CN106890660A - 一种加氢脱硫催化剂及其制备方法 - Google Patents
一种加氢脱硫催化剂及其制备方法 Download PDFInfo
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- CN106890660A CN106890660A CN201510953533.6A CN201510953533A CN106890660A CN 106890660 A CN106890660 A CN 106890660A CN 201510953533 A CN201510953533 A CN 201510953533A CN 106890660 A CN106890660 A CN 106890660A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 6
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 239000008139 complexing agent Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 8
- 238000010025 steaming Methods 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 5
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 claims description 2
- 238000005352 clarification Methods 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- HIYNGBUQYVBFLA-UHFFFAOYSA-D cobalt(2+);dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Co+2].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HIYNGBUQYVBFLA-UHFFFAOYSA-D 0.000 claims description 2
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 claims 1
- 238000012216 screening Methods 0.000 claims 1
- CMSWHGFRLICZCA-UHFFFAOYSA-N trihydroxy(dimethyl)-$l^{5}-phosphane Chemical compound CP(C)(O)(O)O CMSWHGFRLICZCA-UHFFFAOYSA-N 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 abstract description 13
- 239000011593 sulfur Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 238000006477 desulfuration reaction Methods 0.000 abstract description 7
- 230000023556 desulfurization Effects 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 238000004073 vulcanization Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 150000003017 phosphorus Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 239000000969 carrier Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 241001120493 Arene Species 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 235000019838 diammonium phosphate Nutrition 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- -1 transition metal nitride Chemical class 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000899793 Hypsophrys nicaraguensis Species 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- ZQRGREQWCRSUCI-UHFFFAOYSA-N [S].C=1C=CSC=1 Chemical compound [S].C=1C=CSC=1 ZQRGREQWCRSUCI-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical group 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
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- 238000000967 suction filtration Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
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- 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
- C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- 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
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
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Abstract
本发明涉及一种加氢脱硫催化剂及其制备方法，该催化剂包括活性组分和载体，活性组分包括磷、硫和活性金属组分，活性金属组分选自由Co、Mo、Ni和W所组成群组中的至少一种，活性金属组分分别与磷和硫以金属磷化物和金属硫化物的形式负载于载体上，载体为改性的多孔载体。该制备方法，包括以下步骤：将含活性金属的盐、磷盐和络合剂溶于水中，配制成澄清的溶液，将配好的溶液加入到载体中，然后将浸渍完活性金属和磷的载体在80-150℃干燥10小时，制得催化剂前躯体；将催化剂前躯体进行预硫化处理，得到加氢处理催化剂。该催化剂具有高的碳硫键断裂的选择性和高的深度脱硫活性；该催化剂的制备方法工艺流程简单、易于工业化生产。
Description
技术领域
本发明涉及一种一种加氢脱硫催化剂的制备方法，特别适用于高芳烃催化汽油加氢处理，属于新材料、石油炼制和石油化工技术领域。
背景技术
建设资源节约型、环境友好型的炼油工业已成为我国国民经济和社会可持续发展亟待解决的重大关键问题之一。近期，为解决日益严重的全国城市空气污染问题，我国加快了油品质量升级的步伐，从2014年1月1日全面实行相当于欧IV标准的国IV清洁汽油标准(硫≤50mg/kg)，到2017年底全国达到国V标准要求(硫≤10mg/kg)。
我国汽油构成以FCC汽油组份为主，普遍占汽油池70％左右，重整汽油、烷基化和异构化油、MTBE等高辛烷值汽油组分比例低，因此汽油质量升级的关键在于FCC汽油的清洁化。目前，FCC汽油清洁化采用的主流技术路线是FCC汽油选择性加氢脱硫技术。代表性的技术为Axens公司的Prime-G+技术以及CDTECH公司的CD Hydro/CD HDS技术。其中，Prime-G+技术的脱硫选择性在世界处于前沿水平，其全球应用套数也最多(达200余套)。但是在加工高硫、劣质催化汽油原料时都存在不同程度的脱硫率不够高、选择性差、辛烷值损失大等问题。
CN102337153A公开了一种汽油馏分油的加氢处理方法，涉及到催化汽油原料的加氢处理方法，通过硫分离系统实现汽油中硫化物的富集，分离出高硫含量的高芳烃萃取油和高烯烃含量的萃余油，高含量的烯烃组分的萃余油进入芳构化装置，产生高辛烷值的芳烃；催化剂为临氢芳构化脱硫催化剂，高硫、高芳烃组分进入特定加氢脱硫装置进行加氢脱硫反应，实现硫化物的脱除。这部分组分硫含量在800-2000mg/kg之间，其中80％以上是较难脱除的噻吩类硫，芳烃含量在60-90％之间，属于高硫、高芳烃组分，对其加氢处理需要特定的较高脱硫活性的催化剂。
目前，工业上较常采用的是Co、Mo、Ni和W系列催化剂，催化科学工作者在不断尝试开发新的油品加氢精制催化材料，如过渡金属氮化物、碳化物、硼化物和磷化物等。1990s，Oyama等提出了金属磷化物新材料，并应用于加氢处理领域，发现金属磷化物新材料表现出比传统加氢催化剂更加优异的性能。随后，金属磷化物新材料被当成一种新型的加氢处理材料而广泛研究。
过渡金属磷化物的制备方法很多，这些方法包括：(1)高温和保护气氛下金属和红磷单质的直接化合；(2)金属卤化物与膦(Ca3P2、Na3P等)的固态置换反应；(3)金属卤化物与PH3的反应；(4)有机金属化合物的分解；(5)熔融盐的电解；(6)金属磷酸盐的还原等。这些方法有的需要高温，有的需要非常昂贵的原料，或者生产的副产物会造成磷化物污染或环境污染。
目前，过渡金属磷化物催化剂一般采用程序升温还原法制备，该方法需要在较高温度下进行，在高温还原过渡金属离子的过程中，容易导致过渡金属与载体生成惰性物种，降低金属利用率，使得负载型过渡金属磷化物催化剂加氢处理活性较低。
因此，急需为高硫、富芳烃汽油组分提供一种高脱硫活性、低成本的加氢精制催化剂，解决高硫、劣质汽油的加工难题，产品满足国V及更高标准要求，同时降低辛烷值损失，为企业降本增效提供技术支持。
发明内容
本发明的目的是提供一种加氢脱硫催化剂及其制备方法，该催化剂具有高的碳硫键断裂的选择性和高的深度脱硫活性；该催化剂的制备方法工艺流程简单、易于工业化生产。
为达到上述目的，本发明提供一种加氢脱硫催化剂，该催化剂包括活性组分和载体，所述活性组分包括磷、硫和活性金属组分，所述活性金属组分选自由Co、Mo、Ni和W所组成群组中的至少一种，所述活性金属组分分别与磷和硫以金属磷化物和金属硫化物的形式负载于所述载体上，所述载体为改性的多孔载体。
本发明所述的加氢脱硫催化剂，其中，以催化剂为100％计，所述金属磷化物最好占催化剂重量的1-15％，所述金属硫化物最好占催化剂重量的10-35％，所述载体最好占催化剂重量的50-75％。
本发明所述的加氢脱硫催化剂，其中，所述多孔载体优选为分子筛和/或氧化物。
本发明所述的加氢脱硫催化剂，其中，所述分子筛最好选自由ZSM-5、β分子筛、MCM-41和SBA-15所组成群组中的至少一种，所述氧化物优选为SiO2和/或Al2O3。
本发明还提供一种加氢脱硫催化剂的制备方法，包括以下步骤：
(a)将含活性金属的盐、磷盐和络合剂溶于水中，配制成澄清的溶液，将配好的溶液加入到载体中，然后将浸渍完活性金属和磷的载体在80-150℃干燥10小时，制得催化剂前躯体；
(b)将步骤(a)制得的催化剂前躯体进行预硫化处理，得到加氢处理催化剂。
本发明所述的加氢脱硫催化剂的制备方法，步骤(a)中，所述含活性金属的盐最好选自由钼酸铵、三氧化钼、磷钼酸铵、硝酸镍、硝酸钴、碱式碳酸镍和碱式碳酸钴所组成群组中的至少一种。
本发明所述的加氢脱硫催化剂的制备方法，步骤(a)中，所述磷源优选为含有Ni或Co的次亚磷酸盐、磷酸、次磷酸盐、磷酸氢二铵、二甲基亚磷酸或三苯基磷。
本发明所述的加氢脱硫催化剂的制备方法，步骤(b)中，所述预硫化条件优选为：硫化剂为含CS21.0-3.0wt％的直馏汽油，压力为1-2MPa，升温程序为以1-20℃/h的升温速率从室温升至160-230℃，并恒温4-8小时，然后以1-20℃/h的升温速率升至260-280℃，恒温4-8小时。
本发明制备的加氢脱硫催化剂用于油品深度加氢处理过程中，加氢处理反应在固定床反应器中进行，反应温度在200-280℃，反应压力1.0-2.5MPa。
本发明的有益效果为：
所述加氢脱硫催化剂中的金属磷化物和金属硫化物，不仅具有较高的碳硫键断裂的选择性和深度脱硫活性，而且具有很强的抗硫中毒性能，满足催化剂长周期稳定运行要求。该催化剂具有很好的催化加氢脱硫性能同时辛烷值损失较小。
所述加氢脱硫催化剂的制备方法具有制备流程简单、不需要高温、原料价格便宜、以易于成型的分子筛或氧化物为载体。
附图说明：
图1为实施例4制得的加氢脱硫催化剂的HRTEM透射电镜谱图(100nm)；
图2为实施例4制得的加氢脱硫催化剂的HRTEM透射电镜谱图(5nm)；
图3为实施例4制得的加氢脱硫催化剂的EDS能谱图。
具体实施方式
以下通过实施例进一步说明本发明，但本发明并不限于这些实施例。
实施例1
称取700g工业拟薄水铝石，在挤条机上挤成外接圆直径为1.8mm的三叶草型，在120℃下烘干，500℃焙烧4h，制得催化剂载体Z1。
以Z1为载体，称取7.4g硝酸镍、8.5磷钼酸铵、1.2g磷酸氢二铵配置成混合溶液，定容41ml，浸渍于50g载体Z1中6小时，120℃下烘干，然后，进行预硫化，预硫化条件：含CS22.5wt％的直馏汽油，压力：2.0MPa；升温程序：以10℃/h的升温速率从室温升至230℃，并恒温6小时，然后以10℃/h的升温速率升至260℃，恒温6小时；氢油比：200:1；空速：1.5h-1。制得加氢脱硫催化剂，记为C1。
实施例2
与实施例1的不同之处在于：预硫化条件的终点温度为280℃，制得加氢脱硫催化剂，记为C2。
实施例3
称取3.1g次亚磷酸镍、2.5g碱式碳酸镍、11.9g三氧化钼及1.5g工业磷酸溶解，最后定容41ml溶液，浸渍于50g载体Z1中6小时，120℃下烘干，然后，进行预硫化，预硫化条件：含CS22.5wt％的直馏汽油，压力：2.0MPa；升温程序：以10℃/h的升温速率从室温升至230℃，并恒温6小时，然后以10℃/h的升温速率升至260℃，恒温6小时；氢油比：200:1；空速：1.5h-1。制得加氢脱硫催化剂，记为C3。
实施例4
称取3.1g次亚磷酸镍、2.3g碱式碳酸镍、8.9g三氧化钼、2.8g钨酸铵及1.1g工业磷酸溶解，最后定容41ml溶液，浸渍于50g载体Z1中6小时，120℃下烘干，然后，进行预硫化，预硫化条件：含CS22.5wt％的直馏汽油，压力：2.0MPa；升温程序：以10℃/h的升温速率从室温升至230℃，并恒温6小时，然后以10℃/h的升温速率升至260℃，恒温6小时；氢油比：200:1；空速：1.5h-1。制得加氢脱硫催化剂，记为C4，该催化剂进行透射电镜扫描和能谱扫描，见附图1-3。
实施例5
称取3.0g次亚磷酸钴、2.1g碱式碳酸钴、11.9g三氧化钼及1.5g工业磷酸溶解，最后定容41ml溶液，浸渍于50g载体Z1中6小时，120℃下烘干，然后，进行预硫化，预硫化条件：含CS22.5wt％的直馏汽油，压力：2.0MPa；升温程序：以10℃/h的升温速率从室温升至230℃，并恒温6小时，然后以10℃/h的升温速率升至260℃，恒温6小时；氢油比：200:1；空速：1.5h-1。制得加氢脱硫催化剂，记为C5。
实施例6
载体制备按Al2O3比SiO2重量1：2投料，称取硝酸铝和硅溶胶(含SiO230％)，然后加稀氨水滴定，调节pH值7.0-8.0，老化90min，抽滤，将滤饼在120℃干燥8h后，在挤条机上挤条成型，再经500℃焙烧4h，制得SiO2-Al2O3复合载体Z2。
称取3.1g次亚磷酸镍、2.5g碱式碳酸镍、11.9g三氧化钼及1.5g工业磷酸溶解，最后定容39ml溶液，浸渍于50g载体Z2中6小时，120℃下烘干，然后，进行预硫化，预硫化条件：含CS22.5wt％的直馏汽油，压力：2.0MPa；升温程序：以10℃/h的升温速率从室温升至230℃，并恒温6小时，然后以10℃/h的升温速率升至260℃，恒温6小时；氢油比：200:1；空速：1.5h-1。制得加氢脱硫催化剂，记为C6。
实施例7
在MCM-41粉体中添加粘结剂，然后经混捏、挤条，在120℃下烘干6h，再经550℃焙烧4h，制得MCM-41载体Z3。
以Z3为载体，称取7.4g硝酸镍、8.5磷钼酸铵、1.2g磷酸氢二铵配置成混合溶液，定容45ml，浸渍于50g载体Z3中6小时，120℃下烘干，然后，进行硫化，硫化条件：含CS22.5wt％的直馏汽油，压力：2.0MPa；升温程序：以10℃/h的升温速率从室温升至230℃，并恒温6小时，然后以10℃/h的升温速率升至260℃，恒温6小时；氢油比：200:1；空速：1.5h-1。制得加氢脱硫催化剂，记为C7。
对比例1
专利200410050729.6公开的一种柴油馏分加氢处理方法中FDS-4催化剂，其中，Co和Mo占催化剂重量百分比24％。记为D1。
实施例8
采用高芳烃催化汽油为原料，原料性质见表1。
表1 催化剂活性评价原料油性质
对实施例1-7和对比例1中的催化剂进行相同条件的微反评价试验，采用高芳烃催化汽油为原料，运转稳定后取样分析产品硫、氮含量、研究法辛烷值，分析结果取平均值见表2。催化剂的装填和评价条件如下：
评价用装置是100ml固定床反应器，反应器中间段可以实现恒温控制，评价催化剂取长度在2-5mm之间，装填在反应器中间段利于反应温度的控制，上下段用φ2、φ3惰性瓷球装填。
评价条件：反应压力2.0MPa、反应温度230℃、原料体积空速1.5h-1、氢油比200：1。
表2 催化剂评价结果
由表2中数据可以说明，由本发明提供的催化剂具有较高的加氢脱硫性能，能够处理高硫、高芳烃催化汽油原料生产高标准车用汽油产品，是一种经济可行的汽油质量升级技术方案。
当然，本发明还可有其它多种实施例，在不背离本发明精神及其实质的情况下，熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形，但这些相应的改变和变形都应属于本发明的保护范围。
Claims (8)
1.一种加氢脱硫催化剂，该催化剂包括活性组分和载体，其特征在于，所述活性组分包括磷、硫和活性金属组分，所述活性金属组分选自由Co、Mo、Ni和W所组成群组中的至少一种，所述活性金属组分分别与磷和硫以金属磷化物和金属硫化物的形式负载于所述载体上，所述载体为改性的多孔载体。
2.根据权利要求1所述的加氢脱硫催化剂，其特征在于，以催化剂为100％计，所述金属磷化物占催化剂重量的1-15％，所述金属硫化物占催化剂重量的10-35％，所述载体占催化剂重量的50-75％。
3.根据权利要求1所述的加氢脱硫催化剂，其特征在于，所述多孔载体为分子筛和/或氧化物。
4.根据权利要求3所述的加氢脱硫催化剂，其特征在于，所述分子筛选自由ZSM-5、β分子筛、MCM-41和SBA-15所组成群组中的至少一种，所述氧化物为SiO2和/或Al2O3。
5.一种加氢脱硫催化剂的制备方法，其特征在于，包括以下步骤：
(a)将含活性金属的盐、磷盐和络合剂溶于水中，配制成澄清的溶液，将配好的溶液加入到载体中，然后将浸渍完活性金属和磷的载体在80-150℃干燥10小时，制得催化剂前躯体；
(b)将步骤(a)制得的催化剂前躯体进行预硫化处理，得到加氢处理催化剂。
6.根据权利要求5所述的加氢脱硫催化剂的制备方法，其特征在于，步骤(a)中，所述含活性金属的盐选自由钼酸铵、三氧化钼、磷钼酸铵、硝酸镍、硝酸钴、碱式碳酸镍和碱式碳酸钴所组成群组中的至少一种。
7.根据权利要求5所述的加氢脱硫催化剂的制备方法，其特征在于，步骤(a)中，所述磷源为含有Ni或Co的次亚磷酸盐、磷酸、次磷酸盐、磷酸氢二铵、二甲基亚磷酸或三苯基磷。
8.根据权利要求5所述的加氢脱硫催化剂的制备方法，其特征在于，步骤(b)中，所述预硫化条件为：硫化剂为含CS2 1.0-3.0wt％的直馏汽油，压力为1-2MPa，升温程序为以1-20℃/h的升温速率从室温升至160-230℃，并恒温4-8小时，然后以1-20℃/h的升温速率升至260-280℃，恒温4-8小时。
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| CN111215123A (zh) * | 2020-02-27 | 2020-06-02 | 青岛理工大学 | 可同时脱除垃圾气化中cos和h2s的催化剂及其制备方法 |
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