CN112934209A - High-desulfurization-activity hydrotreating catalyst carrier and preparation method of catalyst - Google Patents
High-desulfurization-activity hydrotreating catalyst carrier and preparation method of catalyst Download PDFInfo
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- CN112934209A CN112934209A CN202110164287.1A CN202110164287A CN112934209A CN 112934209 A CN112934209 A CN 112934209A CN 202110164287 A CN202110164287 A CN 202110164287A CN 112934209 A CN112934209 A CN 112934209A
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- boehmite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 230000000694 effects Effects 0.000 title claims abstract description 28
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 23
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000004898 kneading Methods 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007822 coupling agent Substances 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000007598 dipping method Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000007865 diluting Methods 0.000 claims abstract description 9
- 238000001125 extrusion Methods 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- 239000011148 porous material Substances 0.000 claims description 32
- 230000023556 desulfurization Effects 0.000 claims description 18
- 229920006395 saturated elastomer Polymers 0.000 claims description 16
- 238000005470 impregnation Methods 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003502 gasoline Substances 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- -1 fatty acid ester Chemical class 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 24
- 239000004408 titanium dioxide Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 241000219793 Trifolium Species 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- 241000219782 Sesbania Species 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 229910017318 Mo—Ni Inorganic materials 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
-
- 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
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/0234—Impregnation and coating simultaneously
-
- 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
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
The invention discloses a preparation method of a high-desulfurization-activity hydrotreating catalyst carrier and a preparation method of a catalyst, wherein the preparation method of the carrier comprises the following steps: diluting titanate coupling agent with solvent to prepare coating liquid for standby; dipping the coating liquid on the pseudo-boehmite powder in a dipping mode, and drying to obtain coating modified pseudo-boehmite; mixing the coating modified pseudo-boehmite with a peptizing agent, an extrusion aid and deionized water, kneading, molding, drying and roasting to obtain the hydrotreating catalyst carrier. The invention has the beneficial effects that: the invention has the advantages of less titanium dioxide consumption in the carrier, high utilization rate and simple preparation process of the carrier and the catalyst.
Description
Technical Field
The invention relates to a hydrocarbon hydrotreating catalyst carrier and a catalyst preparation method, in particular to a high-desulfurization-activity hydrotreating catalyst carrier and a catalyst preparation method.
Background
The fixed bed residual oil hydrotreating technology is the most mature heavy oil and residual oil processing and utilizing technology in the industry at present, has the advantages of low investment cost, low operation cost and safe and simple operation, and is the first choice of the heavy oil and residual oil hydrotreating technology.
Residual oil Hydrodesulfurization (HDS) is generally a Ni-Mo-based supported catalyst, and the carrier is mostly active alumina (gamma-Al) with high specific surface area and good thermal stability2O3). But gamma-Al2O3Is an inert carrier, the activity and antitoxicity of which still need to be improved, and in order to improve the activity of the catalyst and improve the interaction between the carrier and the active metal, Al is traditionally used2O3Hydrodesulfurization catalysts that are supported have been difficult to meet, and modification of the alumina support is often required.
TiO2Can improve the dispersion of active components on the surface of the carrier, promote the reduction of the active components, also has the function of an electronic promoter, can obviously improve the hydrodesulfurization performance of the catalyst in HDS reaction, however, TiO2Has the defects of small specific surface area, poor high-temperature thermal stability and the like, and restricts the industrial application of the TiO compound2For Al2O3Modifying to concentrate TiO at the same time2And Al2O3Its supported catalyst has high hydrodesulfurizing activity while retaining Al2O3Large specific surface area and good thermal stability. Such as:
chinese patent publication No. CN1227332C discloses a heavy oil and residual oil hydrodesulfurization catalyst and a preparation method thereof, wherein the catalyst uses gamma-Al2O3Using VIB group and VIII group metals as active components, using Ti as active adjuvant, introducing Ti in the process of aluminium hydroxide gel-forming under ultrasonic wave to make catalystThe agent is prepared by a full kneading method;
chinese patent publication No. CN1766048A discloses a preparation method of a hydrocarbon hydrotreating catalyst, which uses gamma-Al as a catalyst2O3The catalyst is prepared by a full mixing kneading method by taking VIB group and VIII group metals as active components and Ti as an active additive, wherein the Ti is prepared by dripping a titanium salt solution in the gelling process of preparing aluminum hydroxide by a carbonization method;
chinese patent publication No. CN104971706A discloses a method for preparing titanium oxide-alumina composite and its application, which comprises dissolving soluble aluminate in water to obtain solution A, dissolving tetraethyl titanate in benzene to obtain solution B, mixing ammonium bicarbonate and ammonia water to obtain ammonium water mixed solution C, precipitating solution A, B and C at 65-95 deg.C in parallel, controlling the flow of solution C to make the pH value of mixed solution of A, C and C appear alternately in the two ranges of 5.0-6.5 and 8.0-9.5, and staying for 6-10min, and calcining the precipitate to obtain composite.
In the above patent documents, titanium oxide is added during the synthesis of alumina, and the disadvantage is that titanium oxide is easily wrapped, so that the performance of titanium oxide is not exerted.
Chinese patent publication No. CN102247864A discloses a preparation method of a light oil hydrodesulfurization and denitrification catalyst, which comprises a carrier, an auxiliary agent, and an active metal; the carrier comprises alumina, titanium oxide and silicon oxide; the titanium oxide in the carrier is added into the macroporous alumina powder by metatitanic acid or nano-titanium dioxide and is introduced by kneading, and the defect is that the titanium oxide is not uniformly dispersed, thereby influencing the activity of the catalyst.
Chinese patent publication No. CN102049269A discloses a gasoline selective hydrogenation catalyst and a preparation method thereof, wherein the catalyst carrier is composed of alumina modified with titanium oxide or zirconium oxide, carbon and silicon oxide, wherein titanium oxide or zirconium oxide is introduced in the pulping process after alumina gelling; the disadvantage is that the preparation process is complicated.
At present, the traditional high desulfurization activity hydrotreating catalyst carrier has the problems of uneven titanium oxide dispersion, non-ideal pore structure and the like, so that the desulfurization activity of the catalyst is limited, and therefore, the development of the high desulfurization activity hydrotreating catalyst carrier with the advantages of uniform titanium oxide distribution, large pore volume, large pore diameter and the like is indispensable.
Disclosure of Invention
In order to better improve the catalytic performance of the desulfurization active catalyst, the invention provides a preparation method of a high-desulfurization-activity hydrotreating catalyst carrier with large pore volume and large pore diameter and a catalyst containing the carrier, which are particularly suitable for hydrodesulfurization of heavy oil and residual oil.
In order to realize the aim, the invention provides a hydrotreating catalyst carrier with high desulfurization activity and a preparation method of the catalyst; the preparation method of the hydrotreating catalyst carrier comprises the following steps:
(1) diluting titanate coupling agent with solvent to prepare coating liquid for standby;
(2) dipping the coating liquid obtained in the step (1) on the pseudo-boehmite powder in a dipping mode, and drying to obtain coating modified pseudo-boehmite;
(3) and (3) mixing the coating modified pseudo-boehmite obtained in the step (2) with a peptizing agent, an extrusion aid and deionized water, kneading, molding, drying and roasting to obtain the hydrotreating catalyst carrier.
Wherein, in the step (1): the solvent is one or more of gasoline, toluene, xylene, petroleum ether, solvent oil and benzene alcohol, and preferably gasoline; the titanate coupling agent is a mono-alkoxy fatty acid titanate coupling agent, a mono-alkoxy titanate or a mono-alkoxy tri-titanate, preferably a mono-alkoxy titanate; the titanium content in the coating liquid is 5.5g/L-20 g/L.
In the step (2): the impregnation mode is saturated impregnation or supersaturated impregnation, and saturated impregnation is preferred; the pseudo-boehmite powder is pore volume>1.0mL/g, specific surface area 280m2/g-340m2Per gram, 65-75% of dry basis, granularity>180 meshes; the drying temperature is 60-200 ℃, and the drying time is 2-8 hours.
In the step (3), the peptizing agent is one or more of nitric acid, acetic acid, citric acid and methyl cellulose, preferably nitric acid; the extrusion aid is sesbania powder or graphite, preferably sesbania powder;
the mixing weight ratio of the modified pseudo-boehmite, the peptizing agent, the extrusion assistant and the deionized water is 1: (0.005-0.06): (0.01-0.05): (0.8-1.8);
the molding is spherical, cylindrical strip, clover or clover;
the drying temperature is 100-160 ℃, and the drying time is 2-10 hours; the roasting temperature is 500-800 ℃, and the roasting time is 2-8 hours.
The hydrotreating catalyst carrier obtained by the preparation method has the following properties: the pore volume is 0.75-0.95 mL/g; the specific surface area is 180-250m 2/g; the content of titanium dioxide is 2.5-5.5 wt%.
In order to better achieve the above object, the present invention further provides a preparation method of a hydrotreating catalyst with high desulfurization activity, which specifically comprises: impregnating a carrier with an active metal component, drying and roasting to obtain the hydrotreating catalyst; wherein the carrier is a hydrotreating catalyst carrier prepared by the preparation method; the active metal component comprises VIII group metal and VIB group metal, wherein the VIII group metal is nickel and/or cobalt, and the VIB group metal is tungsten and/or molybdenum; based on the mass of the hydrotreating catalyst, the VIII group metal accounts for 1-8wt% of oxides, and the VIB group metal accounts for 8-20wt% of oxides; the active metal is loaded by adopting an impregnation method, and saturated impregnation is preferred; the drying temperature is 100-160 ℃, and the drying time is 2-10 hours; the roasting temperature is 400-600 ℃, and the roasting time is 1-5 hours.
The hydrotreating catalyst carrier obtained by the preparation method has the following properties: the pore volume is 0.55-0.85cm 3/g; the specific surface area is 140-220 m 2/g; the VIII group metal accounts for 1-8wt% of oxides, the VIB group metal accounts for 8-20wt% of oxides, and the content of titanium dioxide is 1.5-4.5 wt%.
The invention has the beneficial effects that: the titanium dioxide in the carrier is less in dosage and high in utilization rate, and the preparation processes of the carrier and the catalyst are simple; when the hydrotreating catalyst carrier is prepared, firstly, a titanate coupling agent is used for carrying out coating modification treatment on boehmite, alkoxy of the titanate coupling agent directly and chemically reacts with trace carboxyl or hydroxyl adsorbed on the surface of pseudo-boehmite powder to generate chemical combination on the interface of the pseudo-boehmite powder, and the titanate coupling agent has extremely unique performance and can form monomolecular films on the inner surface and the outer surface of the pseudo-boehmite powder, so that the support effect of a pore space is achieved, the structural stability and the anti-extrusion capacity of the pseudo-boehmite are improved, the prepared catalyst can retain more powder macropores, and the diffusion of reactants and products is facilitated; in addition, when the carrier is roasted at high temperature, the titanate coupling agent is decomposed, and the titanium dioxide is plated on the surface of the alumina, so that the characteristic of high performance of titanium oxide hydrodesulfurization is retained.
Detailed Description
In order to clearly illustrate the technical features of the present solution, the present solution is explained below by way of specific embodiments.
EXAMPLE 1 vector Z-1
The embodiment of the invention provides a preparation method of a hydrotreating catalyst carrier with high desulfurization activity, which comprises the following steps:
(1) diluting the monoalkoxy titanate by using solvent gasoline to prepare coating liquid with the titanium content of 10 g/L;
(2) the coating liquid is dipped in the pore volume of 1.15mL/g and the specific surface area of 320m in the same volume by adopting a saturated dipping mode2Drying the pseudo-boehmite powder with 70 percent of dry basis and 200 meshes of granularity for 6 hours at 120 ℃ to obtain modified pseudo-boehmite;
(3) 100g of modified pseudo-boehmite, 1.5g of nitric acid, 3g of sesbania powder and 135g of deionized water are respectively weighed, added into a kneading machine for kneading and molding into a clover shape, then dried for 5 hours at 120 ℃, and roasted for 3 hours at 600 ℃ to obtain the catalyst carrier Z-1 of the embodiment of the invention.
Example 2 vector Z-2
The embodiment of the invention provides a preparation method of a hydrotreating catalyst carrier with high desulfurization activity, which comprises the following steps:
(1) diluting monoalkoxy trititanate with toluene solvent to obtain coating liquid with titanium content of 18 g/L;
(2) the coating liquid is dipped in the pore volume of 1.15mL/g and the specific surface area of 320m in the same volume by adopting a saturated dipping mode2Drying the pseudo-boehmite powder with 70 percent of dry basis and 200 meshes of granularity for 6 hours at 120 ℃ to obtain modified pseudo-boehmite;
(3) 100g of modified pseudo-boehmite, 1.5g of nitric acid, 3g of sesbania powder and 135g of deionized water are respectively weighed, added into a kneading machine for kneading and molding into a clover shape, then dried for 5 hours at 120 ℃, and roasted for 3 hours at 600 ℃ to obtain the catalyst carrier Z-2 of the embodiment of the invention.
EXAMPLE 3 vector Z-3
The embodiment of the invention provides a preparation method of a hydrotreating catalyst carrier with high desulfurization activity, which comprises the following steps:
(1) diluting the monoalkoxy titanate by using solvent gasoline to prepare coating liquid with the titanium content of 10 g/L;
(2) the coating liquid is dipped in the pore volume of 1.05mL/g and the specific surface area of 300m in the same volume by adopting a saturated dipping mode2Drying the pseudo-boehmite powder with dry basis of 68 percent and granularity of 250 meshes for 6 hours at 120 ℃ to obtain modified pseudo-boehmite;
(3) 100g of modified pseudo-boehmite, 1.5g of nitric acid, 3g of sesbania powder and 135g of deionized water are respectively weighed, added into a kneading machine for kneading and molding into a clover shape, then dried for 5 hours at 120 ℃, and roasted for 3 hours at 600 ℃ to obtain the catalyst carrier Z-3 of the embodiment of the invention.
EXAMPLE 4 vector Z-4
The embodiment of the invention provides a preparation method of a hydrotreating catalyst carrier with high desulfurization activity, which comprises the following steps:
(1) diluting the monoalkoxy titanate by using solvent gasoline to prepare coating liquid with the titanium content of 8 g/L;
(2) the coating liquid is dipped in the pore volume of 1.15mL/g and the specific surface area of 320m in the same volume by adopting a saturated dipping mode2(g) 70% dry basis and 200 mesh particle size pseudo-boehmiteDrying the stone powder for 6 hours at 120 ℃ to obtain modified pseudo-boehmite;
(3) 100g of modified pseudo-boehmite, 1.0g of nitric acid, 2g of sesbania powder and 135g of deionized water are respectively weighed and added into a kneading machine for kneading and forming into a clover shape, and then the mixture is dried for 5 hours at 120 ℃ and roasted for 3 hours at 650 ℃ to obtain the catalyst carrier Z-4 of the embodiment of the invention.
In the step (2): the impregnation mode is saturated impregnation or supersaturated impregnation, and saturated impregnation is preferred; the pseudo-boehmite powder is pore volume>1.0mL/g, specific surface area 280m2/g-340m2Per gram, 65-75% of dry basis, granularity>180 meshes; the drying temperature is 60-200 ℃, and the drying time is 2-8 hours.
EXAMPLE 5 vector Z-5
The embodiment of the invention provides a preparation method of a hydrotreating catalyst carrier with high desulfurization activity, which comprises the following steps:
(1) diluting the mono-alkoxy fatty acid titanate coupling agent by using solvent petroleum ether to prepare coating liquid with the titanium content of 15 g/L;
(2) the coating liquid is dipped in the pore volume of 1.65mL/g and the specific surface area of 335m in the same volume by adopting a saturated dipping mode2Drying the pseudo-boehmite powder with 65 percent of dry basis and 200 meshes of granularity on the pseudo-boehmite powder for 3 hours at 200 ℃ to obtain modified pseudo-boehmite;
(3) 100g of modified pseudo-boehmite, 1.5g of nitric acid, 3g of graphite and 135g of deionized water are respectively weighed, added into a kneading machine for kneading and molding into a cylindrical strip shape or a spherical shape, dried at 120 ℃ for 5 hours and roasted at 800 ℃ for 3 hours to obtain the catalyst carrier Z-5 of the embodiment of the invention.
EXAMPLE 6 vector Z-6
The embodiment of the invention provides a preparation method of a hydrotreating catalyst carrier with high desulfurization activity, which comprises the following steps:
(1) diluting the mono-alkoxy tri-titanate by using solvent petroleum ether to prepare coating liquid with the titanium content of 7 g/L;
(2) the coating solution is dipped in the pore volume of 1.35mL/g and the specific surface area of 290m in the same volume by adopting a saturated dipping mode2Per g, 73 percent of dry basis,Drying the pseudo-boehmite powder with the granularity of 220 meshes for 8 hours at 80 ℃ to obtain modified pseudo-boehmite;
(3) 100g of modified pseudo-boehmite, 4.5g of acetic acid, 2g of sesbania powder and 150g of deionized water are respectively weighed, added into a kneading machine for kneading and molding into a clover shape, dried at 160 ℃ for 10 hours and roasted at 700 ℃ for 2 hours to obtain the catalyst carrier Z-6 of the embodiment of the invention.
Example 7 catalysts C-1, C-2, C-3
The embodiment of the invention provides a preparation method of a hydrotreating catalyst with high desulfurization activity, which comprises the following steps: soaking the carrier in the active metal component solution in a saturated soaking mode, drying at 120 ℃ for 6 hours, and roasting at 450 ℃ for 3 hours to respectively obtain the hydrotreating catalyst;
wherein, the carrier can be selected from hydrotreating catalyst carriers Z-1, Z-2 and Z-3 prepared in examples 1-3, and the corresponding hydrotreating catalysts are respectively C-1, C-2 and C-3;
the active metal component solution is a Mo-Ni active metal component solution comprising 15.0 wt% MoO3And 3.8 wt% NiO.
EXAMPLE 8 catalyst C-4
The embodiment of the invention provides a preparation method of a hydrotreating catalyst with high desulfurization activity, which comprises the following steps: soaking the carrier in the active metal component solution in a saturated soaking mode, drying at 120 ℃ for 6 hours, and roasting at 500 ℃ for 3 hours to obtain the hydrotreating catalyst;
wherein, the carrier can be the hydrotreating catalyst carrier Z-4 prepared in the embodiment 4, and the carrier is C-4 corresponding to a hydrotreating catalyst;
the active metal component solution is a Mo-Ni active metal component solution comprising 18.0 wt% MoO3And 4.2 wt% NiO.
EXAMPLE 9 catalyst C-5
The embodiment of the invention provides a preparation method of a hydrotreating catalyst with high desulfurization activity, which comprises the following steps: soaking the carrier in the active metal component solution in a saturated soaking mode, drying at 160 ℃ for 2 hours, and roasting at 400 ℃ for 5 hours to obtain the hydrotreating catalyst;
wherein the carrier is the hydrotreating catalyst carrier Z-5 prepared in example 5, and the carrier is C-5 corresponding to a hydrotreating catalyst;
the active metal component solution is a Mo-Ni active metal component solution comprising 10.0 wt% MoO3And 6.3 wt% NiO.
EXAMPLE 10 catalyst C-6
The embodiment of the invention provides a preparation method of a hydrotreating catalyst with high desulfurization activity, which comprises the following steps: soaking the carrier in the active metal component solution in a saturated soaking mode, drying at 100 ℃ for 8 hours, and roasting at 450 ℃ for 4 hours to obtain the hydrotreating catalyst;
wherein the carrier is the hydrotreating catalyst carrier Z-6 prepared in example 6, and the corresponding hydrotreating catalyst is C-6;
the active metal component solution is a Mo-Ni active metal component solution comprising 15.0 wt% MoO3And 2.5 wt% NiO.
Comparative example 1 Carrier DZ-1, catalyst DC-1
Comparative example 1 is a catalyst support DZ-1 and catalyst DCThe preparation method of the compound comprises the following steps:
weighing 100g of pseudo-boehmite powder with the pore volume of 1.15mL/g, the specific surface area of 320m2/g, the dry basis of 70% and the granularity of 200 meshes, adding the pseudo-boehmite powder into a kneading machine, respectively weighing 1.5g of nitric acid, 3g of sesbania powder and 135g of deionized water, adding the mixture into the kneading machine for kneading and forming into a clover shape, drying the clover shape at 120 ℃ for 5 hours, and roasting the clover shape at 600 ℃ for 3 hours to obtain a catalyst carrier DZ-1；
Preparing a mixture containing 15.0 wt% of MoO33.8 wt% NiO, and impregnating DZ-1 carrier, dried at 120 ℃ for 6 hours and then calcined at 450 ℃ for 3 hours to obtain catalyst DC-1。
Comparative example 2 Carrier DZ-2, catalyst DC-2
Comparative example 2 is a catalyst support DZ-2 and catalyst DCThe preparation method of the compound comprises the following steps:
weighing 100g of pseudo-boehmite powder with the pore volume of 1.15mL/g, the specific surface area of 320m2/g, the dry basis of 70% and the particle size of 200 meshes, adding the pseudo-boehmite powder into a kneading machine, respectively weighing 21g of monoalkoxy trititanate, 1.5g of nitric acid, 3g of sesbania powder and 135g of deionized water, adding the mixture into the kneading machine for kneading and forming into a clover shape, drying the mixture at 120 ℃ for 5 hours, and roasting the mixture at 600 ℃ for 3 hours to obtain a catalyst carrier DZ-2；
Preparing a mixture containing 15.0 wt% of MoO33.8 wt% NiO, and impregnating DZ-2 carrier, dried at 120 ℃ for 6 hours and then calcined at 450 ℃ for 3 hours to obtain catalyst DC-2。
Comparative example 3 Carrier DZ-3, catalyst DC-3
Comparative example 2 is a catalyst support DZ-3 and catalyst DCThe preparation method of the compound comprises the following steps:
weighing 100g of pseudo-boehmite powder with the pore volume of 1.15mL/g, the specific surface area of 320m2/g, the dry basis of 70% and the particle size of 200 meshes, adding the pseudo-boehmite powder into a kneader, respectively weighing 3.2g of metatitanic acid (containing 85% of titanium dioxide and 200 meshes), 1.5g of nitric acid, 3g of sesbania powder and 135g of deionized water, adding the materials into the kneader to be kneaded and formed into a clover shape, drying the clover shape at 120 ℃ for 5 hours, and roasting the clover shape at 600 ℃ for 3 hours to obtain a catalyst carrier DZ-3；
Preparing a mixture containing 15.0 wt% of MoO33.8 wt% NiO, and impregnating DZ-3 carrier, dried at 120 ℃ for 6 hours and then calcined at 450 ℃ for 3 hours to obtain catalyst DC-3。
Comparative experiment 1: analysis of physical Properties
In this comparative test, the specific surface area, pore volume, pore distribution and other characteristics of the carrier and catalyst of each of the above examples and comparative examples were analyzed by a low-temperature liquid nitrogen adsorption method, and the test results are shown in table 1.
Table 1 comparative examples catalyst carrier and catalyst analysis results
As shown in Table 1, the boehmite is subjected to coating modification treatment by using the titanate coupling agent, so that the support effect of the pore space is achieved, the structural stability and the anti-extrusion capacity of the pseudo-boehmite are improved, and the prepared carrier and the prepared catalyst have larger pore volume and pore diameter; specifically, compared with the comparative examples, the pore volumes of the carrier and the catalyst obtained by the methods of the examples 1 to 4 of the invention are obviously larger than the pore volumes of 3 comparative examples, the pore distribution rate of the carrier and the catalyst of the examples 1 to 4 of the invention, which is larger than 6nm, is at least 10% higher than that of the 3 comparative examples, and the carrier and the catalyst prepared by the method of the invention have larger pore volumes and pore diameters, which are beneficial to the diffusion of reactants and products.
Comparative experiment 2: analysis of catalytic Properties of catalyst
The catalysts C-1, C-4 and D to be prepared in the experimentC-1 and DC-2, evaluation was performed on a 200mL residuum hydrotreater, and the evaluation results are shown in table 2.
Table 2 evaluation results of catalysts prepared in examples and comparative examples
As shown in Table 2, the catalyst prepared by the preparation method of the invention has fewer small holes, larger pore volume and pore diameter, and the catalyst has higher scale capacity and smooth reactant and product diffusion channels while the utilization rate of the catalyst is improved, so that the catalyst has higher impurity removal rate.
Claims (10)
1. A preparation method of a hydrotreating catalyst carrier with high desulfurization activity is characterized by comprising the following steps:
(1) diluting titanate coupling agent with solvent to prepare coating liquid for standby;
(2) dipping the coating liquid obtained in the step (1) on the pseudo-boehmite powder in a dipping mode, and drying to obtain coating modified pseudo-boehmite;
(3) and (3) mixing the coating modified pseudo-boehmite obtained in the step (2) with a peptizing agent, an extrusion aid and deionized water, kneading, molding, drying and roasting to obtain the hydrotreating catalyst carrier.
2. The production method according to claim 1, wherein in the step (1): the solvent is one or more of gasoline, toluene, xylene, petroleum ether and solvent oil;
the titanate coupling agent is of a monoalkoxy fatty acid ester type.
3. The production method according to claim 1 or 2, wherein in the step (1), the titanate coupling agent is a monoalkoxy fatty acid titanate coupling agent, a monoalkoxy titanate, or a monoalkoxy tri-titanate.
4. The method according to claim 1, wherein the titanium content in the coating liquid is 5.5g/L to 20 g/L.
5. The production method according to claim 1, wherein in the step (2):
the impregnation mode is saturated impregnation or supersaturated impregnation.
6. The method according to claim 1, wherein in the step (2), the boehmite powder is pore volume>1.0mL/g, specific surface area 280m2/g-340m2Per gram, 65-75% of dry basis, granularity>180 meshes; the drying temperature is 60-200 ℃, and the drying time is 2-8 hours.
7. The production method according to claim 1, wherein, in the step (3),
the peptizing agent is one or more of nitric acid, acetic acid, citric acid and methyl cellulose;
the extrusion aid is sesbania powder or graphite;
the mixing weight ratio of the modified pseudo-boehmite, the peptizing agent, the extrusion assistant and the deionized water is 1: (0.005-0.06): (0.01-0.05): (0.8-1.8);
the drying temperature is 100-160 ℃, and the drying time is 2-10 hours; the roasting temperature is 500-800 ℃, and the roasting time is 2-8 hours.
8. A preparation method of a hydrotreating catalyst with high desulfurization activity is characterized by comprising the following steps: impregnating a carrier with an active metal component, drying and roasting to obtain the hydrotreating catalyst; wherein the carrier is a carrier for a hydroprocessing catalyst prepared by the production method as recited in any one of claims 1 to 7.
9. The method of claim 8, wherein the active metal component comprises a group VIII metal and a group VIB metal, wherein the group VIII metal is nickel and/or cobalt, and the group VIB metal is tungsten and/or molybdenum.
10. The production method according to claim 9,
based on the mass of the hydrotreating catalyst, the VIII group metal accounts for 1-8wt% of oxides, and the VIB group metal accounts for 8-20wt% of oxides;
the drying temperature is 100-160 ℃, and the drying time is 2-10 hours; the roasting temperature is 400-600 ℃, and the roasting time is 1-5 hours.
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| US20200222887A1 (en) * | 2017-07-21 | 2020-07-16 | Albemarle Europe Srl | Hydrotreating catalyst with a titanium containing carrier and organic additive |
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| JPH02239169A (en) * | 1989-03-09 | 1990-09-21 | Sekisui Plastics Co Ltd | Porous titania sintered body and production thereof |
| JP2005000833A (en) * | 2003-06-12 | 2005-01-06 | Toyota Motor Corp | Catalyst for purifying exhaust gas and method for purifying exhaust gas |
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