CN110841674B - 挤出的残油脱金属催化剂 - Google Patents
挤出的残油脱金属催化剂 Download PDFInfo
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- CN110841674B CN110841674B CN201910997489.7A CN201910997489A CN110841674B CN 110841674 B CN110841674 B CN 110841674B CN 201910997489 A CN201910997489 A CN 201910997489A CN 110841674 B CN110841674 B CN 110841674B
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- titania
- alumina
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 126
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 262
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 124
- 239000011148 porous material Substances 0.000 claims abstract description 80
- 229910052751 metal Inorganic materials 0.000 claims abstract description 75
- 239000002184 metal Substances 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 54
- 230000008569 process Effects 0.000 claims abstract description 45
- 150000002739 metals Chemical class 0.000 claims abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 19
- 239000011593 sulfur Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 58
- 150000002430 hydrocarbons Chemical class 0.000 claims description 58
- 239000004215 Carbon black (E152) Substances 0.000 claims description 51
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 238000002441 X-ray diffraction Methods 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 11
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 11
- 229910052753 mercury Inorganic materials 0.000 claims description 11
- 230000000737 periodic effect Effects 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 6
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 5
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 5
- 238000002459 porosimetry Methods 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims 4
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 150000003609 titanium compounds Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000000295 fuel oil Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 18
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 239000000758 substrate Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000002243 precursor Substances 0.000 description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 150000002736 metal compounds Chemical class 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- JEGSVFUREJDEAP-UHFFFAOYSA-L aluminum;titanium(4+);sulfate Chemical compound [Al+3].[Ti+4].[O-]S([O-])(=O)=O JEGSVFUREJDEAP-UHFFFAOYSA-L 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- -1 phosphorus compound Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004231 fluid catalytic cracking Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
Classifications
-
- 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
- C10G45/10—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 platinum group metals or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—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
- B01J23/74—Iron group metals
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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
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
-
- 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
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Abstract
本发明涉及挤出的残油脱金属催化剂。公开了催化剂载体、担载的催化剂,以及制备和使用用于使含金属重油原料的脱金属的催化剂的方法。催化剂载体包含氧化铝和5%或更少的氧化钛。由载体制备的催化剂,其孔体积的至少30‑80体积%为直径200‑500埃的孔。本发明的催化剂对于在氢转化过程期间从重原料中去除金属显示改进的催化活性和稳定性。催化剂也显示提高的硫和MCR转化率。
Description
本申请是申请日为2013年2月14日,申请号为201380020504.3,发明名称为“挤出的残油脱金属催化剂”的发明专利申请的分案申请。
相关申请的交叉引用
本申请要求2012年2月17日提交的标题为“EXTRUDED RESID DEMETALLATIONCATALYST(挤出残油脱金属催化剂)”的美国临时专利申请号61/600,022的提交日权益,其公开内容通过引用并入本文。
发明领域
本发明涉及包含进料流的液体烃的催化氢化处理。特别地,本发明涉及催化剂载体、使用载体制备的催化剂组合物、制备所述催化剂组合物的方法和使用上述催化剂组合物减少烃重原料中的金属含量的方法。
发明背景
在石油精炼工业中,通过氢化处理提升某些油和馏分,如重油和残油,经常是有用的。这些氢化处理过程的实例为氢化脱金属、氢化脱硫和氢化脱氮。在这些方法中,原料在氢的存在下在升高的压力和温度下与氢转化催化剂接触。由于生态规定施行的严格要求,精炼工业变得越来越多的集中在生产具有高品质和最小污染物(如硫、氮和重金属)含量的更清洁的燃料。
用于氢化处理过程的催化剂通常包含来自元素周期表6、9和10族的催化活性金属且通常担载在氧化铝上,所述氧化铝可与其它的无机耐高温材料如二氧化硅、氧化镁、氧化钛、氧化锆等结合。第二助催化剂或添加剂如卤素、磷和硼,也用于增强催化性质。为了实现氢化处理过程的最大效果,需要优化催化剂活性和选择性至所需的氢化处理反应。催化剂活性和选择性由以下这些因素决定和影响:催化剂载体的特性和性质、催化剂、助催化剂的活性和选择性以及使用的制备和活化方法。
其中重原料包含有机金属化合物,氢化处理以及下游催化剂的有效性易于相对快速地衰减,特别当杂质超过约10-20ppm金属,例如溶解的镍和钒。据称这些金属杂质沉积在这些催化剂的表面上及孔内,降低它们的有效性。对金属杂质问题的一种方法为改变氢化处理催化剂的孔结构。然而,确定使用哪种孔结构是不可预料的并且不易获得。在考虑最佳孔结构方面在本领域还有冲突。若干专利已经讨论过这种冲突,包括美国专利号4,066,574;美国专利号4,113,661和美国专利号4,341,625。
具有低Conradson炭残留(CCR)的经氢化处理的烃原料在精炼工业也是高度期望的。炭残留为烃形成焦炭的趋势的度量。用重量%表示,炭残留可按微炭残留(MCR)测量。经氢化处理的残余原料中的MCR含量是重要的参数,因为经氢化处理的残留物通常作为进料通往炼焦器或流体催化裂化(FCC)单元。减少经氢化处理的残留物中的MCR含量减少在炼焦器产生的低值焦炭的量并提高在FCC单元产生的汽油的量。
为了这个目的,仍需要开发催化剂组合物,其更便宜和/或更有效地在氢化处理过程期间从烃进料流去除金属和/或硫污染物,特别是重烃进料流。还需要在氢化处理过程期间提供良好的MCR转化率的改进的氢化脱金属和/或氢化脱硫催化剂。
发明概要
本发明基于以下发现:基于氧化钛氧化铝的总重量,包含5重量%或更少氧化钛的氧化钛氧化铝的高温煅烧,意外地提供了具有独特孔结构的挤出的催化剂载体,由该催化剂载体可制备对于在氢化处理过程期间去除金属具有提高的催化活性和稳定性的担载的催化剂。有利地,本发明的载体提供较低成本的经济效益,因为由其制备的催化剂组合物使用较低的催化活性金属含量同时保持高的催化性能。
在本发明的一个方面,提供具有独特孔结构的挤出的氧化钛氧化铝载体。本发明的载体具有的孔径分布由压汞孔隙率法测定,满足以下:总孔体积为约0.7-约1.2cc/g,总孔体积的大于40%为直径大于的孔,总孔体积的约30%或更多为约-约的孔,且总孔体积的大于10%为直径以上的孔。
本发明还提供挤出的氧化钛氧化铝载体,其包含至少90重量%的具有约0.4-约1.7氧化铝R值的氧化钛氧化铝,R值定义为2θ=32°的X射线衍射峰的积分强度和2θ=46°的X射线衍射峰的积分强度之间的比率。
在本发明的另一方面,提供改进的氢化处理催化剂用于在氢化处理过程期间减少包含金属的重烃原料中的金属含量。本发明的催化剂通过以下制备:在本发明的挤出的载体上,浸渍催化活性的6、9和10族金属或前体金属化合物,及任选的磷化合物。
在本发明的又一个方面,提供改进的氢化处理催化剂,其能够减少经氢化处理的重烃馏分中的金属含量,同时减少硫和微炭残留(MCR)的含量。
本发明也提供制造具有独特孔径分布的挤出的氧化钛氧化铝载体的方法。
本发明的另一方面提供了制造包含挤出的氧化钛氧化铝载体的催化剂组合物的方法,所述载体包含至少90重量%具有约0.4-约1.7的氧化铝R值并包含5重量%或更少氧化钛的氧化钛氧化铝,基于氧化钛氧化铝的总重量。
在本发明的又一个方面,提供使用本发明的担载的催化剂组合物和方法的改进的氢化处理过程。
本发明的这些和其它方面在以下更详细地描述。
发明详述
本发明提供由以下组成的催化剂组合物:元素周期表6、9和10族的催化活性金属或金属的前体金属化合物以及任选的磷化合物,所述催化剂组合物担载在挤出的氧化钛氧化铝载体上。在本发明的一个实施方案中,用于制备本发明的催化剂的载体材料包含含有5重量%或更少氧化钛的氧化钛氧化铝,基于氧化钛氧化铝组合物的总重量。在本发明的另一个实施方案中,载体材料包含小于5重量%的氧化钛,基于氧化钛氧化铝组合物的总重量。在本发明的又一个实施方案中,载体材料包含约2.5-约4重量%的氧化钛,基于氧化钛氧化铝组合物的总重量。在本发明的又一个实施方案中,载体材料包含约0.3-约1重量%的氧化钛,基于氧化钛氧化铝组合物的总重量。
在本发明的优选实施方案中,用于制备本发明载体的氧化钛氧化铝包含至少90重量%的具有γ-氧化铝和δ-和/或θ-氧化铝的混合物的氧化铝,使得氧化钛氧化铝组合物表现为约0.40-约1.7的氧化铝R值范围,优选约0.6-约1.4。如本文所用的术语“R值”用于表明2θ=32°的X射线衍射峰的积分强度和2θ=46°的X射线衍射峰的积分强度之间的比率。R值通过美国专利5,888,380公开和描述的方法测定,该专利的全体内容在此通过引用结合。
R值可通过下式表示:
其中[I(2θ)=32°]和[I(2θ)=46°]分别表示X射线衍射谱的2θ角在32°和46°的峰的积分强度。在本说明书中,使用PANalytical X’Pert X射线衍射仪。使用以下测量条件和设备:CuK α射线容器,容器电压50kV,容器电流30mA,双轴垂直测角器,扫描速率0.867°/分钟,发射缝隙宽度1°,散射缝隙宽度1°,接收缝隙宽度0.3mm,2θ角4°≤2θ≤82°。出现在2θ=46°的峰归因于γ-氧化铝,而出现在2θ=32°的峰归因于δ-和/或θ-氧化铝。在这个角度,后两种氧化铝类型不能通过X射线衍射彼此区分。在2θ=46°和2θ=32°的两个峰没有重叠且因此可易于积分计算积分强度。计算积分强度时,背景强度不计入,如本领域技术人员所熟知。
在该方面,注意R值应在无催化活性金属存在的载体上测定。
本发明的氧化钛氧化铝载体通常包含至少90重量%的如本文描述的氧化钛氧化铝。优选地,载体材料包含至少95重量%的氧化钛氧化铝,最优选大于99重量%,所述重量%基于载体的总重量%。载体材料因此可“基本上由”如本文描述的氧化钛氧化铝“组成”。本文所用的涉及载体材料的组成的短语“基本上由……组成”在本文用于表明所述载体材料可包含氧化钛氧化铝和其它组分,只要这些其它组分对最终氢转化催化剂组合物的催化性质没有实质作用或影响。
有利地,本发明的氧化钛氧化铝载体具有表面积、孔体积和孔体积分布的特定性质。除非本文另作说明,否则如本文限定的氧化钛氧化铝载体的孔体积和孔径分布性质通过压汞孔隙率法测定。所述氧化铝载体材料的孔体积和孔径分布的汞测量使用任何适合的汞测孔仪进行,满足大气压-约4000巴的压力范围,接触角2θ=140°,汞表面张力为0.47N/m,室温。
本文定义的表面积通过BET表面积分析测定。测量表面积的BET法由Brunauer,Emmett和Teller在J.Am.Chem.Soc.60(1938)309-319中详述,其通过引用并入本文。
本发明的氧化钛氧化铝载体的表面积为约50m2/g-约150m2/g。在本发明的优选实施方案中,氧化钛氧化铝载体的表面积为约90m2/g-约140m2/g。
本发明的氧化钛氧化铝载体具有约0.7cc/g-约1.2cc/g的总孔体积。在本发明的一个实施方案中,载体的总孔体积为约0.8cc/g-约1.0cc/g。
然而,本发明的氧化钛氧化铝载体可通过形成氧化钛氧化铝载体的任何常规方法制备,只要最终载体材料包含具有5重量%或更少氧化钛且具有所需孔结构的氧化钛氧化铝。通常,本发明的载体通过以下制备:形成包含5重量%或更少氧化钛的可挤出的氧化钛氧化铝粉末;任选使所述氧化钛氧化铝粉末胶溶;将氧化钛氧化铝粉末挤出以形成挤出的材料;此后在约960℃-约1050℃的温度下,优选980℃-约1040℃,将挤出的材料煅烧约1小时-约3小时,以形成具有如本文以上所述的孔径分布的载体。
在本发明的一个实施方案中,本发明的氧化钛氧化铝载体通过以下制备:使含水氧化铝硫酸盐和硫酸氧钛共沉淀,硫酸氧钛的量足以在共沉淀的氧化钛氧化铝粉末中提供5重量%或更少的氧化钛。根据该实施方案,氧化铝硫酸盐和硫酸氧钛与包含铝酸钠的含水流混合,并保持在约7.5-约10.0的pH和约50℃-约80℃的温度下以沉淀氧化钛氧化铝粉末。沉淀的粉末经过滤,用水洗涤并在约100℃-约150℃的温度下干燥直到获得具有20重量%-40重量%的水分含量的粉末,如水分分析器在955℃下所分析。
干燥的氧化钛氧化铝粉末此后用胶溶剂处理,以使氧化铝粉末胶溶。适合的胶溶剂包括但不限于强一元酸如硝酸或盐酸,有机酸如甲酸、乙酸或丙酸,和含水碱如氢氧化铵。胶溶的粉末经挤出并在约100℃-约150℃温度下干燥约10分钟-约2小时。
干燥的挤出物此后在约960℃-1050℃高温下煅烧约1小时-约3小时,以获得具有所需孔结构的最终载体。优选地,干燥的挤出物在约980℃-约1040℃的温度下煅烧以获得最终载体。
在本发明的另一个实施方案中,本发明的氧化钛氧化铝载体通过以下制备:将具有所需R值的沉淀氧化铝粉末与氧化钛源共研磨或共混合以形成包含5重量%或更少氧化钛的氧化钛氧化铝粉末。可用于制备氧化钛氧化铝粉末的氧化钛的适合来源包括但不限于热解法氧化钛、沉淀氧化钛等。氧化钛氧化铝粉末此后任选地用胶溶剂例如硝酸等胶溶。得到的粉末然后挤出形成氧化钛氧化铝挤出物。氧化钛氧化铝挤出物在约960℃-约1050℃的高温下,优选约980℃-约1040℃下,煅烧约1小时-约3小时以提供最终的催化剂载体。
在本发明的又一个实施方案中,氧化钛氧化铝载体通过将具有所需R值的氧化铝粉末(优选沉淀的氧化铝)用含钛化合物的水溶液浸渍来制备,所述含钛化合物的量足以提供氧化铝中5重量%或更少的氧化钛。适合的含钛化合物包括但不限于,硫酸钛、氯化钛、磷酸钛、烷醇钛等。将得到的氧化钛氧化铝挤出并在约100℃-约150℃的温度下干燥约10分钟-约2小时。经干燥的氧化钛氧化铝挤出物此后在大约约960℃-约1050℃的高温下,优选约980℃-约1040℃下,煅烧约1小时-约3小时以提供最终的催化剂载体。
本发明的挤出的载体可具有不同的几何形式,如圆柱、环和对称和/或不对称的多叶形,例如三或四叶形。挤出物的标称尺寸可变化。直径通常为约1-约10mm,和长度为约1-约30mm。在本发明的一个实施方案中,直径为约1-约2mm且长度为约2-约6mm。如催化剂领域的技术人员应理解的,由所述载体产生的催化剂颗粒具有与载体相似的大小和形状。
本发明的催化剂如下制备:将氧化钛氧化铝载体与至少一种催化活性金属或前体金属化合物的水溶液接触以将所需的金属均匀分布在载体上。优选,金属均匀分布遍及载体的孔。在本发明的优选实施方案中,催化剂通过将催化剂载体用所需催化活性金属或前体化合物的水溶液浸渍至初湿来制备。
对制备本发明的催化剂组合物有用的催化活性金属和/或前体金属化合物,包括但不限于,选自元素周期表6族、元素周期表9族、元素周期表10族和它们的组合的金属或金属的化合物。优选6族金属包括但不限于钼和钨。优选9和10族金属包括但不限于钴和镍。
在本发明的优选实施方案中,优选镍和钼催化剂的组合。在本发明的更优选实施方案中,得到的催化剂包含Mo浓度为约4-约6重量%,及Ni浓度约0.1-约1重量%,所述重量%基于总催化剂组合物。
适合的9和10族金属的前体金属化合物包括但不限于金属盐类如硝酸盐、醋酸盐等。适合的6族化合物的前体金属化合物包括但不限于钼酸铵、钼酸、三氧化钼等。
预期用于本发明的载体的催化活性金属优选以金属的氧化物和/或硫化物的形式使用。优选,催化活性金属以氧化物的形式使用。
本发明的催化剂组合物还可包含磷组分。在这种情况下,除所需的催化活性金属或前体金属化合物之外,浸渍溶液还可包含磷化合物,例如磷酸、磷酸盐等。基于总催化剂组合物,约0.1-约1重量%的磷浓度适用于本发明的催化剂。
接着用催化活性金属或前体化合物的水溶液处理载体,催化剂任选在约100℃-约200℃的温度下干燥约10分钟-约2小时。经干燥的催化剂此后在足以将至少部分,优选全部金属组分或前体转化为氧化物形式的温度下煅烧一定时间,即约300℃-约600℃的范围,经过约1小时-约3小时。
如本领域技术人员清楚的,在用于将催化活性金属担载在催化剂载体上的浸渍法中有宽范围的变化。有可能应用多个浸渍步骤或浸渍溶液可包含一种或多种要沉积的组分或前体,或它们的一部分。代替浸渍技术,可使用浸入法,喷洒法等。在多次浸渍、浸入等的情况下,可在步骤之间进行干燥和/或煅烧。
本发明的催化剂对于在氢化处理过程期间使包含金属的重烃原料氢化脱金属显示提高的催化活性和稳定性。可用于本发明的重烃原料可由烃的任何适合来源获得,包括例如石油原油和沥青砂烃,例如由沥青砂提取的重油。重烃原料可为石油原油或沥青砂烃的真空残油或大气残油组分。重烃原料还可包括轻的和重的柴油,以及与柴油共混的石油原油,常压渣油和减压渣油,特别是减压柴油、原油、页岩油和沥青砂油。
重烃原料通常包括衍生自原油或沥青砂烃材料或其它重烃来源的烃混合物。所述混合物的重烃的一部分(优选主要部分)的沸点超过约343℃(650°F)。重烃原料因此定义为具有的沸程(通过ASTM测试程序D-1160测定)可使得重烃原料的至少约20重量%在超过524℃(975°F)的温度下沸腾。优选的重烃原料具有的沸程可使得至少30重量%在超过524℃(975°F)的温度下沸腾,和最优选重烃原料的至少40重量%在超过524℃(975°F)的温度下沸腾。
重烃原料的API重量可为约3-约20,但是更具体地说,API重量为4-15,更具体地说为4-11。
重烃原料可具有超过5重量%的Conradson炭残留含量,更具体地说,Conradson炭残留含量为8重量%-30重量%,通过ASTM测试方法D-189测定。
如先前说明,重烃原料中包含的金属可包括镍或钒或两者。重烃原料中的镍浓度可超过10的百万分率重量(ppmw)或可超过30ppmw。更具体地说,重烃原料中的镍浓度可为40ppmw-500ppmw。重烃原料中的钒浓度可超过50ppmw或可超过100ppmw。更具体地说,重烃原料中的钒浓度可为150ppmw-1500ppmw。
本发明的催化剂也可用于在氢化处理过程(其中要处理的烃原料包含硫和金属两者)期间脱金属时提高硫去除。进料的硫含量通常在0.1重量%以上且通常多于1重量%。氮含量通常在500ppm以上且通常在500ppm-4000ppm。
此外,本发明的催化剂在氢化处理过程期间提供了与之前的脱金属和/或脱硫催化剂相比经提高的微炭残留(MCR)转化,所述脱金属和/或脱硫催化剂由氧化铝或氧化铝氧化钛载体制备,其中载体在低温(即低于960℃)下经煅烧。因此,与起始重烃原料的MCR含量相比,获得的经氢化处理的烃馏分显示了减少的MCR含量。
使用本发明的催化剂组合物的氢化处理过程可在设备中的氢化处理过程条件下进行,由此获得催化剂组合物与包含所述金属的原料和包含游离氢的气体紧密接触,以生产具有降低含量的金属(例如镍和钒)和任选硫的含烃产物。根据本发明,氢化处理过程可使用固定催化剂床进行。氢化处理过程可按分批法或连续法进行,所述连续法包含一个或多个固定催化剂床或并联或串联的多个固定床反应器。
可用于本发明的典型氢化处理过程条件包括但不限于,300°-450℃的温度,25-200巴的氢压,150-1500Nl/1的H2∶油比率,和0.1-5的空速(hr-1)。在本发明的一个实施方案中,包含金属的烃原料脱硫过程的操作条件包括:350℃-400℃的反应区温度,100-200巴的压力和300-约1000标准升/升进料油的氢进料比率。
为了进一步说明本发明和它们的优点,给出以下具体实施例。给出的实施例作为要求保护的发明的具体说明。然而应理解,本发明不旨在限于实施例中阐述的具体细节。
除非另作说明,否则实施例以及本说明书的剩余部分中的全部份数和百分数是指按重量计的固体组成或浓度。然而,实施例以及本说明书的剩余部分中涉及气体组成的全部份数和百分数为按摩尔计或按体积计,除非另作说明。
此外,本说明书或权利要求中陈述的任何数值范围,例如表示特定组的性质、测量单位、条件、物理状态或百分数,预期在字面上明确地通过引用结合到本文,或者结合落在该范围内的任何数值,包括所述任何范围内的数值的任何子集。
实施例
制备五种催化剂(催化剂A、B、C、D和E)并评价它们的性能。实施例中催化剂的R值如上文所述计算。
实施例1
将氧化铝假勃姆石粉末(使用美国专利号US 4,154,812公开和描述的方法制备)通过在批料混合器中与硝酸水溶液混合而胶溶。湿混合物经过具有1.3mm的标称孔径的纽扣挤出。挤出的基底颗粒在120℃干燥,然后在1040℃下煅烧,以提供具有0.75R值的挤出的基底材料。
通过将水、75%磷酸、三氧化钼13%硝酸镍按0.4∶1.0∶0.3的比率混合制备浸渍溶液。首先添加水、75%磷酸和三氧化钼并在90℃下加热1小时。得到的溶液冷却到65℃以下,然后添加硝酸镍以形成最终金属溶液。将挤出的基底用该溶液浸渍为初湿。经浸渍的基底在120℃干燥,然后在510℃煅烧。成品催化剂,认定为催化剂A,具有5重量%Mo和0.25重量%Ni的标称活性金属含量。催化剂性质在以下表1中确定。
实施例2
硫酸铝(7%Al2O3)和硫酸钛(9%TiO2)的含水流以9∶1的比率混合以形成铝-钛硫酸盐混合物。将水(234加仑)添加到平展槽(strike tank)中并加热到63℃,且在过程的剩余时间,平展槽中的内含物保持在该温度。将6加仑铝-钛硫酸盐混合物添加到平展槽。然后将铝-钛硫酸盐混合物和铝酸钠的流相伴加入到平展槽中。改变铝酸钠流速以保持平展槽中pH 8.6恒定。在同步的铝-钛硫酸盐混合物和铝酸钠流开始50分钟之后,使铝-钛硫酸盐混合物流停止。铝酸钠流减少至0.7加仑/分钟并当在平展槽中达到pH 9.2时关闭。然后,沉淀的氧化钛-氧化铝混合物在过滤带上经过滤和洗涤以去除残余的硫酸钠。得到的滤饼然后经喷雾干燥。然后,干燥的氧化钛-氧化铝粉末用于制造催化剂载体。
氧化铝-氧化钛粉末(2600g)通过在批料混合器中与硝酸的水溶液(2900g水中7g硝酸)混合而胶溶。湿的混合物通过具有1.3mm的标称孔径的按钮挤出。挤出的基底颗粒在120℃干燥,然后在1040℃煅烧以给出具有1.33R值的挤出的基底材料。
通过将水(1500g)、75%磷酸(170g)、三氧化钼(400g)和13%硝酸镍(100g)混合制备浸渍溶液。首先添加水、75%磷酸和三氧化钼并在90℃加热1小时。得到的溶液冷却至低于65℃,然后添加硝酸镍以形成最终金属溶液。挤出的基底用该溶液浸渍为初湿。经浸渍的基底在120℃干燥,然后在510℃煅烧。成品催化剂,认定为催化剂B,具有3重量%的标称氧化钛含量,和5重量%Mo以及0.25重量%Ni的标称金属含量。催化剂性质在以下表1中确定。
实施例3
如以上实施例1所述制备氧化铝粉末。氧化铝粉末(2650g)与热解法氧化钛粉末(100g)混合并通过在批料混合器中与硝酸的水溶液(2800g水中10g硝酸)混合而胶溶。湿混合物通过具有1.3mm的标称孔径的按钮挤出。挤出的基底颗粒在120℃干燥,然后在1000℃下煅烧以提供具有0.93R值的挤出的基底材料。
通过将水(1500g)、75%磷酸(170g)、三氧化钼(400g)和13%硝酸镍(100g)混合制备浸渍溶液。首先添加水、75%磷酸和三氧化钼并在90℃加热1小时。得到的溶液冷却至低于65℃,然后添加硝酸镍以形成最终金属溶液。挤出的基底用该溶液浸渍为初湿。经浸渍的基底在120℃干燥,然后在510℃煅烧。成品催化剂,认定为催化剂C,具有5重量%的标称氧化钛含量,和5重量%Mo以及0.25重量%Ni的标称金属含量。催化剂性质在以下表1中确定。
实施例4
如以上实施例1所述制备干燥的氧化铝粉末。氧化铝粉末(2700g)与硝酸的水溶液(28g)、硫酸钛(80g)和水(2550g)在批料混合器中混合。湿混合物通过具有1.3mm的标称孔径的按钮挤出。挤出的颗粒在120℃干燥,然后在1000℃下煅烧以提供具有0.58R值的挤出的基底材料。
通过将水(1500g)、75%磷酸(170g)、三氧化钼(400g)和13%硝酸镍(100g)混合制备浸渍溶液首先添加。水、75%磷酸和三氧化钼并在90℃加热1小时。得到的溶液冷却至低于65℃,然后添加硝酸镍以形成最终金属溶液。挤出的基底用该溶液浸渍为初湿。经浸渍的基底在120℃干燥,然后在510℃煅烧。成品催化剂,认定为催化剂D,具有5重量%Mo和0.25重量%Ni和0.5重量%氧化钛的标称活性金属含量。催化剂性质在以下表1中确定。
表1催化剂A-D的催化剂性质
实施例5
如实施例2所述制备催化剂(催化剂E),不同之处在于基底在600℃的低温煅烧。催化剂的孔结构在本发明的孔径分布之外。催化剂E和Rocha等公开的催化剂的催化剂性质显示在以下表2中。催化剂E具有0.11的R值。
表2:催化剂E的性质
实施例6
如下文所述在氢化处理过程中测试催化剂A、B、C、D和E。催化剂粒料装载在活塞流反应器中。进料由常压残油和氢组成。残油具有362ppm V和71ppm Ni的金属含量,4.6重量%的硫含量和16.6重量%的微炭残留(MCR)含量。反应器温度保持在378℃,且每小时平均空速为0.75L/(L.h)。反应产物按24小时等分试样收集并分析它的金属、硫和MCR含量。金属、硫和MCR转化率的比较结果在以下表3给出。在三个不同的连续在线时间(time-on-stream,TOS)值(209、401和785小时)给出结果。
如以上表3所见,催化剂B、C和D,用具有本发明的孔结构的不同量的氧化钛助催化,显示了比不包含氧化钛的催化剂A更高的金属转化率。同时,当与使用催化剂A获得的硫和MCR转化率相比时,发明催化剂B、C和D的硫和MCR转化率提高。低温煅烧的催化剂E包含3重量%氧化钛并具有在期望的本发明孔结构之外的差的孔结构。如以上表4所见,催化剂E去除金属的性能低于发明催化剂(催化剂B、C和D)的性能。此外,虽然当与发明催化剂B、C和D相比时,催化剂E显示对于硫和MCR转化率的初始优异性能,但是催化剂E对于金属、硫和MCR转化率的性能出乎意料地随时间急速衰减,证明缺少稳定性。在具有高含量金属的重烃进料的工业精炼中不期望这种稳定性缺乏。
在不偏离本发明范围的情况下,可在所述公开内容和所附权利要求的范围内进行本发明的合理变化、改进和修改。
Claims (39)
1.制备用于担载催化活性金属的多孔载体材料的方法,所述催化活性金属适于在氢化处理条件下使包含金属的重烃馏分氢化脱金属,所述方法包含
a)制备可挤出的具有大于或等于0.3重量%且小于5重量%的氧化钛含量的氧化钛氧化铝,基于所述氧化钛氧化铝的总重量计;
b)任选地,使所述氧化钛氧化铝胶溶;
c)挤出所述氧化钛氧化铝以形成氧化钛氧化铝挤出物;和
d)在960℃-1050℃的温度下煅烧所述挤出物以获得经煅烧的载体,
其中:
(i)所述载体具有0.7-1.2立方厘米/克的总孔体积,
(ii)该总孔体积的大于40%具有直径大于200Å的孔,
(iii)该总孔体积的30%或更多具有200Å-500Å的孔,且
(iv)该总孔体积的大于10%具有直径大于1000Å的孔,且
其中所述载体包含具有大于或等于0.3重量%且小于5重量%的氧化钛含量的氧化钛氧化铝,基于所述氧化钛氧化铝的总重量计。
2.权利要求1的方法,其中可挤出的氧化钛氧化铝具有0.3重量%到4重量%的氧化钛含量,基于所述氧化钛氧化铝的总重量计,且所述载体包含具有0.3重量%到4重量%的氧化钛含量的氧化钛氧化铝,基于所述氧化钛氧化铝的总重量计。
3.权利要求1的方法,其中可挤出的氧化钛氧化铝具有0.3重量%到2.5重量%的氧化钛含量,基于所述氧化钛氧化铝的总重量计,且所述载体包含具有0.3重量%到2.5重量%的氧化钛含量的氧化钛氧化铝,基于所述氧化钛氧化铝的总重量计。
4.权利要求1的方法,其中所述载体的氧化钛氧化铝包含至少90重量%的具有0.4-1.7的R值的氧化铝,所述R值定义为2θ=32°的X射线衍射峰的积分强度和2θ=46°的X射线衍射峰的积分强度之间的比率。
5.权利要求1的方法,其中步骤(a)的氧化钛氧化铝 如下形成:使硫酸铝和硫酸钛与铝酸钠共沉淀,使用的硫酸钛的量足以提供包含具有所述氧化钛含量的氧化钛氧化铝的多孔载体。
6.权利要求1的方法,其中步骤(a)的氧化钛氧化铝如下形成:混合氧化铝和氧化钛,所述氧化钛的量足以提供包含具有所述氧化钛含量的氧化钛氧化铝的载体,基于所述氧化钛氧化铝的总重量计。
7.权利要求1的方法,其中步骤(a)的氧化钛氧化铝如下形成:用钛化合物浸渍氧化铝粉,所述钛化合物的量足以提供包含具有所述氧化钛含量的氧化钛氧化铝的载体,基于所述氧化钛氧化铝的总重量计。
8.权利要求1的方法,其中所述载体在980℃-1040℃的温度下煅烧。
9.通过前述权利要求任一项的方法制备的催化剂载体。
10.包含氧化钛氧化铝的催化剂载体,所述氧化钛氧化铝基于总氧化钛氧化铝具有大于或等于0.3重量%且小于5重量%的氧化钛含量,所述载体具有0.7-1.2cc/g总孔体积,且孔体积分布使得该总孔体积的大于40%具有直径大于200Å的孔,该总孔体积的30%或更多具有200Å-500Å的孔,该总孔体积的大于10%具有直径大于1000Å的孔。
11.权利要求10的载体,其中存在于所述氧化钛氧化铝中的氧化钛的量为0.3重量%-4重量%,基于所述氧化钛氧化铝的总重量计。
12.权利要求10的载体,其中存在于所述氧化钛氧化铝中的氧化钛的量为0.3重量%-2.5重量%,基于所述氧化钛氧化铝的总重量计。
13.权利要求10的载体,其中存在于所述氧化钛氧化铝中的氧化钛的量为大于或等于2.5重量%且小于5重量%氧化钛的量,基于所述氧化钛氧化铝的总重量计。
14.权利要求10或13的载体,其中所述载体包含至少90重量%的具有0.4-1.7的氧化铝R值的氧化钛氧化铝,所述R值定义为2θ=32°的X射线衍射峰的积分强度和2θ=46°的X射线衍射峰的积分强度之间的比率。
15.权利要求10的载体,其中所述总孔体积的50%-90%为直径大于200Å的孔。
16.权利要求10的载体,其中所述总孔体积的30%-80%为直径200-500Å的孔。
17.权利要求10的载体,其中所述载体的总孔体积的大于15%具有直径大于1000Å的孔。
18.权利要求10的载体,其中所述孔体积和孔径分布性质通过压汞孔隙率法测定,使用汞孔隙仪,在大气压力-4000巴的压力范围,接触角θ=140°,且汞表面张力为0.47N/m,25℃的条件下测定。
19.一种制备催化剂的方法,所述催化剂对于在氢化处理过程中使包含金属的重烃馏分氢化脱金属具有高活性和稳定性,该方法包含用包含至少一种催化剂或催化剂前体的水溶液浸渍多孔挤出载体,所述催化剂或催化剂前体包含:
(I)至少一种选自元素周期表6族的金属;和
(II)至少一种选自以下的金属:元素周期表9族的金属和元素周期表10族的金属以及它们的组合;以及
(III)任选磷;
所述催化剂或催化剂前体可热转化为金属氧化物,且此后干燥及煅烧得到的经浸渍的载体以提供担载的催化剂,所述载体通过权利要求1-8中任一项的方法制备。
20.通过权利要求19的方法制备的催化剂。
21.对于重烃的氢化脱金属具有改进的活性和稳定性的催化剂,其包含
a)挤出的氧化铝载体,其包含具有大于或等于0.3重量%且小于5重量%的氧化钛含量的氧化钛氧化铝,基于所述氧化钛氧化铝的总重量计;和
b)催化剂或催化剂前体,其包含:
(i)至少一种选自元素周期表6族的金属;和
(ii)至少一种选自以下的金属:元素周期表9族的金属和元素周期表10族的金属以及它们的组合;以及
(iii)任选磷;
c)其中所述载体具有50-150m2/g的表面积和0.7-1.2立方厘米/克的总孔体积,该总孔体积的大于40%具有直径大于200Å的孔,该总孔体积的30%或更多具有200Å-500Å的孔,且该总孔体积的大于10%具有直径大于1000Å的孔。
22.权利要求21的催化剂,其中所述氧化钛氧化铝具有0.3重量%到4重量%的氧化钛含量,基于所述氧化钛氧化铝的总重量计。
23.权利要求21的催化剂,其中所述氧化钛氧化铝具有0.3重量%到2.5重量%的氧化钛含量,基于所述氧化钛氧化铝的总重量计。
24.权利要求21的催化剂,其中所述载体已在960℃-1050℃的温度下煅烧。
25.权利要求24的催化剂,其中所述经煅烧的载体包含氧化钛氧化铝,所述氧化钛氧化铝包含至少90重量%的具有0.4-17的R值的氧化铝,所述R值定义为2θ=32°的X射线衍射峰的积分强度和2θ=46°的X射线衍射峰的积分强度之间的比率。
26.权利要求21的催化剂,其中所述载体的孔体积和孔径分布性质通过压汞孔隙率法测定,使用汞孔隙仪,在大气压力-4000巴的压力范围,接触角θ=140°,且汞表面张力为0.47N/m,25℃的条件下测定。
27.权利要求21的催化剂,其包含共沉淀的氧化钛氧化铝。
28.权利要求21的催化剂,其中所述至少一种催化剂或催化剂前体包含选自钴、镍、钼的金属,磷,以及它们的组合。
29.权利要求21的催化剂,其中所述载体的总孔体积的30%-80%为直径200-500Å的孔。
30.权利要求21的催化剂,其中所述载体的总孔体积的50%-90%为直径大于200Å的孔。
31.氢化处理含金属的重烃进料以去除金属的方法,该方法包含将所述重烃进料在氢化处理过程条件下与权利要求20或21的催化剂接触,并减少所述重烃馏分中的金属含量。
32.权利要求31的方法,其中所述重烃进料在以下条件下与所述催化剂接触:300℃-450℃的反应温度,25-200巴的氢压力,H2 :油比率为150-1500Nl/l,和空速为0.1-5 hr-1。
33.权利要求31的方法,其中所述重烃进料包含选自镍、钒和它们的组合的金属。
34.权利要求31的方法,其中所述重烃进料还包含硫,且硫的含量随金属的减少同时减少。
35.权利要求34的方法,其中所述重烃进料具有微碳残留(MCR)含量且所述MCR含量随着金属减少同时减少。
36.减少重烃进料中的微碳残留(MCR)含量的方法,其包含使具有MCR含量的重烃进料与权利要求20或21的催化剂在氢化处理过程条件下接触,并提供与所述重烃进料的MCR含量相比具有减少的MCR含量的经氢化处理的烃馏分。
37.权利要求36的方法,其中所述重烃进料在以下条件下与所述催化剂接触:300℃-450℃的反应温度,25-200巴的氢压力,H2 :油比率为150-1500Nl/l,和空速为0.1-5hr-1。
38.权利要求37的方法,其中所述重烃进料还包含选自镍、钒和它们的组合的金属,且其中所述经氢化处理的烃馏分与所述重烃进料相比具有减少的金属含量。
39.权利要求38的方法,其中所述重烃进料还包含硫,且其中所述经氢化处理的烃馏分与所述重烃进料相比具有减少的硫含量。
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- 2013-02-14 CN CN201910997489.7A patent/CN110841674B/zh active Active
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- 2013-02-14 EP EP13749186.6A patent/EP2814602A4/en active Pending
- 2013-02-14 CN CN201380020504.3A patent/CN104411401B/zh active Active
- 2013-02-14 KR KR1020147025792A patent/KR102133607B1/ko active IP Right Grant
- 2013-02-14 JP JP2014557764A patent/JP6298771B2/ja active Active
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CN104411401A (zh) | 2015-03-11 |
KR20140126379A (ko) | 2014-10-30 |
JP6298771B2 (ja) | 2018-03-20 |
JP2015508708A (ja) | 2015-03-23 |
CN110841674A (zh) | 2020-02-28 |
SG11201404827WA (en) | 2014-09-26 |
TW201343249A (zh) | 2013-11-01 |
KR102133607B1 (ko) | 2020-07-13 |
TWI611836B (zh) | 2018-01-21 |
CA2864799C (en) | 2018-04-10 |
CA2864799A1 (en) | 2013-08-22 |
EP2814602A1 (en) | 2014-12-24 |
WO2013123166A1 (en) | 2013-08-22 |
US20160017240A1 (en) | 2016-01-21 |
EP2814602A4 (en) | 2015-12-30 |
CN104411401B (zh) | 2019-11-15 |
ZA201406208B (en) | 2016-01-27 |
US10584288B2 (en) | 2020-03-10 |
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