AU8151298A - Conversion of synthesis gas to lower olefins using modified molecular sieves - Google Patents
Conversion of synthesis gas to lower olefins using modified molecular sieves Download PDFInfo
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- AU8151298A AU8151298A AU81512/98A AU8151298A AU8151298A AU 8151298 A AU8151298 A AU 8151298A AU 81512/98 A AU81512/98 A AU 81512/98A AU 8151298 A AU8151298 A AU 8151298A AU 8151298 A AU8151298 A AU 8151298A
- Authority
- AU
- Australia
- Prior art keywords
- catalyst
- molecular sieves
- group
- sapo
- synthesis gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims description 57
- 230000015572 biosynthetic process Effects 0.000 title claims description 27
- 238000003786 synthesis reaction Methods 0.000 title claims description 27
- 150000001336 alkenes Chemical class 0.000 title claims description 21
- 238000006243 chemical reaction Methods 0.000 title description 26
- 239000003054 catalyst Substances 0.000 claims description 72
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 52
- 239000002808 molecular sieve Substances 0.000 claims description 49
- 239000007789 gas Substances 0.000 claims description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 239000012018 catalyst precursor Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000010457 zeolite Substances 0.000 claims description 15
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 13
- 239000011651 chromium Substances 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 9
- 239000010948 rhodium Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 229910052676 chabazite Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052675 erionite Inorganic materials 0.000 claims description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 241000269350 Anura Species 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- -1 ethylene, propylene Chemical group 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical class O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052649 zeolite group Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
WO 98/57743 PCT/US98/12703 1 Conversion of Synthesis Gas to Lower Olefins Using Modified Molecular Sieves This application claims priority to U.S. Provisional Patent 5 Application No. 60/050,144, filed June 18, 1997. Field of the Invention The invention relates to a process for incorporating catalysts for the 10 conversion of synthesis gas, preferably synthesis gas comprising carbon dioxide and hydrogen, into molecular sieves. More particularly, the invention relates to a process for incorporating into molecular sieves a catalyst selected from the group consisting of iron, cobalt, nickel, chromium, manganese, and rhodium, in an amount sufficient to catalyze 15 the conversion of synthesis gas to lower olefins. Background of the Invention Lower olefins, such as ethylene, propylene, and butenes, serve as feeds 20 for the production of numerous chemicals. Olefins traditionally are produced by petroleum cracking. Because of the limited supply and/or the high cost of petroleum sources, the cost of producing olefins from petroleum sources has increased steadily. 25 A known alternative feedstock for the production of lower olefins is synthesis gas. Synthesis gas is a combination of hydrogen with either carbon monoxide or carbon dioxide. Synthesis gas can be made from non-petroleum organic sources, such as coal, recycled plastics, and municipal wastes. 30 WO 98/57743 PCT/US98/12703 2 The catalysts used to convert synthesis gas to olefins are known as one type of Fischer-Tropsch catalysts. Fischer-Tropsch catalysts typically are supported on various solids such as molecular sieves. Molecular sieves are ordered, porous crystalline materials with a definite three dimensional 5 crystal structure within which are a large number of small channels or pores. The channels and pores in any specific molecular sieve material are precisely uniform in size. The pores accept for adsorption molecules which are small enough to pass through the pores, while rejecting molecules of larger size. Molecular sieves are used in various ways 10 which take advantage of this property; for example, as catalysts or as supports for catalysts which may be incorporated into the molecular sieve as a framework. Most research focuses on the conversion of carbon monoxide rich 15 synthesis gas to olefins--a reaction which tends to be non-specific, yielding a variety of products. In order for synthesis gas to be attractive as a feedstock to produce lower olefins, methods are needed to increase the selectivity of the conversion process to the desired olefin products. 20 The use of a synthesis gas feedstock which is rich in carbon dioxide instead of carbon monoxide would be commercially attractive--particularly if the process specificity could be manipulated to produce varying amounts of ethylene, propylene, and butenes. Such a commercially attractive alternative can only be realized if suitable catalysts are 25 developed. Summary of the Invention The present invention provides a method for incorporating one or more 30 Fischer Tropsch catalysts into molecular sieves comprising contacting untreated molecular sieves with a catalyst precursor in an inert WO 98/57743 PCT/US98/12703 3 atmosphere under first conditions effective to form complexes comprising said catalyst precursor and said molecular sieves; and, exposing said complexes to an inert atmosphere and to second conditions effective to dissociate volatile components from said catalyst precursor and to 5 evaporate solvent from said complexes, forming modified molecular sieves comprising a catalytically effective amount of a catalyst selected from the group consisting of iron, cobalt, nickel, chromium, manganese, and rhodium. 10 Detailed Description of the Invention The present invention provides catalysts which will convert a carbon dioxide rich synthesis gas to olefins, and which can be manipulated to produce varying amounts of ethylene, propylene, and butenes. 15 Substantially any molecular sieves may be used in the invention. One group of suitable molecular sieves is the zeolite group. The structural formula of a zeolite is best expressed for the crystallographic unit cell as Mxu[(AIO 2 )x(SiO 2 )yl e wH 2 0 20 where M = a cation of valence n, and w = the number of water molecules, and the ratio y/x usually has values of 1-5000, depending upon the structure. The sum (x+y) is the total number of SiO 4 plus A10 4 tetrahedra in the 25 unit cell. The portion within brackets represents the framework composition. Several types of zeolites exist, each of which exhibit different properties and different utilities. Perhaps the best known zeolites are synthetic 30 crystalline aluminosilicate zeolites, which have a rigid three-dimensional WO 98/57743 PCT/US98/12703 4 network of Si04 and A10 4 tetrahedra, which are cross-linked through shared oxygen atoms. The electronegativity of the aluminum-containing tetrahedra is balanced by the inclusion in the crystal of a cation, typically monovalent or divalent, such as an alkali metal (e.g., sodium) or an 5 alkaline earth metal. Synthetic crystalline aluminosilicate zeolites include MFI zeolites and ZSM-5, which is described, for example, in US-A 3,702,886 to Argauer et al. Less well known are the ferrisilicate molecular sieves, such as ZSM-12. 10 ZSM-12 type molecular sieves consist structurally of a three-dimensional network of SiO 4 , FeO 4 , and optionally A10 4 , GaO 4 , GeO 4 tetrahedra which are interlinked by oxygen atoms. Suitable zeolites for use in the invention include, but are not necessarily 15 limited to ZSM-34, erionite, chabazite, and offretite. Zeolites with a relatively high silica-to-alumina atomic ratio are preferred. The silica-to alumina atomic ratio may be in the range of from about 20 to about 4000, preferably from about 40 to about 2000, and most preferably from about 100 to about 800. The most effective silica-to-alumina ratio appears to be 20 in the range of from about 200 to about 300. Silicoaluminophosphates ("SAPO's") are another group of molecular sieves that are useful in the invention. SAPO's have a three-dimensional microporous crystal framework of PO 2 *, A10 2 , and SiO 2 tetrahedral units. 25 The chemical composition (anhydrous) is: mR:(SixAlyP.)O2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system: "m" represents the moles of "R" present per mole of (SixAlyPz)O 2 and has a value of from zero to 0.3, the maximum 30 value in each case depending upon the molecular dimensions of the WO 98/57743 PCT/US98/12703 5 templating agent and the available void volume in the pore system of the particular SAPO species involved, and "x", "y", and "z" represent the mole fractions of silicon, aluminum and phosphorus, respectively. "R" may be removed at elevated temperatures. 5 Suitable SAPO's for use in the invention include, but are not necessarily limited to SAPO-34, SAPO-18, SAPO-17, SAPO-11, and SAPO-5. SAPO's and zeolites may be synthesized according to US-A-4,440,871, incorporated herein by reference, and Zeolites, Vol. 17, pp. 512-522 10 (1996), incorporated herein by reference. Aluminophospho catalysts ("ALPO's") are another type of molecular sieves useful in the present invention. Suitable ALPO's for use in the invention include, but are not necessarily limited to ALPO-17, ALPO-5, 15 ALPO-1 1, ALPO-20, and ALPO-25. US-A- 4,310,440, incorporated herein by reference, gives a good general description of ALPO's. Crystalline metal silico- aluminophosphates (MeAPSO's) and crystalline metal aluminophospho oxides (MeAPO's) also may be useful in the 20 present invention. Suitable MeAPSO's and MeAPO'S include, but are not necessarily limited to SAPO's and alumino phospho oxides comprising preferably in the range of from about 0.005 to about 0.05 moles of a metal selected from the group consisting of magnesium, zinc, iron, cobalt, nickel, manganese, chromium, and mixtures thereof. US-A-4,567,029 is a 25 good general description of MeAPSO's. Preferred molecular sieves for use in the invention are (a) intermediate pore zeolites with a silicon to aluminum ratio in the range of from about 100 to about 800, preferably in the range of from about 200 to about 300, 30 and (b) small pore SAPO's.
WO 98/57743 PCTIUS98/12703 6 The preparation of the framework for molecular sieves is well known in the art and is described in U.S. Patent Nos.: 4,554,143; 4,440,871; 4,853,197; 4,793,984, 4,732,651; and 4,310,440, all of which are 5 incorporated herein by reference. In order to prepare the molecular sieves of the present invention, the molecular sieves should be treated to incorporate a catalyst selected from the group consisting of iron, cobalt, nickel, chromium, manganese, and 10 rhodium. The catalyst may be incorporated into the molecular sieves by many different methods, such as the techniques of incipient wetness, wet impregnation, solid state mixing, soxhlet impregnation, vapor deposition, and other techniques. 15 The catalyst typically is contacted with the molecular sieves in the form of a catalyst precursor. Suitable catalyst precursors include, but are not necessarily limited to compounds comprising the catalyst and a volatile material which relatively easily disassociates from the catalyst, especially at high temperatures. Suitable catalyst precursors are selected from the 20 group consisting of metal carbonyls, metal alkoxides, metal carboxylates, organometallics, and combinations thereof. Preferred catalyst precursors are carbonyls, including but not limited to iron carbonyls, other metal carbonyls, and mixed metal carbonyl cluster 25 compounds. Suitable carbonyl precursors may be anionic, cationic, non ionic, or radical. Examples of suitable catalyst precursors include, but are not necessarily limited to: Fe(CO) 4 ; Fe(CO) 5 ; Fe 2
(CO)
9 ; Fe 3
(CO)
12 ; Na 2 Fe(CO) 4 ; NaHFe 3
(CO)
11 ; Na 2 Fe 4
(CO)
13 ; CsH 5 Fe(CO) 2
CH
3 ;
C
4
H
4 Fe(CO) 3 ; C 4
H
8 Fe(CO) 3 ; C 4
H
6 Fe(CO) 3 ; C 4 HsOHFe(CO) 3 ; 30 [CsH 5 Fe(CO) 2 1 2 ; (C 5
H
5
)
4 Fe 4
(CO)
4 ; HFe 4
(CO)
12 (CH); Co 2 (CO)a; Ni(CO) 4 ; Cr(CO) 6 ; HOs 3
(CO)
1 1
(OC
6
H
5 ); Mn 2 Fe(CO) 1 4 ; KMnFe(CO); WO 98/57743 PCT/US98/12703 7
[(CH
3
)
3
(CH
2
C
6
H
5 )]Fe 2 Rh 4
(CO)
1 6 . Suitable iron carbonyls also may include other organic or inorganic ligands besides hydrogen in addition to a carbonyl or other volatile organic group, an example being a cyclopentadienyl group. 5 In a preferred method for modifying the molecular sieves, the catalyst precursor should be dissolved in a suitable solvent. Suitable solvents include, but are not necessarily limited to lower alcohols and ketones, such as methanol, ethanol, ethylene glycol, acetone, etc. Preferred 10 solvents are methanol and ethanol. The solvent should be used in an amount large enough to dissolve and complex the catalyst precursor with the molecular sieves but small enough to evaporate off the resulting complexes in a reasonably short period of time, preferably no longer than about 8-16 hours. 15 The molecular sieves preferably should be placed in an inert environment, such as a nitrogen purged box, at a pressure in the range of from about 1.01 kPa (1 x 102 atm) to about 1.01 x 105 kPa (1 x 103 atm), preferably from about 10.1 kPa (0.1 atm) to about 5.07 x 104 kPa (5 x 102 atm), most 20 preferably from about 50.67 kPa (0.5 atm) to about 3.04 x 104 kPa (3 x 102 atm). The precursor solution should be added, and the mixture should be stirred for an amount of time sufficient to complex the precursor with the molecular sieves. The stirring time may range from about 10 minutes to about 16 hours, depending upon the size of the catalyst precursor 25 molecules and temperature. Larger precursor molecules require a longer period of stirring in order to be incorporated into the molecular sieves. Another aliquot of the precursor solution should be added and the resulting complexes should be allowed to dry at ambient temperature, typically around 25 *C, in an inert atmosphere for at least about 4 hours or 30 until the solvent evaporates. The mixture then should be subjected to vacuum for at least about 2 hours, preferably in the range of from about 8 WO 98/57743 PCT/US98/12703 8 -16 hours. The procedure may be repeated, as necessary, until a desired amount of catalyst is incorporated into the molecular sieves. The complexes then should be heated to a temperature sufficient to disassociate volatile components of said catalyst precursor from said 5 catalyst. Heating to about 120 *C in air for at least about 2 hours, preferably for about 12 hours, should be sufficient. The complexes then should be calcined. Preferred temperatures for calcination are in the range of from about 300 *C to about 800 *C, preferably in the range of from about 350 *C to about 650 *C, most preferably about 480 *C. 10 The amount of catalyst incorporated into the molecular sieve may vary over a wide range depending, at least in part, on the selected catalyst and the incorporation method. Preferably, the total weight percent of catalyst on the molecular sieves should be the following where the listed metal is 15 the catalyst: for iron based catalysts, in the range of from about 1.0 wt% to about 40 wt%; for nickel based catalysts, in the range of from about 0.5 wt% to about 30 wt%; for cobalt based catalysts, in the range of from about 0.5 wt% to about 30 wt%; for chromium based catalysts, in the range of from about 0.5 wt% to about 25 wt%; for osmium based catalysts, 20 in the range of from about 0.5 wt% to about 25 wt%; and for catalysts comprising 2 or more metals, in the range of from about 0.5 wt% to about 40 wt%. In general, a preferred total weight percent of catalyst will be in the range of from about 0.01 wt% to about 80 wt%, preferably in the range of from about 0.1 wt% to about 60 wt%, most preferably in the range of 25 from about 0.5 wt% to about 40 wt% The conversion process employs a feed of synthesis gas comprising hydrogen and either carbon monoxide or carbon dioxide. Although it is preferred to use a synthesis gas rich in carbon dioxide, the catalysts of 30 the present invention also are effective to convert synthesis gas which is rich in carbon monoxide. In a most preferred embodiment, the synthesis WO 98/57743 PCTIUS98/12703 9 gas consists essentially of hydrogen and carbon dioxide at a molar ratio in the range of from about 1:1 to about 10:1, preferably from about 2:1 to about 6:1, most preferably of about 3:1. Where the synthesis gas contains carbon monoxide, a preferred ratio of CO:hydrogen is in the 5 range of from about 0.01:10, preferably from about 0.1:5, most preferably from about 0.2:2. The conversion of feed to olefins preferably should be carried out in the vapor phase. Preferably, the feedstock should be contacted in the vapor 10 phase in a reaction zone with the defined molecular sieves at effective process conditions so as to produce the desired olefins, i.e., an effective temperature, pressure, GHSV (Gas Hourly Space Velocity) and, optionally, an effective amount of diluent, correlated to produce olefins. Alternately, the process may be carried out in the liquid phase in the 15 presence of solvent. When the process is carried out in the liquid phase, different conversion rates and selectivities of feedstock-to-product may result depending upon the composition of the liquid. The temperature employed in the conversion process may vary over a 20 wide range depending, at least in part, on the selected catalyst. Although not limited to a particular temperature, best results will be obtained if the process is conducted at temperatures in the range of from about 130 0C to about 600 *C, preferably in the range of from about 180 *C to about 450 0C, most preferably in the range of from about 220 0C to about 350 *C. 25 Lower temperatures generally result in lower rates of reaction. However, at higher temperatures, the process may not form an optimum amount of lower olefin products, and the coking rate may become too high. Lower olefin products will form--although not necessarily in optimum 30 amounts--at a wide range of pressures, including but not limited to autogenous pressures and pressures in the range of from about 0.1 kPa WO 98/57743 PCT/US98/12703 10 (9.8 x 104 atm) to about 100 MPa (98 atm). A preferred pressure is in the range of from about 6.9 kPa (6.76 x 102 atm) to about 34 MPa (3.33 X 102 atm), most preferably from about 48 kPa (0.47 atm) to about 0.34 MPa (3.33 atm). The foregoing pressures are exclusive of diluent, if any, and 5 refer to the partial pressure of the feedstock as it relates to synthesis gas. Pressures outside of the stated ranges may operate and are not excluded from the scope of the invention. Lower and upper extremes of pressure may adversely affect selectivity, conversion, coking rate, and/or reaction rate; however, lower olefins still may form. 10 The process should be continued for a period of time sufficient to produce the desired lower olefins. The reaction time may vary from tenths of seconds to a number of hours. The reaction time is largely determined by the reaction temperature, the pressure, the catalyst selected, the weight 15 hourly space velocity, the phase (liquid or vapor), and the selected process design characteristics. A wide range of gas hourly space velocity (GHSV) for the feedstock will function in the present invention. The GHSV generally should be in the 20 range of from about 10 - 100,000 hr-, preferably in the range of from about 100 - 10,000 hr 1 , and most preferably in the range of from about 500 - 5000 hr-. The catalyst may contain other materials which act as inerts, fillers, or binders; therefore, the GHSV is calculated on the volume basis of synthesis gas feed and catalyst. 25 The feed may contain one or more diluents in an amount in the range of from about 1-99 vol%, preferably in the range of from about 5-90 vol%, most preferably in the range of from about 10-50 vol%, based on the total number of moles of all feed and diluent components fed to the reaction 30 zone (or catalyst). Diluents which may be employed in the process WO 98/57743 PCT/US98/12703 11 include, but are not necessarily limited to, helium, argon, nitrogen, water, and mixtures thereof. Preferred diluents are argon and nitrogen. The process may be carried out in a batch, semi-continuous, or 5 continuous fashion. The process may use a single reaction zone or a number of reaction zones arranged in series or in parallel. The process may be intermittent or continuous in an elongated tubular zone or a number of such zones. When multiple reaction zones are used, one or more of the catalysts advantageously may be used in series to provide for 10 a desired product mixture. A dynamic bed system, or any system that includes a variety of transport beds rather than fixed beds, may be desirable. If regeneration of the catalyst is required, such a system would permit introduction of the 15 catalyst as a moving bed to a regeneration zone where, e.g., carbonaceous material could be removed or oxidized. Preferably, the catalyst should be regenerated by burning off carbonaceous deposits that accumulate during the process. 20 The following examples illustrate, but should not be construed to limit the present invention. Example I 25 In a nitrogen box, 7.022 gms of a ZSM-5 molecular sieve with a Si:AI ratio of 28 was mixed with an aliquot of 5 cc methanol containing 1.33 gms of Fe 3
(CO)
1 2 purchased from Aldrich Chemical Co. The mixture was dried under nitrogen overnight. Another aliquot of 5 cc methanol containing a similar amount of Fe 3
(CO)
12 was added to the dried material. This mixture 30 was allowed to dry under nitrogen overnight. The procedure was repeated four more times. After the final drying, the mixture was placed WO 98/57743 PCT/US98/12703 12 under vacuum for about 60 hours at room temperature. The mixture then was heated at 120 *C for about 12 hours, followed by calcination at about 480 *C for about 8 hours. 5 Example i The procedures of Example I were repeated using 7.007 g of a ZSM-5 molecular sieve with a Si:AI ratio of 180. 10 Example Ill The procedures of Example I were repeated using 7.003 g of a ZSM-5 molecular sieve with a Si:AI ratio of 1000. 15 Example IV In a nitrogen purged box, 45 cc of methanol was added to 12.0 g of 7.022 g of .Fe 3
(CO)
1 2 in methanol, which was purchased from Aldrich Chemical Co. The mixture was stirred under nitrogen overnight. To 7.003 g of 20 SAPO-34 powder, obtained from UOP, Des Plaines, Illinois, was added 5 cc of the solution, and the mixture was allowed to dry overnight under nitrogen. Another 5 cc of the methanol/precursor solution was added to the mixture and allowed to dry overnight under nitrogen two subsequent times. The resulting material was then placed in a vacuum dessicator and 25 kept under vacuum overnight at room temperature. The product then was heated to 120 *C in air and kept at that temperature for 12 hours. The temperature was then raised at 10 0 C per minute to 480 0 C. The mixture was calcined at this temperature for about 8 hours. The product powder then was pelletized and sized for performance evaluation. 30 WO 98/57743 PCT/US98/12703 13 Example V The procedures of Example IV were repeated using 7.002 g of SAPO-17 powder. 5 Example VI 5.0 cc (approximately 2.5 g) of the ZSM-5 supported catalyst prepared in Example I was mixed with 15 cc of quartz beads and loaded into a 3/4" 10 outer diameter 316 stainless steel tubular reactor which was heated by a three-zone electric furnace. The center zone of the furnace was adjusted to give the desired reaction temperature of 260*C. A feed gas with a composition of 75 vol% of hydrogen and 25 vol% of CO was passed over the catalyst at a GHSV of 1000 h-1 . The products were analyzed with an 15 on-line gas chromatograph equipped with both a thermal conductivity detector and a flame ionization detector to analyze the products. 10%
CO
2 conversion and 45 wt% total selectivity of ethylene and propylene were observed. 20 Example VII 5.0 cc of the ZSM-5 supported catalyst prepared in Example I was evaluated as in Example VI. Gas chromatographic analysis revealed 20%
CO
2 conversion and 65 wt% total selectivity of ethylene and propylene. 25 Example VIII 5.0 cc of the ZSM-5 supported catalyst in Example IlIl was evaluated as in Example VI. Gas chromatographic analysis revealed 8% CO 2 conversion and 35 wt% total selectivity of ethylene and propylene. 30 WO 98/57743 PCT/US98/12703 14 Example IX 5.0 cc of the SAPO-34 supported catalyst prepared according to Example IV was evaluated as in example VI, except that the feed was of the 5 following composition: 90% argon, 7.5% H2, and 2.5% CO 2 (by volume). Gas chromatographic analysis showed about 12% CO 2 conversion, with 3.9 wt% methane, 10.6 wt% C 2 ", 19.0 wt% C 3 ", 27.7 wt% of dimethylether, and 18.4 wt% methanol selectivities, the rest being C 4 ' products. 10 Example X 5.0 cc of SAPO-17 catalyst prepared according to Example V was evaluated as in example IV. Gas chromatographic analysis showed about 5% CO 2 conversion, with 2.9 wt% methane, 4.9 wt% C2, 46.8 wt% C 3 ", 15 3.9 wt% methanol selectivities, the rest being C 4 * products. From the foregoing, it was concluded that the specificity of ZSM-5 supported catalysts to ethylene and propylene can be optimized by selecting a ZSM-5 catalyst with a suitable silicon-to-aluminum ratio. It 20 also was concluded that higher yields of C 3 ' products could be achieved by using smaller pore SAPO-1 7 or SAPO-34 supported iron catalysts. Persons of ordinary skill in the art will recognize that many modifications may be made to the present invention without departing from the spirit and 25 scope of the present invention. The embodiments described herein are meant to be illustrative only and should not be taken as limiting the invention, which is defined in the following claims.
Claims (17)
1. A method for incorporating one or more Fischer Tropsch catalysts into molecular sieves comprising: 5 contacting untreated molecular sieves with a catalyst precursor in an inert atmosphere under first conditions effective to form complexes comprising said catalyst precursor and said molecular sieves; and, exposing said complexes to an inert atmosphere and to second 10 conditions effective to dissociate volatile components from said catalyst precursor and to evaporate solvent from said complexes, forming modified molecular sieves comprising a catalytically effective amount of a catalyst selected from the group consisting of iron, cobalt, nickel, chromium, manganese, and rhodium. 15
2. The method of claim 1 wherein said second conditions comprise: drying said complexes in an inert atmosphere under third conditions effective to produce dried complexes; and heating said dried complexes in an inert atmosphere under 20 conditions effective to produce said modified molecular sieves.
3. The method of claim 2 wherein said (a) contacting said untreated molecular sieves with a catalyst precursor and said (b) drying said complexes in an inert atmosphere under third conditions are 25 repeated sequentially until said modified molecular sieves comprise said catalytically effective amount of said catalyst.
4. The method of claim 1 wherein said precursor comprises said catalyst in the form of a compound selected from the group WO 98/57743 PCT/US98/12703 16 consisting of metal carbonyls, metal alkoxides, metal carboxylates, organometallics, and combinations thereof.
5. The method of claim 2 wherein said precursor comprises said 5 catalyst in the form of a compound selected from the grbup consisting of metal carbonyls, metal alkoxides, metal carboxylates, organometallics, and combinations thereof.
6. The method of claim 1 wherein said precursor comprises a 10 carbonyl of said catalyst.
7. The method of claim 2 wherein said precursor comprises a carbonyl of said catalyst. 15 8. The method of claim 3 wherein said precursor comprises a carbonyl of said catalyst.
9. The method of claim 6 wherein said catalyst comprises iron; and, 20 said carbonyl is selected from the group consisting of Fe(CO) 5 , Fe 2 (CO), and Fe 3 (CO)1 2 .
10. The method of claim 7 wherein said catalyst comprises iron; and 25 said carbonyl is selected from the group consisting of Fe(CO) 5 , Fe 2 (CO), and Fe 3 (CO) 12 .
11. The method of claim 8 wherein said catalyst comprises iron; and, WO 98/57743 PCT/US98/12703 17 said carbonyl is selected from the group consisting of Fe(CO) 5 , Fe 2 (CO) 9 , and Fe 3 (CO) 12 .
12. The method of claim 1 wherein said modified molecular sieves 5 comprise in the range of from about 0.1-60 wt% of said catalyst.
13. The method of claim 1 wherein said modified molecular sieves comprise in the range of from about 0.5-40 wt% of said catalyst. 10 14. A method comprising contacting synthesis gas with a catalyst supported on molecular sieves other than ZSM-5 under conditions effective to convert said synthesis gas to lower olefins; wherein said molecular sieves are selected from the group 15 consisting of small pore and intermediate pore molecular sieves; and, wherein said catalyst is selected from the group consisting of iron, cobalt, nickel, chromium, manganese, and rhodium. 20 15. A method comprising contacting synthesis gas consisting essentially of carbon dioxide and hydrogen with a catalyst supported on molecular sieves other than ZSM-5 under conditions effective to convert said synthesis gas to lower olefins; 25 wherein said molecular sieves are selected from the group consisting of small pore and intermediate pore molecular sieves; and, wherein said catalyst is selected from the group consisting of iron, cobalt, nickel, chromium, manganese, and rhodium. WO 98/57743 PCT/US98/12703 18
16. The method of claim 14 wherein said molecular sieve are selected from the group consisting of zeolites, aluminophospho catalysts, and silicoaluminophosphate catalysts. 5
17. A method comprising contacting synthesis gas with a catalyst selected from the group consisting of iron, cobalt, nickel, chromium, manganese, and rhodium under conditions effective to convert said synthesis gas to lower olefins, wherein said catalyst is supported 10 on a zeolite other than ZSM-5 and said zeolite comprises a silica to alumina ratio of in the range of from about 100-800.
18. The method of claim 17 wherein said synthesis gas consists essentially of carbon dioxide and hydrogen. 15
19. The method of claim 17 wherein said molecular sieves comprise a silicon to aluminum ratio in the range of from about 200 to about
300. 20 20. The method of claim 18 wherein said molecular sieves comprise a silicon to aluminum ratio in the range of from about 200 to about 300. 21. The method of claim 15 wherein said molecular sieves are is 25 selected from the group consisting of ZSM-34, chabazite, erionite, offretite, SAPO-34, SAPO-17, SAPO-18, SAPO-11, SAPO-5, ALPO-1 7, ALPO-1 1, ALPO-5, and combinations thereof. 22. The method of claim 16 wherein said molecular sieves are selected 30 from the group consisting of ZSM-34, chabazite, erionite, offretite, WO 98/57743 PCTIUS98/12703 19 SAPO-34, SAPO-17, SAPO-18, SAPO-11, SAPO-5, ALPO-17, ALPO-1 1, ALPO-5, and combinations thereof. 23. A catalyst comprising: 5 a zeolite besides ZSM-5 comprising a silica to alumina ratio in the range of from about 100 to about 800; and, a catalytically effective amount of a catalyst selected from the group consisting of iron, cobalt, nickel, chromium, manganese, and rhodium.
Applications Claiming Priority (3)
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US5014497P | 1997-06-18 | 1997-06-18 | |
US60050144 | 1997-06-18 | ||
PCT/US1998/012703 WO1998057743A2 (en) | 1997-06-18 | 1998-06-18 | Conversion of synthesis gas to lower olefins using modified molecular sieves |
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AU8151298A true AU8151298A (en) | 1999-01-04 |
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AU81512/98A Abandoned AU8151298A (en) | 1997-06-18 | 1998-06-18 | Conversion of synthesis gas to lower olefins using modified molecular sieves |
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EP (1) | EP0989908A2 (en) |
CN (1) | CN1260823A (en) |
AR (1) | AR013002A1 (en) |
AU (1) | AU8151298A (en) |
CA (1) | CA2289993A1 (en) |
NO (1) | NO996308L (en) |
TW (1) | TW482750B (en) |
WO (1) | WO1998057743A2 (en) |
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US7241716B2 (en) | 2003-11-10 | 2007-07-10 | Exxonmobil Chemical Patents Inc. | Protecting catalytic sites of metalloaluminophosphate molecular sieves |
BG109246A (en) * | 2005-07-29 | 2005-11-30 | АНГЕЛОВ Чавдар | Method for producing hydrocarbons from hydrogen dioxide |
EP1887071A1 (en) * | 2006-07-31 | 2008-02-13 | Edmund Dr.-Ing. Wagner | Process for the production of synthetic hydrocarbons and derivatives from carbon dioxide and hydrogen used as synthesis gas |
KR100903439B1 (en) | 2007-10-15 | 2009-06-18 | 한국화학연구원 | Preparation method of direct synthesis of light hydrocarbons from natural gas |
JP2010116328A (en) * | 2008-11-11 | 2010-05-27 | Nippon Oil Corp | Method for producing unsaturated hydrocarbon and oxygen-containing compound, catalyst and method for producing the same |
TWI473652B (en) | 2008-12-26 | 2015-02-21 | Nippon Oil Corp | Hydrogenated isomerization catalyst, method for producing the same, dewaxing method for hydrocarbon oil and method for producing lubricating base oil |
RU2587078C2 (en) * | 2009-12-18 | 2016-06-10 | Басф Се | Iron-containing zeolite, method of producing iron-containing zeolites and method for catalytic reduction of nitrogen oxides |
JP6436495B2 (en) | 2013-07-04 | 2018-12-12 | トタル リサーチ アンド テクノロジー フエリユイ | Catalyst composition comprising small size molecular sieve crystals deposited on a porous material |
CN107774302B (en) * | 2016-08-26 | 2020-08-14 | 中国科学院大连化学物理研究所 | Method for preparing liquid fuel and co-producing low-carbon olefin by directly converting catalyst and synthesis gas |
CN109704900B (en) * | 2017-10-26 | 2021-11-30 | 中国石油化工股份有限公司 | Method for preparing olefin by synthesis gas one-step method |
CN109704899B (en) * | 2017-10-26 | 2022-07-08 | 中国石油化工股份有限公司 | Method for preparing olefin from synthesis gas |
CN109701634B (en) * | 2017-10-26 | 2021-09-03 | 中国石油化工股份有限公司 | Catalyst composition for preparing low-carbon hydrocarbon from synthesis gas and application thereof |
CN109701631B (en) * | 2017-10-26 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst for directly preparing low-carbon hydrocarbon from synthetic gas and its use method |
CN109701628A (en) | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Composite catalyst containing phosphate aluminium molecular sieve and its application in one-step method from syngas alkene |
CN111111763B (en) * | 2018-10-30 | 2022-10-11 | 中国石油化工股份有限公司 | Catalyst for directly preparing low-carbon olefin by carbon dioxide hydrogenation and application method thereof |
CN111111760B (en) * | 2018-10-30 | 2022-10-11 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation and application thereof |
CN111111762B (en) * | 2018-10-30 | 2022-10-11 | 中国石油化工股份有限公司 | Catalyst composition for directly preparing low-carbon olefin by carbon dioxide hydrogenation and application thereof |
CN111111766A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Method for utilizing carbon dioxide |
CN111346671B (en) | 2018-12-21 | 2023-03-24 | 中国科学院大连化学物理研究所 | Catalyst and method for preparing low aromatic hydrocarbon liquid fuel by directly converting synthesis gas |
US11691933B2 (en) | 2019-03-28 | 2023-07-04 | Exxonmobil Chemical Patents Inc. | Processes and systems for converting benzene and/or toluene via methylation |
US11827579B2 (en) | 2019-03-28 | 2023-11-28 | ExxonMobil Technology and Engineering Company | Processes for converting benzene and/or toluene via methylation |
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1998
- 1998-06-18 EP EP98931364A patent/EP0989908A2/en not_active Withdrawn
- 1998-06-18 AU AU81512/98A patent/AU8151298A/en not_active Abandoned
- 1998-06-18 CN CN 98806239 patent/CN1260823A/en active Pending
- 1998-06-18 CA CA002289993A patent/CA2289993A1/en not_active Abandoned
- 1998-06-18 WO PCT/US1998/012703 patent/WO1998057743A2/en not_active Application Discontinuation
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CN1260823A (en) | 2000-07-19 |
CA2289993A1 (en) | 1998-12-23 |
NO996308L (en) | 2000-02-07 |
WO1998057743A2 (en) | 1998-12-23 |
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