CN112973779A - Post-treatment method of ZSM-22 molecular sieve and application of post-treatment method in preparation of liquid fuel by synthesis gas one-step method - Google Patents
Post-treatment method of ZSM-22 molecular sieve and application of post-treatment method in preparation of liquid fuel by synthesis gas one-step method Download PDFInfo
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- CN112973779A CN112973779A CN201911292488.9A CN201911292488A CN112973779A CN 112973779 A CN112973779 A CN 112973779A CN 201911292488 A CN201911292488 A CN 201911292488A CN 112973779 A CN112973779 A CN 112973779A
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- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 57
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 32
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 31
- 239000000446 fuel Substances 0.000 title claims abstract description 30
- 239000007788 liquid Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 21
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000004480 active ingredient Substances 0.000 claims abstract description 6
- 239000006227 byproduct Substances 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000523 sample Substances 0.000 claims description 10
- 238000003795 desorption Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 150000001282 organosilanes Chemical class 0.000 claims description 3
- 239000003495 polar organic solvent Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- 229910010413 TiO 2 Inorganic materials 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 26
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 35
- 239000011572 manganese Substances 0.000 description 19
- 239000011701 zinc Substances 0.000 description 19
- 239000003502 gasoline Substances 0.000 description 15
- 239000002243 precursor Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000011261 inert gas Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- UWKQJZCTQGMHKD-UHFFFAOYSA-N 2,6-di-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=N1 UWKQJZCTQGMHKD-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 235000012501 ammonium carbonate Nutrition 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910016300 BiOx Inorganic materials 0.000 description 2
- 229910003320 CeOx Inorganic materials 0.000 description 2
- 229910005535 GaOx Inorganic materials 0.000 description 2
- 229910016978 MnOx Inorganic materials 0.000 description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910007667 ZnOx Inorganic materials 0.000 description 2
- -1 ammonium ions Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000011049 filling 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
- 229910052734 helium Inorganic materials 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 239000012702 metal oxide precursor Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 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 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
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- 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
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
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- 230000002378 acidificating effect Effects 0.000 description 1
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- 238000005804 alkylation reaction Methods 0.000 description 1
- TYYRFZAVEXQXSN-UHFFFAOYSA-H aluminium sulfate hexadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O TYYRFZAVEXQXSN-UHFFFAOYSA-H 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
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- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
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- 230000006690 co-activation Effects 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
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- FYWVTSQYJIPZLW-UHFFFAOYSA-K diacetyloxygallanyl acetate Chemical compound [Ga+3].CC([O-])=O.CC([O-])=O.CC([O-])=O FYWVTSQYJIPZLW-UHFFFAOYSA-K 0.000 description 1
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
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Images
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
- B01J29/7884—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
-
- 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
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- 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
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Abstract
本发明提供一种催化剂及合成气直接转化制液体燃料的方法，其以合成气为反应原料，在固定床或移动床上进行转化反应，所述催化剂为复合催化剂，由组分Ⅰ和组分Ⅱ以机械混合方式复合在一起，组分I的活性成份为金属氧化物，组分II为经后处理的ZSM‑22分子筛；组分Ⅰ中的活性成分与组分Ⅱ中活性成分的重量比在0.1‑20倍范围之间。反应过程具有很高的产品收率和选择性，由C5‑C11组成的液体燃料选择性可以达到50‑80％，C5‑C11中芳烃选择性低于30％，同时副产物甲烷选择性低于5％，具有很好的应用前景。The present invention provides a catalyst and a method for directly converting synthesis gas to liquid fuel. The synthesis gas is used as a reaction raw material, and the conversion reaction is carried out on a fixed bed or a moving bed. The catalyst is a composite catalyst, which is composed of component I and component II. Compounded together by mechanical mixing, the active ingredient of component I is metal oxide, and component II is post-treated ZSM-22 molecular sieve; the weight ratio of the active ingredient in component I to the active ingredient in component II is in between 0.1-20 times. The reaction process has high product yield and selectivity, the selectivity of liquid fuels composed of C5-C11 can reach 50-80%, the selectivity of aromatic hydrocarbons in C5-C11 is lower than 30%, and the selectivity of by-product methane is lower than 5%, which has a good application prospect.
Description
Technical Field
The invention belongs to the field of liquid fuel preparation by synthesis gas, and particularly relates to a ZSM-22 molecular sieve based catalyst and a method for preparing liquid fuel with low aromatic hydrocarbon content by directly converting synthesis gas.
Background
With the development of economy and the improvement of living standard, the demand of liquid fuels and chemicals is also sharply increased year by year. Gasoline production is currently predominantly obtained by catalytic reforming of heavy naphtha. With the gradual consumption of global petroleum resources, particularly for China with insufficient petroleum resources, over 60 percent of petroleum consumption depends on import every year, a replaceable process route is sought, and a method for preparing liquid fuel by using non-oil-based carbon resources such as coal, biomass and the like is developed and utilized, so that the method has important social and strategic meanings.
China is rich in coal resources, and the coal is used as a raw material to obtain synthesis gas (namely CO and H) through gasification2The mixed gas) is converted into methanol, the technical route that the methanol is used for preparing gasoline through dimethyl ether is mature, and the route is industrialized, and the route provides an important new route for preparing liquid fuel from carbon resources such as coal, natural gas and the like. However, if the direct conversion of the synthesis gas can be realized without a direct route of methanol synthesis and methanol dehydration for preparing dimethyl ether, the process flow can be simplified, unit operation can be reduced, and investment and energy consumption can be reduced. The traditional Fischer-Tropsch route can realize the direct conversion of synthesis gas to prepare liquid fuel, but is limited by the reaction mechanism of the synthesis gas, namely CO and H2Dissociative adsorption of molecules on the surface of the catalyst to generate surface C atoms and O atoms, and reaction between the C atoms and the O atoms and hydrogen adsorbed on the surface of the catalyst to form CHxIntermediate, with the production of water molecules. CH (CH)xThe intermediate undergoes free polymerization at the catalyst surface to produce hydrocarbon products having different numbers of carbon atoms (from one to thirty, and sometimes even up to hundreds of carbon atoms). The whole reaction hydrocarbon product has wide carbon atom number distribution and low selectivity of target products, such as gasoline with the selectivity lower than 50%. The prior literature reports that CO activation and C-C coupling can be separated into two active centers by using a dual-function catalyst consisting of oxide and molecular sieveThe method breaks through the limitation of product selectivity in the traditional Fischer-Tropsch process, and the low-carbon olefin is prepared with high selectivity. This indicates that it is possible to obtain a highly selective gasoline component using this active center separation process. The gasoline has huge consumer market in China, and the demand of the gasoline is increased year by year, so that the development of a method for directly preparing high-selectivity gasoline by using synthesis gas has important significance.
Disclosure of Invention
The invention solves the problems: the invention provides a catalyst and a method for preparing liquid fuel by directly converting synthesis gas, wherein the catalyst can be used for regulating the product converted from the synthesis gas to the liquid fuel through simple post-treatment, so that the selectivity of gasoline in the liquid fuel is greatly improved, and the selectivity of aromatic hydrocarbon and methane is very low.
The technical scheme of the invention is as follows:
the invention provides a bifunctional composite catalyst, which comprises a component I and a component II, wherein the component I and the component II are compounded together in a mechanical mixing mode, the active component of the component I is a metal oxide, and the component II is a post-treated ZSM-22 molecular sieve;
the metal oxide is MnOx、MnaCr(1-a)Ox、MnaAl(1-a)Ox、MnaZr(1-a)Ox、MnaIn(1-a)Ox、ZnOx、ZnaCr(1-a)Ox、ZnaAl(1-a)Ox、ZnaGa(1-a)Ox、ZnaIn(1-a)Ox、CeOx、CoaAl(1-a)Ox、FeaAl(1-a)Ox、GaOx、BiOx、InOx、InaAlbMn(1-a-b)Ox、InaGabMn(1-a-b)OxOne or more than two of them;
the MnOx、ZnOx、CeOx、GaOx、BiOx、InOxHas a specific surface area of 1 to 100m2(ii)/g; the preferred specific surface area is 50 to 100m2/g；
The Mn isaCr(1-a)Ox、MnaAl(1-a)Ox、MnaZr(1-a)Ox、MnaIn(1-a)Ox、ZnaCr(1-a)Ox、ZnaAl(1-a)Ox、ZnaGa(1-a)Ox、ZnaIn(1-a)Ox、CoaAl(1-a)Ox、FeaAl(1-a)Ox、InaAlbMn(1-a-b)Ox、InaGabMn(1-a-b)OxHas a specific surface area of 5 to 150m2A preferred specific surface area is from 50 to 150m2/g；
In the invention, a, b, (1-a), (1-a-b) and x only represent the relative proportion of the chemical compositions of elements in the metal oxide, and all the metal oxides with the same proportion are regarded as the same metal oxide.
The value range of x is 0.7-3.7, and the value range of a is 0-1; the value range of a + b is 0-1;
the component II is a post-processed ZSM-22 molecular sieve with TON topological structure.
The post-treatment is that ZSM-22 molecular sieve is treated by organic silane reagent for 2 to 4 hours in nonpolar organic solvent at the temperature of between 60 and 80 ℃. The non-polar organic solvent is preferably n-hexane and the organosilane reagent is preferably TEOS.
The strong acid content in the outer surface of the post-treated ZSM-22 molecular sieve is reduced by 20% to 100%, preferably 30% to 100%, more preferably 40% to 100%.
The ZSM-22 molecular sieve has medium strong acid, and the amount of the medium strong acid sites is 0.05-0.5mol/kg, preferably 0.05-0.4mol/kg, and more preferably 0.05-0.3 mol/kg. The quantity of the medium strong acid sites is the quantity of the total medium strong acid sites in the molecular sieve; the medium-strong acid is ZSM-22 molecular sieve total medium-strong acid including external oneA surface. Wherein the medium strong acid corresponds to NH3-acid having a peak top temperature in the TPD desorption peak in the range of 275-500 ℃; acetone is used as a probe molecule, and the acetone is used as a probe molecule,13the C-NMR chemical shifts are in the range of 210-220 ppm.
The strong acid amount in the outer surface of the molecular sieve is determined by 2, 6-di-tert-butylpyridine in-situ adsorption infrared experiments.
The molecular sieve in the component II can be synthesized by self or be a commercial product, and needs to meet the scope defined by the invention.
The NH3TPD is according to NH3The desorption peak position refers to the position of desorption NH recorded by TCD under the standard test condition and under the test condition that the ratio (w/f) of the mass w of the sample to the flow rate f of the carrier gas is 100 g.h/L and the temperature rise rate is 10 ℃/min3Drawing a desorption curve according to the thermal conductivity signal, and dividing the inorganic solid into three kinds of acid strength according to the vertex of the peak position of the curve; weak acid means NH3Desorbing an acid site with the temperature of less than 275 ℃; the medium strong acid being NH3The desorption temperature is 275 ℃ and 500 ℃; the strong acid being NH3The desorption temperature is higher than the acid position of 500 ℃.
Acetone is used as a probe molecule, and the acetone is used as a probe molecule,13the C-NMR chemical shifts are in the range of 210-220 ppm.
1616cm in the 2, 6-di-tert-butylpyridine in-situ adsorption infrared experiment-1The peak area of the zeolite is in positive correlation with the amount of strong acid in the outer surface, and the reduction range of the amount of the strong acid in the outer surface before and after the post-treatment of the same ZSM-22 molecular sieve can be 1616cm in a 2, 6-di-tert-butylpyridine in-situ adsorption infrared experiment-1The peak area of (a).
Based on the above technical scheme, the weight ratio of the active ingredient in the component I to the component II is preferably 0.1-20, and preferably 0.3-5.
Based on the technical scheme, preferably, a dispersant is further added into the component I, and the metal oxide is dispersed in the dispersant; the dispersant is Al2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3Active carbon, graphene and carbon nanoOne or more than two of the rice pipes.
Based on the technical scheme, preferably, in the component I, the content of the dispersant is 0.05-90 wt%, and the balance is metal oxide.
Based on the technical scheme, preferably, H can be connected or not connected to the O element of the molecular sieve framework of the component II.
The invention provides a method for preparing liquid fuel by directly converting synthesis gas, which takes the synthesis gas as a reaction raw material to carry out conversion reaction on a fixed bed or a moving bed, wherein the adopted catalyst is the bifunctional catalyst.
Based on the technical scheme, preferably, the pressure of the synthesis gas is 0.5-10MPa, preferably 1-8 MPa; the reaction temperature is 300-600 ℃, preferably 320-450 ℃; space velocity of 300-12000h-1Preferably 1000--1More preferably 1000--1(ii) a The synthesis gas is H2Mixed gas of/CO, H2The ratio/CO is between 0.2 and 3.5, preferably between 0.3 and 2.5.
Based on the technical scheme, the bifunctional composite catalyst is used for preparing the liquid fuel by directly converting the synthesis gas in one step, wherein the selectivity of the liquid fuel can reach 50-80%, preferably 60-80%, more preferably 70-80%, and C5-C11The selectivity of the medium aromatic hydrocarbon is lower than 30 percent, and the selectivity of the byproduct methane is lower than 5 percent.
The invention has the following advantages:
1. the technology is different from the traditional Fischer-Tropsch synthesis technology, the synthesis gas can be converted into the liquid fuel with high selectivity, and the gasoline fraction has high selectivity and is not limited by an ASF model.
2. The selectivity of liquid fuel in the product is high and can reach 50-80%, the selectivity of methane is extremely low and is less than 5%, and the product can be separated without deep cooling, so that the energy consumption and the cost of separation are greatly reduced, and the method has a very high application prospect.
3. The active component metal oxide of the component I in the catalyst has higher specific surface area, so that the surface of the metal oxide has more active sites, which is more beneficial to the catalytic reaction.
4. The component II in the catalyst is coupled with the component I to convert the active gas-phase intermediate generated by the component I to obtain liquid fuel, particularly gasoline. The component II can promote the activation and conversion of the component I to the synthesis gas to improve the conversion rate due to the action of the component II on the balance pulling of the series reaction, and on the other hand, the special pore channel structure of the molecular sieve in the component II can promote the generation of the liquid fuel, so that more liquid fuel components can be obtained with high selectivity.
5. The use of component I or component II, respectively, as described in the present invention alone, does not achieve the functionality of the present invention at all, for example, the methane selectivity in the product of component I alone is very high and the conversion is very low, while the use of component II alone hardly activates the reformed syngas, and only the synergistic effect of component I and component II can achieve a high efficiency of syngas conversion and achieve excellent selectivity. The post-treated ZSM-22 molecular sieve selected by the invention greatly reduces the medium-strength acid amount on the outer surface, inhibits the alkylation reaction on the surface of aromatic hydrocarbon, greatly reduces the selectivity of the aromatic hydrocarbon in the obtained product and improves the quality of liquid fuel components.
Drawings
FIG. 1 shows the results of 2, 6-di-tert-butylpyridine in-situ adsorption infrared experiments
Detailed Description
The invention is further illustrated by the following examples, but the scope of the claims of the invention is not limited by these examples. Meanwhile, the embodiments only give some conditions for achieving the purpose, but do not mean that the conditions must be satisfied for achieving the purpose.
The specific surface area of the sample can be measured by nitrogen or argon physical adsorption.
The metal oxide of the present invention can be obtained by purchasing commercially available metal oxides with a high specific surface area, or can be obtained by the following methods:
preparation of catalyst component I
Synthesizing a ZnO material with a high specific surface by a precipitation method:
(1) 3 parts, 0.446g (1.5mmol) of Zn (NO) are weighed out separately3)2·6H2And O, respectively weighing 0.300g (7.5mmol), 0.480g (12mmol) and 0.720g (18mmol) of NaOH in 3 containers, sequentially adding the weighed NaOH into the 3 containers, respectively weighing 30ml of deionized water, adding the deionized water into the 3 containers, stirring the mixture at 70 ℃ for more than 0.5h to uniformly mix the solution, and naturally cooling the solution to room temperature. Centrifugally separating the reaction liquid, collecting the precipitate after centrifugal separation, and washing the precipitate for 2 times by using deionized water to obtain a ZnO metal oxide precursor;
(2) roasting: and drying the obtained product in air, and roasting in the atmosphere to obtain the ZnO material with high specific surface. The atmosphere is inert gas, reducing gas or oxidizing gas; the inert gas being N2One or more of He and Ar; the reducing gas being H2One or two of CO and the reducing gas can also contain inert gas; the oxidizing gas being O2、O3、NO2And the oxidizing gas may contain an inert gas. The roasting temperature is 300-700 ℃, and the time is 0.5-12 h.
The purpose of calcination is to decompose the precipitated metal oxide precursor into oxide nanoparticles with high specific surface area at high temperature, and the decomposed oxide surface adsorbed species can be treated cleanly by the high-temperature treatment of calcination.
Specific samples and their preparation conditions are shown in Table 1 below, in which ZnO #4 is a commercially available ZnO single crystal of low specific surface area as a comparative example.
TABLE 1 preparation of ZnO materials and their parametric properties
(II) synthesizing MnO materials with high specific surface area by a coprecipitation method:
the preparation process is the same as the ZnO #2, except that the precursor of Zn is replaced by the corresponding precursor of Mn, which can be one of manganese nitrate, manganese chloride and manganese acetate, in which the precursor is manganese nitrate, and the corresponding product is producedDefined as MnO; the specific surface area is: 23m2/g。
(III) coprecipitation method for synthesizing CeO with high specific surface area2Materials:
the preparation process is the same as that of ZnO #2, except that the precursor of Zn is replaced by the corresponding precursor of Ce, which can be one of cerium nitrate, cerium chloride and cerium acetate, wherein the corresponding product is defined as CeO2(ii) a The specific surface area is: 92m2/g。
Synthesis of Ga having high specific surface area by coprecipitation method2O3Materials:
the preparation process is the same as that of ZnO #2, except that the precursor of Zn is replaced by the corresponding precursor of Ga, which can be one of gallium nitrate, gallium chloride and gallium acetate, and the corresponding product is defined as Ga2O3(ii) a The specific surface area is: 55m2/g。
(V) coprecipitation method for synthesizing Bi with high specific surface area2O3Materials:
the preparation process is the same as the ZnO #2, except that the precursor of Zn is replaced by the corresponding precursor of Bi, and the precursor can be one of bismuth nitrate, bismuth chloride and bismuth acetate, and is bismuth nitrate. The corresponding product is defined as Bi2O3(ii) a The specific surface areas are: 87m2/g。
(VI) Synthesis of In having a high specific surface area by coprecipitation2O3Materials:
the preparation process is the same as that of ZnO #2, except that Zn precursor is replaced by corresponding precursor of In, which can be one of indium nitrate, indium chloride and indium acetate, In this case, the corresponding product is defined as In2O3(ii) a The specific surface area is: 52m2/g
(VII) Synthesis of Mn with high specific surface area by precipitationaCr(1-a)Ox、MnaAl(1-a)Ox、MnaZr(1-a)Ox、MnaIn(1-a)Ox、ZnaCr(1-a)Ox、ZnaAl(1-a)Ox、ZnaGa(1-a)Ox、ZnaIn(1-a)Ox、CoaAl(1-a)Ox、FeaAl(1-a)Ox、InaAlbMn(1-a-b)Ox、InaGabMn(1-a-b)Ox：
Zinc nitrate, aluminum nitrate, chromium nitrate, manganese nitrate, zirconium nitrate, indium nitrate, cobalt nitrate and ferric nitrate are used as precursors and mixed with ammonium carbonate in water at room temperature (wherein the ammonium carbonate is used as a precipitator, and the feeding proportion is that the ammonium carbonate is excessive or the proportion of ammonium ions and metal ions is 1:1 preferably); and (3) aging the mixed solution, taking out, washing, filtering and drying, and roasting the obtained solid in an air atmosphere to obtain the metal oxide with the high specific surface, wherein specific samples and preparation conditions thereof are shown in the following table 2.
TABLE 2 preparation of high specific surface area metal oxides and their performance parameters
(VIII) dispersant Cr2O3、Al2O3Or ZrO2Dispersed metal oxide
With dispersant Cr2O3、Al2O3Or ZrO2As carrier, preparing Cr by precipitation deposition2O3、Al2O3Or ZrO2A dispersed metal oxide. Taking the preparation of dispersed ZnO as an example, commercial Cr is used2O3(specific surface area about 5 m)2/g)、Al2O3(specific surface area about 20 m)2/g) or ZrO2(specific surface area about 10 m)2/g) as carrier, dispersing in water in advance, and then using zinc nitrate as raw material and sodium hydroxidePrecipitating with a precipitant, Zn, mixed at room temperature2+In a molar concentration of 0.067M, Zn2+The mol part ratio of the organic silicon compound to the precipitant is 1: 8; then aging at 160 ℃ for 24 hours to obtain Cr2O3、Al2O3Or ZrO2ZnO dispersed as a carrier (the content of the dispersant in the component I is 0.1 wt%, 20 wt%, 85 wt% in sequence). The obtained sample is roasted for 1h at 500 ℃ in the air, and the products are sequentially defined as dispersed oxides 1-3, and the specific surface areas are sequentially as follows: 148m2/g，115m2/g，127m2/g。
In the same manner, SiO can be obtained2(specific surface area about 2 m)2/g)、Ga2O3(specific surface area about 10 m)2Per g) or TiO2(specific surface area about 15 m)2(g) MnO oxide dispersed as a support (the content of the dispersant in component I is 5 wt.%, 30 wt.%, 60 wt.% in this order), and the product is defined as dispersed oxide 4 to 6 in this order. The specific surface area is as follows: 97m2/g，64m2/g，56m2/g。
In the same manner, activated carbon (specific surface area about 1000 m) was obtained2Per gram), graphene (specific surface area about 500 m)2Per g) or carbon nanotubes (specific surface area about 300 m)2The ZnO oxide dispersed as a carrier (the content of the dispersant in component I is 5 wt%, 30 wt%, 60 wt% in this order), and the product is defined as a dispersed oxide 7 to 9 in this order. The specific surface area is as follows: 177m2/g，245m2/g，307m2/g。
Secondly, preparation of ZSM-22 with component II after post-treatment
The ZSM-22 molecular sieve has a structure of a 1D ten-membered ring through channel.
The medium-strong acid described in the invention can be used for H spectrum, NH of solid nuclear magnetism3TPD, infrared, chemical titration, etc. However, the acidic test method is not limited to the above test method.
The molecular sieve can be a ZSM-22 molecular sieve with the acid density meeting the requirement of the invention, or a self-synthesized molecular sieve, and the molecular sieve prepared by a hydrothermal synthesis method is taken as an example.
The ZSM-22 molecular sieve is synthesized by a hydrothermal method, and the specific preparation process comprises the following steps:
with n (SiO)2)/n(Al2O3)＝40、n(K2O)/n(SiO2)＝0.105、n(H2O)/n(SiO2)＝40、n(DAH)/n(SiO2) A ratio of 0.3 is an example.
Step 1, mixing and uniformly stirring raw materials of aluminum sulfate hexadecahydrate, potassium hydroxide, silica sol, 1, 6-hexanediamine (DAH) and deionized water at room temperature according to the feeding ratio, and aging for 2 hours at room temperature under the condition of vigorous stirring. Transferring the obtained gel into a hydrothermal kettle, and crystallizing for 72 hours at 160 ℃.
And 2, after crystallization is finished, quenching the reaction kettle to room temperature in a water bath, and repeatedly centrifuging and washing until the pH value of the supernatant is 7. The resulting precipitate was dried in a 60 ℃ oven for 6h and then transferred to a 110 ℃ oven for drying overnight. Then roasting the mixture for 12 hours at 550 ℃ in the air to obtain the potassium ZSM-22.
And 3, mixing the obtained potassium ZSM-22 with 1mol/L ammonium nitrate solution, stirring for 2 hours at 80 ℃ for three times, and roasting for 4 hours at 550 ℃ to obtain the hydrogen ZSM-22 molecular sieve.
And 4, carrying out post-treatment on the obtained hydrogen type ZSM-22 molecular sieve. Heating and refluxing for 4h at 70 deg.C water bath according to the ratio of 1g molecular sieve to 25ml n-hexane to 0.15ml TEOS, evaporating the solution to dryness, drying the obtained solid in 60 deg.C oven for 4h, and transferring to 120 deg.C oven for 4 h. And then roasting the mixture for 4 hours in a muffle furnace at 500 ℃ to obtain the needed post-treated ZSM-22 molecular sieve.
The composition of the framework elements of the ZSM-22 molecular sieve can be one or more than two of Si-O, Si-Al-O, Si-B-O, Si-Al-B-O, Al-O-B; and connecting H to O elements of part of the framework, changing the type and proportion of the precursor, specifically referring to Table 3, and obtaining different types of ZSM-22 subjected to one-time post-treatment, which are sequentially defined as 1-6. The molecular sieves shown in table 3 are all the molecular sieves which are synthesized according to the feed ratio shown in table 3 and modified by ammonium exchange and post-treatment in the steps 2-4.
TABLE 3 preparation of post-treated ZSM-22 molecular sieves and their Performance parameters
And (4) sequentially naming the molecular sieves obtained by processing the fractions 1-6 again according to the method in the step 4 as fractions 7-12. And (4) treating the fractions 7-12 again according to the method in the step 4 to obtain the molecular sieves, which are sequentially named as fractions 13-18. The total medium-strong acid amount of the molecular sieve after the post-treatment in the step 4 is basically unchanged or slightly reduced, but the medium-strong acid amount of the outer surface is obviously reduced. The H-ZSM-22 molecular sieve prepared by the step 1-3 is marked as Z0. FIG. 1 shows the results of in situ adsorption infrared experiments of 2, 6-di-tert-butylpyridine Z0, 1, 7 and 13. It is 1616cm-1The peak areas of (A) were 2.192, 1.574, 0.695 and 0.094, respectively. The strong acid content in the outer surface of the part 1 is reduced by 28.2% compared with that in the outer surface of Z0, the strong acid content in the outer surface of the part 7 is reduced by 68.3% compared with that in the outer surface of Z0, and the strong acid content in the outer surface of the part 13 is reduced by 95.7% compared with that in the outer surface of Z0.
Preparation of catalyst
The component I and the component II in required proportion are added into a container, the purposes of separation, crushing, uniform mixing and the like are realized by utilizing one or more than two of extrusion force, impact force, shearing force, friction force and the like generated by the high-speed movement of the materials and/or the container, the conversion of mechanical energy, heat energy and chemical energy is realized by regulating the temperature and the carrier gas atmosphere, and the interaction among different components is further regulated.
In the mechanical mixing process, the mixing temperature can be set to be 20-100 ℃, and the mixing can be carried out in an atmosphere or directly in air, wherein the atmosphere is selected from any of the following gases:
a) nitrogen and/or inert gas;
b) a mixed gas of hydrogen and nitrogen and/or inert gas, wherein the volume of the hydrogen in the mixed gas is 5-50%;
c) the mixed gas of CO and nitrogen and/or inert gas, wherein the volume of CO in the mixed gas is 5-20%;
d)O2mixed with nitrogen and/or inert gases, in which O2The volume of the inert gas in the mixed gas is 5-20%, and the inert gas is one or more than two of helium, argon and neon.
The mechanical mixing can be one or more of mechanical stirring, ball milling, table mixing and mechanical grinding, and specifically comprises the following steps:
mechanical stirring: in the stirring tank, the component I and the component II are mixed by a stirring rod, and the mixing degree of the component I and the component II can be adjusted by controlling the stirring time (5min-120min) and the stirring speed (30-300 r/min).
Ball milling: the grinding material and the catalyst are rolled in a grinding tank at a high speed to generate strong impact and rolling on the catalyst, so that the effects of dispersing and mixing the component I and the component II are achieved. By controlling the abrasive (the material can be stainless steel, agate and quartz, and the size range is 5mm-15 mm). The ratio of the catalyst to the catalyst (mass ratio range: 20-100: 1).
A shaking table mixing method: premixing the component I and the component II, and filling the mixture into a container; mixing the component I and the component II by controlling the reciprocating oscillation or the circumferential oscillation of the shaking table; the uniform mixing is realized by adjusting the oscillation speed (range: 1-70 r/min) and the time (range: 5min-120 min).
Mechanical grinding method: premixing the component I and the component II, and filling the mixture into a container; under a certain pressure (range: 5 kg-20 kg), the catalyst is ground and moved relatively to the mixed catalyst (speed range: 30-300 r/min) to realize uniform mixing.
Specific catalyst preparations and their parametric characteristics are shown in table 4.
TABLE 4 preparation of the catalyst and its parametric characterization
Examples of catalytic reactions
Fixed bed reactions are exemplified, but the catalyst is also suitable for use in moving bed reactors. The device is provided with a gas mass flow meter and an on-line product analysis chromatograph (tail gas of a reactor is directly connected with a quantitative valve of the chromatograph to carry out periodic real-time sampling analysis).
2g of the catalyst of the present invention was placed in a fixed bed reactor, and the air in the reactor was replaced with Ar, followed by H2Raising the temperature to 300 ℃ in the atmosphere, and switching the synthesis gas (H)2The mol ratio of/CO is 0.2-3.5), the pressure of the synthetic gas is 0.5-10MPa, the temperature is raised to the reaction temperature of 300-. The product was analyzed by on-line chromatographic detection.
Changing temperature, pressure and space velocity and H in syngas2The molar ratio of/CO can vary the reaction properties. Wherein is formed by C5-C11The selectivity of the liquid fuel can reach 50-80%; because the surface hydrogenation activity of the catalyst metal compound is not high, the generation of a large amount of methane is avoided, and the methane selectivity is low. Table 5 lists the specific application of the catalyst and its effectiveness data.
TABLE 5 specific use of the catalyst and Effect data thereof
Comparative example 1 catalyst component I was ZnO1 and component II was a commercially available ZSM-5 with a three-dimensional ten-membered ring channel structure.
The molecular sieve in the catalyst used in comparative example 2 is a commercially available commercial SAPO-34 with three-dimensional cross-channel, eight-membered ring pore opening diameter.
The molecular sieve in the catalyst employed in comparative example 3 is a commercial ZSM-35 having a two-dimensional eight-and ten-membered ring channel structure.
The molecular sieve in the catalyst used in comparative example 4 was a commercial MOR having twelve-membered ring through channels and eight-membered ring side pocket structure.
The molecular sieve in the catalyst adopted in the comparative example 5 is a commercial MCM-68 with a three-dimensional ten-membered ring and twelve-membered ring coexisting channel structure.
The reaction results of comparative examples 1-5 show that molecular sieves of different structures have significant modulation of product selectivity. SAPO-34 with three-dimensional eight-membered ring channel structure is not favorable for C5Formation of the above hydrocarbons is suitable for formation of short carbon chain hydrocarbons (C)2-C4) The product of (1). In the ZSM-35 molecular sieve with two-dimensional eight-membered ring and ten-membered ring coexisting, the product is mainly low-carbon hydrocarbon. The ZSM-5 molecular sieve with three-dimensional ten-element pore channels is suitable for generating gasoline fractions, but the selectivity of aromatic hydrocarbon in gasoline is too high. The MOR molecular sieve with twelve-membered ring through channels and eight-membered ring edge bag structure is not favorable for producing liquid fuel components and is suitable for producing short-carbon paraffin. MCM-68 molecular sieves with three-dimensional ten-and twelve-membered rings have high selectivity for long carbon chains in the product, but have too high aromatic content relative to the ZSM-22 molecular sieves after post-treatment. Only the post-treated ZSM-22 molecular sieve is suitable for producing liquid fuel with low aromatic hydrocarbon and low methane content.
Comparative example 6 use of single-crystal ZnO 4, which has a lower specific surface area: (<1m2/g), the reactivity is poor.
The catalyst adopted in the comparative example 7 only contains the component I ZnO1, does not contain the ZSM-22 molecular sieve sample after post-treatment, has low reaction conversion rate, mainly takes dimethyl ether, methane and other byproducts as the main products, and hardly generates liquid fuel.
The catalyst used in comparative example 8 was a component II only molecular sieve, and the catalyst reaction was almost inactive for the sample containing no component I.
Comparative examples 7 and 8 show that the reaction effect is extremely poor when only component I or component II is used, and the excellent reaction performance of the present invention is not achieved at all.
The catalysts employed in comparative example 9 were ZSM-22 molecular sieve untreated with step 4 and ZnCr2O4The oxide can find that the selectivity of gasoline components is only 56.2 percent, and the selectivity of methane and the content of aromatic hydrocarbon in the gasoline are respectively 10.2 percent and 43.3 percent. Compared with the ZSM-22 molecular sieve after the post-treatment of the step 4 and the same ZnCr2O4The selectivity of gasoline component of the oxide composite catalyst is too low, and the selectivity of methane and aromatic hydrocarbon is too high.
From the above table it can be seen that the structure of the molecular sieve, and the match between the metal oxide and the molecular sieve, is critical and directly affects the carbon monoxide conversion and the liquid fuel selectivity.
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