CN105618073B - Light hydrocarbons mercaptan-eliminating catalyst and its preparation method based on the regulation and control of aluminium oxide crystal face - Google Patents
Light hydrocarbons mercaptan-eliminating catalyst and its preparation method based on the regulation and control of aluminium oxide crystal face Download PDFInfo
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- CN105618073B CN105618073B CN201610187374.8A CN201610187374A CN105618073B CN 105618073 B CN105618073 B CN 105618073B CN 201610187374 A CN201610187374 A CN 201610187374A CN 105618073 B CN105618073 B CN 105618073B
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- alumina
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000003054 catalyst Substances 0.000 title claims abstract description 123
- 239000013078 crystal Substances 0.000 title claims abstract description 62
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 52
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 64
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 150000001993 dienes Chemical class 0.000 claims abstract description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 14
- 239000011733 molybdenum Substances 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 230000001105 regulatory effect Effects 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 46
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 17
- 230000002378 acidificating effect Effects 0.000 claims description 16
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 15
- 150000001336 alkenes Chemical class 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 11
- 238000005470 impregnation Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 238000004898 kneading Methods 0.000 claims description 7
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000004523 catalytic cracking Methods 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000001802 infusion Methods 0.000 claims description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 238000004939 coking Methods 0.000 claims description 2
- DBRMBYFUMAFZOB-UHFFFAOYSA-N molybdenum nitric acid Chemical compound [Mo].[N+](=O)(O)[O-] DBRMBYFUMAFZOB-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000003009 desulfurizing effect Effects 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 30
- 238000010335 hydrothermal treatment Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 19
- 239000000843 powder Substances 0.000 description 17
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 14
- 239000003921 oil Substances 0.000 description 13
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 239000005864 Sulphur Substances 0.000 description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006477 desulfuration reaction Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- -1 mercaptan anion Chemical class 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 238000011017 operating method Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- AWOORJZBKBDNCP-UHFFFAOYSA-N molybdenum;oxotungsten Chemical compound [Mo].[W]=O AWOORJZBKBDNCP-UHFFFAOYSA-N 0.000 description 1
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005732 thioetherification reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/88—Molybdenum
- C07C2523/883—Molybdenum and nickel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
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Abstract
The present invention provides the light hydrocarbons mercaptan-eliminating catalyst regulated and controled based on aluminium oxide crystal face and its preparation method, which is using the gamma-alumina after hydro-thermal process of the present invention regulation and control as carrier, using nickel and molybdenum as active metal.Light hydrocarbons mercaptan-eliminating catalyst of the present invention is high activity and high-selectivity catalyst, it can be used for mercaptan and alkadienes effect generation macromolecular sulfide in catalysis light hydrocarbons, and it can also be catalyzed the selective hydrogenation saturation of diolefin, compared with existing catalyst, catalyst desulfurizing alcohol activity provided by the present invention is high, diolefin hydrogenation selectivity is high, and active component is not lost in, not easy in inactivation, thus the catalyst runs period is long, has preferable prospects for commercial application.
Description
Technical field
The present invention relates to the light hydrocarbons mercaptan-eliminating catalysts and its preparation method regulated and controled based on aluminium oxide crystal face, belong to oil production
Product technical field of refinement.
Background technology
Increasingly strict with environmental regulation, countries in the world propose the quality of refinery products increasingly stringenter
It is it is required that particularly more and more stringenter to the limitation of refinery products sulfur content.Contained vulcanization owner in oils
To be mercaptan (RSH), thioether (RSR) etc., wherein influence of the mercaptan to product quality is maximum, very strong not only with foul smell
Corrosivity can also influence the stability of product.
The mercaptan removal technique of oils continues to use the Merox catalytic oxidation desulfurization alcohol techniques of Uop Inc.'s exploitation always,
Its principle is faintly acid and mercaptan anion using thiol molecule easily by oxidation generation disulphide the two characteristics removing sulphur
Alcohol, main chemical reaction are：
NaOH+RSH→RSNa+H2O (1)
2RSNa+0.5O2+H2O→RSSR+2NaOH (2)
Main problem existing for above-mentioned Merox techniques is：It is only capable of converting mercaptan, it is impossible to realize the depth of oil product
Spend desulfurization；A large amount of alkaline residue discharge is generated, seriously pollutes environment.
CN101077984B discloses a kind of method of liquefied petroleum gas deep desulfuration, and this method is deodorized skill for no caustic alkali
Art；CN100462146C discloses the preparation method of the catalyst for converting mercaptan in gasoline, belongs to non-alkali liquor deodorization
Technology, both the above technology are respectively necessary for constantly adding lye or water in use, thus there is no really solve lightweight
Problem of environmental pollution caused by deep desulfuration problem and the liquid base discharge of refinery products.
In view of the above-mentioned problems, US6692635B2 discloses a kind of method for producing the low gasoline of sulfur content, adopted in this method
With new mercaptan removal technique.Full distillation gasoline raw material is passed through a selective hydrogenation reactor by the technology, makes mercaptan and gasoline
In alkene or alkadienes etherification reaction occur generate high boiling sulfur-containing compound, then to selection in a fractionating column
Property hydrogenation products be fractionated, obtain without the higher heavy petrol of mercaptan and the relatively low light gasoline fraction of total sulfur content and sulfur content
Fraction.The characteristics of technology is to realize mercaptan from effective removing in light gasoline fraction by the addition reaction of mercaptan and alkadienes
With the transfer to heavy naphtha, while the removing of mercaptan and the reduction of light petrol total sulfur content are realized, overcome tradition
Merox techniques are unable to deep desulfuration and there are problems that alkaline residue discharge.
CN1229838A discloses a kind of method for transformation of hydrocarbon ils, and this method is to be catalyzed feedstock oil and a kind of hydrofinishing
Agent removal of mercaptans under the process conditions of hydro-sweetening, the Hydrobon catalyst contain the oxygen of load on the alumina support
Change tungsten (molybdenum), nickel oxide and cobalt oxide, the wherein content of tungsten oxide (molybdenum) is 4~10wt%, the content of nickel oxide for 1~
5wt%, the content of cobalt oxide are 0.01~0.1wt%, the total atom number of nickel and cobalt and nickel, cobalt, tungsten (molybdenum) total atom number it
Than being 0.3~0.9.The catalyst is when for handling FCC gasoline, although can mercaptans content be reduced to 10 μ g/ from 212 μ g/g
G, but gasoline Research octane number (RON) loses 3.3 units, and motor octane number (MON) loses 3.0 units.
CN102451694A discloses a kind of hydrodesulfurization alcohol catalyst and its preparation method and application.The catalyst is with oxygen
It is carrier to change aluminium or silicon-containing alumina, using phosphorus as adjuvant component, using copper and zinc as active component, and on the basis of catalyst quality,
The content of auxiliary agent phosphorus is 0.5~3.0wt%, and the content of zinc oxide is 3~15wt%, and the content of copper oxide is 5~30wt%.Cause
The catalyst has very strong hydrogenation activity, and when for handling full fraction FCC gasoline, mercaptans content is reduced to 3 μ by 38 μ g/g
G/g, while olefin(e) centent is also reduced to 20v% by 25v%, RON losses are up to 1.3 units.
Road in summary, the defects of to overcome the more than prior art, finding a kind of completely new hydrodesulfurization alcohol catalyst is
One of the most urgent problems to be solved by those skilled in the art.
Invention content
To solve the above problems, the purpose of the present invention is to provide the method for hydro-thermal process regulation and control gama-alumina crystal face, it should
Method can make gained gama-alumina have highly exposed (111) and (110) crystal face.
Another object of the present invention is to provide the gama-alumina after being regulated and controled by the hydro-thermal process that the method obtains.
It is still another object of the present invention to provide the lightweights using the gama-alumina after hydro-thermal process regulation and control as carrier
Hydrocarbon desulfurization alcohol catalyst.The catalyst can be in efficient removal liquefied petroleum gas, FCC gasoline, catalytic cracking gasoline and/or coking
In the case of mercaptan and/or alkadienes in the light fractions such as gasoline, retain the alkene in raw material, the octane number RON of gasoline only drops
Low 0.3 point or so realizes the high value added utilization of light hydrocarbons.
Preparation method and application it is still another object of the present invention to provide the light hydrocarbons mercaptan-eliminating catalyst.
To achieve the above object, one aspect of the present invention provides a kind of method of hydro-thermal process regulation and control gama-alumina crystal face, institute
The method of stating includes：By gama-alumina (γ-Al2O3) raw material is added in acidic aqueous solution, hydro-thermal process is filtered, washed, dries
And roast hydro-thermal process regulation and control after gama-alumina.
By hydro-thermal process of the present invention regulation and control gama-alumina crystal face the obtained modified gama-alumina of method with not
Modified gama-alumina has visibly different physico-chemical property, and most notable one difference is the gama-alumina after hydrothermal modification
With higher crystallinity, and more (111) and (110) two kinds of crystal faces, the crystalline substance of both new exposures are exposed on its surface
Face causes the gama-alumina after hydrothermal modification to have more acid sites and more alkali centers simultaneously.Using the hydro-thermal process
Regulation and control gama-alumina can prepare catalyst of the present invention, which has excellent performance as described below.
Specific embodiment according to the present invention, in the method for hydro-thermal process of the present invention regulation and control gama-alumina crystal face
In, the temperature of hydro-thermal process is 120~200 DEG C；It is preferred that 3~12h of hydro-thermal process.
Specific embodiment according to the present invention, in the method for hydro-thermal process of the present invention regulation and control gama-alumina crystal face
In, calcination temperature is 400~550 DEG C；It is preferred that 5~15h of roasting.
Specific embodiment according to the present invention, in the method for hydro-thermal process of the present invention regulation and control gama-alumina crystal face
In, the specific surface area of the gama-alumina raw material is 200~400m20.3~0.8cm of/g, Kong Rongwei3/g。
Specific embodiment according to the present invention, in the method for hydro-thermal process of the present invention regulation and control gama-alumina crystal face
In, the acidic aqueous solution is included in aqueous solution of nitric acid, hydrochloric acid, oxalic acid aqueous solution, aqueous acetic acid and aqueous citric acid solution
It is one or more of；Preferably, the pH value of the acidic aqueous solution is 0~4；It is further preferred that acidic aqueous solution used is nitre
Aqueous acid；It is highly preferred that the aqueous solution of nitric acid that it is 0~4 that the acidic aqueous solution, which is pH value,.
Specific embodiment according to the present invention, in the method for hydro-thermal process of the present invention regulation and control gama-alumina crystal face
In, the mass ratio of the gama-alumina raw material and the acidic aqueous solution is 1:1~1:6；It is preferred that 1:2~1:4.
Specific embodiment according to the present invention, in the method for hydro-thermal process of the present invention regulation and control gama-alumina crystal face
In, the temperature of hydro-thermal process is 120~200 DEG C, preferably 160~200 DEG C.It is further preferred that hydrothermal conditions for 3~
12h, such as 5~12.
Specific embodiment according to the present invention, in the method for hydro-thermal process of the present invention regulation and control gama-alumina crystal face
In, the washing is to adopt to be washed with deionized.
Specific embodiment according to the present invention, in the method for hydro-thermal process of the present invention regulation and control gama-alumina crystal face
In, the temperature of the drying is 80~200 DEG C, preferably 100~150 DEG C.
Specific embodiment according to the present invention, in the method for hydro-thermal process of the present invention regulation and control gama-alumina crystal face
In, the roasting is to roast 5~15h at 100~550 DEG C；Preferred calcination temperature is 400~550 DEG C.
Specific embodiment according to the present invention, in the method for hydro-thermal process of the present invention regulation and control gama-alumina crystal face
In, hydro-thermal process temperature as described above, and calcination temperature it is as described above.Preferably, hydro-thermal process temperature and hydro-thermal process when
Between as described above, and calcination temperature and roasting time it is as described above.
Specific embodiment according to the present invention, in the method for hydro-thermal process of the present invention regulation and control gama-alumina crystal face
In, the type of acidic aqueous solution as described above, and hydro-thermal process temperature it is as described above.Preferably, the type of acidic aqueous solution and
Dosage as described above, and hydro-thermal process temperature and hydrothermal conditions it is as described above.
Specific embodiment according to the present invention, in the method for hydro-thermal process of the present invention regulation and control gama-alumina crystal face
In, the type of acidic aqueous solution as described above, and calcination temperature it is as described above.Preferably, the type and dosage of acidic aqueous solution
As described above, and calcination temperature and roasting time it is as described above.
Specific embodiment according to the present invention, in the method for hydro-thermal process of the present invention regulation and control gama-alumina crystal face
In, the type of acidic aqueous solution as described above, hydro-thermal process temperature as described above, and calcination temperature it is as described above.Preferably, it is sour
The type and dosage of property aqueous solution as described above, hydro-thermal process temperature and time as described above, and calcination temperature and roasting time
As described above.
In another aspect, the present invention provides the hydro-thermal obtained by the method for hydro-thermal process regulation and control gama-alumina crystal face
Gama-alumina after reason regulation and control.Compared to existing gama-alumina, the gama-alumina after hydro-thermal process regulation and control has higher
Crystallinity and more (111) and (110) crystal faces, the crystal face of both new exposures cause the gama-alumina after hydrothermal modification
There are more acid sites and more alkali centers simultaneously.
Specific embodiment according to the present invention, the specific surface of the gama-alumina after hydro-thermal process regulation and control of the present invention
Product is 150~300m20.3~1.0cm of/g, Kong Rongwei3/g。
In another aspect, the present invention provides a kind of light hydrocarbons mercaptan-eliminating catalyst based on the regulation and control of aluminium oxide crystal face, this is urged
Agent is using the gama-alumina after hydro-thermal process of the present invention regulation and control as carrier, using nickel and molybdenum as active metal.Preferably,
Active metal nickel is deposited on the crystal face (111) of the gama-alumina after the hydro-thermal process regulation and control, and active metal molybdenum is deposited on institute
On the crystal face (110) for stating the gama-alumina after hydro-thermal process regulation and control.
Light hydrocarbons mercaptan-eliminating catalyst of the present invention is high activity and high-selectivity catalyst, can be used for catalysis light
Mercaptan and alkadienes (or alkene) effect generation macromolecular sulfide in matter hydro carbons.Compared with existing catalyst, institute of the present invention
The catalyst desulfurizing alcohol activity of offer is high, diolefin hydrogenation selectivity is high, and active component is not lost in, not easy in inactivation, thus urges
Agent is long service cycle, has preferable prospects for commercial application.
Preferably, in light hydrocarbons mercaptan-eliminating catalyst of the present invention, using the total weight of the catalyst as 100%
Meter, including：Gama-alumina after the hydro-thermal process regulation and control of 50~85wt%；
The nickel oxide of 5~20wt%；It is preferred that the nickel oxide of 10~20wt% and
The molybdenum oxide of 2~15wt%；It is preferred that the molybdenum oxide of 4~12wt%.
It is further preferred that in light hydrocarbons mercaptan-eliminating catalyst of the present invention, using the total weight of the catalyst as
100% meter, including：
Gama-alumina after the hydro-thermal process regulation and control of 50~85wt%；
The nickel oxide of 10~20wt% and
The molybdenum oxide of 4~12wt%.
The carrier of catalyst of the present invention is the gama-alumina after hydro-thermal process of the present invention regulation and control, as described above,
The gama-alumina is characterized in that it with highly exposed (111) and (110) crystal face so that in catalyst of the present invention
Active metal nickel (Ni) and molybdenum (Mo) can realize that crystal face selection preferably loads on the gama-alumina crystal face, W metal is preferential
It is supported on newly (111) crystal face of exposure, and metal Mo is preferentially supported on newly (110) crystal face of exposure.Meanwhile two kinds of activity
Metal is brilliant also by two different activity are formd with the effect of modified gama-alumina (111) and (110) crystal face respectively
Face, so as to obtain high activity and highly selective light hydrocarbons mercaptan-eliminating catalyst.The catalyst can liquefy in efficient removal
In the case of mercaptan and/or alkadienes in the light fractions such as oil gas, FCC gasoline, catalytic cracking gasoline and coker gasoline, retain
Alkene in raw material, the octane number RON of gasoline only reduces by 0.3 point or so, so as to fulfill the high value added utilization of light hydrocarbons.
In another aspect, the present invention provides the preparation method of the light hydrocarbons mercaptan-eliminating catalyst, the method includes such as
Lower step：
Kneading after gama-alumina, auxiliary agent and aqueous solution of nitric acid after (a) hydro-thermal process of the present invention is regulated and controled mix,
Extrusion forming, drying and roasting, obtain catalyst carrier；
(b) presoma of the presoma of metallic nickel, metal molybdenum is supported on by catalyst made from step (a) using infusion process
On carrier, after drying and roasting, the light hydrocarbons mercaptan-eliminating catalyst is obtained.
Specific embodiment according to the present invention, in the preparation method of light hydrocarbons mercaptan-eliminating catalyst of the present invention
In, it is counted using the total weight of the catalyst carrier as 100%, the dosage of the auxiliary agent is 1.0~3.5wt%, the nitric acid aqueous solution
The mass fraction of solution is 50~70%, and dosage is 3.0~6.0wt%.
Specific embodiment according to the present invention, in the preparation method of light hydrocarbons mercaptan-eliminating catalyst of the present invention
In, the extrusion forming is by material ball up particle, cylindrical particle or the trilobes particle after kneading；Preferably,
The equivalent diameter of the particle is 2~10mm.
Specific embodiment according to the present invention, in the preparation method of light hydrocarbons mercaptan-eliminating catalyst of the present invention
In step (a), the drying be temperature be 80~150 DEG C of dry 2~10h.
Specific embodiment according to the present invention, in the preparation method of light hydrocarbons mercaptan-eliminating catalyst of the present invention
In step (a), the roasting is to roast 5~10h for 300~600 DEG C in temperature.
Specific embodiment according to the present invention, in the preparation method of light hydrocarbons mercaptan-eliminating catalyst of the present invention
In step (b), the drying is in 70~140 DEG C of dry 2~6h.
Specific embodiment according to the present invention, in the preparation method of light hydrocarbons mercaptan-eliminating catalyst of the present invention
In step (b), the roasting is to roast 3~10h at 400~600 DEG C.
Specific embodiment according to the present invention, in the preparation method of light hydrocarbons mercaptan-eliminating catalyst of the present invention
In, the calcination temperature and time in step (a) are as described above, calcination temperature and time in step (b) are as described above.
Specific embodiment according to the present invention, in the preparation method of light hydrocarbons mercaptan-eliminating catalyst of the present invention
In, the presoma of the metallic nickel includes one or more of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate；It is preferred that nitric acid
Nickel and/or nickel acetate.
Specific embodiment according to the present invention, in the preparation method of light hydrocarbons mercaptan-eliminating catalyst of the present invention
In, the presoma of the metal molybdenum includes molybdate and/or nitric acid molybdenum；Preferably, the molybdate is ammonium molybdate.
Preferably, in the preparation method of light hydrocarbons mercaptan-eliminating catalyst of the present invention, the forerunner of the metallic nickel
Body is nickel nitrate, and the presoma of the metal molybdenum is ammonium molybdate.
In the preparation method of light hydrocarbons mercaptan-eliminating catalyst of the present invention, helping in above-mentioned method for preparing catalyst
Agent can be conventional pore creating material, such as sesbania powder.
Specific embodiment according to the present invention, in the preparation method of light hydrocarbons mercaptan-eliminating catalyst of the present invention
In, the infusion process is co-impregnation or step impregnation method.Preferably, the co-impregnation is isometric co-impregnation；It is described
Often step is equi-volume impregnating in step impregnation method.It is highly preferred that the infusion process is isometric co-impregnation.
In another aspect, the present invention provides the application of the light hydrocarbons mercaptan-eliminating catalyst, the application is to be catalyzed this
Agent is applied to removing liquefied petroleum gas, FCC gasoline, catalytic cracking gasoline and/or mercaptan and/or alkadienes in coker gasoline；
Or the application is to be used to the catalyst be catalyzed diolefin selective hydrogenation.
It as described above, can be in efficient removal liquefied petroleum gas, FCC using light hydrocarbons mercaptan-eliminating catalyst of the present invention
In the case of mercaptan and/or alkadienes in the light hydrocarbons such as gasoline, catalytic cracking gasoline and/or coker gasoline, retain raw material
In alkene, the octane number RON of gasoline only reduces by 0.3 point or so, realizes the high value added utilization of light hydrocarbons.
In conclusion present invention generally provides the method for hydro-thermal process regulation and control gama-alumina crystal face and based on gained water
The light hydrocarbons mercaptan-eliminating catalyst of gama-alumina after heat treatment regulation and control.It is prepared based on hydrothermal modification gama-alumina of the present invention
Catalyst have visibly different physico-chemical property, most significant feature is that two kinds of active metals are realized on gamma-alumina
Crystal face selection preferentially loads, i.e., W metal is preferentially supported on newly (111) crystal face of exposure, and metal Mo is preferentially supported on newly
On exposed (110) crystal face.Meanwhile two kinds of active metals are also by respectively with being modified gama-alumina (111) and (110) crystal face
Effect form respectively two different active crystal faces.
Description of the drawings
Gama-alumina and the gamma oxidation of non-hydrothermal treatment after the hydrothermal treatment that Fig. 1 is prepared for embodiment 1
Aluminium X-ray diffraction (XRD) spectrogram；
Transmission electron microscope (TEM) photo of gama-alumina after the hydrothermal treatment that Fig. 2 is prepared for embodiment 1；
Fig. 3 be embodiment 1 be prepared using the catalyst RM-1's obtained by the gama-alumina after hydrothermal treatment
TEM photos；
Fig. 4 is the TEM photos using the catalyst PH-1 prepared by non-hydrothermal treatment gama-alumina；
Fig. 5 is two kinds of catalyst of RM-1 and PH-1 to gasoline simulated compound (ethyl mercaptan and isoamyl alkene) sweetening reaction
The evaluation result of performance；
Fig. 6 is the comparison figure of the sulphur content cloth and the sulphur content cloth in feedstock oil in the product after RM-1 catalysts.
Specific embodiment
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, in conjunction with specific implementation
Example and attached drawing carry out technical scheme of the present invention described further below, it should be understood that these examples be merely to illustrate the present invention without
For limiting the scope of the invention.
Embodiment 1
The present embodiment provides a kind of light hydrocarbons mercaptan-eliminating catalyst based on the regulation and control of gama-alumina crystal face and its preparation sides
Method, through the following steps that implement：
(1) hydro-thermal process of gama-alumina raw material
1L deionized waters and 1g mass fractions for 65% concentrated nitric acid are mixed, are configured to salpeter solution, then thereto
Add in 250g γ-Al2O3Powder, the γ-Al2O3The specific surface area of powder is 280m2/ g, Kong Rongwei 0.71cm3/ g is uniformly mixed
It is fitted into reaction kettle afterwards, in an oven after 170 DEG C of incubation water heatings handle 7h, filters out solid product, in 120 DEG C of dry 2h,
Then 520 DEG C of roasting 4h are to get the gama-alumina powder after the present embodiment hydrothermal treatment.
Gama-alumina and the gama-alumina XRD of non-hydrothermal treatment after Fig. 1 hydrothermal treatments obtained by the present embodiment
Spectrogram.(a) is the XRD spectra of alumina precursor boehmite (product before roasting) in wherein Fig. 1, and (b) is roasting in Fig. 1
The XRD spectra of alumina product after burning.From figure 1 it appears that two kinds of products and boehmite, oxygen before and after hydro-thermal process
The peak for changing aluminium standard x RD cards is essentially identical, while being remarkably reinforced occurs in the characteristic diffraction peak after hydrothermal treatment, especially
In Fig. 1 (a) occur (131) and (151) diffraction maximum and Fig. 1 in (b) appearance (400) and (440) diffraction peak intensity it is all big
Width increases, this shows that the gama-alumina after hydrothermal treatment exposes new crystal face.
Fig. 2 is the TEM photos of the gama-alumina after hydrothermal treatment obtained by the present embodiment, and (a) and (b) is in wherein Fig. 2
The TEM photos of aluminium oxide { 110 } crystal face, and (c) and (d) is the TEM photos of aluminium oxide { 111 } crystal face in Fig. 2, above-mentioned TEM shines
Piece can prove that new (111) and (110) crystal face occurs in the surface of the gama-alumina after hydrothermal treatment.
(2) preparation of catalyst carrier
By the gama-alumina powder after the above-mentioned hydrothermal treatments of 100g and the gamma oxidation of the above-mentioned non-hydrothermal treatments of 100g
With 2g sesbania powders, the concentrated nitric acid that 4.5g mass fractions are 65%, 50g water kneadings, the spherical shape of a diameter of 3mm is made respectively in aluminium powder
Particle, in 120 DEG C of dry 4h, in 520 DEG C of constant temperature calcining 3h, prepared by the gama-alumina after respectively obtaining based on hydrothermal treatment
Catalyst carrier and the catalyst carrier for preparing of gama-alumina based on non-hydrothermal treatment.
(3) preparation of light hydrocarbons mercaptan-eliminating catalyst
78g above two catalyst carriers, co-impregnation load 50g nickel nitrates and 9g ammonium molybdates are taken respectively, 520 after drying
DEG C constant temperature calcining 4h, is subsequently cooled to room temperature, and call number is that being prepared based on the gama-alumina after hydrothermal treatment for RM-1 is light
Light hydrocarbons prepared by the gama-alumina based on non-hydrothermal treatment that matter hydrocarbon desulfurization alcohol catalyst and number are PH-1 take off
Mercaptan catalyst.
Fig. 3 and Fig. 4 is the TEM photos of two kinds of catalyst of RM-1 and PH-1 respectively, as can be seen that being urged in RM-1 from photo
Active metal realizes crystal face selection and preferentially loads in agent, i.e. active metal Ni is preferentially carried on (111) crystal face and generates
(101) crystal face, and active metal Mo is preferentially carried on generation (100) crystal face on (110) crystal face.And it is not seen in PH-1 catalyst
Observe the selective load phenomena of similar active metal.
Embodiment 2
Present embodiments provide a kind of light hydrocarbons mercaptan-eliminating catalyst regulated and controled based on gama-alumina crystal face and its preparation
Method, through the following steps that implement：
(1) hydro-thermal process of gama-alumina raw material
1L deionized waters and 2g acetic acid are mixed, are configured to acetic acid solution, then adds in 400g γ-Al thereto2O3Powder
End, the γ-Al2O3The specific surface area of powder is 320m2/ g, Kong Rongwei 0.75cm3/ g, is fitted into reaction kettle after mixing,
5h are handled in 190 DEG C of incubation water heatings in baking oven, filter out solid product, in 120 DEG C of dry 4h, in 520 DEG C of constant temperature calcining 4h, i.e.,
Obtain the gama-alumina powder after the present embodiment hydrothermal treatment.
(2) preparation of catalyst carrier
It is 65% by the gama-alumina powder after the above-mentioned hydrothermal treatments of 100g and 2g sesbania powders, 4.5g mass fractions
A diameter of 2mm is made, the spheric granules that length is 3~4mm, in 120 DEG C of dry 4h, in 500 DEG C of perseverances in concentrated nitric acid, 50g water kneadings
5h is to get the present embodiment catalyst carrier for temperature roasting.
(3) preparation of light hydrocarbons mercaptan-eliminating catalyst
78g said catalyst carriers, step load 56g nickel nitrates and 10g ammonium molybdates are taken, is roasted after dry in 500 DEG C of constant temperature
4h is burnt, is subsequently cooled to room temperature to get the present embodiment light hydrocarbons mercaptan-eliminating catalyst, number RM-2.
Embodiment 3
Present embodiments provide a kind of light hydrocarbons mercaptan-eliminating catalyst regulated and controled based on gama-alumina crystal face and its preparation
Method, through the following steps that implement：
(1) hydro-thermal process of gama-alumina raw material
1L deionized waters and 1g mass fractions for 65% concentrated nitric acid are mixed, are configured to salpeter solution, is then added thereto
Enter 400g γ-Al2O3Powder, the γ-Al2O3The specific surface area of powder is 260m2/ g, Kong Rongwei 0.78cm3/ g, after mixing
It is fitted into reaction kettle, handles 6h in 180 DEG C of incubation water heatings in an oven, solid product is filtered out, in 120 DEG C of dry 4h, 500
DEG C constant temperature calcining 4h is to get the gama-alumina powder after the present embodiment hydrothermal treatment.
(2) preparation of catalyst carrier
It is 65% by the gama-alumina powder after the above-mentioned hydrothermal treatments of 100g and 2g sesbania powders, 4.5g mass fractions
A diameter of 2mm is made, the cloverleaf pattern particle that length is 3~4mm, in 120 DEG C of dry 4h, 500 in concentrated nitric acid, 50g water kneadings
DEG C constant temperature calcining 5h is to get the present embodiment catalyst carrier.
(3) preparation of light hydrocarbons mercaptan-eliminating catalyst
78g said catalyst carriers, co-impregnation load 56g nickel nitrates and 9g ammonium molybdates are taken, is roasted after dry in 500 DEG C of constant temperature
4h is burnt, is subsequently cooled to room temperature to get the present embodiment light hydrocarbons mercaptan-eliminating catalyst, number RM-3.
Embodiment 4
The present embodiment has investigated two kinds of catalyst of RM-1 and PH-1 to analog gasoline compound (ethyl mercaptan and isoamyl alkene)
The reactivity worth of removal of mercaptans, is specifically implemented according to the following steps：
RM-1 the and PH-1 catalyst granules of a diameter of 2~4mm of 3g is loaded into micro fixed-bed reactor respectively,
During loading catalyst, bed both ends are filled with quartz sand；Two kinds of catalyst are handled first by presulfurization, presulfurization condition
For：Pressure is 2.8MPa, and the volume ratio of hydrogen/presulfurization oil is 200:1, volume space velocity is 2h during the liquid of presulfurization oil-1, reaction
Device temperature uses control method, 150 DEG C of constant temperature 2h, 230 DEG C, 260 DEG C, 290 DEG C and 320 DEG C difference constant temperature 4h；Then into
Row sweetening reaction, reaction condition are：Pressure is 2.0MPa, temperature is 135 DEG C, hydrogen to oil volume ratio 10:1st, liquid phase volume is empty
Speed is 3.5h-1。
Sample introduction stablizes the analysis of 48h post-samplings, then sampling analysis is carried out to reactor product every 8h, using gas chromatograph
With the sulphur content cloth and mercaptans content of sulphur matter chemiluminescence detector (GC-SCD) detection sample.Fig. 5 is the present embodiment RM-1 and PH-
1 two kinds of catalyst are to the evaluation result of analog gasoline (ethyl mercaptan and isoamyl alkene) sweetening reaction performance.It can from Fig. 5
Go out：RM-1 catalyst can be catalyzed ethyl mercaptan, and the reaction was complete, and removal of mercaptans rate is 100%；And the ethyl mercaptan conversion ratio of PH-1 catalyst
Only 87.7%, hence it is evident that less than RM-1 catalyst, the reaction product obtained on two catalyst is identical, shows two kinds of catalyst
Reaction mechanism it is identical.
Embodiment 5
The present embodiment has investigated sweetening reaction performance of the RM-1 catalyst to catalytically cracked gasoline, specifically according to following step
It is rapid to implement：
Operating procedure in the present embodiment is same as Example 4, loaded catalyst, type of feed, presulfurization condition with
And analysis method of product etc. is also same as Example 4.The specific reaction condition of demercaptaning for gasoline by catalyst cracking is：Pressure is
2.0MPa, temperature are 130 DEG C, hydrogen to oil volume ratio 10:1st, liquid phase volume air speed is 3.5h-1.Acquired results are as shown in table 1 below.
Table 1RM-1 evaluating catalyst results
| Project | FCC feedstock | RM-1 reaction products |
| Density, g/mL | 0.721 | 0.725 |
| Sulphur, ppm | 754 | 746 |
| Mercaptan sulfur, ppm | 31 | 2 |
| Olefin(e) centent, v% | 55.41 | 54.89 |
| Octane number, RON | 88.24 | 88.08 |
| Yield of gasoline, wt% | 98.89 |
As can be seen from Table 1, after sweetening reaction, the mercaptan sulfur content in gained reaction product be reduced to 10ppm with
Under, while total sulfur content holding is basically unchanged, this shows that the sulphur transfer i.e. etherificate of mercaptan and alkadienes only has occurred during this
Reaction, without hydrodesulfurization reaction occurs；The olefin(e) centent of reaction products therefrom is also basically unchanged, this illustrates that the catalyst has
There is good selectivity, do not occur alkene plus hydrogen saturation, and the yield of product is also more than 98.5%, the octane number of gasoline
RON only reduces by 0.3 point or so.Fig. 6 is the sulphur content cloth spectrogram of RM-1 catalyst prods and feedstock oil, as seen from Figure 6, former
All thioetherification has occurred in low-carbon mercaptan (methyl mercaptan, ethyl mercaptan, isopropyl mercaptan and n-propyl mercaptan) in material, generates height
Carbon sulfur-containing compound, and the content of the thiophenes such as thiophene, methylthiophene is basically unchanged, it is excellent that this shows that the catalyst has
Different selectivity and sweetening reaction activity.
Embodiment 6
The present embodiment investigates sweetening reaction performance of the RM-2 catalyst to coker gasoline, specifically according to following steps reality
It applies：
Operating procedure in the present embodiment is same as Example 4, loaded catalyst, type of feed, presulfurization condition with
And analysis method of product etc. is also same as Example 4, but reaction raw materials are the higher coker gasoline of mercaptans content.Its removal of mercaptans
Specific reaction condition be：Pressure is 2.5MPa, reaction temperature is 135 DEG C, hydrogen to oil volume ratio 8:1st, liquid phase volume air speed is
3h-1.The results are shown in Table 2 for RM-2 evaluating catalysts product.
Two kinds of evaluating catalyst results of table 2RM-2
| Project | Coker gasoline | RM-2 reaction products |
| Density, g/mL | 0.744 | 0.740 |
| Sulphur, ppm | 2110 | 2098 |
| Mercaptan sulfur, ppm | 214 | 7 |
| Olefin(e) centent, v% | 32.78 | 31.42 |
| Octane number, RON | 72.45 | 72.12 |
| Yield of gasoline, wt% | 98.98 |
Table 2 and the result of table 1 are essentially identical, this shows that the catalyst also has coker gasoline excellent selectivity and takes off
Thiol reaction activity.
Embodiment 7
The present embodiment investigates sweetening reaction performance of the RM-3 catalyst to liquefied petroleum gas, specifically according to following steps reality
It applies：
Operating procedure in the present embodiment is same as Example 4, loaded catalyst, type of feed, presulfurization condition with
And analysis method of product etc. is also same as Example 4, but reaction raw materials are liquefied petroleum gas.The specific reaction condition of its removal of mercaptans
For：Pressure is 2.0MPa, reaction temperature is 110 DEG C, hydrogen to oil volume ratio 6:1st, liquid phase volume air speed is 3h-1.RM-3 catalyst
The reaction result of catalytic liquefied petroleum gas sweetening reaction is as shown in table 3.
The reaction result of table 3RM-3 catalyst
| Composition | Raw material | Product |
| Hydrogen sulfide, ppm | 8.2 | 0 |
| Methyl mercaptan, ppm | 414.9 | 4.3 |
| Ethyl mercaptan, ppm | 217.5 | 1.7 |
| Alkene, v% | 59.74 | 57.74 |
| Yield, wt% | 94.57 |
As can be seen from Table 3, the hydrogen sulfide in liquefied petroleum gas and mercaptan are removed substantially, and olefin(e) centent varies less,
This shows that the catalyst also has liquefied petroleum gas high removal of mercaptans activity.
What is finally illustrated is：Above example is merely to illustrate the implementation process and feature of the present invention, and unrestricted is sent out
Bright technical solution, although the present invention has been described in detail with reference to the above embodiments, those of ordinary skill in the art should
Work as understanding：It is still possible to modify or equivalently replace the present invention, without departing from the spirit and scope of the present invention any
Modification or part are replaced, and should all be covered in protection scope of the present invention.
Claims (18)
1. a kind of application of the light hydrocarbons mercaptan-eliminating catalyst based on the regulation and control of aluminium oxide crystal face, wherein, the application is to pass through
Mercaptan acts on alkene and is used to the catalyst remove liquefied petroleum gas, FCC gasoline, catalytic cracking gasoline and/or coker gasoline
In mercaptan and/or alkene；
Wherein, the light hydrocarbons mercaptan-eliminating catalyst based on the regulation and control of aluminium oxide crystal face be γ after being regulated and controled with hydro-thermal process-
Aluminium oxide is carrier, using nickel and molybdenum as active metal；
Active metal nickel is deposited on the crystal face (111) of the gama-alumina after the hydro-thermal process regulation and control；
Active metal molybdenum is deposited on the crystal face (110) of the gama-alumina after the hydro-thermal process regulation and control；
It is counted using the total weight of the catalyst as 100%, including：
Gama-alumina after the hydro-thermal process regulation and control of 50~85wt%；
The nickel oxide of 10~20wt%；And
The molybdenum oxide of 4~12wt%；
What the gama-alumina after the hydro-thermal process regulation and control was prepared as follows：
Gama-alumina raw material is added in acidic aqueous solution, hydro-thermal process, is filtered, washed, dries and roasts and to obtain hydro-thermal process
Gama-alumina after regulation and control.
2. a kind of application of the light hydrocarbons mercaptan-eliminating catalyst based on the regulation and control of aluminium oxide crystal face, wherein, the application is to pass through
Mercaptan acts on alkadienes and is used to the catalyst remove liquefied petroleum gas, FCC gasoline, catalytic cracking gasoline and/or coking vapour
Mercaptan and/or alkadienes in oil；
Wherein, the light hydrocarbons mercaptan-eliminating catalyst based on the regulation and control of aluminium oxide crystal face be γ after being regulated and controled with hydro-thermal process-
Aluminium oxide is carrier, using nickel and molybdenum as active metal；
Active metal nickel is deposited on the crystal face (111) of the gama-alumina after the hydro-thermal process regulation and control；
Active metal molybdenum is deposited on the crystal face (110) of the gama-alumina after the hydro-thermal process regulation and control；
It is counted using the total weight of the catalyst as 100%, including：
Gama-alumina after the hydro-thermal process regulation and control of 50~85wt%；
The nickel oxide of 10~20wt%；And
The molybdenum oxide of 4~12wt%；
What the gama-alumina after the hydro-thermal process regulation and control was prepared as follows：
Gama-alumina raw material is added in acidic aqueous solution, hydro-thermal process, is filtered, washed, dries and roasts and to obtain hydro-thermal process
Gama-alumina after regulation and control.
3. application according to claim 1 or 2, wherein, the specific surface area of the gama-alumina after hydro-thermal process regulation and control is
150~300m20.3~1.0cm of/g, Kong Rongwei3/g。
4. application according to claim 1 or 2, wherein, the temperature of the hydro-thermal process is 120~200 DEG C；Hydro-thermal process
Time is 3~12h.
5. application according to claim 1 or 2, wherein, the calcination temperature is 400~550 DEG C；Roasting time for 5~
15h。
6. application according to claim 1 or 2, wherein, the specific surface area of the gama-alumina raw material is 200~400m2/
0.3~0.8cm of g, Kong Rongwei3/g。
7. application according to claim 1 or 2, wherein, the acidic aqueous solution includes aqueous solution of nitric acid, hydrochloric acid, oxalic acid
One or more of aqueous solution, aqueous acetic acid and aqueous citric acid solution.
8. application according to claim 7, wherein, the pH value of the acidic aqueous solution is 0~4.
9. application according to claim 7, wherein, the mass ratio of the gama-alumina raw material and the acidic aqueous solution
It is 1:1~1:6.
10. application according to claim 9, wherein, the temperature of hydro-thermal process is 120~200 DEG C；Calcination temperature is 400
~550 DEG C.
11. application according to claim 1 or 2, wherein, the light hydrocarbons removal of mercaptans based on the regulation and control of aluminium oxide crystal face
What catalyst was prepared as follows, described method includes following steps：
(a) it is kneading after gama-alumina, auxiliary agent and aqueous solution of nitric acid after the hydro-thermal process is regulated and controled mix, extrusion forming, dry
Dry and roasting, obtains catalyst carrier；
(b) presoma of the presoma of metallic nickel, metal molybdenum is supported on by catalyst carrier made from step (a) using infusion process
On, after drying and roasting, obtain the light hydrocarbons mercaptan-eliminating catalyst regulated and controled based on aluminium oxide crystal face.
12. application according to claim 11, wherein, in step (a), using the total weight of the catalyst carrier as
100% meter, the dosage of the auxiliary agent is 1.0~3.5wt%, and the mass fraction of the aqueous solution of nitric acid is 50~70%, is used
It measures as 3.0~6.0wt%.
13. application according to claim 11, wherein, in step (a), the extrusion forming is by the material after kneading
Ball up particle, cylindrical particle or trilobes particle；The equivalent diameter of particle is 2~10mm after extrusion forming.
14. application according to claim 11, wherein, in step (b), the presoma of the metallic nickel includes nitric acid
One or more of nickel, nickel acetate, nickel chloride and nickel sulfate.
15. application according to claim 11, wherein, in step (b), the presoma of the metal molybdenum includes molybdate
And/or nitric acid molybdenum.
16. application according to claim 11, wherein, the infusion process is co-impregnation or step impregnation method.
17. application according to claim 11, wherein, roasting described in step (a) is to be roasted in temperature for 300~600 DEG C
Burn 5~10h；Roasting described in step (b) is to roast 3~10h at 400~600 DEG C.
18. application according to claim 16, wherein, roasting described in step (a) is to be roasted in temperature for 300~600 DEG C
Burn 5~10h；Roasting described in step (b) is to roast 3~10h at 400~600 DEG C.
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