CN112973711A - Distillate oil hydrorefining catalyst and preparation method thereof - Google Patents
Distillate oil hydrorefining catalyst and preparation method thereof Download PDFInfo
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- CN112973711A CN112973711A CN202011490411.5A CN202011490411A CN112973711A CN 112973711 A CN112973711 A CN 112973711A CN 202011490411 A CN202011490411 A CN 202011490411A CN 112973711 A CN112973711 A CN 112973711A
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- catalyst
- acid
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- alumina
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 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 85
- 229910052751 metal Inorganic materials 0.000 claims abstract description 49
- 239000002184 metal Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims description 30
- 239000011148 porous material Substances 0.000 claims description 26
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 18
- 150000002736 metal compounds Chemical class 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000001805 chlorine compounds Chemical group 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 21
- 239000002283 diesel fuel Substances 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 15
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 24
- 238000005470 impregnation Methods 0.000 description 19
- 239000003921 oil Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 14
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 12
- 235000018660 ammonium molybdate Nutrition 0.000 description 12
- 239000011609 ammonium molybdate Substances 0.000 description 12
- 229940010552 ammonium molybdate Drugs 0.000 description 12
- 238000004523 catalytic cracking Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 239000011268 mixed slurry Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000011363 dried mixture Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910052927 chalcanthite Inorganic materials 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 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
- 238000009826 distribution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011733 molybdenum 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
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- -1 VIB group metal oxide Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/881—Molybdenum and iron
-
- 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
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/885—Molybdenum and copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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- B01J35/615—
-
- B01J35/633—
-
- B01J35/635—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the field of hydrogenation catalysts, and discloses a distillate oil hydrofining catalyst and a preparation method thereof. The catalyst comprises a carrier and an active component, wherein the carrier is metal modified alumina, and the active component is selected from Mo and/or W; based on catalysisThe total weight of the catalyst, the content of the metal for modification contained in the carrier in oxide is 2-20 wt%, and Al2O3Is 50 to 93 wt%, and the content of the active component is 5 to 30 wt% calculated by oxide; wherein the metal is selected from one or more of Fe, Co, Ni, Cu and Zn. The catalyst is applied to the hydrofining process of catalytic diesel oil, and has higher catalytic hydrogenation activity.
Description
Technical Field
The invention relates to the field of hydrogenation catalysts, in particular to a distillate oil hydrofining catalyst and a preparation method thereof.
Background
With the increasing strictness of environmental regulations, new diesel oil standards put more strict requirements on the sulfur mass fraction, the aromatic hydrocarbon mass fraction and the cetane number of diesel oil products. The yield of the catalytic cracking diesel oil is about 30 percent of the total yield of the diesel oil, and the catalytic cracking diesel oil cannot be directly used as the diesel oil due to low cetane number, high mass fractions of sulfur, nitrogen and colloid, dark color of an oil product and poor stability. The hydrogenation process is one of the most effective process means for improving the quality of oil products, and the hydrogenation catalyst is the most important and key technology in the hydrogenation process.
Hydrogenation catalysts generally consist of a metal or metal oxide having a hydrogenation function and a carrier, and commonly used metal components are group VIB and group VIII metals, such as cobalt, molybdenum, nickel, tungsten, etc., and such catalysts generally have the metal active component supported on the carrier by an impregnation method. Commonly used supports are alumina or siliceous alumina. In order to further improve the activity and stability of the catalyst, the carrier is often modified to make it more suitable for deep hydrofining of poor diesel oil fractions.
CN1133723C discloses a distillate oil hydrorefining catalyst and a preparation method thereof, wherein, alumina pellets containing 5-15 wt% of silicon dioxide are used as carriers and contain MoO321-28 wt%, NiO 22-8 wt% and CoO 0.03-2.0 wt%, and two-stage spray soaking is adopted. The catalyst has higher hydrodesulfurization and hydrodenitrogenation activities at the same time, and is suitable for hydrofining of inferior distillate oil containing more sulfur and nitrogen at the same time.
WO2007084438 discloses a selective hydrodesulphurisation catalyst comprising 8-30 wt% of molybdenum selected from group VIB, 2-8 wt% of cobalt selected from group VIII, and a suitable amount of organic substance as complexing agent on a silicon carrier. When the catalyst is used for treating catalytic cracking gasoline raw materials, the olefin saturation rate is low.
CN1123765.1 discloses a diesel hydrotreating catalyst, which contains a carrier and indium and/or tungsten and nickel and/or cobalt loaded on the carrier, and is characterized in that the carrier is composed of alumina and zeolite, the weight ratio of the alumina to the zeolite is 90:10-50:50, the alumina is alumina compounded by small-pore alumina and large-pore alumina according to the weight ratio of 75:25-50:50, wherein the small-pore alumina is alumina with the diameter of less than 80 angstrom pores accounting for more than 95% of the total pore volume, and the large-pore alumina is alumina with the diameter of 60-600 angstrom pores accounting for more than 70% of the total pore volume.
CN1049679C discloses a diesel oil hydro-conversion catalyst, which takes alumina and Y-shaped molecular sieve as carriers and contains at least one VIB group metal and at least one VIll group metal, and is characterized in that the catalyst carrier comprises 40-90 w% of alumina, 0-20 w% of amorphous silica-alumina and 5-40 w% of molecular sieve, wherein the Y-shaped molecular sieve has a pore volume of 0.40-0.52ml/g and a specific surface of 750-900 m-2Unit cell constant 2.420-2.500nm, SiO2/A12O3In the ratio of 7-15, the content of VIB group metal oxide in the catalyst is 10-30 w%, and the content of VIll group metal oxide in the catalyst is 2-15 w%. It is suitable for the hydrogenation conversion of 150-400 deg.C petroleum fraction, especially for the conversion of catalytic cracking Light Cycle Oil (LCO) with high sulfur, nitrogen and aromatic hydrocarbon contents and low sixteen kang value, and features that under the milder condition, the contents of sulfur, nitrogen and aromatic hydrocarbon are reduced and the sixteen kang value of the product is greatly raised.
CN1289828A discloses a new compound prepared from gamma-Al2O3Or by containing SiO2gamma-Al of (2)2O3The hydrofining catalyst as carrier has W, Mo, Ni and P as active components. With SiO2Modified Al2O3The hydrogenation catalyst which is a carrier has improved performance, but the carrier has lower acid content and fewer strong acid centers, is not beneficial to ring opening and breaking of nitrogen heterocycles, and has poor denitrification activity.
Disclosure of Invention
The invention aims to overcome the problem of low catalyst activity caused by low dispersion degree of metal active components in hydrogenation catalysts in the prior art, and provides a distillate oil hydrofining catalyst and a preparation method thereof, in particular to a hydrofining catalyst for catalyzing diesel oil and a preparation method thereof. The hydrogenation catalyst prepared by the method has higher hydrodesulfurization and hydrodenitrogenation activity, and can be used for ultra-deep hydrogenation treatment of oil products including light, medium and heavy distillate oils.
In order to achieve the above object, the first aspect of the present invention provides a distillate oil hydrorefining catalyst, which comprises a carrier and an active component, wherein the carrier is metal modified alumina, and the active component is selected from Mo and/or W; the content of the metal for modification contained in the carrier in the catalyst is 2-20 wt% in terms of oxide, based on the total weight of the catalyst, and Al2O3Is 50 to 93 wt%, and the content of the active component is 5 to 30 wt% calculated by oxide; wherein the metal is selected from one or more of Fe, Co, Ni, Cu and Zn.
In a second aspect, the present invention provides a method for preparing a catalyst, comprising:
(1) mixing pseudo-boehmite and a metal compound with water for realizing slurrying and acid under stirring to obtain slurry; wherein the weight ratio of the acid to the alumina in the pseudo-boehmite is 0.05-0.5: 1;
aging the slurry at 15-90 ℃ for 0.5-24 hours, and drying to obtain a metal modified alumina precursor;
(2) molding the metal modified alumina precursor, and roasting at 550-800 ℃ for 2-5 hours to obtain a modified alumina carrier;
(3) and (2) impregnating the modified alumina carrier with a solution containing Mo salt and/or W salt, drying, and roasting at 650 ℃ for 2-5 hours to obtain the catalyst.
By adopting the technical scheme, the acid solution is adopted to modify the pseudoboehmite carrier, so that the pore size distribution of the carrier can be effectively improved, the macropores are increased, and the acidity of the catalyst is adjusted; more importantly, the dispersity of the added metal in the carrier is increased, the added metal can interact with aluminum, and the stability of the carrier is increased. The synergistic effect of the modified metal and Mo and/or W in the active component can make the catalyst prepared by said invention possess more catalytic hydrogenation activity.
The catalyst provided by the invention can be used for carrying out ultra-deep hydrogenation treatment on oil products including light, medium and heavy distillate oil and the like, and other suitable hydrogenation treatment occasions such as hydrodesulfurization, hydrodenitrogenation and the like.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The present invention will be described in detail below by way of examples, which are intended to help the reader better understand the nature and advantageous effects of the present invention, but should not be construed as limiting the operable scope of the present invention in any way.
The invention provides a distillate oil hydrofining catalyst, which comprises a carrier and an active component, wherein the carrier is metal modified alumina, and the active component is selected from Mo and/or W; the content of the metal for modification contained in the carrier in the catalyst is 2-20 wt% in terms of oxide, based on the total weight of the catalyst, and Al2O3Is 50 to 93 wt%, and the content of the active component is 5 to 30 wt% calculated by oxide; wherein the metal is selected from one or more of Fe, Co, Ni, Cu and Zn.
In the catalyst provided by the invention, the alumina is modified by the specific metal, so that the pore structure of the finally formed catalyst can be adjusted and improved. Preferably, the catalyst has a pore volume of 0.4-0.6mL/g and a specific surface area of 250-400m2(ii) in terms of/g. Can be determined by the BET test method. It may be preferred that the pore volume be 0.4mL/g, 0.45mL/g, 0.5mL/g, 0.55mL/g, 0.6mL/g, and ranges consisting of any two of the foregoing values; the specific surface area is preferably 290-300m2/g。
Preferably, the catalyst is in the shape of a sphere, a strip-shaped tablet or a particle, preferably a strip; preferably the strips are cylindrical, trilobal or quadralobal.
In some embodiments of the present invention, when the composition of the catalyst cannot satisfy the above conditions at the same time, the catalyst cannot have good interaction, which is not favorable for the hydrorefining of the catalytic cracking diesel oil to obtain good desulfurization and denitrification effects. For example, the selection of metals other than Fe, Co, Ni, Cu, Zn, or the respective components not falling within the above-defined ranges is not favorable for obtaining the hydrogenation effect as in the present invention.
Further preferably, in the catalyst, the content of the metal for modification in terms of oxide contained in the carrier may be 2 wt%, 4 wt%, 6 wt%, 8 wt%, 10 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, 20 wt%, and a range consisting of any two of the above values; al (Al)2O3Can be present in an amount of 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 93 wt%, and ranges consisting of any two of the foregoing values; the active component is present in an amount of 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, calculated as an oxide, and ranges consisting of any two of the foregoing values.
In a second aspect, the present invention provides a method for preparing a catalyst, comprising:
(1) mixing pseudo-boehmite and a metal compound with water for realizing slurrying and acid under stirring to obtain slurry; wherein the weight ratio of the acid to the alumina in the pseudo-boehmite is 0.05-0.5: 1;
aging the slurry at 15-90 ℃ for 0.5-24 hours, and drying to obtain a metal modified alumina precursor;
(2) molding the metal modified alumina precursor, and roasting at 550-800 ℃ for 2-5 hours to obtain a modified alumina carrier;
(3) and (2) impregnating the modified alumina carrier with a solution containing Mo salt and/or W salt, drying, and roasting at 650 ℃ for 2-5 hours to obtain the catalyst.
In the method provided by the invention, the steps (1) and (2) are firstly realized to obtain the metal modified alumina as a carrier. In a preferred embodiment, metal modification is used. The metal may be introduced into the pseudo-boehmite by means of the use of a metal compound. Firstly, preparing slurry, then obtaining a metal modified alumina precursor, adding acid to modify the pseudo-boehmite, and enabling the metal compound to have better metal dispersibility in the prepared modified alumina carrier. Preferably, the weight ratio of the acid in the step (1) to the alumina in the pseudo-boehmite is 0.06-0.3: 1. Further, the weight ratio may preferably be 0.06, 0.1, 0.15, 0.2, 0.25, 0.3, and a range consisting of any two of the above values. The proper acid amount for treating the pseudo-boehmite can effectively improve the pore size distribution of the further obtained alumina, increase macropores, adjust the acidity of the carrier and obtain better modification effect on the pseudo-boehmite, thereby providing the pore volume and the specific surface area of the catalyst, modulating the interaction between the carrier and the metal active component, improving the dispersibility of the metal component and improving the performance of the catalyst. As in some embodiments of the invention, hydrodesulfurization and denitrogenation of the catalyzed diesel fuel are more effective. The technical effects of the present invention cannot be obtained with the weight ratio more than 0.5 or less than 0.05.
In some embodiments of the present invention, preferably, the acid is an inorganic acid or an organic acid, preferably one or more selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, oxalic acid and citric acid, and more preferably hydrochloric acid and/or nitric acid. The acid is practically used in the form of an aqueous solution containing the acid, for example, in a concentration of 10 to 30% by weight. The amount of the acid used in the step (1) is the weight of the acid actually supplied, which is calculated from the amount of the aqueous solution in which the acid is used and the concentration of the acid.
In some embodiments of the invention, the metal compound is a water-soluble compound, preferably the metal compound is a nitrate, chloride, sulfate, carbonate or oxide of a metal. The metal compound contains one or more metals selected from Fe, Co, Ni, Cu and Zn, can be beneficial to the modification of alumina, can interact with aluminum to increase the stability of the carrier, and provides the carrier which is beneficial to improving the hydrogenation effect.
In some embodiments of the invention, the solution containing Mo and/or W salts is used to introduce Mo and/or W as active components into the catalyst. The Mo salt and/or the W salt are water-soluble compounds, and the active components can be conveniently loaded on the carrier by an impregnation mode. Preferably chlorides or nitrates of Mo and/or W, preferably chlorides such as molybdenum chloride and/or tungsten chloride. The impregnation can be made by conventional impregnation methods, such as by isovolumetric impregnation.
In some embodiments of the present invention, the hydrogenation catalyst required for the preparation of the present invention is provided in the preparation process in amounts of the respective materials used. Preferably, the pseudo-boehmite, the metal compound, the solution containing the Mo salt and/or the W salt are added in an amount such that the metal compound provides a metal content of 2 to 20% by weight in terms of oxide, a Mo and/or W content of 5 to 30% by weight in terms of oxide, and Al in the resulting catalyst based on the total weight of the catalyst2O3Is contained in an amount of 50 to 93 wt%.
In some embodiments of the present invention, preferably, the method further comprises: before the forming in the step (2), adding one or more of peptizing agent, extrusion assistant and alumina dry glue powder into the metal modified alumina precursor. The specifically adopted substance and the addition amount can be, for example, the peptizing agent can be one or more of nitric acid, phosphoric acid, hydrochloric acid and sulfuric acid, and the addition amount is 3-10% of the total weight of a sample to be molded (the sample refers to the metal modified alumina precursor, the same below); the extrusion aid can be sesbania powder, and the dosage of the extrusion aid is 2-6% of the total weight of a sample to be molded.
In the preparation method of the catalyst provided by the invention, the molding in the step (2) can be dropping ball molding, extrusion molding and tabletting molding, and the extrusion molding is the best. The catalyst may be in the form of spheres, rods (including cylinders, trilobes, quadralobes, etc.), tablets or granules, with the rods being preferred.
In some embodiments of the present invention, if the preparation method of the catalyst cannot simultaneously satisfy the preparation steps and conditions, the metal-modified support and the further prepared catalyst provided by the present invention cannot be obtained. When the respective contents of the metal and the active component in the catalyst are out of the range of the invention, the catalyst cannot have good interaction, which is not beneficial to hydrofining of catalytic cracking diesel oil to obtain good desulfurization and denitrification effects.
The invention also provides a method for hydrorefining catalytic cracking diesel, which comprises the following steps: the catalytic cracking diesel oil is subjected to hydrofining reaction in the presence of a hydrofining catalyst, and the hydrofining catalyst is the distillate oil hydrofining catalyst.
The catalytic cracking diesel oil may be diesel oil produced from a catalytic cracking process of petroleum refining. The conditions of the hydrofinishing reaction may be: the temperature is 300--1The volume ratio of the hydrogen to the raw material catalytic cracking diesel oil is 200-500: 1.
By using the hydrofining catalyst, the hydrodesulfurization rate of catalytic cracking diesel oil can reach 100%, and the hydrodenitrogenation rate can reach more than 91%.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the amount of acid is the weight of the acid actually used. The specific surface area and the pore volume of the catalyst are measured by a BET test method;
the composition of the catalyst was determined by fluorescence analysis;
the sulfur content in the raw oil and the hydrogenation product is measured by a gas chromatography method;
the hydrodesulfurization rate is 1- (the content of sulfur in the raw oil-the content of sulfur in the hydrogenated product)/the content of sulfur in the raw oil is multiplied by 100 percent;
the hydrogenation denitrification rate is 1- (the content of nitrogen in the raw oil-the content of nitrogen in the hydrogenation product)/the content of nitrogen in the raw oil is multiplied by 100%.
Example 1
1258g of pseudoboehmite (solid content)62%, the same below), 67.8g FeCl3·6H2O, 4900g of deionized water and 78g (acid to alumina weight ratio of 0.10 by weight) of hydrochloric acid were mixed with stirring; aging the obtained mixed slurry at 70 ℃ for 2 hours, and drying the aged mixed slurry at 120 ℃ for 4 hours to obtain a modified alumina precursor;
the modified alumina precursor and 39g of sesbania powder (the addition is about 4 wt%) are uniformly mixed, 500g of distilled water is added, and the mixture is mixed, extruded and formed. Then drying the mixture for 2 hours at 120 ℃, and roasting the dried mixture for 3 hours at 700 ℃ to obtain the modified alumina carrier.
272g of ammonium molybdate and 1000g of distilled water are taken and uniformly stirred to obtain an impregnation liquid, the obtained impregnation liquid is uniformly mixed with the modified alumina carrier for 1h, and then the mixture is dried at 200 ℃ for 12h and then is roasted at 600 ℃ for 3h to obtain the catalyst A1. The catalyst composition, specific surface area and pore volume measurements are shown in Table 1.
Example 2
1000g of pseudo-boehmite, 280g of Co (NO)3)2·6H2O, 4000g of deionized water and 93g (acid to alumina weight ratio of 0.15, by weight) of hydrochloric acid were mixed with stirring; aging the obtained mixed slurry at room temperature for 6 hours, and drying the mixed slurry at 120 ℃ for 4 hours to obtain a modified alumina precursor;
the modified alumina precursor and 30g of sesbania powder (the addition is about 2 wt%) are uniformly mixed, 500g of distilled water is added, and the mixture is mixed, extruded and formed. Then drying at 120 ℃ for 2 hours, and roasting at 750 ℃ for 2 hours to obtain the modified alumina carrier.
204g of ammonium molybdate, 160g of ammonium metatungstate and 900g of distilled water are taken and uniformly stirred to obtain an impregnation liquid, the obtained impregnation liquid is uniformly mixed with the modified alumina carrier for 1 hour, then the mixture is dried at 120 ℃ for 8 hours and then is roasted at 650 ℃ for 2 hours to obtain the catalyst A2. The catalyst composition, specific surface area and pore volume measurements are shown in Table 1.
Example 3
1339g of pseudo-boehmite, 293g of nickel nitrate, 5000g of deionized water and 166g (acid to alumina weight ratio of 0.20 by weight) of hydrochloric acid were mixed with stirring; aging the obtained mixed slurry at 60 ℃ for 12 hours, and drying the aged mixed slurry at 120 ℃ for 8 hours to obtain a modified alumina precursor;
the modified alumina precursor and 40g of nitric acid (the addition is about 8 wt%) are uniformly mixed, 850g of distilled water is added, and the mixture is mixed, extruded and formed. Then drying at 80 ℃ for 12 hours, and roasting at 650 ℃ for 5 hours to obtain the modified alumina carrier.
53g of ammonium metatungstate and 1000g of distilled water are taken and uniformly stirred to obtain an impregnation liquid, the obtained impregnation liquid is uniformly mixed with the modified alumina carrier for 1 hour, and then the mixture is dried at 120 ℃ for 8 hours and then is roasted at 550 ℃ for 3 hours to obtain the catalyst A3. The catalyst composition, specific surface area and pore volume measurements are shown in Table 1.
Example 4
1048g of pseudo-boehmite, 249g of CuSO4·5H2O, 4100g of deionized water and 39g (acid to alumina weight ratio of 0.06, by weight) of hydrochloric acid were mixed with stirring; aging the obtained mixed slurry at 60 ℃ for 12 hours, and drying the aged mixed slurry at 120 ℃ for 8 hours to obtain a modified alumina precursor;
the modified alumina precursor and 52g of nitric acid (the addition amount is about 4 wt%) are uniformly mixed, 700g of distilled water is added, and the mixture is mixed, extruded and formed. Then drying at 120 ℃ for 12 hours, and roasting at 800 ℃ for 2 hours to obtain the modified alumina carrier.
469g of ammonium molybdate and 700g of distilled water are taken and stirred uniformly to obtain an impregnation solution, the obtained impregnation solution is mixed uniformly with the modified alumina carrier for 1h, and then the mixture is dried at 120 ℃ for 8h and then is roasted at 600 ℃ for 5h to obtain the catalyst A4. The catalyst composition, specific surface area and pore volume measurements are shown in Table 1.
Example 5
806g of pseudo-boehmite, 334g of zinc chloride, 3000g of deionized water and 60g (acid to alumina weight ratio of 0.12, by weight) of hydrochloric acid were mixed with stirring; aging the obtained mixed slurry at room temperature for 6 hours, and drying the mixed slurry at 120 ℃ for 8 hours to obtain a modified alumina precursor;
the modified alumina precursor and 30g of nitric acid (the addition amount is about 3 wt%) are uniformly mixed, 600g of distilled water is added, and the mixture is mixed, extruded and formed. Then drying at 120 ℃ for 12 hours, and roasting at 800 ℃ for 2 hours to obtain the modified alumina carrier.
And uniformly stirring 136g of ammonium molybdate, 334g of ammonium metatungstate and 700g of distilled water to obtain an impregnation liquid, uniformly mixing the impregnation liquid with the modified alumina carrier for 1 hour, drying at 120 ℃ for 8 hours, and roasting at 650 ℃ for 5 hours to obtain the catalyst A5. The catalyst composition, specific surface area and pore volume measurements are shown in Table 1.
Comparative example 1
1258g of pseudo-boehmite and 39g of sesbania powder are mixed uniformly, 30g of nitric acid (the weight ratio of acid to alumina is 0.04) and 500g of distilled water are added, and the mixture is mixed, extruded and formed into strips. Then drying the mixture for 2 hours at 120 ℃, and roasting the dried mixture for 3 hours at 700 ℃ to obtain the modified alumina carrier.
272g of ammonium molybdate and 1000g of distilled water are taken and uniformly stirred to obtain an impregnation solution, the obtained impregnation solution and the modified alumina carrier are uniformly mixed for 1h, and then the mixture is dried at 200 ℃ for 12h and then is roasted at 600 ℃ for 3h to obtain a comparative catalyst D1. The catalyst composition, specific surface area and pore volume measurements are shown in Table 1.
Comparative example 2
1258g of pseudo-boehmite and 39g of sesbania powder are mixed uniformly, 30g of nitric acid (the weight ratio of acid to alumina is 0.04) and 500g of distilled water are added, and the mixture is mixed, extruded and formed into strips. Then drying the mixture for 2 hours at 120 ℃, and roasting the dried mixture for 3 hours at 700 ℃ to obtain the modified alumina carrier.
272g of ammonium molybdate and 67.8g of FeCl are taken3·6H2And stirring O and 1000g of distilled water uniformly to obtain an impregnation liquid, uniformly mixing the impregnation liquid with the modified alumina carrier for 1h, drying at 200 ℃ for 12h, and then roasting at 600 ℃ for 3h to obtain a comparative catalyst D2. The catalyst composition, specific surface area and pore volume measurements are shown in Table 1.
TABLE 1
| Catalyst and process for preparing same | A1 | A2 | A3 | A4 |
| Metal compound | FeCl3·6H2O | Co(NO3)2·6H2O | Nickel nitrate | CuSO4·5H2O |
| Metal, wt.% | 2 | 7.28 | 11.99 | 7.38 |
| Mo salt and/or W salt | Ammonium molybdate | Ammonium molybdate + ammonium metatungstate | Ammonium metatungstate | Ammonium molybdate |
| Active ingredient, wt.% | 20 | 30.1 | 4.96 | 32.09 |
| Al2O3Per weight percent | 78 | 62.61 | 83.05 | 60.53 |
| Pore volume, mL/g | 0.46 | 0.5 | 0.46 | 0.55 |
| Specific surface area, m2/g | 310 | 280 | 320 | 295 |
Note: metal, active component, all in terms of oxide
TABLE 1 (continuation)
| Catalyst and process for preparing same | A5 | D1 | D2 |
| Metal compound | Zinc chloride | - | FeCl3·6H2O |
| Metal, wt.% | 17.94 | 0 | 2 |
| Mo salt and/or W salt | Ammonium molybdate + ammonium metatungstate | Ammonium molybdate | Ammonium molybdate |
| Active ingredient, wt.% | 37.1 | 20.39 | 19.99 |
| Al2O3Per weight percent | 44.96 | 79.61 | 79.61 |
| Pore volume, mL/g | 0.49 | 0.3 | 0.28 |
| Specific surface area, m2/g | 296 | 180 | 165 |
Examples 6 to 10
The catalysts A1-A5 were subjected to hydrodesulfurization and denitrification reactions in accordance with the feed oils and evaluation conditions provided in Table 2. The reaction evaluation results are shown in Table 3.
TABLE 2
Comparative examples 3 to 4
Catalysts D1-D2 were subjected to hydrodesulfurization and denitrogenation in the same manner as in examples 6-10. The reaction evaluation results are shown in Table 3.
TABLE 3
| Numbering | Name of catalyst | Hydrodesulfurization of | Hydrodenitrogenation,% |
| Example 6 | A1 | 100 | 95.6 |
| Example 7 | A2 | 100 | 92.8 |
| Example 8 | A3 | 100 | 95.0 |
| Example 9 | A4 | 100 | 91.3 |
| Example 10 | A5 | 100 | 94.2 |
| Comparative example 3 | D1 | 85.6 | 65.5 |
| Comparative example 4 | D2 | 90.5 | 66.6 |
The results in table 3 show that the catalyst provided by the invention has higher catalytic hydrogenation activity, and the catalytic diesel hydrogenation performance of the catalyst is obviously superior to that of a comparative catalyst.
Claims (10)
1. A distillate oil hydrorefining catalyst comprises a carrier and an active component, wherein the carrier is metal modified alumina, and the active component is selected from Mo and/or W; the content of the metal for modification contained in the carrier in the catalyst is 2-20 wt% in terms of oxide, based on the total weight of the catalyst, and Al2O3Is 50 to 93 wt%, and the content of the active component is 5 to 30 wt% calculated by oxide; wherein the metal is selected from one or more of Fe, Co, Ni, Cu and Zn.
2. The catalyst of claim 1, wherein the catalysis isThe pore volume of the agent is 0.4-0.6mL/g, the specific surface area is 250-400m2/g；
Preferably, the catalyst is in the shape of a sphere, a strip-shaped tablet or a particle, preferably a strip; the strips are cylindrical, trilobal or quadralobal.
3. A method for preparing the catalyst of claim 1 or 2, comprising:
(1) mixing pseudo-boehmite and a metal compound with water for realizing slurrying and acid under stirring to obtain slurry; wherein the weight ratio of the acid to the alumina in the pseudo-boehmite is 0.05-0.5: 1;
aging the slurry at 15-90 ℃ for 0.5-24 hours, and drying to obtain a metal modified alumina precursor;
(2) molding the metal modified alumina precursor, and roasting at 550-800 ℃ for 2-5 hours to obtain a modified alumina carrier;
(3) and (2) impregnating the modified alumina carrier with a solution containing Mo salt and/or W salt, drying, and roasting at 650 ℃ for 2-5 hours to obtain the catalyst.
4. The method according to claim 3, wherein the weight ratio of the acid to the alumina in the pseudoboehmite in step (1) is 0.06-0.3: 1.
5. The method according to claim 3 or 4, wherein the acid is an inorganic acid or an organic acid, preferably one or more selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, oxalic acid and citric acid, more preferably hydrochloric acid and/or nitric acid.
6. The production method according to any one of claims 3 to 5, wherein the metal compound is a nitrate, chloride, sulfate, carbonate or oxide of a metal.
7. The method according to any one of claims 3 to 6, wherein the metal is selected from one or more of Fe, Co, Ni, Cu, Zn.
8. The production method according to any one of claims 3 to 7, wherein the method further comprises: before the forming in the step (2), adding one or more of peptizing agent, extrusion assistant and alumina dry glue powder into the metal modified alumina precursor.
9. The production method according to any one of claims 3 to 8, wherein the Mo-and/or W-containing salt is a chloride or nitrate, preferably a chloride, of Mo and/or W.
10. The production method according to any one of claims 3 to 9, wherein the pseudo-boehmite, the metal compound, the solution containing the Mo salt and/or the W salt are added in an amount such that the metal compound provides a metal content of 2 to 20% by weight in terms of oxide, a Mo and/or W content of 5 to 30% by weight in terms of oxide, and Al in the produced catalyst based on the total weight of the catalyst2O3Is contained in an amount of 50 to 93 wt%.
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| CN1952077A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Refining catalyst for paraffin-hydrogenating and its preparing process and uses |
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| CN1868590A (en) * | 2006-06-16 | 2006-11-29 | 中国石油化工股份有限公司 | Catalyst for hydrogen refining of paraffin wax, prepn. method and application thereof |
| CN106607038A (en) * | 2015-10-23 | 2017-05-03 | 中国石油化工股份有限公司 | Presulfurized hydrodesulfurization catalyst and preparation method thereof |
| CN106607068A (en) * | 2015-10-23 | 2017-05-03 | 中国石油化工股份有限公司 | Hydrofinishing catalyst and preparation method thereof |
| RU2607925C1 (en) * | 2015-12-09 | 2017-01-11 | Акционерное Общество "Газпромнефть - Московский Нпз" (Ао "Газпромнефть - Мнпз") | Catalyst and method for hydroskimming diesel distillates |
| WO2018019203A1 (en) * | 2016-07-29 | 2018-02-01 | 武汉凯迪工程技术研究总院有限公司 | Boron-modified hydrofining catalyst having high loading amount and preparation method therefor |
| CN106582597A (en) * | 2016-12-09 | 2017-04-26 | 中国石油天然气股份有限公司 | Silicon-modified alumina, as well as preparation method and application thereof |
| CN108273529A (en) * | 2018-01-27 | 2018-07-13 | 陕西煤业化工技术研究院有限责任公司 | One kind is for coal tar light fraction catalyst for hydrogenation and preparation method thereof |
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