CN110227539A - A kind of synthesis gas directly converts bifunctional catalyst, the preparation method and application of producing light olefins - Google Patents
A kind of synthesis gas directly converts bifunctional catalyst, the preparation method and application of producing light olefins Download PDFInfo
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- CN110227539A CN110227539A CN201910542828.2A CN201910542828A CN110227539A CN 110227539 A CN110227539 A CN 110227539A CN 201910542828 A CN201910542828 A CN 201910542828A CN 110227539 A CN110227539 A CN 110227539A
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- China
- Prior art keywords
- synthesis gas
- light olefins
- bifunctional catalyst
- producing light
- directly converts
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 41
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 38
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 38
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 239000002808 molecular sieve Substances 0.000 claims abstract description 25
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002905 metal composite material Substances 0.000 claims abstract description 21
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 229910002796 Si–Al Inorganic materials 0.000 claims abstract description 11
- 239000010457 zeolite Substances 0.000 claims abstract description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052738 indium Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 230000004913 activation Effects 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 18
- 230000001376 precipitating effect Effects 0.000 claims description 17
- 230000032683 aging Effects 0.000 claims description 16
- 238000001556 precipitation Methods 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000320 mechanical mixture Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000012495 reaction gas Substances 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 24
- 239000000047 product Substances 0.000 abstract description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- -1 solve the problems Chemical class 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000004448 titration Methods 0.000 description 7
- 238000007873 sieving Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006690 co-activation Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 description 2
- 229910021213 Co2C Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/783—CHA-type, e.g. Chabazite, LZ-218
-
- 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]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C2529/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention provides bifunctional catalyst, the preparation method and application that a kind of synthesis gas directly converts producing light olefins, mainly solve the problems, such as in the prior art CO conversion per pass is low and product in selectivity of light olefin it is poor, the bifunctional catalyst is (0.1 ~ 10) by mass ratio: 1 A, B two parts form, part A is the metal composite oxide that the oxide of two kinds of metallic elements of M and N forms, wherein M and N is any two kinds of combination in Mn, Zr, Ce, Cr, In, Ga, Zn, Al, Mo, Ag, and the molar ratio of M and N are (0.05 ~ 20): 1；Part B is Si-Al zeolite molecular sieve.Bifunctional catalyst of the invention directly converts in reaction for preparing light olefins in synthesis gas, CO conversion per pass is high, and the overall selectivity of low-carbon alkene can reach 80% or more, and byproduct methane selectivity is below 5%, and catalyst has fabulous stability, prospects for commercial application is boundless.
Description
Technical field
The invention belongs to syngas catalytic conversion technical fields, and low-carbon alkene processed is directly converted more particularly, to a kind of synthesis gas
The bifunctional catalyst of hydrocarbon.The invention further relates to the preparation methods that the synthesis gas directly converts the catalyst of producing light olefins.
Background technique
Low-carbon alkene (ethylene, propylene, butylene) is most important basic chemical raw materials in petroleum and chemical industry, in its people
In occupation of vital position in economical production.The yield of the low-carbon alkenes such as ethylene, propylene, butylene especially has " petrochemical industry work
The ethylene of the title of the mother of industry " even more measures the important symbol of a national economic development level.In industrial scale, ethylene and
Propylene is mainly used in Plastics Industry, and butylene is the important source material for producing synthetic rubber.It is passed through at present by raw material of synthesis gas
The dilute hydrocarbon of methanol low-carbon (MTO) technique has realized commercialization, but its economic competitiveness is mainly by market methanol and oil price wave
Dynamic influence, in addition, using methanol product as intermediate product, the choosing of low-carbon alkene is improved by methanol conversion for this technology
Selecting property, while also leading to the problems such as process flow is complicated, and production line is long, and unit process is more, water consume and high energy consumption.China
With more rich coal resources, exploitation directly converts producing light olefins technology with the synthesis gas of coal gasification, can save synthesis first
The pilot process of alcohol, process simplification reduce water consume and energy consumption of production process etc., are the change skills of low-carbon alkene synthesis
Art developing direction.
Synthesis gas directly converts producing light olefins using traditional Fischer-Tropsch synthesis path, is loaded with porous carrier
Iron or cobalt be catalyst, but iron, cobalt metal have stronger chain growth ability, C-C coupling be difficult to accuracy controlling, by A-S-F
The overall selectivity of the limitation of the regularity of distribution, lower carbon number hydrocarbons is not higher than 60%.2016, Shanghai Advanced Research Institute, Chinese Academy of Sciences grandson gave
It is rare that (Nature, 538 (2016), 84-87) is waited to develop a kind of Co2C catalyst, CO conversion ratio can reach 31.8%, low-carbon
The selectivity of alkene reaches 60.8%, in the patent (105107523 A of CN) of their published applications, by control metal Co with
The activity of the controllable catalyst of ratio between auxiliary agent Mn and the selectivity of product, but product C5+Selectivity be still higher than
20%, product distribution fails to break A-S-F distribution limitation completely.
2016, (Science, 351 (2016), 1065- are believed and waited to Dalian Inst of Chemicophysics, Chinese Academy of Sciences's packet
1068) control accurate for realizing C-C coupling activates CO using the Zn-Cr metal oxide of partial reduction, and the intermediate of generation produces
Object carries out C-C coupling by SAPO-34 molecular sieve, CO conversion ratio can be made to reach 17%, selectivity of light olefin reaches 80%, changes
Become reaction condition, CO conversion ratio can be made to be increased to 35%, but the selectivity of low-carbon alkene is then reduced to 69%.Based on same strategy,
Xiamen University Wang Ye etc. (Angewandte Chemie International Edition, 55 (2016), 4725-4728)
CO activation and carbon carbon coupling reaction occurs Deng using Zn-Zr oxide and SAPO-34 molecular sieve, CO conversion ratio can be made to reach
10%, selectivity of light olefin reaches 70%, and when increasing reaction pressure to 2.0 MPa, the selectivity of low-carbon alkene is down to 36%.Its
It in disclosed patent (CN 106345514A), is mixed using double-micropore zeolites molecular sieve with zirconium base solid solution, double-micropore zeolites point
The diffusion of reaction product can be improved in son sieve, and the work of catalyst can be improved in zirconium base solid solution and metal oxide in the case where coexisting
Property, inhibit the hydrogenation reaction of low-carbon alkene, thus the low-carbon alkene generated in stable product.
Producing light olefins are directly converted by synthesis gas, compared to traditional Fischer-Tropsch synthesis path, are urged using difunctional
The strategy of agent makes CO activation couple generation with C-C in the different activities site of same catalyst, although low-carbon alkene in product
Overall selectivity it is higher, can reach 80% or more, but the activity of catalyst is still to be improved, current CO conversion ratio is generally below
20%, it will lead to the secondary of low-carbon alkene if improving CO conversion ratio and be hydrogenated to low-carbon alkanes, to reduce low-carbon in product
The selectivity of alkene.
Summary of the invention
In view of the above-mentioned problems, directly converting the difunctional of producing light olefins the present invention provides a kind of by one step of synthesis gas and urging
Agent, preparation method and application, the catalyst regulate and control CO and H using novel metal composite oxide2Activation, using sial
The conversion of molecular sieve control intermediate product.Metal composite oxide and Si-Al molecular sieve catalytic mechanical ground and mixed of the invention
Afterwards, the CO conversion per pass of synthesis gas can be made to reach 30% or more, while guaranteeing that the selectivity of low-carbon alkene is more than 80%, by-product
The selectivity of methane is down to 5% or less.
In order to achieve the above technical purposes, specific technical solution adopted by the present invention is as follows.
A kind of synthesis gas directly converts the bifunctional catalyst of producing light olefins, which is characterized in that described difunctional to urge
Agent is formed through mechanical mixture by A, B two parts and is prepared, wherein the part A is the oxide group of two kinds of metallic elements of M and N
At metal composite oxide, wherein M and N be Mn, Zr, Ce, Cr, In, Ga, Zn, Al, Mo, Ag in any two kinds of combination,
The molar ratio of M and N is (0.05 ~ 20): 1；The part B is Si-Al zeolite molecular sieve；The two-part mass ratio of A, B is
(0.1 ~ 10): 1.
Synthesis gas as described above directly converts the bifunctional catalyst of producing light olefins, which is characterized in that the group of M and N
It closes any one in preferred Mn-Zn, Mn-In, Zr-Ce, Ga-Al, Zr-Ga, Zn-Ga, Zr-Ag, Mn-Ga, Zr-Mo, Ga-Ce
Group.
A preferred technical solution is that synthesis gas as described above directly converts the double-function catalyzing of producing light olefins
Agent, which is characterized in that the part A forms compound for the oxide by two kinds of metallic elements of M and N of alkali metal promoter modification
Metal oxide, alkali metal is at least one of Na or K in the alkali metal promoter；The alkali metal promoter is in composition metal
Shared mass fraction is no more than 1% in oxide.
Further, the Si-Al molecular sieve component structure can be any of CHA, AEI, MFI, MOR, AFX, MEL, MFS
One kind, preferably any one of CHA, AEI structure, Si/Al ratio are preferably 0 ~ 50, and the middle strong acid acid amount of molecular sieve is 0.01
~0.8 mmol·g-1, preferably 0.05 ~ 0.15 mmolg-1, in preferred molecular sieve SAPO-34, SSZ-13, SAPO-18
Any one.
A kind of above-mentioned synthesis gas directly converts the preparation method of the bifunctional catalyst of producing light olefins, including walks as follows
It is rapid:
1) it prepares mixing salt solution: the inorganic salts comprising M and N element with distilled water being mixed and stirred for being configured to certain density
Mixed solution, wherein total ion molar concentration range of mixing salt solution is 0.05 ~ 3.0 mol/L；
2) prepare precipitant solution: precipitating reagent being dissolved in water and is configured to precipitant solution, the precipitant solution it is mole dense
Degree is 0.05 ~ 3.0 mol/L.
3) parallel-flow precipitation coprecipitation reaction: is occurred into for precipitating reagent obtained in the salting liquid obtained in step 1) and step 2
Reaction, at 20 ~ 90 DEG C, the pH value of precipitating is controlled 6.0 ~ 12.0, through 40 ~ 90 DEG C of agings 1 ~ 10 for the precipitation temperature control
H, gained presoma then obtain metal composite oxide after Muffle kiln roasting through 110 DEG C of dryings.
4) by obtained metal oxide oxidation catalyst object and molecular sieve physical mixed, compression molding is made described difunctional
Catalyst.
Further, in above-mentioned preparation method, during roasting prepares metal composite oxide, maturing temperature be 380 ~
650 DEG C, calcining time is 2 ~ 20 h.
Further, in above-mentioned preparation method, metal oxide precursor salt is nitrate, acetate, hydrochloride, sulfuric acid
At least one of salt.Preferably nitrate and acetate.
Further, in above-mentioned preparation method, used precipitating reagent includes ammonium carbonate, ammonium hydrogen carbonate, sodium carbonate, carbonic acid
One or more of potassium, sodium hydroxide, potassium hydroxide, ammonium hydroxide, preferred embodiment are sodium carbonate, ammonium hydroxide, sodium hydroxide.
Further, mechanical stirring, mechanical lapping, ball can be used in metal composite oxide and molecular sieve physical admixture
The one or more of mill, shaking table hybrid mode.The quality of O composite metallic oxide catalyst and the silicoaluminophosphate molecular sieve catalyst
Than controlling 0.1 ~ 10.
Above-mentioned bifunctional catalyst carries out synthesis gas direct catalytic conversion producing light olefins in fixed bed reactors and answers
With.Before reaction, the bifunctional catalyst for directly converting producing light olefins to synthesis gas first carries out pre-activate, activation condition are as follows:
400 ~ 550 DEG C of activation temperature, activation phenomenon H2, CO, Ar or CO/H2At least one of mixed gas, activation time be 1 ~
10 h；It then switches to synthesis gas and carries out directly conversion reaction for preparing light olefins, reaction condition are as follows: reaction temperature 370 ~ 450
DEG C, reaction pressure 5 ~ 80 bar, reaction gas H2/ CO molar ratio 0.5 ~ 4,1500 ~ 12000 mL/ of gas space velocity (gh).
The progress of advantage and substance of the invention is as follows:
(1) traditional Fischer-Tropsch route is overcome since ASF distribution limitation causes selectivity of light olefin is not high (to be difficult to break through
60%) and the low problem of Catalyst Conversion, the catalyst CO conversion ratio conversion per pass of invention preparation can reach 30% very
To higher, the selectivity of low-carbon alkene is more than 80%, while can control the selectivity of byproduct methane below 5%.
(2) compared to industrialized MTO technique producing light olefins, " one-step method " provided by the present invention convert at present
Producing light olefins technique needs not move through the separative unit of synthesising gas systeming carbinol technique, can realize in a reactor by synthesis gas
The direct synthesizing low-carbon alkene with high selectivity of one step conversion, has been greatly saved investment, the producing cost of equipment, and reduce water consume
And energy consumption.
(3) catalyst preparation process is simple, is easy to large-scale production, and the bifunctional catalyst of the invention is shown
Fabulous stability, can be stable operation 600 hours, and prospects for commercial application is wide.
Specific embodiment
Further describe preparation method disclosed in this patent below by specific embodiment explanation, but the present invention not by
The limitation of following embodiments.
Embodiment 1
Four 22.1 parts of water acetic acid manganese quality are weighed by metal molar ratio Mn:Zn=9:1,2.2 parts of Zinc diacetate dihydrate quality, are dissolved in
Distilled water is configured to the aqueous solution of 2.0 mol/L, the aqueous solution of 2.0 mol/L is configured to as precipitating reagent with sodium carbonate, using simultaneously
The mode that stream is added dropwise carries out coprecipitation reaction, and controlling the pH value in precipitation process by control rate of addition is 7.5 ± 0.2, sinks
Shallow lake temperature is controlled at 80 DEG C, and in 80 DEG C of 1 h of aging, the product after aging is washed through deionized water into the sediment after titration
Property is dried overnight in 110 DEG C and is placed on 380 DEG C of 2 h of Muffle kiln roasting.Gained catalyst quality percentage composition are as follows:
MnO2 90.4%、ZnO 9.4%、Na2O 0.2%。
8 parts of metal composite oxide of preparation, SSZ-13 molecular sieve (Si/Al=7.5, middle strong acid acid amount are weighed in mass ratio
0.1 mmol·g-1) 1 part, the two is homogenously mixed together using ball mill, and then tabletting, sieving (20 ~ 40 mesh) prepare double function
It can catalyst.
Bifunctional catalyst after taking a certain amount of granulation is packed into high pressure fixed bed reactors, using H2Gas is 420
DEG C, 4h is activated under normal pressure, boosting to reaction pressure is 25 bar, unstripped gas is then switched to, according to the work of catalyst in table one
Change condition and evaluation condition are reacted, the sampling analysis after stable reaction, and catalyst activity evaluation response result sees attached list two.
Embodiment 2
Mn:Ga=5:1 weighs 17.9 parts of quality of manganese nitrate (50% aqueous solution) in molar ratio, and nine 4.2 parts of nitric hydrate gallium quality are molten
It is configured to the aqueous solution of 1.0 mol/L in distilled water, the aqueous solution of 1.0 mol/L is configured to using sodium hydroxide as precipitating reagent,
Coprecipitation reaction is occurred using the method that cocurrent is added dropwise, makes pH value 7.5 ± 0.2 in precipitation process by controlling rate of addition,
Precipitation temperature is controlled at 60 DEG C, is deposited in 60 DEG C of 2 h of aging after titration, and it is heavy that the product after aging is washed through deionized water
It forms sediment, after 110 DEG C of drying, is placed in 400 DEG C of 5 h of Muffle kiln roasting.Gained catalyst quality percentage composition are as follows: MnO2
82.2%、Ga2O3 17.7%、Na2O 0.08%。
Weigh 2 parts of the metal composite oxide (20 ~ 40 mesh) of preparation in mass ratio, SAPO-34 molecular sieve (Si/Al=0.6,
Middle 0.12 mmolg of strong acid acid amount-1) 1 part, the two shaking table is homogenously mixed together, is spare.
The activation condition and evaluation condition of catalyst see attached list one, and activity rating reaction result sees attached list two.
Embodiment 3
Zr:Ga=5:1 weighs five 21.5 parts of water zirconium nitrate quality in molar ratio, and nine 4.2 parts of nitric hydrate gallium quality are dissolved in distillation
Water is configured to the aqueous solution of 1.0 mol/L, and the aqueous solution of 1.0 mol/L is configured to using ammonium hydroxide as precipitating reagent, is dripped using cocurrent
Coprecipitation reaction occurs for the method added, and controlling the pH value in precipitation process by control rate of addition is 7.2 ± 0.2, precipitating temperature
Degree control is deposited in 60 DEG C of 1 h of aging after titration at 30 DEG C, and the product after aging is washed through deionized water and precipitated, in 110
DEG C drying after, be placed in 450 DEG C of 15 h of Muffle kiln roasting.Gained catalyst quality percentage composition are as follows: ZrO2 86.8%、
Ga2O3 13.2%。
4 parts of metal composite oxide of preparation, SAPO-34 molecular sieve (Si/Al=0.1, middle strong acid acid are weighed in mass ratio
Measure 0.08 mmolg-1) 1 part, the two is ground in agate and is homogenously mixed together, then tabletting, sieving (20 ~ 40 mesh), standby
With.
The activation condition and evaluation condition of catalyst see attached list one, and activity rating reaction result sees attached list two.
Embodiment 4
Zn:Ga=2:1 ratio weighs 13.2 parts of Zinc diacetate dihydrate quality in molar ratio, and nine 12.5 parts of nitric hydrate gallium quality are dissolved in
Distilled water is configured to the aqueous solution of 3.0 mol/L, and the aqueous solution of 3.0 mol/L is configured to using potassium carbonate as precipitating reagent, uses
Coprecipitation reaction occurs for the method that cocurrent is added dropwise, and controlling the pH value in precipitation process by control rate of addition is 6.5 ± 0.2,
Precipitation temperature is controlled at 70 DEG C, is deposited in 70 DEG C of 5 h of aging after titration, and it is heavy that the product after aging is washed through deionized water
It forms sediment, after 110 DEG C of drying, is placed in 600 DEG C of 4 h of Muffle kiln roasting.Gained catalyst quality percentage composition are as follows: ZnO
62.9%、Ga2O3 36.3%、K2O 0.8%。
1 part of metal composite oxide of preparation, SAPO-18 molecular sieve (Si/Al=0.1, middle strong acid acid are weighed in mass ratio
Measure 0.20 mmolg-1) 4 parts, the two is ground in agate and is homogenously mixed together, then tabletting, sieving (20 ~ 40 mesh), standby
With.
The activation condition and evaluation condition of catalyst see attached list one, and activity rating reaction result sees attached list two.
Embodiment 5
Ga:Al=1:8 weighs nine 4.2 parts of nitric hydrate gallium quality in molar ratio, 30.0 parts of ANN aluminium nitrate nonahydrate quality, is dissolved in steaming
Distilled water is configured to the aqueous solution of 0.5 mol/L, and the aqueous solution of 0.5 mol/L is configured to using potassium hydroxide as precipitating reagent, uses
Coprecipitation reaction occurs for the method that cocurrent is added dropwise, and controlling the pH value in precipitation process by control rate of addition is 11.0 ± 0.2,
Precipitation temperature is controlled at 45 DEG C, is deposited in 70 DEG C of 6 h of aging after titration, and it is heavy that the product after aging is washed through deionized water
It forms sediment, after 110 DEG C of drying, is placed in 550 DEG C of 3 h of Muffle kiln roasting.Gained catalyst quality percentage composition are as follows: Ga2O3
18.7%、Al2O3 81.2%、K2O 0.1%。
1 part of metal composite oxide of preparation, SAPO-18 molecular sieve (Si/Al=0.2, middle strong acid acid are weighed in mass ratio
Measure 0.40 mmolg-1) 8 parts, the two is ground in agate and is homogenously mixed together, then tabletting, sieving (20 ~ 40 mesh), standby
With.
The activation condition and evaluation condition of catalyst see attached list one, and activity rating reaction result sees attached list two.
Embodiment 6
Zr:Ag=16:1 weighs five 68.7 parts of water zirconium nitrate quality in molar ratio, 1.7 parts of silver nitrate quality, is dissolved in distilled water preparation
At the aqueous solution of 1.0 mol/L, it is configured to the aqueous solution of 2.0 mol/L using sodium carbonate as precipitating reagent, is added dropwise using cocurrent
Coprecipitation reaction occurs for method, and controlling the pH value in precipitation process by control rate of addition is 9.0 ± 0.2, precipitation temperature control
System is deposited in 65 DEG C of 4 h of aging after titration at 65 DEG C, and the product after aging is washed through deionized water and precipitated, in 110 DEG C
After drying, it is placed in 650 DEG C of 4 h of Muffle kiln roasting.Gained catalyst quality percentage composition are as follows: ZrO2 92.1%、Ag2O
7.2%、Na2O 0.7%。
1 part of metal composite oxide of preparation, SAPO-34 molecular sieve (Si/Al=0.05, middle strong acid acid are weighed in mass ratio
Measure 0.06 mmolg-1) 1 part, the two is ground in agate and is homogenously mixed together, then tabletting, sieving (20 ~ 40 mesh), standby
With.
The activation condition and evaluation condition of catalyst see attached list one, and activity rating reaction result sees attached list two.
Embodiment 7
Ga:Ce=1:2 weighs nine 12.5 parts of water gallium nitrate quality in molar ratio, and six 26.0 parts of nitric hydrate cerium quality are dissolved in distillation
Water is configured to the aqueous solution of 0.5 mol/L, the aqueous solution of 1.0 mol/L is configured to using sodium carbonate as precipitating reagent, using cocurrent
Coprecipitation reaction occurs for the method for dropwise addition, and controlling the pH value in precipitation process by control rate of addition is 7.0 ± 0.2, precipitating
Temperature is controlled at 45 DEG C, is deposited in 45 DEG C of 1 h of aging after titration, and the product after aging is washed through deionized water and precipitated, in
After 110 DEG C of drying, it is placed in 500 DEG C of 4 h of Muffle kiln roasting.Gained catalyst quality percentage composition are as follows: Ga2O3 21.3%、
CeO2 78.3%、Na2O 0.4%。
3 parts of metal composite oxide of preparation, SSZ-13 molecular sieve (Si/Al=16, middle strong acid acid amount are weighed in mass ratio
0.5 mmol·g-1) 1 part, the two is ground in agate and is homogenously mixed together, then tabletting, sieving (20 ~ 40 mesh), spare.
The activation condition and evaluation condition of catalyst see attached list one, and activity rating reaction result sees attached list two.
The difunctional activation of catalyst condition of table one and catalyze and synthesize gas conversion producing light olefins evaluation response condition
| Number | Activation phenomenon | Activation temperature (DEG C) | Reaction temperature (DEG C) | Reaction pressure (bar) | Reaction velocity mL/ (gh) | H2/ CO molar ratio |
| Embodiment 1 | H2 | 420 | 380 | 25 | 4800 | 3.5 |
| Embodiment 2 | CO | 430 | 420 | 20 | 1500 | 2.5 |
| Embodiment 3 | Ar | 400 | 400 | 30 | 12000 | 2.0 |
| Embodiment 4 | H2/CO | 450 | 380 | 8 | 6000 | 0.8 |
| Embodiment 5 | Ar | 450 | 425 | 45 | 9000 | 3.0 |
| Embodiment 6 | H2 | 550 | 450 | 40 | 1800 | 1.0 |
| Embodiment 7 | H2 | 420 | 390 | 75 | 3000 | 1.5 |
Two bifunctional catalyst of table catalyzes and synthesizes gas conversion producing light olefins Activity evaluation
| Number | CO conversion ratio/% | CH4Selectivity/% | C2-C4Olefine selective/% | C2-C4Overall selectivity/% | Alkene alkane molar ratio O/P | C5+Selectivity/% | CO2Selectivity/% |
| Embodiment 1 | 20.2 | 4.9 | 81.2 | 90.9 | 8.4 | 4.2 | 46.1 |
| Embodiment 2 | 38.5 | 3.5 | 80.2 | 92.8 | 6.4 | 3.7 | 46.8 |
| Embodiment 3 | 30.5 | 2.5 | 90.8 | 94.3 | 25.9 | 3.2 | 41.4 |
| Embodiment 4 | 19.9 | 5.2 | 81.5 | 90.4 | 9.1 | 4.4 | 46.5 |
| Embodiment 5 | 22.3 | 3.9 | 79.6 | 87.9 | 9.6 | 8.2 | 41.2 |
| Embodiment 6 | 22.0 | 4.8 | 80.1 | 89.0 | 9.0 | 6.2 | 42.8 |
| Embodiment 7 | 58.5 | 2.7 | 84.6 | 93.8 | 9.2 | 3.5 | 43.4 |
Note: the selective calculation method of all hydro carbons removes CO2It obtains.
The present invention provides one kind by the bifunctional catalyst of synthesis gas " one-step method " highly selective preparing low-carbon olefins,
Its catalytic action mechanism is to regulate and control CO and H using novel metal composite oxide2Activation, Si-Al molecular sieve control is intermediate produces
The conversion of object is commented according to bifunctional catalyst activation condition in table one and evaluating catalyst reaction condition in conjunction with activity in table two
Valence result activates the dissociation of hydrogen it is found that metal composite oxide of the invention plays fabulous activation to reaction gas CO
Ability is moderate, to can effectively avoid while improving CO conversion per pass, alkene is secondary to be hydrogenated to alkane, to realize
By one-step method from syngas high activity and preparing low-carbon olefins with high selectivity, can preferably solve in traditional Fischer-Tropsch synthesis
Selectivity of light olefin low (total lower carbon number hydrocarbons is less than 60%) and the bifunctional catalyst CO difficulty that conversion per pass is low (< 20%)
Topic.In addition, test result is also shown that catalyst of the invention has fabulous catalytic stability, it can be stable operation 600 hours
Without there is obvious inactivation.
Claims (10)
1. the bifunctional catalyst that a kind of synthesis gas directly converts producing light olefins, which is characterized in that the double-function catalyzing
Agent is formed through mechanical mixture by A, B two parts and is prepared, wherein the part A is that the oxide of two kinds of metallic elements of M and N forms
Metal composite oxide, wherein M and N be Mn, Zr, Ce, Cr, In, Ga, Zn, Al, Mo, Ag in any two kinds of combination, M
Molar ratio with N is (0.05 ~ 20): 1；The part B is Si-Al zeolite molecular sieve；The two-part mass ratio of A, B is
(0.1 ~ 10): 1.
2. the bifunctional catalyst that synthesis gas as described in claim 1 directly converts producing light olefins, which is characterized in that M and N
Group be combined into it is any one in Mn-Zn, Mn-In, Zr-Ce, Ga-Al, Zr-Ga, Zn-Ga, Zr-Ag, Mn-Ga, Zr-Mo, Ga-Ce
Group.
3. the bifunctional catalyst that synthesis gas as claimed in claim 1 or 2 directly converts producing light olefins, which is characterized in that
Before with B two parts mechanical mixture, the part A is modified through alkali metal promoter first；Alkali metal in the alkali metal promoter
For Na or K；Alkali metal promoter mass fraction shared in the metal composite oxide after modification is no more than 1%.
4. the bifunctional catalyst that synthesis gas as claimed in claim 3 directly converts producing light olefins, which is characterized in that described
Si-Al zeolite molecular sieve structure is any one in CHA, AEI, MFI, MOR, AFX, MEL, MFS.
5. the bifunctional catalyst that synthesis gas as claimed in claim 4 directly converts producing light olefins, which is characterized in that described
Si-Al zeolite molecular sieve is the SAPO-18 of SAPO-34 or SSZ-13 or the AEI structure of CHA structure；The Si-Al zeolite molecule
Si/Al ratio is 0 ~ 50 in sieve structure, middle strong acid acid amount is 0.01 ~ 0.8 mmolg-1。
6. a kind of synthesis gas of any of claims 1 or 2 directly converts the preparation method of the bifunctional catalyst of producing light olefins,
Include the following steps:
1) it prepares mixing salt solution: the inorganic salts comprising metallic element M and metallic element N being mixed and stirred for distilled water, are matched
Certain density mixing salt solution is made, total ion molar concentration of the mixing salt solution is 0.05 ~ 3.0 mol/L；
2) it prepares precipitant solution: precipitating reagent being dissolved in the water and is configured to precipitant solution, mole of the precipitant solution
Concentration is 0.05 ~ 3.0 mol/L；
3) parallel-flow precipitation coprecipitation reaction: is occurred into for the mixing salt solution that step 1) obtains and the precipitant solution that step 2 obtains
Reaction, the temperature control of precipitating in 20 ~ 90 DEG C, the pH value control of precipitating 6.0 ~ 12.0, in 40 ~ 90 DEG C of 1 ~ 10 h of aging,
Gained presoma then obtains metal composite oxide after Muffle kiln roasting through 110 DEG C of dryings；
4) metal composite oxide for obtaining step 3) and Si-Al molecular sieve physical mixed, mixed process aoxidize composition metal
The mass ratio of object and Si-Al molecular sieve is controlled in (0.1 ~ 10): 1, then compression molding, is made the bifunctional catalyst.
7. synthesis gas as claimed in claim 6 directly converts the preparation method of the bifunctional catalyst of producing light olefins, special
Sign is, during Muffle kiln roasting prepares metal composite oxide, maturing temperature is 380 ~ 650 DEG C, calcining time
For 2 ~ 20 h.
8. synthesis gas as claimed in claim 6 directly converts the preparation method of the bifunctional catalyst of producing light olefins, special
Sign is that the inorganic salts of the metallic element M and N are any one in the nitrate of M and N, acetate, hydrochloride, sulfate
Group.
9. synthesis gas as claimed in claim 6 directly converts the preparation method of the bifunctional catalyst of producing light olefins, special
Sign is, the precipitating reagent is ammonium carbonate, ammonium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, one in ammonium hydroxide
Kind is several.
10. the bifunctional catalyst that synthesis gas described in a kind of any one of claim 3 to 5 directly converts producing light olefins exists
The application of synthesis gas direct catalytic conversion producing light olefins is carried out in fixed bed reactors, which is characterized in that right first before reaction
The bifunctional catalyst that synthesis gas directly converts producing light olefins carries out pre-activate, activation condition are as follows: activation temperature 400 ~ 550
DEG C, activation phenomenon H2, CO, Ar or CO/H2At least one of mixed gas, activation time are 1 ~ 10 h；It then switches to close
It carries out directly converting reaction for preparing light olefins, reaction condition are as follows: 370 ~ 450 DEG C of reaction temperature, reaction pressure 5 ~ 80 at gas
Bar, reaction gas H2/ CO molar ratio 0.5 ~ 4,1500 ~ 12000 mL/ of gas space velocity (gh).
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