CN1134303C - 加氢处理催化剂的制备 - Google Patents
加氢处理催化剂的制备 Download PDFInfo
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- CN1134303C CN1134303C CNB008038228A CN00803822A CN1134303C CN 1134303 C CN1134303 C CN 1134303C CN B008038228 A CNB008038228 A CN B008038228A CN 00803822 A CN00803822 A CN 00803822A CN 1134303 C CN1134303 C CN 1134303C
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- 238000000034 method Methods 0.000 claims description 63
- 229910052751 metal Inorganic materials 0.000 claims description 49
- 239000002184 metal Substances 0.000 claims description 49
- 239000012018 catalyst precursor Substances 0.000 claims description 31
- 238000004073 vulcanization Methods 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 150000002739 metals Chemical class 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
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- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 238000005486 sulfidation Methods 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 claims 3
- 150000008040 ionic compounds Chemical class 0.000 claims 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 230000000694 effects Effects 0.000 description 22
- 239000005864 Sulphur Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 238000005987 sulfurization reaction Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000002243 precursor Substances 0.000 description 9
- -1 aromatic hydroxy compound Chemical class 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 8
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- 238000001354 calcination Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
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- 238000007796 conventional method Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
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- 238000005345 coagulation Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
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- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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- 238000010561 standard procedure Methods 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
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- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/74—Iron group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
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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
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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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- 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
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
提供一种制备催化剂的方法,其中用一个或多个步骤来降低浸渍载体的挥发物含量,其中在含硫化合物存在的情况下,进行至少一个挥发物含量降低的步骤。
Description
技术领域
本发明涉及烃进料的催化加氢处理。
背景技术
石油进料的特征在于相对高含量的杂质,所述杂质包括硫、氮、康拉逊残炭、芳烃化合物和诸如镍、钒和铁的金属。在催化加氢处理过程中,在高温和高压下、在氢存在的情况下,将非均相催化剂与进料接触,以降低进料中杂质的浓度。该加氢处理方法促进诸如加氢脱硫(HDS)、加氢脱氮(HDN)、脱康拉逊残炭、加氢脱金属(HDM)和芳烃饱和的反应,伴随生成低沸点的产品。当硫和氮组分转化成硫化氢和氨时,金属沉积到该催化剂上。其结果包括生产出诸如燃料的生态清洁烃类产品并保护其它下游精制催化剂免于失活。
在本技术领域从进料中脱除杂原子的方法,由于催化剂具有这种脱除杂质的功能,而是众所周知的。典型地,加氢处理催化剂含有负载于多孔难熔氧化物上的第VI族和/或第VIII族活性金属组分,所述氧化物诸如氧化铝、氧化铝-氧化硅、氧化硅、沸石、二氧化钛、氧化锆、氧化硼、氧化镁以及它们的结合。这种催化剂通常是通过将活性金属与载体结合而制备的。将所述含有金属组分的载体,典型地在约370℃-600℃的温度范围内干燥并焙烧,以除去任何溶剂并将金属转化成氧化物的形式。然后,通过与诸如硫化氢、有机硫化合物的含硫化合物或单质硫接触,以把金属氧化物转化成催化活性金属硫化物来典型地活化焙烧后的金属氧化物催化剂。
为了得到高质量的石油产品并改善炼油厂的经济状况,在精制催化剂技术领域中,一个重要并持续的目的是开发新的高性能加氢处理催化剂。人们已尝试着改变组成性能或制备加氢处理催化剂的方法来实现这些目的。
在本技术领域已知的是,不焙烧的催化剂通常提供活性组分更高的分散性,由此提高加氢处理活性。对不焙烧的催化剂来说必需的是,诸如第VI族和/或第VIII族金属化合物的活性组分,和诸如磷的助剂,在高温步骤中不转化成氧化物形式。也就是说,在没有化学分解的情况下维持活性组分直到硫化。例如,US5198100、US5336654和US5338717公开了一种通过用第VI族金属的盐和用第VIII族金属的杂多酸来浸渍难熔载体以制备加氢处理催化剂的方法。该催化剂不焙烧或不经受高温,由此使杂多酸在载体上维持原来的形式;但是,在使该催化剂硫化之前,需要在高度真空干燥步骤中除去催化剂中的全部水分。
通常,当不焙烧的催化剂的活性增加时,为生产给定的石油产品所需要的加氢处理条件就变得更缓和。为达到所需产品的技术规格,诸如硫、氮、康拉逊残炭、金属和芳烃的容许值,更缓和的条件要求更少的资本投资,并且由于结焦较少和其它因素而延长催化剂的寿命。
令人惊奇地发现,采用组合的挥发物含量降低-硫化步骤来制备不焙烧的催化剂,使待要制备的催化剂在低温下、用更少的步骤并且不用焙烧,就能生成具有极好的加氢处理活性和稳定性的催化剂。
本发明公开的内容
本发明的方法使人们在使用组合的挥发物含量降低-硫化步骤时,能制备一种催化剂。该方法包括:
提供多孔载体;
使所述载体与一种或多种催化活性金属结合,由此制成含有挥发性组分的催化剂前体;和
在一个或多个步骤中,降低催化剂前体的挥发物含量,其中,在至少一种含硫化合物存在的情况下,进行至少一个挥发物含量降低的步骤;
其中,在所述至少一个组合的挥发物含量降低-硫化步骤之前,催化剂前体没有达到焙烧温度。
还提供一种制备适于烃进料的加氢处理的催化剂的方法,所述方法包括:
将多孔载体与一种或多种选自周期表第VI族和第VIII族的催化活性金属结合,由此制成含有挥发性组分的催化剂前体;和
在一个或多个步骤中,降低催化剂前体的挥发物含量,其中,在至少一种含硫化合物存在的情况下,进行至少一个挥发物含量降低的步骤;
其中,在所述至少一个组合的挥发物含量降低-硫化步骤之前,催化剂前体没有达到焙烧温度。
另外,提供一种加氢处理烃进料的方法,所述方法包括:将所述进料在高温和高压下、在氢存在的情况下,与一个或多个催化剂床层接触;其中,至少一个催化剂床层含有通过下述方法制备的催化剂,该方法包括:将多孔载体与一种或多种选自周期表第VI族和第VIII族的催化活性金属结合,由此制成含有挥发性组分的催化剂前体,和在一个或多个步骤中,降低催化剂前体的挥发物含量,其中,在一种或多种含硫化合物存在的情况下,进行至少一个挥发物含量降低的步骤;并且其中,在所述至少一个组合的挥发物含量降低-硫化步骤之前,催化剂前体没有达到焙烧温度。
还提供一种通过下述方法制备的催化剂,该方法包括:将多孔载体与一种或多种催化活性金属结合,由此制成含有挥发性组分的催化剂前体;和在一个或多个步骤中,降低催化剂前体的挥发物含量,其中,在至少一种含硫化合物存在的情况下,进行至少一个挥发物含量降低的步骤;其中,在所述至少一个组合的挥发物含量降低-硫化步骤之前,所述催化剂前体没有达到焙烧温度。
附图的简要说明
图1表示根据本发明的方法制备的催化剂与根据常规方法制备的催化剂相比,达到88%的加氢脱硫活性时所需的加权平均床层温度(WABT)。
图2表示根据本发明的方法制备的催化剂与工业催化剂相比,达到88%的加氢脱硫活性时所需的WABT。
图3表示根据本发明的方法制备的催化剂与工业催化剂相比,脱除30%的氮所需的温度。
图4表示根据本发明的方法制备的催化剂与工业催化剂相比,脱除30%的碱性氮所需的温度。
本发明的详细说明
在硫化催化剂的常规制备中,将无机载体干燥、焙烧并与一种或多种催化活性金属结合,以制成催化剂前体。然后,将该前体非必需地老化,并通过干燥从前体的孔中除去水分。然后,将该催化剂前体在高温下以直接与热气接触的方式焙烧,以除去残留水分,并将金属前体转化成氧化物形式。在此所用的“焙烧温度”应表示在本技术领域中典型使用的400℃-600℃的焙烧温度。当完成焙烧时,将前体硫化以制成催化剂。
根据本发明的方法,通过将多孔载体与一种或多种催化活性金属结合,以制成含有挥发性组分的催化剂前体,从而制备催化剂。然后,在一个或多个步骤中降低催化剂前体的挥发物含量。挥发物含量降低,例如可通过在空气中及在低于焙烧温度的温度下处理前体,或仅通过在常温下脱水来进行。在一种或多种含硫化合物存在的情况下,进行至少一个挥发物含量降低的步骤,并且在这种组合的挥发物含量降低-硫化步骤之前,不允许催化剂前体达到焙烧温度。
可以在原位或器外进行组合的挥发物含量降低-硫化步骤。在完成挥发物含量降低和硫化之后,可在高温下进一步采用液相活化来使催化剂活化。例如,如果采用在器外预硫化,可将催化剂与更轻的进料接触,以生产担载于载体上的金属硫化物催化剂。可使用多种其它的硫化技术来生产硫化催化剂,并同时减少催化剂孔中的溶剂。不需要任何的焙烧催化剂或催化剂前体的常规高温。
在处理过程中,由于除去诸如溶剂和/或有机和无机配位体(与金属形成配位键的具有一对或多对电子的官能配位团)的挥发性化合物,催化剂经受重量损失。如这里所用的“挥发物含量”应表示按下述的将试样暴露于482℃空气中2小时来计算的重量损失:
这里所用的“催化剂前体”表示一种载体,该载体已经与一种或多种尚未活化的催化活性金属结合。
这里所用的“硫化”表示将催化剂前体与一种或多种含硫化合物接触。“硫化催化剂”是一种催化剂,其中至少部分活性金属组分转化成金属硫化物。
在本发明的方法中,不焙烧催化剂前体,也就是带有沉积的活性金属和非必需的助剂的载体。在一种或多种含硫化合物存在的情况下,进行至少一个挥发物含量降低的步骤。在使催化剂前体进行组合的挥发物含量降低-硫化步骤之前,催化剂前体的挥发物含量,典型地是不小于约0.5%,优选为2%-25%,更优选为3-10%,最优选为6-10%。当使用本发明的方法时,所需的或要进行的是不焙烧催化剂前体,并且实际上,对所看到的结果来说,使催化剂前体达到焙烧温度是有害的。可以在原位(在将要使用该催化剂的反应器中)或器外进行组合的挥发物含量降低-硫化步骤。与通过常规方法制备的催化剂相比,大大地改进了生成的催化剂的加氢处理性能,并且通过除去常规方法的高温焙烧步骤而使该方法简化。
将多孔载体典型地用于担载催化活性金属。对于加氢处理催化剂来说,载体典型地是氧化铝、氧化铝-氧化硅、氧化硅、二氧化钛、氧化锆、氧化硼、氧化镁、沸石和它们的结合。也可使用诸如活性碳和/或多孔石墨的多孔碳基材料。本发明中优选的载体是氧化铝基和氧化铝-氧化硅基载体。将典型地选自周期表第VI族和第VIII族的催化活性金属沉积到该载体上。该金属典型地是选自钼、钨、钴、镍和它们的混合物。可用诸如磷的助剂与催化活性金属结合。催化剂制备方法中的变化包括浸渍、共同研成糊状物、共沉淀。本发明中优选的方法是浸渍,最优选的方法是初期湿浸渍。水溶液是经常使用的;但是,还可将诸如脂肪族和芳香族的烃、醇、酮等的有机溶剂,用于将可溶性的活性组分和助剂沉积到载体上。水溶液的实例包括那些含有钼酸盐(诸如二钼酸盐和七钼酸盐)、磷钼酸盐和磷钨酸盐和硅酸盐、多氧代金属取代物(诸如杂多酸及其过渡金属络合物)、各种金属螯合物、胺络合物等的水溶液。水溶液的PH值典型地为1-12。用于浸渍的溶液的制备技术和方法在本技术领域是已知的。
本发明的催化剂前体,可具有某些在空气中包括常温在内的低于焙烧温度的温度下降低的挥发物含量,或可将它直接转移到硫化步骤。如果挥发物含量降低是在原位进行,那么降低部分挥发物的含量以除去物理吸附的溶剂(浸渍步骤中残留的)则有助于传送催化剂。
不依赖特殊的理论,人们可以认为,本发明的方法通过将催化金属与含硫化合物在低于焙烧温度的情况下直接相互作用,能控制催化剂孔中松散的金属氧化物相的形成,以使活性组分不发生热凝聚。在形成大量的松散金属氧化物之前,在将该前体硫化时,硫化合物代替溶剂并且硫与金属反应以制成高分散的金属硫化物。在本发明的方法中,将含有残留水分的催化剂前体,在使金属前体转化成催化活性金属硫化物并除去催化剂孔中的水分的温度下,置于含硫化合物中。
典型的原位硫化,既可使用在氢存在情况下的气态硫化氢,也可使用诸如包括烷基硫化物和多硫化物、硫醇、亚砜等的有机硫化合物的液相硫化剂。
在器外硫化中,将该催化剂典型地以“预硫化”的形式供给用户(精炼商),在这种形式中金属氧化物至少部分地转化成金属硫化物。工业的器外硫化方法包括,例如,在US5468372和US5688736中公开的ACTICAT法(CRI International Inc.)和SULFICAT法(Eurecat USInc.)。在本发明的实践中,优选器外硫化。
在本发明中,在将催化剂与硫化合物接触之前,通过不在高温下焙烧催化剂而对所述的已知的器外和原位方法作了改进。在一种或多种含硫化合物存在的情况下,进行至少一个挥发物含量降低的步骤。与通过分别干燥、焙烧和硫化步骤的常规方法制备的催化剂相比,不焙烧的催化剂显著地达到了更高的活性和稳定性。人们相信,在催化剂的制备中因为不发生热凝聚,所以活性组分更高的分散,由此达到了更高的加氢处理活性。
可以将通过本发明的方法制备的催化剂,用于从烃进料中脱除杂原子和其它杂质并伴有沸点降低的方法中。这种方法包括在高温高压下、有氢存在的情况下,采用一个或多个催化剂床层,使催化剂与进料接触。温度典型地是在约200℃-约470℃范围内,总压典型地是在约443kPa(50psig)-约24233kPa(3500psig)范围内,液时空速(LHSV)典型地在0.05-25h-1范围内。
实施例
催化剂活性测试
以体积为基准,使用滴流式微型反应器将下述实施例的催化剂的加氢处理活性进行对比。将相同的催化剂体积、基准密堆积密度,用于每套测试条件。在等温状态下运行该反应器。为确保合适的浸润和活塞流的特性,按催化剂与稀释剂的体积比为1∶1(测试条件1-3)或1∶2.5(测试条件4)的条件,将三叶形的挤出成型的催化剂片剂用180-250微米(80-60目)SiC来稀释,并将其按4等分装入反应器。
原位催化剂硫化
将含5%H2S的氢的气体混合物用于催化剂硫化。将硫化压力维持在约443kPa(50psig)(测试条件1-3)和1128kPa(150psig)(测试条件4)。在硫化过程中按如下方式升温:按1.5℃/min的速率从室温升到204℃,维持2小时;按2℃/min的速率加热到316℃,维持1小时;按3℃/min的速率加热到371℃,维持2小时;冷却到204℃并引入测试进料。
器外催化剂预硫化
使用ACTICAT法进行器外预硫化。以催化剂的金属含量计,将催化剂试样用化学计量的、以全部催化剂的量计超量1.0%重量的粉末状单质硫处理,随后将掺入硫的催化剂在液态烯烃存在的情况下加热。将预硫化催化剂前体采用标准液相活化来原位活化。
液相催化剂活化
将器外预硫化催化剂前体放入到滴流式微型反应器中,并用柴油进料来活化以将孔上的硫化合物转化成金属硫化物。在单位压力为900psig、氢流量为220ml/min、柴油进料LHSV为1.5h-1的条件下进行催化剂活化。使温度升高到135℃并维持1小时;按24℃/小时的速率升高到371℃并维持1小时;并且降温到204℃并维持2小时,随后引入测试进料。
测试条件1:
催化剂:100cc复合床层:
工业HDM催化剂-33.3%
实验催化剂-66.7%
压力:13201kPa(1900psig)
LHSV:0.33hr-1(整个系统)
WABT:385℃
气体速率:712.4m3H2/m3(4,000scf H2/bbl)
测试进料:直馏常压渣油:
硫 4.34%重量
氮 0.26%重量
镍 18.5ppm
钒 62.0ppm
碱性氮 667ppm
微碳残渣 11.4%重量
在15℃时的密度 0.97g/l测试条件2:
催化剂:50cc单床层
压力:6996kPa(1000psig)
LHSV:1.5hr-1
WABT:354℃
气体速率:356.2m3H2/m3(2,000scf H2/bbl)
测试进料:减压重瓦斯油
硫 1.07%重量
氮 0.29%重量
镍 0.8ppm
0.6ppm
碱性氮 930ppm
微碳残渣 0.3%重量
在15℃时的密度 0.92g/l测试条件3:
催化剂:25cc单床层
压力:14580kPa(2100psig)
LHSV:0.3hr-1
WABT:385℃
气体速率:356.2m3H2/m3(2,000scf H2/bbl)
测试进料:脱金属减压渣油
硫 2.15%重量
氮 0.39%重量
镍 19.0ppm
钒 33.0ppm
碱性氮 1354ppm
微碳残渣 12.0%重量
在15℃时的密度 0.98g/l测试条件4:
催化剂:20cc单床层
压力:11478kPa(1650psig)
LHSV:2.2hr-1
WABT:343℃和363℃
气体速率:623.35m3H2/m3(3,500scf H2/bbl)
测试进料:直馏柴油
硫 1.80%重量
氮 0.0448%重量
在15℃时的密度 0.86g/l实施例1
将氧化铝挤出物(1.2mm三叶形)在482℃下、在空气中干燥2小时。该挤出物具有下述物理性能:
密堆积密度 0.475g/cc
水孔体积 0.94cc/g
B.E.T表面积 296m2/g
通过在60℃下100g去离子水中溶解39.1g磷钼酸(75%,由ACROS获得)和9.72g NiCO3以制成浸渍溶液。在完全溶解之后,加入7.02g 85%的H3PO4。调整该溶液的体积到与载体的水孔体积相等的值。将200g载体用该溶液浸渍并老化2小时。负载的金属的量(干基)是8%重量的Mo、2%重量的Ni和1%重量的P。
为除去过量的水分,将催化剂前体在低于85℃下进行空气处理1小时,并将挥发物含量降低到6%,然后回收仍含有残留水分的前体。在与ACTICAT法中硫化的同时,将该前体进一步脱水。不采用焙烧步骤。将制成的催化剂记作催化剂A。
将催化剂A放到微型反应器中并用柴油进料活化,随后根据测试条件1进行测试。催化剂A的HDS活性,如达到88%的加氢脱硫活性所必需的加权平均床层温度(WABT),在图1中示出。
对比例2
将具有下述性能的氧化铝挤出物(1.2mm三叶形)用于制备催化剂B:
密堆积密度 0.484g/cc
水孔体积 0.95cc/g
B.E.T表面积 308m2/g
通过如实施例1中所述的载体的孔体积浸渍、随后在121℃下空气干燥4小时并在482℃的空气流中焙烧2小时来制备催化剂B。然后将该催化剂用如下所述的含5%H2S的氢混合物经常规方法原位硫化。在两个分开的步骤中将催化剂B焙烧并硫化。
将催化剂B在测试条件1下测试。催化剂B的HDS活性,如达到88%的加氢脱硫活性所必需的WABT,在图1中示出。
实施例3
将工业1.3三叶形挤出载体#1用于制备催化剂C。
通过将21.62g NiO、35.2g MoO3、9.05g 86.1%磷酸和去离子水一起搅拌而制备浸渍溶液。该混合物的体积大约是168ml。在搅拌的同时,将该混合物加热到99℃维持约3小时,直到浸渍溶液组分溶解。然后将该混合物冷却到室温。将溶液的体积调整到如实施例1中所述200g浸渍载体的孔体积。负载的金属含量是3.8%重量Ni、13.6%重量Mo和2.0%重量P(干基)。
将催化剂前体在99℃下、在空气中脱水4小时直到挥发物含量为6%。然后不采用任何焙烧步骤将该催化剂前体用ACTICAT法来进行处理。将制成的催化剂记作催化剂C。
对照通过采用独立的焙烧和预硫化步骤的标准ACTICAT法处理的工业催化剂(催化剂D),将催化剂C在测试条件1下测试。催化剂C和D的HDS活性,如达到88%的加氢脱硫活性所必需的WABT,在图2中示出。
实施例4
用于制备催化剂E和F的氧化铝挤出物(1.2mm三叶形)的性能如下:
密堆积密度 0.505g/cc
水孔体积 0.87cc/g
B.E.T表面积 277m2/g
通过将5.25g NiCO3和16.67g二钼酸铵(NH4)2Mo2O7(56.45%重量Mo)溶解于60ml 14.8%NH3的水溶液中,来制备浸渍溶液。将该溶液的体积调整到87cc,并将100g载体如实施例1中所述浸渍。负载的金属是2.3%重量Ni和8.0%重量Mo(干基)。将该催化剂前体整夜在空气中127℃下脱水以除去过量的水分和氨,然后冷却到室温并将其分成两等份。如实施例3所述,将第一份不经任何焙烧步骤用ACTICAT法直接预硫化,以除去残留水分并将硫负载到该催化剂上。将制成的催化剂记作催化剂E。将第二份在482℃下进行常规焙烧2小时,并用H2/H2S气体混合物进行原位硫化(催化剂F)。
对照催化剂F,用测试条件1来测试催化剂E。在400小时运转中,催化剂E比催化剂F的HDS相对体积活性(对两种催化剂来说,都是从二级反应速度常数推算出来)要高出25%。
实施例5
对照与催化剂C使用相同的载体的工业催化剂(催化剂G),用测试条件2来测试催化剂C。用H2/H2S气体混合物对(预焙烧)工业催化剂进行原位硫化。对比测试结果在图3和4中给出。
实施例6
对照工业参比催化剂(除了利用H2/H2S气体混合物在原位进行预焙烧催化剂的硫化之外,与催化剂D相同)测试催化剂C。将该工业催化剂称作催化剂H。
采用测试条件3对两种催化作用的HDS活性进行对比。在400小时运转中,催化剂C比催化剂H的HDS相对体积活性(对两种催化剂来说,都是从二级反应速度常数推算出来)要高出25%。
实施例7
将工业1.3三叶形挤出载体#2用于制备催化剂I。使用实施例6中所述的过程来制备浸渍溶液;但是金属含量(干基)如下所示:13.0%重量Mo、3.0%重量Ni、3.2%重量P。将催化剂前体在空气中99℃下脱水3小时,直到挥发物含量为8%。然后不用任何额外的干燥/焙烧步骤将该催化剂前体用ACTICAT法进行处理。
对照与催化剂I具有相同的载体和金属含量的工业催化剂(催化剂J),用测试条件4来测试催化剂I。使用H2/H2S气体混合物对(预焙烧)工业催化剂进行原位硫化。在343℃WABT下200小时的运转中,催化剂I比催化剂J的HDN相对体积活性(对两种催化剂来说,都是从一级反应速度常数推算出来)要高出20%,在363℃下300小时的运转中,催化剂I比催化剂J的HDN相对体积活性要高出40%。
对比例8
利用测试条件1,将通过采用独立的焙烧和预硫化步骤的标准ACTICAT法处理的工业催化剂(催化剂D)与相同类型的、用H2/H2S气体混合物原位硫化的工业催化剂(催化剂K)作比较。在试验运行(在1400小时运转中)过程中,催化剂D和催化剂K在HDS和HDN性能方面,从统计角度讲是难区分的,实验说明所看到的由本发明的方法的效果不是由于预硫化过程的不同。
如在实施例中所示的和在图1-4中所看到的,根据本发明的方法制备的催化剂(催化剂A、C、E和I)的HDS和HDN活性,明显地高于通过利用干燥、焙烧和硫化的独立步骤的标准方法制备的催化剂的HDS和HDN活性。因此,通过将干燥/硫化步骤组合起来并除去焙烧步骤,是能实现石油产品中显著低的硫和/或氮的含量的。在生产特殊产品时,较高活性的催化剂能在不太苛刻的条件下使工业装置开工。这也会增加催化剂的寿命并降低生产费用。
Claims (10)
1.一种制备催化剂的方法,所述方法包括:
提供多孔载体;
使所述载体与一种或多种催化活性金属结合,所述金属存在于溶于溶剂的化合物中,或存在于具有足够蒸汽压以便可通过化学汽相沉积而涂敷的化合物中,或存在于具有除金属以外的离子的化合物中,或存在于具有有机或无机配位体的化合物中,由此制成挥发物含量大于0.5%的催化剂前体;和
在一个或多个步骤中,降低催化剂前体的挥发物含量,其中,在至少一种含硫化合物存在的情况下,进行至少一个挥发物含量降低的步骤;
其中,在所述至少一个组合的挥发物含量降低-硫化步骤之前,所述催化剂前体没有达到焙烧温度。
2.一种权利要求1的方法,其中所述至少一个挥发物含量降低-硫化步骤是在器外或原位完成。
3.一种权利要求1的方法,其中所述一种或多种催化活性金属选自周期表第VI族和第VIII族的金属,并且所述催化剂为适于烃进料的加氢处理的加氢处理催化剂。
4.一种权利要求3的方法,其中所述一种或多种催化活性金属是选自钼、钨、钴、镍和氧化物、硫化物以及它们的混合物。
5.一种权利要求3的方法,其中所述多孔载体是选自氧化铝、氧化硅-氧化铝、氧化硅、二氧化钛、氧化硼、沸石、氧化锆、氧化镁和它们的结合。
6.一种用于被杂原子污染的烃进料的催化加氢处理的方法,所述方法包括:将所述进料在高温和高压下、在氢存在的情况下,与一个或多个催化剂床层接触;其中,至少一个催化剂床层含有通过下述方法制备的催化剂,该方法包括:将多孔载体与一种或多种选自周期表第VI族和第VIII族的催化活性金属结合,所述金属存在于溶于溶剂的化合物中,或存在于具有足够蒸汽压以便可通过化学汽相沉积而涂敷的化合物中,或存在于具有除金属以外的离子的化合物中,或存在于具有有机或无机配位体的化合物中,由此制成挥发物含量大于0.5%的催化剂前体,和在一个或多个步骤中,降低催化剂前体的挥发物含量,其中,在一种或多种含硫化合物存在的情况下,进行至少一个挥发物含量降低的步骤;并且其中,在所述至少一个组合的挥发物含量降低-硫化步骤之前,所述催化剂前体没有达到焙烧温度。
7.一种权利要求6的方法,其中,在液相硫化过程中,进行至少一个挥发物含量降低的步骤。
8.一种可从下述方法得到的催化剂,该方法包括:将多孔载体与一种或多种催化活性金属结合,所述金属存在于溶于溶剂的化合物中,或存在于具有足够蒸汽压以便可通过化学汽相沉积而涂敷的化合物中,或存在于具有除金属以外的离子的化合物中,或存在于具有有机或无机配位体的化合物中,由此制成挥发物含量大于0.5%的催化剂前体;和在一个或多个步骤中,降低催化剂前体的挥发物含量,其中,在至少一种含硫化合物存在的情况下,进行至少一个挥发物含量降低的步骤;其中,在所述至少一个组合的挥发物含量降低-硫化步骤之前,所述催化剂前体没有达到焙烧温度。
9.一种权利要求8的催化剂,其中该催化剂是适于烃进料的加氢处理的加氢处理催化剂,并且其中所述一种或多种催化活性金属选自周期表第VI族和第VIII族。
10.一种权利要求9的催化剂,其中所述一种或多种催化活性金属是选自钼、钨、钴、镍和氧化物、硫化物以及它们的混合物,并且其中所述多孔载体是选自氧化铝、氧化硅-氧化铝、氧化硅、二氧化钛、氧化硼、沸石、氧化锆、氧化镁和它们的结合。
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-
1999
- 1999-02-15 US US09/250,208 patent/US6218333B1/en not_active Expired - Lifetime
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2000
- 2000-02-08 CN CNB008038228A patent/CN1134303C/zh not_active Expired - Lifetime
- 2000-02-08 BR BR0008224-4A patent/BR0008224A/pt not_active Application Discontinuation
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- 2000-02-08 AU AU35925/00A patent/AU754251B2/en not_active Ceased
- 2000-02-08 JP JP2000598267A patent/JP5264029B2/ja not_active Expired - Fee Related
- 2000-02-08 WO PCT/US2000/003219 patent/WO2000047321A1/en active IP Right Grant
- 2000-02-08 CA CA002362466A patent/CA2362466C/en not_active Expired - Lifetime
- 2000-02-08 ID IDW00200101759A patent/ID30051A/id unknown
- 2000-02-08 RU RU2001125423/04A patent/RU2244592C2/ru active
- 2000-02-08 DK DK00914550T patent/DK1154855T3/da active
- 2000-02-08 KR KR1020017009968A patent/KR100621251B1/ko not_active IP Right Cessation
- 2000-02-08 DE DE60012887T patent/DE60012887T2/de not_active Expired - Fee Related
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DE60012887D1 (de) | 2004-09-16 |
AU754251B2 (en) | 2002-11-07 |
ATE273072T1 (de) | 2004-08-15 |
US6218333B1 (en) | 2001-04-17 |
RU2244592C2 (ru) | 2005-01-20 |
KR20010101813A (ko) | 2001-11-14 |
EP1154855A1 (en) | 2001-11-21 |
US6290841B1 (en) | 2001-09-18 |
DE60012887T2 (de) | 2005-08-25 |
JP5264029B2 (ja) | 2013-08-14 |
WO2000047321A1 (en) | 2000-08-17 |
BR0008224A (pt) | 2001-10-30 |
DK1154855T3 (da) | 2004-12-13 |
ID30051A (id) | 2001-11-01 |
KR100621251B1 (ko) | 2006-09-13 |
AU3592500A (en) | 2000-08-29 |
EP1154855B1 (en) | 2004-08-11 |
CN1339986A (zh) | 2002-03-13 |
CA2362466C (en) | 2007-10-30 |
JP2002536166A (ja) | 2002-10-29 |
ZA200106590B (en) | 2002-08-12 |
CA2362466A1 (en) | 2000-08-17 |
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