CN116060049A - Hydrogenation catalyst and preparation method and application thereof - Google Patents
Hydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- CN116060049A CN116060049A CN202111279510.3A CN202111279510A CN116060049A CN 116060049 A CN116060049 A CN 116060049A CN 202111279510 A CN202111279510 A CN 202111279510A CN 116060049 A CN116060049 A CN 116060049A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 100
- 239000002184 metal Substances 0.000 claims abstract description 99
- 238000001035 drying Methods 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011148 porous material Substances 0.000 claims abstract description 27
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000005470 impregnation Methods 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 14
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 239000000376 reactant Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 30
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 22
- 239000012670 alkaline solution Substances 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000001569 carbon dioxide Substances 0.000 claims description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 14
- 229910052708 sodium Inorganic materials 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- 239000003921 oil Substances 0.000 description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 9
- 239000003518 caustics Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- -1 VIB metals Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a hydrogenation catalyst, a preparation method and application thereof. The preparation method comprises the following steps: (1) Preparing an active metal solution A, dipping active metal on active carbon powder, drying and roasting to obtain a metal pre-loaded carbon carrier; (2) Heating the metal pre-loaded carbon carrier in the step (1) and ammonium hypophosphite solid under vacuum to react, and keeping the two reactants out of contact; (3) Mixing the sample treated in the step (2) with pseudo-boehmite, extruding strips, and drying to obtain a catalyst precursor; (4) Mixing the catalyst precursor prepared in the step (3) with an active metal solution B, carrying out secondary impregnation, drying and roasting to obtain the catalyst. The catalyst provided by the invention has the advantages of higher metal loading, uniform dispersion, higher mechanical strength, proper pore distribution and specific surface area, and outstanding catalytic efficiency in residual oil hydrotreatment.
Description
Technical Field
The invention relates to a hydrogenation catalyst and a preparation method and application thereof, in particular to a residual oil hydrogenation catalyst and a preparation method and application thereof.
Background
At present, the residual oil hydrogenation catalyst mainly uses alumina or silicon dioxide as a carrier, active metal components such as Ni, mo, co and the like are loaded on the carrier through an impregnation method or a kneading method, and then the hydrogenation catalyst is obtained through high-temperature roasting. In the existing method, when the active metal load is large, the phenomenon of agglomeration or uneven distribution of metal particles is easy to occur. In addition, in the roasting process, the formation of metal-oxygen-aluminum bonds can be caused due to the strong interaction between the metal and the carrier, so that the catalytic efficiency of the catalyst is affected, and finally, the hydrogenation activity of the catalyst is reduced.
CN103055908A discloses a method for preparing a hydrotreating catalyst. Firstly pulping aluminum hydroxide or aluminum oxide to prepare slurry, and adding concentrated phosphoric acid to react to obtain sol; then taking the sol as a binder, kneading with macroporous alumina and small pore alumina, forming, drying and roasting to obtain an alumina carrier; then, the alumina carrier is impregnated with the active metal component impregnation liquid, and the hydrotreating catalyst is prepared by drying and roasting. The method takes concentrated phosphoric acid as a structural auxiliary agent, and introduces the concentrated phosphoric acid onto an alumina carrier to improve the load dispersity of active metal and reduce the total acid content of the carrier, and simultaneously can improve the pore structure of the alumina carrier.
CN105582945a discloses a method for preparing a hydrotreating catalyst. The method comprises the steps of firstly soaking an alumina carrier by urea aqueous solution, then spraying and soaking the alumina carrier by polyol or monosaccharide aqueous solution according to the sequence of the concentration from high to low, so that the concentration of the polyol and/or monosaccharide is distributed on the carrier in a gradient manner from outside to inside, and then loading active metal components. The method ensures that the subsequent active metal center has the characteristic of gradually increasing the activity from outside to inside due to the gradient distribution of the carbonized shell layers, thereby greatly reducing the blocking rate of the pore canal. However, this method requires multi-step spray impregnation to form the polymer carbonized shell layer, and has high requirements for solution concentration, and the actual operation process is complicated.
The preparation method of the hydrogenation catalyst disclosed in CN102451704A is a synthesis method of impregnating active components after mechanical mixing and molding of amorphous silica-alumina and alumina, and the hydrocracking catalyst can be obtained after drying and calcining treatment. The method avoids strong interaction between the active metal and the carrier, and the catalyst can be molded without roasting after being impregnated, although the method is favorable for uniform distribution of the metal on the carrier. But also has the defects of weaker mechanical strength of the catalyst, easy loss of metal components and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrogenation catalyst, and a preparation method and application thereof. The catalyst provided by the invention has the advantages of higher metal loading, uniform dispersion, higher mechanical strength, proper pore distribution and specific surface area, and outstanding catalytic efficiency in residual oil hydrotreatment.
The first aspect of the invention provides a preparation method of a hydrogenation catalyst, which comprises the following steps:
(1) Preparing an active metal solution A, dipping active metal on active carbon powder, drying and roasting to obtain a metal pre-loaded carbon carrier;
(2) Heating the metal pre-loaded carbon carrier in the step (1) and ammonium hypophosphite solid under vacuum to react, and keeping the two reactants out of contact;
(3) Mixing the sample treated in the step (2) with pseudo-boehmite, extruding strips, and drying to obtain a catalyst precursor;
(4) Mixing the catalyst precursor prepared in the step (3) with an active metal solution B, carrying out secondary impregnation, drying and roasting to obtain the catalyst.
Further, in the step (3), the preferred preparation method of the pseudo-boehmite is as follows:
(a) Respectively preparing a first aluminum-containing alkaline solution and a second aluminum-containing alkaline solution with two different alumina concentrations;
(b) Reacting the first aluminum-containing alkaline solution with a mixed gas containing carbon dioxide until the pH value of the solution is 4-6 to obtain a seed crystal solution;
(c) Adding bottom water into a reaction kettle, heating to the reaction temperature, adding the seed crystal solution in the step (b) and the second aluminum-containing alkaline solution into the reaction kettle in parallel flow for reaction, keeping the pH value constant, and aging, washing and drying after the reaction is finished to obtain the pseudo-boehmite.
Further, in the step (a), the alkaline solution containing aluminum is one or two of sodium metaaluminate solution or potassium metaaluminate solution, preferably sodium metaaluminate solution; the concentration of the first alkaline solution containing aluminum is Al 2 O 3 Is 40 to 100g Al 2 O 3 Preferably 60 to 70gAl 2 O 3 and/L. The caustic ratio of the first aluminum-containing alkaline solution is 1.1-2; the concentration of the second alkaline solution containing aluminum is Al 2 O 3 130-350 gAl 2 O 3 Preferably 160 to 240Al 2 O 3 and/L. The second aluminum-containing alkaline solution has a caustic ratio of 1.1 to 2.
Further, in the step (b), the volume fraction of carbon dioxide in the mixed gas is 10% -25%, and the mixed gas containing carbon dioxide can be a mixed gas of carbon dioxide and air; the reaction time is 1-5 min. The initial reaction temperature of the reaction carried out by introducing the mixed gas containing carbon dioxide is 15-65 ℃, the reaction is exothermic, the temperature of the system is gradually increased, the whole reaction process does not need to be cooled to keep low temperature, and the temperature of the slurry is 40-75 ℃ when the reaction is finished.
Further, in the step (c), before the parallel flow reaction, adding bottom water into the reaction kettle, wherein the bottom water accounts for 1/10-1/5 of the volume of the reaction container; the co-current reaction is carried out with stirring. The temperature of the parallel flow reaction is 40 ℃ to 75 ℃, preferably 45 ℃ to 70 ℃.
Further, in the step (c), the parallel flow feeding time of the second aluminum-containing alkaline solution is controlled to be 30-150 min.
Further, in the step (c), the second alkaline solution containing aluminum is added into the reaction kettle, and simultaneously, the first alkaline solution is added into the carbonized slurry, and the pH value of the slurry in the reaction kettle is controlled to be 8-9 by adjusting the flow rate of the slurry.
Further, in the step (c), the aging temperature is 60-90 ℃ and the aging time is 40-90 min; the washing is to wash the mixture to be neutral by water at the temperature of 60-90 ℃; the drying condition is that the drying is carried out for 4 to 10 hours at the temperature of 100 to 120 ℃.
Further, in the step (1), the specific surface area of the activated carbon is 350-480 m 2 And/g. The water absorption rate of the activated carbon is in the range of 0.7-1.5 mL/g.
Further, in the step (1), the impregnation method adopts saturated impregnation.
Further, in the step (1), the active metal in the active metal solution a is at least one selected from cobalt and nickel, preferably cobalt, which are metals of group VIII; the load is 30% -50% of the mass of the VIII group total active metal oxide in the catalyst in terms of oxide; wherein the concentration of the active metal solution A calculated by active metal oxide is 0.02-0.4 g/mL.
Further, in the step (1), the drying temperature is 100-120 ℃ and the drying time is 2-5 h; the roasting temperature is 400-450 ℃, inert atmosphere and/or nitrogen protection are/is introduced for 2-3 hours, and the inert atmosphere is at least one of Ar and He.
Further, in the step (2), the mass ratio of the ammonium hypophosphite to the active metal in the metal pre-loaded carbon carrier is 1-10.
Further, in the step (2), the heating temperature is 250-280 ℃ and the time is 1-2 h.
Further, in the step (2), the vacuum degree of the vacuum is-0.10-0 MPa.
Further, in the step (3), the mass ratio of the sample treated in the step (2) to the pseudo-boehmite is 0.05-0.3. An extrusion aid can be added in the extrusion process, the extrusion aid can be sesbania powder, and the addition amount of the extrusion aid is 1-6% of the mass of the pseudo-boehmite.
Further, in the step (3), the drying temperature is 80-120 ℃ and the time is 4-6 h.
Further, in the step (4), the impregnation adopts saturated impregnation; the active metal in the active metal solution B is selected from at least one of VIB group metal and at least one of VIII group metal, wherein the VIB group metal is preferably at least one of Mo and W, more preferably Mo, and the VIII group metal is preferably at least one of Co and Ni, more preferably Co.
Further, the amount of the VIII group active metal introduced into the catalyst from the step (4) accounts for 50-70% of the mass of the VIII group total active metal oxide in the catalyst in terms of oxide.
Further, in the step (4), after the twice impregnation, the mass content of the group VIB metal in the obtained catalyst is 15% -25% of the total mass of the catalyst in terms of oxide, and the mass content of the group VIII metal in the obtained catalyst is 3% -8% of the total mass of the catalyst in terms of oxide.
Further, in the step (4), the material is dried after being immersed, the drying temperature is 80-120 ℃, the drying time is 2-5 hours, and the material is baked after being dried, the baking temperature is 400-650 ℃, and the baking time is 3-5 hours.
In a second aspect the present invention provides a hydrogenation catalyst obtainable by the process according to the first aspect.
Further, in the catalyst, the active metal is at least one of group VIB metals and at least one of group VIII metals, wherein the group VIB metals are preferably at least one of Mo and W, more preferably Mo, and the group VIII metals are preferably at least one of Co and Ni, more preferably Co.
Further, in the catalyst, the active metal load is 15% -25% of the content of the VIB group metal and 3% -8% of the content of the VIII group metal based on the mass of the oxide.
Further, the catalyst also contains phosphorus, and the mass content of the phosphorus is 0.2% -2%.
Further, in the catalyst, the dispersity of the active metal is as follows: i VIB /I Al (. Times.100) is 8.5-10, I VIII /I Al (. Times.100) is 4 to 5.5.
Further, the specific surface area of the catalyst is 160-225 m 2 Preferably 179 to 220m 2 Per gram, the pore volume is 0.8-1.1 cm 3 Per gram, mechanical strength of 16 to 20N/mm, preferably 18 to 20N/mm, pore size>The pore volume of the pores with the diameter of 15nm accounts for 7.5-15% of the total pore volume, and the pore diameter<The pore volume of the pores at 8nm is 7% or less, preferably 4% to 6.5% of the total pore volume.
Further, the acid amount of the catalyst is 0.3 to 0.6mmol/g, preferably 0.35 to 0.50mmol/g.
The third aspect of the invention provides the application of the hydrogenation catalyst in a residual oil hydrogenation process.
Further, the residuum and hydrogen-containing gas are contacted and reacted under hydrogenation reaction conditions in the presence of the residuum hydrogenation catalyst or the residuum hydrogenation catalyst obtained according to the above preparation method.
In the residual oil hydrogenation reaction, the residual oil material is selected from one of atmospheric residual oil, vacuum residual oil and high-temperature coal tar.
In the above-mentioned residuum hydrogenation reaction, the hydrogen-containing gas is hydrogen or a mixed gas of hydrogen and other gases, and the hydrogen volume content in the mixed gas is generally not less than 80%, preferably not less than 85%, and more preferably not less than 95%.
In the residuum hydrogenation process, the residuum hydrogenation operation conditions are as follows: the reaction pressure is 5-20 MPaG, the reaction temperature is 280-400 ℃, and the liquid hourly space velocity is 0.1-3.0 h -1 The volume ratio of the hydrogen oil is 100-1000.
Compared with the prior art, the invention has the following advantages:
firstly, in the preparation method of the catalyst of the invention, in the first metal impregnation process, the active phase VIII metal is firstly loaded on a carbon carrier, and after being heated together with the ammonium hypophosphite in vacuum, the ammonium hypophosphite is heated at pH 3 The form decomposition leads the VIII group metal on the surface of the carbon carrier to be partially phosphorylated to form a VIII group metal-P semiconductor, when the active metal is secondarily loaded, a metal-semiconductor heterojunction can be formed on the contact interface of the VIII group metal and the VIII group metal-P semiconductor, the migration rate of electrons between metals is accelerated, the interaction force between the VIII group metals is enhanced, the metal dispersibility is improved, and the metal load is increasedThe amount of the catalyst can greatly weaken the electron migration efficiency between the active metal and the alumina carrier, so that the adsorption and bond forming actions between the active metal and the alumina carrier are weakened, and the activity of the synthesized catalyst is higher in the residual oil hydrogenation process.
Furthermore, the synthesis process of pseudo-boehmite preferably adopts the seed crystal method provided by the invention, the quick crystallization is carried out in a first reaction kettle, and pseudo-boehmite particles with larger crystal grains are continuously generated in a second reaction kettle. In the preparation method, the concentration variable range of the alkaline solution is wider, the operability is stronger, the reaction is less influenced by environmental conditions, the production efficiency is high, and the process is simple. The hydrogenation catalyst prepared from the pseudo-boehmite has higher metal dispersity, higher mechanical strength, larger pore volume and better desulfurization, nitrogen and metal performances.
Finally, the hydrogenation catalyst obtained by the invention is used for the residual oil hydrogenation reaction, shows good desulfurization, denitrification and carbon residue removal performances, and also shows excellent catalytic performances in the aspect of demetallization.
Detailed Description
The technical scheme and effect of the present invention are further described below by examples. The embodiments and specific operation procedures are given on the premise of the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments.
In the invention, a nitrogen adsorption and desorption curve of a sample is tested by adopting an ASAP2020 type full-automatic physical adsorption instrument of Micromeritics company in the United states at the temperature of minus 196 ℃, and the specific surface area, pore volume and pore diameter distribution are measured.
In the invention, the mechanical strength is tested by adopting a large-connection intelligent testing machine factory ZQJ-III type intelligent particle strength tester, and the average mechanical strength of a group of samples with the length of 4-6mm is measured.
In the invention, the metal dispersity is obtained by measuring XPS peak intensity ratio of active metal and aluminum element by XRS (model Kratos Axis Ultra DLD).
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores.
Example 1
(1) Preparing two sodium metaaluminate solutions with low concentration of 65g/L Al 2 O 3 The caustic ratio of the solution is 1.15, and the high concentration is 160g/L Al 2 O 3 The caustic ratio of the solutions was 1.35. 3000mL of low-concentration sodium metaaluminate solution is added into the first reaction kettle, and carbon dioxide gas is introduced until the pH value of the solution is reduced to 5.5, and the reaction time is controlled within 5min. Adding 500mL of deionized water into 5000mL of a second reaction kettle, stirring and heating, adding 800mL of high-concentration sodium metaaluminate solution into the second reaction kettle at a flow rate of 6mL/min when the temperature reaches 70 ℃, simultaneously adding carbonized slurry in parallel, controlling the pH value of the slurry in the second reaction kettle to be 8.6 constant by adjusting the flow rate of the carbonized slurry, and after the carbonized slurry is completely added, finishing the reaction, starting aging and heating, wherein the aging temperature is 90 ℃ and the time is 90min. And then washing the product fully by deionized water at the temperature of 75 ℃ and drying the product at the temperature of 120 ℃ for 6 hours to obtain the pseudo-boehmite.
(2) 80mL of active metal solution with CoO content of 0.135g/mL is saturated and immersed to 100g, and the specific surface area is 420m 2 And (3) drying the activated carbon powder/g for 4 hours at 110 ℃, and roasting the activated carbon powder at 430 ℃ for 3 hours under the protection of nitrogen atmosphere to obtain the metal pre-loaded carbon carrier, wherein the mass of Co introduced into the catalyst in the step (2) accounts for 31.3% of the total Co in the catalyst.
(3) Weighing 100g of the metal pre-loaded carbon carrier and 50g of ammonium hypophosphite solid, and carrying out non-contact heating reaction for 2h under the vacuum condition of 270 ℃ and minus 0.05 MPa.
(4) Weighing 100g of the treated sample, mixing with 500g of pseudo-boehmite and 15g of sesbania powder, extruding, and drying at 120 ℃ for 4 hours to obtain a catalyst precursor.
(5) Preparing MoO-containing 3 Impregnating the catalyst precursor with impregnating solution of 0.309g/mL and CoO of 0.058g/mL, drying at 120deg.C for 5 hr after impregnation, and calcining at 650deg.C for 3 hr to obtain final hydrogenation catalyst A, the physicochemical properties of whichSee table 1.
Example 2
Other synthesis procedures were the same as in example 1 except that the addition amount of the ammonium hypophosphite solid was changed to 95g to obtain a final hydrogenation catalyst B, the physicochemical properties of which are shown in Table 1.
Example 3
Other synthetic procedures were similar to those in example 2, except that the CoO concentration in the first step of impregnating solution was changed to 0.206g/mL, and the MoO concentration in the second step of impregnating solution 3 And CoO solution, wherein MoO 3 The concentration is changed to 0.312g/mL, the CoO concentration is 0.045g/mL, the roasting temperature is changed to 450 ℃ after impregnation, and the final hydrogenation catalyst C (the physical and chemical properties are shown in table 1) is obtained, wherein the mass of Co introduced into the catalyst in the step (2) accounts for 46.9% of the total Co in the catalyst.
Example 4
Other synthesis procedures were the same as in example 1 except that the concentrations of the two sodium metaaluminate solutions were adjusted to 70g/L and 220g/L, respectively, to obtain final hydrogenation catalyst D, the physicochemical properties of which are shown in Table 1.
Comparative example 1
(1) Preparing two sodium metaaluminate solutions with low concentration of 65g/L Al 2 O 3 The caustic ratio of the solution is 1.15, and the high concentration is 160g/L Al 2 O 3 The caustic ratio of the solutions was 1.35. 3000mL of low-concentration sodium metaaluminate solution is added into the first reaction kettle, and carbon dioxide gas is introduced until the pH value of the solution is reduced to 5.5, and the reaction time is controlled within 5min. Adding 500mL of deionized water into 5000mL of a second reaction kettle, stirring and heating, adding 800mL of high-concentration sodium metaaluminate solution into the second reaction kettle at a flow rate of 6mL/min when the temperature reaches 70 ℃, simultaneously adding carbonized slurry in parallel, controlling the pH value of the slurry in the second reaction kettle to be 8.6 constant by adjusting the flow rate of the carbonized slurry, and after the carbonized slurry is completely added, finishing the reaction, starting aging and heating, wherein the aging temperature is 90 ℃ and the time is 90min. Then washing with 75 ℃ deionized water fully, and drying at 120 ℃ for 6 hours to obtain pseudo-boehmite.
(2) 80mL of active metal solution with CoO content of 0.135g/mL is saturated and immersed to 100g, and the specific surface area is 420m 2 Activated carbon powder/gDrying for 4 hours at 110 ℃, and roasting for 3 hours at 430 ℃ under the protection of nitrogen atmosphere to obtain the metal pre-loaded carbon carrier. Wherein the amount of Co introduced into the catalyst in step (2) is 31.3% of the total Co in the catalyst based on the mass of the oxide.
(3) Weighing 100g of the treated sample, mixing with 500g of pseudo-boehmite and 15g of sesbania powder, extruding, and drying at 120 ℃ for 4 hours to obtain a catalyst precursor.
(4) Preparing MoO-containing 3 The catalyst precursor was saturated impregnated with an impregnating solution of 0.309g/mL and 0.058g/mL CoO, dried at 120℃for 5 hours after the impregnation was completed, and calcined at 650℃for 3 hours to give the final hydrogenation catalyst E, the physicochemical properties of which are shown in Table 1.
Comparative example 2
(1) Preparing two sodium metaaluminate solutions with low concentration of 65g/L Al 2 O 3 The caustic ratio of the solution is 1.15, and the high concentration is 160g/L Al 2 O 3 The caustic ratio of the solutions was 1.35. 3000mL of low-concentration sodium metaaluminate solution is added into the first reaction kettle, and carbon dioxide gas is introduced until the pH value of the solution is reduced to 5.5, and the reaction time is controlled within 5min. Adding 500mL of deionized water into 5000mL of a second reaction kettle, stirring and heating, adding 800mL of high-concentration sodium metaaluminate solution into the second reaction kettle at a flow rate of 6mL/min when the temperature reaches 70 ℃, simultaneously adding carbonized slurry in parallel, controlling the pH value of the slurry in the second reaction kettle to be 8.6 constant by adjusting the flow rate of the carbonized slurry, and after the carbonized slurry is completely added, finishing the reaction, starting aging and heating, wherein the aging temperature is 90 ℃ and the time is 90min. Then washing with 75 ℃ deionized water fully, and drying at 120 ℃ for 6 hours to obtain pseudo-boehmite.
(2) 80mL of active metal solution with CoO content of 0.284g/mL is saturated and immersed to 100g and specific surface area of 420m 2 And (3) drying the activated carbon powder/g at 110 ℃ for 4 hours, and roasting at 430 ℃ for 3 hours under the protection of nitrogen atmosphere to obtain the metal pre-loaded carbon carrier. Wherein the amount of Co introduced into the catalyst in step (2) is 64.5% of the total Co in the catalyst based on the mass of the oxide.
(3) Weighing 100g of the metal pre-loaded carbon carrier and 50g of ammonium hypophosphite solid, and carrying out non-contact heating reaction for 2h under the vacuum condition of 270 ℃ and minus 0.05 MPa.
(4) Weighing 100g of the treated sample, mixing with 500g of pseudo-boehmite and 15g of sesbania powder, extruding, and drying at 120 ℃ for 4 hours to obtain a catalyst precursor.
(5) Preparing MoO-containing 3 The catalyst precursor was saturated impregnated with an impregnating solution of 0.312g/mL and 0.030g/mL of CoO, dried at 120℃for 5 hours after the impregnation was completed, and calcined at 650℃for 3 hours to give a final hydrogenation catalyst F, the physicochemical properties of which are shown in Table 1.
Comparative example 3
(1) 3000mL of 65gAl was added to a 5.0L reactor 2 O 3 And (3) introducing mixed gas of carbon dioxide with the carbon dioxide content of 80% (volume fraction) and air into the sodium metaaluminate solution with the caustic ratio of 1.35, wherein the initial reaction temperature is 25 ℃, cooling the solution to maintain the slurry temperature unchanged, and controlling the reaction time to be 45min to reduce the pH value of the sodium metaaluminate solution to 8.8. The slurry was filtered, washed with deionized water at 75 ℃ and dried at 120 ℃ for 6 hours after the washing was completed to obtain pseudo-boehmite.
(2) 80mL of active metal solution with CoO content of 0.135g/mL is saturated and immersed to 100g, and the specific surface area is 420m 2 And (3) drying the activated carbon powder/g at 110 ℃ for 4 hours, and roasting at 430 ℃ for 3 hours under the protection of nitrogen atmosphere to obtain the metal pre-loaded carbon carrier. Wherein the amount of Co introduced into the catalyst in step (2) is 31.3% of the total Co in the catalyst based on the mass of the oxide.
(3) Weighing 100g of the metal pre-loaded carbon carrier and 50g of ammonium hypophosphite solid, and carrying out non-contact heating reaction for 2h under the vacuum condition of 270 ℃ and minus 0.05 MPa.
(4) Weighing 100g of the treated sample, mixing with 500g of pseudo-boehmite and 15g of sesbania powder, extruding, and drying at 120 ℃ for 4 hours to obtain a catalyst precursor.
(5) Preparing MoO-containing 3 Impregnating the catalyst precursor with impregnating solution of 0.309G/mL and CoO of 0.058G/mL, drying at 120deg.C for 5 hr after impregnation, and calcining at 650deg.C for 3 hr to obtain final hydrogenation catalyst GThe chemical properties are shown in Table 1.
Example 5
Examples 1-4 and comparative examples 1-3 were used in residuum hydrogenation reactions, respectively, with feedstock properties shown in Table 2, and evaluation conditions and results shown in Table 3.
TABLE 1 physicochemical Properties of hydrogenation catalysts
TABLE 2 oil Properties of raw materials
| Density (20 ℃ C.) kg/m 3 | 987.5 |
| S，wt％ | 3.56 |
| N，ppm | 2426 |
| CCR，wt％ | 12.5 |
| Ni，ppm | 23.6 |
| V，ppm | 73.1 |
Table 3 evaluation conditions and evaluation results of the hydrogenation catalysts obtained in each example
Claims (18)
1. A method for preparing a hydrogenation catalyst, comprising the steps of:
(1) Preparing an active metal solution A, dipping active metal on active carbon powder, drying and roasting to obtain a metal pre-loaded carbon carrier;
(2) Heating the metal pre-loaded carbon carrier in the step (1) and ammonium hypophosphite solid under vacuum to react, and keeping the two reactants out of contact;
(3) Mixing the sample treated in the step (2) with pseudo-boehmite, extruding strips, and drying to obtain a catalyst precursor;
(4) Mixing the catalyst precursor prepared in the step (3) with an active metal solution B, carrying out secondary impregnation, drying and roasting to obtain the catalyst.
2. The method according to claim 1, wherein in the step (3), the pseudo-boehmite is prepared as follows:
(a) Respectively preparing a first aluminum-containing alkaline solution and a second aluminum-containing alkaline solution with two different alumina concentrations;
(b) Reacting the first aluminum-containing alkaline solution with a mixed gas containing carbon dioxide until the pH value of the solution is 4-6 to obtain a seed crystal solution;
(c) Adding bottom water into a reaction kettle, heating to the reaction temperature, adding the seed crystal solution in the step (b) and the second aluminum-containing alkaline solution into the reaction kettle in parallel flow for reaction, keeping the pH value constant, and aging, washing and drying after the reaction is finished to obtain the pseudo-boehmite.
3. The method according to claim 1 or 2, wherein in the step (1), the specific surface area of the activated carbon is 350 to 480m 2 /g。
4. The preparation method according to claim 1 or 2, wherein in step (1), the active metal in the active metal solution a is selected from at least one of group VIII metal cobalt, nickel, preferably cobalt; the load is 30% -50% of the mass of the VIII group total active metal oxide in the catalyst in terms of oxide; wherein the concentration of the active metal solution A calculated by active metal oxide is 0.02-0.4 g/mL.
5. The preparation method according to claim 1 or 2, wherein in the step (1), the drying temperature is 100-120 ℃ and the drying time is 2-5 hours; the roasting temperature is 400-450 ℃, and inert atmosphere and/or nitrogen protection are/is introduced for 2-3 hours.
6. The preparation method according to claim 1 or 2, wherein in the step (2), the mass ratio of the ammonium hypophosphite to the active metal in the metal pre-loaded carbon carrier is 1-10.
7. The method according to claim 1 or 2, wherein in the step (2), the heating temperature is 250 to 280 ℃ for 1 to 2 hours.
8. The preparation method according to claim 1 or 2, wherein in the step (3), the mass ratio of the sample treated in the step (2) to the pseudo-boehmite is 0.05-0.3.
9. The method according to claim 1 or 2, wherein in step (4), the impregnation is saturated impregnation; the active metal in the active metal solution B is selected from at least one of VIB group metal and at least one of VIII group metal, wherein the VIB group metal is preferably at least one of Mo and W, more preferably Mo, and the VIII group metal is preferably at least one of Co and Ni, more preferably Co.
10. The preparation method according to claim 1 or 2, wherein in the step (4), after the two impregnations, the mass content of the group VIB metal in the obtained catalyst is 15% -25% of the total mass of the catalyst in terms of oxide, and the mass content of the group VIII metal in the catalyst is 3% -8% of the total mass of the catalyst in terms of oxide.
11. The method according to claim 1 or 2, wherein in the step (4), the material is dried after impregnation at a drying temperature of 80 to 120 ℃ for 2 to 5 hours, and is baked after the drying at a baking temperature of 400 to 650 ℃ for 3 to 5 hours.
12. A hydrogenation catalyst obtainable by the process of any one of claims 1 to 11.
13. The hydrogenation catalyst according to claim 12, wherein in the catalyst the active metal is at least one of a group VIB metal and at least one of a group VIII metal, wherein the group VIB metal is preferably at least one of Mo, W, more preferably Mo, the group VIII metal is preferably at least one of Co, ni, more preferably Co; in the catalyst, the active metal load is 15% -25% of the content of the VIB group metal and 3% -8% of the content of the VIII group metal based on the mass of the oxide.
14. The hydrogenation catalyst according to claim 13, further comprising phosphorus, wherein the mass content of phosphorus is 0.2% -2%.
15. The hydrogenation catalyst according to claim 12 or 13, wherein the catalyst has an active metal dispersity of: i VIB /I Al (. Times.100) is 8.5-10, I VIII /I Al (. Times.100) is 4 to 5.5.
16. The hydrogenation catalyst according to claim 12 or 13, wherein in the catalyst, the specific surface area of the catalyst is 160-225 m 2 Preferably 179 to 220m 2 Per gram, the pore volume is 0.8-1.1 cm 3 Per gram, a mechanical strength of 16 to 20N/mm, preferably 18 to 20N/mm, pore size>15 The pore volume of the nm pores accounts for 7.5% -15% of the total pore volume, and the pore diameter is the same as that of the total pore volume<The pore volume of the pores of 8nm accounts for less than 7 percent of the total pore volume, and is preferably 4 to 6.5 percent; the acid amount of the catalyst is 0.3-0.6 mmol/g, preferably 0.35-0.50 mmol/g.
17. Use of the hydrogenation catalyst of any one of claims 12-16 in a residuum hydrogenation process.
18. The use according to claim 17, characterized in that the operating conditions for the hydrogenation of residuum are as follows: the reaction pressure is 5-20 MPaG, the reaction temperature is 280-400 ℃, and the liquid hourly space velocity is 0.1-3.0 h -1 The volume ratio of the hydrogen oil is 100-1000.
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