CN114433135A - Hydrogenation catalyst with high denitrification activity - Google Patents
Hydrogenation catalyst with high denitrification activity Download PDFInfo
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- CN114433135A CN114433135A CN202011198553.4A CN202011198553A CN114433135A CN 114433135 A CN114433135 A CN 114433135A CN 202011198553 A CN202011198553 A CN 202011198553A CN 114433135 A CN114433135 A CN 114433135A
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- Prior art keywords
- catalyst
- viii
- sulfide
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- group metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 35
- 230000000694 effects Effects 0.000 title claims abstract description 21
- 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 66
- 238000001035 drying Methods 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 40
- 239000003350 kerosene Substances 0.000 claims abstract description 30
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- -1 VIB metal oxide Chemical class 0.000 claims abstract description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 3
- 230000023556 desulfurization Effects 0.000 claims abstract description 3
- 239000012716 precipitator Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 59
- 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 20
- 230000032683 aging Effects 0.000 claims description 13
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 12
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 12
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 11
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical group S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 6
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical group [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 6
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000004073 vulcanization Methods 0.000 abstract description 31
- 238000004898 kneading Methods 0.000 abstract description 10
- 238000000465 moulding Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 69
- 239000008367 deionised water Substances 0.000 description 35
- 229910021641 deionized water Inorganic materials 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 19
- 229920002472 Starch Polymers 0.000 description 19
- 229910017604 nitric acid Inorganic materials 0.000 description 19
- 235000019698 starch Nutrition 0.000 description 19
- 239000008107 starch Substances 0.000 description 19
- 239000002994 raw material Substances 0.000 description 13
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 238000002791 soaking Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N carbon disulfide Substances S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- HTIRHQRTDBPHNZ-UHFFFAOYSA-N Dibutyl sulfide Chemical compound CCCCSCCCC HTIRHQRTDBPHNZ-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/08—Jet fuel
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)
- Catalysts (AREA)
Abstract
A hydrogenation catalyst with high denitrification activity comprises a carrier and an active component, wherein the carrier is alumina; the active components are VIB group metal sulfide, VIII group metal sulfide and VIII group metal oxide, wherein the VIB group metal sulfide and VIII group metal sulfide are dispersed in the interior and on the surface of the catalyst carrier, and the VIII group metal oxide is dispersed on the surface of the catalyst. The catalyst is prepared by mixing and coprecipitating aluminum salt, a group VIII metal salt solution and a precipitator to obtain pseudo-boehmite powder, kneading and molding the pseudo-boehmite powder with a group VIB metal salt or a group VIB metal oxide, impregnating the group VIII metal salt solution after vulcanization, and drying the impregnated group VIII metal salt solution. The catalyst is applied to the processes of light distillate oil, aviation kerosene hydrotreating and gas desulfurization and denitrification, and has better denitrification effect and stronger mechanical strength.
Description
Technical Field
The invention relates to the technical field of oil product hydrogenation, in particular to a hydrogenation catalyst with high denitrification activity.
Background
The hydrogenation process of aviation kerosene comprises a plurality of complex chemical reactions, wherein the reactions of hydrogenation sweetening, deacidification, denitrification, olefin and naphthalene series saturation and the like solve the problem of aviation kerosene corrosion, improve the stability of aviation kerosene and moderately improve the smoke point of aviation kerosene. Therefore, the aviation kerosene hydrogenation catalyst should have high reaction activities of hydrogenation sweetening, deacidification, denitrification and olefin and naphthalene series saturation.
With the increase of the demand of aviation kerosene, the refinery increases the aviation kerosene yield, and the improvement of the dry point of the straight-run aviation kerosene raw material is an effective section for increasing the aviation kerosene yield. With the increase of the dry point of the aviation kerosene raw material, the freezing point of the aviation kerosene raw material rises, the smoke point of the aviation kerosene raw material is reduced, and the nitrogen content is increased, so that the hydrodenitrogenation activity of the aviation kerosene hydrogenation catalyst needs to be improved.
CN00123149.9 discloses a hydrogenation catalyst and a preparation method thereof, wherein a carrier of the hydrogenation catalyst mainly comprises alumina, metal components are nickel and molybdenum, the catalyst is prepared under the conditions that the hydrogen pressure is 1.0-2.5MPa, the volume ratio of hydrogen to oil is 50-400, the reaction temperature is 120--1Under the reaction condition of (3), the aviation kerosene produced by medium-pressure hydrocracking is treated, and qualified 3# jet fuel can be directly produced. The catalyst is impregnated for multiple times to obtain the catalyst with high nickel content, the reduced hydrogenation catalyst is obtained after reduction, and along with the progress of hydrogenation reaction, nickel in the catalyst is easy to aggregate, so that the activity of the catalyst is reduced.
CN200610046928.9 discloses a method for hydro-upgrading inferior aviation kerosene distillate. The inferior aviation kerosene fraction is used as raw oil, and a single-stage process flow is adopted to produce a high-quality aviation kerosene product under the condition of hydrogenation modification. Wherein at least one catalyst in the hydrogenation modification reaction zone is bulk phase catalyst which is composite oxide NixWyOzAnd oxide MoO3In a weight ratio of 1: 10-10: 1 constituent, composite oxide NixWyOzAnd oxide MoO3Accounting for 40 to 100 percent of the total weight of the catalyst composition. The bulk phase catalyst is adopted for hydrogenation reaction, the hydrogenation activity of the catalyst is very high, but the pore volume and the pore diameter of the bulk phase catalyst are very small, and the carbon deposition resistance of the catalyst is poor.
Disclosure of Invention
In order to solve the problem of low denitrification activity of hydrogenation catalysts applied to oil products such as aviation kerosene and the like in the prior art, the invention provides a hydrogenation catalyst with high denitrification activity, which can be applied to the aviation kerosene hydrogenation process to produce qualified 3# aviation kerosene products.
The technical purpose of the invention is realized by the following technical scheme:
the technical purpose of the first aspect of the invention is to provide a hydrogenation catalyst with high denitrification activity, which comprises a carrier and an active component, wherein the carrier is alumina; the active components are a VIB group metal sulfide, a VIII group metal sulfide and a VIII group metal oxide, the VIB group metal sulfide is molybdenum sulfide and/or tungsten sulfide, the VIII group metal sulfide is nickel sulfide and/or cobalt sulfide, the VIII group metal oxide is nickel oxide and/or cobalt oxide, based on the total weight of the catalyst, the VIB group metal sulfide is 2-20% by weight of sulfide, preferably 8-15%, the VIII group metal sulfide is 2-8% by weight of sulfide, preferably 3-5%, the VIII group metal oxide is 2-8% by weight of oxide, preferably 3-5%, and the rest is an alumina carrier; wherein, the VIB group metal sulfide and the VIII group metal sulfide are dispersed in the inner part and the surface of the catalyst carrier, and the VIII group metal oxide is dispersed on the surface of the catalyst.
Further, the specific surface area of the catalyst is 200-300m2Per g, poreThe volume is 0.5-1.0cm3The crushing strength is 150-250N/cm.
The technical purpose of the second aspect of the present invention is to provide a preparation method of the hydrogenation catalyst with high denitrification activity, which comprises the following steps:
(1) mixing aluminum salt, a group VIII metal salt solution and a precipitating agent, carrying out precipitation reaction, and then aging, filtering and drying to obtain pseudo-boehmite powder containing group VIII metal;
(2) uniformly mixing the pseudo-boehmite powder containing the VIII group metal prepared in the step (1) with a VIB group metal salt or a VIB group metal oxide, a peptizing agent and an extrusion aid, extruding into strips, forming, drying and vulcanizing to obtain a catalyst precursor;
(3) and (4) dipping a VIII family metal salt solution into the catalyst precursor prepared in the step (3), and drying to obtain the catalyst.
Further, the aluminum source in the step (1) is selected from Al2(SO4)3、AlCl3Or Al (NO)3)3The group VIII metal salt solution is at least one of nitrate, chloride or sulfate of group VIII metal, the group VIII metal is Ni and/or Co, and the precipitator is NaOH or NH4OH or NaAlO2At least one of (1).
Further, the precipitation reaction conditions in the step (1): the pH value is 7-10, the temperature is 50-95 ℃, and the time is 30-120 min.
Further, the aging conditions in the step (1) are as follows: the temperature is 50-90 ℃, the pH value is 8-11, and the time is 3-24 h; the drying conditions were: drying at 50-90 deg.C for 3-10 hr, and drying at 90-250 deg.C for 3-6 hr.
Further, the group VIB metal salt in step (2) is at least one of a phosphate or an ammonium salt of a group VIB metal, more specifically, at least one selected from ammonium molybdate, phosphomolybdic acid, phosphotungstic acid and ammonium metatungstate, and the group VIB metal is W and/or Mo.
Further, the peptizing agent and the extrusion aid in the step (2) are well known to those skilled in the art, and as a more specific embodiment, the peptizing agent is selected from at least one of nitric acid, phosphoric acid or acetic acid, and the extrusion aid is selected from at least one of starch and polyethylene glycol.
Further, the drying conditions in the step (2) are as follows: the temperature is 100-200 ℃ and the time is 3-12 h.
Further, the sulfiding treatment in step (2) is a sulfiding process in preparing a hydrogenation catalyst well known to those skilled in the art, and as a more specific embodiment, dry sulfiding or wet sulfiding is generally adopted, the dry sulfiding agent is hydrogen sulfide, and the wet sulfiding agent is at least one of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide; the vulcanization pressure is 3.2-6.4MPa, the vulcanization temperature is 250-400 ℃, and the vulcanization time is 4-12 h.
Further, the group VIII metal salt solution described in the step (3) is well known to those skilled in the art, and as a more specific embodiment, at least one selected from nitrate, acetate or sulfate solutions of group VIII metals, preferably nitrate; the mass concentration of the VIII group metal salt solution is 0.1-1.0 g/mL, an equal-volume impregnation mode can be adopted, and the VIII group metal is Ni and/or Co.
Further, the impregnation in step (3) is performed in an inert atmosphere or a reducing atmosphere.
Further, the drying conditions in step (3) are as follows: in the process of being selected from N2And inert gas at 30-100 deg.C for 4-16 h.
The technical purpose of the third aspect of the invention is to provide the application of the hydrogenation catalyst with high denitrification activity in the hydrogenation treatment process of light distillate oil and aviation kerosene and the desulfurization and denitrification process of gas.
Furthermore, the catalyst is firstly subjected to vulcanization treatment during the catalytic hydrogenation reaction. The vulcanization treatment is well known to those skilled in the art, and as a more specific embodiment, dry vulcanization or wet vulcanization is generally employed, the dry vulcanization vulcanizing agent being hydrogen sulfide, and the wet vulcanization vulcanizing agent being at least one of carbon disulfide, dimethyl disulfide, methyl sulfide, and n-butyl sulfide; the vulcanization pressure is 1.0-4.0MPa, the vulcanization temperature is 160-300 ℃, and the vulcanization time is 4-12 h.
Compared with the prior art, the method has the following advantages:
(1) in the hydrogenation catalyst, the VIB group metal sulfide and the VIII group metal sulfide are dispersed in and on the catalyst carrier, the interaction between the VIB group metal sulfide and the catalyst carrier is strong, the VIII group metal oxide is dispersed on the surface of the catalyst, the interaction between the VIII group metal oxide and the catalyst carrier is weak, and the hydrogenation and denitrification activity is favorably improved.
(2) When the catalyst is prepared, the VIB group metal and the VIII group metal are firstly vulcanized and then dipped in the VIII group metal, so that on one hand, the VIB group metal which is difficult to be vulcanized can be vulcanized, the vulcanization temperature of the catalyst is reduced, and the dispersion degree of the VIII group metal is improved; on the other hand, the VIB group metal and the VIII group metal can interact with the pseudo-boehmite, so that the interaction between the post-impregnated VIII group metal and the carrier is reduced, and the hydrodenitrogenation activity of the catalyst is improved.
(3) Part of group VIII metal elements and pseudo-boehmite are coprecipitated, and the precipitate of the group VIII metal covers the surface of the pseudo-boehmite, so that on one hand, the acidity of the surface of alumina can be modified, the interaction between the alumina and other active metals is weakened, and the hydrogenation activity of the catalyst is improved; on one hand, the content of the VIII family metal in the catalyst can be improved, so that the hydrodenitrogenation activity of the catalyst is improved; on the other hand, the VIII group metal element modifies the pseudo-boehmite, which is beneficial to improving the bonding strength among particles, thereby improving the mechanical strength of the catalyst.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The catalyst composition provided by the invention can be combined by inductively coupled plasma ICP and XPS energy spectrumThe method comprises the steps of firstly characterizing the total content of VIB group metals and the total content of VIII group metals in a catalyst by ICP (inductively coupled plasma), and then quantitatively characterizing the content of metal elements with different valence states in the catalyst by an XPS (X-ray diffraction) spectrometer. The catalyst provided by the invention has metal vulcanization degree of Mo4+Or W4+The content represents the degree of metal sulfidation of the catalyst. Using 30mL/min of H at 320 DEG C2S sulfurizing for 2h, characterizing the metal valence state of the surface of the sample by an XPS PEAK spectrometer, respectively fitting and peak-splitting the energy spectrums of Mo3d, W4f, Co2p and Ni2p by adopting XPSPEAK version4.0, and calculating according to the peak area to obtain the metal sulfurization degree and the proportion of Co-Mo-S, Ni-Mo-S, Co-W-S, Ni-W-S.
Example 1
(1) Adding 1L of deionized water into a reaction tank as a base solution, respectively placing 1L of a mixed solution of aluminum sulfate and nickel sulfate and 1L of a sodium hydroxide solution into a raw material tank, and controlling the temperature of the reaction tank at 60 ℃. And (3) injecting the aluminum sulfate solution into the reaction tank at the speed of 10mL/min, simultaneously injecting the sodium hydroxide solution and adjusting the speed of the sodium hydroxide solution to ensure that the pH value of the solution in the reaction tank is constant at 8.0, and finishing neutralization after 120 min. Keeping the temperature constant at 85 ℃ and the pH value constant at 8.5 in a reaction tank, carrying out aging treatment for 5h, then washing for 3 times by using deionized water, filtering, drying a filter cake for 3h at 60 ℃, and then drying for 5h at 110 ℃ to obtain the modified alumina powder. Based on the modified alumina powder, the mass fraction of nickel oxide is 5.0 percent, and the balance is alumina.
(2) Uniformly mixing the modified alumina powder prepared in the step (1) with nitric acid, starch, molybdenum oxide and deionized water, wherein the modified alumina powder: nitric acid: starch: molybdenum oxide: deionized water with the mass ratio of 150:4:3:16:60, kneading, extruding into strips, drying at 150 ℃ for 3H, and then adopting a mixture containing 1.5% of H2Sulfurizing S hydrogen at 320 deg.C under 3.2MPa for 4 hr, and adding N2And cooling to room temperature in the atmosphere to obtain the modified alumina.
(3) And (3) soaking 0.2g/mL of nickel nitrate solution into the modified alumina in the step (2) in an equal volume, and then drying at 120 ℃ for 3h in a nitrogen atmosphere to obtain the catalyst C-1.
The catalyst C-1 comprises the following components in percentage by weight: 10.1% of molybdenum sulfide, 4.6% of nickel sulfide, 4.3% of nickel oxide and the balance of aluminum oxide.
Example 2
(1) Adding 1L of deionized water into a reaction tank as a base solution, respectively placing 1L of mixed solution of aluminum sulfate and nickel sulfate and 1L of sodium hydroxide solution into a raw material tank, and controlling the temperature of the reaction tank at 60 ℃. And (3) injecting the aluminum sulfate solution into the reaction tank at the speed of 12mL/min, simultaneously injecting the sodium hydroxide solution and adjusting the speed of the sodium hydroxide solution to ensure that the pH value of the solution in the reaction tank is constant at 8.5, and finishing the neutralization after 120 min. Keeping the temperature constant at 80 ℃ and the pH value constant at 9.0 in a reaction tank, carrying out aging treatment for 5h, then washing for 3 times by using deionized water, filtering, drying the filter cake at 65 ℃ for 5h, and then drying at 120 ℃ for 3h to obtain the modified alumina powder. Based on the modified alumina powder, the mass fraction of nickel oxide is 6.0 percent, and the balance is alumina.
(2) Uniformly mixing the modified alumina powder prepared in the step (1) with nitric acid, starch, ammonium molybdate and deionized water, wherein the modified alumina powder is prepared by the following steps: nitric acid: starch: ammonium molybdate: deionized water with the mass ratio of 150:5:5:25:80, kneading, extruding into strips, drying at 180 ℃ for 3h, and then adopting a mixture containing 3.0% of CS2Carrying out vulcanization treatment on the aviation kerosene, wherein the vulcanization temperature is 340 ℃, the vulcanization pressure is 3.6MPa, the vulcanization time is 6h, and then the vulcanization is carried out under the condition of N2And cooling to room temperature in the atmosphere to obtain the modified alumina.
(3) And (3) soaking 0.2g/mL cobalt nitrate solution into the modified alumina in the step (2) in an equal volume, and then drying at 110 ℃ for 3h in a nitrogen atmosphere to obtain the catalyst C-2.
The catalyst C-2 comprises the following components in percentage by weight: 11.4% of molybdenum sulfide, 5.4% of nickel sulfide, 4.2% of cobalt oxide and the balance of aluminum oxide.
Example 3
(1) Adding 1L of deionized water into a reaction tank as a base solution, and respectively placing 1L of a mixed solution of aluminum sulfate and cobalt sulfate and 1L of a sodium metaaluminate solution into a raw material tank, wherein the temperature of the reaction tank is controlled at 60 ℃. And (3) injecting the aluminum sulfate solution into the reaction tank at the speed of 12mL/min, simultaneously injecting the sodium hydroxide solution and adjusting the speed of the sodium hydroxide solution to ensure that the pH value of the solution in the reaction tank is constant at 9.0, and finishing neutralization after 120 min. Keeping the temperature constant at 85 ℃ and the pH value constant at 9.0 in a reaction tank, carrying out aging treatment for 4h, then washing for 3 times by using deionized water, filtering, drying a filter cake for 5h at 70 ℃, and then drying for 3h at 120 ℃ to obtain the modified alumina powder. Based on the modified alumina powder, the mass fraction of the cobalt oxide is 6.0 percent, and the balance is alumina.
(2) Uniformly mixing the modified alumina powder prepared in the step (1) with nitric acid, starch, ammonium molybdate and deionized water, wherein the modified alumina powder is prepared by the following steps: nitric acid: starch: ammonium molybdate: deionized water with the mass ratio of 150:5:5:25:80, kneading, extruding into strips, drying at 160 ℃ for 3h, and adding 3.0% CS2Carrying out vulcanization treatment on the aviation kerosene, wherein the vulcanization temperature is 360 ℃, the vulcanization pressure is 3.2MPa, the vulcanization time is 5h, and then the vulcanization is carried out under the condition of N2And cooling to room temperature in the atmosphere to obtain the modified alumina.
(3) And (3) soaking 0.22g/mL cobalt nitrate solution into the modified alumina in the step (2) in an equal volume, and then drying at 110 ℃ for 3h in a nitrogen atmosphere to obtain the catalyst C-3.
The catalyst C-3 comprises the following components in percentage by weight: 11.4% of molybdenum sulfide, 5.4% of cobalt sulfide, 4.2% of cobalt oxide and the balance of aluminum oxide.
Example 4
(1) Adding 1L of deionized water into a reaction tank as a base solution, and respectively placing 1L of a mixed solution of aluminum sulfate and nickel sulfate and 1L of a sodium metaaluminate solution into a raw material tank, wherein the temperature of the reaction tank is controlled at 60 ℃. And (3) injecting the aluminum sulfate solution into the reaction tank at the speed of 15mL/min, simultaneously injecting the sodium hydroxide solution and adjusting the speed of the sodium hydroxide solution to ensure that the pH value of the solution in the reaction tank is constant at 8.5, and finishing neutralization after 120 min. Keeping the temperature constant at 85 ℃ and the pH value constant at 8.5 in a reaction tank, carrying out aging treatment for 3h, then washing for 3 times by using deionized water, filtering, drying a filter cake for 4h at 80 ℃, and then drying for 3h at 130 ℃ to obtain the modified alumina powder. Based on the modified alumina powder, the mass fraction of nickel oxide is 6.0 percent, and the balance is alumina.
(2) Mixing the modified alumina powder prepared in the step (1) with nitric acid, starch, ammonium metatungstate and deionized waterHomogeneous, wherein the modified alumina powder: nitric acid: starch: ammonium metatungstate: deionized water with the mass ratio of 150:5:5:25:80, kneading, extruding into strips, drying at 150 ℃ for 3h, and then adopting a mixture containing 3.0% of CS2The aviation kerosene is vulcanized, the vulcanization temperature is 320 ℃, the vulcanization pressure is 3.6MPa, the vulcanization time is 4h, and then the vulcanization is carried out under the condition of N2And cooling to room temperature in the atmosphere to obtain the modified alumina.
(3) And (3) soaking 0.18g/mL of nickel nitrate solution into the modified alumina in the step (2) in an equal volume, and then drying at 120 ℃ for 3h in a nitrogen atmosphere to obtain the catalyst C-4.
The catalyst C-4 comprises the following components in percentage by weight: 13.6% of tungsten sulfide, 5.9% of nickel sulfide, 4.1% of nickel oxide and the balance of aluminum oxide.
Example 5
(1) Adding 1L of deionized water into a reaction tank as a base solution, and respectively placing 1L of a mixed solution of aluminum sulfate and cobalt sulfate and 1L of a sodium metaaluminate solution into a raw material tank, wherein the temperature of the reaction tank is controlled at 70 ℃. And (3) injecting the aluminum sulfate solution into the reaction tank at the speed of 12mL/min, simultaneously injecting the sodium hydroxide solution and adjusting the speed of the sodium hydroxide solution to ensure that the pH value of the solution in the reaction tank is constant at 8.5, and finishing the neutralization after 120 min. Keeping the temperature constant at 80 ℃ and the pH value constant at 8.5 in a reaction tank, carrying out aging treatment for 3h, then washing for 3 times by using deionized water, filtering, drying a filter cake for 4h at 60 ℃, and then drying for 5h at 120 ℃ to obtain the modified alumina powder. Based on the modified alumina powder, the mass fraction of the cobalt oxide is 6.0 percent, and the balance is alumina.
(2) Uniformly mixing the modified alumina powder prepared in the step (1) with nitric acid, starch, ammonium metatungstate and deionized water, wherein the modified alumina powder: nitric acid: starch: ammonium metatungstate: deionized water with the mass ratio of 150:5:5:25:80, kneading, extruding into strips, drying at 150 ℃ for 3H, and then adopting a mixture containing 1.5% of H2Sulfurizing S hydrogen at 320 deg.C under 3.6MPa for 4 hr, and adding N2And cooling to room temperature in the atmosphere to obtain the modified alumina.
(3) And (3) soaking 0.15g/mL cobalt nitrate solution into the modified alumina obtained in the step (2) in an equal volume, and then drying the solution at 130 ℃ for 3 hours in a nitrogen atmosphere to obtain the catalyst C-5.
The catalyst C-5 comprises the following components in percentage by weight: 13.6 percent of tungsten sulfide, 5.9 percent of cobalt sulfide, 4.1 percent of cobalt oxide and the balance of aluminum oxide.
Example 6
(1) Adding 1L of deionized water into a reaction tank as a base solution, and respectively placing 1L of a mixed solution of aluminum sulfate and nickel sulfate and 1L of a sodium metaaluminate solution into a raw material tank, wherein the temperature of the reaction tank is controlled at 80 ℃. And (3) injecting the aluminum sulfate solution into the reaction tank at the speed of 15mL/min, simultaneously injecting the sodium hydroxide solution and adjusting the speed of the sodium hydroxide solution to ensure that the pH value of the solution in the reaction tank is constant at 8.0, and finishing neutralization after 120 min. Keeping the temperature constant at 85 ℃ and the pH value constant at 8.0 in a reaction tank, carrying out aging treatment for 3h, then washing for 3 times by using deionized water, filtering, drying a filter cake for 4h at 70 ℃, and then drying for 5h at 130 ℃ to obtain the modified alumina powder. Based on the modified alumina powder, the mass fraction of nickel oxide is 6.0 percent, and the balance is alumina.
(2) Uniformly mixing the modified alumina powder prepared in the step (1) with nitric acid, starch, ammonium heptamolybdate, ammonium metatungstate and deionized water, wherein the modified alumina powder: nitric acid: starch: ammonium heptamolybdate: ammonium metatungstate: deionized water with the mass ratio of 150:5:5:12:12:80, kneading, extruding into strips, drying at 130 ℃ for 3H, and then adopting a mixture containing 1.5% of H2Sulfurizing S hydrogen at 340 deg.C under 3.2MPa for 4 hr, and adding N2And cooling to room temperature in the atmosphere to obtain the modified alumina.
(3) And (3) soaking 0.2g/mL cobalt nitrate solution into the modified alumina in the step (2) in an equal volume, and then drying at 130 ℃ for 3h in a nitrogen atmosphere to obtain the catalyst C-6.
The catalyst C-6 comprises the following components in percentage by weight: 6.0% of molybdenum sulfide, 6.0% of tungsten sulfide, 6.0% of nickel sulfide, 4.1% of cobalt oxide and the balance of aluminum oxide.
Comparative example 1
(1) Adding 1L of deionized water into a reaction tank as a base solution, respectively placing 1L of a mixed solution of aluminum sulfate and nickel sulfate and 1L of a sodium metaaluminate solution into a raw material tank, and controlling the temperature of the reaction tank at 80 ℃. And (3) injecting the aluminum sulfate solution into the reaction tank at the speed of 15mL/min, simultaneously injecting the sodium hydroxide solution and adjusting the speed of the sodium hydroxide solution to ensure that the pH value of the solution in the reaction tank is constant at 8.0, and finishing neutralization after 120 min. Keeping the temperature constant at 80 ℃ and the pH value constant at 8.0 in a reaction tank, carrying out aging treatment for 3h, then washing for 3 times by using deionized water, filtering, and drying a filter cake for 5h at 150 ℃ to obtain the modified alumina powder. Based on the modified alumina powder, the mass fraction of nickel oxide is 6.0 percent, and the balance is alumina.
(2) Uniformly mixing the modified alumina powder prepared in the step (1) with nitric acid, starch, ammonium heptamolybdate and deionized water, wherein the modified alumina powder is prepared by the following steps: nitric acid: starch: ammonium heptamolybdate: the mass ratio of the deionized water is 150:5:5:25:80, then kneading, extruding and molding, drying at 150 ℃ for 3h, and roasting at 600 ℃ for 3h to obtain the modified alumina.
(3) And (3) soaking 0.2g/mL cobalt nitrate solution into the modified alumina in the step (2) in an equal volume, and then drying at 130 ℃ for 3h in a nitrogen atmosphere to obtain the catalyst CS-1.
The catalyst CS-1 comprises the following components in percentage by weight: 11.5% of molybdenum oxide, 5.1% of nickel oxide, 4.2% of cobalt oxide and the balance of aluminum oxide.
Comparative example 2
(1) Adding 1L of deionized water into a reaction tank as a base solution, respectively placing 1L of aluminum sulfate solution and 1L of sodium metaaluminate solution into a raw material tank, and controlling the temperature of the reaction tank at 70 ℃. And (3) injecting the aluminum sulfate solution into the reaction tank at the speed of 12mL/min, simultaneously injecting the sodium hydroxide solution and adjusting the speed of the sodium hydroxide solution to ensure that the pH value of the solution in the reaction tank is constant at 8.5, and finishing the neutralization after 120 min. Keeping the temperature constant at 70 ℃ and the pH value constant at 8.5 in a reaction tank, carrying out aging treatment for 3 hours, then washing for 3 times by using deionized water, filtering, and drying a filter cake for 5 hours at 130 ℃ to obtain the alumina powder.
(2) Uniformly mixing the alumina powder prepared in the step (1) with nitric acid, starch, ammonium heptamolybdate and deionized water, wherein the modified alumina powder is prepared by the following steps: nitric acid: starch: ammonium heptamolybdate: the mass ratio of the deionized water is 150:5:5:25:80, then kneading, extruding and molding, drying at 150 ℃ for 3h, and roasting at 600 ℃ for 3h to obtain the modified alumina.
(3) Soaking 0.15g/mL solution of nickel nitrate and 0.15g/mL solution of cobalt nitrate into the modified alumina in the step (2) in equal volume, and then drying at 150 ℃ for 3h in a nitrogen atmosphere to obtain the catalyst CS-2.
The catalyst CS-2 comprises the following components in percentage by weight: 11.0% of molybdenum oxide, 4.0% of nickel oxide, 4.0% of cobalt oxide and the balance of aluminum oxide.
Comparative example 3
(1) Adding 1L of deionized water into a reaction tank as a base solution, respectively placing 1L of aluminum sulfate solution and 1L of sodium metaaluminate solution into a raw material tank, and controlling the temperature of the reaction tank at 70 ℃. And (3) injecting the aluminum sulfate solution into the reaction tank at the speed of 12mL/min, simultaneously injecting the sodium hydroxide solution and adjusting the speed of the sodium hydroxide solution to ensure that the pH value of the solution in the reaction tank is constant at 8.5, and finishing the neutralization after 120 min. Keeping the temperature constant at 70 ℃ and the pH value constant at 8.5 in a reaction tank, carrying out aging treatment for 3h, then washing for 3 times by using deionized water, filtering, and drying a filter cake for 5h at 130 ℃ to obtain the alumina powder.
(2) Uniformly mixing the alumina powder prepared in the step (1) with nitric acid, starch and deionized water, wherein the modified alumina powder is prepared by the following steps: nitric acid: starch: the mass ratio of the deionized water is 150:3:3:60, then kneading, extruding and molding, drying for 3h at 140 ℃, and roasting for 3h at 600 ℃ to obtain the aluminum oxide.
(3) And (3) soaking a solution containing cobalt nitrate, nickel nitrate and phosphomolybdic acid into the alumina obtained in the step (2) in an equal volume, and then drying the solution at 120 ℃ for 3 hours in a nitrogen atmosphere to obtain the catalyst CS-3.
The catalyst CS-3 comprises the following components in percentage by weight: 11.0% of molybdenum oxide, 4.0% of nickel oxide, 4.0% of cobalt oxide and the balance of aluminum oxide.
The catalysts C-1 to C-6 prepared in the above examples, and the catalysts CS-1 to CS-3 prepared in the comparative examples were subjected to a degree of sulfidation analysis and a ratio analysis of Co-Mo-S, Ni-Mo-S, Co-W-S, Ni-W-S, and the results are shown in Table 1.
Table 1.
Example 7
This example illustrates the performance of the catalyst of the present invention in hydrodenitrogenation reactions of aviation kerosene.
The evaluation raw oil is straight-run aviation kerosene provided by a certain petrochemical refinery, and the nitrogen content of the raw oil is 7-10 mu g/g.
The performance of the hydrodenitrogenation reaction was evaluated for catalysts C-1 to C-6 and comparative examples CS-1 to CS-3 using a 200 mL fixed bed trickle hydrogenation apparatus.
Presulfurizing conditions of the catalyst: using a catalyst containing 3wt% of CS2The space velocity of the aviation kerosene is 1.5h-1The catalyst is presulfurized at an operating pressure of 3.2MPa with a hydrogen-oil volume ratio of 300: 1.
The pre-vulcanization process comprises the following steps: feeding pre-vulcanized oil at 120 ℃, feeding oil for 2h, vulcanizing at constant temperature for 2h, heating to 150 ℃ at 15 ℃/h, vulcanizing at constant temperature for 6h, heating to 250 ℃ at 6 ℃/h, vulcanizing at constant temperature for 10h, naturally cooling to 150 ℃, and finishing the pre-vulcanization.
The evaluation reaction conditions were: the operating pressure is 2.0MPa, the reaction temperature is 200 ℃, the hydrogen/oil volume ratio is 200:1, and the volume space velocity is 1.5h-1The evaluation results are shown in Table 2.
Table 2.
The catalyst properties in table 1 and the evaluation results in table 2 show that the active metal of the catalyst of the present invention has high sulfidation degree and high mechanical strength, and achieves high denitrification performance when used in the hydrogenation denitrification reaction of aviation kerosene.
Claims (12)
1. A hydrogenation catalyst with high denitrification activity comprises a carrier and an active component, and is characterized in that the carrier is alumina; the active components are a VIB group metal sulfide, a VIII group metal sulfide and a VIII group metal oxide, the VIB group metal sulfide is molybdenum sulfide and/or tungsten sulfide, the VIII group metal sulfide is nickel sulfide and/or cobalt sulfide, the VIII group metal oxide is nickel oxide and/or cobalt oxide, and on the basis of the total weight of the catalyst, the VIB group metal sulfide accounts for 2-20% of sulfide, preferably 8-15%, the VIII group metal sulfide accounts for 2-8% of sulfide, the VIII group metal oxide accounts for 2-8% of oxide, and the balance is an alumina carrier; wherein, the VIB group metal sulfide and the VIII group metal sulfide are dispersed in the inner part and the surface of the catalyst carrier, and the VIII group metal oxide is dispersed on the surface of the catalyst.
2. The hydrogenation catalyst as claimed in claim 1, wherein the specific surface area of the catalyst is 200-300m2Per g, pore volume of 0.5-1.0cm3The crushing strength is 150-250N/cm.
3. A method for preparing a hydrogenation catalyst with high denitrification activity according to claim 1 or 2, comprising the steps of:
(1) mixing aluminum salt, a group VIII metal salt solution and a precipitating agent, carrying out precipitation reaction, and then aging, filtering and drying to obtain pseudo-boehmite powder containing group VIII metal;
(2) uniformly mixing the pseudo-boehmite powder containing the VIII group metal prepared in the step (1) with a VIB group metal salt or a VIB group metal oxide, a peptizing agent and an extrusion aid, extruding into strips, forming, drying and vulcanizing to obtain a catalyst precursor;
(3) and (4) dipping a VIII family metal salt solution into the catalyst precursor prepared in the step (3), and drying to obtain the catalyst.
4. The method of claim 3, wherein the aluminum source in step (1) is selected from Al2(SO4)3、AlCl3Or Al (NO)3)3The group VIII metal salt solution is at least one of nitrate, chloride or sulfate of group VIII metal, the group VIII metal is Ni and/or Co, and the precipitator is NaOH or NH4OH or NaAlO2At least one of (1).
5. The method according to claim 3, wherein the precipitation reaction conditions in step (1): the pH value is 7-10, the temperature is 50-95 ℃, and the time is 30-120 min.
6. The production method according to claim 3, wherein the aging conditions in the step (1) are: the temperature is 50-90 deg.C, pH is 8-11, and the time is 3-24 h.
7. The production method according to claim 3, wherein the drying conditions in the step (1) are: drying at 50-90 deg.C for 3-10 hr, and drying at 90-250 deg.C for 3-6 hr.
8. The method according to claim 3, wherein the group VIB metal salt in step (2) is at least one selected from the group consisting of ammonium molybdate, phosphomolybdic acid, phosphotungstic acid and ammonium metatungstate.
9. The method according to claim 3, wherein the drying conditions in the step (2) are: the temperature is 100-200 ℃ and the time is 3-12 h.
10. The method according to claim 3, wherein the impregnation in the step (3) is performed in an inert atmosphere or a reducing atmosphere.
11. The method according to claim 3, wherein the drying conditions in the step (3) are: in the process of being selected from N2And at least one inert gas, and drying at 30-100 deg.C for 4-16 h.
12. Use of the hydrogenation catalyst with high denitrification activity according to claim 1 or 2 in light distillate, aviation kerosene hydrotreating processes and gas desulfurization and denitrification processes.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4344867A (en) * | 1979-08-13 | 1982-08-17 | Exxon Research & Engineering Co. | Hydroprocessing catalysts |
| CN103055932A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Residual oil hydrotreating catalyst and preparation method thereof |
| CN106179414A (en) * | 2015-04-30 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of sulfurized hydrogenation catalyst for refining and preparation method thereof |
| CN106582734A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Hydrodenitrogenation catalyst for LCO (light cycle oil) and preparation method of hydrodenitrogenation catalyst |
| CN107020104A (en) * | 2009-03-06 | 2017-08-08 | 阿尔比马尔欧洲有限公司 | The body mixed metal catalyst and its manufacture method and the purposes in alcohols is converted synthesis gas to of vulcanization |
| CN110404552A (en) * | 2018-04-27 | 2019-11-05 | 中国石油化工股份有限公司 | A kind of hydrodenitrogenation catalyst and its application |
-
2020
- 2020-10-31 CN CN202011198553.4A patent/CN114433135B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4344867A (en) * | 1979-08-13 | 1982-08-17 | Exxon Research & Engineering Co. | Hydroprocessing catalysts |
| CN107020104A (en) * | 2009-03-06 | 2017-08-08 | 阿尔比马尔欧洲有限公司 | The body mixed metal catalyst and its manufacture method and the purposes in alcohols is converted synthesis gas to of vulcanization |
| CN103055932A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Residual oil hydrotreating catalyst and preparation method thereof |
| CN106179414A (en) * | 2015-04-30 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of sulfurized hydrogenation catalyst for refining and preparation method thereof |
| CN106582734A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Hydrodenitrogenation catalyst for LCO (light cycle oil) and preparation method of hydrodenitrogenation catalyst |
| CN110404552A (en) * | 2018-04-27 | 2019-11-05 | 中国石油化工股份有限公司 | A kind of hydrodenitrogenation catalyst and its application |
Non-Patent Citations (1)
| Title |
|---|
| 唐兆吉;杨占林;王继锋;姜虹;温德荣;姜艳;: "浸渍液性质对加氢脱氮催化剂性能的影响", 石油化工, no. 02, pages 177 - 182 * |
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Effective date of registration: 20231215 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |