CN107774302A - The method that a kind of catalyst and synthesis gas directly convert preparing liquid fuel co-producing light olefins - Google Patents
The method that a kind of catalyst and synthesis gas directly convert preparing liquid fuel co-producing light olefins Download PDFInfo
- Publication number
- CN107774302A CN107774302A CN201610727837.5A CN201610727837A CN107774302A CN 107774302 A CN107774302 A CN 107774302A CN 201610727837 A CN201610727837 A CN 201610727837A CN 107774302 A CN107774302 A CN 107774302A
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- Prior art keywords
- catalyst
- component
- synthesis gas
- kinds
- oxygen
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 37
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 34
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 15
- 239000000446 fuel Substances 0.000 title claims abstract description 15
- 239000007788 liquid Substances 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 21
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 21
- 239000002808 molecular sieve Substances 0.000 claims abstract description 21
- 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 21
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 33
- 229910052760 oxygen Inorganic materials 0.000 claims description 33
- 239000001301 oxygen Substances 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 32
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910019114 CoAl2O4 Inorganic materials 0.000 claims description 7
- 229910001677 galaxite Inorganic materials 0.000 claims description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 6
- 229910001691 hercynite Inorganic materials 0.000 claims description 6
- 229910001676 gahnite Inorganic materials 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 36
- 229910052799 carbon Inorganic materials 0.000 abstract description 27
- 239000003502 gasoline Substances 0.000 abstract description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 14
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 46
- 238000002360 preparation method Methods 0.000 description 27
- 239000011787 zinc oxide Substances 0.000 description 23
- 229930195733 hydrocarbon Natural products 0.000 description 19
- 150000002430 hydrocarbons Chemical class 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 230000008569 process Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 238000005530 etching Methods 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 11
- 239000008246 gaseous mixture Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 10
- 239000011261 inert gas Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000001747 exhibiting effect Effects 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910001868 water 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 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
- 239000000320 mechanical mixture Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229960004011 methenamine Drugs 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- -1 Carbon olefin Chemical class 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 229910018666 Mn—K Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 230000008859 change Effects 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
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000010457 zeolite Substances 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
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 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
- FQHYQCXMFZHLAE-UHFFFAOYSA-N 25405-85-0 Chemical compound CC1(C)C2(OC(=O)C=3C=CC=CC=3)C1C1C=C(CO)CC(C(C(C)=C3)=O)(O)C3C1(O)C(C)C2OC(=O)C1=CC=CC=C1 FQHYQCXMFZHLAE-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910017767 Cu—Al Inorganic materials 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910007470 ZnO—Al2O3 Inorganic materials 0.000 description 1
- NGOXCJHJHMOPMQ-UHFFFAOYSA-N [Ge].[N+](=O)(O)[O-] Chemical group [Ge].[N+](=O)(O)[O-] NGOXCJHJHMOPMQ-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000005119 centrifugation Methods 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
- 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 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229940071229 oxygen 45 % Drugs 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 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
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000000352 supercritical drying Methods 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000010977 unit operation Methods 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
-
- 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
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Abstract
The invention belongs to synthesis gas to prepare liquid fuel co-producing light olefins, and in particular to the method that a kind of catalyst and synthesis gas directly convert preparing liquid fuel co-producing light olefins.Using synthesis gas as reaction raw materials, reacted in fixed bed or moving bed, the catalyst contains A and B component, and component A is reactive metal oxides, and component B is that the molecular sieve of the AEL structure of molecular sieve or metal-modified with AEL structure is one or two or more kinds of；Spacing is between 2nm 20mm between the geometric center of catalyst A and catalyst B particles；Catalyst A and catalyst B weight ratio is 0.1 20.Synthesis atmospheric pressure is 0.1 6MPa, and reaction temperature is 300 600 DEG C, and air speed is 500 8000h 1.React the high gasoline of main product octane number, co-production low-carbon alkene, while byproduct methane it is selectively low (<10%), there is good application prospect.
Description
Technical field
The invention belongs to synthesis gas to prepare liquid fuel co-producing light olefins, and in particular to a kind of catalyst and synthesis gas are straight
The method of switching through preparing liquid fuel co-producing light olefins.
Background technology
With the economic development and improvement of living standards, the demand of liquid fuel and chemicals also year by year drastically on
Rise.Gasoline production is mainly obtained by the catalytic reforming of heavy naphtha at present.As Global Oil resource increasingly consumes and occupied height not
Under crude oil price, for China especially deficient to petroleum resources, import is relied on per year over nearly 60% consumption of petroleum amount,
Seek a kind of process route that can be substituted, develop the side that low-carbon alkene is prepared by the non-oil base carbon resource such as coal, biomass
Method, there is important social effect and strategic importance.
Rich coal resources in China, using coal as raw material, synthesis gas (i.e. CO and H2 gaseous mixture) is obtained by gasification, will
Synthesis gas changes into methanol, and the brief introduction technology path that methanol produces gasoline through dimethyl ether again is ripe, and steps into industrialization, should
The carbon resource preparing liquid fuels such as route is coal, natural gas provide an important variation route.If however, it can realize that synthesis gas is straight
Switching through, and without methanol-fueled CLC and the direct route of preparing dimethyl ether by dewatering methanol, not only can with simplification of flowsheet, and
Unit operation can be reduced, reduces investment and energy consumption.Traditional Fischer-Tropsch path can realize that the direct conversion of synthesis gas prepares liquid
Fuel, but limited by its reaction mechanism, CO and H2In catalyst surface Dissociative occurs for molecule, generates surface C atom
And O atom, C atoms and O atom react with hydrogen of the absorption in catalyst surface, methylene (CH is formed2) intermediate, simultaneously
Release hydrone.Methylene intermediate carries out free crowd by migrating intercalation reaction, in catalyst surface, and generation contains different carbon
The hydrocarbon product of atomicity (ten from one to three, even arriving individual carbon atoms up to a hundred sometimes).Whole reaction hydrocarbon product carbon number
Distribution is wide, and the selectivity of target product is low, as the selectivity of gasoline is less than 50%.
Low-carbon alkene (Light Olefins), it is the foundation stone of modern chemical industry mainly including ethene, propylene and butylene,
Low-carbon alkene is mainly prepared by naphtha pyrolysis at present.Synthesis gas is obtained by coal gasification, is then converted into methanol or dimethyl ether,
Methanol or dimethyl ether are then converted into the technology relative maturity of the multiple reactors of multistep of low-carbon alkene, have been carried out industry
Change.In order to simplify reaction process, shorten process route, people based on traditional fischer-tropsch reaction catalyst, such as Fe base catalyst to entering
Row modification and improvement, add the additive of different compositions, such as alkali metal K, Na and transient metal Mn, Cu, can be effectively improved
The selectivity of low-carbon alkene.German Rule chemical company develops the Fe-Zn-Mn-K catalyst of multicomponent auxiliary agent promotion, is used for
The synthesis [12] of low-carbon alkene.The report such as Beijing University of Chemical Technology Zhang Jingchang is urged by Fe-Mn-K/AC prepared by presoma of ferric oxalate
Agent is in air speed 600h-1, at 15bar and 320 DEG C, CO high conversion rate is up to 97%, C2 =-C4 =Selection in hydrocarbon
Property for 68% [Zhang Jingchang, defend the country guest, Cao Weiliang, is catalyzed journal 24 (2003) 259-264], exceeded pre- by ASF distributed models
The C of survey2-C4The selectivity of hydrocarbon.The carrier of catalyst is also important to the selectivity of product by the interaction with Fe species
Modification.Dutch de Jong seminars are reported with carbon nano-fiber (CNF) and α-Al recently2O3For carrier, with citric acid
Sideramines is 12wt%Fe catalyst prepared by presoma, at low pressure (1bar), 350 DEG C, and H2Under the conditions of/CO=1, reaction 15 is small
When, CO conversion ratios are 0.5-1.0%, selectivity of the low-carbon alkene in hydrocarbon be 60% [H.M.T.Galvis,
J.H.Bitter,C.B.Hhare,M.Ruitenbeek,A.L.Dugulan,K.P.de Jong,Science 335(2012)
835-838].Same catalyst exists, H2/ CO=1,20bar, air speed 1500h-1Under, obtain turning for 70-88%
Rate, FTY are respectively 2.98 × 10-5Mol CO/gFes and 1.35 × 10-5Mol CO/gFes, CO2Selectivity be 42-
46%, wherein selectivity of the low-carbon alkene in hydrocarbon is 52-53%.Then they have found, micro in catalyst
0.03%S, 0.2% or so Na, there is obvious facilitation to the selectivity of reactivity and low-carbon alkene
[H.M.T.Galvis,A.C.J.Koeken,J.H.Bitter,T.Davidian,M.Ruitenbeek,A.I.Dugulan,
K.P.de Jong,J.Catal.303(2013)22-30].The Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences has made system to absorbent charcoal carrier
In-depth study, it is found that product deviates ASF distributions [Shen Jianyi, Lin Liwu, Zhang Su, Liang Dong on activated carbon supported iron catalyst
In vain, chemistry of fuel journal 19 (1991) 289-297；Marvin's is put down, Ding Yunjie, Luo Hongyuan etc., is catalyzed journal 22 (2001) 279-
282].In addition, the preparation method and technique of catalyst, such as roasting process, reducing condition, can directly affect active component
Scattered and size, so as to the activity of modulation reaction and the selectivity of product.Beijing University of Chemical Technology is using supercritical fluid combination skill
Art (i.e. chemical precipitation, gellike, the method for supercritical drying) makes active component Fe and auxiliary agent high degree of dispersion, is prepared for nanoscale
Fe base catalyst, CO conversion ratio are more than 96%, and selectivity of the low-carbon alkene in hydrocarbon is more than 54% [Beijing chemical industry
University, a kind of nanocatalyst and preparation method for preparation of low carbon olefines by synthetic gas：China, 101396662 [P] .2009-
04-01]。
Therefore, also there is researcher to try the coupling of multiple processes, and substantial amounts of trial is carried out.Xu etc. is by CuO-
ZnO-Al2O3 mixes with ZSM-5, obtained catalyst, and the product obtained in syngas conversion reactor is synthesized is mainly dimethyl ether
[M.Xu,J.H.Lunsford,D.W.Goodman,A.Bhattacharyya,Appl.Catal.A.General 149(1997)
289；D.Mao,W.Yang,J.Xia,B.Zhang,Q.Song,Q.Chen,J.Catal.230(2005)140].Erena etc. will
The multicomponent metal composite such as CuO/ZnO/Al2O3 mixes with ZSM-5 molecular sieve, catalyzes and synthesizes gas conversion, obtained product master
To be gasoline [J.Erena, J.M.Arandes, J.Bilbao, A.G.Gayubo, H.I.De Lasa, Chemical
Engineering Science 2000,55,1845；J.Erena,J.M.Arandes,R.Garona,A.G.Gayubo,
J.Bilbao,Journal of Chemical Technology and Biotechnology 2003,78,161].Park etc.
By dual bed reactor, 300 DEG C, 10atm, GHSV=3600h first on first reactor Fe-Cu-Al catalyst-1Under
Fischer-tropsch reaction is carried out, then by ZSM-5 catalyst for cracking beds at second 500 DEG C of reactor, by substantial amounts of C5+Product cracks
For low-carbon alkene, the selectivity of lower carbon number hydrocarbons is 52% in thus obtained hydrocarbon, and low-carbon alkene is in output aggregate
Selectivity for 28% [J.L.Park, Y.J.Lee, K.W.Jun, J.W.Bae, N.Viswanadham, Y.H.Kim,
J.Ind.Eng.Chem.15(2009)847-853]。
The content of the invention
In view of the above-mentioned problems, the invention provides a kind of catalyst and synthesis gas directly to convert preparing liquid fuel coproduction low-carbon
The method of alkene, the catalyst invented can catalyze and synthesize gas and directly be converted into liquid fuel co-producing light olefins, and gasoline evaporates
Component selections can reach 50-80%.
The technical scheme is that：
The catalyst is composite catalyst A+B, and component A active ingredient is reactive metal oxides, component B be with
One or two or more kinds in the molecular sieve of AEL structure or the molecular sieve with AEL structure of metal-modified；Active metal aoxidizes
Thing is MnO, Cr2O3、MnCr2O4、MnAl2O4、MnZrO4、ZnO、ZnCr2O4、ZnAl2O4、CeO2、CoAl2O4、FeAl2O4In
It is one or two or more kinds of.
Catalytic component A is preferably MnO, Cr2O3、MnCr2O4、MnAl2O4,MnZrO4、ZnAl2O4、CeO2、CoAl2O4、
FeAl2O4In one or two or more kinds；More preferably MnO, Cr2O3、MnCr2O4、MnAl2O4,MnZrO4、CeO2、CoAl2O4、
FeAl2O4In one or two or more kinds.
Molecular sieve preferred SAPO11, ALPO11, GeAPO11 with AEL structure, MnAPO11 molecular sieves, more preferably
SAPO11,GeAPO11,MnAPO11。
Between the geometric center of component A reactive metal oxides and component B particle spacing between 20nm-20mm it
Between, preferably 50nm-5mm, more preferably 100nm-1mm.
The weight ratio between active ingredient and component B in component A is between 0.1-20 times of scope, preferably 0.3-5.
Reactive metal oxides are made up of the crystal grain that size is 5-30nm, are from grain surface to intra-die direction depth
In 0.3nm distance range, a large amount of oxygen vacancies be present, surface Lacking oxygen percentage concentration is defined as that (100- oxygen atom moles account for
Theoretical stoichiometric is than oxygen molar content), oxygen vacancy concentration is preferably 20-90%, more preferably 40-90%, most preferably 50-
90%.
Dispersant, dispersant Al are also added with the catalyst A2O3、Cr2O3、ZrO2、TiO2In one kind or two
Kind, reactive metal oxides are scattered in dispersant, and for content of the dispersant in catalyst A in 10-90wt%, remaining is activity
Metal oxide.
The preparation process of reactive metal oxides is：Etched using oleic acid, methenamine, ethylenediamine, ammoniacal liquor, hydrazine hydrate etc.
One or two or more kinds in agent, metal oxide is soaked in etchant solution；By above-mentioned suspension at 100-150 DEG C
30-90 minutes are heated, washing and filtering is then taken out, obtains the reactive metal oxides material with exhibiting high surface oxygen vacancies；Will
Filtrate dries reduction treatment in atmosphere, and atmosphere is inert gas or inert gas and reducing atmosphere gaseous mixture, inertia
Gas is N2, one or two or more kinds in He and Ar, reducing atmosphere H2, CO one or two or more kinds, it is lazy in gaseous mixture
Property gas and reducibility gas volume ratio be 100/10~0/100, handle 0.5-5 hours, treatment temperature be 20-350 DEG C.
Catalyst A and catalyst B are combined with each other in a manner of mechanical mixture；The mechanical mixture can use mechanical agitation,
One or two or more kinds in ball milling, shaking table mixing, mechanical lapping carry out compound.
Using synthesis gas as reaction raw materials, conversion reaction is carried out in fixed bed or moving bed, used catalyst is to appoint
One above-mentioned catalyst.
The pressure of the synthesis gas is 0.1-10MPa, preferably 1-8MPa, more preferably 2-8MPa；Reaction temperature is
300-600 DEG C, preferably 300-500 DEG C；Air speed is 500-8000h-1；The reaction is H with synthesis gas2/ CO mixtures, wherein
H2/ CO ratios are 0.2-3.5, preferably 0.3-2.5, more preferably 0.5-2.5.
The liquid fuel is mainly gasoline, and based on high-octane isomery hydro carbons, while co-producing light olefins, it is low
Carbon olefin refers to the one or two or more kinds in the alkene containing 2 C2-C4 to 4 carbon numbers, including ethene, propylene, butylene.
The invention has the advantages that：
1. this technology is different from traditional technique for preparing gasoline by methanol (referred to as MTG), a step is realized directly by synthesis gas
Convert preparing liquid fuel and low-carbon alkene.
2. gasoline fraction selectivity is high in product, 50-80% is can reach, and space-time yield is high, it is main in remaining product
For the low-carbon alkene of high added value, selectivity of light olefin can reach 15-30%.
3. compared to traditional F- T synthesis technology, in gasoline composition based on high-octane isomery hydro carbons, straight-chain hydrocarbons
Class is selectively low, and oil quality is high；And byproduct methane is selectively low, less than 10%.
4. the preparation process simple condition of the composite catalyst in patent is gentle；And there is course of reaction very high product to receive
Rate and selectivity, there is good application prospect.
Embodiment
The present invention is further elaborated below by embodiment, but scope of the presently claimed invention is not by these realities
Apply the limitation of example.Meanwhile embodiment has been merely given as realizing the partial condition of this purpose, but it is not meant to must to be fulfilled for these
Condition can just reach this purpose.
Embodiment 1
First, catalyst A preparation
(1), ZnO material of the etching method synthesis with polar surfaces：
(1) 0.446g (1.5mmol) Zn (NO are weighed3)2·6H2O and 0.480g (12mmol) NaOH, then measure 30ml and go
Ionized water is added thereto, and stirring more than 0.5h is well mixed solution.Temperature is warming up to as 160 DEG C, reaction time 20h, is sunk
Resolve into zinc oxide in shallow lake；Naturally cool to room temperature.Reaction solution centrifuges the sediment collected after centrifuging, and uses deionized water
2 acquisition ZnO oxides of washing；
(2) using etching agents such as oleic acid, methenamine, ethylenediamine, ammoniacal liquor, hydrazine hydrates, surpass at normal temperatures with ZnO oxides
Sound is mixed, and ZnO oxides are soaked in etchant solution, and etching agent forms complexing or direct reduction reactor with zinc oxide；Will be upper
Suspension heating is stated, washing and filtering is then taken out, obtains the nano ZnO material with exhibiting high surface oxygen vacancies.
In table 1：The mass ratio of catalyst and etching agent is 1:3.The mass ratio of oleic acid and methenamine is 1:1, it is not molten
Agent, the mass ratio of oleic acid -5wt% hydrazine hydrates is 95:5, without solvent；When specific treatment conditions include etching agent, temperature, processing
Between and atmosphere species it is as shown in table 1 below.
(3), dry or dry and reduce：
The product of above-mentioned acquisition is by centrifugation or filtering, after being cleaned with deionized water, be dried in atmosphere or
Dry and reduction treatment, atmosphere is inert gas or inert gas and reducing atmosphere gaseous mixture, inert gas N2, He and
One or two or more kinds in Ar, reducing atmosphere H2, CO one or two or more kinds, dry reduction gaseous mixture in indifferent gas
The volume ratio of body and reducibility gas is 100/10~0/100, dries and the temperature of reduction treatment is 350 degrees Celsius, the time is
4h.Obtain the ZnO material that surface is rich in Lacking oxygen.Specific sample and its preparation condition such as table 1 below.Wherein surface Lacking oxygen is dense
Degree is defined as (the reasonable opinion stoichiometric proportion oxygen molar content % of 100%- oxygen atom moles).
The preparation of the ZnO material of table 1 and its performance parameters
For the surface Lacking oxygen to be in 0.3nm distance range from grain surface to intra-die direction depth, oxygen is former
The reasonable percentage by stoichiometric proportion oxygen molar content of sub- mole；
As a comparison case, ZnO 9 of the surface without Lacking oxygen without (2) step etching, and the gold that Zn is reduced completely
Belong to Zn 10；
(2), MnO material of the etching method synthesis with polar surfaces：With above-mentioned (one), difference is preparation process
Zn presoma has been changed into Mn corresponding presoma, has been one kind in manganese nitrate, manganese chloride, manganese acetate.
Etch processes are with described in the product ZnO 3 of (2) in above-mentioned (one), ZnO 5, ZnO8 preparation process, synthesis tool
There is the catalyst of exhibiting high surface Lacking oxygen；Surface Lacking oxygen 56%, 36%, 27%；
Corresponding product is defined as MnO 1-3；
(3), CeO of the etching method synthesis with polar surfaces2Material：With above-mentioned (one), difference is preparation process
Zn presoma has been changed into Ce corresponding presoma, has been one kind in cerous nitrate, cerium chloride, cerous acetate.
With described in product ZnO3, ZnO4, ZnO8 preparation process of (2) in above-mentioned (one), synthesis has etch processes
The catalyst of exhibiting high surface Lacking oxygen；Surface Lacking oxygen 67%, 38%, 25%；
Corresponding product is defined as CeO 1-3；
(4), Cr of the etching method synthesis with polar surfaces2O3Material：
For preparation process with above-mentioned (one), difference is the corresponding presoma that Zn presoma has been changed into Cr, is
One kind in chromic nitrate, chromium chloride, chromic acetate.
With described in product ZnO3, ZnO4, ZnO8 preparation process of (2) in above-mentioned (one), synthesis has etch processes
The catalyst of exhibiting high surface Lacking oxygen；Surface Lacking oxygen 45%, 29%, 20%；
Corresponding product is defined as Cr2O31-3；
(5), synthesis is with high-specific surface area, the nanometer Zn Cr of high surface energy2O4、ZnAl2O4、MnCr2O4、MnAl2O4,
MnZrO4Spinelle：
Zinc nitrate, aluminum nitrate, chromic nitrate, manganese nitrate, zirconium nitrate are used as presoma, with the urea phase in water at room temperature
Mutually mixing；Above-mentioned mixed liquor is aged, washing, filtering is then taken out and dries, the solid of gained is calcined, obtained in air atmosphere
Obtain the spinel oxide along the growth of (110) crystal plane direction.Sample also passes through etching method processing, and synthesis has exhibiting high surface oxygen empty
The catalyst of position；Etching processing and last handling process with (2) and (3) in above-mentioned (one) Suo Shu, the sample have bigger serface,
Surface defect is more, can be applied to catalyze and synthesize gas conversion.
Specific sample and its preparation condition such as table 2 below.Equally, surface Lacking oxygen is defined as that (1- oxygen atom moles are reasonable
By stoichiometric proportion oxygen molar content).
The preparation of the spinel of table 2 and its performance parameter
(5), synthesis is with high-specific surface area, the nanometer Fe Al of high surface energy2O4、CoAl2O4Spinelle：Preparation process is same
(2) in above-mentioned (four) are described, and difference is the corresponding presoma that Zn presoma has been changed into Fe or Co, is nitric acid
One kind in a kind of or cobalt nitrate, cobalt chloride, cobalt acetate in iron, iron chloride, ironic citrate.
With described in the product ZnO 3 of (2) in above-mentioned (one), the preparation process of ZnO 5, synthesis has a large amount of etch processes
The catalyst of surface Lacking oxygen；Surface Lacking oxygen 77%, 51%；
Corresponding product is defined as spinelle 6, spinelle 7；
(6), Cr2O3、Al2O3Or ZrO2Scattered reactive metal oxides
With Cr2O3、Al2O3Or ZrO2For carrier, precipitation sedimentation prepares Cr2O3、Al2O3Or ZrO2Scattered active metal
Oxide.Exemplified by disperseing the preparation of ZnO oxides, by business Cr2O3、Al2O3Or ZrO2Carrier is scattered in the liquid of bottom in advance, so
Zinc nitrate is used afterwards as raw material, with sodium hydroxide pellets agent mixed precipitation at room temperature, Zn2+Molar concentration be 0.067M, Zn2 +Molfraction ratio with precipitating reagent is 1：8；Then it is aged 24 hours at 160 DEG C, obtains Cr2O3、Al2O3Or ZrO2For carrier
Scattered ZnO oxides (content of the dispersant in catalyst A is followed successively by 0.1wt%, 10wt%, 90wt%).
With described in the product ZnO 3 of (2) in above-mentioned (one), ZnO 5, the preparation process of ZnO 8, synthesis has big etching process
The catalyst of scale face Lacking oxygen；Surface Lacking oxygen 65%, 30%, 25%；Last handling process is with above-mentioned (one) 3) it is described；
Product is corresponded to from top to bottom is defined as dispersal oxide 1-3；
In the same way, Cr can be obtained2O3、Al2O3Or ZrO2For the MnO oxides of support dispersion, (dispersant is in urging
Content in agent A is followed successively by 5wt%, 30wt%, 60wt%), surface Lacking oxygen 62%, 27%, 28%；Correspond to from top to bottom
Product is defined as dispersal oxide 4-6.
2nd, the preparation of molecular sieve, i.e. component B with AEL topological structures：
1) specific preparation process is：
It is described：SAPO11, ALPO11, GeAPO11, MnAPO11 preparation method reference literature：
U.S.patent(4310440),1982；Zeolites,7(1987),160；Zeolites,19(1997),449；
J.Phys.Chem.,92(1988),2734；
Si sources are：Ludox 30wt%, boehmite, phosphoric acid, di-n-propylamine,
The molar percentage to feed intake is according to SDA：Al2O3：P2O5：SiO2：H2O=2:1:1:0.1:50
Mixing aging is carried out, obtains sol precursor, the sol precursor seals crystallization in water heating kettle.
200 DEG C of hydrothermal temperature, crystallization time 24h.
ALPO11, GeAPO, the MnAPO11, it is in preparation process respectively；Ludox is added without, with nitric acid germanium substituted for silicon
Colloidal sol, manganese nitrate substitute Ludox, carry out Hydrothermal Synthesiss, and remaining process is similar.
The SAPO11 with AEL structure, ALPO11, GeAPO11, MnAPO11 samples is prepared.
3rd, the preparation of catalyst
The component A of required ratio and component B is added in container, produced using the high-speed motion of these materials and/or container
Raw extruding force, impact, cut more than one or both of power, frictional force etc. effect realize separation, it is broken, the mesh such as mix
, the conversion of mechanical energy, heat energy and chemical energy is realized by modulation temperature and carrier gas atmosphere, further between regulation different component
Interaction.
During mechanical mixture, 20-100 DEG C of mixing temperature can be set, can in atmosphere or directly in atmosphere
Carry out, atmosphere is：A) nitrogen and/or inert gas, b) hydrogen and nitrogen and/or inert gas gaseous mixture, wherein hydrogen in
Volume in gaseous mixture is 5~50%, c) gaseous mixture of CO and nitrogen and/or inert gas, bodies of the wherein CO in gaseous mixture
Product is 5~20%, d) O2With nitrogen and/or the gaseous mixture of inert gas, wherein O2Volume in gaseous mixture is 5-20%, institute
It is more than one or both of helium, argon gas, neon to state inert gas.
Mechanical agitation：In tank diameter, component A and B are mixed using stirring rod, by controlling mixing time
(5min-120min) and speed (30-300 turns/min), component A and B mixability and relative distance can be adjusted.
Ball milling：Rolled at a high speed in grinding pot with catalyst using abrasive material, intense impact is produced to catalyst, is rolled, is reached
To scattered, mixed composition A and B effect.By controlling abrasive material, (material can be stainless steel, agate, quartz.Size range：
5mm-15mm).(quality compares scope with the ratio of catalyst：20-100:1) granularity and relative distance of catalyst can, be adjusted.
Shaking table mixing method：Component A and B are pre-mixed, and are fitted into container；By the reciprocating vibration or circumference that control shaking table
Vibration, realizes component A and B mixing；By adjusting hunting speed (scope：1-70 revs/min) and time (scope：5min-
120min), realize and uniformly mix and adjust its relative distance.
Mechanical milling method：Component A and B are pre-mixed, and are fitted into container；In certain pressure (scope:5 kilogram -20 public
Jin) under, relative motion (speed range is carried out with the catalyst mixed by lap tool：30-300 turns/min), reach regulation catalysis
Agent granularity, relative distance and realize mixed uniformly effect.
Specific catalyst preparation and its parameter attribute are as shown in table 3.
The preparation of the catalyst of table 3 and its parameter attribute
Catalytic reaction example
By taking fixed bed reaction as an example, but catalyst is also applied for moving-burden bed reactor.The device is equipped with gas mass flow
(tail gas of reactor is directly connected with the proportional valve of chromatogram, carries out cycle real-time sampling point for gauge, online product analysis chromatogram
Analysis).
The catalyst of the invention described above is placed in fixed bed reactors, using the air in Ar metathesis reactors, then
Again in H2300 DEG C are warming up in atmosphere, switching and merging gas (H2/ CO mol ratios=0.2-3.5), the pressure of synthesis gas is 0.5-
10MPa, 300-600 DEG C of reaction temperature is warming up to, adjusts the air speed of reactor feed gas to 500-8000ml/g/h.Product is by online
Chromatogram tests and analyzes.
1. change temperature, pressure and air speed, thus it is possible to vary reactivity worth.Gasoline fraction selectivity is high in product, can reach
50-80%, and predominantly the low-carbon alkene of high added value, selectivity of light olefin can reach 15-30% in remaining product.
Synthetic technology is opened up compared to traditional expense, byproduct methane is selectively extremely low, less than 10%；And gasoline composition in
Based on high-octane isomery hydro carbons and aromatic hydrocarbons, straight chain hydrocarbon is selectively low, and oil quality is high.
The application of the catalyst of table 4 and its effect
ZnO does not have oxygen vacancies in the catalyst of comparative example 1, therefore its activity is very low.
ZnO is reduced into metallic state completely in the catalyst of comparative example 2, causes the selectivity of methane in product very high.
The catalyst that comparative example 3 uses is component A metal ZnCo, and component B is SAPO11, ZnCo mol ratios 1：1, ZnCo with
SAPO11 mass ratioes 1：1, remaining parameter and mixed process etc. are the same as catalyst A.
The catalyst component A that comparative example 4 uses is TiO of the surface without oxygen vacancies2, component B is SAPO11, remaining parameter and
Mixed process etc. is the same as catalyst A.
Molecular sieve is purchased from the commodity SAPO-34 of Catalyst Factory, Nankai Univ in the catalyst that comparative example 5 uses.
Molecular sieve is purchased from the commodity ZSM-5 of Catalyst Factory, Nankai Univ, full micropore knot in the catalyst that comparative example 6 uses
Structure, wherein Si/Al=30.
The distance between metal oxide and molecular sieve is 30mm in the catalyst that comparative example 7 uses, remaining parameter and mixed
Conjunction process etc. is the same as catalyst A.
Metal oxide is located in molecular sieve pore passage in the catalyst that comparative example 8 uses, both close contacts, remaining parameter
Deng with catalyst A.
Comparative example 9 is using the iron catalyst of CNT confinement, and wherein iron load capacity is 10%, 270 DEG C, 51bar,
14000h-1, wherein selectivity of the C5+ products in hydrocarbon is 29%.
Reaction result explanation：
Illustrate one：
The reaction result of comparative example 5 and 6 shows that AEL topological structure is most important to the modulation of selectivity of product,
SAPO34 has port sizeThe generation of suitable C2-C4 hydro carbons, wherein C3 hydrocarbon products are most；And ZSM-5 port sizes
ForTherefore component B is the hydro carbons that the product obtained on ZSM-5 catalyst is mainly C4 hydro carbons even more Long carbon chain.
Molecular sieve port size containing AEL is 4.0*6.5, and it is special to show the advantage that other structures molecular sieve does not have
Property, its product is mainly gasoline fraction, and the content of isoparaffin is high.Co-producing light olefins simultaneously.
Illustrate two：
The distance between metal oxide and molecular sieve is 30mm in the catalyst that comparative example 7 uses, remaining parameter and mixed
Conjunction process etc. is the same as catalyst A.
Metal oxide is located in molecular sieve pore passage in the catalyst that comparative example 8 uses, both close contacts, remaining parameter
Deng with catalyst A.
The reaction result of comparative example 7 and comparative example 8 shows, apart from remote and closely to result in very much methane selectively very high, and
It is unfavorable for the generation of gasoline fraction.
The structure of molecular sieve as can be seen from the above table, includes AEL topological structure, and metal oxide and molecular sieve it
Between distance matching it is most important, directly affect the selectivity of gasoline fraction and low-carbon alkene.
Claims (9)
- A kind of 1. catalyst, it is characterised in that：The catalyst is composite catalyst A+B, and component A active ingredient is activity gold Belong to oxide, component B be one kind in the molecular sieve with AEL structure of molecular sieve with AEL structure or metal-modified or More than two kinds；Reactive metal oxides are MnO, MnCr2O4、MnAl2O4、MnZrO4、ZnO、ZnCr2O4、ZnAl2O4、CeO2、 CoAl2O4、FeAl2O4In one or two or more kinds.
- 2. according to the catalyst described in claim 1, it is characterised in that：Catalytic component A is preferably MnO, Cr2O3、MnCr2O4、 MnAl2O4,MnZrO4、ZnAl2O4、CeO2、CoAl2O4、FeAl2O4In one or two or more kinds；More preferably MnO, Cr2O3、 MnCr2O4、MnAl2O4,MnZrO4、CeO2、CoAl2O4、FeAl2O4In one or two or more kinds；One or two or more kinds in molecular sieve preferred SAPO11, ALPO11, GeAPO11, MnAPO11 with AEL structure；Point One or two or more kinds in son sieve more preferably SAPO11, GeAPO11, MnAPO11.
- 3. according to the catalyst described in claim 1 or 2, it is characterised in that：Component A reactive metal oxides and component B's Spacing is between 20nm-20mm between the geometric center of particle, preferably 50nm-5mm, more preferably 100nm-1mm.
- 4. according to the catalyst described in claim 1,2 or 3, it is characterised in that：Between active ingredient and component B in component A Weight ratio between 0.1-20 times of scope, preferably 0.3-5.
- 5. according to the catalyst described in claim 1,3 or 4, it is characterised in that：Reactive metal oxides are 5-30nm by size Crystal grain form, from grain surface to intra-die direction depth for 0.3nm distance range in, a large amount of oxygen vacancies be present, with Theoretical stoichiometric is 100% meter than oxygen molar content, and surface Lacking oxygen percentage concentration is defined as (100%- oxygen atom moles The reasonable percentage by stoichiometric proportion oxygen molar content), oxygen vacancy concentration is preferably 20-90%, more preferably 40-90%, Most preferably 50-90%.
- 6. according to the catalyst described in claim 1, it is characterised in that：Dispersant, dispersant are also added with the catalyst A For Al2O3、Cr2O3、ZrO2、TiO2In one kind or two kinds, reactive metal oxides are scattered in dispersant, and dispersant is in catalysis In 10-90wt%, remaining is reactive metal oxides for content in agent A.
- 7. a kind of method that synthesis gas directly converts preparing liquid fuel co-producing light olefins, it is characterised in that：Its using synthesis gas as Reaction raw materials, carry out conversion reaction in fixed bed or moving bed, and used catalyst is claim 1-6 any described Catalyst.
- 8. in accordance with the method for claim 7, it is characterised in that：The pressure of the synthesis gas is 0.1-10MPa, preferably 1- 8MPa, more preferably 2-8MPa；Reaction temperature is 300-600 DEG C, preferably 300-500 DEG C；Air speed is 500-8000h-1。
- 9. according to the method described in claim 7 or 8, it is characterised in that：The reaction is H with synthesis gas2/ CO mixtures, wherein H2/ CO ratios are 0.2-3.5, preferably 0.3-2.5, more preferably 0.5-2.5.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109651036A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | A method of by preparing low-carbon olefin |
| WO2019144952A1 (en) * | 2018-01-26 | 2019-08-01 | 中国科学院大连化学物理研究所 | Supported catalyst and method for directly converting synthesis gas into low-carbon olefin |
| CN111346671A (en) * | 2018-12-21 | 2020-06-30 | 中国科学院大连化学物理研究所 | Catalyst and method for preparing low aromatic hydrocarbon liquid fuel by directly converting synthesis gas |
| CN111346669A (en) * | 2018-12-21 | 2020-06-30 | 中国科学院大连化学物理研究所 | Method for preparing low-carbon olefin by catalyzing synthesis gas through heteroatom-doped molecular sieve |
| CN112691697A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Synthetic gas conversion coupling catalyst and application thereof |
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| EP3900829A4 (en) * | 2018-12-21 | 2022-03-09 | Dalian Institute of Chemical Physics, Chinese Academy of Sciences | Method for the preparation of low-carbon olefin in high selectivity from synthesis gas catalyzed by heteroatom-doped molecular sieve |
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| CN109651036A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | A method of by preparing low-carbon olefin |
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| CN111346671A (en) * | 2018-12-21 | 2020-06-30 | 中国科学院大连化学物理研究所 | Catalyst and method for preparing low aromatic hydrocarbon liquid fuel by directly converting synthesis gas |
| CN111346669A (en) * | 2018-12-21 | 2020-06-30 | 中国科学院大连化学物理研究所 | Method for preparing low-carbon olefin by catalyzing synthesis gas through heteroatom-doped molecular sieve |
| EP3900829A4 (en) * | 2018-12-21 | 2022-03-09 | Dalian Institute of Chemical Physics, Chinese Academy of Sciences | Method for the preparation of low-carbon olefin in high selectivity from synthesis gas catalyzed by heteroatom-doped molecular sieve |
| CN111346671B (en) * | 2018-12-21 | 2023-03-24 | 中国科学院大连化学物理研究所 | Catalyst and method for preparing low aromatic hydrocarbon liquid fuel by directly converting synthesis gas |
| CN112691697A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Synthetic gas conversion coupling catalyst and application thereof |
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| CN112973783A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | Hierarchical pore catalyst, synthesis gas and C4Method for preparing low liquid fuel from components |
| CN112973783B (en) * | 2019-12-14 | 2022-06-03 | 中国科学院大连化学物理研究所 | Hierarchical pore catalyst, synthesis gas and C4Method for preparing low liquid fuel from components |
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