CN113000055A - Shell type hydrogenation catalyst and preparation method thereof - Google Patents
Shell type hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN113000055A CN113000055A CN201911319223.3A CN201911319223A CN113000055A CN 113000055 A CN113000055 A CN 113000055A CN 201911319223 A CN201911319223 A CN 201911319223A CN 113000055 A CN113000055 A CN 113000055A
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- shell
- metal
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- hydrogenation catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 60
- 239000002184 metal Substances 0.000 claims abstract description 60
- 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 23
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002739 metals Chemical class 0.000 claims abstract description 5
- 238000005470 impregnation Methods 0.000 claims description 38
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 20
- 102000002322 Egg Proteins Human genes 0.000 claims description 19
- 108010000912 Egg Proteins Proteins 0.000 claims description 19
- 210000003278 egg shell Anatomy 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000001935 peptisation Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- -1 VIB metal compound Chemical class 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 9
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000009826 distribution Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 238000001354 calcination Methods 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000009828 non-uniform distribution Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 210000000969 egg white Anatomy 0.000 description 1
- 235000014103 egg white Nutrition 0.000 description 1
- 210000002969 egg yolk Anatomy 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement 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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B01J35/397—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- 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
Abstract
The invention relates to a shell hydrogenation catalyst which is prepared from Al2O3Or Al containing silicon2O3The catalyst is used as a carrier, metals of a VIII group and a VIB group are used as active components, phosphorus is used as an auxiliary agent, metal compounds formed by the active components are distributed on the carrier in a shell layer manner, the content of the metal of the VIII group is 0.5-5.0 wt% by oxide, the content of the metal of the VIB group is 10.0-28.0 wt% by oxide, and the content of the auxiliary agent is P2O5Calculated as 0.3 wt% -7.0 wt%, and the content of the carrier is 65.0 wt% -85.0 wt%. The invention also relates to a preparation method of the shell hydrogenation catalyst.
Description
Technical Field
The invention relates to a shell type hydrogenation catalyst and a preparation method thereof, in particular to a shell type hydrogenation catalyst which can be used for hydrofining distillate oil, especially diesel oil fraction, and a preparation method thereof.
Background
With the increasing environmental awareness, China sets up increasingly strict vehicle fuel quality standards and puts forward increasingly strict requirements on sulfur content indexes in oil products. The oil refining enterprises are forced to pay more attention to the development of clean fuel production technology, and how to economically and reasonably produce ultra-low sulfur oil products becomes one of the key problems to be solved by the oil refining enterprises at present and in a certain period in the future. The development of hydrogenation catalysts with higher activity and selectivity is one of the most economical methods for producing clean oils.
In order to fully utilize the role of the active component in the catalyst during the catalytic reaction, it is generally desirable that the active component is uniformly distributed on the support to obtain an effective active surface. However, in the course of heterogeneous catalytic reaction, the catalytic reaction on the surface of the solid catalyst is subjected to the steps of internal diffusion, adsorption, reaction, desorption, and external diffusion. The concentration distribution of the active component of the supported catalyst needs to be specially designed according to various factors such as reaction control steps, poisoning, sintering behavior, wear resistance requirements, economical efficiency of the preparation process and the like. According to the different distribution positions of the active components in the catalyst particles, the catalyst can be divided into four types of uniform distribution, "eggshell" distribution, "yolk" distribution and "egg white" distribution, wherein the eggshell "distribution is favorable for quick reaction because the active components are mainly distributed on the outer surface of the carrier, and the distribution can reduce the consumption of active metals in the catalyst, reduce the density of the catalyst and the cost of raw materials and is favorable for improving the market competitiveness of the catalyst.
CN101143325A discloses a method for preparing a catalyst, which comprises preparing a soluble compound containing a supported component, spraying the prepared solution onto a rolling carrier or a carrier previously supported with an active metal component, heating the carrier while spraying, and drying or calcining the prepared product. The catalyst with obvious shell distribution can be obtained by repeatedly spraying and drying the carrier, and the catalyst is sprayed and dried.
CN101462080A discloses a method for preparing a catalyst with non-uniform distribution of active metal components, which comprises introducing an effective amount of at least one metal component selected from group VIII and at least one metal component selected from group VIB onto a carrier by an impregnation method, wherein the impregnation method comprises the following steps: (1) one or more acids selected from nitric acid, phosphoric acid, oxalic acid, citric acid, tartaric acid, pimelic acid and adipic acid are mixed with at least one compound containing a metal component of a VIB group, at least one compound containing a metal component of a VIII group and water to form a solution. (2) Soaking the carrier in the prepared mixed solution for 1-5 hours; (3) drying the impregnated carrier at 60-160 ℃ for 2-10 hours, and roasting at 400-600 ℃ for 2-5 hours.
Disclosure of Invention
Based on the above, the present invention aims to provide a shell type hydrogenation catalyst and a preparation method thereof, wherein the shell type hydrogenation catalyst is particularly suitable for producing vehicle fuel by hydrofining straight-run diesel oil fractions. And the shell-type hydrogenation catalyst prepared by the method has the characteristics of low metal content, low catalyst density, high desulfurization activity and mild device operation conditions.
Therefore, the invention provides a shell type hydrogenation catalyst which is prepared from Al2O3Or Al containing silicon2O3The catalyst is used as a carrier, metals of a VIII group and a VIB group are used as active components, phosphorus is used as an auxiliary agent, metal compounds formed by the active components are distributed on the carrier in an egg-shell shape, the content of the metal of the VIII group is 0.5 wt% -5.0 wt% by oxide, the content of the metal of the VIB group is 10.0 wt% -28.0 wt% by oxide, and the content of the auxiliary agent is P2O5Calculated as 0.3 wt% -7.0 wt%, and the content of the carrier is 65.0 wt% -85.0 wt%.
In the shell type hydrogenation catalyst, preferably, the group VIII metal is nickel, and the group VIB metal is molybdenum.
In the shell-type hydrogenation catalyst of the present invention, it is preferable that the silicon-containing Al is2O3With Al2O3On a basis of SiO2The content of (A) is 0.1 wt% -5.0 wt%.
In the shell-type hydrogenation catalyst of the present invention, it is preferable that the silicon-containing Al is2O3With Al2O3On a basis of SiO2The content of (A) is 2 wt% -4.0 wt%.
In the shell-type hydrogenation catalyst, preferably, the content of the oxide of the VIII family metal is 3.0-5.0 wt%, the content of the oxide of the VIB family metal is 16.0-24.0 wt%, and the content of the auxiliary agent is P2O5Calculated as 2.0wt percent to 5.0wt percent.
The invention also provides a preparation method of the shell type hydrogenation catalyst, which is the preparation method of the shell type hydrogenation catalyst and comprises the following steps:
(1) uniformly mixing pseudo-boehmite or silicon-containing pseudo-boehmite with a forming auxiliary agent, adding a peptizing agent and deionized water for kneading, extruding, drying and roasting to prepare a formed alumina or silicon-containing alumina carrier;
(2) and loading the VIII family metal, the VIB family metal and the auxiliary agent on the carrier by an impregnation method, and then curing, drying and roasting to prepare the shell catalyst.
In the preparation method of the shell-type hydrogenation catalyst, the peptization index of the pseudo-boehmite or the silicon-containing pseudo-boehmite is preferably more than 90%. The core of the preparation method is to prepare the catalyst with the active metal component distributed as a shell layer by utilizing the relevance of the peptization of the pseudo-boehmite and the distribution of the active metal component on the surface of the carrier.
In the preparation method of the shell-type hydrogenation catalyst, the peptization index of the pseudo-boehmite or the silicon-containing pseudo-boehmite is preferably 92-96%.
In the preparation method of the shell-type hydrogenation catalyst, preferably, an impregnation solution adopted by the impregnation method contains a group VIII metal compound, a group VIB metal compound and a phosphorus compound, wherein the group VIII metal compound is selected from at least one of nickel nitrate, nickel sulfate, basic nickel carbonate, nickel acetate and nickel oxalate; the group VIB metal compound is at least one selected from ammonium heptamolybdate, ammonium tetramolybdate and molybdenum trioxide; the phosphorus compound is at least one selected from phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
In the preparation method of the shell-type hydrogenation catalyst, the peptizing agent is preferably at least one selected from nitric acid, citric acid, acetic acid and tartaric acid.
In the preparation method of the shell-type hydrogenation catalyst, it is preferable that in the step (1), the drying conditions are as follows: the temperature is 60-180 ℃, and the time is 2-12 h; the roasting conditions are as follows: the temperature is 300-600 ℃, the time is 2-12 h, and the heating speed is 1-3 ℃/min.
In the preparation method of the shell-type hydrogenation catalyst, preferably, in the step (2), the curing conditions are as follows: the temperature is 10-50 ℃, and the time is 1-3 h; the drying conditions are as follows: the temperature is 80-160 ℃, and the time is 2-8 h; the roasting conditions are as follows: the temperature is 400-600 ℃, the time is 3-8 h, and the heating speed is 1-3 ℃/min.
In the preparation method of the shell-type hydrogenation catalyst, the forming assistant is preferably an extrusion assistant, including but not limited to sesbania powder.
The shell type hydrogenation catalyst of the invention has the following specific preparation steps:
(1) taking a certain amount of pseudo-boehmite powder, adding a certain proportion of extrusion aid, uniformly mixing, adding peptizer and deionized water, kneading, rolling, molding by using a strip extruder, drying the molded carrier at 60-180 ℃ for 2-12 h, roasting at 300-600 ℃ for 2-12 h in a high-temperature furnace, wherein the temperature rise speed of roasting is 1-3 ℃/min.
(2) Impregnating an impregnating solution containing metal compounds of VIII family and VIB family and a phosphorus-containing compound by a saturated impregnation method, curing the impregnated wet strip at room temperature for 1-3 h, drying at 80-160 ℃ for 2-8 h, roasting at 400-600 ℃ in a high-temperature furnace for 3-8 h at the heating rate of 1-3 ℃/min, and preparing the catalyst finished product.
The pseudoboehmite peptization index of the invention is known to those skilled in the art and can be analyzed according to the following method:
weighing 10g of pseudoboehmite (A1) with particle size less than 80 μm2O3Mass fraction of W1) Placing in 250mL conical flask, adding appropriate amount of distilled water, stirring, adding appropriate amount of nitric acid, stirring for 10min, centrifuging, pouring out upper suspension, and weighing mass mAnalysis of A12O3Mass fraction (W) of2) The peptization index (DI) is calculated from the following formula:
DI＝m*W2/(10Wl)。
the present invention has no particular requirement for the method for preparing the impregnation fluid, and can be carried out with reference to the prior art, and according to a preferred embodiment of the present invention, the method for preparing the solution containing the group VIII metal compound, the group VIB metal compound and the phosphorus-containing compound can be carried out as follows: adding a nickel (and/or cobalt) containing compound and a molybdenum containing compound into an aqueous solution of a phosphorus containing compound, and heating and stirring to form the aqueous solution.
The impregnation method of the present invention is not particularly limited, and various impregnation methods in the prior art may be used, for example, spray impregnation, equal-volume impregnation or excess liquid impregnation, and among them, equal-volume impregnation and saturation impregnation are preferred.
In the present invention, the amount of the solution can be selected according to the specific impregnation method, and those skilled in the art can know that, for example, when the impregnation is equal-volume impregnation, the amount of the solution is the saturated water absorption capacity of the carrier.
The active components in the shell type hydrogenation catalyst are distributed in an egg shell type. By "eggshell" catalyst is meant: the catalyst has a shell factor sigma of 0-0.95. Wherein the shell factor σ is a ratio of a concentration of the metal component at a center of the catalyst particle to a concentration at an outer surface; the concentration at the outer surface of the catalyst refers to the average value of 20 numerical point counting rates near the outer surface along the radial direction of the carrier in the SEM-EDS characterization result; the concentration at the center of the catalyst refers to the average value of the recording rate of 20 values around the central point along the radial direction of the carrier in the SEM-EDS characterization result.
And in the SEM-EDS characterization result, the counting rate of each point along the radial direction of the carrier corresponds to the metal content of the point, and the size of the counting rate reflects the metal content of the point but does not represent the real content of the metal of the point. The σ value represents the distribution form of the active component on the catalyst and quantitatively indicates the degree of unevenness in the case of uneven distribution.
In the present invention, σ M represents the ratio of the concentration of the metal active component at the center of the catalyst particle to the concentration at the outer surface, and σ Mo, for example, represents the ratio of the concentration of metallic molybdenum at the center of the catalyst particle to the concentration at the outer surface.
In the invention, the catalyst element composition is determined by adopting an X-ray fluorescence spectrometry after the catalyst is roasted at 550 ℃ for 4 h.
The catalyst provided by the invention has the advantages that the content of the VIB group metal compound calculated by oxide is more than 10 wt%, and the content of the VIII group metal compound calculated by oxide is more than 2 wt%. The method of the invention has simple operation and little environmental pollution, and the prepared catalyst can be used for hydrofining of light petroleum fractions, especially diesel oil fractions, and has high hydrodesulfurization activity.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The shell type hydrogenation catalyst provided by the invention is prepared from Al2O3Or Al containing silicon2O3The catalyst is used as a carrier, metals of a VIII group and a VIB group are used as active components, phosphorus is used as an auxiliary agent, metal compounds formed by the active components are distributed on the carrier in an egg-shell shape, the content of the metal of the VIII group is 0.5 wt% -5.0 wt% by oxide, the content of the metal of the VIB group is 10.0 wt% -28.0 wt% by oxide, and the content of the auxiliary agent is P2O5Calculated as 0.3 wt% -7.0 wt%, and the content of the carrier is 65.0 wt% -85.0 wt%.
In some embodiments, the group VIII metal is nickel and the group VIB metal is molybdenum.
In some embodiments, the silicon-containing Al2O3With Al2O3On a basis of SiO2The content of (A) is 0.1 wt% -5.0 wt%.
In some embodiments, the silicon-containing Al2O3With Al2O3On a basis of SiO2The content of (A) is 2 wt% -4.0 wt%.
In some embodiments, the content of the oxide of the VIII group metal is 3.0-5.0 wt%, the content of the oxide of the VIB group metal is 16.0-24.0 wt%, and the content of the auxiliary agent is P2O5Calculated as 2.0wt percent to 5.0wt percent.
The invention provides a preparation method of a shell type hydrogenation catalyst, which is a preparation method of the shell type hydrogenation catalyst and comprises the following steps:
(1) uniformly mixing pseudo-boehmite with a forming aid, adding a peptizing agent and deionized water for kneading, extruding, drying and roasting to prepare a formed carrier;
wherein the peptization index of the pseudo-boehmite is more than 90%;
(2) and loading the VIII family metal, the VIB family metal and the auxiliary agent on the carrier by an impregnation method, and then curing, drying and roasting to prepare the shell catalyst.
In some embodiments, the pseudoboehmite is a non-silicon pseudoboehmite or a silicon-containing pseudoboehmite.
In some embodiments, the pseudoboehmite has a peptization index of 92% to 96%.
In some embodiments, the impregnation method uses an impregnation solution comprising a compound of a group viii metal selected from at least one of nickel nitrate, nickel sulfate, nickel hydroxycarbonate, nickel acetate, and nickel oxalate; the group VIB metal compound is at least one selected from ammonium heptamolybdate, ammonium tetramolybdate and molybdenum trioxide; the phosphorus compound is at least one selected from phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
In some embodiments, the peptizing agent is selected from at least one of nitric acid, citric acid, acetic acid, tartaric acid.
In some embodiments, in step (1), the drying conditions are: the temperature is 60-180 ℃, and the time is 2-12 h; the roasting conditions are as follows: the temperature is 300-600 ℃, the time is 2-12 h, and the heating speed is 1-3 ℃/min.
In some embodiments, in step (2), the curing conditions are: the temperature is 10-50 ℃, and the time is 1-3 h; the drying conditions are as follows: the temperature is 80-160 ℃, and the time is 2-8 h; the roasting conditions are as follows: the temperature is 400-600 ℃, the time is 3-8 h, and the heating speed is 1-3 ℃/min.
In some embodiments, the forming aid is an extrusion aid.
The core of the preparation method is to prepare the catalyst with the active metal component distributed as a shell layer by utilizing the relevance of the peptization of the pseudo-boehmite and the distribution of the active metal component on the surface of the carrier.
The pseudoboehmite peptization index of the invention is known to those skilled in the art and can be analyzed according to the following method:
weighing 10g of pseudoboehmite (A1) with particle size less than 80 μm2O3Mass fraction of W1) Placing in 250mL conical flask, adding appropriate amount of distilled water, stirring, adding appropriate amount of nitric acid, stirring for 10min, centrifuging, collecting upper suspension, weighing mass m, and analyzing A12O3Mass fraction (W) of2) The peptization index (DI) is calculated from the following formula:
DI＝m*W2/(10Wl)。
the present invention has no particular requirement for the method for preparing the impregnation fluid, and can be carried out with reference to the prior art, and according to a preferred embodiment of the present invention, the method for preparing the solution containing the group VIII metal compound, the group VIB metal compound and the phosphorus-containing compound can be carried out as follows: adding a nickel (and/or cobalt) containing compound and a molybdenum containing compound into an aqueous solution of a phosphorus containing compound, and heating and stirring to form the aqueous solution.
The impregnation method of the present invention is not particularly limited, and various impregnation methods in the prior art may be used, for example, spray impregnation, equal-volume impregnation or excess liquid impregnation, and among them, equal-volume impregnation and saturation impregnation are preferred.
In the present invention, the amount of the solution can be selected according to the specific impregnation method, and those skilled in the art can know that, for example, when the impregnation is equal-volume impregnation, the amount of the solution is the saturated water absorption capacity of the carrier.
The active components in the shell type hydrogenation catalyst are distributed in an egg shell type. By "eggshell" catalyst is meant: the catalyst has a shell factor sigma of 0-0.95. Wherein the shell factor σ is a ratio of a concentration of the metal component at a center of the catalyst particle to a concentration at an outer surface; the concentration at the outer surface of the catalyst refers to the average value of 20 numerical point counting rates near the outer surface along the radial direction of the carrier in the SEM-EDS characterization result; the concentration at the center of the catalyst refers to the average value of the recording rate of 20 values around the central point along the radial direction of the carrier in the SEM-EDS characterization result. And in the SEM-EDS characterization result, the counting rate of each point along the radial direction of the carrier corresponds to the metal content of the point, and the size of the counting rate reflects the metal content of the point but does not represent the real content of the metal of the point. The σ value represents the distribution form of the active component on the catalyst and quantitatively indicates the degree of unevenness in the case of uneven distribution.
In the present invention, σ M represents the ratio of the concentration of the metal active component at the center of the catalyst particle to the concentration at the outer surface, and σ Mo, for example, represents the ratio of the concentration of metallic molybdenum at the center of the catalyst particle to the concentration at the outer surface.
In the invention, the catalyst element composition is determined by adopting an X-ray fluorescence spectrometry after the catalyst is roasted at 550 ℃ for 4 h.
Comparative example 1 is for explaining a conventional hydrorefining catalyst in which active components are uniformly distributed and a preparation method thereof; examples 2-6 are provided to illustrate hydrofinishing catalysts having a non-uniform distribution of active components ("eggshell" distribution) and methods for making the same.
Comparative example 1
200 g of silicon-free pseudo-boehmite (peptization index 86%) and 6g of extrusion assistant sesbania powder are weighed and mixed uniformly, 6g of peptizing agent and 180g of deionized water are added for kneading, then a strip extruder (manufacturer: general plant of science and technology industry of south China university, model: F-26) is used for extruding a clover-shaped strip with the circumscribed circle diameter of 1.5 mm, then the clover-shaped strip is dried for 4 hours at 120 ℃ and roasted for 4 hours at 550 ℃ to obtain a carrier Z1, the alumina in the carrier is gamma-alumina, and the saturated impregnation water absorption of the carrier is 77 wt% (based on the weight of the carrier).
Adding 36.6 g of molybdenum trioxide and 15.8 g of basic nickel carbonate (NiO content is 57 wt%) into an aqueous solution containing 17.6 g of phosphoric acid (mass fraction is 85%), heating, stirring and dissolving, and fixing the volume to 110 ml;
100 g of the support Z1 was weighed out and in a 500mL beaker, the support Z1 was immersed in 77 mL of the above solution at room temperature and 20 ℃ for 1 hour, then dried at 120 ℃ for 4 hours and calcined at 480 ℃ for 4 hours to give the catalyst C1, the active metal component of which was uniformly distributed as determined by SEM-EDS.
The composition of catalyst C1, calculated as oxide, after calcination at 480 ℃ for 4 hours is given in Table 1.
Example 1
Weighing 500 g of silicon-free pseudo-boehmite (peptization index is 90%) and 15g of extrusion assistant sesbania powder, uniformly mixing, adding 15g of peptizing agent and 445g of deionized water, kneading, extruding into clover-shaped strips with the diameter of the circumscribed circle of 1.5 mm by using a strip extruding machine (manufacturer: general plant of science and technology industries of south China university, model: F-26), drying at 120 ℃ for 4 hours, roasting at 550 ℃ for 4 hours to obtain a carrier Z2, and characterizing that the alumina in the carrier is gamma-alumina and the saturated impregnation water absorption of the carrier is 75 wt% (based on the weight of the carrier) by X-ray diffraction.
Adding 36.6 g of molybdenum trioxide and 15.8 g of basic nickel carbonate (NiO content is 57 wt%) into an aqueous solution containing 17.6 g of phosphoric acid (mass fraction is 85%), heating, stirring and dissolving, and fixing the volume to 107 ml;
60 g of the support Z2 was weighed out and, in a 500mL beaker, the support Z2 was immersed in 45 mL of the above solution at room temperature and 20 ℃ for 1 hour, then dried at 120 ℃ for 4 hours and calcined at 480 ℃ for 4 hours to give the catalyst C2, the active metal component of which was found to have a heterogeneous "eggshell" type distribution by SEM-EDS measurement. The composition of catalyst C2, calculated as oxide, after calcination at 480 ℃ for 4 hours is given in Table 1.
Example 2
Weighing 500 g of silicon-free pseudo-boehmite (peptization index is 96%) and 15g of extrusion assistant sesbania powder, uniformly mixing, adding 15g of peptizing agent and 445g of deionized water, kneading, extruding into clover-shaped strips with the diameter of 1.5 mm of the circumscribed circle by a strip extruding machine (manufacturer: general scientific and technical industries of south China university, model: F-26), drying at 120 ℃ for 4 hours, roasting at 550 ℃ for 4 hours to obtain a carrier Z3, and characterizing that the alumina in the carrier is gamma-alumina and the saturated impregnation water absorption of the carrier is 74 wt% (based on the weight of the carrier) by X-ray diffraction.
Adding 36.6 g of molybdenum trioxide and 15.8 g of basic nickel carbonate (NiO content is 57 wt%) into an aqueous solution containing 17.6 g of phosphoric acid (mass fraction is 85%), heating, stirring and dissolving, and fixing the volume to 106 ml;
60 g of the support Z3 was weighed out and, in a 500mL beaker, the support Z3 was immersed in 44 mL of the above solution at room temperature and 20 ℃ for 1 hour, then dried at 120 ℃ for 4 hours and calcined at 480 ℃ for 4 hours to give the catalyst C3, the active metal component of which was found to have a heterogeneous "eggshell" type distribution by SEM-EDS measurement. The composition of catalyst C3, calculated as oxide, after calcination at 480 ℃ for 4 hours is given in Table 1.
Example 3
Weighing 500 g of siliceous pseudo-boehmite (peptization index of 92 percent), uniformly mixing with 15g of sesbania powder serving as an extrusion aid, adding 15g of peptizing agent and 445g of deionized water for kneading, extruding into clover-shaped strips with the circumscribed circle diameter of 1.5 mm by using a strip extruding machine (manufacturer: general plant of science and technology industries of south China university, model: F-26), drying at 120 ℃ for 4 hours, roasting at 550 ℃ for 4 hours to obtain a carrier Z4, and characterizing that the alumina in the carrier is gamma-alumina by X-ray diffraction, and the saturated impregnation water absorption of the carrier is 80wt percent (based on the weight of the carrier).
Adding 36.6 g of molybdenum trioxide and 15.8 g of basic nickel carbonate (NiO content is 57 wt%) into an aqueous solution containing 17.6 g of phosphoric acid (mass fraction is 85%), heating, stirring and dissolving, and fixing the volume to 114 ml;
60 g of the support Z4 was weighed out and, in a 500mL beaker, the support Z4 was immersed in 48 mL of the above solution at room temperature and 20 ℃ for 1 hour, then dried at 120 ℃ for 4 hours and calcined at 480 ℃ for 4 hours to give the catalyst C4, the active metal component of which was found to have a heterogeneous "eggshell" type distribution by SEM-EDS measurement. The composition of catalyst C4, calculated as oxide, after calcination at 480 ℃ for 4 hours is given in Table 1.
Example 4
Adding 28.5 g of molybdenum trioxide and 11.8 g of basic nickel carbonate (the NiO content is 57 wt%) into an aqueous solution containing 17.6 g of phosphoric acid (the mass fraction is 85%), heating, stirring and dissolving, and fixing the volume to 106 ml;
60 g of the support Z3 was weighed out and, in a 500mL beaker, the support Z3 was immersed in 44 mL of the above solution at room temperature and 20 ℃ for 1 hour, then dried at 120 ℃ for 4 hours and calcined at 480 ℃ for 4 hours to give the catalyst C5, the active metal component of which was found to have a heterogeneous "eggshell" type distribution by SEM-EDS measurement. The composition of catalyst C5, calculated as oxide, after calcination at 480 ℃ for 4 hours is given in Table 1.
Example 5
Adding 28.5 g of molybdenum trioxide and 11.8 g of basic nickel carbonate (the NiO content is 57 wt%) into an aqueous solution containing 17.6 g of phosphoric acid (the mass fraction is 85%), heating, stirring and dissolving, and fixing the volume to 114 ml;
60 g of the support Z4 was weighed out and, in a 500mL beaker, the support Z4 was immersed in 48 mL of the above solution at room temperature and 20 ℃ for 1 hour, then dried at 120 ℃ for 4 hours and calcined at 480 ℃ for 4 hours to give the catalyst C6, the active metal component of which was found to have a heterogeneous "eggshell" type distribution by SEM-EDS measurement. The composition of catalyst C6 after calcination at 550 ℃ for 4 hours, calculated as oxide, is given in Table 1.
Example 6
Adding 48.8 g of molybdenum trioxide and 19.7 g of basic nickel carbonate (NiO content is 57 wt%) into an aqueous solution containing 17.6 g of phosphoric acid (mass fraction is 85%), heating, stirring and dissolving, and fixing the volume to 106 ml;
60 g of the support Z3 was weighed out and, in a 500mL beaker, the support Z3 was immersed in 44 mL of the above solution at room temperature and 20 ℃ for 1 hour, then dried at 120 ℃ for 4 hours and calcined at 480 ℃ for 4 hours to give the catalyst C7, the active metal component of which was found to have a heterogeneous "eggshell" type distribution by SEM-EDS measurement. The composition of catalyst C7 after calcination at 550 ℃ for 4 hours, calculated as oxide, is given in Table 1.
TABLE 1 composition of the catalysts
From the results of table 1, it can be demonstrated that the hydrorefining catalysts formed by the metal compounds formed by the active components described in examples 1 to 6 distributed in an "eggshell type" on the carrier have higher relative hydrodesulfurization activity, compared to the hydrorefining catalysts formed by the metal compounds formed by the active components described in comparative example 1 distributed uniformly on the carrier. The method realizes the eggshell type distribution of the active components on the carrier by controlling the peptization index of the pseudoboehmite to be more than 90 percent, has simple operation and small environmental pollution, and the prepared catalyst can be used for hydrofining of light petroleum fractions, particularly diesel oil fractions and has higher hydrodesulfurization activity.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (10)
1. A shell-type hydrogenation catalyst is characterized in that Al is used2O3Or Al containing silicon2O3The catalyst is used as a carrier, metals of a VIII group and a VIB group are used as active components, phosphorus is used as an auxiliary agent, metal compounds formed by the active components are distributed on the carrier in an egg-shell shape, the content of the metal of the VIII group is 0.5 wt% -5.0 wt% by oxide, the content of the metal of the VIB group is 10.0 wt% -28.0 wt% by oxide, and the content of the auxiliary agent is P2O5Calculated as 0.3 wt% to 7.0 wt%, ofThe content of the carrier is 65.0 wt% -85.0 wt%.
2. The shell hydrogenation catalyst of claim 1 wherein said group VIII metal is nickel and said group VIB metal is molybdenum.
3. The shell-type hydrogenation catalyst according to claim 1, wherein said silicon-containing Al is2O3With Al2O3On a basis of SiO2The content of (A) is 0.1 wt% -5.0 wt%.
4. The shell-type hydrogenation catalyst according to claim 3, wherein said silicon-containing Al is2O3With Al2O3On a basis of SiO2The content of (A) is 2 wt% -4.0 wt%.
5. The shell-type hydrogenation catalyst as claimed in claim 1, wherein the content of the oxide of the VIII group metal is 3.0-5.0 wt%, the content of the oxide of the VIB group metal is 16.0-24.0 wt%, and the content of the auxiliary agent is P2O5Calculated as 2.0wt percent to 5.0wt percent.
6. A method for producing a shell-type hydrogenation catalyst according to any one of claims 1 to 5, comprising the steps of:
(1) uniformly mixing pseudo-boehmite or silicon-containing pseudo-boehmite with a forming auxiliary agent, adding a peptizing agent and deionized water for kneading, extruding, drying and roasting to prepare a formed alumina or silicon-containing alumina carrier;
wherein the peptization index of the pseudo-boehmite or the silicon-containing pseudo-boehmite is more than 90 percent;
(2) and loading the VIII family metal, the VIB family metal and the auxiliary agent on the carrier by an impregnation method, and then drying and roasting to prepare the shell layer catalyst.
7. The method for preparing the shell-type hydrogenation catalyst according to claim 6, wherein the peptization index of the pseudoboehmite or the siliceous pseudoboehmite is 92-96%.
8. The preparation method of the shell-type hydrogenation catalyst according to claim 6, wherein the impregnation method comprises an impregnation solution containing a group VIII metal compound, a group VIB metal compound and a phosphorus compound, wherein the group VIII metal compound is selected from at least one of nickel nitrate, nickel sulfate, basic nickel carbonate, nickel acetate and nickel oxalate; the group VIB metal compound is at least one selected from ammonium heptamolybdate, ammonium tetramolybdate and molybdenum trioxide; the phosphorus compound is at least one selected from phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
9. The method for preparing a shell-type hydrogenation catalyst according to claim 6, wherein the peptizing agent is at least one selected from nitric acid, citric acid, acetic acid, and tartaric acid.
10. The method for preparing a shell-type hydrogenation catalyst according to claim 6,
in the step (1), the drying conditions are as follows: the temperature is 60-180 ℃, and the time is 2-12 h; the roasting conditions are as follows: the temperature is 300-600 ℃, the time is 2-12 h, and the heating speed is 1-3 ℃/min;
in the step (2), the health preserving conditions are as follows: the temperature is 10-50 ℃, and the time is 1-3 h; the drying conditions are as follows: the temperature is 80-160 ℃, and the time is 2-8 h; the roasting conditions are as follows: the temperature is 400-600 ℃, the time is 3-8 h, and the heating speed is 1-3 ℃/min.
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