GB2053712A - Regenerable catalysts and process for the conversion of relatively low molecular weight hydrocarbons to higher molecular weight hydrocarbons. - Google Patents

Regenerable catalysts and process for the conversion of relatively low molecular weight hydrocarbons to higher molecular weight hydrocarbons. Download PDF

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GB2053712A
GB2053712A GB7924972A GB7824972A GB2053712A GB 2053712 A GB2053712 A GB 2053712A GB 7924972 A GB7924972 A GB 7924972A GB 7824972 A GB7824972 A GB 7824972A GB 2053712 A GB2053712 A GB 2053712A
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/024Multiple impregnation or coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/005Spinels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56Platinum group metals
    • B01J23/64Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652Chromium, molybdenum or tungsten
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85Chromium, molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04Alumina
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24Chromium, molybdenum or tungsten
    • C07C2523/26Chromium
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24Chromium, molybdenum or tungsten
    • C07C2523/28Molybdenum
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24Chromium, molybdenum or tungsten
    • C07C2523/30Tungsten
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42Platinum
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44Palladium
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46Ruthenium, rhodium, osmium or iridium
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/52Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals using catalysts, e.g. selective catalysts
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/58Recycling
    • Y02P20/582Recycling of unreacted starting or intermediate materials

Abstract

Regenerable catalysts for the conversion and oligomerization of hydrocarbons, e.g. methane, to produce products containing ethylene and/or benzene, comprise (1) a Group VIII noble metal having an atomic number of 45 or greater, nickel, or Group I-B noble metal having an atomic number of 47 or greater; (2) a Group VI-B metal oxide which is capable of being reduced to a lower oxide, or admixture of metal oxides which includes one or more of such metal oxides; and, (3) magnesium, strontium or barium, composited with a spinel-coated refractory support, notably an inorganic oxide support, or calcium composited with a non-zinc containing spinel-coated refractory support; preferably alumina.

Description

SPECIFICATION Process for the conversion of relatively low molecular weight hydrocarbons to higher molecular weight hydrocarbons, catalyst reagents for such use in such process, and the regeneration thereof It is the business of many refineries and chemical plants to obtain, process and upgrade relatively low value hydrocarbons to more valuable feeds, or chemical raw materials. For example, methane, the simpliest of the saturated hydrocarbons, is often available in rather large quantities either as an undersirable by product in admixture with other more valuble higher molecular weight hydrocarbons, or as a component of an off gas from a process unit, or units.Though methane is useful in some chemical reactions, e.g., as a reactant in the commercial product of methanol and formaldehyde, it is not as useful a chemical raw material as most of the higher molecular weight hydrocarbons. For this reason process streams which contain methane are usually burned as fuel.

Methane is also the principal component of natural gas, which is composed of an admixture of normally gaseous hydrocarbons ranging C4 and lighter and consists principally of methane admixed with ethane, propane, butane and other saturated, and some unsaturated hydrocarbons. Natural gas is produced in considerable quantities in oil and gas fields, often at remote locations and in difficult terrains, e.g., off-shore sites, arctic sites, swamps, deserts and the like. Under such circumstances the natural gas is often flared while the oil is recovered, or the gas is shut in, if the field is too remote for the gas to be recovered on a commercial basis. The construction of pipelines to carry the gas is often not economical, due particularly to the costs of connecting numerous well sites with a main line.Transport of natural gas under such circumstances is also uneconomical because methane at atmospheric pressure boils at -258 F and transportation economics distate that the gas be liquefiable at substantially atmospheric pressures to reduce its volume. Even though natural gas contains components higher boiling than methane, and such mixtures can be liquefied at somewhat higher temperatures than pure methane, the temperatures required for condensation of the admixture is nonetheless too low for natural gas to be liquefied and shipped economically. Under these circumstances the natural gas, or methane, is not even of sufficient value for use as fuel, and it is wasted.

The though of utilizing methane from these sources, particularly avoiding the tremendous and absolute waste of a natural resource in this manner, has challenged many minds but has produced few solutions. It is highly desirable to convert mthane to hydrocarbons of higher molecular weight than methane (hereinafter, C2+) particularly admixtures of C2+ hydrocarbon products which can be economically liquified at remote sites; especially admixtures of C2+ hydrocarbons rich in ethylene or benzene, or both. Ethylene and benzene are known to be particularly valuable chemical raw materials for use in the petroleum, petrochemical, pharmaceutical, plastics and heavy chemicals industries.Ethylene is thus useful forthe production of ethyl and ethylene compounds including ethyl alcohol, ethyl ethers, ethylbenzene, styrene, ethylene oxide, ethylene dichloride, ethylene dibromide, acetic acid, polyethylene and the like. Benzene is useful in the production of ethylbenzene, styrene, and numerous other alkyl aromatics which are suitable as chemical and pharmaceutical intermediates, or suitable in themselves as end products, e.g., as solvents or high octane gasoline components.

It is a primary objective of the present invention to provide the art with novel catalysts, and a catalyst process for the production of higher molecular weight hydrocarbons from lower moelcular weight hydrocarbons, especially for the production of C2+ hydrocarbons from methane, natural gas, process streams rich in methane, and the like.

A specific object is to provide novel regenerable catalyst-reagents, and a new and improved process utilizing said regenerable catalyst-reagents, for the conversion, and oligomerization of methane at relatively low temperatures to higher molecular weight hydrocarbons, particularly products rich in ethylene or benzene, or both, usually in admixture with other hydrocarbons.

These and other objects are achieved in accordance with the present invention which embodies: (a) novel multi-functional regenerable catalyst-reagents which are comprised of (1) a Group VIII noble metal having an atomic number of 45 or greater, nickel, or a Group I-B noble metal having an atomic number of 47 or greater (Periodic Table of the Elements;Sargent Welch Scientific Company, Copyright 1968), or admixture which includes one or more of said metals; (2) a Group VI-B metal oxide of the Periodic Table of the Elements which is capable of being reduced to a lower oxide, or admixture of metal oxides which includes one or more of such metal oxides; and, additionally (3) selected from the group consisting of barium, magnesium, strontium or an admixture which includes one or more of such metals, composited with a suitably passivated, spinel-coated refractory support, notably an inorganic oxide support, preferably alumina; or calcium, composited with a suitbly passivated, non-zinc containing spinel coated refractory support, notably an inorganic oxide support preferably alumina; (b) a novel hydrocarbon conversion process wherein a hydrocarbon feed, notably methane, or methane-containing gas, is contacted with a catalyst-reagent as characterized in (a), supra, at temperature ranging from about 11 50 F to about 1 600 F, preferably from about 1 2500F, to about 1 3500F at sub-atmosphere, or supra atmospheric pressure sufficient to react and form 02+ hydrocarbons; and (c) a process for regeneration of said catalyst-reagent which has become inactivated as by use in the process characterized in (b), supra, by contact thereof in an exothermic reaction with water, oxygen or an oxygen-containing gas, preferably air, at temperatures sufficient to reoxidize the Group Vl-B metal oxide, or metal oxides, and preferably also sufficient to provide the required sensible heat to said novel hydrocarbon conversion process (b), supra on recycle of the catalyst-reagent; which suitably ranges from about 1000F,,to about 1600"F, preferably from about 1250onto about 1450"F, carbon dioxide and water being released in the regeneration redaction.

The novel catalyst-reagents are multi-functional and, though the exact nature of the reaction paths are by no means certain, the included components are believed to play different mechanistic functions in the production of oligomers from the low molecular weight hydrocarbon feeds, notably methane. The Group I-B (silver, gold) or VIII (rhodium, palladium, osmium, iridium and platinum) noble metals, or nickel, the first essential component, of which the Group VII noble metals notably platinum, iridium and palladium, but particularly platinum, are preferred, is believed to enter into a dissociative chemisorption reaction with the hydrocarbon feed and cause it to lose hydrogen.For example, in the reaction with methane, the Group I-B, Group VIII noble metal, or nickel, functions to cause dissociative chemisorption of the methane onto the surface of the catalyst to produce species which can react to form ethylene directly, another species which reacts to form ethane and higher molecular weight aliphatic hydrocarbons, or both, and other species which can directly react with the Group VI-B metal oxide to form water.

The Group VI-B metal oxide, the second essential component, is characterized as an oxide which is capable of being reduced in the reaction to a lower oxide or the zero valent metal, or both. The reducible Group VI-B metal oxide component, comprising an oxide, or oxides, of the multivalent metals chromium, molybdenum and tungsten, is believed to provide a catalytic function, in addition to the reagent function which is a function of the change of oxidation state of the metal. Thus, it acts as a reagent in that it is believed to donate oxygen for reaction with abstracted hydrogen to form water and thereby provide the energy necessary to sustain the reaction.In its catalytic function, it is believed that the low valence oxides of the Group VI-B metal, or the completely reduced metal, provide a cyclization function whereby acetylene, acetylides and the like, and perhaps even ethylene are converted into aromatics, notably benzene. Thus, it is one or more of the products of the reagent function of the Group VI-B metal oxide components which are believed to provide the catalytic function of the Group VI-B metals.

It has also been found that the activity of the Group Vl-B reducible metal oxide to react with abstracted hydrogen and form water can be supplemented, or enhanced, by the additional presence of oxides of (i) Group III-A metals having an atomic number of 31 or greater (gallium, indium and thailium), (ii) Group IV-B transition metals of atomic number ranging from 22 to 40 (titanium' and zirconium), (iii) Group V-B transition metals (vanadium, niobium and tan-talum), (iv) Group VII-B transition metals (manganese and rhenium), Group VIII non-noble metals of atomic number ranging from 26 to 27 (iron and cobalt), (vi) metals of the lanthanum series of atomic number ranging from 58 to 71 (cerium, praseodymium, neodynium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium), and (vii) metals of the actinum series of atomic number ranging from 90 to 92 (thorium and uranium. Of these ,the preferred oxygen donor compounds comprise the oxides of vanadium, niobium, rhenium, cerium and uranium.

The Group Il-A metals (magnesium, calcium, strontium and barium,) of which barium is highly preferred, constitute the third essential component of the catalyst. The Group Il-A metal is put on the catalyst support as an oxide and, in performing its function, is believed to form a Group Il-A metal carbide, or carbides as intermediates during the course of the reaction. This, of course, does not suggest that other species containing the Group Il-A metal are not formed, and possibly active during the reaction. However, in an initial stage it is believed that the oxide of the Group Il-A metal supplies oxygen which reacts with abstracted hydrogen to form water, thus providing some of the energy for the reaction. Barium particularly as barium peroxide (BaO2) ab initio, is believed to function particularly well in this aspect.The Group Il-A metal carbides, particularly carbides of the heavier Group Il-A metals, are also believed to form compounds which possess carbon-carbon bonds, or polycarbon-carbides which are through to be intermediates, or precursors of intermediates, in the formation of cyclic compounds. While most of these polycarbon-carbides are believed to be C2 species, making barium, in particular is believed to form some C3 species, making barium especially preferred for generation of cyclic hydrocarbons by the present process.

It is also essential in the formation of these catalysts that the several components be composited with a passivated surface, spinel-coated inorganic metal oxide support, preferably a spinel-coated alumina upon which the several components are sequentially impregnated, or co-impregnated by any of the common techniques in use for the preparation of heterogeneous catalysts. The term "spinel", as used herein, designats a binary oxide which is characterized as having either a normal or inverse spinel structure. The normal spinel structure can be represented by the formula MY204 wherein M and Y are cations of different metals, and inverse spinel structure can be represented by the formula Y (XY)04 wherein Y and X are cations of different metals. The sum of the cationic charges of a spinel, whether normal or inverse, is equal to 8. A description of the spinel-type structures is found in Structural Inorganic Chemistry, A.F. Wells, 3rd Edition, Oxford, the Clarendon Press, 1962, at pages 487-488, herewith incorporated by reference.

While calcium is the preferred Group Il-A reagent metal it is nonetheless essential that calcium reagent not be employed in the presence of zinc. This is true even when the zinc is present as a constituent or part of the passivated, spinel-coated surface, e.g., as when the calcium is deposited on a zinc aluminate spinel carrier, or zinc aluminate spinel coated support. The presence of zinc, among other things causes the formation of considerable amounts of coke with drastic reduction in the formation of the desired products.

Thermodynamic considerations of the possible reaction paths favor the formation of a considerable amount of coke and/or carbon dioxide, with little or no yield of potentially valuable products, a conclusion which fits well with the results of many past experiments. However, pursuant to the practice of this invention, albeit some coke, polymeric, or carbonaceous material is produced, essentially all of this material that is formed in the reaction is burned to carbon dioxide and fully utilized in the regeneration stage to provide process heat. On the other side of the process, relatively little carbon dioxide is formed in the reactions taking place in the main reactor.It has been demonstrated that the catalyst-reagents of this invention, under the desired conditions for conducting the process, produce products containing an admixture of valuable oligomers, particularly ethylene and benzene.

Though the exact nature of the reaction paths if by no means certain, as suggested, it is believed that the Group I-B noble metals and Group VIII noble metals, inclusive of nickel, function to cause one or more dissociative chemisorptions of the methane onto the surface of the catalyst to produce species which may react to form ethylene directly, or another species which may react to form ethance and higher molecular weight aliphatic hydrocarbons, or both, and another species such as adsorbed hydrogen, which may react directly with the transition metal or other oxide to form water. Or such species may react with the Group Il-A carbides to liberate ethylene, form acetylene, or other products, form intermediates which lead to cyclization, or react with cyclization or polymerization products to form benzene or other products which appear in the exit gases from the reactor.The group VI-B metal oxide also may react directly with abstracted or liberated hydrogen to form water, and by interaction with a Group I-B noble metal or Group VIII noble metal, or nickel, is believed to form water and a species which further reacts to form ethylene. Where methane is used as a feed, it is thus envisioned that the reaction mechanisms with a mutlivalent Group I-B noble metal or Group VIII noble metal, or nickel, referred to as "M", may include the following sequences of reactions, to wit:: <img class="EMIRef" id="027057240-00030001" />

(2) 2MCH3# < 2M + H3C-CH3 (3) MCH3 + M < M=CH2 + MH (4) 2M=CH2 < 2M + H2C=CH2 and, <img class="EMIRef" id="027057240-00030002" />

It is also envisioned that the multivalent transition metal oxide, M'On, the transition metal being designated as M', the oxygen atoms associated with M', or the ratio of oxygen atoms to M atoms in the association since n need not be an integer, reacts with the intermediate MH [Equation (1), supral as follows:: (6) 2MH + MlOn < M + M'On-1 + H2O and with abstracted and liberated hydrogen as follow; (7) M'On + H2~ M'OnI + H2O and, M' participates with M in reacting with methane, as follows: (8) M'On + OH4 + M0 M'On-i + H2O + M=CH2 Likewise, MOn1 and M'On-i can further react in similar manner to produce additional water, ethylene, ethane, and other hydrocarbons until the valance of M, M' and M" have been reduced to some lower level or to zero, at which time further reactions such as described are no longer possible without reoxidation of the catalyst by regeneration.

The presence of the Group Il-A metal component, favors the production of larger amounts of benzene in the products of the reaction. In this type of reaction, it is believed that the methane or organometallic intermediates interact with the Group Il-A metal component to form metal carbides and water. The carbides, acetylides, propadiynides and the like, it is believed, react in turn with the water or abstracted or liberated hydrogen to generate benzene, ethylene, and/or the other products of the process.

It is known that acetylene can be trimerized at certain conditions to yield benzene, but it is also known that free acetylene also has a propensity to react to form coke; which form of reacting is high undesirable. Such reaction can thus be represented by the following equation, to wit: (9) C2H2 # Heat + (C2)x + H2 (or Coke + H2) In the catalytic reaction of this invention, however, it is not believed that free acetylene is formed and whereinafter C2H2 is represented in the equation, the acetylene is believed present only as a transient, or molecular species complexed with one or more metal atoms, and which is rapidly converted into benzene, ethylene or other hydrocarbon or coke. Therefore, it is theorized that the reaction pathway to the formation of benzene may be shown by equations 10-16, infra.Representing Group Il-A metals as M", panda carbide, acetylide, or the like of such metals as M"mC, M"mC2, M"mC3, the designations denoting the degree of association of carbon/carbide anions within the material, all of which generally fit in the "metal carbide" category, and the subscripts denoting generally the number of metal atoms associated with each carbide anion carbon or group of carbons, the following reactions are believed to occur informing the carbides, acetylides, to wit: (10) 2M"O + CH4 # M2"C + 2H2O (11) M"O2 + CH4 # M"C + 2H2O (12) M"2C, M"C, etc. # M"C2, M"C3, M"2C3, etc.

The acetylene forming reaction is represented by the following equation, to wit: (13) M"C2+H2OM"O+C2H2 The acetylene trimerization may be represented by the following equation: (14) 3C2H2 + Catalyst, C6H6 + Catalyst Where the catalyst is M' or lower valent M'Oz and a similar sort of dimerization of C3 materials is likewise possible. An alternate more likely cyclization route can also take place directly from the carbide, to wit: (15) 3M"C2 + M'O2~ 2M"O + M'C6, etc.

(16) M'C6+ 6MH # 6M + C6H6 (17) 2M"C3 + M'O2# 2M"O + M'C6 (18) M'Cs + 6CH4 + 6M < M' + 6MCH3 + C6H6 Another alternate pathway for the cyclization to benzene involves the dehydrogenation and cyclization of three ethylenes via ractions on the M and M' catalyst and reagent metals.

However, it is also possible that the reaction pathway to 02+ hydrocarbons, inclusive of ethylene and benzene may be through the catalytic or thermal formation of a particular type of "coke" which catalytically or thermally decomposes in the reaction to form the thermally stable volatile products, benzene and ethylene, to wit: (19) CH4 + Catalysts "Coke" + Catalyst + H2O (20) "Coke" + Catalyst (+2CH4) # Coke + C2H4 + C6H8 The catalyst or feed, or both, may be furnishing hydrogen to decompose the "Coke" as, to wit:: (21) M + CH4 # MH + "Coke" (22) MH + "Coke" # M + C2H4 + C6H6 In the preparation of the catalyst-reagents, a porous metal oxide support, preferably one which has been desurfaced by contact with steam, is first passivated and the surface thereof converted to a spinel. This is accomplished bytreatmentofth support with at least one metal component, (otherthan zinc when calcium is to be deposited on the support), preferably a Group Il-A metal, such that the sum of the ionic charges of the metal of the metal oxide support and the metallic element, or metallic elements, of the metal component used to treat the support satisfy the requirement for spinel formation, i.e., that the sum of the valences equals 8 and the ionic radii of the metals satisfy the requirements for formation of the normal or inverse spinel type structures. Exemplary of materials which can be used as supports are magnesium oxide, titanium oxide, zirconium oxide, hafnium oxide, and the like, preferably alumina.Suitably, the metal oxide support, preferably one having an initial surface area ranging from about 50 m2/g to about 250 m2/g, preferably about 150 m2/g, is treated by contact, and impregnation with a solution of a compound of the desired metal component which is deposited on the metal oxide support. The treated or impregnated metal oxide is subsequently calcined, suitably at a temperature ranging from about 925"F to about 1 825 F, this producing a surface spinel or spinel-coating on the metal oxide support. The spinel surfaced support is then treated with a solution, or solutions, containing compounds which provide the essential substitutents characterized in (a), supra.

The several components are deposited on the passivated spinel-coated support by the impregnation method. Pursuant to this method, a compound, or compounds which contain the desired metal, or metals, are dissolved in solution in the desired concentration. The support in solvated, dry or calcined state is contacted with the metal or metals-containing solution, or solutions, and thereby impregnated by either the so-called "incipient wetness" technique, or technique embodying adsorption from a dilute solution, or solutions, with subsequent drying of the support.In the impregnation procedure, the Group Il-A metal is generally first impregnated onto the passivated, spinel-coated support; the amount added to the support being additional to any such similar or dissimilar metal which may have been used to form the spinel-coating, since that used in forming the spinel is not contained thereon in active form. The Group Il-A metal impregnated support is then, preferably, calcined in an inert or oxidizing atmosphere and the Group VI-B is then impregnated onto the support, and again calcined. Suitably, also, compounds of the Group Il-A and VI-B metals can be coimpregnated onto the passivated, spinel-coated surface and the support then dried and calcined.It is essential, in either event, after deposition of the Group VI-B metal to calcine the catalyst-reagent in an oxidizing atmosphere, i.e., in the presence of air or an oxygen-containing gas, to convert the Group VI-B metal to an oxide. The Group Ill-A, and transition metals of IV-B, V-B, VII-B, inclusive also of the lanthanide and actinium series metals, and iron and cobalt, alone or in admixture with other metals are similarly impregnated onto the support and the impregnated support calcined in an oxidizing atmosphere to form an oxide, or oxides of the metal.The Group I-B or Group VIII noble metal, or nickel, is generally impregnated onto the passivated, spinel-coated support after deposition of the other essential components and then calcined, suitably in nitrogen; or added by coimpregnation with one or more of the other essential or non-essential components. Where the impregnating compound contains halogen, or other undesirable component, wet calcination may be employed to remove the halide from the catalyst-reagent. In all embodiments, the support can be treated by contact with a single solution containing the desired amounts of a metal, or metals, or treated sequentially by contact with a solution containing one metal, and then with a solution which contains another metal, or metals, in the desired amounts.Large particles, whether pilled, pelleted, beaded or extruded, can be so-treated and then crushed to the desired size, or the particle can be pre-reduced in size, and then treated. The catalyst-reagent, in either instance, can then be dried, calcined and then contacted as a fixed, fluidized or moving bed with the feed at the desired reaction conditions.

In the preparation of the catalyst-reagents, the Group I-B or Group VIII noble metals, or nickel, is deposited on the support in concentration ranging from about 0.01 percent to about 2 percent, preferably from about 0.1 to about 1 percent, calculated as metallic metal based on the weight of the total catalyst-reagent (dry basis). The reducable Group VI-B metal oxide is deposited on the catlyst-reagent in concentration sufficient to supply at least one-half of an atom of oxygen for each hydrocarbon molecule which is to be oligomerized, and preferably at least one atom of oxygen for each hydrocarbon which is to be oligomerized. Generally, at least bout 1.1:1 to at least 1.5:1 atoms of oxygen are supplied for each molecule of methane when high ethylene content is desired in the product.At lest 1.5:1 atoms of oxygen are supplied for each molecule of methane when high benzene content is desired in the product. The Group VI-B metal is deposited on the catalyst-reagent in concentration ranging from about 1 percent to about 20 percent, preferablyfrom about 3 percent to about 10 percent, calculated as metallic metal based on the weight of the total catalyst-reagent (dry basis). Suitably also the oxides of the Group I1I-A metals, the oxides of the Group IV-B, V-B, VII-B transitional metals, the oxides of iron, cobalt and the oxides of the metals of the lanthanide and actinide series are deposited on the catalyst in concentration ranging from about 0.01 percent to about 25 percent, preferably from about 5 percent to about 15 percent calculated as metallic metal based on the weight of the total catalyst-reagent (dry basis).The oxide of the Group Il-A, or alkaline earth metal is deposited on the catalyst-reagent in concentration ranging from about 1 percent to about 30 percent, preferably from about 5 percent to about 25 percent calculated as metallic metal based on the weight of the total catalyst-reagent (dry basis). In compositing these metals with the catalyst-reagent, the Group Il-A metal is composited in an amount sufficient to provide an atomic ratio of at least about 3:1 relative to the Group VI-B metal, and preferably the ratio of the Group II metal/Group VI-B metal ranges from about 3:1 to about 40:1, preferably from about 5:1 to about 12:1 when a relatively high concentration of benzene is desired in the product.

The catalyst-reagent, particularly in view of its dual role as reagent and catalyst, eventually loses its activity and its activity must be restored. Restoration of the activity of the catalyst-reagent is performed by oxidative regeneration, i.e., by contact of the catalyst-reagent with water, oxygen or oxygen-containing gas, preferably air, at temperatures sufficiently elevated to burn off accumulated coke and reoxidize the Group VI-B metals and Group Il-A metals; as well as the metals of Groups Ill-A, IV-B, VII-B, iron, cobalt and the lanthanides and actinides, to the extent they are present in the catalyst-reagent. Temperatures on the order of about 700"F are generally adequat to reoxidize these metals and restore the activity of the catalyst-reagent, but preferably temperatures on the order of about 10000to about 1600"F, more preferably from about 1250"F to about 1450"F, are employed in the regeneration zone and the hot regenerated catalyst-reagent is recycled to the hydrocarbon reaction zone in quantity sufficient to supplythe sensible heat needed for the reaction. Generally, adequate heat is maintained by burning the coke from the catalyst-reagent during the regeneration. Pressure, while not critical, is generally maintained above atmospheric, suitably between atmospheric and about 20 atmospheres.

The invention will be more fully understood by reference to the following non-limiting examples which illustrate its more salient features. All parts are in terms of weight except as otherwise specified.

Example 1 A catalyst-reagent, Catalyst A, was prepared from a MgAI204 spinel blocked alumina support made by impregnating via the incipient wetness technique a commercially available, high purity gamma alumina calcined at 1 0000F for two hours to product an alumina having a surface area of 193 m2/g (B.E.T.) with an aqueous solution of magnesium nitrate. The magnesium solution was added to the support in amount calculated to deposit 2.9 percent Mg onto the support. The impregnated support was dried, and then subjected to a subsequent calcination at 1000"F for four hours, and at 1300"F for an additional hour.The MgAI2O4 spinel blocked alumina support was then impregnated with an aqueous barium nitrate solution and calcined for 4 hours at 1000 F. The barium nitrate impregnation was also via the incipient wetness technique with subsequent calcination, alternate impregnations and calcinations having been conducted nine times in sequence to bring the barium concentration up to 6.9 percent. After the final calcination, a chromium nitrate solution was then impregnated onto the catalyst-reagent to provide chromium concentration of 5.0 percent after calcination for 4 hours at 1 0000F with subsequent calcination in air at 1300"F for 1 hour.The calcined catalyst-reagent was then impregnated by adsorption from dilute solution with a hexchloroplatinic acid, H2PtCI4, solution sufficient to provide 0.3 weight percent platinum on the catalyst-reagent and again calcined for 16 hours in air at 1300"F.

Example 2 A 5 gram portion of Catalyst-reagent A was charged into a quartz tube furnace and heated slowly at essentially ambient pressure with a flowing stream of nitrogen over a period of 6 hrs. to 13000F. The flow of nitrogen was then discontinued, and then a stream of essentially pure methane (99.4%) was passed across the catalyst-reagent for 30 minutes. The flow of methane was then discontinued and nitrogen was again introduced, the nitrogen having been substituted at the end of this period to act as a carrier gas. The entire effluent was collected in a neoprene rubber bag during the time that hydrocarbons were evolved from the system. A sample of the collected product was then subjected to a mass spectrometric gas analysis. The following Table I shows the hydrocarbon components present in the gaseous product in significant quantity.

TABLE 1 Component Mol Percent Weight Percent CH4 55.480 39.441 C2H4 4.000 4.983 C2H8 1.634 2.178 C4H8 0.014 0.028 n-C4H10 0.001 0.002 C6H6 2.367 8.192 The coke on the catalyst was measured at 1.04 wt.%, approximately 44.8 mole percent of the methane having been converted with a maximum of 19.3 mole percent of the methane having formed coke; for a significant amount of the coke is carbides which are capable of further conversion. Approximately 25.4 mole percent of the methane was converted to C2+ product, 8 mole percent of the methane having formed ethylene, 3.26 mole percent of the mathane having formed ethane, and 14.4 percent of the methane having formed benzene.

Example 3 An additional series of catalysts, prepared as in Example 1, but with the impregnation of other essential metallic or metal oxide components, or other blocking agent for preparation of the spinel; and these catalysts employed in a series of runs at conditions similar to that described in Example 2. The results obtained are tabulated in Table II.

TABLE II Catalyst A B B' B" C D Use Original Original Regenerated(2) Regenerated(2) Original Original Base Material &gamma;-Al2O3 &gamma;-Al2O3 &gamma;-Al2O3 &gamma;-Al2O3 &gamma;-Al2O3 &gamma;-Al2O3 Blocking Metal Mg Mg Mg Mg Ba Mg Concentration Blocking Metal 2.9 3.7 3.7 3.7 4.3 4.1 Metal M Pt Pt Pt Pt Pt/Ir Pt/Ir Concentration M (Wt. %) 0.3 0.1 0.1 0.1 0.1/0.1 0.1/0.1 Metal M' Cr Cr Cr Cr W Cr Concentration M' (Wt. %) 5.0 3.9 3.9 3.9 9.5 5.4 Metal M" Ba Ba Ba Ba Ba Ba Concentration M" (Wt. %) 6.9 12.3 12.3 12.3 12.6 16.2 Metal M'" -- V V V U U Concentration M'" (Wt. %) 0.0 10.1 10.1 10.1 5.7 9.8 Product Analysis Component (Mole %) CH4 55.58 44.33 45.72 42;;69 51.30 36.71 C2H2 -- 0.01 -- -- 0.00 - C2H4 4.00 3.54 3.95 3.02 5.68 2.53 C2H6 1.63 0.25 0.40 0.56 1.92 0.03 C3H6 -- -- 0.01 -- 0.02 - C3H8 -- -- 0.00 -- 0.01 - C4H8 0.01 0.64 0.01 0.00 -- -n-C4H10 0.00 -- 0-00 -- 0.01 - C6H6 2.37 3.89 3.56 3.67 1.84 3.95 N2 Balance Balance Balance Balance Balance Balance Coke on Catalyst (Wt. %) (3) 1.04 9.56 0.78 1.13 1.57 0.34 Coke on Catalyst After Regeneration (Wt. %) 0.03 0.09 0.17 0.02 0.31 0.01 (1) B' is Catalyst B once regenerated.

(2) B" is Catalyst B once further regenerated.

(3) "Coke on Catalyst" may also include significant quantities of metal carbide "carbon".

Example 4 Catalyst-reagents were prepared from spinel blocked alumina supports made by impregnating via the incipient wetness technique a commercially available, high purity gamma alumina calcined at 1000F for two hours to produce an alumina having a surface area of 193 m2/g (B.E.T.) with an aqueous solution of a salt of the blocking metal. For example, in the preparation of a CaAI204 spinel blocked alumina support, a calcium nitrate solution was formed by dissolving calcium nitrate in water, and the calcium solution was then added to the support in amount calculated to deposit 3.5 percent Ca onto the support. The impregnated support was dried, and then subjected to a subsequent calcination at 1 0000F for four hours, and at 1 3000F for an additional hour.The CaA1204 spinel blocked alumina support was then impregnated with an aqueous solution of a salt of the desired Group Il-A metal, e.g., calcium nitrate, as in the preparation of Catalyst F, and calcined for 4 hours at 1000 F. Impregnation was also via the incipient wetness technique with subsequent calcination, alternate impregnations and calcinations having been conducted a number of times in sequence to bring the Group Il-A metal concentration to the desired concentration. After the final calcination, a Group VI-B metal, Cr was deposited from a solution of a salt of the Group VI-B metal onto the catalyst-reagent to provide the desired Group Vl-B metal concentration after calcination for 4 hours at 1 0000F with subsequent calcination in air at 1300 Ffor 1 hour.The calcined catalyst-reagent was then impregnated by adsorption from dilute solution with an acid salt of the Group VIII noble metal, e.g., a hexachloroplatinic acid, H2PtC14, solution sufficient to provide the desired concentration of platinum on the catalyst-reagent, and again calcined for 16 hours in air at 13000F.

A 5 gram portion of each catalyst was charged into a quartz tube furnace and heated slowly at essentially ambient pressure with a flowing stream of nitrogen over a period of 6 hrs. to 1 3000F. The flow of nitrogen was then discontinued and then a stream of essentially pure methane (99.4%) was passed across the catalyst-reagent for 30 minutes. The flow of methane was then discontinued and nitrogen was again introduced the nitrogen having been subsituted at the end of this period to act as a carrier gas. The entire effluent was collected in a neoprene rubber bag during the time that hydrocarbons were evolved from the system. A sample of the collected product was then subjected to a mass spectrometric gas analysis to determine the hydrocarbon quantity, and the amount of coke deposited on the catalyst was measured.

The results obtained are given in Table III below TABLE III Testing of catalyst reagents for methane polymerization Test Run Number 7 8 9 10 Catalyst Designation E F F2 G Nominal Catalyst Type CaCrPt CaCrPt CaCrPt CaMoVPt Use Original(2) Original'"' Regenerated(2) Original Base Material M""' mOn y-Al2O3 y-Al2O2 y-Al203 y-A12O3 Blocking Metal M"" Zn Ca(3) Ca(3) Ca(3 Concentration Blocking Metal 5.7 3.5 3.5 3.4 M"" (Wt. %) Metal M Pt Pt Pt Pt Concentration M (Wt. %) 0.2 0.2 0.2 0.3 Metal M' Cr Cr Cr Mo Concentration M' (Wt. %) 3.8 3.8 3.8 7.0 Metal M" Ca Ca Ca Ca Concentration M" (Wt. %) 8.3 8.3 8.3 9.2 Metal M"' -- -- -- V Concentration M"' (Wt. %) 0.0 0.0 0.0 10.2 ProductAnalysis Component (Mole %) CH4 63.24 39.95 46.20 44.75 C2H2 -- -- -- 0.03 C2H4 0.03 2.33 t.87 3.64 C2H6 0.16 0.38 0.46 0.19 C3H6 -- -- -- 0.02 C3H8 -- 0.01 - 0.00 C4H8 0.005 -- 0.01 0.00 n-C4H1o 0.01 -- 0.02 0.01 C6H5 0.00 2.14 2.46 1.99 N2 36.55 55.21 47.98 49.37 Product Composition Component (Wt. /OJ CH4 49.61 26.34 31.23 30.34 C2H2 -- -- -- 0.03 C2H4 0.04 2.69 3.39 4.32 CHe 0.24 0.47 0.58 0.24 C3H8 -- -- -- 0.04 C3H8 -- 0.02 -- 0.00 C4H8 0.01 -- 0.02 0.01 n-C4H1o 0.03 -- 0.05 0.02 C6H6 0.00 6.87 8.10 6.57 N2 50.07 63.60 56.63 58.44 Coke on Catalyst (Wt. %) (4) 28;;73 2.48 2.16 1.74 Coke on Catalyst After Regeneration (Wt. %)(6) 0.24 0.11 0.22 0.16 (1) Original catalysts used in first cycle of methane polymerization.

(2) F2 Catalyst F once regenerated, used in the second cycle of methan polymerization.

(3) Concentration of blocking reagent metal M"" used for spinel formation is not included as part of M" concentration even though the identical metal was used for both purposes.

(4) "Coke on Catalyst" may also include significant quantities of metal carbide "carbon".

(5) Testing at 1 atm, pressure, pure CH4 feed, N2 purge before and after, 0.5 hrs/run except first cycle on B above at 4.0 hrs.

(6) Regeneration by final 700 C air burning.

From these data it will be observed that catalysts which contain the Group Il-A metal catalyst component, except where zinc is present (Test Run Number 7), are quite effective in oligomerizing methane to produce product compositions rich in ethylene and benzene. Where zinc is present, however, a major amount of the methane is converted to coke, with minimal production of C2+ gases.

It is apparent that various modifications and changes can be made without departing the spirit and scope of the invention.

Temperatures expressed herein in "F are converted to OC by substracting 32 and then dividing by 1.8.

Claims (14)

1. A multi-functional regenerable catalyst-reagent composition suitable for the oligomerization of hydrocarbons, particularly methane, comprising (1) a Group VIII noble metal having an atomic number of 45 or greater, nickel, or a Group I-B noble metal having an atomic number of 47 or greater, (2) a Group VI-B metal oxide which is capable of being reduced to a lower oxide, and (3) a Group Il-A metal selected from the Group consisting of barium, magnesium, strontium and an admixture which includes one or more such metals, composited with a spinel-coated refractory support, or calcium composited with a non-zinc containing spinel-coated refractory support.
2. A composition according to claim 1 in which the Group VIII noble metal is platinum, iridium or palladium.
3. A composition according to claim 1 or claim 2 in which the Group VI-B metal is chromium, molybdenum or tungsten.
4. A composition according to any one of claims 1-3 in which the spinel-coated inorganic oxide is alumina.
5. A composition according to any one of claims 1-4 additionally containing a Group III-A metal having an atomic number of 31 or greater, a IV-B, V-B or VII-B transition metal, iron, cobalt, or a metal of the actinide or lanthanide series.
6. A composition according to any one of claims 1-5 in which the said Group Vlil noble metal or said Group I-B metal is present in a concentration in the range of from 0.01 percent to 2 percent, the said Group VI-B metal oxide is present in a concentration in the range of from 1 percent to 20 percent and said Group Il-A metal is present in a concentration in the range of from 1 percent to 30 percent, said concentrations being calculated as metallic metal based on the total weight of the composition.
7. A composition according to any one of claims 1-6 in which the said Group Il-A metal is present in an atomic ratio of at least 3:1 relative to the said GroupVl-B metal.
8. A multi-functional regenerable catalyst-reagent composition according to any one of claims 1-7 substantially as herein before described.
9. A composition according to claim 8 substantialy as herein before described with reference to the Examples.
10. A process for the regeneration of th catalyst-reagent composition of any one of claims 1 to 9 which has become inactivated during use in a hydrocarbon conversion reaction comprising contacting said inactivated composition with water, oxygen or an oxygen-containing gas at a temperature in the range of from 1000"F (537.8"C) to 1600"F (871.1"C).
11. A regeneration process according to claim 10 substantially as hereinbefore described.
12. A process for the oligomerization of a hydrocarbon feed, preferably a methane containing-feed, comprising contacting said hydrocarbon feed with a catalyst-reagent composition of any one of claims 1 to 9 at a temperature in the range of from 11 500F (621 .10C) to 1600"F (871 .10C).
13. An oligomerization process according to claim 12 substantially as hereinbefore described.
14. Oligomers produced by the process of claims 12 or claim 13.
GB7924972A 1979-07-18 1979-07-18 Regenerable catalysts and process for the conversion of relatively low molecular weight hydrocarbons to higher molecular weight hydrocarbons Expired GB2053712B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
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EP0262947A1 (en) * 1986-09-30 1988-04-06 Johnson Matthey Public Limited Company Catalytic generation of hydrogen from hydrocarbons
GB2284769A (en) * 1993-12-16 1995-06-21 Inst Francais Du Petrole Dehydrogenation catalysts for C3-C20 paraffins, and preparation thereof.
WO2005072866A1 (en) * 2004-01-28 2005-08-11 Statoil Asa Fischer-tropsch catalysts
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US9242229B2 (en) 2010-08-09 2016-01-26 Gtl.F1 Ag Fischer-tropsch catalysts

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Publication number Priority date Publication date Assignee Title
EP0262947A1 (en) * 1986-09-30 1988-04-06 Johnson Matthey Public Limited Company Catalytic generation of hydrogen from hydrocarbons
US4897253A (en) * 1986-09-30 1990-01-30 Johnson Matthey Public Limited Company Catalytic generation of hydrogen from hydrocarbons
GB2284769A (en) * 1993-12-16 1995-06-21 Inst Francais Du Petrole Dehydrogenation catalysts for C3-C20 paraffins, and preparation thereof.
GB2284769B (en) * 1993-12-16 1998-02-11 Inst Francais Du Petrole Dehydrogenation catalysts for C3-C20 paraffins, and preparation thereof
WO2005072866A1 (en) * 2004-01-28 2005-08-11 Statoil Asa Fischer-tropsch catalysts
JP2007520336A (en) * 2004-01-28 2007-07-26 スタトイル・エーエスエー Fischer-Tropsch catalyst
GB2410449B (en) * 2004-01-28 2008-05-21 Statoil Asa Fischer-Tropsch catalysts
JP2012183536A (en) * 2004-01-28 2012-09-27 Statoil Asa Fisher-tropsch catalyst
US10040054B2 (en) 2009-11-18 2018-08-07 Gtl.Fi Ag Fischer-Tropsch synthesis

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