CN108940355A - A kind of method of base-modified catalyst and carbon monoxide hydrogenation ethylene - Google Patents
A kind of method of base-modified catalyst and carbon monoxide hydrogenation ethylene Download PDFInfo
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- CN108940355A CN108940355A CN201710382261.8A CN201710382261A CN108940355A CN 108940355 A CN108940355 A CN 108940355A CN 201710382261 A CN201710382261 A CN 201710382261A CN 108940355 A CN108940355 A CN 108940355A
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- catalyst
- ethylene
- selectivity
- metal oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000005977 Ethylene Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000002808 molecular sieve Substances 0.000 claims abstract description 18
- 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 18
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004480 active ingredient Substances 0.000 claims abstract description 7
- 239000000320 mechanical mixture Substances 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 31
- 239000001301 oxygen Substances 0.000 claims description 31
- 229910052760 oxygen Inorganic materials 0.000 claims description 31
- 230000015572 biosynthetic process Effects 0.000 claims description 25
- 238000003786 synthesis reaction Methods 0.000 claims description 25
- 239000008246 gaseous mixture Substances 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 14
- 229910018516 Al—O Inorganic materials 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 150000007530 organic bases Chemical class 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 229910018557 Si O Inorganic materials 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 150000002391 heterocyclic compounds Chemical group 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 229910019114 CoAl2O4 Inorganic materials 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 229910001677 galaxite Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002240 furans Chemical class 0.000 claims description 3
- 229910001676 gahnite Inorganic materials 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 claims description 3
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003233 pyrroles Chemical class 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002475 indoles Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims 3
- 229910001691 hercynite Inorganic materials 0.000 claims 3
- RABBMOYULJIAFU-UHFFFAOYSA-N 1h-pyrrole;thiophene Chemical class C=1C=CNC=1.C=1C=CSC=1 RABBMOYULJIAFU-UHFFFAOYSA-N 0.000 claims 1
- 210000000988 bone and bone Anatomy 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 30
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 20
- 229930195733 hydrocarbon Natural products 0.000 abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 150000001336 alkenes Chemical class 0.000 description 13
- 239000011261 inert gas Substances 0.000 description 13
- 239000011787 zinc oxide Substances 0.000 description 13
- 238000005530 etching Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 108020001612 μ-opioid receptors Proteins 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000001747 exhibiting effect Effects 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- -1 ethylene, propylene Chemical group 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 150000001721 carbon Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 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
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 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
- 229960004011 methenamine Drugs 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 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 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 2
- DTBDAFLSBDGPEA-UHFFFAOYSA-N 3-methylquinoline Chemical compound C1=CC=CC2=CC(C)=CN=C21 DTBDAFLSBDGPEA-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
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- 239000003082 abrasive agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000000908 ammonium hydroxide Substances 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
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 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
- 229910017052 cobalt Inorganic materials 0.000 description 2
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- 230000001276 controlling effect Effects 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229910052734 helium Inorganic materials 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
- 238000010907 mechanical stirring Methods 0.000 description 2
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- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
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- 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
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- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical class CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 description 1
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- 239000002028 Biomass Substances 0.000 description 1
- 101100276977 Caenorhabditis elegans dapk-1 gene Proteins 0.000 description 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101001122476 Homo sapiens Mu-type opioid receptor Proteins 0.000 description 1
- 101000931682 Homo sapiens Protein furry homolog-like Proteins 0.000 description 1
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- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
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- 101100350262 Mus musculus Olfr16 gene Proteins 0.000 description 1
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- 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
- 238000010521 absorption reaction Methods 0.000 description 1
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- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- VQKFNUFAXTZWDK-UHFFFAOYSA-N alpha-methylfuran Natural products CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910001417 caesium ion Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910001567 cementite Inorganic materials 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
- 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 1
- 239000003245 coal Substances 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
- 230000000536 complexating effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment 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
- 230000008676 import Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 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
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 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
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940103062 oxygen 25 % Drugs 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 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
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LGERWORIZMAZTA-UHFFFAOYSA-N silicon zinc Chemical compound [Si].[Zn] LGERWORIZMAZTA-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
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- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
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- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
The invention belongs to co hydrogenation directly conversions to prepare ethylene, more particularly to the method for a kind of base-modified catalyst and carbon monoxide hydrogenation ethylene, it is using carbon monoxide and hydrogen mixed gas as reaction raw materials, conversion reaction is carried out in fixed bed or moving bed, the catalyst is composite catalyst, it is combined with each other in a manner of mechanical mixture by component A and B component, the active ingredient of component A is metal oxide, and B component is the molecular sieve of the MOR structure of organic alkali modification；The weight ratio between active ingredient and B component in component A is between 0.1-20 range, preferably 0.3-8.Reaction process has very high product yield and selectivity, C2-C3 olefine selective is up to 86-92%, wherein it is lower than 7% containing hydrocarbon products more than 4 C atoms, byproduct methane is selectively extremely low (< 5%), and ethylene selectivity and space-time yield significantly improve, selectivity reaches 75-85%, has a good application prospect.
Description
Technical field
The invention belongs to co hydrogenation producing light olefins high level chemicals, and in particular to a kind of base-modified catalyst
And the method for carbon monoxide hydrogenation ethylene.
Background technique
Ethylene is very important basic chemical raw materials, is one of maximum chemical products of yield in the world, ethylene industry
It is the core of petrochemical industry, occupies an important position in national economy.Low-carbon alkene refers to that carbon atom number is less than or waits
In 4 alkene.It is very important basic organic chemical industry raw material using ethylene, propylene as the low-carbon alkene of representative, as China passes through
The rapid growth of Ji, ethylene industry development in China's is swift and violent, and in the world, Market for Ethylene occupies an important position.For a long time, low-carbon
Supply falls short of demand in alkene market.Currently, the production of ethylene mainly uses naphtha, the petrochemical industry route of Pyrolysis Reaction of Gas Oil or second
The technology of alkane cracking, since China's oil relies on import for a long time, the energy security in China there are greater risk, develop not by urgent need
Rely on the ethylene of petroleum.By coal, natural gas, biomass and other recyclable materials etc. be converted into carbon monoxide and
Gaseous mixture, that is, synthesis gas of hydrogen, carbon monoxide is different and different with raw material with the ratio of hydrogen in synthesis gas；Again with these
Synthesis gas is raw material, after the ratio to suitable value by adjusting carbon monoxide and hydrogen, makes carbon monoxide and hydrogen suitable
Catalyst action under, by Fischer-Tropsch synthesis directly be made carbon atom number less than or equal to 4 low-carbon alkene process, this
Sample can produce alkene with a step, which produces ethylene for naphtha pyrolysis technology and provide an alternative solution.The technique without
Alkene need to be further prepared, simplification of flowsheet greatly reduces as indirect method technique from synthesis gas through methanol or dimethyl ether
Investment.
It is always one of the research hotspot that synthesis gas directly produces alkene by the direct preparing low-carbon olefins of F- T synthesis.
In patent CN1083415A disclosed in Dalian Chemiclophysics Inst., Chinese Academy of Sciences, with the Group IIAs such as MgO alkali metal oxide or high silicon
Iron-Mn catalyst system that zeolite molecular sieve (or phosphorus aluminium zeolite) supports, makees auxiliary agent with highly basic K or Cs ion, in synthesis gas system
Low-carbon alkene reaction pressure is 1.0~5.0Mpa, at 300~400 DEG C of reaction temperature, can get higher active (CO conversion ratio
90%) and it is selective (selectivity of light olefin 66%).In the patent ZL03109585.2 that Beijing University of Chemical Technology is declared, use
Vacuum impregnation technology prepares the Fe/ activated-carbon catalyst that manganese, copper, zinc silicon, potassium etc. are auxiliary agent and reacts for preparation of low carbon olefines by synthetic gas,
Under conditions of no unstripped gas recycles, CO conversion ratio 96%, selectivity 68% of the low-carbon alkene in hydrocarbon.Above-mentioned report
The catalyst in road is to use metallic iron or cementite for active component, and reaction follows the chain propagation reaction mechanism of metal surface,
The selectivity of product low-carbon alkene is lower, and especially the selectivity of single product such as ethylene is lower than 30%.2016, Shanghai height etc. was ground
Study carefully institute Sun Yuhan researcher and Zhong Liangshu researcher reports a kind of preferentially exposure [101] and [020] manganese and helps carbonization cobalt-based catalyst
Agent realizes under 31.8% CO conversion ratio, 60.8% selectivity of light olefin, and methane selectively 5%.But ethylene list
One selectivity is but lower than 20%.Dalian Inst of Chemicophysics, Chinese Academy of Sciences's packet is believed and reports aluminium oxide with Pan Xiu lotus team
The ZnCr of load2O4Oxide and the compound bifunctional catalyst of multi-stage porous SAPO-34 molecular sieve (Jiao et al., Science
351 (2016) 1065-1068), when realizing CO conversion ratio 17%, the selectivity of low-carbon alkene 80%, but the selectivity of ethylene
Lower than 30%.In the patent 201610600945.6 that they apply, using containing oxygen vacancies and the compound double function of MOR molecular sieve
Energy catalyst is used for one step olefine reaction of synthesis gas, and the selectivity of ethylene is improved to 30-75%, but carbon atom in by-product
Number be more than 3 hydro carbons it is more, affect the application of the technology.And the acidity that the present invention further passes through modulation MOR molecular sieve is special
It is low further to make the selectivity of methane byproduct for point, and the selectivity of the hydrocarbon product of C4 or more also further decreases.
Summary of the invention
The technology of the present invention solves the problems, such as: overcoming the deficiencies of the prior art and provide the base-modified catalyst of one kind and an oxidation
The method of carbon hydrogenation reaction ethylene, the catalyst invented can catalytic CO add hydrogen directly convert it is highly selective generate it is low
Carbon olefin, and the selectivity of C2-C3 alkene is up to 86-92%, and the selectivity of single product ethylene may be up to 75-85%, first
Alkane is selectively lower than 5%, C4 and the above hydrocarbon selective lower than 7%.
The technical solution of the present invention is as follows: a kind of catalyst, is combined with each other in a manner of mechanical mixture by component A and B component,
The active ingredient of component A is metal oxide, and B component is the molecular sieve of MOR topological structure, it is characterised in that: in B component, institute
The molecular sieve for stating MOR topological structure is modified using organic base, and the organic base is heterocyclic compound.
The heterocyclic compound can be furans, thiophene, pyrroles, thiazole, imidazoles, pyridine, pyrazine, pyrimidine, pyridazine, Yin
Diindyl, quinoline, pteridine, acridine.The heterocyclic compound can have methyl, ethyl, amino, one or more of nitro
Substituent group.It is preferred that meta position, contraposition replaces.8 annulus ducts can be entered using heterocyclic compound to avoid organic base molecule, but
The B acid site for occupying 12 annulus of selectivity.And the molecule that bit-by-bit replaces between use can cause to avoid space steric effect
Organic base contacted with B acid it is weaker, absorption loosely the problem of.
Between 0.1-20 times of range, weight ratio is preferably the weight ratio between active ingredient and B component in component A
0.3-8, multicomponent collaboration could to react effective progress, one of excessive or very few progress that can be all unfavorable for reaction.
Metal oxide is made of the crystal grain that size is 5-30nm, is from grain surface to intra-die direction depth
In the distance range of 0.3nm, there are a large amount of oxygen vacancies, i.e., oxygen atom mole is reasonable by stoichiometric ratio oxygen molar content
80% hereinafter, it is preferred that oxygen atom the mole reasonable 80%-10% by stoichiometric ratio oxygen molar content, more preferably 60-
10%, most preferably 50-10%；Surface Lacking oxygen is defined as that (1- oxygen atom mole is reasonable to be contained by stoichiometric ratio oxygen mole
Amount), corresponding oxygen vacancy concentration is preferably 20-90%, more preferably 40-90%, most preferably 50-90%, and oxygen vacancies is very little
It is unfavorable for the activation of CO, it is too many that excessive hydrogenation is easy to cause to reduce olefine selective.
Dispersing agent, dispersing agent Al are also added in component A2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3One of or
Two kinds or more, metal oxide dispersion is in dispersing agent, and content of the dispersing agent in component A is in 0.05-90wt%, preferably
0.05-25wt%, remaining is metal oxide, can contribute to the dispersion of active component with inertia dispersing agent, improves active group
The utilization efficiency divided.
The MOR topological structure is a kind of rhombic system, has the one-dimensional channels for the oval straight channels being parallel to each other
Structure contains 8 annulus pockets and 12 annulus one-dimensional channels.
The backbone element composition of the molecular sieve with MOR topological structure can be Si-Al-O, Ga-Si-O, Ga-Si-
One of Al-O, Ti-Si-O, Ti-Al-Si-O, Ca-Al-O, Ca-Si-Al-O or two kinds or more.
The preparation process of metal oxide is: using in the etching agents such as oleic acid, methenamine, ethylenediamine, ammonium hydroxide, hydrazine hydrate
One or two or more kinds, metal oxide is soaked in etchant solution；Above-mentioned suspended matter is heated at 100-150 DEG C
30-90 minutes, washing filtering is then taken out, the metal oxide materials with exhibiting high surface oxygen vacancies are obtained；Filtrate is existed
Dry reduction treatment in atmosphere, atmosphere are inert gas or inert gas and reducing atmosphere gaseous mixture, inert gas N2、
One of He and Ar or two kinds or more, reducing atmosphere H2, CO one or two or more kinds, in gaseous mixture inert gas with
The volume ratio of reducibility gas is 100/10~0/100, is handled 0.5-5 hours, and treatment temperature is 20-350 DEG C.
The method that the organic base is modified is first to control temperature on vacuum line and be dehydrated to sieve sample to take off
350-500 DEG C of gas disposal temperature, pressure 1Pa-10-5Pa, time 4h-24h are further exposed to 10Pa- to the molecular sieve of degassing
In the atmosphere of the organic base of 100kPa or in the atmosphere of the diluted organic base of inert gas, control adsorption temp is room temperature to 300
DEG C, and the molecular sieve of organic alkali modification is obtained after carrying out purging 30min-12h at 200-330 DEG C with inorganic gas.
Mechanical stirring, ball milling, shaking table mixing, one of mechanical lapping or two kinds can be used with enterprising in the mechanical mixture
Row is compound.
The method that the gaseous mixture of a kind of carbon monoxide and hydrogen directly converts ethylene processed is related to carbon monoxide and hydrogen
Gaseous mixture is reaction raw materials, can also contain a certain amount of carbon dioxide in gaseous mixture, be turned in fixed bed or moving bed
Change reaction, ethylene can be generated with high selectivity, used catalyst is above-mentioned catalyst.
The pressure of mixture gas is 0.5-10MPa, preferably 1-8MPa, more preferably 2-8MPa；Reaction temperature is 300-
600 DEG C, preferably 300-450 DEG C；Air speed is 300-10000h-1, preferably 500-9000h-1, more preferably 500-6000h-1,
Higher space-time yield can be obtained.
The reaction gaseous mixture H2/ CO molar ratio is 0.2-3.5, and preferably 0.3-2.5 can obtain higher space-time
Yield and selectivity.CO can also be contained in synthesis gas2, wherein CO2Volumetric concentration in synthesis gas is 0.1-50%.
The dual-function composite catalyst directly converts ethylene processed or the alkene of C2-C3 for one-step method from syngas,
Wherein the selectivity of C2-C3 alkene is up to 86-92%, and ethylene selectivity reaches 75-85%, with byproduct methane selectivity when going back
Extremely low (< 5%), C4 and the above hydrocarbon selective are lower than 7%.
The present invention has the advantage that
(1) present invention is different from traditional preparing light olefins from methanol technology (referred to as MTO), and realizing a step will directly close
Ethylene processed is converted at gas.
(2) the single selectivity of product of ethylene is high in product of the present invention, can reach 75-85%, and high (the alkene receipts of space-time yield
Rate up to 1.42mmol/hg), product is easily isolated, and is had a good application prospect.
(3) catalyst of the present invention and 201610600945.6 and 201710129620.9 difference of patent application above-mentioned
It is, component B is modified using heterocycle organic base in catalyst of the present invention, is catalyzed and synthesized gas and is converted to obtain single component ethylene
Selectivity be up to 75-85%, and methane selectively is lower than 5%, and greatly suppresses the selectivity of the hydro carbons of C4 or more, and
Catalyst reaction in aforementioned 201610600945.6 and 201710129620.9 is the result is that product is wider, methane and C4 or more hydrocarbon
Class is more, is not able to satisfy above-mentioned condition.
Specific 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 is not meant to must satisfy these
Condition just can achieve this purpose.
Embodiment 1
One, the preparation of component A
(1) etching method synthesis has the ZnO material of polar surfaces:
(1) 4 parts, every part of 0.446g (1.5mmol) Zn (NO are weighed respectively3)2·6H2O is in 4 containers, then weighs respectively
0.300g (7.5mmol), 0.480g (12mmol), 0.720g (18mmol), 1.200g (30mmol) NaOH sequentially add above-mentioned 4
In a container, then each 30ml deionized water that measures is added in 4 containers, and stirring 0.5h or more is uniformly mixed solution.Heating
It is 160 DEG C, reaction time 20h to temperature, precipitating resolves into zinc oxide；Cooled to room temperature.Reaction solution centrifuge separation is received
Sediment after collection centrifuge separation, is washed with deionized 2 acquisition ZnO oxides；
The product of wherein 0.480g (12mmol) NaOH dosage is taken to carry out following processing:
(2) super with ZnO oxide at normal temperature using etching agents such as oleic acid, methenamine, ethylenediamine, ammonium hydroxide, hydrazine hydrates
Sound mixes, and ZnO oxide is soaked in etchant solution, and etching agent and zinc oxide form complexing or direct reduction reactor；
Above-mentioned suspended matter is heated, washing filtering is then taken out, obtains the nano-ZnO material with exhibiting high surface oxygen vacancies
Material.
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, not molten
The mass ratio of agent, oleic acid -5wt% hydrazine hydrate is 95:5, without solvent；When specific treatment conditions include etching agent, temperature, processing
Between and atmosphere type it is as shown in table 1 below.
(3) dry or dry and reduction
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 are inert gas or inert gas and reducing atmosphere gaseous mixture, inert gas N2, He and
One of Ar or two kinds or more, reducing atmosphere H2, CO one or two or more kinds, indifferent gas in dry reduction gaseous mixture
The volume ratio of body and reducibility gas is 100/10~0/100, and dry and reduction treatment temperature is 350 degrees Celsius, and the time is
4h.Obtain the ZnO material that surface is rich in Lacking oxygen.Specific sample and its preparation condition such as the following table 1.Wherein surface Lacking oxygen is fixed
Justice is (1- oxygen atom mole is reasonable to discuss stoichiometric ratio oxygen molar content).
The preparation and its performance parameters of table 1ZnO material
It is in the distance range of 0.3nm that the surface Lacking oxygen, which is from grain surface to intra-die direction depth, and oxygen is former
The reasonable percentage by stoichiometric ratio oxygen molar content of sub- mole；
As a comparison case, ZnO4 of the surface without Lacking oxygen without (2) step etching, and the metal that Zn is restored completely
Zn 5；
(2), etching method synthesis has the MnO material of polar surfaces: preparation process corresponds to (1) in above-mentioned (one)
The product of 0.480g (12mmol) NaOH dosage and (3) are described, the difference is that the presoma of Zn to have been changed into the correspondence of Mn
Presoma, can be one of manganese nitrate, manganese chloride, manganese acetate, be herein manganese nitrate.
Described in 3 preparation process of product ZnO of the etch processes with (2) in above-mentioned (one), synthesis has exhibiting high surface oxygen
The catalyst in vacancy；Surface Lacking oxygen 67%；
Corresponding product is defined as MnO 1；
(3) etching method synthesis has the CeO of polar surfaces2Material: preparation process corresponds to (1) in above-mentioned (one)
The product of 0.480g (12mmol) NaOH dosage and (3) are described, the difference is that the presoma of Zn to have been changed into the correspondence of Ce
Presoma, can be one of cerous nitrate, cerium chloride, cerous acetate, be herein cerous nitrate.
Described in 3 preparation process of product ZnO of the etch processes with (2) in above-mentioned (one), synthesis has exhibiting high surface oxygen
The catalyst in vacancy；Surface Lacking oxygen 56%；
Corresponding product is defined as CeO 1；
(4) synthesis has the nanometer Zn Cr of high-specific surface area, high surface energy2O4、ZnAl2O4、MnCr2O4、MnAl2O4,
MnZrO4Spinelle:
Use zinc nitrate, aluminum nitrate, chromic nitrate, manganese nitrate, zirconium nitrate for presoma, with the urea phase in water at room temperature
Mutually mixing；Above-mentioned mixed liquor is aged, washing, filtering and drying are then taken out, resulting solid is roasted in air atmosphere, obtained
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 described in (2) and (3) in above-mentioned (one), 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 the following table 2.Equally, surface Lacking oxygen is defined as that (1- oxygen atom mole is reasonable
By stoichiometric ratio oxygen molar content).
The preparation and its performance parameter of 2 spinel of table
(5) synthesis has the nanometer Fe Al of high-specific surface area, high surface energy2O4、CoAl2O4Spinelle: preparation process is same
(2) in above-mentioned (four) are described, can be nitre the difference is that the presoma of Zn to have been changed into the corresponding presoma of Fe or Co
One of sour iron, iron chloride, ironic citrate or one of cobalt nitrate, cobalt chloride, cobalt acetate are herein ferric nitrate, nitre
Sour cobalt.
Described in 3 preparation process of product ZnO of the etch processes with (2) in above-mentioned (one), synthesis has exhibiting high surface oxygen
The catalyst in vacancy；Surface Lacking oxygen 77%, 51%；
Corresponding product is defined as spinelle 6, spinelle 7；
(6) Cr2O3、Al2O3Or ZrO2The metal oxide of dispersion
With Cr2O3、Al2O3Or ZrO2For carrier, precipitates sedimentation and prepare Cr2O3、Al2O3Or ZrO2The metal of dispersion aoxidizes
Object.For dispersing the preparation of ZnO oxide, by business Cr2O3、Al2O3Or ZrO2Carrier is scattered in advance in the liquid of bottom, is then adopted
It is raw material with zinc nitrate, with sodium hydroxide pellets agent mixed precipitation at room temperature, Zn2+Molar concentration be 0.1M, Zn2+With it is heavy
The molfraction ratio of shallow lake agent is 1:6；Then it is aged 24 hours at 120 DEG C, obtains Cr2O3、Al2O3Or ZrO2For support dispersion
ZnO oxide.
Described in 3 preparation process of product ZnO of the etching process with (2) in above-mentioned (one), synthesis has exhibiting high surface Lacking oxygen
Catalyst (content of the dispersing agent in component A is followed successively by 0.2wt%, 10wt%, 90wt%)；Surface Lacking oxygen 25%,
30%, 65%；Last handling process is the same as described in (3) in above-mentioned (one)；
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 oxide of support dispersion, (dispersing agent is in urging
Content in agent A is followed successively by 7wt%, 30wt%, 60wt%), surface Lacking oxygen 22%, 47%, 68%；It corresponds to from top to bottom
Product is defined as dispersal oxide 4-6.
Two, the preparation of B component (molecular sieve of MOR topological structure)
The MOR topological structure is a kind of rhombic system, has the one-dimensional channels for the oval straight channels being parallel to each other
Structure contains 8 annulus one-dimensional straight channels parallel with 12 annulus, and there are 8 annulus pockets to be connected to for 12 annulus main aperture road sides.
Specific preparation process are as follows:
According to n (SiO2)/n(Al2O3)=15, n (Na2O)/n(SiO2)=0.2, n (H2O)/n(SiO2)=26.
Aluminum sulfate is mixed with sodium hydroxide solution, silica solution is then added, stirring 1h obtains the Primogel of homogeneous phase,
It transfers it in Autoclaves for synthesis, 180 DEG C of static crystallizations are quenched afterwards for 24 hours, wash, drying to get modenite sample is arrived
Product are labeled as Na-MOR.
Take Na-MOR, it mixed with the ammonium chloride solution of 1mol/L, 3h is stirred at 90 DEG C, wash, drying, continuously into
Row 4 times, 450 degree of roasting 6h obtain h-mordenite.
By the above process preparation the molecular sieve with MOR topological structure backbone element form can be Si-Al-O,
One of Ga-Si-O, Ga-Si-Al-O, Ti-Si-O, Ti-Al-Si-O, Ca-Al-O, Ca-Si-Al-O；
H is connected on the O element of part skeleton, corresponding product is successively defined as MOR1-8；
Table 3 has the preparation and its performance parameter of the molecular sieve of MOR topological structure
The molecular sieve that will be prepared takes and carries out dehydration degassing process under vacuum in right amount, and 400 DEG C of temperature, pressure 10-4Pa,
After being down to 300 DEG C after 10h, it is passed through the organic base gas of 200Pa into vacuum cavity, is taken off at the same temperature after balancing 10h
Attached 1h.
MOR1 is successively used: furans, thiophene, pyrroles, thiazole, imidazoles, pyridine, pyrazine, pyrimidine, pyridazine, indoles, quinoline
Quinoline, pteridine, acridine handle to obtain MOR9-21.
In order to illustrate the modification of the heterocyclic compound containing substituent group, MOR2 is obtained into MOR22 through 1- methylfuran；
MOR3 handles to obtain MOR23 through 1- methylpyrrole；MOR4 handles to obtain MOR24 through 3,5- lutidines；MOR5 is through 4- ethyl pyrrole
Pyridine handles to obtain MOR25；MOR6 handles to obtain MOR26 through 3- methylquinoline；MOR7 handles to obtain by 4- methyl indol
MOR27；MOR8 handles to obtain MOR28 by 5- methylacridine.
Three, the preparation of catalyst
The component A of required ratio and B component are added to the container, produced using the high-speed motion of these materials and/or container
The mesh such as separation, broken, mixing are realized in the effect of one or more of raw extruding force, impact force, cutting power, frictional force etc.
, the conversion of mechanical energy, thermal energy and chemical energy is realized by modulation temperature and carrier gas atmosphere, further between adjusting different component
Interaction.
During mechanical mixture, can be set 20-100 DEG C of mixing temperature, can in atmosphere or directly in air
Carry out, atmosphere are as follows: a) nitrogen and/or inert gas, b) gaseous mixture of hydrogen and nitrogen and/or inert gas, wherein hydrogen in
Volume in gaseous mixture is the gaseous mixture of 5~50%, c) CO and nitrogen and/or inert gas, wherein body of the CO in gaseous mixture
Product is 5~20%, d) O2With the gaseous mixture of nitrogen and/or inert gas, wherein O2Volume in gaseous mixture is 5-20%, institute
Stating inert gas is one or more of helium, argon gas, neon.
Mechanical stirring: in stirred tank, being mixed component A and B component using stirring rod, by controlling mixing time
(5min-120min) and rate (30-300 turns/min), the mixability and relative distance of adjustable component A and B component.
Ball milling: being rolled at a high speed in grinding pot using abrasive material and catalyst, is generated intense impact to catalyst, is rolled, reaches
To dispersion, the effect of mixing component A and B component.By control abrasive material, (material can be stainless steel, agate, quartz.Size model
Enclose: 5mm-15mm) with the ratio (quality is than range: 20-100:1) of catalyst, the granularity of adjustable catalyst and it is opposite away from
From.
Shaking table mixing method: component A and B component are pre-mixed, and are fitted into container；By control shaking table reciprocating vibration or
Circumferential oscillation realizes the mixing of component A and B component；By adjust hunting speed (range: 1-70 revs/min) and time (range:
5min-120min), it realizes and uniformly mixes and adjust its relative distance.
Mechanical milling method: component A and B component are pre-mixed, and are fitted into container；Certain pressure (range: 5 kilograms-
20 kilograms) under, relative motion (speed range: 30-300 turns/min) is carried out with mixed catalyst by lap tool, reaches adjusting
Catalyst grain size, relative distance and the mixed uniformly effect of realization.
Specific catalyst preparation and its parameter attribute are as shown in table 4.
The preparation of 4 catalyst of table and its parameter attribute
Catalysis 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 connect with the proportional valve of chromatography, carries out period real-time sampling point for meter, online product analysis chromatography
Analysis).
The catalyst 2g of aforementioned present invention is placed in fixed bed reactors, using the air in Ar metathesis reactor, so
Afterwards again in H2300 DEG C are warming up in atmosphere, switching and merging gas (H2/ CO molar ratio=0.2-3.5), the pressure of synthesis gas is 0.5-
10MPa is warming up to 300-600 DEG C of reaction temperature, adjusts the air speed of reactor feed gas to 500-8000ml/g/h.Product is by online
Chromatography tests and analyzes.
Change temperature, pressure and air speed, thus it is possible to vary reactivity worth.The selectivity of ethylene, propylene in the product is up to 83-
90%, feed stock conversion 10-60%；Since molecular sieve effectively acts synergistically with oxide, a large amount of generations of methane are avoided,
Methane selectively is lower than 5%, and wherein the selectivity of ethylene reaches 75-85%.
The application of 5 catalyst of table and its effect
The catalyst that comparative example 3 uses is component A metal ZnCo+MOR26, ZnCo molar ratio 1:1, ZnCo and point 1 mass
Than 1:1, remaining parameter and mixed process etc. are the same as catalyst C.
The catalyst that comparative example 4 uses is surface without oxygen vacancies TiO2+ MOR27, remaining parameter and mixed process etc. are same
Catalyst C.
It is bright to catalytic performance regulating and controlling effect that the reaction result of comparative example 5 and 6 shows that MOR is post-processed using organic base
Aobvious, compared to the catalyst regulated and controled without using organic base, the catalyst after regulation further reduced methane and and C4 or more
The selectivity of hydro carbons, and have the space-time yield and ethylene selectivity more increased.
Above embodiments are provided just for the sake of the description purpose of the present invention, and are not intended to limit the scope of the invention.This
The range of invention is defined by the following claims.It does not depart from spirit and principles of the present invention and the various equivalent replacements made and repairs
Change, should all cover within the scope of the present invention.
Claims (10)
1. a kind of catalyst, is made of component A and B component, component A and B component are combined with each other in a manner of mechanical mixture, A group
The active ingredient divided is metal oxide, and B component is the molecular sieve of MOR topological structure, it is characterised in that: described in B component
The molecular sieve of MOR topological structure is modified using organic base, and the organic base is heterocyclic compound.
2. catalyst according to claim 1, it is characterised in that: the heterocyclic compound is furans, thiophene, pyrroles, thiophene
Azoles, imidazoles, pyridine, pyrazine, pyrimidine, pyridazine, indoles, quinoline, pteridine and/or acridine；Preferably, the heterocyclic compound has
Methyl, ethyl, amino, the substituent group of one or more of nitro, preferably meta position and/or contraposition replace.
3. catalyst according to claim 1, it is characterised in that: in the active ingredient of the component A, metal oxide is
MnO、MnCr2O4、MnAl2O4、MnZrO4、ZnO、ZnCr2O4、ZnAl2O4、CeO2、CoAl2O4、FeAl2O4One of or two kinds
More than；Preferably MnO, MnCr2O4、MnAl2O4、MnZrO4、ZnAl2O4、CeO2、CoAl2O4、FeAl2O4One of or two kinds
More than；More preferably MnO, MnCr2O4、MnAl2O4,MnZrO4、CeO2、CoAl2O4、FeAl2O4One of or two kinds or more.
4. catalyst according to claim 1, it is characterised in that: between the active ingredient and B component in the component A
Weight ratio is 0.1-20, and weight ratio is preferably 0.3-8.
5. catalyst according to claim 1-4, it is characterised in that: the metal oxide from grain surface to
Intra-die direction depth is in the distance range of 0.3nm, and there are surface Lacking oxygen, the surface Lacking oxygen percentage composition is
20% or more, preferably 20-90%, more preferably 40-90%, most preferably 50-90%.
6. catalyst according to claim 1-5, it is characterised in that: dispersing agent is also added in the component A,
Dispersing agent is Al2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3One of or two kinds or more, metal oxide dispersion is in dispersion
In agent, for content of the dispersing agent in component A in 0.05-90wt%, preferably 0.05-25wt%, remaining is metal oxide.
7. according to catalyst described in any one of claims 1-6, it is characterised in that: the bone of the MOR topological structure molecular sieve
Frame element composition is Si-Al-O, Ga-Si-O, Ga-Si-Al-O, Ti-Si-O, Ti-Al-Si-O, Ca-Al-O, Ca-Si-Al-O
One of or two kinds or more.
8. a kind of method of carbon monoxide hydrogenation ethylene, it is characterised in that: with carbon monoxide and hydrogen mixed gas be anti-
Raw material is answered, conversion reaction is carried out in fixed bed or moving bed, obtains the low-carbon alkene product based on ethylene, used catalysis
Agent is catalyst as claimed in claim 1 to 7.
9. according to the method described in claim 8, it is characterized by: the pressure of the gaseous mixture is 0.5-10MPa, preferably 1-
8MPa, more preferably 2-8MPa；Reaction temperature is 300-600 DEG C, preferably 300-400 DEG C；Air speed is 300-10000h-1, excellent
It is selected as 500-9000h-1, more preferably 500-6000h-1。
10. method according to claim 8 or claim 9, it is characterised in that: the gaseous mixture is to contain H2With the gaseous mixture of CO,
H2/ CO molar ratio is 0.2-3.5, preferably 0.3-2.5；CO can also be contained in the synthesis gas2, wherein CO2In synthesis gas
Volumetric concentration be 0.1-50%.
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| CN110314698A (en) * | 2018-03-28 | 2019-10-11 | 中国科学院大连化学物理研究所 | A kind of preparation method of composite catalyst, preparation method and ethane |
| CN111346665A (en) * | 2018-12-21 | 2020-06-30 | 中国科学院大连化学物理研究所 | MOR-based bifunctional catalyst and method for preparing ethylene by directly converting synthesis gas |
| CN113023744A (en) * | 2021-03-17 | 2021-06-25 | 中国矿业大学 | Organic base modification method for dimethyl ether carbonylation mordenite |
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| CN108940355B (en) | 2020-12-29 |
| WO2018214476A1 (en) | 2018-11-29 |
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