CN110935466B - Preparation method of hydrotreating catalyst - Google Patents
Preparation method of hydrotreating catalyst Download PDFInfo
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- CN110935466B CN110935466B CN201811114175.XA CN201811114175A CN110935466B CN 110935466 B CN110935466 B CN 110935466B CN 201811114175 A CN201811114175 A CN 201811114175A CN 110935466 B CN110935466 B CN 110935466B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 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 127
- 239000011148 porous material Substances 0.000 claims abstract description 75
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 37
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 22
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 18
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 18
- 238000005470 impregnation Methods 0.000 claims abstract description 17
- 238000007789 sealing Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005507 spraying Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000009738 saturating Methods 0.000 claims abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
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- -1 VIB group metals Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 3
- 238000001465 metallisation Methods 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 7
- 229910000480 nickel oxide Inorganic materials 0.000 description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910018104 Ni-P Inorganic materials 0.000 description 2
- 229910018536 Ni—P Inorganic materials 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 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 description 1
- 229940024545 aluminum hydroxide Drugs 0.000 description 1
- 229940024546 aluminum hydroxide gel Drugs 0.000 description 1
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical group O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
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- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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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
- 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
-
- 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
- C10G2300/10—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
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
-
- 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
- C10G2300/205—Metal content
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a preparation method of a hydrotreating catalyst, which comprises the following steps: (1) unsaturated spraying and impregnating the hydrogenation active component impregnating solution I into a macroporous alumina carrier, and then drying and roasting to prepare a carrier SI; (2) mixing the carrier SI, ammonium bicarbonate and water, then carrying out sealing heat treatment, drying and roasting the heat-treated materials to obtain a carrier SII; (3) and (3) saturating and spraying the hydrogenation active component impregnation liquid II to impregnate the carrier SII, and then drying and roasting to prepare the hydrogenation catalyst. The catalyst prepared by the method has proper action of active metal and a carrier, simultaneously has high content of active metal with a surface rod-shaped structure and higher activity, and the surface rod-shaped structure forms an open pore channel, so that the metal deposition resistance and the carbon deposition resistance of the catalyst are improved, and the catalyst is suitable for the hydrotreating process of heavy oil.
Description
Technical Field
The invention relates to the field of catalysis, in particular to a method for hydrotreating a catalyst, which is particularly suitable for the field of residue hydrogenation.
Background
With the aggravation of crude oil deterioration and heaviness, the efficient conversion of heavy oil and the improvement of the yield of light oil products become an important trend in the development of oil refining technology. The residue fixed bed hydrogenation technology is an effective means for realizing the high-efficiency conversion of heavy oil. By adopting the technical route, the impurities such as metal, sulfur, nitrogen, carbon residue and the like in the residual oil can be effectively removed, high-quality feed is provided for catalytic cracking, and the strict environmental protection regulation requirements are met while the yield of light oil products is increased. The hydrodemetallization catalyst mainly removes metal impurities including nickel and vanadium in raw oil, so as to protect downstream catalysts from losing activity due to deposition of a large amount of metals. Hydrodemetallization catalysts generally consist of an alumina support carrying an active metal component. The carrier is used as a framework of the catalyst, reaction channels and surfaces are provided, and meanwhile, the active metal can be highly dispersed, so that the channel structure of the carrier has an important influence on the reaction performance of the catalyst.
CN101890372A discloses an alumina carrier and a preparation method thereof. The alumina carrier is aluminum hydroxide gel prepared by a fused salt super-solubilization micelle method as a raw material, and the gel contains a surfactant and hydrocarbon components, so that after molding and roasting, nano alumina particles formed by dehydrating polymerized aluminum hydroxide still have a rod-like basic structure and are randomly stacked into a frame structure. The process of preparing the macroporous alumina carrier by the technology is complex, in addition, the alumina with the rod-like structure prepared by the technology is in disordered accumulation, the formed pore channel is large, and although the diffusion of macromolecules such as colloid, asphaltene and the like is facilitated, the time for reaction molecules to stay in the pore channel of the catalyst is short, so that the activity of the catalyst is low.
CN106268969A discloses a catalyst carrier and its preparation method and its demetallization catalyst. The catalyst carrier is formed by stacking a plurality of nano rod-shaped alumina monomers, the catalyst carrier is provided with open pore channels, the length of each nano rod-shaped alumina monomer is 100-500nm, and the diameter of each nano rod-shaped alumina monomer is 10-50 nm. The catalyst carrier is formed by stacking a plurality of nano-rod-shaped alumina monomers, the formed pore channel is large, the diffusion of macromolecules such as colloid, asphaltene and the like is facilitated, and the defect that the activity of the catalyst is low due to the fact that reaction molecules stay in the pore channel of the catalyst for a short time is also existed.
CN102861617A discloses a preparation method of an alumina carrier with a double-pore structure. The method comprises weighing a certain amount of pseudoboehmite dry glue powder, mixing with a proper amount of peptizer and extrusion aid uniformly, then adding a proper amount of ammonium bicarbonate aqueous solution into the above materials, kneading the obtained materials into a plastic body, extruding the plastic body into strips, placing the formed materials into a sealed container, carrying out hydrothermal treatment, and roasting to obtain the alumina carrier. The pore channels of the alumina carrier prepared by the technology are uniformly distributed in the radial direction of the catalyst, and in the process of the hydrogenation demetallization reaction, metal impurities such as nickel, vanadium and the like in a metal compound are deposited on the surface layer and the near surface layer of the catalyst, so that the pore channels of the catalyst are blocked, and the catalyst is inactivated.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a hydrotreating catalyst, the active metal of the catalyst prepared by the method has proper action with a carrier, the active metal content of the surface rod-shaped structure is high, the catalyst has higher activity, and the surface rod-shaped structure forms an open pore channel, so that the metal deposition resistance and the carbon deposition resistance of the catalyst are improved, and the method is suitable for the hydrotreating process of heavy oil.
The preparation method of the hydrotreating catalyst comprises the following steps:
(1) and (3) unsaturated spraying and impregnating the hydrogenation active component impregnating solution I into the macroporous alumina carrier, and then drying and roasting to prepare the modified alumina carrier SI.
(2) Mixing the modified alumina carrier SI, ammonium bicarbonate and water obtained in the step (1), then carrying out sealing heat treatment, drying and roasting the heat-treated material to obtain a carrier SII, wherein the carrier SII is an alumina carrier with a surface growing rod-shaped structure;
(3) and (3) saturating and spraying the hydrogenation active component impregnation liquid II to impregnate the carrier SII, and then drying and roasting to prepare the hydrogenation catalyst.
In the method, the hydrogenation active component impregnation liquid is a solution containing VIB and/or VIII group metals, the VIB group metal is molybdenum and/or tungsten, and the VIII group metal is cobalt and/or nickel; the hydrogenation active component impregnation liquid can be one of an acid solution, an aqueous solution or an ammonia solution containing the hydrogenation active component.
In the method, the content of VIB group metal in the hydrogenation active component impregnating solution I in the step (1) is 2.0-3.5g/100ml calculated by metal oxide, and the content of VIII group metal is 0.5-1.5g/100ml calculated by metal oxide. The dosage of the active component impregnation liquid I is 5-10% of the saturated water absorption capacity of the macroporous oxygen carrier in the step (1), the drying temperature is 100-160 ℃, and the drying time is 6-10 hours. The roasting temperature is 450-550 ℃, and the roasting time is 4-6 hours.
In the method, the properties of the macroporous alumina carrier in the step (1) are as follows: the specific surface area is 150-260m2The pore volume is 0.7-1.2mL/g, and the average pore diameter is 10-30 nm; the preferred pore size distribution is as follows: the pore volume of pores with the diameter of less than 8nm accounts for less than 50 percent of the total pore volume, the pore volume of pores with the diameter of 8-20nm accounts for 30-50 percent of the total pore volume, the pore volume of pores with the diameter of more than 100nm accounts for less than 15 percent of the total pore volume, the pore volume of pores with the diameter of more than 1000nm accounts for less than 2 percent of the total pore volume, and further the pore volume of pores with the diameter of more than 1000nm accounts for less than 1 percent of the total pore volume; the macroporous alumina carrier can be prepared by a commercial product or a conventional method, and the pore-expanding method can be a conventional method, such as adding a pore-expanding agent. In the preparation method, the pore-expanding agent in the step (1) is one or a mixture of carbon black powder, wood chips, polyvinyl alcohol and water-soluble starch. The particle size of the physical pore-enlarging agent is less than 1 mu m, preferably less than 800 nm. The addition amount of the pore-expanding agent is 3-5 wt% of the weight of the alumina.
In the method of the present invention, the preparation method of the macroporous alumina carrier in step (1) may adopt the following method: kneading the pseudo-boehmite and the pore-expanding agent for molding, drying and roasting the molded product to obtain the alumina carrier. The kneading molding is carried out by adopting a conventional method in the field, and in the molding process, conventional molding aids, such as one or more of peptizing agents, extrusion aids and the like can be added according to the needs. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid and the like; the addition amount of the peptizing agent is 0.5-3 wt% of the weight of the alumina carrier. The extrusion aid is sesbania powder; the addition amount of the extrusion aid is 0.1-0.5 wt% of the weight of the alumina carrier. The drying temperature is 100-160 ℃, and the drying time is 6-10 hours; the roasting temperature is 600-750 ℃, and the roasting time is 4-6 hours; the calcination is carried out in an oxygen-containing atmosphere, preferably an air atmosphere. The shape of the macroporous alumina carrier can be the shape of a conventional alumina carrier, such as a sphere, the particle diameter of the macroporous alumina carrier is generally 0.5-8.0mm, such as a strip shape, a clover shape and the like, the diameter of the macroporous alumina carrier is about 0.2-3.0mm, and the length of the macroporous alumina carrier is about 0.5-8.0 mm.
In the method, the mass ratio of the ammonium bicarbonate to the modified alumina carrier SI to the water in the step (2) is 1.75:1:5-3:1:10, and the ammonium bicarbonate can be added independently or mixed with the water firstly and added in the form of an ammonium bicarbonate solution.
In the method of the present invention, the sealing heat treatment conditions in step (2) are as follows: the temperature is 120-160 ℃, the constant temperature treatment time is 4-8 hours, and the heating rate is 5-20 ℃/min.
In the method of the invention, the step (2) is preferably carried out before the sealing heat treatment, the sealing pretreatment is carried out, the pretreatment temperature is 60-100 ℃, the constant temperature treatment time is 2-4 hours, the temperature rise rate before the pretreatment is 10-20 ℃/min, the temperature rise rate after the pretreatment is 5-10 ℃/min, and the temperature rise rate after the pretreatment is at least 3 ℃/min, preferably at least 5 ℃/min lower than that before the pretreatment.
In the method of the invention, the drying temperature in the step (2) is 100-160 ℃, and the drying time is 6-10 hours. The roasting temperature is 450-750 ℃, and the roasting time is 4-6 hours.
In the method, the support SII is an alumina support with a surface growing rod-shaped structure, and comprises main alumina and rod-shaped alumina, wherein at least part of the rod-shaped alumina is distributed on the outer surface of the main alumina support, and the rod-shaped alumina is 1-12 mu m long and 100-300nm in diameter.
In the method of the present invention, in the support SII, the alumina having a rod-like structure is substantially distributed on the outer surface of the main alumina. Wherein the length of the rod-shaped alumina distributed on the outer surface of the main alumina is 3-8 μm, namely, the length of the rod-shaped alumina on the outer surface of the main alumina is 3-8 μm, wherein more than 85% of the rod-shaped alumina by weight is on the outer surface of the main alumina. Wherein, the alumina with a rod-shaped structure on the outer surface of the main alumina carrier is randomly and mutually crossly distributed. Wherein one end of at least part of the rod-shaped alumina is attached to the outer surface of the main alumina, and preferably one end of at least part of the rod-shaped alumina is combined on the outer surface of the main alumina, and the other end of the rod-shaped alumina extends outwards and is integrated with the main alumina; further preferably, one end of the alumina having a rod-like structure on the outer surface of the main alumina is bonded to the outer surface of the main alumina, and the other end thereof is protruded outward to be integrated with the main alumina.
In the method of the invention, the coverage rate of the rod-shaped alumina on the outer surface of the main alumina of the carrier SII is 70% -95%, wherein the coverage rate refers to the percentage of the surface of the main alumina, which is occupied by the rod-shaped alumina, on the outer surface of the main alumina.
In the method of the present invention, the properties of the vector SII are as follows: the specific surface area is 150-260m2The pore volume is 0.75-1.5mL/g, the diameters of several pores are 10-50nm, 100-500nm and 500-1000nm, and the crushing strength is 110-140N/cm.
In the method, the content of the VIB group metal in the hydrogenation active component impregnating solution II in the step (3) is 6.5-15.0g/100ml calculated by metal oxide, and the content of the VIII group metal is 1.5-3.5g/100ml calculated by metal oxide. The drying temperature is 100-160 ℃, and the drying time is 6-10 hours. The roasting temperature is 450-550 ℃, and the roasting time is 4-6 hours.
The method of the invention has the following advantages:
(1) the modified alumina with novel form is taken as a carrier, the modified alumina carrier comprises main alumina and rod-shaped alumina, wherein rod-shaped alumina is distributed on the outer surface of the main alumina, and the rod-shaped alumina is crossed to form loose through pore channels, which is beneficial to being influenced by the diffusion effect of the surface pore structure, and can prevent metal elements from depositing on the outer surface of the alumina carrier to block the pore channels, so that the prepared hydrotreating catalyst has excellent permeability and higher metal content, and the blockage of the pore channels on the surface of the catalyst due to metal deposition is reduced, thereby not only ensuring the activity of the catalyst, but also ensuring the good stability of the catalyst, and prolonging the operation period of the device.
(2) According to the invention, part of active metal components are pre-impregnated on the surface of the macroporous alumina carrier, the active metal components are loaded on the surface of the alumina carrier in an oxide form during roasting, and when the modified carrier is subjected to sealing heat treatment in an ammonium bicarbonate aqueous solution, the active metal is in a closed carbon dioxide and ammonia gas and hydrothermal environment, and is redispersed on the surface of the carrier under the condition, so that the action of the active metal and the carrier is greatly improved, and the activity of the final catalyst is improved.
(3) The invention mixes the modified alumina carrier with ammonium bicarbonate and water, then carries out sealing heat treatment, and in the heat treatment process, the alumina reacts with the ammonium bicarbonate to form NH4Al(OH)2CO3NH on the outer surface4Al(OH)2CO3Grow outwards to form a rod-shaped structure, and no rod-shaped structure is generated in the nanometer-scale pore canal. External surface NH during subsequent firing4Al(OH)2CO3Decomposed to form a rod-shaped alumina structure, and NH is generated inside the pore channel4Al(OH)2CO3The carbon dioxide, ammonia and hydrothermal effect that take place to decompose the production play fine reaming effect simultaneously, make the connectivity of pore more again, the pore is more even.
(4) The catalyst prepared by the method is suitable for the hydrotreating process of heavy raw oil, and is particularly suitable for serving as a hydrogenation protective agent, a demetallization agent and the like.
Drawings
Fig. 1 is an SEM image of a cut surface of the support I prepared in example 1.
Wherein the reference numbers are as follows: 1-bulk alumina, 2-rod alumina.
Detailed Description
The technical solutions of the present invention are further illustrated below with reference to examples, but are not limited to the following examples. Wherein, in the present invention, wt% represents a mass fraction.
The BET method: application N2Physical adsorption-desorption characterization of the pore structures of the carriers of the examples and the comparative examples, the specific operations are as follows: adopting ASAP-2420 type N2And the physical adsorption-desorption instrument is used for characterizing the pore structure of the sample. A small amount of samples are taken to be treated for 3 to 4 hours in vacuum at the temperature of 300 ℃, and finally, the product is placed under the condition of liquid nitrogen low temperature (-200 ℃) to be subjected to nitrogen absorption-desorption test. Wherein the specific surface area is obtained according to a BET equation, and the distribution rate of the pore volume and the pore diameter below 20nm is obtained according to a BJH model.
Mercury pressing method: the pore diameter distribution of the carriers of the examples and the comparative examples is characterized by applying a mercury porosimeter, and the specific operation is as follows: and characterizing the distribution of sample holes by using an American microphone AutoPore9500 full-automatic mercury porosimeter. The samples were dried, weighed into an dilatometer, degassed for 30 minutes while maintaining the vacuum conditions given by the instrument, and filled with mercury. The dilatometer was then placed in the autoclave and vented. And then carrying out a voltage boosting and reducing test. The mercury contact angle is 130 degrees, and the mercury interfacial tension is 0.485N.cm-1The distribution of pore diameters above 100nm is determined by mercury intrusion.
A scanning electron microscope is used for representing the microstructure of the alumina carrier, and the specific operation is as follows: and a JSM-7500F scanning electron microscope is adopted to represent the microstructure of the carrier, the accelerating voltage is 5KV, the accelerating current is 20 muA, and the working distance is 8 mm.
Example 1
(1) Weighing 300 g of pseudo-boehmite (self-made by an aluminum sulfate method and with the dry basis weight content of 70 wt%), 7 g of carbon black powder and 1g of sesbania powder, uniformly mixing the materials physically, adding a proper amount of aqueous solution dissolved with 4.5 g of acetic acid, kneading, extruding into strips, drying the formed product at 140 ℃ for 6 hours, and roasting the dried product at 750 ℃ for 5 hours to obtain the macroporous alumina carrier, wherein the macroporous alumina carrier has the following properties: specific surface area of 176m2The pore volume is 0.81mL/g, and the pore distribution is as follows: the pore volume of pores with diameter less than 8nm accounts for 26% of the total pore volume, the pore volume of pores with diameter of 8-20nm accounts for 31% of the total pore volume, and the pore diameterThe pore volume of pores with the diameter of more than 100nm accounts for 4 percent of the total pore volume, and the pores with the diameter of more than 1000nm accounts for 0.8 percent of the total pore volume.
(2) Weighing 100 g of the macroporous alumina carrier in the step (1), placing the macroporous alumina carrier in a spray-dip rolling pot, and adding 8.4ml of Mo-Ni-P solution (MoO in a dipping solution)3Concentration of 3.2g/100ml and NiO concentration of 0.94g/100 ml), and drying the impregnated materials at 120 ℃ for 6 hours, and then roasting at 500 ℃ for 5 hours to obtain the modified alumina carrier.
(3) Weighing 100 g of the modified alumina carrier in the step (2) and 230 g of ammonium bicarbonate, adding 930 g of distilled water into the materials, stirring for 20 minutes, transferring the mixed materials into a high-pressure kettle, sealing, heating to 95 ℃ at a speed of 10 ℃/min, keeping the temperature for 3 hours, heating to 140 ℃ at a speed of 5 ℃/min, keeping the temperature for 5.5 hours, drying the carrier at 110 ℃ for 6 hours, and roasting the dried carrier at 700 ℃ for 5 hours to obtain the alumina carrier S-1, wherein the properties of the carrier are shown in Table 1.
(4) Weighing 50 g of alumina carrier in the step (3), and adding 100ml of Mo-Ni-P solution (MoO in impregnating solution)3Concentration of 8.68g/100ml, NiO concentration of 2.92g/100 ml), filtering to remove excessive solution, drying at 120 ℃ for 6 hours, and roasting at 500 ℃ for 5 hours to obtain a hydrotreating catalyst C1, wherein the content of molybdenum oxide and nickel oxide in the catalyst are respectively 8.89wt% and 2.98 wt%.
Example 2
Same as example 1 except that MoO in the active metal impregnation liquid of step (2)3The concentration is 2.9g/100ml, the NiO concentration is 0.83g/100ml, and the consumption of the active metal impregnation liquid is 7.3 ml; in the step (3), the addition amount of ammonium bicarbonate is 265 g, the sealing pretreatment temperature is 80 ℃, the treatment time is 4 hours, the heat treatment temperature is 130 ℃, and the treatment time is 6.5 hours, so that the alumina carrier S-2 is prepared, wherein the properties of the carrier are shown in Table 1. MoO in the active metal impregnation liquid in the step (4)3The catalyst C2 was prepared at a concentration of 8.51g/100ml and a NiO concentration of 2.85g/100ml, with a molybdenum oxide content of 8.71wt% and a nickel oxide content of 2.85 wt%.
Example 3
Same as example 1 except for step (2) active metal impregnationIn-liquid MoO3The concentration is 2.6g/100ml, the NiO concentration is 1.1g/100ml, and the dosage of the active metal impregnation liquid is 9.1 ml; and (3) adding 243 g of ammonium bicarbonate, performing heat treatment at 150 ℃ for 4 hours to obtain the alumina carrier S-3, wherein the properties of the carrier are shown in Table 1. MoO in the active metal impregnation liquid in the step (4)3The treated catalyst C3 was prepared at a concentration of 8.84g/100ml and a NiO concentration of 2.79g/100ml, with a molybdenum oxide content of 9.03wt% and a nickel oxide content of 2.91 wt%.
Example 4
Same as example 1 except that MoO in the active metal impregnation liquid of step (2)3The concentration is 3.4g/100ml, the NiO concentration is 0.75g/100ml, and the dosage of the active metal impregnation liquid is 6.5 ml; and (3) adding 180 g of ammonium bicarbonate, performing heat treatment at 120 ℃ for 7 hours to obtain the alumina carrier S-4, wherein the properties of the carrier are shown in Table 1. MoO in the active metal impregnation liquid in the step (4)3The treated catalyst C4 was prepared at a concentration of 8.46g/100ml and a NiO concentration of 3.13g/100ml, with a molybdenum oxide content of 8.65wt% and a nickel oxide content of 3.17wt% in the catalyst.
Comparative example 1
Similar to example 1, except that the alumina carrier of step (2) was added to distilled water for sealing heat treatment without adding ammonium bicarbonate, and ammonium bicarbonate of the same mass was added during the molding of the macroporous alumina carrier to prepare a comparative alumina carrier S-5, the properties of which are shown in table 1, and the molybdenum oxide content and the nickel oxide content in the catalyst were 8.93wt% and 3.02wt%, respectively.
Comparative example 2
A comparative alumina support S-6 was prepared as in example 1 except that ammonium bicarbonate was replaced by ammonium carbonate of the same mass, the properties of the support are shown in Table 1, and the catalyst contained 8.95wt% molybdenum oxide and 3.04wt% nickel oxide.
Comparative example 3
The same as example 1, except that the same amount of active metal was loaded on the alumina carrier by one-step impregnation, the properties of the comparative carrier S-7 are shown in Table 1, and the content of molybdenum oxide and nickel oxide in the catalyst is 8.91wt% and 3.0 wt%.
Comparative example 4
A comparative example alumina support was prepared as in example 1, except that the heat treatment temperature was 220 ℃.
Comparative example 5
A comparative example alumina support was prepared as in example 1, except that the heat treatment temperature was 80 ℃.
Examples 1-4 and comparative example 3 the prepared alumina carrier comprises main alumina and rod-like alumina, wherein at least part of the rod-like alumina is distributed on the outer surface of the main alumina carrier, and the rod-like alumina has the length of 1-12 mu m and the diameter of 100-300 nm. The alumina carrier prepared in comparative examples 1, 2, 4 and 5 has no alumina with a rod-like structure on the surface.
TABLE 1 Properties of the alumina Supports
Evaluation of catalytic performance:
the hydrotreatment catalyst (C1-C7) prepared above was evaluated for catalytic performance by the following method:
the vacuum residue listed in Table 2 was used as a raw material, and the catalytic performance of C1-C7 was evaluated on a fixed bed residue hydrogenation reactor, the catalyst diameter was 2-3mm long strips, the reaction temperature was 380 ℃, the hydrogen partial pressure was 13MPa, and the liquid hourly volume space velocity was 1.0 hour-1The volume ratio of hydrogen to oil was 1000, the content of each impurity in the produced oil was measured after 2000 hours of reaction, the impurity removal rate was calculated, and the evaluation results are shown in table 3.
TABLE 2 Properties of the feed oils
TABLE 3 comparison of catalyst hydrogenation performance
As can be seen from the data in Table 3, the catalyst prepared by the present invention has higher hydrodemetallization activity and stability compared with the comparative catalyst.
Claims (6)
1. A method of preparing a hydroprocessing catalyst, comprising: (1) unsaturated spraying and impregnating the hydrogenation active component impregnating solution I into a macroporous alumina carrier, and then drying and roasting to prepare a modified alumina carrier SI; (2) mixing the modified alumina carrier SI in the step (1), ammonium bicarbonate and water, then carrying out sealing heat treatment, drying and roasting the heat-treated material to obtain a carrier SII, wherein the carrier SII is an alumina carrier with a surface growing rod-shaped structure; (3) saturating and spraying the hydrogenation active component impregnation liquid II to impregnate the carrier SII, and then drying and roasting to prepare a hydrogenation catalyst; the hydrogenation active component impregnation liquid is a solution containing VIB and/or VIII group metals; the sealing heat treatment conditions in the step (2) are as follows: the temperature is 120-; the carrier SII is an alumina carrier with a surface growing rod-shaped structure, and comprises main alumina and rod-shaped alumina, wherein at least part of the rod-shaped alumina is distributed on the outer surface of the main alumina carrier, the length of the rod-shaped alumina is 1-12 mu m, and the diameter of the rod-shaped alumina is 100-300 nm;
in the carrier SII, more than 85 percent of rod-shaped alumina on the outer surface of the main alumina has the length of 3-8 μm by weight; wherein, the alumina with a rod-shaped structure on the outer surface of the main alumina carrier is randomly and mutually crossly distributed; in the carrier SII, the coverage rate of the rod-shaped alumina on the outer surface of the main alumina is 70-95%, wherein the coverage rate refers to the percentage of the surface of the outer surface of the main alumina, which is occupied by the rod-shaped alumina, on the outer surface of the main alumina; the properties of the vector SII are as follows: the specific surface area is 150-260m2The pore volume is 0.75-1.5mL/g, the diameters of several pores are 10-50nm, 100-500nm and 500-1000nm, and the crushing strength is 110-140N/cm.
2. The method of claim 1, wherein: the content of VIB group metals in the hydrogenation active component impregnating solution I in the step (1) is 2.0-3.5g/100mL calculated by metal oxides, and the content of VIII group metals is 0.5-1.5g/100mL calculated by metal oxides; the dosage of the active component impregnation liquid I is 5-10% of the saturated water absorption capacity of the macroporous oxygen carrier in the step (1).
3. The method of claim 1, wherein: the properties of the macroporous alumina carrier in the step (1) are as follows: the specific surface area is 150-260m2The pore volume is 0.7-1.2mL/g, and the average pore diameter is 10-30 nm; the pore size distribution is as follows: the pore volume of pores with the diameter of less than 8nm accounts for less than 50 percent of the total pore volume, the pore volume of pores with the diameter of 8-20nm accounts for 30-50 percent of the total pore volume, the pore volume of pores with the diameter of more than 100nm accounts for less than 15 percent of the total pore volume, and the pore volume of pores with the diameter of more than 1000nm accounts for less than 2 percent of the total pore volume.
4. The method of claim 1, wherein: in the step (2), the mass ratio of the ammonium bicarbonate to the modified alumina carrier SI to the water is 1.75:1:5-3:1: 10.
5. The method of claim 1, wherein: and (2) performing sealing pretreatment before sealing heat treatment, wherein the pretreatment temperature is 60-100 ℃, the constant temperature treatment time is 2-4 hours, the temperature rise rate before the pretreatment is 10-20 ℃/min, the temperature rise rate after the pretreatment is 5-10 ℃/min, and the temperature rise rate after the pretreatment is at least 3 ℃/min lower than that before the pretreatment.
6. The method of claim 1, wherein: the content of the VIB group metal in the hydrogenation active component impregnating solution II in the step (3) is 6.5-15.0g/100mL calculated by metal oxide, and the content of the VIII group metal is 1.5-3.5g/100mL calculated by metal oxide.
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