the catalyst. Hence, operating temperatures within the range of about 350° C. to about 450° C., but preferably in the range of about 375° C. to about 425° C. in the second reactor 34 balance increased selectivity of the desired C5+ hydrocarbons and lower rates of deactivation due to lesser carbonaceous coke formation or heavy product accumulation on the catalyst, against higher conversion per pass, which minimizes the quantity of catalyst, recycle rates and equipment size required.
In some embodiments, the catalyst may be periodically regenerated in situ. One suitable method of regenerating the catalyst is to isolate reactor 34 from the normal process flow, purge it with an inert gas via line 70 at a pressure in a range from about 1 to about 5 bar at an elevated temperature in the range of about 400° C. to about 650° C. This should remove unreacted alkyl bromides and heavier hydrocarbon products adsorbed on the catalyst insofar as is practical. Optionally, the catalyst then may be subsequently oxidized by addition of air or inert gas-diluted oxygen to reactor 34 via line 70 at a pressure in the range of about 1 bar to about 5 bar at an elevated temperature in the range of about 400° C. to about 650° C. Carbon dioxide and residual air or inert gas may be vented from reactor 34 via line 75 during the regeneration period. In most cases it is preferable to route the regeneration off-gas from reactor 34 via line 75 to the oxidation portion of the process (not illustrated) such that trace amounts of bromine, resulting from oxidation of HBr or alkyl bromides adsorbed on the catalyst, may be recovered and reused within the process.
The effluent from reactor 34, which comprises hydrobromic acid and olefins, higher molecular weight hydrocarbons or mixtures thereof, may be withdrawn from the second reactor 34 via line 35. It can be cooled if desired to a temperature in the range of 0° C. to about 100° C. (for example, in exchanger 36). It may be combined with vapor effluent in line 12 from hydrocarbon stripper 47, which contains feed gas and residual hydrocarbons stripped-out by contact with the feed gas in hydrocarbon stripper 47. The combined vapor mixture can then be passed to a scrubber 38, wherein it may be contacted with a concentrated aqueous partially-oxidized metal bromide salt solution containing metal hydroxide, metal oxide, metal oxy-bromide species or mixtures of these substances, which may be transported to scrubber 38 via line 41 by any suitable means (such as pump 42). The preferred bromide salt is Fe(III), Cu(II) or Zn(II) salt, or mixtures thereof, as these are less expensive and readily oxidize at lower temperatures in the range of about 120° C. to about 180° C., beneficially allowing the use of glass-lined or fluoropolymer-lined equipment. As recognized by those skilled in the art however, Co(II), Ni(II), Mn(II), V(II), Cr(II) or other transition-metals that are capable of forming oxidizable bromide salts also may be suitable in the processes of the present invention. Alternatively, alkaline-earth metals which also form oxidizable bromide salts, such as Ca (II) or Mg(II), may be suitable as well. Optionally, any liquid hydrocarbons condensed in scrubber 38 may be skimmed and withdrawn in line 37, and then added to liquid hydrocarbons exiting the product recovery unit 52 in line 54. Hydrobromic acid should be dissolved in the aqueous solution, and then neutralized by the metal hydroxide, metal oxide, metal oxy-bromide, or mixtures of these species to yield metal bromide salt in solution and water. This can be removed from the scrubber 38 via line 44.
Any suitable method of dehydration and liquids recovery used to process natural gas or refinery gas streams to recover products such as olefins and higher molecular weight hydrocarbons, for example, solid-bed dessicant adsorption followed by refrigerated condensation, cryogenic expansion, or circulating absorption oil or other solvent, as, may be employed in the processes of the present invention. In some embodiments, the residual vapor stream comprising olefins, higher molecular weight hydrocarbons or mixtures thereof that is removed as effluent from the scrubber 38 may be forwarded via line 39 to dehydrator 50 to remove substantially all water via line 53 from the vapor stream. The water can be removed from dehydrator 50 via line 53. The dried vapor stream comprising the olefins, higher molecular weight hydrocarbons or mixtures thereof can be further passed to product recovery unit 52 (for example, via line 51) to recover olefins, the C5+ gasoline-range hydrocarbon fraction or mixtures thereof as a liquid product in line 54. The residual vapor effluent from product recovery unit 52 can be split into a purge stream 57, which may be utilized as fuel for the process, and a recycled residual vapor, which can be compressed via compressor 58. The recycled residual vapor discharged from compressor 58 can be split into at least two fractions. If desired, a first fraction (that may be equal to at least 2.5 times the feed gas molar volume) can be transported via line 62 to be combined with dry liquid bromine conveyed by pump 24, heated in exchanger 26 to vaporize the bromine, and fed into first reactor 30. A second fraction can be drawn off of line 62 via line 63 (which can regulated by control valve 60), at a rate sufficient to dilute the alkyl bromide concentration to reactor 34 and absorb the heat of reaction such that reactor 34 is maintained at the selected operating temperature, preferably in the range of about 350° C. to about 450° C. In most instances, this temperature range appears to maximize conversion versus selectivity and to minimize the rate of catalyst deactivation due to the deposition of carbon. Thus, the dilution provided by the recycled vapor effluent permits selectivity of bromination in the first reactor 30 to be controlled in addition to moderating the temperature in second reactor 34.
Optionally, the water containing metal bromide salt in solution which is removed from scrubber 38 via line 44 can be passed to hydrocarbon stripper 47 wherein residual dissolved hydrocarbons can be stripped from the aqueous phase, e.g., by contact with incoming feed gas transported via line 11. After the stripping process, the stripped aqueous solution can transported from hydrocarbon stripper 47 via line 65 to a heat exchanger (e.g., heat exchanger 46) to be cooled to a temperature in the range of about 0° C. to about 70° C. Cooling the stripped aqueous solution may be desirable because it may suppress the hydrobromic acid vapor pressure of the aqueous solution minimizing or substantially eliminating the loss thereof to the oxidation vent stream 67. The cooled stripped aqueous solution can be then passed to absorber 48 in which residual bromine can be recovered from vent stream in line 67. This recovered bromine can be recycled and used again in the process.
The aqueous solution effluent from scrubber 48 can be transported via line 49 to a heat exchanger 40 to be vaporized and/or preheated to a temperature in the range of about 100° C. to about 600° C., and most preferably in the range of about 120° C. to about 180° C. and passed to third reactor 16. Oxygen or air can be delivered via line 10 by blower or compressor 13 at a pressure in the range of about ambient to about 5 bar to bottom-heated bromine stripper 14 to strip residual bromine from water. Water is removed from stripper 14 in line 64 and is combined with water stream 53 from dehydrator 50 to form water effluent stream in line 56 which is removed from the process. The oxygen or air leaving bromine stripper 14 is fed via line 15 to reactor 16 which operates at a pressure in the range of about ambient to about 5 bar and at a temperature in the range of about 100° C. to about 600° C., but most preferably in the range of about 120° C. to about 180° C. so as to oxidize an aqueous metal bromide salt solution to yield elemental bromine and metal hydroxide, metal oxide, metal oxy-bromide, or mixtures of these species. As stated above, although any oxidizable bromide salt may be used, either alone or in combination with other bromide salts, the preferred metal of the bromide salt is Fe(III), Cu(II), or Zn(II), or mixtures thereof, as these are less expensive and readily oxidize at lower temperatures in the range of about 120° C. to about 180° C., allowing the use of glass-lined or fluoropolymer-lined equipment. Alternatively, alkaline-earth metals which also form oxidizable bromide salts, such as Ca (II) or Mg(II) could be used.
Hydrobromic acid reacts with the metal hydroxide, metal oxide, metal oxy-bromide, or mixtures of these species so formed to once again yield the metal bromide salt and water. Heat exchanger 18 in reactor 16 supplies heat to vaporize water and bromine. Thus, the overall reactions result in the net oxidation of hydrobromic acid produced in first reactor 30 and second reactor 34 to elemental bromine and steam in the liquid phase catalyzed by the metal bromide/metal oxide or metal hydroxide operating in a catalytic cycle. In the case of the metal bromide being Fe(III)Br3, the reactions are believed to be:
Fe(+3a)+6Br(−a)+3H(+a)+ 3/2O2(g)=3Br2(g)+Fe(OH)3 1)
3HBr(g)+H2O=3H(+a)+3Br(−a)+H2O 2)
3H(+a)+3Br(−a)+Fe(OH)3=Fe(+3a)+3Br(−a)+3H2O 3)
The elemental bromine and water and any residual oxygen or nitrogen (if air is utilized as the oxidant) leaving as vapor from the outlet of third reactor 16 via line 19, are cooled in condenser 20 at a temperature in the range of about 0° C. to about 70° C. and a pressure in the range of about ambient to 5 bar to condense the bromine and water and passed to three-phase separator 22. In three-phase separator 22, since liquid water has a limited solubility for bromine, on the order of about 3% by weight, any additional bromine which is condensed forms a separate, denser liquid bromine phase. The liquid bromine phase, however, has a notably lower solubility for water, on the order of less than 0.1%. Thus a substantially dry bromine vapor may be easily obtained by condensing liquid bromine and water, decanting water by simple physical separation and subsequently re-vaporizing liquid bromine.
Liquid bromine is pumped in line 25 from three-phase separator 22 via pump 24 to a pressure sufficient to mix with vapor stream 62. Thus bromine is recovered and recycled within the process. The residual oxygen or nitrogen and any residual bromine vapor which is not condensed exits three-phase separator 22 and is passed via line 23 to bromine scrubber 48, wherein residual bromine is recovered by solution into and by reaction with reduced metal bromides in the aqueous metal bromide solution stream 65. Water is removed from separator 22 via line 27 and introduced into stripper 14.
In another embodiment of the invention, referring to
In first reactor 130, the lower molecular weight alkanes are reacted exothermically with dry bromine vapor at a relatively low temperature in the range of about 250° C. to about 600° C., and at a pressure in the range of about 1 bar to about 30 bar to produce gaseous alkyl bromides and hydrobromic acid vapors. As will be evident to a skilled artisan with the benefit of this disclosure, the bromination reaction in first reactor 30 may be an homogeneous gas-phase reaction or a heterogeneous catalytic reaction. Nonlimiting examples of suitable catalysts that may be used in first reactor 30 include platinum, palladium, or supported non-stoichiometric metal oxy-halides, such as FeOxBry or FeOxCly or supported metal oxy-halides, such as TaOF3, NbOF3, ZrOF2, SbOF3 as described in Olah, et al, J. Am. Chem. Soc. 1985, 107, 7097-7105. The upper limit of the operating temperature range is greater than the upper limit of the reaction initiation temperature range to which the feed mixture is heated due to the exothermic nature of the bromination reaction. In the case of methane, the formation of methyl bromide is believed to occur in accordance with the following general reaction:
CH4(g)+Br2(g)→CH3Br(g)+HBr(g)
Due to the free-radical mechanism of the gas-phase bromination reaction, di-bromomethane and some tri-bromomethane and other alkyl bromides are also formed. However, this reaction in accordance with the processes of the present invention often occurs with a relatively high degree of selectivity to methyl bromide due to the alkane to bromine ratio employed in first reactor 130. For example, in the case of the bromination of methane, a methane to bromine ratio of about 6:1 is believed to increase the selectivity to mono-halogenated methyl bromide to average approximately 88%, depending on reaction conditions, such as residence time, temperature, and turbulent mixing. At these conditions, some dibromomethane and only extremely small amounts of tribromomethane approaching the detectable limits also may be formed in the bromination reaction. If a lower methane to bromine ratio of approximately 2.6 to 1 is utilized, selectivity to the mono-halogenated methyl bromide may fall to the range of approximately 65 to 75% depending on other reaction conditions. At a methane to bromine ratio significantly less than about 2.5 to 1, unacceptable low selectivities to methyl bromide occurs, and, moreover, significant formation of undesirable di-bromomethane, tri-bromomethane, and carbonaceous soot is observed. The residence time of the reactants in first reactor 130 necessary to achieve such selectivity to mono-halogenated methyl bromide is relatively short and may be as little as 1-5 seconds under adiabatic reaction conditions. Higher alkanes, such as ethane, propane and butane, also may be brominated, resulting in mono and multiple brominated species such as ethyl bromides, propyl bromides and butyl bromides Further, in some embodiments, the dry bromine vapor that is feed into first reactor 130 may be substantially water-free. Applicant has discovered that, at least in some instances, this may be preferred because it appears that elimination of substantially all water vapor from the bromination step in first reactor 130 substantially eliminates the formation of unwanted carbon dioxide. This may increase the selectivity of alkane bromination to alkyl bromides, thus possibly eliminating the large amount of waste heat generated in the formation of carbon dioxide from alkanes.
The effluent that contains alkyl bromides and hydrobromic acid can be withdrawn from the first reactor 130 via line 13. In some embodiments, this effluent can be partially cooled to a temperature in the range of about 150° C. to 500° C. in heat exchanger 132 before flowing to a second reactor 134. The temperature to which the effluent is partially cooled in heat exchanger 132 is in the range of about 150° C. to about 400° C. when it is desired to convert the alkyl bromides to higher molecular weight hydrocarbons in second reactor 134, or to range of about 150° C. to about 450° C. when it is desired to convert the alkyl bromides to olefins a second reactor 134. Second reactor 134 is thought to dehydrohalogenate and oligomerize the resultant alkyl moieties so as to form products that comprise olefins, higher molecular weight hydrocarbons or mixtures thereof. The catalyst used in second reactor 134 and the temperature at which the reactor 134 is operated can be selected to achieve the desired hydrocarbon product as described above with respect to reactor 34. In certain embodiments, second reactor 134 may comprise a fixed bed 133 of the catalyst. A fluidized-bed of synthesis catalyst may also be used in certain circumstances, particularly in larger applications and may have certain advantages, such as constant removal of coke and a steady selectivity to product composition.
The catalyst may be periodically regenerated in situ, by isolating reactor 134 from the normal process flow, purging with an inert gas via line 170 at a pressure in the range of about 1 bar to about 5 bar and an elevated temperature in the range of 400° C. to 650° C. to remove unreacted material adsorbed on the catalyst insofar as is practical, and then subsequently oxidizing the deposited carbon to CO2 by addition of air or inert gas-diluted oxygen via line 170 to reactor 134 at a pressure in the range of about 1 bar to about 5 bar and an elevated temperature in the range of 400° C. to 650° C. Carbon dioxide and residual air or inert gas are vented from reactor 134 via line 175 during the regeneration period. In most cases, it is preferable to route the regeneration off-gas from reactor 134 via line 175 to the oxidation portion of the process (not illustrated) such that trace amounts of bromine, resulting from oxidation of HBr or alkyl bromides adsorbed on the catalyst, may be recovered and reused within the process.
The effluent which comprises hydrobromic acid, and higher molecular weight hydrocarbons, olefins or mixtures thereof is withdrawn from the second reactor 134 via line 135, cooled to a temperature in the range of about 0° C. to about 100° C. in exchanger 136, and combined with vapor effluent in line 112 from hydrocarbon stripper 147. The mixture is then passed to a scrubber 138 and contacted with a stripped, recirculated water that is transported to scrubber 138 in line 164 by any suitable means, such as pump 143, and is cooled to a temperature in the range of about 0° C. to about 50° C. in heat exchanger 155. Any liquid hydrocarbon product condensed in scrubber 138 may be skimmed and withdrawn as stream 137 and added to liquid hydrocarbon product 154. Hydrobromic acid is dissolved in scrubber 138 in the aqueous solution which is removed from the scrubber 138 via line 144, and passed to hydrocarbon stripper 147 wherein residual hydrocarbons dissolved in the aqueous solution are stripped-out by contact with feed gas 111. The stripped aqueous phase effluent from hydrocarbon stripper 147 is cooled to a temperature in the range of about 0° C. to about 50° C. in heat exchanger 146 and then passed via line 165 to absorber 148 in which residual bromine is recovered from vent stream 167.
The residual vapor phase comprising olefins, higher molecular weight hydrocarbons or mixtures thereof is removed as effluent from the scrubber 138 and forwarded via line 139 to dehydrator 150 to remove substantially all water from the gas stream to prevent formation of liquid water, or freezing, or formation of hydrates in product recovery unit 152. Dehydrator 150 may be used, if desired, via line 153. The dried gas stream containing the olefins, higher molecular weight hydrocarbons or mixtures thereof is further passed via line 151 to product recovery unit 152 to recover olefins, the higher molecular weight hydrocarbon fraction or mixtures thereof as a liquid product in line 154. Any conventional method of dehydration and liquids recovery such as solid-bed dessicant adsorption followed by, for example, refrigerated condensation, cryogenic expansion, or circulating absorption oil, or other solvents as used to process natural gas or refinery gas streams and recover olefinic hydrocarbons, as known to a skilled artisan, may be employed in the implementation of this invention. The residual vapor effluent from product recovery unit 152 is then split into a purge stream 157 that may be utilized as fuel for the process and a recycled residual vapor which is compressed via compressor 158. The recycled residual vapor discharged from compressor 158 is split into two fractions. A first fraction that is equal to at least 2.5 times the feed gas volume is transported via line 162, combined with the liquid bromine conveyed in line 125 and passed to heat exchanger 126 wherein the liquid bromine is vaporized and fed into first reactor 130. The second fraction which is drawn off line 162 via line 163 and is regulated by control valve 160, at a rate sufficient to dilute the alkyl bromide concentration to reactor 134 and absorb the heat of reaction such that reactor 134 is maintained at the selected operating temperature, preferably in the range of about 350° C. to about 450° C. in order to maximize conversion vs. selectivity and to minimize the rate of catalyst deactivation due to the deposition of carbon. Thus, the dilution provided by the recycled vapor effluent permits selectivity of bromination in the first reactor 130 to be controlled in addition to moderating the temperature in second reactor 134.
Oxygen, oxygen enriched air, or air 110 may be added to bromine stripper 114 by any suitable device or method (for example, via compressor 113) at a pressure in the range of about ambient to about 5 bar. This may be desirable where it is advantageous to strip residual bromine from water. The stripped water may exit stripper 114 via line 164, and can be divided into at least two portions. The first portion of the stripped water can be recycled via line 164, cooled in heat exchanger 155 to a temperature in the range of about 20° C. to about 50° C., and maintained at a pressure sufficient to enter scrubber 138 by any suitable means, such as pump 143. The portion of water that is recycled is selected such that the hydrobromic acid solution effluent removed from scrubber 138 via line 144 has a concentration in the range from about 10% to about 50% by weight hydrobromic acid, but more preferably in the range of about 30% to about 48% by weight to minimize the amount of water which must be vaporized in exchanger 141 and preheater 119 and to minimize the vapor pressure of HBr over the resulting acid. A second portion of water from stripper 114 is removed from line 164 and the process via line 156.
The dissolved hydrobromic acid that is contained in the aqueous solution effluent from scrubber 148 can be mixed with the oxygen, oxygen enriched air, or air leaving bromine stripper 114 in line 115. This mixture can be preheated to a temperature in the range of about 100° C. to about 600° C. and most preferably in the range of about 120° C. to about 250° C., for example, by heat exchanger 141 and preheater 119. Once preheated, the mixture may be added to third reactor 117 that contains a metal bromide salt or metal oxide. Any suitable bromide salt or combination of bromide salts may be used. The preferred metal of the bromide salt or metal oxide is Fe(III), Cu(II) or Zn(II) or mixtures thereof. The metal bromide salt in the oxidation reactor 117 may be utilized as a concentrated aqueous solution or preferably, the concentrated aqueous salt solution may be imbibed into a porous, low to medium surface area, acid resistant inert support such as a silica gel. More preferably, the oxide form of the metal in a range of 10 to 20% by weight is deposited on an inert support such as alumina with a specific surface area in the range of 5 to 200 m2/g. The oxidation reactor 117 operates at a pressure in the range of about ambient to about 5 bar and at a temperature in the range of about 100° C. to 600° C., but most preferably in the range of about 130° C. to 350° C.; therein, the metal bromide is oxidized by oxygen, yielding elemental bromine and metal hydroxide, metal oxide or metal oxy-bromide species or, metal oxides in the case of the supported metal bromide salt or metal oxide operated at higher temperatures and lower pressures at which water may primarily exist as a vapor. In either case, the hydrobromic acid reacts with the metal hydroxide, metal oxy-bromide or metal oxide species and is neutralized, restoring the metal bromide salt and yielding water. Thus, the overall reaction results in the net oxidation of hydrobromic acid produced in first reactor 130 and second reactor 134 to elemental bromine and steam, catalyzed by the metal bromide/metal hydroxide or metal oxide operating in a catalytic cycle. In the case of the metal bromide being Fe(III)Br3 in an aqueous solution and operated in a pressure and temperature range in which water may exist as a liquid the reactions are believed to be:
Fe(+3a)+6Br(−a)+3H(+a)+ 3/2O2(g)=3Br2(g)+Fe(OH)3 1)
3HBr(g)+H2O=3H(+a)+3Br(−a)+H2O 2)
3H(+a)+3Br(−a)+Fe(OH)3=Fe(+3a)+3Br(−a)+3H2O 3)
In the case of the metal bromide being Cu(II)Br2 supported on an inert support and operated at higher temperature and lower pressure conditions at which water primarily exists as a vapor, the reactions are believed to be:
2Cu(II)Br2=2Cu(I)Br+Br2(g) 1)
2Cu(I)Br+O2(g)=Br2(g)+2Cu(II)O 2)
2HBr(g)+Cu(II)O=Cu(II)Br2+H2O(g) 3)
The elemental bromine and water and any residual oxygen or nitrogen (if air or oxygen enriched air is utilized as the oxidant) leaving as vapor from the outlet of third reactor 117, are transported via line 127 and cooled in the second side of exchanger 141 and condenser 120 to a temperature in the range of about 0° C. to about 70° C. wherein the bromine and water are condensed and passed to three-phase separator 122. In three-phase separator 122, since liquid water has a limited solubility for bromine, on the order of about 3% by weight, any additional bromine which is condensed forms a separate, denser liquid bromine phase. The liquid bromine phase, however, has a notably lower solubility for water, on the order of less than 0.1%. Thus, a substantially dry bromine vapor may be easily obtained by condensing liquid bromine and water, decanting water by simple physical separation and subsequently re-vaporizing liquid bromine. It is important to operate at conditions that result in the near complete reaction of HBr so as to avoid significant residual HBr in the condensed liquid bromine and water, as HBr increases the miscibility of bromine in the aqueous phase, and at sufficiently high concentrations, results in a single ternary liquid phase.
Optionally, liquid bromine can be pumped from three-phase separator 122 via pump 124 to a pressure sufficient to mix with vapor stream 162. Thus, in these embodiments, the bromine can be recovered and recycled within the process, which can be beneficial. The residual air, oxygen enriched air or oxygen and any bromine vapor which is not condensed may exit three-phase separator 122 to bromine scrubber 148, wherein residual bromine can be recovered by dissolution into the hydrobromic acid solution stream conveyed to scrubber 148 via line 165. Water can be removed from the three-phase separator 122 via line 129 and passed to stripper 114.
Thus, in certain embodiments of the processes of the present invention, the metal bromide/metal hydroxide, metal oxy-bromide or metal oxide operates in a catalytic cycle allowing bromine to be recycled for reuse within the process. The metal bromide is readily oxidized by oxygen, oxygen enriched air or air either in the aqueous phase or the vapor phase at temperatures in the range of about 100° C. to about 600° C. and most preferably in the range of about 120° C. to about 350° C. to yield elemental bromine vapor and metal hydroxide, metal oxy-bromide or metal oxide. Operation at temperatures below about 180° C. is advantageous, thereby allowing the use of low-cost corrosion-resistant fluoropolymer-lined equipment. Hydrobromic acid is neutralized by reaction with the metal hydroxide or metal oxide yielding steam and the metal bromide.
The elemental bromine vapor and steam are condensed and easily separated in the liquid phase by simple physical separation, yielding substantially dry bromine. The absence of significant water allows selective bromination of alkanes, without production of CO2 and the subsequent efficient and selective reactions of alkyl bromides to primarily higher molecular weight hydrocarbons which contains substantial branched alkanes, substituted aromatics, or mixtures thereof. Byproduct hydrobromic acid vapor from the bromination reaction and subsequent reaction in reactor 134 are readily dissolved into an aqueous phase and neutralized by the metal hydroxide or metal oxide species resulting from oxidation of the metal bromide.
In accordance with another embodiment of the processes of the present invention illustrated in
In first reactor 230, the lower molecular weight alkanes are reacted exothermically with dry bromine vapor at a relatively low temperature in the range of about 250° C. to about 600° C., and at a pressure in the range of about 1 bar to about 30 bar to produce gaseous alkyl bromides and hydrobromic acid vapors. As will be evident to a skilled artisan with the benefit of this disclosure, the bromination reaction in first reactor 30 may be an exothermic reaction or a catalytic reaction. Nonlimiting examples of suitable catalysts that may be used in first reactor 30 include platinum, palladium, or supported non-stoichiometric metal oxy-halides, such as FeOxBry or FeOxCly or supported metal oxy-halides, such as TaOF3, NbOF3, ZrOF2, SbOF3 as described in Olah, et al, J. Am. Chem. Soc. 1985, 107, 7097-7105. The upper limit of the operating temperature range is greater than the upper limit of the reaction initiation temperature range to which the feed mixture is heated due to the exothermic nature of the bromination reaction. In the case of methane, the formation of methyl bromide occurs in accordance with the following general reaction:
CH4(g)+Br2(g)→CH3Br(g)+HBr(g)
Due to the free-radical mechanism of the gas-phase bromination reaction, di-bromomethane and some tri-bromomethane and other alkyl bromides are also formed. However, this reaction in accordance with the processes of the present invention often occurs with a relatively high degree of selectivity to methyl bromide due to the alkane to bromine ratio employed in first reactor 230. For example, in the case of the bromination of methane, a methane to bromine ratio of about 6:1 is believed to increase the selectivity to mono-halogenated methyl bromide to average approximately 88%, depending on reaction conditions, such as residence time, temperature, and turbulent mixing. At these conditions, some dibromomethane and only extremely small amounts of tribromomethane approaching the detectable limits also may be formed in the bromination reaction. If a lower methane to bromine ratio of approximately 2.6 to 1 is utilized, selectivity to the mono-halogenated methyl bromide may fall to the range of approximately 65 to 75% depending on other reaction conditions. At a methane to bromine ratio significantly less than about 2.5 to 1, unacceptable low selectivities to methyl bromide occurs, and, moreover, significant formation of undesirable di-bromomethane, tri-bromomethane, and carbon soot is observed. The residence time of the reactants in first reactor 230 necessary to achieve such selectivity to mono-halogenated methyl bromide is relatively short and may be as little as 1-5 seconds under adiabatic reaction conditions. Higher alkanes, such as ethane, propane and butane, also may be brominated, resulting in mono and multiple brominated species such as ethyl bromides, propyl bromides and butyl bromides. Further, in some embodiments, the dry bromine vapor that is feed into first reactor 230 may be substantially water-free. Applicant has discovered that, at least in some instances, this may be preferred because it appears that elimination of substantially all water vapor from the bromination step in first reactor 230 substantially eliminates the formation of unwanted carbon dioxide. This may increase the selectivity of alkane bromination to alkyl bromides, thus possibly eliminating the large amount of waste heat generated in the formation of carbon dioxide from alkanes.
The effluent that contains alkyl bromides and hydrobromic acid is withdrawn from the first reactor 230 via line 231. In some embodiments, the effluent may be partially cooled in heat exchanger 232 before flowing to a second reactor 234. The temperature to which the effluent is partially cooled in heat exchanger 232 is in the range of about 150° C. to about 390° C. when it is desired to convert the alkyl bromides to higher molecular weight hydrocarbons in second reactor 234, or to range of about 150° C. to about 450° C. when it is desired to convert the alkyl bromides to olefins a second reactor 234. Second reactor 234 is thought to dehydrohalogenate and oligomerize the resultant alkyl moieties so as to form products that comprise olefins, higher molecular weight hydrocarbons or mixtures thereof. The catalyst used in second reactor 234 and the temperature at which the reactor 234 is operated can be selected to achieve the desired hydrocarbon product as described above with respect to reactor 34. In certain embodiments, second reactor 234 may comprise a fixed bed 233 of the catalyst. A fluidized-bed of synthesis catalyst may also be used in certain circumstances, particularly in larger applications and may have certain advantages, such as constant removal of coke and a steady selectivity to product composition.
The catalyst may be periodically regenerated in situ, by isolating reactor 234 from the normal process flow, purging with an inert gas via line 270 at a pressure in the range of about 1 bar to about 5 bar and an elevated temperature in the range of about 400° C. to about 650° C. to remove unreacted material adsorbed on the catalyst insofar as is practical, and then subsequently oxidizing the deposited carbon to CO2 by addition of air or inert gas-diluted oxygen via line 270 to reactor 234 at a pressure in the range of about 1 bar to about 5 bar and an elevated temperature in the range of about 400° C. to about 650° C. Carbon dioxide and residual air or inert gas are vented from reactor 234 via line 275 during the regeneration period. In most cases it is preferable to route the regeneration off-gas from reactor 134 via line 175 to the oxidation portion of the process (not illustrated) such that trace amounts of bromine, resulting from oxidation of HBr or alkyl bromides adsorbed on the catalyst, may be recovered and reused within the process.
The effluent which comprises hydrobromic acid and higher molecular weight hydrocarbons, olefins, or mixtures thereof is withdrawn from the second reactor 234 via line 235 and cooled to a temperature in the range of about 100° C. to about 600° C. in exchanger 236. As illustrated in
2HBr+MO→MBr2+H2O
The steam resulting from this reaction is transported together with the high molecular hydrocarbons in line 244, 218 and 216 via opened valve 219 to heat exchanger 220 wherein the mixture is cooled to a temperature in the range of about 0° C. to about 70° C. This cooled mixture is forwarded to dehydrator 250 to remove substantially all water from the gas stream. The water is then removed from the dehydrator 250 via line 253. The dried gas stream containing olefins, higher molecular weight hydrocarbons or mixtures thereof is further passed via line 251 to product recovery unit 252 to recover olefins, the C5+ fraction or mixtures thereof as a liquid product in line 254. Any conventional method of dehydration and liquids recovery such as solid-bed dessicant adsorption followed by, for example, refrigerated condensation, cryogenic expansion, or circulating absorption oil or other solvent, as used to process natural gas or refinery gas streams and recover olefinic hydrocarbons, as known to a skilled artisan, may be employed in the implementation of this invention. The residual vapor effluent from product recovery unit 252 is then split into a purge stream 257 that may be utilized as fuel for the process and a recycled residual vapor which is compressed via compressor 258. The recycled residual vapor discharged from compressor 258 is split into two fractions. A first fraction that is equal to at least 1.5 times the feed gas volume is transported via line 262, combined with the liquid bromine and feed gas conveyed in line 225 and passed to heat exchanger 226 wherein the liquid bromine is vaporized and fed into first reactor 230 in a manner as described above. The second fraction which is drawn off line 262 via line 263 and is regulated by control valve 260, at a rate sufficient to dilute the alkyl bromide concentration to reactor 234 and absorb the heat of reaction such that reactor 234 is maintained at the selected operating temperature, preferably in the range of about 300° C. to about 450° C. in order to maximize conversion vs. selectivity and to minimize the rate of catalyst deactivation due to the deposition of carbon. Thus, the dilution provided by the recycled vapor effluent permits selectivity of bromination in the first reactor 230 to be controlled in addition to moderating the temperature in second reactor 234.
Oxygen, oxygen enriched air or air 210 is delivered via blower or compressor 213 at a pressure in the range of about ambient to about 10 bar to bromine via line 214, line 215 and valve 249 through heat exchanger 215, wherein oxygen, oxygen enriched air or air is preheated to a temperature in the range of about 100° C. to about 500° C. to a second vessel or reactor 246 containing a bed 299 of a solid phase metal bromide. Oxygen reacts with the metal bromide in accordance with the following general reaction wherein M represents the metal:
MBr2+½O2→MO+Br2
In this manner, a dry, substantially HBr free bromine vapor is produced thereby eliminating the need for subsequent separation of water or hydrobromic acid from the liquid bromine. Reactor 246 is operated below 600° C., and more preferably between about 300° C. to about 500° C. The resultant bromine vapor is transported from reactor 246 via line 247, valve 248 and line 242 to heat exchanger or condenser 221 where the bromine is condensed into a liquid. The liquid bromine is transported via line 242 to separator 222 wherein liquid bromine is removed via line 225 and transported via line 225 to heat exchanger 226 and first reactor 230 by any suitable means, such as by pump 224. The residual air or unreacted oxygen is transported from separator 222 via line 227 to a bromine scrubbing unit 223, such as venturi scrubbing system containing a suitable solvent, or suitable solid adsorbant medium, as selected by a skilled artisan, wherein the remaining bromine is captured. The captured bromine is desorbed from the scrubbing solvent or adsorbant by heating or other suitable means and the thus recovered bromine transported via line 212 to line 225. The scrubbed air or oxygen is vented via line 229. In this manner, nitrogen and any other substantially non-reactive components are removed from the system of the present invention and thereby not permitted to enter the hydrocarbon-containing portion of the process; also loss of bromine to the surrounding environment is avoided.
One advantage of removing the HBr by chemical reaction in accordance with this embodiment, rather than by simple physical solubility, is the substantially complete scavenging of the HBr to low levels at higher process temperatures. Another distinct advantage is the elimination of water from the bromine removed thereby eliminating the need for separation of bromine and water phases and for stripping of residual bromine from the water phase.
Reactors 240 and 246 may be operated in a cyclic fashion. As illustrated in
When oxygen is utilized as the oxidizing gas transported in via line 210 to the reactor being used to oxidize the solid metal bromide contained therein, the embodiment of the processes of the present invention illustrated in
In the embodiment of the present invention illustrated in
In the embodiment illustrated in
In accordance with another embodiment of the processes of the present invention that is illustrated in
2M2Brn+Br2→2M2Brn+1
In this manner, bromine is stored as a second metal bromide, i.e. 2M2Brn+1, in reactor 320 while the resultant vapor containing residual air or oxygen is vented from reactor 320 via line 324, valve 326 and line 318.
The gas stream containing lower molecular weight alkanes, comprised of mixture of a feed gas (line 211) and a recycled gas stream, is transported or conveyed via line 262, heat exchanger 352, wherein the gas stream is preheated to a temperature in the range of about 150° C. to about 600° C., valve 304 and line 302 to a second vessel or reactor 310 containing a bed 312 of a solid phase metal bromide in an oxidized valence state. The metal of the metal bromide in an oxidized valence state is selected from copper (Cu), iron (Fe), or molybdenum (Mo). The metal is selected for the impact of its physical and thermodynamic properties relative to the desired temperature of operation, and also for potential environmental and health impacts and cost. Preferably, copper or iron are employed as the metal, with iron being the most preferred. The solid metal bromide in an oxidized state is preferably immobilized on a suitable attrition-resistant support, for example a synthetic amorphous silica such as Davicat Grade 57, manufactured by Davison Catalysts of Columbia, Md. More preferably the metal is deposited in an oxide state in a range of 10 to 20 wt % supported on an alumina support with a specific surface area of about 50 to 200 m2/g. The temperature of the gas stream is from about 150° C. to about 600° C., and preferably from about 150° C. to about 300° C. In second reactor 310, the temperature of the gas stream thermally decomposes the solid phase metal bromide in an oxidized valence state to yield elemental bromine vapor and a solid metal bromide in a reduced state in accordance with the following general reaction wherein M2 represents the metal:
2M2Brn+1→2M2Brn+Br2
In addition, at temperatures of about 200° C. and higher the lower molecular weight alkanes contained in the gas stream may react over the heated bed of the solid metal bromide in an oxidized state to produce gaseous alkyl bromides, hydrobromic acid vapors and a solid metal bromide in a reduced state in accordance with the following general reaction wherein M2 represents the metal:
CH4(g)+2M2Brn+1→CH3Br(g)+HBr(g)+M2Brn
By controlling the temperature of the gas stream and therefore the temperature of the bed 312 of the solid phase metal bromide in an oxidized valence state, the degree to which bromine is liberated and the lower molecular weight alkanes are brominated in second vessel or reactor 310 may be controlled. While the exact mechanism by which the lower molecular weight alkanes react over the heated bed of the solid metal bromide in an oxidized state to produce gaseous alkyl bromides is not completely understood, it is applicant's belief that bromination may occur on the solid surface of the support for the metal bromide thereby allowing the reaction to proceed at lower temperatures, for example about 200° C. to about 300° C. thereby inhibiting free-radical gas phase bromination and minimizing the production of multi-brominated alkanes.
The resultant bromine vapor, alkyl bromide and hydrobromic acid are transported with the gas stream containing lower molecular weight alkanes via lines 314, 315, valve 317, line 330, heat exchanger 226 prior to being introduced into alkyl bromination reactor 230. If significant amounts of the lower molecular weight gaseous alkanes are brominated in second vessel or reactor 310, heat exchanger 226 and bromination reactor 230 may be eliminated from the process schematic and the gas stream may be transported directly to second reactor 234 via exchanger 232. This may be accomplished by passing the gas stream through heat exchanger 226 and reactor 230 without heating the gas stream or both of these components may be eliminated or bypassed as will be evident to a skilled artisan.
Reactors 310 and 320 may be operated in a cyclic fashion. As illustrated in
In the embodiment of the present invention illustrated in
A block flow diagram generally depicting the processes of the present invention is illustrated in
In accordance with the processes of the present invention as previously noted, the feed gas containing predominantly methane and acceptable amounts of C2+ lower molecular weight alkane components may be reacted exothermically in the bromination reactor with dry bromine vapor at a relatively low temperature in the range of about 250° C. to about 600° C., and at a pressure in the range of about 1 bar to about 30 bar to produce gaseous alkyl bromides and hydrobromic acid vapors. As will be evident to a skilled artisan with the benefit of this disclosure, the bromination reaction in first reactor 30 may be an exothermic reaction or a catalytic reaction. Nonlimiting examples of suitable catalysts that may be used in first reactor 30 include platinum, palladium, or supported non-stoichiometric metal oxy-halides, such as FeOxBry or FeOxCly or supported metal oxy-halides, such as TaOF3, NbOF3, ZrOF2, SbOF3 as described in Olah, et al, J. Am. Chem. Soc. 1985, 107, 7097-7105. The upper limit of the operating temperature range is greater than the upper limit of the reaction initiation temperature range to which the feed mixture is heated due to the exothermic nature of the bromination reaction. In the case of methane, the formation of methyl bromide is believed to occur in accordance with the following general reaction:
CH4(g)+Br2(g)→CH3Br(g)+HBr(g)
Due to the free-radical mechanism of the gas-phase bromination reaction, di-bromomethane and some tri-bromomethane and other alkyl bromides may be also formed. Bromination often occurs in the bromination reactor with a relatively high degree of selectivity to methyl bromide due to the alkane to bromine ratio employed. For example, in the case of the bromination of methane, a methane to bromine ratio of about 6:1 is believed to increase the selectivity to mono-halogenated methyl bromide to average approximately 88%, depending on reaction conditions, such as residence time, temperature, and turbulent mixing. At these conditions, some dibromomethane and only extremely small amounts of tribromomethane approaching the detectable limits may also be formed in the bromination reaction. If a lower methane to bromine ratio of approximately 2.6 to 1 is utilized, selectivity to the mono-halogenated methyl bromide may fall to the range of approximately 65 to 75% depending on other reaction conditions. At a methane to bromine ratio significantly less than about 2.5 to 1, unacceptable low selectivities to methyl bromide occurs, and, moreover, significant formation of undesirable di-bromomethane, tri-bromomethane, and carbon soot is observed. The relatively high methane to bromine ratio employed in the bromination reactor also ensures that bromine is substantially consumed in the bromination reactor thereby effectively inhibiting subsequent formation of free-radical bromination in subsequent stages of the processes of the present invention due to the presence of elemental bromine. The residence time of the reactants in the bromination reactor necessary to achieve such selectivity to mono-halogenated methyl bromide is relatively short and may be as little as 1-5 seconds under adiabatic reaction conditions. Higher alkanes, such as ethane, propane and butane, also may be brominated, resulting in mono and multiple brominated species such as ethyl bromides, propyl bromides and butyl bromides. Further, in some embodiments, the dry bromine vapor that is feed into the bromination reactor may be substantially water-free. Applicant has discovered that, at least in some instances, this may be preferred because it appears that elimination of substantially all water vapor from the bromination step substantially eliminates the formation of unwanted carbon dioxide. This may increase the selectivity of alkane bromination to alkyl bromides, thus possibly eliminating the large amount of waste heat generated in the formation of carbon dioxide from alkanes.
The C2+ lower molecular weight alkane components removed from the liquid hydrocarbon product in the product stabilizer column may be combined with the effluent withdrawn from the bromination reactor that comprises alkyl bromides and hydrobromic acid and introduced into a shift reactor. [The small amount of unreacted bromine which is not reacted in the bromination reactor and which may be present in the effluent from the bromination reactor is readily consumed by thermal bromination reaction with C2+ hydrocarbons prior to or upon introduction into the shift reactor.] In the shift reactor, a significant portion of the di and tri brominated alkanes that may be present in the alkyl bromides contained in the effluent from the bromination reactor may be selectively converted upon reaction with C2+ components to mono brominated alkanes. As an example, where C3 and di methylbromide are the reactants, it is believed that the conversion occurs in accordance with the following general reaction:
C3H8+CH2Br2→CH3Br+C3H7Br
Although this reaction may proceed thermally without a catalyst, it has been determined that such thermal reaction requires unacceptably long residence time within the shift reactor and does not achieve satisfactory conversion rates to mono brominated alkanes. Accordingly, it is preferred that the shift reactor contain a bed of suitable catalyst selected from Group VIII metals, Group VIB metals, Group IB metals, aluminum, zinc, vanadium, magnesium, calcium, titanium, and mixtures thereof. Group VIII metals include iron, cobalt, nickel, platinum, palladium, rhodium, ruthenium, iridium, osmium or mixtures of two or more thereof. Group VIB metals include tungsten, molybdenum or chromium. Group IB metals include copper or silver. Preferably, the Group VIII metal used in this embodiment of the present invention is a noble metal selected from platinum, palladium, rhodium, ruthenium, iridium, osmium, or mixtures of two or more thereof, and more preferably the Group VIII metal is platinum. Most preferably, the Group VIII metal is iron employed as a metal bromide, metal oxide or non-stoichometric metal oxy-bromide. Preferably the Group VIB metals are molybdenum or tungsten. Preferably the Group IB metal is copper employed as a metal bromide, metal oxide or metal oxy-bromide. Nonlimiting examples of suitable metal catalysts listed above which may form more than one thermally reversible bromide salt as used in the processes of the present invention are iron, molybdenum, tungsten, copper, vanadium, chromium or mixtures of two or more thereof. Nonlimiting examples of suitable catalysts listed above which may form single bromide salts as used in the processes of the present invention are cobalt, nickel, silver, zinc, magnesium, calcium, titanium, aluminum or mixtures of two or more thereof. These metals which form more than one thermally reversible bromide salt or a single bromide salt may be initially employed in the processes of the present invention as a bromide salt or an oxide since they would be exist and function as bromides in the shift reactor due to conversion to bromide salts via a reaction with hydrobromic acid under the conditions employed in the shift reactor. Suitable supports are selected to have relatively low acidity to inhibit thermal decomposition and cracking of polybrominated alkanes and have relatively low surface area to inhibit adsorption of the polybrominated alkanes onto the support. Nonlimiting examples of suitable supports for use with the catalyst in the shift reactor are silica, titania, zirconia or low surface area alumina, preferably having a specific surface area less than about 50 m2/g.
The catalyst is loaded and dispersed upon a suitable support to yield high activity in a cost effective manner as will be evident to a skilled artisan. For example, it is preferred to use a loading of from about 0.1 wt % to about 1 wt % and more preferably from about 0.3 wt % to about 0.5 wt % when platinum is employed as the catalyst in the shift reactor bed, while a loading of from about 1 wt % to about 10 wt % and more preferably 3 wt % to about 10 wt % is employed when palladium is employed as the catalyst. In the case of the preferred non-noble metals such as iron, molybdenum or mixtures thereof with higher loadings in the range of about 10% to about 20% or greater (as metal oxide) are cost-effective. When using a catalyst in the shift reactor, it is preferred to operate the reactor at from about 200° C. to about 500° C., more preferably from about 300° C. to about 400° C. The residence time of the reactants in the shift reactor necessary to achieve the desired selectivity to mono-brominated alkanes is relatively short and may be as little as 2 to 8 seconds.
The effluent from shift reactor 410 which contains a significantly increased ratio of mono brominated alkanes to di or tri brominated alkanes may be transported to a synthesis reactor and reacted over a suitable catalyst (as described above in conjunction with reactor 34) in the presence of hydrobromic acid to form olefins, higher molecular weight hydrocarbons or mixtures thereof. The particular olefins, higher molecular weight hydrocarbons or mixtures thereof produced is dependent upon the catalyst employed in the synthesis, the composition of the alkyl bromides introduced into this reactor and the exact operating parameters employed in this reactor.
Hydrobromic acid may be removed from olefins, higher molecular weight hydrocarbons or mixtures in a hydrobromic acid (HBr) removal stage and may be conveyed to a bromine recovery stage wherein hydrobromic acid may be neutralized by a partially oxidized metal bromide salt to yield a metal bromide salt. The resultant metal bromide salt may be contacted with oxygen or air in the bromide recovery stage of the present invention to yield elemental bromine which may be recycled to the alkane bromination stage as a dry bromine vapor and a partially oxidized metal bromide salt which may be used to neutralize and remove additional hydrobromic acid removed from the olefins and higher molecular weight hydrocarbons produced by the process.
A block flow diagram generally depicting the processes of the present invention is illustrated in
In accordance with the embodiments of the processes of the present invention described above and generally illustrated in
To illustrate a specific embodiment of the processes of the present invention that is generally illustrated in
In accordance with this embodiment, a gas stream containing lower molecular weight alkanes may be transported or conveyed via line, pipe or conduit 211, mixed with steam and high molecular hydrocarbons in line 216 and conveyed to dehydrator 250 to remove substantially all water from the gas stream. The water may be then removed from the dehydrator 250 via line 253. The dried gas stream containing the higher molecular weight hydrocarbons may be transported via line 251 to product recovery unit 252 to recover C3 and C4 as desired, but primarily the C5+ fraction in line 254. Any conventional method of dehydration and liquids recovery such as solid-bed dessicant adsorption followed by, for example, refrigerated condensation, cryogenic expansion, or circulating absorption oil, as used to process natural gas or refinery gas streams, as known to a skilled artisan, may be employed in the implementation of this invention. In accordance with this embodiment of the present invention, the stream in line 254 may be conveyed to a stabilizer column in which is operated at conditions sufficient to remove at least a portion of the C2-C5 hydrocarbons in a gaseous phase from the remaining higher molecular weight hydrocarbons which are transported from the stabilizer 450 via line 412 to heat exchanger 456 where any residual C2-C5 hydrocarbons may be removed from the higher molecular weight hydrocarbons and transported back to the stabilizer column 450. The higher molecular weight hydrocarbons may be removed from the process 454 as a fuel product, a blend or for further processing. The C2-C5 hydrocarbons may be removed from stabilizer column 450 a gaseous phase in line 460 and pressurized in a compressor 462 for further use in the process as hereinafter described. While C2-C5 hydrocarbons may be removed from stabilizer column 450 and introduced with the feed into the shift reactor 410, it is preferred that the stabilizer column is operated at conditions to maximize the C3 content of this hydrocarbon stream.
The vapor effluent from product recovery unit 252 that contains lower molecular weight alkanes may be split into a purge stream 257 that may be utilized as fuel for the process and a feed gas which is compressed via compressor 258. The gas discharged from compressor 258 may be split into two fractions. A first fraction is transported via line 262 to heat exchanger 352, wherein the gas stream may be preheated to a temperature in the range of about 150° C. to about 600° C. The heated gas stream may be then passed through valve 304 and line 302 to a second vessel or reactor 310 containing a bed 312 of a solid phase metal bromide in an oxidized valence state wherein the temperature of the gas stream thermally decomposes the solid phase metal bromide in an oxidized valence state to yield elemental bromine vapor and a solid metal bromide in a reduced state. In addition, the lower molecular weight alkanes contained in the gas stream may react over the heated bed 312 of the solid metal bromide in an oxidized state to produce gaseous alkyl bromides, hydrobromic acid vapors and a solid metal bromide in a reduced state. By controlling the temperature of the gas stream and therefore the temperature of the bed 312 of the solid phase metal bromide in an oxidized valence state, the degree to which bromine is liberated and to which the lower molecular weight alkanes are brominated in second vessel or reactor 310 may be controlled. The resultant bromine vapor, alkyl bromide and hydrobromic acid may be transported with the gas stream containing lower molecular weight alkanes via lines 314, 315, valve 317, line 330, heat exchanger 226 and line 225 prior to being introduced into alkyl bromination reactor 230 for further bromination of lower molecular weight alkanes contained in the gas stream. If significant amounts of the lower molecular weight gaseous alkanes are brominated in second vessel or reactor 310, the heat exchanger 226 and bromination reactor 230 may be eliminated from the process. While small amounts of C2 and C3, for example about 0.1 to about 1.0 mole %, may be tolerated in the bromination reaction, higher concentrations of C2 and C3 in reactor 230 result in rapid formation of carbon-containing, coke-like solids which cause fouling and plugging in reactors 230 and 234. This adverse condition is substantially inhibited in the process illustrated in
The effluent that contains alkyl bromides and hydrobromic acid may be withdrawn from the first reactor 230 (or the second vessel or reactor 310 depending upon the extent of bromination achieved therein) via line 402. The second fraction vapor effluent from product recovery unit 252 may be drawn off line 262 via line 263, introduced into the effluent from the first reactor 230 in line 402, and regulated by control valve 260. The rate at which the second fraction may be introduced into the first reactor effluent in line 402 is sufficient to dilute the alkyl bromide concentration fed to reactor 234 and absorb the heat of reaction such that reactor 234 may be maintained at the selected operating temperature. Thus, the dilution provided by the second fraction of vapor effluent permits selectivity of bromination in the first reactor 230 to be controlled in addition to moderating the temperature in second reactor 234. In accordance with the embodiment illustrated in
In shift reactor 410, a significant portion of the di and tri brominated alkanes that are present in the alkyl bromides contained in the effluent from first reactor 230 may be selectively converted upon reaction with C2-C5 hydrocarbons to mono brominated alkanes. As an example, where C3 and di methylbromide are the reactants, it is believed that the conversion occurs in accordance with the following general reaction:
C3H8+CH2Br2→CH2Br+C3H7Br
Although this reaction may proceed thermally without a catalyst, it has been determined that such thermal reaction requires unacceptably long residence time within shift reactor 410 and does not achieve satisfactory conversions, thus it is preferred that shift reactor 410 contain a bed 412 of suitable catalyst selected as set forth above with respect to
A high selectivity to mono brominated alkanes in the stream introduced into second reactor 234 in accordance with the embodiment of
Although the embodiment of
Another embodiment of the processes of the present invention illustrated in
While the shift reactor has been described above and illustrated in
To facilitate a better understanding of the present invention, the following examples of certain aspects of some embodiments are given. The following examples should not be read or construed in any manner to limit, or define, the entire scope of the invention.
A mixture of methane and vaporized bromine at various mixture ratios is flowed vertically upward through a un-packed tubular reactor which is externally heated in three zones using electrical heating elements. The top (outlet) zone is maintained at an average temperature of about 494° C., the middle zone is maintained at an average temperature of about 450° C. and the inlet (preheat) zone is operated at various temperatures over the range of about 150° C. to about 300° C. Reaction residence times ranged from about 2.0 to 4.5 seconds. As depicted in
The processes of the present invention are less expensive than conventional processes since the processes of the present invention operate at low pressures in the range of about 1 bar to about 30 bar and at relatively low temperatures in the range of about 20° C. to about 600° C. for the gas phase, and preferably about 200° C. to about 180° C. for the liquid phase. These operating conditions permit the use of less expensive equipment of relatively simple design that are constructed from readily available metal alloys or glass-lined equipment for the gas phase and polymer-lined or glass-lined vessels, piping and pumps for the liquid phase. The processes of the present invention are also more efficient because less energy is required for operation and the production of excessive carbon dioxide as an unwanted byproduct is minimized. The reactors and process equipment utilized in the processes of the present invention may be of any suitable design as will be evident to a skilled artisan.
The processes of the present invention are capable of directly producing higher molecular weight hydrocarbons containing various molecular-weight components in the liquefied petroleum gas (LPG), olefin and motor gasoline fuels range that have substantial aromatic content thereby significantly increasing the octane value of the gasoline-range fuel components. These higher molecular weight hydrocarbons may be used directly as a product, as an intermediate product and/or as a feedstock for further processing depending upon the particular catalyst employed in and the operating parameters of the process. For example, the higher molecular weight hydrocarbons obtained by the processes of the present invention may be used directly as a motor gasoline fuel having a substantial aromatic content, as a fuel blending stock or as feedstock for further processing.
Where olefins are produced by the processes of the present invention, such olefins may be used as feed to a process for producing polyolefins.
While the foregoing preferred embodiments of the invention have been described and shown, it is understood that the alternatives and modifications, such as those suggested and others, may be made thereto and fall within the scope of the invention.
This application is a continuation-in-part of copending U.S. patent application Ser. No. 12/112,926 flied Apr. 30, 2008 and entitled “Process for Converting Gaseous Alkanes to Olefins” which is a continuation of U.S. patent application Ser. No. 11/254,438 filed on Oct. 19, 2005 now abandoned and entitled “Process for Converting Gaseous Alkanes to Olefins,” which is a continuation-in-part of Ser. No. 11/101,886 filed Apr. 8, 2005 U.S. Pat. No. 7,348,464 issued on Mar. 25, 2008 and entitled “Process for Converting Gaseous Alkanes to Liquid Hydrocarbons,” which is a continuation-in-part of Ser. No. 10/826,885 filed Apr. 16, 2004 U.S. Pat. No. 7,244,867 issued on Jul. 17, 2007 and entitled “Process for Converting Gaseous Alkanes to Liquid Hydrocarbons”.
| Number | Name | Date | Kind |
|---|---|---|---|
| 2168260 | Heisel et al. | Aug 1939 | A |
| 2246082 | Vaughan et al. | Jun 1941 | A |
| 2488083 | Gorin et al. | Nov 1949 | A |
| 2677598 | Crummett et al. | May 1954 | A |
| 2941014 | Rothweiler et al. | Jun 1960 | A |
| 3076784 | Schulte-Huermann et al. | Feb 1963 | A |
| 3172915 | Borkowski et al. | Mar 1965 | A |
| 3246043 | Rosset et al. | Apr 1966 | A |
| 3273964 | Rosset | Sep 1966 | A |
| 3294846 | Livak et al. | Dec 1966 | A |
| 3310380 | Lester | Mar 1967 | A |
| 3346340 | Louvar et al. | Oct 1967 | A |
| 3353916 | Lester | Nov 1967 | A |
| 3353919 | Stockman | Nov 1967 | A |
| 3496242 | Berkowitz et al. | Feb 1970 | A |
| 3562321 | Borkowski et al. | Feb 1971 | A |
| 3598876 | Bloch | Aug 1971 | A |
| 3657367 | Blake et al. | Apr 1972 | A |
| 3670037 | Dugan | Jun 1972 | A |
| 3673264 | Kuhn | Jun 1972 | A |
| 3679758 | Schneider | Jul 1972 | A |
| 3702886 | Argauer et al. | Nov 1972 | A |
| 3705196 | Turner | Dec 1972 | A |
| 3799997 | Schmerling | Mar 1974 | A |
| 3865886 | Schindler et al. | Feb 1975 | A |
| 3876715 | McNulty et al. | Apr 1975 | A |
| 3879473 | Stapp | Apr 1975 | A |
| 3879480 | Riegel et al. | Apr 1975 | A |
| 3883651 | Woitun et al. | May 1975 | A |
| 3886287 | Kobayashi et al. | May 1975 | A |
| 3894103 | Chang et al. | Jul 1975 | A |
| 3894104 | Chang et al. | Jul 1975 | A |
| 3894105 | Chang et al. | Jul 1975 | A |
| 3894107 | Butter et al. | Jul 1975 | A |
| 3907917 | Forth | Sep 1975 | A |
| 3919336 | Kurtz | Nov 1975 | A |
| 3920764 | Riegel et al. | Nov 1975 | A |
| 3923913 | Antonini et al. | Dec 1975 | A |
| 3928483 | Chang et al. | Dec 1975 | A |
| 3965205 | Garwood et al. | Jun 1976 | A |
| 3974062 | Owen et al. | Aug 1976 | A |
| 3987119 | Kurtz et al. | Oct 1976 | A |
| 3992466 | Plank et al. | Nov 1976 | A |
| 4006169 | Anderson et al. | Feb 1977 | A |
| 4011278 | Plank et al. | Mar 1977 | A |
| 4025571 | Lago | May 1977 | A |
| 4025572 | Lago | May 1977 | A |
| 4025575 | Chang et al. | May 1977 | A |
| 4025576 | Chang et al. | May 1977 | A |
| 4035285 | Owen et al. | Jul 1977 | A |
| 4035430 | Dwyer et al. | Jul 1977 | A |
| 4039600 | Chang | Aug 1977 | A |
| 4044061 | Chang et al. | Aug 1977 | A |
| 4046825 | Owen et al. | Sep 1977 | A |
| 4049734 | Garwood et al. | Sep 1977 | A |
| 4052471 | Pearsall | Oct 1977 | A |
| 4052472 | Given et al. | Oct 1977 | A |
| 4058576 | Chang et al. | Nov 1977 | A |
| 4060568 | Rodewald | Nov 1977 | A |
| 4071753 | Fulenwider et al. | Jan 1978 | A |
| 4072733 | Hargis et al. | Feb 1978 | A |
| 4087475 | Jordan | May 1978 | A |
| 4088706 | Kaeding | May 1978 | A |
| 4092368 | Smith | May 1978 | A |
| 4105755 | Darnell et al. | Aug 1978 | A |
| 4110180 | Nidola et al. | Aug 1978 | A |
| 4117251 | Kaufhold et al. | Sep 1978 | A |
| 4129604 | Tsao | Dec 1978 | A |
| 4133838 | Pearson | Jan 1979 | A |
| 4133966 | Pretzer et al. | Jan 1979 | A |
| 4138440 | Chang et al. | Feb 1979 | A |
| 4156698 | Dwyer et al. | May 1979 | A |
| 4169862 | Eden | Oct 1979 | A |
| 4172099 | Severino | Oct 1979 | A |
| 4187255 | Dodd | Feb 1980 | A |
| 4191618 | Coker et al. | Mar 1980 | A |
| 4194990 | Pieters et al. | Mar 1980 | A |
| 4197420 | Ferraris et al. | Apr 1980 | A |
| 4219680 | Konig et al. | Aug 1980 | A |
| 4249031 | Drent et al. | Feb 1981 | A |
| 4270929 | Dang Vu et al. | Jun 1981 | A |
| 4272338 | Lynch et al. | Jun 1981 | A |
| 4282159 | Davidson et al. | Aug 1981 | A |
| 4300005 | Li | Nov 1981 | A |
| 4300009 | Haag et al. | Nov 1981 | A |
| 4301253 | Warren | Nov 1981 | A |
| 4302619 | Gross et al. | Nov 1981 | A |
| 4307261 | Beard, Jr. et al. | Dec 1981 | A |
| 4308403 | Knifton | Dec 1981 | A |
| 4311865 | Chen et al. | Jan 1982 | A |
| 4317800 | Sloterdijk et al. | Mar 1982 | A |
| 4317934 | Seemuth | Mar 1982 | A |
| 4317943 | Knifton | Mar 1982 | A |
| 4320241 | Frankiewicz | Mar 1982 | A |
| 4333852 | Warren | Jun 1982 | A |
| 4347391 | Campbell | Aug 1982 | A |
| 4350511 | Holmes et al. | Sep 1982 | A |
| 4371716 | Paxson et al. | Feb 1983 | A |
| 4373109 | Olah | Feb 1983 | A |
| 4376019 | Gamlen et al. | Mar 1983 | A |
| 4380682 | Leitert et al. | Apr 1983 | A |
| 4384159 | Diesen | May 1983 | A |
| 4389391 | Dunn, Jr. | Jun 1983 | A |
| 4410714 | Apanel | Oct 1983 | A |
| 4412086 | Beard, Jr. et al. | Oct 1983 | A |
| 4418236 | Cornelius et al. | Nov 1983 | A |
| 4431856 | Daviduk et al. | Feb 1984 | A |
| 4433189 | Young | Feb 1984 | A |
| 4433192 | Olah | Feb 1984 | A |
| 4439409 | Puppe et al. | Mar 1984 | A |
| 4440871 | Lok et al. | Apr 1984 | A |
| 4443620 | Gelbein et al. | Apr 1984 | A |
| 4462814 | Holmes et al. | Jul 1984 | A |
| 4465884 | Degnan et al. | Aug 1984 | A |
| 4465893 | Olah | Aug 1984 | A |
| 4467130 | Olah | Aug 1984 | A |
| 4467133 | Chang et al. | Aug 1984 | A |
| 4489210 | Judat et al. | Dec 1984 | A |
| 4489211 | Ogura et al. | Dec 1984 | A |
| 4492657 | Heiss | Jan 1985 | A |
| 4496752 | Gelbein et al. | Jan 1985 | A |
| 4497967 | Wan | Feb 1985 | A |
| 4499314 | Seddon et al. | Feb 1985 | A |
| 4506105 | Kaufhold | Mar 1985 | A |
| 4509955 | Hayashi | Apr 1985 | A |
| 4513092 | Chu et al. | Apr 1985 | A |
| 4513164 | Olah | Apr 1985 | A |
| 4523040 | Olah | Jun 1985 | A |
| 4524227 | Fowles et al. | Jun 1985 | A |
| 4524228 | Fowles et al. | Jun 1985 | A |
| 4524231 | Fowles et al. | Jun 1985 | A |
| 4538014 | Miale et al. | Aug 1985 | A |
| 4538015 | Miale et al. | Aug 1985 | A |
| 4540826 | Banasiak et al. | Sep 1985 | A |
| 4543434 | Chang | Sep 1985 | A |
| 4544781 | Chao et al. | Oct 1985 | A |
| 4547612 | Tabak | Oct 1985 | A |
| 4550217 | Graziani et al. | Oct 1985 | A |
| 4550218 | Chu | Oct 1985 | A |
| 4568660 | Klosiewicz | Feb 1986 | A |
| 4579977 | Drake | Apr 1986 | A |
| 4579992 | Kaufhold et al. | Apr 1986 | A |
| 4579996 | Font Freide et al. | Apr 1986 | A |
| 4587375 | Debras et al. | May 1986 | A |
| 4588835 | Torii et al. | May 1986 | A |
| 4590310 | Townsend et al. | May 1986 | A |
| 4599474 | Devries et al. | Jul 1986 | A |
| 4605796 | Isogai et al. | Aug 1986 | A |
| 4605803 | Chang et al. | Aug 1986 | A |
| 4621161 | Shihabi | Nov 1986 | A |
| 4621164 | Chang et al. | Nov 1986 | A |
| 4633027 | Owen et al. | Dec 1986 | A |
| 4634800 | Withers, Jr. et al. | Jan 1987 | A |
| 4642403 | Hyde et al. | Feb 1987 | A |
| 4642404 | Shihabi | Feb 1987 | A |
| 4652688 | Brophy et al. | Mar 1987 | A |
| 4654449 | Chang et al. | Mar 1987 | A |
| 4655893 | Beale | Apr 1987 | A |
| 4658073 | Tabak | Apr 1987 | A |
| 4658077 | Kolts et al. | Apr 1987 | A |
| 4665259 | Brazdil et al. | May 1987 | A |
| 4665267 | Barri | May 1987 | A |
| 4665270 | Brophy et al. | May 1987 | A |
| 4675410 | Feitler et al. | Jun 1987 | A |
| 4690903 | Chen et al. | Sep 1987 | A |
| 4695663 | Hall et al. | Sep 1987 | A |
| 4696985 | Martin | Sep 1987 | A |
| 4704488 | Devries et al. | Nov 1987 | A |
| 4704493 | Devires et al. | Nov 1987 | A |
| 4709108 | Devries et al. | Nov 1987 | A |
| 4720600 | Beech, Jr. et al. | Jan 1988 | A |
| 4720602 | Chu | Jan 1988 | A |
| 4724275 | Hinnenkamp et al. | Feb 1988 | A |
| 4735747 | Ollivier et al. | Apr 1988 | A |
| 4737594 | Olah | Apr 1988 | A |
| 4748013 | Saito et al. | May 1988 | A |
| 4769504 | Noceti et al. | Sep 1988 | A |
| 4774216 | Kolts et al. | Sep 1988 | A |
| 4775462 | Imai et al. | Oct 1988 | A |
| 4777321 | Harandi et al. | Oct 1988 | A |
| 4781733 | Babcock et al. | Nov 1988 | A |
| 4783566 | Kocal et al. | Nov 1988 | A |
| 4788369 | Marsh et al. | Nov 1988 | A |
| 4788377 | Chang et al. | Nov 1988 | A |
| 4792642 | Rule et al. | Dec 1988 | A |
| 4795732 | Barri | Jan 1989 | A |
| 4795737 | Rule et al. | Jan 1989 | A |
| 4795843 | Imai et al. | Jan 1989 | A |
| 4795848 | Teller et al. | Jan 1989 | A |
| 4804797 | Minet et al. | Feb 1989 | A |
| 4804800 | Bortinger et al. | Feb 1989 | A |
| 4808763 | Shum | Feb 1989 | A |
| 4814527 | Diesen | Mar 1989 | A |
| 4814532 | Yoshida et al. | Mar 1989 | A |
| 4814535 | Yurchak | Mar 1989 | A |
| 4814536 | Yuchak | Mar 1989 | A |
| 4849562 | Buhs et al. | Jul 1989 | A |
| 4849573 | Kaefing | Jul 1989 | A |
| 4851602 | Harandi et al. | Jul 1989 | A |
| 4851606 | Ragonese et al. | Jul 1989 | A |
| 4886925 | Harandi | Dec 1989 | A |
| 4886932 | Leyshon | Dec 1989 | A |
| 4891463 | Chu | Jan 1990 | A |
| 4895995 | James, Jr. et al. | Jan 1990 | A |
| 4899000 | Stauffer | Feb 1990 | A |
| 4899001 | Kalnes et al. | Feb 1990 | A |
| 4899002 | Harandi et al. | Feb 1990 | A |
| 4902842 | Kalnes et al. | Feb 1990 | A |
| 4925995 | Robschlager | May 1990 | A |
| 4929781 | James, Jr. et al. | May 1990 | A |
| 4939310 | Wade | Jul 1990 | A |
| 4939311 | Washecheck et al. | Jul 1990 | A |
| 4945175 | Hobbs et al. | Jul 1990 | A |
| 4950811 | Doussain et al. | Aug 1990 | A |
| 4950822 | Dileo et al. | Aug 1990 | A |
| 4956521 | Volles | Sep 1990 | A |
| 4962252 | Wade | Oct 1990 | A |
| 4973776 | Allenger et al. | Nov 1990 | A |
| 4973786 | Karra | Nov 1990 | A |
| 4982024 | Lin et al. | Jan 1991 | A |
| 4982041 | Campbell | Jan 1991 | A |
| 4988660 | Campbell | Jan 1991 | A |
| 4990696 | Stauffer | Feb 1991 | A |
| 4990711 | Chen et al. | Feb 1991 | A |
| 5001293 | Nubel et al. | Mar 1991 | A |
| 5004847 | Beaver et al. | Apr 1991 | A |
| 5013424 | James, Jr. et al. | May 1991 | A |
| 5013793 | Wang et al. | May 1991 | A |
| 5019652 | Taylor et al. | May 1991 | A |
| 5026934 | Bains et al. | Jun 1991 | A |
| 5026937 | Bricker | Jun 1991 | A |
| 5026944 | Allenger et al. | Jun 1991 | A |
| 5034566 | Ishino et al. | Jul 1991 | A |
| 5043502 | Martindale et al. | Aug 1991 | A |
| 5055235 | Brackenridge et al. | Oct 1991 | A |
| 5055633 | Volles | Oct 1991 | A |
| 5055634 | Volles | Oct 1991 | A |
| 5059744 | Harandi et al. | Oct 1991 | A |
| 5068478 | Miller et al. | Nov 1991 | A |
| 5071449 | Sircar | Dec 1991 | A |
| 5071815 | Wallace et al. | Dec 1991 | A |
| 5073656 | Chafin et al. | Dec 1991 | A |
| 5073657 | Warren | Dec 1991 | A |
| 5082473 | Keefer | Jan 1992 | A |
| 5082816 | Teller et al. | Jan 1992 | A |
| 5085674 | Leavitt | Feb 1992 | A |
| 5087779 | Nubel et al. | Feb 1992 | A |
| 5087786 | Nubel et al. | Feb 1992 | A |
| 5087787 | Kimble et al. | Feb 1992 | A |
| 5093542 | Gaffney | Mar 1992 | A |
| 5096469 | Keefer | Mar 1992 | A |
| 5097083 | Stauffer | Mar 1992 | A |
| 5099084 | Stauffer | Mar 1992 | A |
| 5105045 | Kimble et al. | Apr 1992 | A |
| 5105046 | Washecheck | Apr 1992 | A |
| 5107032 | Erb et al. | Apr 1992 | A |
| 5107051 | Pannell | Apr 1992 | A |
| 5107061 | Ou et al. | Apr 1992 | A |
| 5108579 | Casci | Apr 1992 | A |
| 5118899 | Kimble et al. | Jun 1992 | A |
| 5120332 | Wells | Jun 1992 | A |
| 5132343 | Zwecker et al. | Jul 1992 | A |
| 5138112 | Gosling et al. | Aug 1992 | A |
| 5139991 | Taylor et al. | Aug 1992 | A |
| 5146027 | Gaffney | Sep 1992 | A |
| 5157189 | Karra | Oct 1992 | A |
| 5160502 | Kimble et al. | Nov 1992 | A |
| 5166452 | Gradl et al. | Nov 1992 | A |
| 5175382 | Hebgen et al. | Dec 1992 | A |
| 5178748 | Casci et al. | Jan 1993 | A |
| 5185479 | Stauffer | Feb 1993 | A |
| 5188725 | Harandi | Feb 1993 | A |
| 5191142 | Marshall et al. | Mar 1993 | A |
| 5194244 | Brownscombe et al. | Mar 1993 | A |
| 5202506 | Kirchner et al. | Apr 1993 | A |
| 5202511 | Salinas, III et al. | Apr 1993 | A |
| 5210357 | Kolts et al. | May 1993 | A |
| 5215648 | Zones et al. | Jun 1993 | A |
| 5223471 | Washecheck | Jun 1993 | A |
| 5228888 | Gmelin et al. | Jul 1993 | A |
| 5233113 | Periana et al. | Aug 1993 | A |
| 5237115 | Makovec et al. | Aug 1993 | A |
| 5243098 | Miller et al. | Sep 1993 | A |
| 5243114 | Johnson et al. | Sep 1993 | A |
| 5245109 | Kaminsky et al. | Sep 1993 | A |
| 5254772 | Dukat et al. | Oct 1993 | A |
| 5254790 | Thomas et al. | Oct 1993 | A |
| 5264635 | Le et al. | Nov 1993 | A |
| 5268518 | West et al. | Dec 1993 | A |
| 5276226 | Horvath et al. | Jan 1994 | A |
| 5276240 | Timmons et al. | Jan 1994 | A |
| 5276242 | Wu | Jan 1994 | A |
| 5284990 | Peterson et al. | Feb 1994 | A |
| 5300126 | Brown et al. | Apr 1994 | A |
| 5306855 | Periana et al. | Apr 1994 | A |
| 5316995 | Kaminsky et al. | May 1994 | A |
| 5319132 | Ozawa et al. | Jun 1994 | A |
| 5334777 | Miller et al. | Aug 1994 | A |
| 5345021 | Casci et al. | Sep 1994 | A |
| 5354916 | Horvath et al. | Oct 1994 | A |
| 5354931 | Jan et al. | Oct 1994 | A |
| 5366949 | Schubert | Nov 1994 | A |
| 5371313 | Ostrowicki | Dec 1994 | A |
| 5382704 | Krespan et al. | Jan 1995 | A |
| 5382743 | Beech, Jr. et al. | Jan 1995 | A |
| 5382744 | Abbott et al. | Jan 1995 | A |
| 5385650 | Howarth et al. | Jan 1995 | A |
| 5385718 | Casci et al. | Jan 1995 | A |
| 5395981 | Marker | Mar 1995 | A |
| 5399258 | Fletcher et al. | Mar 1995 | A |
| 5401890 | Parks | Mar 1995 | A |
| 5401894 | Brasier et al. | Mar 1995 | A |
| 5406017 | Withers, Jr. | Apr 1995 | A |
| 5414173 | Garces et al. | May 1995 | A |
| 5430210 | Grasselli et al. | Jul 1995 | A |
| 5430214 | Smith et al. | Jul 1995 | A |
| 5430219 | Sanfilippo et al. | Jul 1995 | A |
| 5436378 | Masini et al. | Jul 1995 | A |
| 5444168 | Brown | Aug 1995 | A |
| 5446234 | Casci et al. | Aug 1995 | A |
| 5453557 | Harley et al. | Sep 1995 | A |
| 5456822 | Marcilly et al. | Oct 1995 | A |
| 5457255 | Kumata et al. | Oct 1995 | A |
| 5464799 | Casci et al. | Nov 1995 | A |
| 5465699 | Voigt | Nov 1995 | A |
| 5470377 | Whitlock | Nov 1995 | A |
| 5480629 | Thompson et al. | Jan 1996 | A |
| 5486627 | Quarderer, Jr. et al. | Jan 1996 | A |
| 5489719 | Le et al. | Feb 1996 | A |
| 5489727 | Randolph et al. | Feb 1996 | A |
| 5500297 | Thompson et al. | Mar 1996 | A |
| 5510525 | Sen et al. | Apr 1996 | A |
| 5523503 | Funk et al. | Jun 1996 | A |
| 5525230 | Wrigley et al. | Jun 1996 | A |
| 5538540 | Whitlock | Jul 1996 | A |
| 5563313 | Chung et al. | Oct 1996 | A |
| 5565092 | Pannell et al. | Oct 1996 | A |
| 5565616 | Li et al. | Oct 1996 | A |
| 5571762 | Clerici et al. | Nov 1996 | A |
| 5571885 | Chung et al. | Nov 1996 | A |
| 5599381 | Whitlock | Feb 1997 | A |
| 5600043 | Johnston et al. | Feb 1997 | A |
| 5600045 | Van Der Aalst et al. | Feb 1997 | A |
| 5609654 | Le et al. | Mar 1997 | A |
| 5633419 | Spencer et al. | May 1997 | A |
| 5639930 | Penick | Jun 1997 | A |
| 5653956 | Zones | Aug 1997 | A |
| 5656149 | Zones et al. | Aug 1997 | A |
| 5661097 | Spencer et al. | Aug 1997 | A |
| 5663465 | Clegg et al. | Sep 1997 | A |
| 5663474 | Pham et al. | Sep 1997 | A |
| 5675046 | Ohno et al. | Oct 1997 | A |
| 5675052 | Menon et al. | Oct 1997 | A |
| 5679134 | Brugerolle et al. | Oct 1997 | A |
| 5679879 | Mercier et al. | Oct 1997 | A |
| 5684213 | Nemphos et al. | Nov 1997 | A |
| 5693191 | Pividal et al. | Dec 1997 | A |
| 5695890 | Thompson et al. | Dec 1997 | A |
| 5698747 | Godwin et al. | Dec 1997 | A |
| 5705712 | Frey et al. | Jan 1998 | A |
| 5705728 | Viswanathan et al. | Jan 1998 | A |
| 5705729 | Huang | Jan 1998 | A |
| 5708246 | Camaioni et al. | Jan 1998 | A |
| 5720858 | Noceti et al. | Feb 1998 | A |
| 5728897 | Buysch et al. | Mar 1998 | A |
| 5728905 | Clegg et al. | Mar 1998 | A |
| 5734073 | Chambers et al. | Mar 1998 | A |
| 5741949 | Mack | Apr 1998 | A |
| 5744669 | Kalnes et al. | Apr 1998 | A |
| 5750801 | Buysch et al. | May 1998 | A |
| 5770175 | Zones | Jun 1998 | A |
| 5776871 | Cothran et al. | Jul 1998 | A |
| 5780703 | Chang et al. | Jul 1998 | A |
| 5798314 | Spencer et al. | Aug 1998 | A |
| 5814715 | Chen et al. | Sep 1998 | A |
| 5817904 | Vic et al. | Oct 1998 | A |
| 5821394 | Schoebrechts et al. | Oct 1998 | A |
| 5847224 | Koga et al. | Dec 1998 | A |
| 5849978 | Benazzi et al. | Dec 1998 | A |
| 5866735 | Cheung et al. | Feb 1999 | A |
| 5895831 | Brasier et al. | Apr 1999 | A |
| 5898086 | Harris | Apr 1999 | A |
| 5905169 | Jacobson | May 1999 | A |
| 5906892 | Thompson et al. | May 1999 | A |
| 5908963 | Voss et al. | Jun 1999 | A |
| 5928488 | Newman | Jul 1999 | A |
| 5952538 | Vaughn et al. | Sep 1999 | A |
| 5959170 | Withers, Jr. et al. | Sep 1999 | A |
| 5968236 | Bassine | Oct 1999 | A |
| 5969195 | Stabel et al. | Oct 1999 | A |
| 5977402 | Sekiguchi et al. | Nov 1999 | A |
| 5983476 | Eshelman et al. | Nov 1999 | A |
| 5986158 | Van Broekhoven et al. | Nov 1999 | A |
| 5994604 | Reagen et al. | Nov 1999 | A |
| 5998679 | Miller | Dec 1999 | A |
| 5998686 | Clem et al. | Dec 1999 | A |
| 6002059 | Hellring et al. | Dec 1999 | A |
| 6015867 | Fushimi et al. | Jan 2000 | A |
| 6018088 | Olah | Jan 2000 | A |
| 6022929 | Chen et al. | Feb 2000 | A |
| 6034288 | Scott et al. | Mar 2000 | A |
| 6056804 | Keefer et al. | May 2000 | A |
| 6068679 | Zheng | May 2000 | A |
| 6072091 | Cosyns et al. | Jun 2000 | A |
| 6087294 | Klabunde et al. | Jul 2000 | A |
| 6090312 | Ziaka et al. | Jul 2000 | A |
| 6093306 | Hanrahan et al. | Jul 2000 | A |
| 6096932 | Subramanian | Aug 2000 | A |
| 6096933 | Cheung et al. | Aug 2000 | A |
| 6103215 | Zones et al. | Aug 2000 | A |
| 6107561 | Thompson | Aug 2000 | A |
| 6117371 | Mack | Sep 2000 | A |
| 6124514 | Emmrich et al. | Sep 2000 | A |
| 6127588 | Kimble et al. | Oct 2000 | A |
| 6130260 | Hall et al. | Oct 2000 | A |
| 6143939 | Farcasiu et al. | Nov 2000 | A |
| 6169218 | Hearn et al. | Jan 2001 | B1 |
| 6180841 | Fatutto et al. | Jan 2001 | B1 |
| 6187871 | Thompson et al. | Feb 2001 | B1 |
| 6187983 | Sun | Feb 2001 | B1 |
| 6203712 | Bronner et al. | Mar 2001 | B1 |
| 6207864 | Henningsen et al. | Mar 2001 | B1 |
| 6225517 | Nascimento et al. | May 2001 | B1 |
| 6248218 | Linkous et al. | Jun 2001 | B1 |
| 6265505 | McConville et al. | Jul 2001 | B1 |
| 6281405 | Davis et al. | Aug 2001 | B1 |
| 6320085 | Arvai et al. | Nov 2001 | B1 |
| 6337063 | Rouleau et al. | Jan 2002 | B1 |
| 6342200 | Rouleau et al. | Jan 2002 | B1 |
| 6368490 | Gestermann | Apr 2002 | B1 |
| 6369283 | Guram et al. | Apr 2002 | B1 |
| 6372949 | Brown et al. | Apr 2002 | B1 |
| 6376731 | Evans et al. | Apr 2002 | B1 |
| 6380328 | McConville et al. | Apr 2002 | B1 |
| 6380423 | Banning et al. | Apr 2002 | B2 |
| 6380444 | Bjerrum et al. | Apr 2002 | B1 |
| 6395945 | Randolph | May 2002 | B1 |
| 6403840 | Zhou et al. | Jun 2002 | B1 |
| 6406523 | Connor et al. | Jun 2002 | B1 |
| 6423211 | Randolph et al. | Jul 2002 | B1 |
| 6426441 | Randolph et al. | Jul 2002 | B1 |
| 6426442 | Ichikawa et al. | Jul 2002 | B1 |
| 6452058 | Schweizer et al. | Sep 2002 | B1 |
| 6455650 | Lipian et al. | Sep 2002 | B1 |
| 6462243 | Zhou et al. | Oct 2002 | B1 |
| 6465696 | Zhou et al. | Oct 2002 | B1 |
| 6465699 | Grosso | Oct 2002 | B1 |
| 6472345 | Hintermann et al. | Oct 2002 | B2 |
| 6472572 | Zhou et al. | Oct 2002 | B1 |
| 6475463 | Elomari et al. | Nov 2002 | B1 |
| 6475464 | Rouleau et al. | Nov 2002 | B1 |
| 6479705 | Murata et al. | Nov 2002 | B2 |
| 6482997 | Petit-Clair et al. | Nov 2002 | B2 |
| 6486368 | Zhou et al. | Nov 2002 | B1 |
| 6495484 | Holtcamp | Dec 2002 | B1 |
| 6509485 | Mul et al. | Jan 2003 | B2 |
| 6511526 | Jagger et al. | Jan 2003 | B2 |
| 6514319 | Keefer et al. | Feb 2003 | B2 |
| 6518474 | Sanderson et al. | Feb 2003 | B1 |
| 6518476 | Culp et al. | Feb 2003 | B1 |
| 6525228 | Chauvin et al. | Feb 2003 | B2 |
| 6525230 | Grosso | Feb 2003 | B2 |
| 6528693 | Gandy et al. | Mar 2003 | B1 |
| 6538162 | Chang et al. | Mar 2003 | B2 |
| 6540905 | Elomari | Apr 2003 | B1 |
| 6545191 | Stauffer | Apr 2003 | B1 |
| 6547958 | Elomari | Apr 2003 | B1 |
| 6548040 | Rouleau et al. | Apr 2003 | B1 |
| 6552241 | Randolph et al. | Apr 2003 | B1 |
| 6566572 | Okamoto et al. | May 2003 | B2 |
| 6572829 | Linkous et al. | Jun 2003 | B2 |
| 6585953 | Roberts et al. | Jul 2003 | B2 |
| 6616830 | Elomari | Sep 2003 | B2 |
| 6620757 | McConville et al. | Sep 2003 | B2 |
| 6632971 | Brown et al. | Oct 2003 | B2 |
| 6635793 | Mul et al. | Oct 2003 | B2 |
| 6641644 | Jagger et al. | Nov 2003 | B2 |
| 6646102 | Boriack et al. | Nov 2003 | B2 |
| 6669846 | Perriello | Dec 2003 | B2 |
| 6672572 | Werlen | Jan 2004 | B2 |
| 6679986 | Da Silva et al. | Jan 2004 | B1 |
| 6680415 | Gulotty, Jr. et al. | Jan 2004 | B1 |
| 6692626 | Keefer et al. | Feb 2004 | B2 |
| 6692723 | Rouleau et al. | Feb 2004 | B2 |
| 6710213 | Aoki et al. | Mar 2004 | B2 |
| 6713087 | Tracy et al. | Mar 2004 | B2 |
| 6713655 | Yilmaz et al. | Mar 2004 | B2 |
| RE38493 | Keefer et al. | Apr 2004 | E |
| 6723808 | Holtcamp | Apr 2004 | B2 |
| 6727400 | Messier et al. | Apr 2004 | B2 |
| 6740146 | Simonds | May 2004 | B2 |
| 6753390 | Ehrman et al. | Jun 2004 | B2 |
| 6765120 | Weber et al. | Jul 2004 | B2 |
| 6797845 | Hickman et al. | Sep 2004 | B1 |
| 6797851 | Martens et al. | Sep 2004 | B2 |
| 6821924 | Gulotty, Jr. et al. | Nov 2004 | B2 |
| 6822123 | Stauffer | Nov 2004 | B2 |
| 6822125 | Lee et al. | Nov 2004 | B2 |
| 6825307 | Goodall | Nov 2004 | B2 |
| 6825383 | Dewkar et al. | Nov 2004 | B1 |
| 6831032 | Spaether | Dec 2004 | B2 |
| 6838576 | Wicki et al. | Jan 2005 | B1 |
| 6841063 | Elomari | Jan 2005 | B2 |
| 6852896 | Stauffer | Feb 2005 | B2 |
| 6866950 | Connor et al. | Mar 2005 | B2 |
| 6869903 | Matsunaga | Mar 2005 | B2 |
| 6875339 | Rangarajan et al. | Apr 2005 | B2 |
| 6878853 | Tanaka et al. | Apr 2005 | B2 |
| 6888013 | Paparatto et al. | May 2005 | B2 |
| 6900363 | Harth et al. | May 2005 | B2 |
| 6902602 | Keefer et al. | Jun 2005 | B2 |
| 6903171 | Rhodes et al. | Jun 2005 | B2 |
| 6909024 | Jones et al. | Jun 2005 | B1 |
| 6921597 | Keefer et al. | Jul 2005 | B2 |
| 6933417 | Henley et al. | Aug 2005 | B1 |
| 6946566 | Yaegashi et al. | Sep 2005 | B2 |
| 6953868 | Boaen et al. | Oct 2005 | B2 |
| 6953873 | Cortright et al. | Oct 2005 | B2 |
| 6956140 | Ehrenfeld | Oct 2005 | B2 |
| 6958306 | Holtcamp | Oct 2005 | B2 |
| 6984763 | Schweizer et al. | Jan 2006 | B2 |
| 7001872 | Pyecroft et al. | Feb 2006 | B2 |
| 7002050 | Fernandez et al. | Feb 2006 | B2 |
| 7011811 | Elomari | Mar 2006 | B2 |
| 7019182 | Grosso | Mar 2006 | B2 |
| 7026145 | Mizrahi et al. | Apr 2006 | B2 |
| 7026519 | Fernandez et al. | Apr 2006 | B2 |
| 7037358 | Babicki et al. | May 2006 | B2 |
| 7045670 | Johnson et al. | May 2006 | B2 |
| 7049388 | Boriack et al. | May 2006 | B2 |
| 7053252 | Boussand et al. | May 2006 | B2 |
| 7057081 | Allison et al. | Jun 2006 | B2 |
| 7060865 | Ding et al. | Jun 2006 | B2 |
| 7064238 | Waycuilis | Jun 2006 | B2 |
| 7064240 | Ohno et al. | Jun 2006 | B2 |
| 7067448 | Weitkamp et al. | Jun 2006 | B1 |
| 7083714 | Elomari | Aug 2006 | B2 |
| 7084308 | Stauffer | Aug 2006 | B1 |
| 7091270 | Zilberman et al. | Aug 2006 | B2 |
| 7091387 | Fong et al. | Aug 2006 | B2 |
| 7091391 | Stauffer | Aug 2006 | B2 |
| 7094936 | Owens et al. | Aug 2006 | B1 |
| 7098371 | Mack et al. | Aug 2006 | B2 |
| 7105710 | Boons et al. | Sep 2006 | B2 |
| 7138534 | Forlin et al. | Nov 2006 | B2 |
| 7141708 | Marsella et al. | Nov 2006 | B2 |
| 7145045 | Harmsen et al. | Dec 2006 | B2 |
| 7148356 | Smith, III et al. | Dec 2006 | B2 |
| 7148390 | Zhou et al. | Dec 2006 | B2 |
| 7151199 | Martens et al. | Dec 2006 | B2 |
| 7161050 | Sherman et al. | Jan 2007 | B2 |
| 7169730 | Ma et al. | Jan 2007 | B2 |
| 7176340 | Van Broekhoven et al. | Feb 2007 | B2 |
| 7176342 | Bellussi et al. | Feb 2007 | B2 |
| 7182871 | Perriello | Feb 2007 | B2 |
| 7193093 | Murray et al. | Mar 2007 | B2 |
| 7196239 | Van Egmond et al. | Mar 2007 | B2 |
| 7199083 | Zevallos | Apr 2007 | B2 |
| 7199255 | Murray et al. | Apr 2007 | B2 |
| 7208641 | Nagasaki et al. | Apr 2007 | B2 |
| 7214750 | McDonald et al. | May 2007 | B2 |
| 7220391 | Huang et al. | May 2007 | B1 |
| 7226569 | Elomari | Jun 2007 | B2 |
| 7226576 | Elomari | Jun 2007 | B2 |
| 7230150 | Grosso et al. | Jun 2007 | B2 |
| 7230151 | Martens et al. | Jun 2007 | B2 |
| 7232872 | Shaffer et al. | Jun 2007 | B2 |
| 7238846 | Janssen et al. | Jul 2007 | B2 |
| 7244795 | Agapiou et al. | Jul 2007 | B2 |
| 7244867 | Waycuilis | Jul 2007 | B2 |
| 7250107 | Benazzi et al. | Jul 2007 | B2 |
| 7250542 | Smith, Jr. et al. | Jul 2007 | B2 |
| 7252920 | Kurokawa et al. | Aug 2007 | B2 |
| 7253327 | Janssens et al. | Aug 2007 | B2 |
| 7253328 | Stauffer | Aug 2007 | B2 |
| 7265193 | Weng et al. | Sep 2007 | B2 |
| 7267758 | Benazzi et al. | Sep 2007 | B2 |
| 7268263 | Frey et al. | Sep 2007 | B1 |
| 7271303 | Sechrist et al. | Sep 2007 | B1 |
| 7273957 | Bakshi et al. | Sep 2007 | B2 |
| 7282603 | Richards | Oct 2007 | B2 |
| 7285698 | Liu et al. | Oct 2007 | B2 |
| 7304193 | Frey et al. | Dec 2007 | B1 |
| 7342144 | Kaizik et al. | Mar 2008 | B2 |
| 7348295 | Zones et al. | Mar 2008 | B2 |
| 7348464 | Waycuilis | Mar 2008 | B2 |
| 7357904 | Zones et al. | Apr 2008 | B2 |
| 7361794 | Grosso | Apr 2008 | B2 |
| 7390395 | Elomari | Jun 2008 | B2 |
| 20020102672 | Mizrahi | Aug 2002 | A1 |
| 20020193649 | O'Rear et al. | Dec 2002 | A1 |
| 20020198416 | Zhou et al. | Dec 2002 | A1 |
| 20030004380 | Grumann | Jan 2003 | A1 |
| 20030065239 | Zhu | Apr 2003 | A1 |
| 20030069452 | Sherman et al. | Apr 2003 | A1 |
| 20030078456 | Yilmaz et al. | Apr 2003 | A1 |
| 20030120121 | Sherman et al. | Jun 2003 | A1 |
| 20030125589 | Grosso | Jul 2003 | A1 |
| 20030166973 | Zhou et al. | Sep 2003 | A1 |
| 20040006246 | Sherman et al. | Jan 2004 | A1 |
| 20040062705 | Leduc | Apr 2004 | A1 |
| 20040152929 | Clarke | Aug 2004 | A1 |
| 20040158107 | Aoki | Aug 2004 | A1 |
| 20040158108 | Snoble | Aug 2004 | A1 |
| 20040171779 | Matyjaszewski et al. | Sep 2004 | A1 |
| 20040187684 | Elomari | Sep 2004 | A1 |
| 20040188324 | Elomari | Sep 2004 | A1 |
| 20040220433 | Van Der Heide | Nov 2004 | A1 |
| 20050027084 | Clarke | Feb 2005 | A1 |
| 20050038310 | Lorkovic et al. | Feb 2005 | A1 |
| 20050042159 | Elomari | Feb 2005 | A1 |
| 20050047927 | Lee et al. | Mar 2005 | A1 |
| 20050148805 | Jones | Jul 2005 | A1 |
| 20050171393 | Lorkovic | Aug 2005 | A1 |
| 20050192468 | Sherman et al. | Sep 2005 | A1 |
| 20050215837 | Hoffpauir | Sep 2005 | A1 |
| 20050234276 | Waycuilis | Oct 2005 | A1 |
| 20050245771 | Fong et al. | Nov 2005 | A1 |
| 20050245772 | Fong | Nov 2005 | A1 |
| 20050245777 | Fong | Nov 2005 | A1 |
| 20050267224 | Herling | Dec 2005 | A1 |
| 20060025617 | Begley | Feb 2006 | A1 |
| 20060100469 | Waycuilis | May 2006 | A1 |
| 20060135823 | Jun | Jun 2006 | A1 |
| 20060138025 | Zones | Jun 2006 | A1 |
| 20060138026 | Chen | Jun 2006 | A1 |
| 20060149116 | Slaugh | Jul 2006 | A1 |
| 20060229228 | Komon et al. | Oct 2006 | A1 |
| 20060229475 | Weiss et al. | Oct 2006 | A1 |
| 20060270863 | Reiling | Nov 2006 | A1 |
| 20060288690 | Elomari | Dec 2006 | A1 |
| 20070004955 | Kay | Jan 2007 | A1 |
| 20070078285 | Dagle | Apr 2007 | A1 |
| 20070100189 | Stauffer | May 2007 | A1 |
| 20070129584 | Basset | Jun 2007 | A1 |
| 20070142680 | Ayoub | Jun 2007 | A1 |
| 20070148067 | Zones | Jun 2007 | A1 |
| 20070148086 | Zones | Jun 2007 | A1 |
| 20070149778 | Zones | Jun 2007 | A1 |
| 20070149789 | Zones | Jun 2007 | A1 |
| 20070149819 | Zones | Jun 2007 | A1 |
| 20070149824 | Zones | Jun 2007 | A1 |
| 20070149837 | Zones | Jun 2007 | A1 |
| 20070197801 | Bolk | Aug 2007 | A1 |
| 20070197847 | Liu | Aug 2007 | A1 |
| 20070213545 | Bolk | Sep 2007 | A1 |
| 20070238905 | Arredondo | Oct 2007 | A1 |
| 20070238909 | Gadewar et al. | Oct 2007 | A1 |
| 20070276168 | Garel | Nov 2007 | A1 |
| 20070284284 | Zones | Dec 2007 | A1 |
| 20080022717 | Yoshida et al. | Jan 2008 | A1 |
| 20080171898 | Waycuilis | Jul 2008 | A1 |
| 20080183022 | Waycuilis | Jul 2008 | A1 |
| 20080188697 | Lorkovic | Aug 2008 | A1 |
| 20090247796 | Waycuilis et al. | Oct 2009 | A1 |
| Number | Date | Country |
|---|---|---|
| 0210054 | Aug 2004 | BR |
| 1099656 | Apr 1981 | CA |
| 1101441 | May 1981 | CA |
| 1202610 | Apr 1986 | CA |
| 2447761 | Nov 2002 | CA |
| 2471295 | Jul 2003 | CA |
| 2542857 | May 2005 | CA |
| 2236126 | Aug 2006 | CA |
| 2203115 | Sep 2006 | CA |
| 2510093 | Dec 2006 | CA |
| 0164798 | Dec 1985 | EP |
| 0418971 | Mar 1991 | EP |
| 0418974 | Mar 1991 | EP |
| 0418975 | Mar 1991 | EP |
| 0510238 | Oct 1992 | EP |
| 0526908 | Feb 1993 | EP |
| 0346612 | Aug 1993 | EP |
| 0560546 | Sep 1993 | EP |
| 0976705 | Jul 1998 | EP |
| 1186591 | Mar 2002 | EP |
| 1253126 | Oct 2002 | EP |
| 1312411 | May 2003 | EP |
| 1395536 | Mar 2004 | EP |
| 1404636 | Apr 2004 | EP |
| 1235769 | May 2004 | EP |
| 1435349 | Jul 2004 | EP |
| 1440939 | Jul 2004 | EP |
| 1474371 | Nov 2004 | EP |
| 1235772 | Jan 2005 | EP |
| 1661620 | May 2006 | EP |
| 1760057 | Mar 2007 | EP |
| 1689728 | Apr 2007 | EP |
| 1808227 | Jul 2007 | EP |
| 1837320 | Sep 2007 | EP |
| 5125 | Feb 1912 | GB |
| 156122 | Mar 1922 | GB |
| 294100 | Jun 1929 | GB |
| 363009 | Dec 1931 | GB |
| 402928 | Dec 1933 | GB |
| 474922 | Nov 1937 | GB |
| 536491 | May 1941 | GB |
| 553950 | Jun 1943 | GB |
| 586483 | Mar 1947 | GB |
| 775590 | May 1957 | GB |
| 793214 | Apr 1958 | GB |
| 796048 | Jun 1958 | GB |
| 796085 | Jun 1958 | GB |
| 883256 | Nov 1961 | GB |
| 883256 | Nov 1961 | GB |
| 950975 | Mar 1964 | GB |
| 950976 | Mar 1964 | GB |
| 991303 | May 1965 | GB |
| 995960 | Jun 1965 | GB |
| 1015033 | Dec 1965 | GB |
| 1104294 | Feb 1968 | GB |
| 1133752 | Nov 1968 | GB |
| 1172002 | Nov 1969 | GB |
| 1212240 | Nov 1970 | GB |
| 1233299 | May 1971 | GB |
| 1253618 | Nov 1971 | GB |
| 1263806 | Feb 1972 | GB |
| 1446803 | Aug 1976 | GB |
| 1542112 | Mar 1979 | GB |
| 2095243 | Sep 1982 | GB |
| 2095245 | Sep 1982 | GB |
| 2095249 | Sep 1982 | GB |
| 2116546 | Sep 1982 | GB |
| 2120249 | Nov 1983 | GB |
| 2185754 | Jul 1987 | GB |
| 2191214 | Dec 1987 | GB |
| 2004-529189 | Sep 2004 | JP |
| 8300859 | Mar 1983 | WO |
| 8504863 | Nov 1985 | WO |
| 8504867 | Nov 1985 | WO |
| 9008120 | Jul 1990 | WO |
| 9008752 | Aug 1990 | WO |
| 9118856 | Dec 1991 | WO |
| 9203401 | Mar 1992 | WO |
| 9212946 | Aug 1992 | WO |
| 9316798 | Sep 1993 | WO |
| 9622263 | Jul 1996 | WO |
| 9744302 | Nov 1997 | WO |
| 9812165 | Mar 1998 | WO |
| 9907443 | Feb 1999 | WO |
| 0007718 | Feb 2000 | WO |
| 0009261 | Feb 2000 | WO |
| 0114300 | Mar 2001 | WO |
| 0138275 | May 2001 | WO |
| 0144149 | Jun 2001 | WO |
| 02094749 | Nov 2002 | WO |
| 02094750 | Nov 2002 | WO |
| 02094751 | Nov 2002 | WO |
| 02094752 | Nov 2002 | WO |
| 03000635 | Jan 2003 | WO |
| 03002251 | Jan 2003 | WO |
| 03018524 | Mar 2003 | WO |
| 03020676 | Mar 2003 | WO |
| 03022827 | Mar 2003 | WO |
| 03043575 | May 2003 | WO |
| 03051813 | Jun 2003 | WO |
| 03062143 | Jul 2003 | WO |
| 03062172 | Jul 2003 | WO |
| 03078366 | Sep 2003 | WO |
| 2004018093 | Mar 2004 | WO |
| 2004067487 | Aug 2004 | WO |
| 2005014168 | Feb 2005 | WO |
| 2005019143 | Mar 2005 | WO |
| 2005021468 | Mar 2005 | WO |
| 2005035121 | Apr 2005 | WO |
| 2005037758 | Apr 2005 | WO |
| 2005054120 | Jun 2005 | WO |
| 2005056525 | Jun 2005 | WO |
| 2005058782 | Jun 2005 | WO |
| 2005090272 | Sep 2005 | WO |
| 2005095310 | Oct 2005 | WO |
| 2005105709 | Nov 2005 | WO |
| 2005105715 | Nov 2005 | WO |
| 2005110953 | Nov 2005 | WO |
| 2005113437 | Dec 2005 | WO |
| 2005113440 | Dec 2005 | WO |
| 2006007093 | Jan 2006 | WO |
| 2006015824 | Feb 2006 | WO |
| 2006019399 | Feb 2006 | WO |
| 2006020234 | Feb 2006 | WO |
| 2006036293 | Apr 2006 | WO |
| 2006039213 | Apr 2006 | WO |
| 2006039354 | Apr 2006 | WO |
| 2006043075 | Apr 2006 | WO |
| 2006053345 | May 2006 | WO |
| 2006-067155 | Jun 2006 | WO |
| 2006067188 | Jun 2006 | WO |
| 2006067190 | Jun 2006 | WO |
| 2006067191 | Jun 2006 | WO |
| 2006067192 | Jun 2006 | WO |
| 2006067193 | Jun 2006 | WO |
| 2006069107 | Jun 2006 | WO |
| 2006071354 | Jul 2006 | WO |
| 2006076942 | Jul 2006 | WO |
| 2006083427 | Aug 2006 | WO |
| 2006-100312 | Sep 2006 | WO |
| 2006104909 | Oct 2006 | WO |
| 2006104914 | Oct 2006 | WO |
| 2006111997 | Oct 2006 | WO |
| 2006113205 | Oct 2006 | WO |
| 2006118935 | Nov 2006 | WO |
| 2007001934 | Jan 2007 | WO |
| 2007017900 | Feb 2007 | WO |
| 2007044139 | Apr 2007 | WO |
| 2007046986 | Apr 2007 | WO |
| 2007050745 | May 2007 | WO |
| 2007071046 | Jun 2007 | WO |
| 2007079038 | Jul 2007 | WO |
| 2007091009 | Aug 2007 | WO |
| 2007094995 | Aug 2007 | WO |
| 2007107031 | Sep 2007 | WO |
| 2007111997 | Oct 2007 | WO |
| 2007114479 | Oct 2007 | WO |
| 2007125332 | Nov 2007 | WO |
| 2007130054 | Nov 2007 | WO |
| 2007130055 | Nov 2007 | WO |
| 2007141295 | Dec 2007 | WO |
| 2007142745 | Dec 2007 | WO |
| 2008036562 | Mar 2008 | WO |
| 2008036563 | Mar 2008 | WO |
| 2008106319 | Sep 2008 | WO |
| 2008157043 | Dec 2008 | WO |
| 2008157044 | Dec 2008 | WO |
| 2008157045 | Dec 2008 | WO |
| 2008157046 | Dec 2008 | WO |
| 2008157047 | Dec 2008 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20090005620 A1 | Jan 2009 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 11254438 | Oct 2005 | US |
| Child | 12112926 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12112926 | Apr 2008 | US |
| Child | 12138877 | US | |
| Parent | 11101886 | Apr 2005 | US |
| Child | 11254438 | US | |
| Parent | 10826885 | Apr 2004 | US |
| Child | 11101886 | US |
