CN108067246A - Preparation method of bulk phase hydrogenation catalyst - Google Patents
Preparation method of bulk phase hydrogenation catalyst Download PDFInfo
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- CN108067246A CN108067246A CN201611027279.8A CN201611027279A CN108067246A CN 108067246 A CN108067246 A CN 108067246A CN 201611027279 A CN201611027279 A CN 201611027279A CN 108067246 A CN108067246 A CN 108067246A
- Authority
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- China
- Prior art keywords
- preparation
- hydrogenation catalyst
- phase hydrogenation
- body phase
- catalyst
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 238000001465 metallisation Methods 0.000 claims 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims 1
- 235000018660 ammonium molybdate Nutrition 0.000 claims 1
- 239000011609 ammonium molybdate Substances 0.000 claims 1
- 229940010552 ammonium molybdate Drugs 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 229910001388 sodium aluminate Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- -1 VIB group metal compounds Chemical class 0.000 abstract 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 10
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 9
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 9
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 9
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 9
- 239000002283 diesel fuel Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 3
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 2
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 2
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 2
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 2
- 101000793908 Oryza sativa subsp. japonica Catalase isozyme C Proteins 0.000 description 2
- 108091006231 SLC7A2 Proteins 0.000 description 2
- 108091006230 SLC7A3 Proteins 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- DCAYPVUWAIABOU-UHFFFAOYSA-N alpha-n-hexadecene Natural products CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- DCAYPVUWAIABOU-NJFSPNSNSA-N hexadecane Chemical group CCCCCCCCCCCCCCC[14CH3] DCAYPVUWAIABOU-NJFSPNSNSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical class [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 150000003657 tungsten Chemical class 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- 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
- B01J35/633—Pore volume less than 0.5 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
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a bulk phase hydrogenation catalyst, which comprises the following steps: (1) adding two VIB group metal compounds, at least one VIII group metal compound, an alkaline precipitator and a surfactant into water at one time, stirring, heating to 60-120 ℃ for reaction, controlling the pH value to be 7-9, and controlling the reaction time to be 1-48 h; wherein the weight ratio of the VIII group metal compound to the two VIB group metal compounds is 1: 3-3: 1, and the weight ratio of the VIB group metal compounds is 1: 3-3: 1; and (2) adding a binder into the system obtained in the step (1), filtering, washing, drying, molding and roasting to obtain the bulk phase hydrogenation catalyst. The bulk phase type hydrogenation catalyst prepared by the method has the advantages of short preparation flow, simple process, high catalyst strength and high catalyst hydrogenation activity, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of body phase hydrogenation catalyst preparation methods, belong to petroleum refining technology field.More specifically,
The present invention is suitable for the preparation of intermediate oil Deep Hydrotreating catalyst inferior.
Background technology
In recent years, to reduce environmental pollution, country it is increasingly strict for oil quality requirement, oil quality upgrading paces not
It is disconnected to accelerate, the indexs such as sulfur content, polycyclic aromatic hydrocarbon content, Cetane number in diesel oil are proposed to be strict with.At present Beijing, Shanghai,
The big cities such as Guangzhou have taken the lead in V diesel oil standard of state of enforcement, and the whole nation will implement integrally V diesel oil standard of state within 2017, at present country
State VI diesel oil standard exposure drafts have been issued, in state's V diesel bases, the indexs such as density, polycyclic aromatic hydrocarbon have been proposed more
Strict requirements, it is contemplated that the whole nation will implement integrally state VI diesel quality standards in 2019.
Exploitation high activity diesel oil hydrofining catalyst is the key problem in technology for realizing diesel quality upgrading, and research shows logical
It crosses to conventional supported catalyst support modification and active sites optimization, catalyst activity can improved to a certain degree,
But since loaded catalyst is limited by preparation process, activated centre quantity is limited, and hydrogenation activity is difficult to significantly be promoted.2001
Year, by ExxonMobil, Albemarle and Nippon Ketjen companies have developed jointly a kind of new body phase hydrogenation catalyst
Agent causes domestic and international researcher extensive concern, which is 3 times of existing conventional hydrogenation catalyst or more.
Bulk phase catalyst preparation method mainly has coprecipitation, hydro-thermal method, solid reaction process, sol-gal process, thio salt
Class decomposition method etc..United States Patent (USP) 6620313,6712955,6758963 etc. is reported mutually is urged using coprecipitation preparation NiMoW bodies
Agent, the catalyst preparation process are all using ammonium hydroxide as complexing agent, nickel salt are added drop-wise in the solution of tungsten salt, by filtering,
Washing and shaping obtain NiMoW catalyst.The precipitation method have been modified in CN1951558A, CN1952054A, CN101722007A improvement,
Synthesize NiW composite precursors first, then by NiW composite precursors, with MoO3Compound together with binder, catalyst is shown
Higher hydrogenation activity.
United States Patent (USP) 20020010086,20020010088,20030102254,20030178344 etc. is reported using water
Hot method synthesizes bulk phase catalyst, and group VIII metal salt and two kinds of group vi metallic salts are reacted a timing under hydrothermal conditions
Between, it is filtered after taking-up, drying and moulding obtains bulk phase catalyst.
Chinese patent CN101439289, CN101255356 report a kind of solid reaction process and prepare body phase hydrogenation catalyst
Agent, in urea melting state, with molybdenum trioxide, wolframic acid, basic nickel carbonate, which has been Material synthesis, has Jie of appropriate specific surface area
Pore structure body phase NiMoW catalyst, specific surface area is in more than 200m2/g, pore volume 0.3cm3/g, and and reference catalyst
It compares, hydrodesulfurization (HDS), hydrodenitrogeneration (HDN) and hydrogenation aromatics-removing performance of satisfying significantly improve.
Han Yanmin is prepared for Co-Mo bimetallic bulk phase catalysts using sol-gal process, has been prepared first containing citric acid
Co, Mo active metal solution add in concentrated ammonia liquor and adjust pH value, by solution age plastic, roast and must urge under being protected through drying, nitrogen
Agent premise, then through being molded and roasting and obtaining Co-Mo bimetallic bulk phase catalysts.
Alonso-Nunez is prepared for sulphided state body phase NiMoW catalyst, using two methods of original position and ex situ by Ni
Improved sulphur molybdenum organoammonium tungstate salt, by obtaining NiMoW sulfide catalysts after decomposition, and employs different vulcanizing agents,
Having investigated vulcanizing agent influences catalyst activity.
From above research as can be seen that the various body phase hydrogenation catalyst methods that prepare have a respective advantage, while there is also
Following deficiency：(1) catalyst preparation flow is longer, and technique is more complicated, and rate of metal is not high, and catalyst cost is caused to increase
(2) generally using first preparing catalyst precarsor, the method for aftershaping, catalyst strength is high.
The content of the invention
It is a primary object of the present invention to provide a kind of preparation method of body phase hydrogenation catalyst, to overcome in the prior art
The problem of body phase hydrogenation catalyst preparation flow is complicated, and catalyst strength is low.
The object of the present invention is achieved like this, a kind of preparation method of body phase hydrogenation catalyst, and this method includes as follows
Step：
(1) two kinds of group vib metallic compounds, at least one group VIII metal compound, alkaline precipitating agent and surface are lived
Property agent be disposably added to the water stirring, heat up and reacted for 60~120 DEG C, control ph is 7~9, the reaction time for 1~
48h；Wherein, the weight ratio of group VIII metal compound and two kinds of group vib metallic compounds is 1:3~3:1, two kinds of group vib
Metal compound weight ratio example is 1:3~3:1；And
(2) binding agent is added in into step (1) system, filtering, washing, dry, shaping and roasting obtain body phase hydrogenation catalyst
Agent.
The preparation method of body phase hydrogenation catalyst of the present invention, wherein, the group VIII metal compound is preferably
Cobalt nitrate, cobaltous sulfate, nickel sulfate, nickel chloride and nickel nitrate form one or more of group.
The preparation method of body phase hydrogenation catalyst of the present invention, wherein, the group vib metallic compound is preferably molybdenum
Sour ammonium, sodium molybdate, ammonium tungstate, ammonium metatungstate and sodium tungstate form two kinds in group.
The preparation method of body phase hydrogenation catalyst of the present invention, wherein, the alkaline precipitating agent is preferably ammonium hydroxide.
The preparation method of body phase hydrogenation catalyst of the present invention, wherein, the surfactant is preferably hexadecane
Base trimethylammonium bromide, hexadecyltrimethylammonium chloride, Cetyltrimethylammonium bromide and octadecyl trimethyl chlorination
Ammonium forms one or more of group.
The preparation method of body phase hydrogenation catalyst of the present invention, wherein, the binding agent is preferably Aluminum sol, aluminic acid
Sodium, aluminum hydroxide solid elastomer, Ludox and sodium metasilicate form one or more of group.
The preparation method of body phase hydrogenation catalyst of the present invention, wherein, the drying temperature is preferably 100~130
℃。
The preparation method of body phase hydrogenation catalyst of the present invention, wherein, the calcination temperature is preferably 350~450
℃。
The preparation method of body phase hydrogenation catalyst of the present invention, wherein, step (1) heating rate is preferably 1
℃/min。
Beneficial effects of the present invention：
1st, sunk for deficiency, the present invention existing for the preparation of bulk phase catalyst in the prior art in preparation process using a step
Shallow lake method carries out catalyst preparation, by controlling reaction temperature, adjusts pH value of reaction system, so as to control reaction speed, with dividing
Step coprecipitation method is compared, and preparation flow is obviously shortened, and is added in surfactant in preparation process, is realized catalyst precarsor
Particle size is controllable, while adds in binding agent in system after completion of the reaction, avoids binding agent and metal in catalyst system
Component mixing is uneven, the problem of causing catalyst strength relatively low.
2nd, using the method for the present invention, metal component good dispersion degree, catalyst strength and active higher body phase can be prepared
Type catalyst, the catalyst are mainly used for intermediate oil deep hydrofinishing inferior, meet ultra-deep desulfurization technical need.Its
In, intermediate oil refers mainly to the miscella of straight-run diesel oil, catalytic diesel oil and coker gas oil and above-mentioned diesel oil.
Description of the drawings
Fig. 1 schemes for CAT-1 catalyst SEM；
Wherein, accelerating potential 15kV, amplification factor are 10000 times, and scale is 1 μm；
Fig. 2 schemes for CAT-1 catalyst TEM.
Specific embodiment
It elaborates below to the embodiment of the present invention：The present embodiment is carried out lower based on the technical solution of the present invention
Implement, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
The experimental method of actual conditions is not specified in example, usually according to normal condition.
The present invention provides a kind of preparation methods of body phase hydrogenation catalyst, and this method comprises the following steps：
(1) two kinds of group vib metallic compounds, at least one group VIII metal compound, alkaline precipitating agent and surface are lived
Property agent be disposably added to the water stirring, heat up as 60~95 DEG C, control ph be 7~9；Wherein, group VIII metal compound and
The weight ratio of two kinds of group vib metallic compounds is 1:3~3:1, two kinds of metal compound weight ratio examples of group vib are 1:3~3:
1；And
(2) binding agent is added in into step (1) system, filtering, washing, dry, shaping and roasting obtain body phase hydrogenation catalyst
Agent.
Below by taking NiMoW as an example, the solution of the present invention is described in detail, but be not limited to that this, any two
The present invention program can be achieved in group vib metallic compound and at least one group VIII metal compound.
Embodiment 1
By ammonium metatungstate 24.60g (0.1mol), ammonium heptamolybdate 17.65g (0.1mol), 58.2g nickel nitrates (0.2mol),
25% ammonium hydroxide 30ml (0.4mol), 3.64g (0.01mol) cetyl trimethylammonium bromide, which is added to, fills 500ml water
It in reactor, is heated under conditions of stirring, 1 DEG C/min of the rate of heat addition is heated to 95 DEG C, continues to stir 8h, solution gradually becomes
For grass green, aluminum hydroxide solid elastomer 40g is added in, continues to stir 1h, aging 2h, it is 7 to measure pH value, filters and washs to wash water pH
<7,120 DEG C of dry 4h, 400 DEG C of roasting 4h；Product adds in peptizing agent after being roasted and extrusion aid shaping prepares catalyst
CAT-1, the BET surface area of the catalyst is 212.0m2/ g, pore volume 0.26cm3/ g, intensity 160N/cm, average pore size
6.5nm, NiMoW metal oxide content are 70%.
Embodiment 2
With embodiment 1, nickel nitrate dosage is simply changed, is adjusted to 87.3g nickel nitrates (0.3mol), the catalyst of preparation
Product is named as CAT-2.
Embodiment 3
With embodiment 1, nickel nitrate simply is substituted with basic nickel carbonate, basic nickel carbonate dosage is 75.2g (0.2mol),
25% ammonium hydroxide 7.5ml (0.1mol), the catalyst product of preparation are named as CAT-3.
Embodiment 4
With embodiment 1, cetyl trimethylammonium bromide simply is substituted with Cetyltrimethylammonium bromide, dosage is
3.92g (0.01mol), the catalyst product of preparation are named as CAT-4.
Embodiment 5
With embodiment 1, reaction temperature is simply adjusted to 120 DEG C and is flowed back, the catalyst product of preparation is named as CAT-
5。
Embodiment 6
With embodiment 1, the reaction time is simply adjusted to 20h by 8h, the catalyst product of preparation is named as CAT-6.
Embodiment 7
With embodiment 1, calcination temperature is simply adjusted to 450 DEG C by 400 DEG C, the catalyst product of preparation is named as
CAT-7.
Comparative example
The NiMoW System Catalysts for being commercialized support type is taken to be named as CAT-C as reference agent.
Catalyst and comparative example commercialized catalyst property prepared by Examples 1 to 7 are listed in table 1.
1 embodiment of table and comparative example catalyst Physical Property Analysis
| Sample number into spectrum | Specific surface area/m2/g | Pore volume/mL/g | Average pore size/nm | Intensity/cm |
| CAT-1 | 212 | 0.26 | 6.5 | 160 |
| CAT-2 | 189 | 0.24 | 5.9 | 146 |
| CAT-3 | 208 | 0.25 | 6.2 | 154 |
| CAT-4 | 194 | 0.27 | 6.4 | 142 |
| CAT-5 | 203 | 0.26 | 6.2 | 146 |
| CAT-6 | 172 | 0.21 | 5.3 | 141 |
| CAT-7 | 135 | 0.20 | 6.9 | 130 |
| CAT-C | 265 | 0.31 | 5.8 | 186 |
For body phase hydrogenation catalyst, tenor is higher, how to improve intensity, specific surface area and pore volume, average pore size
It is difficult point.As can be seen from the table：Catalyst prepared by embodiment 1-7 different conditions shows good intensity, is catalyzed
Agent intensity is more than 130N/cm, has been fully able to meet requirement, in addition specific surface area, pore volume, average pore size and commercialization
Support type surface catalyst is quite even above surface type catalyst.
Using high sulfur-containing diesel inferior as raw material, to the catalyst prepared by Examples 1 to 7 and comparative example commercialized catalyst into
Comparison hydrogenation of having gone is evaluated, and is specifically shown in Table 2, table 3, and evaluation condition is reaction pressure 6.4Mpa, 340 DEG C of reaction temperature, air speed
2.0h-1, hydrogen-oil ratio 400:1.
2 feedstock property of table
3 embodiment catalyst of table and comparative example catalyst hydrogenation evaluation comparison
From table 3 it can be seen that bulk phase catalyst prepared in embodiment shows good hydrogenation activity, wherein
CAT-1 catalyst hydrogenation performance highests, hydrogenated products sulphur nitrogen content are respectively less than 1 μ g/g.And commercialized catalyst adds in comparative example
Sulphur, the nitrogen content of hydrogen production are respectively 15.6 μ g/g and 10.7 μ g/g, and higher than embodiment, the hydrogenation activity of catalyst is weaker.
Further CAT-1 catalyst is characterized using SEM, as shown in Figure 1, CAT-1 catalyst n iMoW complexs
Be granularity it is smaller and present high degree of dispersion, there is not agglomeration.It is small for the bulk phase catalyst of high metal content
Particle and present high degree of dispersion state mean in hydrogenation process have more activated centres.Using TEM to CAT-1
Catalyst vulcanization state active phase is characterized, as shown in Fig. 2, CAT-1 catalyst vulcanizations state activity is mutually with higher
The stacking number of plies, and flexuosity is showed, illustrate that catalyst has higher hydrodesulfurization activity.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (9)
1. a kind of preparation method of body phase hydrogenation catalyst, which is characterized in that this method comprises the following steps：
(1) by two kinds of group vib metallic compounds, at least one group VIII metal compound, alkaline precipitating agent and surfactant
Disposably it is added to the water stirring, heats up and reacted for 60~120 DEG C, control ph is 7~9, and the reaction time is 1~48h；Its
In, the weight ratio of group VIII metal compound and two kinds of group vib metallic compounds is 1:3~3:1, two kinds of metallization of group vib
Polymer weight ratio is 1:3~3:1；And
(2) binding agent is added in into step (1) system, filtering, washing, dry, shaping and roasting obtain body phase hydrogenation catalyst.
2. the preparation method of body phase hydrogenation catalyst according to claim 1, which is characterized in that the group VIII metal
It closes object and one or more of group is formed by cobalt nitrate, cobaltous sulfate, nickel sulfate, nickel chloride and nickel nitrate.
3. the preparation method of body phase hydrogenation catalyst according to claim 1, which is characterized in that the group vib metallization
Conjunction object is made of two kinds in group ammonium molybdate, sodium molybdate, ammonium tungstate, ammonium metatungstate and sodium tungstate.
4. the preparation method of body phase hydrogenation catalyst according to claim 1, which is characterized in that the alkaline precipitating agent is
Ammonium hydroxide.
5. the preparation method of body phase hydrogenation catalyst according to claim 1, which is characterized in that the surfactant is
Cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, Cetyltrimethylammonium bromide and octadecyl front three
Ammonium chloride forms one or more of group.
6. the preparation method of body phase hydrogenation catalyst according to claim 1, which is characterized in that the binding agent is molten for aluminium
Glue, sodium aluminate, aluminum hydroxide solid elastomer, Ludox and sodium metasilicate form one or more of group.
7. the preparation method of body phase hydrogenation catalyst according to claim 1, which is characterized in that the drying temperature is
100~130 DEG C.
8. the preparation method of body phase hydrogenation catalyst according to claim 1, which is characterized in that the calcination temperature is
350~450 DEG C.
9. the preparation method of body phase hydrogenation catalyst according to claim 1, which is characterized in that step (1) heating
Rate is 1 DEG C/min.
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