CN1096291C - 高活性催化剂 - Google Patents
高活性催化剂 Download PDFInfo
- Publication number
- CN1096291C CN1096291C CN95192995A CN95192995A CN1096291C CN 1096291 C CN1096291 C CN 1096291C CN 95192995 A CN95192995 A CN 95192995A CN 95192995 A CN95192995 A CN 95192995A CN 1096291 C CN1096291 C CN 1096291C
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- China
- Prior art keywords
- catalyst
- weight
- carbon monoxide
- olefin polymeric
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 121
- 230000000694 effects Effects 0.000 title claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000000034 method Methods 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- 230000003197 catalytic effect Effects 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000007598 dipping method Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 9
- 239000000428 dust Substances 0.000 claims description 8
- 229910000510 noble metal Inorganic materials 0.000 claims description 8
- 238000006424 Flood reaction Methods 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 150000001721 carbon Chemical class 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 230000002902 bimodal effect Effects 0.000 claims description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 5
- 239000003426 co-catalyst Substances 0.000 claims description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052753 mercury Inorganic materials 0.000 claims description 5
- 238000003795 desorption Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 10
- 229910052750 molybdenum Inorganic materials 0.000 claims 10
- 239000011733 molybdenum Substances 0.000 claims 10
- 229910017052 cobalt Inorganic materials 0.000 claims 6
- 239000010941 cobalt Substances 0.000 claims 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 6
- 229910052759 nickel Inorganic materials 0.000 claims 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 2
- 238000001833 catalytic reforming Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 239000010937 tungsten Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 47
- 230000032683 aging Effects 0.000 description 29
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 25
- 229960001484 edetic acid Drugs 0.000 description 24
- 239000002738 chelating agent Substances 0.000 description 19
- 238000001035 drying Methods 0.000 description 19
- 239000000463 material Substances 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 12
- 238000001354 calcination Methods 0.000 description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 10
- 229920006395 saturated elastomer Polymers 0.000 description 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical class O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000004517 catalytic hydrocracking Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 235000015165 citric acid Nutrition 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004643 material aging Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229960001124 trientine Drugs 0.000 description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Substances OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229960005137 succinic acid Drugs 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ZBRIYBRFOLLBPI-UHFFFAOYSA-N acetic acid;n-(2-aminoethyl)hydroxylamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNO ZBRIYBRFOLLBPI-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J23/881—Molybdenum and iron
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- 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
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- 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
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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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- 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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- 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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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
- B01J38/66—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts using ammonia or derivatives 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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming 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
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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Abstract
本发明提供了基于含有γ氧化铝的用一种或多种具有催化活性的金属浸渍过的基材的高活性催化剂,该催化剂在表面还部分含有高至25埃的微晶尺寸的氧化铝的超微晶相。本发明还提供了该高活性的催化剂的制备方法及其应用。
Description
发明的领域
本发明总的来说涉及基于含有γ氧化铝的用一种或多种具有催化活性的金属浸渍过的基材的高活性催化剂,其制备方法及其应用。更具体地说,本发明涉及提高该催化剂的活性的方法,用该方法制备的提高了活性的催化剂,以及各种特定的催化剂及其应用。
有关的现有技术
有关颗粒状的含有多孔γ氧化铝的载体,用各种具有催化活性的金属、金属化合物和/或助催化剂浸渍该载体,以及该浸渍的载体作为催化剂的各种应用发明的现有技术得到广泛而深入的研究。与该领域有关的文献可以列举下列美国专利,所有这些文献均引入作为参考:2935463,3032514,3124418,3152865,3232887,3287280,3297588,3493493,3749664,3778365,3897365,3909453,3983197,4090874,4090982,4154812,4179408,4255282,4328130,4357263,4402865,4444905,4447556,4460707,4530911,4588706,4591429,4595672,4652545,4673664,4677085,4732886,4797196,4861746,5002919,5186818,5232888,5246569和5248412。
虽然现有技术中对这些催化剂进行了不断的改进以提高其催化活性,而且虽然在某些情况下实际上已经达到了理想的高活性,但是在工业上仍然需要具有更高活性的催化剂,本发明提供了这样的催化剂。
作为这一需要的实例有需要具有更高活性的第一步氢化裂解催化剂。在典型的氢化裂解过程中,在通常为经贵金属浸渍的硅铝/沸石的氢化裂解催化剂的存在下,分子量较高的烃类转化成分子量较低的部分。现有的氢化裂解催化剂具有非常高的活性,并能裂解大量的物料。然而,该催化剂对于污染物(如硫、金属和氮化合物)是高度敏感的,因此必须在裂解之前从烃气流中将其除去。这在第一步氢化裂解过程(例如加氢脱氮、加氢脱硫和加氢脱金属)中完成。在这些过程中所用的加氢处理催化剂一般为经第VIB族和第VIII族金属组合浸渍过的氧化铝基材。然而现有的加氢处理催化剂不具有足够的活性以处理与用氢化裂解催化剂能处理的相同的大量物料。这样,第一步氢化裂解成了整个氢化裂解过程的瓶颈,必须在例如氢化处理装置相对于氢化裂解装置的尺寸上进行补偿。
发明综述
本发明的一个方面是提供一种高活性催化剂组合物,它包括表面积至少为每克100平方米(经氮吸附测定)及孔体积至少为每克0.25立方厘米(经汞孔度计测定)的含有γ氧化铝的颗粒状多孔载体,该催化剂组合物经一种或多种具有催化活性的金属浸渍,因此该催化剂在表面还部分含有高至25埃的微晶尺寸的氧化铝的超微晶相。
另一方面,本发明提供了一种高活性催化剂,它包括表面积至少为每克100平方米(经氮吸附测定)及孔体积至少为每克0.25立方厘米(经汞孔度计测定)的含有γ氧化铝的颗粒状多孔载体,该催化剂组合物经一种或多种具有催化活性的金属浸渍,在第一步氢化裂解过程中,经Carruthers和DiCamillo的文章“Pilot PlantTesting of Hydrotreating Catalysts”Applied Catalysts,43(1988)253-276中所述的程序,使用市售的Unocal Corporation,Brea,CA的商标为HC-H(1994年5月)的催化剂作为标准进行测定,该催化剂的相对体积活性(RVA)至少为115,较好至少为120,特别好至少为125。
除了上述催化剂,本发明还提供了一种用于提高催化剂组合物活性的方法,所述催化剂包括表面积至少为每克100平方米(经氮吸附测定)及孔体积至少为每克0.25立方厘米(经汞孔度计测定)的含有γ氧化铝和非晶形氧化铝的颗粒状多孔载体,该催化剂组合物经一种或多种具有催化活性的金属浸渍,其步骤为:
(1)将该催化剂组合物在载体液体中与螯合剂接触使其湿润;
(2)在湿润的同时使该湿润的基材老化;
(3)在一定的温度等条件下使该老化的基材干燥,以基本上挥发载体液体;以及
(4)煅烧该干燥的基材。
该方法能容易地应用于现有的包括含有γ氧化铝和非晶形氧化铝的颗粒状多孔载体的催化剂,或者可用在催化剂制备方法中在用一种或多种具有催化活性的金属和/或其化合物浸渍含有γ氧化铝和非晶形氧化铝的载体之前、同时和/或之后。另外,该方法可用以提高废催化剂再生时的活性,该废催化剂包括含有γ氧化铝和非晶形氧化铝的颗粒状多孔载体,其中将该废催化剂如上述步骤(1)中所述湿润,然后从中去除碳质沉积物,接着进行步骤(2)、(3)和(4)。
通过按上述次序进行这些步骤,可以相信(不期望受任何具体理论的约束)至少在非晶形γ氧化铝、螯合剂和催化活性组分之间发生相互作用,结果出现在高至25埃(较好为8埃至25埃)的表面具有微晶尺寸的氧化铝的超微晶相,与在大于30埃(通常为30埃至70埃)的催化剂表面具有微晶尺寸的γ氧化铝结合。催化剂表面的微晶尺寸可以通过包括透射电子显微镜等众所周知的技术进行测定。
出现超微晶相的同时,该催化剂的表面积也得到增加。另外,在较佳的实例中,使用解吸等温线经氮气孔度计测定,在孔径为40埃或更小的(更好为20埃至40埃)第一区域以及在孔径为50埃或更大的(更好为50埃至150埃)第二区域具有孔隙度峰的至少产生了双峰中孔结构(bimodal mesoporestructure)。
在前面引入的参考文献中对于得到的高活性催化剂在众多领域中的应用已有详细叙述。特别好的应用是在加氢脱氮、加氢脱硫和加氢脱金属中作为第一步氢化裂解催化剂。
本领域的一般技术人员在阅读了下面的详细说明之后,对于本发明的上述的和其它的特征和优点将更容易理解。
较佳实例的详细说明基材
如上所述,适用于制备本发明的催化剂的基材是颗粒状多孔基材,包括至少部分为γ氧化铝和非晶形的氧化铝,较好为至少5%(重量)为非晶形氧化铝,基于基材的重量。作为特定的实例可以提到基本上均为氧化铝的基材,以及复合物基材,其中氧化铝至少部分用作其它基材(如硅铝和沸石)的载体。这些基材及其制备方法,对于本领域的一般技术人员一般是众所周知的,正如前面引入的许多参考文献所举的实例及其所附的有关进一步详情的参考文献所述。具有催化活性的金属
本发明可用于经一种或多种各类具有催化活性的金属浸渍的催化剂,这一点如引入的众多参考文献所例示的,对于本领域的一般技术人员是众所周知的。本发明中,“具有催化活性的金属”包括金属本身以及金属化合物。除了具有催化活性的金属,该催化剂也可用一种或多种已知的助催化剂(如磷、锡、硅和钛(包括其化合物))浸渍。
一般来说,具有催化活性的金属为选自第VIB族金属、第VIII族金属及其组合的过渡金属。当然,可以根据催化剂所需的最终用途具体选择金属、助催化剂和填充剂,本领域的一般技术人员可以根据最终用途容易地对这些变化进行调节。作为其具体实例可以列举如下(%(重量)是基于催化剂的总量):加氢处理操作
加氢脱氮 Ni和/或Co,较好为Ni,其量为高至7%(重量),
以NiO和/或CoO计
Mo和/或W,较好为Mo,其量为高至35%(重量),
以MoO3和/或WO3计
任选的P,较好为P的量为高至10%(重量),
以P2O5计
加氢脱硫 Ni和/或Co,较好为Co,其量为高至9%(重量),
以NiO和/或CoO计
Mo和/或W,较好为Mo,其量为高至35%(重量),
以MoO3和/或WO3计
任选的P,较好为P的量为高至10%(重量),
以P2O5计
加氢脱金属 任选的Ni和/或Co,较好为包括Ni和/或Co,其量为高
5%(重量),以NiO和/或CoO计
Mo和/或W,较好为Mo,其量为高至20%(重量),
以MoO3和/或WO3计
任选的P,较好为P的量为高至10%(重量),
以P2O5计
加氢转化 Ni和/或Co,较好为Ni,其量为高至5%(重量),
以NiO和/或CoO计
Mo和/或W,较好为Mo,其量为高至20%(重量),
以MoO3和/或WO3计
任选的P,较好为P的量为高至6%(重量),
以P2O5计
氢化裂解 Ni和/或Co,较好为Ni,其量为高至5%(重量),
以NiO和/或CoO计
Mo和/或W,较好为Mo,其量为高至20%(重量),
以MoO3和/或WO3计
任选的P,较好为P的量为高至10%(重量),以
P2O5计
加氢/脱氢 一种贵金属,较好为Pt或Pt与Rh结合,其量为2%
(重量),以元素计
重整 一种贵金属,较好为Pt或Pt与另一种贵金属
(如和Re和/或Ir结合,和/或Sn结合,其量为2%(重量),
以元素计非加氢处理操作
异构化 一种贵金属,较好为Pt或Pt与另一种贵金属结合,
其量为2%(重量),以元素计
Klaus法 Ni和/或Co,较好为Ni,其量为高至5%(重量),
以NiO和/或CoO计
Mo和/或W,较好为Mo,其量为高至20%(重量),
以MoO3和/或WO3计
任选的P,较好为P的量为高至6%(重量),以
P2O5计
这些催化剂是用适宜的组分浸渍基材,然后根据最终用途进行各种干燥、形成硫化物和/或煅烧步骤而制备的。这些催化剂的制备,对于本领域的一般技术人员一般是众所周知的,正如前面引入的许多参考文献所例示的及其所附的进一步的详细说明或在该领域已有的众多其它的参考文献之所述。发明方法
如上所述,根据本发明通过下列步骤,提高了浸渍包括γ氧化铝和非晶形氧化铝的载体的具有催化活性的金属的活性:
(1)将该催化剂组合物在载体液中与螯合剂接触使其湿润;
(2)在湿润的同时使该湿润的基材老化;
(3)在一定的温度等条件下使该老化的基材干燥,以基本上挥发载体液;以及
(4)煅烧该干燥的基材。
适用于本发明的螯合剂包括那些已知与过渡金属和铝形成更稳定的复合物,因而具有高的稳定常数。本发明中特别优选的是乙二胺四乙酸(EDTA)及其衍生物,包括如N-羟基乙二胺四乙酸和乙二胺四乙酸二铵。也可使用三(2-氨基乙基)胺和三亚乙基四胺。其它可供选择的有二亚乙基三胺五乙酸、环己二胺四乙酸、乙二醇二(β-氨基乙醚)-N,N’-四乙酸、四亚乙基五胺等等。本领域的一般技术人员通过按本发明处理催化剂样品,可以容易地确定其它螯合剂的适用性,随后借助于透射电子显微镜确定是否形成具有适宜的微晶尺寸的超微晶相氧化铝结构。
对于欲达到一定的效果所需使用螯合剂的量没有规定,但该量对效果的程度有一定的影响。螯合剂用量的变化范围取决于多种因素,例如在载体液中的溶解度,催化剂载体和已浸渍的金属或欲浸渍的金属的种类。一般来说,催化剂组合物应用含有螯合剂的载体液湿润,螯合剂的含量为每克催化剂组合物0.01-1.0克螯合剂。
催化剂组合物可以用常规方法湿润,例如浸渍或喷雾。为了确保该螯合剂充分渗透,浸渍之后最好有一浸透过程。优选的载体液为水/氨溶液。
在基材老化期间,老化时间是温度的函数。在室温下,湿润的基材较好为至少老化10天,更好为至少老化14天。随着温度升高,所需老化的时间减少。在60℃,湿润的基材较好为至少老化1天,更好为至少老化3天。通过将湿润的样品在微波炉中加热,老化可以进一步加速至只需1小时。较好的是老化在20℃至90℃的温度范围内完成。
随后,使该老化的催化剂干燥以基本上去除载体液。较好的是干燥过程在100℃至250℃快速升温下进行。优选使用强制空气加热器以使干燥加速至少于1小时的理想时间。
然后在本领域的一般技术人员已知的条件下煅烧该干燥的催化剂。然而,较好的是分两个阶段进行煅烧:较低温度的第一阶段,在此阶段的温度能使任何残余的螯合剂分离或分解,但不会使该螯合剂燃烧形成碳质沉积物。该第一阶段的温度根据具体的螯合剂而变化,但一般250℃至350℃的温度是足够的。将残余的螯合剂基本去除之后,可以在通常所用的较高温度条件下煅烧该催化剂。
如上所述,本发明的方法不仅能应用于预成型的催化剂,而且也同样能应用于再生的催化剂。具体地,通过已知的程序从废催化剂中去除碳质物质之后,用与上述相同的步骤(1)至(4)处理这些催化剂。
在制备新的催化剂时,也可采用该程序。具体的说,可在载体用适宜的具有催化活性的金属浸渍之前、同时和/或之后将基材用螯合剂/载体液湿润,然后进行上述步骤(2)至(4)。重要的仅仅是确保老化步骤与浸渍过的载体在仍被用于螯合剂和/或浸渍金属的载体液所湿润的同时进行。
如上所述的本发明将通过下面具体的实施例作进一步的解释,这些实施例只是用于说明,而不是对本发明的限制。
这些实施例中的缩写具有下列含义:
EDTA 乙二胺四乙酸
MEA 单乙醇胺
SA(N2) 由氮吸附测得的表面积
SA/gAl2O3 每克氧化铝的表面积
RVA 在第一步氢化裂解测试中,经Carruthers和
DiCamillo的文章“Pilot Plant Testing of Hydrotreating
Catalysts”Applied Catalysts,43(1988)253-276中所述
的程序测得的相对体积活性。该相对体积活性是使用
市售的Unocal Corporation,Brea,CA的商标为HC-H
(1994年5月)的催化剂作为标准测定的。
RWA 相对重量活性,根据上述文章中的方法进行测定。
实施例1
将266克Criterion Catalyst Company(Houston,TX)有售的由含有某些非晶形氧化铝水合物的氧化铝粉末制备的孔体积为0.62cc/g(经汞孔度计测定)且孔径峰在78埃处(使用解吸等温线经氮气孔度计测定)的氧化铝催化剂载体置于一不锈钢篮中在1800ml水溶液浸渍液中浸渍。该浸渍溶液记作‘A’,是通过将900克三氧化钼和221克氧化镍溶解在稀磷酸(在1509g去离子水中的263克85%溶液)中而制备的。向该溶液中加入226克固体EDTA。然后将该溶液在氧化铝载体上循环一小时。然后将湿的浸渍过的载体从篮中取出并离心。
将该湿润的载体分成四份并使其在密封的容器中室温下分别老化2小时、3天、14天和22天。然后用标准干燥程序(250°F(121℃)1小时)或以高速空气流的快速干燥程序(300°F(149℃)20分钟)使其干燥。然后将各样品转移至隔焰炉中并在850°F(454℃)煅烧1小时。得到的催化剂在下面表1中分别记作E1、E2、E3、E4和E5。
用与上述基本相同的方法,只是加入94.3克MEA替代EDTA以制备第二系列催化剂。将湿的浸渍过的载体分成两份,并在室温下分别老化2小时和15天。用快速干燥程序使催化剂干燥,并用如上所述的方法进行煅烧。得到的催化剂在下面表1中分别记作M1和M2。
用与上述基本相同的方法,只是加入183克琥珀酸替代EDTA以制备第三系列催化剂。将湿的浸渍过的载体分成两份,并在室温下分别老化2小时和18天。用快速干燥程序使催化剂干燥,并用如上所述的方法进行煅烧。得到的催化剂在下面表1中分别记作S1和S2。
用与上述基本相同的方法,只是加入216克柠檬酸替代EDTA以制备第四系列催化剂。将湿的浸渍过的载体分成三份,并在室温下分别老化2小时、2天和9天。用快速干燥程序使催化剂干燥,并用如上所述的方法进行煅烧。得到的催化剂在下面表1中分别记作C1、C2和C3。
最后,用与上述基本相同的方法,只是不加入EDTA,以制备对照系列催化剂。将湿的浸渍过的载体分成两份,并在室温下分别老化2小时和12天。用快速干燥程序使催化剂干燥,并用如上所述的方法进行煅烧。得到的催化剂在下面表1中分别记作A1和A2。
虽然老化10天以上的各样品经测定其表面积都有一定程度的增加,但只有加有螯合剂EDTA时,才使催化活性有明显的提高(实施例E4和E5)。同样,与该催化剂活性结果相平行,分析电子显微镜检查法(AEM)显示出经EDTA处理和老化后的样品存在“超微晶相”氧化铝的明显的证据,而用其它试剂处理的其它氧化铝样品以及未处理的氧化铝样品A1和A2均不存在这一现象。
表1
实施例2
样品ID | 试剂 | 老化时间 | 干燥方法 | SA(N2),m2/g | RVA-TN,% |
E1 | EDTA | 2小时 | 快干燥 | 163 | 94 |
E2 | EDTA | 3天 | 快干燥 | 198 | 87 |
E3 | EDTA | 14天 | 慢干燥 | 192 | 107 |
E4 | EDTA | 14天 | 快干燥 | 195 | 120 |
E5 | EDTA | 22天 | 快干燥 | 203 | 125 |
M1 | MEA | 2小时 | 快干燥 | 179 | 100 |
M2 | MEA | 15天 | 快干燥 | 187 | 109 |
S1 | 琥珀酸 | 2小时 | 快干燥 | 180 | 103 |
S2 | 琥珀酸 | 18天 | 快干燥 | 201 | 110 |
C1 | 柠檬酸 | 2小时 | 快干燥 | 181 | 92 |
C2 | 柠檬酸 | 2天 | 快干燥 | 186 | 110 |
C3 | 柠檬酸 | 9天 | 快干燥 | 206 | 100 |
A1 | 无 | 2小时 | 快干燥 | 160 | 98 |
A2 | 无 | 12天 | 快干燥 | 170 | 101 |
按照与实施例1基本相同的方法,用1300ml‘A’溶液处理实施例1中所述的188克氧化铝载体,只是用100克固体EDTA-二铵替代EDTA。
将该湿的浸渍过的载体分成二份,一份在室温(68°F,20℃)下老化2小时,而另一份置于密封容器中并在140°F(60℃)老化17小时。将两份样品在800°F(427℃)下煅烧之前在450°F(232℃)干燥20分钟。得到的催化剂在下面表2中分别记作DE1和DE2。
在140°F(60℃)老化17小时后并快速干燥的样品显示出与上面实施例1中使用EDTA酸时得到的同样高的催化活性。
表2
实施例3
样品ID | 老化时间小时 | 老化温度°F(℃) | SA(N2)m2/g | SA/gAl2O3m2/g | RVA-TN% |
DE1 | 2 | 68(20) | 164 | 253 | 100 |
DE2 | 17 | 140(60) | 170 | 262 | 120 |
用‘B’溶液使具有孔结构的载体饱和,从而浸渍100克实施例1中所述的氧化铝载体,其中的‘B’溶液是将46.7克含有36.8%(重量)三氧化钼、6.5%(重量)氧化镍和10.0%(重量)五氧化二磷的‘C’溶液加入至30克44.7%(重量)EDTA二铵溶液和23ml浓(29%(重量))氨中而制备的。然后将该物质老化2小时并分两步干燥,首先在250°F(121℃)干燥2小时,然后在500°F(260℃)再干燥2小时。
然后用‘D’溶液对该干燥的催化剂进行第二次孔饱和,‘D’溶液含有46.7克用23ml水稀释的‘C’溶液。然后将该湿的浸渍过的载体在密封的容器中于158°F(70℃)烘箱中老化18小时。用与上述相同的方法将该催化剂快速干燥并煅烧。在表3中该催化剂记作‘F1’。
表3
实施例4
样品 | NiO | MoO3 | P2O5 | SA(N2) | SA/gAl2O3 | RVA-TN |
ID | wt% | wt% | wt% | m2/g | m2/g | % |
F1 | 3.86 | 24.2 | 5.75 | 200 | 303 | 121 |
将750克Criterion Catalyst Company(Houston,TX)有售的由含有某些非晶形氧化铝水合物的氧化铝粉末制备的孔体积为0.78cc/g且孔径峰在82埃处的氧化铝催化剂载体置于一不锈钢篮中在5300ml溶液‘E’中浸渍。溶液‘E’含有32%(重量)三氧化钼、7.2%(重量)氧化镍和10.7%(重量)磷酸。然后将该溶液在氧化铝载体上循环一小时,然后将湿润的载体从篮中取出并离心。
将该湿润的载体在室温下老化2小时,然后在烘箱中250°F(121℃)干燥并在800°F(427℃)煅烧1小时。
然后,使用八种不同的螯合剂水溶液对七份100克制成的催化剂样品进行孔体积饱和:
(1)7.6g乙二胺-N,N-二乙酸在47ml溶液中
(2)8.25g次氮基三乙酸在37ml溶液中
(3)12.7g三-(2-氨基乙基)胺在37ml溶液中
(4)8.0g乙二胺在38ml溶液中
(5)8.0g乙二醇在37ml溶液中
(6)11.5g三亚乙基四胺在37ml溶液中
(7)31.5g44.7%(重量)乙二胺四乙酸二铵溶液在40ml溶液中
然后各样品在密封的容器中于167°F(75℃)老化3天,使其冷却,然后在450°F(232℃)快速干燥20分钟,随后在850°F(454℃)煅烧。然后分析各催化剂,并在去除氮的第一阶段氢化裂解催化剂测定中测定活性(表4)。
表4
实施例5
S.A(N2)m2/g | SA/gAl2O3m2/g | RVA% | |
(1)乙二胺-N,N-二乙酸 | 143 | 242 | 108 |
(2)次氮基三乙酸 | 173 | 293 | 102 |
(3)三(2-氨基乙基)胺 | 166 | 281 | 133 |
(4)乙二胺 | 167 | 283 | 106 |
(5)乙二醇 | 137 | 232 | 106 |
(6)三亚乙基四胺 | 160 | 271 | 126 |
(7)EDTA二铵 | 205 | 347 | 137 |
(8)无螯合剂 | 132 | 224 | 101 |
将150克Criterion Catalyst Company(Houston,TX)有售的由含有某些非晶形氧化铝水合物的氧化铝粉末制备的孔体积为0.71cc/g且孔径峰在78埃处的氧化铝催化剂载体用溶液‘F’进行孔饱和,溶液‘F’为每1升水溶液含有240克EDTA-二铵。然后第二份150克载体样品用溶液‘F’和水的混合物(溶液‘F’∶水为66∶33)进行孔饱和。第三份150克载体样品用溶液‘F’和水的混合物(溶液‘F’∶水为50∶50)进行孔饱和。
然后使每种湿的浸渍过的样品静置2小时,接着在烘箱中于450°F(232℃)干燥。随后将各干燥的样品置于一不锈钢篮中并在1200ml溶液‘E’中浸渍(见实施例4)。然后将该溶液在干燥的含有EDTA-二铵的氧化铝载体上循环一小时,然后将其离心并在密封的容器中于140°F(60℃)老化64小时。将该湿润的催化剂在450°F(232℃)空气中快速干燥20分钟,并在800°F(427℃)煅烧1小时。
制成的催化剂的以“每克催化剂”计或以“每克氧化铝”计的表面积均各不相同。在加氢脱氮测定中的催化剂的活性逐步下降,与催化剂表面积的减小,和相应的预浸渍的EDTA-二铵的浓度减小相平行(表5)。
表5
实施例6
S.A(N2)m2/g | SA/gAl2O3m2/g | RVA% | RWA% | |
100%Sol’F’ | 240 | 350 | 124 | 137 |
66%Sol’F’ | 207 | 314 | 116 | 124 |
50%Sol’F’ | 198 | 301 | 118 | 124 |
将150克实施例4中所述的氧化铝载体用溶液‘G’进行孔饱和,溶液‘G’为在114ml水溶液中含有48克EDTA-二铵、9克29%(重量)氢氧化铵和12.7克六水合硝酸镍。使湿润的样品静置2小时,接着在烘箱中250°F(121℃)干燥1小时,然后在375°F(191℃)干燥1小时。随后将干燥的样品置于一不锈钢篮中并在溶液‘H’中浸渍,溶液‘H’含有35.6%(重量)三氧化钼、9.1%(重量)磷酸和7.3%(重量)氧化镍。然后将该溶液在干燥的含有EDTA-二铵的氧化铝载体上循环一小时,然后将其离心。将得到的样品分成两份,一份在室温下老化三个星期(样品6A),而另一份置于密封的容器中,并在167°F(75℃)老化72小时(样品6B)。将这两份样品在450°F(232℃)快速干燥20分钟,并分两步煅烧:在575°F(302℃)煅烧30分钟,然后在850°F(454℃)煅烧1小时。制得的催化剂具有非常类似的表面积和在加氢脱氮测定中的高的活性(表6)。
实施例7
将200克实施例4中所述的氧化铝载体用溶液‘J’进行孔饱和,溶液‘J’含有48克EDTA-二铵、15.3克29%(重量)氢氧化铵和62克溶液‘K’,溶液‘K’含有32.8%(重量)三氧化钼、5.9%(重量)氧化镍和9.0%(重量)磷酸。使湿的浸渍过的载体静置2小时,接着在250°F(121℃)干燥1小时,然后在450°F(232℃)干燥1小时。随后将干燥的样品置于一不锈钢篮中并在1400ml溶液‘H’中浸渍。然后将该溶液在干燥的含有EDTA-二铵的氧化铝载体上循环一小时,然后将其离心。将得到的样品在密封的容器中于167°F(75℃)老化3天(样品7A),随后在450°F(232℃)快速干燥20分钟,并如前面实施例6中所述地分两步煅烧。表面积增加和在加氢脱氮测定中的催化剂活性都非常高。结果也如表6所示。
表6
实施例8
样品ID | 老化时间小时 | 老化温度°F(℃) | SA(N2)m2/g | SA/gAl2O3m2/g | RVA-TN% |
6A | 72 | 167(75) | 244 | 402 | 132 |
6B | 504 | 68(20) | 208 | 343 | 134 |
7A | 161 | 167(75) | 259 | 401 | 136 |
将300克实施例4中所述的氧化铝载体用一种溶液进行孔饱和,该溶液含有80克EDTA-二铵、25.2克29%(重量)氢氧化铵和92克溶液‘K’(参见实施例7)。使湿的浸渍过的载体静置2小时,接着在250°F(121℃)干燥1小时,然后在450°F(232℃)干燥1小时。随后将干燥的样品置于一不锈钢篮中并在1900ml溶液‘H’中浸渍。然后将该溶液在干燥的含有EDTA-二铵的氧化铝载体上循环一小时,然后将其离心。将得到的样品分成两份,一份在167°F(75℃)老化16小时(样品9A),而另一份在密封的容器中在温度设定在使催化剂的温度为167°F(75℃)的微波炉中老化1小时(样品9B)。随后将该样品如前所述地进行快速干燥和煅烧。两种样品的表面积增加和催化活性都是良好的(表7)。
表7
实施例9
样品ID | 老化时间小时 | 老化温度°F(℃) | SA(N2)m2/g | SA/gAl2O3m2/g | RVA-TN% |
9A | 1 | 167(75) | 173 | 284 | 125 |
9B | 16 | 167(75) | 189 | 306 | 127 |
将310克Criterion C-424商品催化剂(Criterion Catalyst Company,Houston,TX)的用过后的再生样品用含有54.7克EDTA-二铵的溶液进行孔饱和。然后将该样品在密封的容器中于140°F(60℃)老化4天,随后如前所述地进行快速干燥和煅烧(样品10A)。在一特意设计的测试中测定再生的商品样品C-424(样品10B)和经EDTA处理的样品的活性以比较催化剂在原料在流化床催化裂解之前进行催化加氢处理中的性能(CFH测试)。测定结果和测定条件如表8所示。可以看出经EDTA处理的再生催化剂与上述再生催化剂相比的HDS和HDN等性能有明显提高。
表8
CFH测试:原料:催化裂解过的重瓦斯油
样品 | 处理情况 | RVA-HDN,% | RVA-HDS,% |
新的C-424 | 100 | 100 | |
10B | 再生的 | 75 | 69 |
10A | 再生的/经EDTA处理 | 90 | 86 |
H2压力:1100psig(76atm)
H2/油:4210SCF/bbl(0.75m3/l)
LHSV:2hr-1
温度:630°F(332℃)
Claims (28)
1.一种催化剂组合物,它包括表面积经氮吸附测定至少为每克100平方米,孔体积经汞孔度计测定至少为每克0.25立方厘米的含有γ氧化铝的颗粒状多孔载体,该催化剂组合物经一种或多种具有催化活性的金属浸渍,其特征在于该催化剂在表面还部分含有高至25埃的微晶尺寸的氧化铝的超微晶相。
2.如权利要求1所述的催化剂组合物,其特征在于该催化剂含有与在催化剂表面具有大于30埃的微晶尺寸的γ氧化铝结合的超微晶相。
3.如权利要求1所述的催化剂组合物,其特征在于氧化铝的超微晶相表面微晶尺寸为8埃至25埃。
4.如权利要求1所述的催化剂组合物,其特征在于该催化剂具有至少双峰中孔结构。
5.如权利要求4所述的催化剂组合物,其特征在于该催化剂经使用解吸等温线经氮气孔度计测定具有在孔径为40埃或更小的第一区域以及在孔径为50埃或更大的第二区域具有孔隙度峰的双峰中孔结构。
6.如权利要求5所述的催化剂组合物,其特征在于该催化剂经使用解吸等温线经氮气孔度计测定具有在孔径为20至40埃的第一区域以及在孔径为50至150埃的第二区域具有孔隙度峰的双峰中孔结构。
7.如权利要求1所述的催化剂组合物,其特征在于所述载体经选自第VIB族和第VIII族金属中的一种或多种具有催化活性的过渡金属浸渍。
8.如权利要求7所述的催化剂组合物,其特征在于该载体用镍、钴、钼和钨中的一种或多种浸渍。
9.如权利要求7或8所述的催化剂组合物,其特征在于该载体再用一种助催化剂浸渍。
10.如权利要求9所述的催化剂组合物,其特征在于该助催化剂为磷。
11.如权利要求8所述的催化剂组合物,其特征在于该载体用钼和钴浸渍,其量以MoO3计为高至35%(重量)的钼和以CoO计为高至9%(重量)的钴,上述量均基于催化剂总重量。
12.如权利要求10所述的催化剂组合物,其特征在于该载体用钼、钴和磷浸渍,其量以MoO3计为高至35%(重量)的钼、以CoO计为高至9%(重量)的钴和以P2O5计为高至10%(重量)磷,上述量均基于催化剂总重量。
13.如权利要求8所述的催化剂组合物,其特征在于该载体用钼和镍浸渍,其量以MoO3计为高至35%(重量)的钼和以NiO计为高至7%(重量)的镍,上述量均基于催化剂总重量。
14.如权利要求10所述的催化剂组合物,其特征在于该载体用钼、镍和磷浸渍,其量以MoO3计为高至35%(重量)的钼、以NiO计为高至7%(重量)的镍和以P2O5计为高至10%(重量)磷,上述量均基于催化剂总重量。
15.如权利要求8所述的催化剂组合物,其特征在于该载体用钼浸渍,其量以MoO3计为高至20%(重量),上述量基于催化剂总重量。
16.如权利要求15所述的催化剂组合物,其特征在于该载体再用钴和/或镍浸渍,其量分别以CoO和/或以NiO计为高至5%(重量),上述量均基于催化剂总重量。
17.如权利要求16所述的催化剂组合物,其特征在于该载体再用磷浸渍,其量以P2O5计为高至10%(重量),上述量基于催化剂总重量。
18.如权利要求7所述的催化剂组合物,其特征在于该载体用贵金属浸渍,其量高至2%(重量),上述量基于催化剂总重量。
19.如权利要求18所述的催化剂组合物,其特征在于所述贵金属为铂。
20.如权利要求1至19中任何一项所述的催化剂组合物,其特征在于该催化剂组合物在第一步氢化裂解过程中的相对体积活性(RVA)至少为115。
21.含烃原料催化加氢脱硫的方法,包括在加氢脱硫的条件下使该原料与如权利要求1至17中任何一项所述的催化剂接触的步骤。
22.含烃原料催化加氢脱氮的方法,包括在加氢脱氮的条件下使该原料与如权利要求1至17中任何一项所述的催化剂接触的步骤。
23.含烃原料催化加氢转化的方法,包括在加氢转化的条件下使该原料与如权利要求1至17中任何一项所述的催化剂接触的步骤。
24.含烃原料催化加氢脱金属的方法,包括在加氢脱金属的条件下使该原料与如权利要求1至17中任何一项所述的催化剂接触的步骤。
25.含烃原料催化氢化裂解的方法,包括在氢化裂解的条件下使该原料与如权利要求1至17中任何一项所述的催化剂接触的步骤。
26.含烃原料催化重整的方法,包括在重整的条件下使该原料与如 1至7、18和19中任何一项所述的催化剂接触的步骤。
27.含烃原料催化氢化-脱氢的方法,包括在氢化-脱氢的条件下使该原料与如权利要求1至7、18和19中任何一项所述的催化剂接触的步骤。
28.含烃原料催化异构化的方法,包括在异构化的条件下使该原料与如权利要求1至7、18和19中任何一项所述的催化剂接触的步骤。
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CN104437664A (zh) * | 2013-09-16 | 2015-03-25 | 中国石油化工股份有限公司 | 一种制备α-氧化铝载体的方法 |
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