CN108568309B - Oil product deep hydrodesulfurization catalyst and preparation method thereof - Google Patents
Oil product deep hydrodesulfurization catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000839 emulsion Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229910001868 water Inorganic materials 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 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 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 9
- 229940010552 ammonium molybdate Drugs 0.000 claims description 9
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 9
- 239000011609 ammonium molybdate Substances 0.000 claims description 9
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 9
- 229920000053 polysorbate 80 Polymers 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 abstract description 58
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 16
- 229910003294 NiMo Inorganic materials 0.000 abstract description 10
- 238000006477 desulfuration reaction Methods 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 8
- 230000023556 desulfurization Effects 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 238000011156 evaluation Methods 0.000 abstract description 5
- 238000005470 impregnation Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052961 molybdenite Inorganic materials 0.000 abstract description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 abstract description 3
- 239000012876 carrier material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 37
- 239000003921 oil Substances 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 239000013335 mesoporous material Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000037361 pathway Effects 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 101100493710 Caenorhabditis elegans bath-40 gene Proteins 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 101710178035 Chorismate synthase 2 Proteins 0.000 description 1
- 101710152694 Cysteine synthase 2 Proteins 0.000 description 1
- 244000282866 Euchlaena mexicana Species 0.000 description 1
- 229910015338 MoNi Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- -1 alkyl dibenzothiophene sulfides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
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Abstract
The invention relates to an oil product deep hydrodesulfurization catalyst and a preparation method thereof, wherein a specific multiple emulsion system is designed to prepare a hollow spherical SBA-15 carrier material, the hydrothermal stability of the SBA-15 is improved and the acid site number of the SBA-15 is increased through aluminum modification, and then an isometric distribution impregnation method is adopted to load metal active components on the carrier to prepare a NiMo/SBA-15-SP catalyst which not only has proper MoS2The catalyst has the advantages of high dispersity, high B, L acid site number, excellent DBT reaction molecule diffusion performance, capability of improving the overall reaction rate, evaluation on the activity of the Dibenzothiophene (DBT) hydrodesulfurization reaction, and excellent DBT desulfurization conversion frequency TOF and rate constant.
Description
Technical Field
The invention relates to the field of petrochemical engineering catalysis, in particular to an oil product deep hydrodesulfurization catalyst and a preparation method thereof.
Background
The problem of environmental pollution caused by automobile exhaust emission becomes an important problem which needs to be solved urgently in national economy and social sustainable development of China. In order to solve the serious problem, increasingly strict environmental protection regulations and emission standards thereof are set by countries in the world, and meanwhile, different coping methods such as improving and updating the structure of an automobile engine, designing and installing an efficient automobile exhaust purification device and the like are adopted. The most fundamental method for realizing the oil production of clean fuel is to adopt the production and processing technology of directly improving the quality of the oil and improving the oil. Compared with other desulfurization technical routes (oxidation desulfurization, adsorption desulfurization, biological desulfurization and the like), the hydrodesulfurization technology is one of the most effective means for producing clean diesel at present. Currently, many refineries operate by changing the operating process parameters of oil production: such as increasing H2 pressure, increasing reaction temperature, reducing space velocity and other parameters to achieve the improvement of desulfurization rate, but at the same time, the method also brings many negative effects of high energy consumption, low liquid yield, high equipment investment and the like. The development of novel and efficient catalysts is the core of the progress of hydrodesulfurization technology.
In the hydrodesulfurization catalyst, the carrier plays an important role, the carrier with excellent performance not only can ensure that the dispersion state of the active component and the auxiliary agent in the catalyst is good, but also can adjust the interaction between the carrier and the active component, and the proper acidity and the pore channel structure are favorable for improving the composition distribution of the product, promoting the hydrodesulfurization reaction activity and improving the quality of the final product. However, the HDS catalyst using alumina as a carrier, which is widely used in the industry at present, has uneven pore channels and large diffusion resistance, so that reactants are difficult to approach the active center of the catalyst; meanwhile, the alumina only has an L acid center, and cannot meet the requirement of deep removal of alkyl dibenzothiophene sulfides with steric hindrance, such as Dibenzothiophene (DBT), so that the hydrodesulfurization effect of the catalyst is influenced. In addition to the acidity of the support, the morphology, pore structure and pore size of the support also have a significant influence on the catalytic performance of the catalyst. For example, it is reported in the literature that the morphology and pore size of SBA-15 have a large effect on the diffusion properties of reactant and product molecules, and also on the dispersion of active components.
SBA-15 has the advantages of high specific surface area, thick pore wall, controllable pore size and the like, and is one of the most widely researched mesoporous materials as a typical mesoporous molecular sieve. However, the framework structure of SBA-15 is completely composed of silicon dioxide, only the silicon hydroxyl groups on the surface of the silicon dioxide have weak acidity, and the acidity of SBA-15 is far lower than that of the microporous molecular sieve with a crystal framework structure. In addition, a large amount of Si-OH groups exist on the surface of SBA-15, and the groups are easily attacked by water molecules to generate hydrolysis reaction of framework Si-O-Si, so that the collapse of the framework structure is caused, and therefore, the general hydrothermal stability of the mesoporous material is generally poor, which severely limits the practical application of the mesoporous material as a catalyst or a catalyst carrier in the field of petrochemical industry. Besides the characteristics of the SBA-15 mesoporous material such as acidity and hydrothermal stability, the particle morphology and the pore structure of the SBA-15 also have great influence on the catalytic performance of the catalyst. The particle morphology and the pore structure of the SBA-15 mainly influence the dispersion degree of the active components and the diffusion performance of the reaction molecules. In addition to modification of the SBA-15 vector, the interaction between SBA-15 and the active ingredient requires further regulation. The strength of the acting force between the carrier and the active component has important influence on the reaction activity of the catalyst; the active component is easy to fall off in the reaction process because the acting force of the carrier and the active component is too weak; conversely, too strong a force of the carrier against the active component will result in the active metal oxide being difficult to reduce. Therefore, a large number of researchers modify the SBA-15 mesoporous material so as to improve the physical and chemical characteristics of the SBA-15, and the modification mainly comprises the morphology control of the SBA-15, the compounding of the SBA-15 mesoporous and microporous molecular sieve, the preparation of other mesoporous materials by an SBA-15 hard template method and the like. Therefore, the design and development of the hydrodesulfurization catalyst with high activity have great significance for producing ultra-clean oil products.
Disclosure of Invention
Aiming at the technical problems, the invention provides an oil product deep hydrodesulfurization catalyst and a preparation method thereof, wherein a specific multiple emulsion system is designed to prepare a hollow spherical SBA-15 carrier material, the hydrothermal stability of the SBA-15 is improved and the acid site number of the SBA-15 is increased through aluminum modification, then an isometric distribution impregnation method is adopted to load metal active components on the carrier, and the prepared NiMo/SBA-15-SP catalyst is used for evaluating the hydrodesulfurization reaction activity of Dibenzothiophene (DBT), so that excellent DBT desulfurization conversion frequency TOF and rate constant are displayed.
The invention is realized by the following technical scheme:
A. adding n-hexane solution containing tween 80 into sodium silicate solution, mixing to form W/O emulsion,
B. adding P123 to the other aqueous solution; then adding tetraethyl orthosilicate into the water solution containing P123 to form W/O emulsion;
C. adding the W/O emulsion obtained in the step B into the W/O emulsion formed in the step A, homogenizing for 11-20 min, finally forming W/O/W multiple emulsion by using the mixed solution, placing the W/O/W multiple emulsion in a water bath at 35 ℃, and stirring and dissolving for 60 min;
D. stirring for dissolving, aging for 24h under static state, transferring into crystallization kettle, and crystallizing for 24h at 100 deg.C;
E. filtering, washing, drying at 80 ℃ for 12h, and then calcining at 550 ℃ at high temperature to remove the surfactant;
F. a certain amount of Al (NO)3)3·9H2Adding O into water for dissolving; then adding 0.5g of SBA-15 solid powder obtained in the step E, and stirring and reacting for 12 hours at room temperature; filtering and washing with deionized water, drying at 100 deg.C for 12 hr, and calcining at 550 deg.C for 6 hr
G. And weighing ammonium molybdate in a certain mass according to the calculated Mo amount, and dissolving in a small amount of water. Adding an ammonium molybdate aqueous solution into the Al-SBA-15 carrier obtained in the step F, uniformly stirring by using a glass rod, placing in a 100 ℃ oven, drying for 4h, placing in a muffle furnace, and roasting for 4h to obtain a product dipped for one time;
H. weighing a certain mass of nickel nitrate, dissolving the nickel nitrate in a proper amount of water, adding a nickel nitrate aqueous solution into the product dipped in the step G, uniformly stirring the product by using a glass rod, placing the product in a 100 ℃ oven, drying the product for 4 hours, placing the product in a muffle furnace, and roasting the product for 4 hours;
I. and G and H are repeated, and the obtained catalyst sample is tabletted and crushed to be prepared into particles of 40-60 meshes for later use.
The volume ratio of the n-hexane to the tween 80 in the step A is 15-20:1, and the mass ratio of the sodium silicate to the n-hexane solution containing the tween 80 is 1-4: 10;
the mass ratio of the P123 to the water in the step B is 1: 8-18 percent of TEOS, wherein the mass percent of TEOS is 10-30 percent;
the mass ratio of the emulsion formed in the step B and the emulsion formed in the step A added in the step C is 2-3: 1;
al (NO) in step F above3)3·9H2The addition amount of O is 0.1-0.3 g;
wherein, the metal active component Mo and the active auxiliary agent Ni are loaded on the carrier by adopting an isometric stepwise impregnation method. Mo in the prepared catalyst is MoO3The mass fraction is 11%; the mass fraction of Ni is 3.5 percent calculated by NiO.
The invention has the beneficial effects that: the hollow spherical MoNi/Al-SBA-15 catalyst prepared by the multiple emulsion method, wherein the selection of the double emulsion and the silicon source is the key for regulating and controlling the appearance of the hollow spherical shape, the hollow spherical shape can not be obtained under the condition that any one or more conditions of the emulsion or the silicon source are changed, and the catalyst not only has proper MoS2The dispersion degree and the B, L acid site number also have excellent DBT reaction molecule diffusion performance, thereby showing higher DBT HDS activity, and reactant molecules DBT can be rapidly diffused out from the inside of the pore channel after entering the pore channel and contacting with the active sites, thereby improving the overall reaction rate. Meanwhile, the HYD/DDS ratio of the hollow spherical NiMo/Al-SBA-15 catalyst is 0.28, while the HYD/DDS ratio of the NiMo/gamma-Al 2O3 catalyst reaches 0.72. This indicates that the DBT hydrodesulfurization pathway of the NiMo/Al-SBA-15 catalyst is mainly carried out in a DDS direct hydrodesulfurization pathway, while for the NiMo/gamma-Al 2O3 catalyst, both the direct hydrodesulfurization pathway (DDS) and the hydrodesulfurization-before-hydrogenation pathway (HYD) have an effect on DBT hydrodesulfurization, which is mainly attributed to MoS2The dispersity is different from the B, L acid site quantity, and the catalyst has higher B acid site quantity, which is beneficial to the direct hydrodesulfurization, so that the hydrodesulfurization performance of DBT is improved.
Drawings
FIG. 1 is an SEM photograph of the catalyst prepared in example 1;
FIG. 2 is a TEM image of the catalyst prepared in example 1;
FIG. 3 is a schematic view of a DBT hydrodesulfurization activity evaluation unit;
fig. 4 is a diagram of the reaction network for DBT hydrodesulfurization over different catalysts.
Detailed Description
The following detailed description is made with reference to the accompanying drawings.
Example 1
An oil product deep hydrodesulfurization catalyst and a preparation method thereof and a DBT deep hydrodesulfurization method are disclosed:
A. adding a normal hexane solution containing tween 80 into a sodium silicate solution, and forming a W/O emulsion by using the mixed solution, wherein the volume ratio of the normal hexane to the tween 80 is 17:1, and the mass ratio of the sodium silicate to the normal hexane solution containing the tween 80 is 3: 10;
B. adding P123 to the other aqueous solution; and then adding tetraethyl orthosilicate into the water solution containing P123 to form W/O emulsion, wherein the mass ratio of P123 to water is 1: 12, the mass percent of TEOS is 20%;
C. adding the W/O emulsion obtained in the step B into the W/O emulsion formed in the step A, homogenizing for 11-20 min, finally forming W/O/W multiple emulsion by using the mixed solution, placing the multiple emulsion in a water bath at 35 ℃, stirring and dissolving for 60min, wherein the mass ratio of the emulsion formed in the step B to the emulsion formed in the step A is 2: 1;
D. stirring for dissolving, aging for 24h under static state, transferring into crystallization kettle, and crystallizing for 24h at 100 deg.C;
E. filtering, washing, drying at 80 ℃ for 12h, and then calcining at 550 ℃ at high temperature to remove the surfactant;
F. 0.2g of Al (NO)3)3·9H2Adding O into water for dissolving; then adding 0.5g of SBA-15 solid powder obtained in the step E, and stirring and reacting for 12 hours at room temperature; filtering and washing with deionized water, drying at 100 deg.C for 12 hr, and roasting at 550 deg.C for 6 hr;
G. and weighing ammonium molybdate in a certain mass according to the calculated Mo amount, and dissolving in a small amount of water. Adding an ammonium molybdate aqueous solution into the Al-SBA-15 carrier obtained in the step F, uniformly stirring by using a glass rod, placing in a 100 ℃ oven, drying for 4h, placing in a muffle furnace, and roasting for 4h to obtain a product dipped for one time;
H. weighing a certain mass of nickel nitrate, dissolving the nickel nitrate in a proper amount of water, adding a nickel nitrate aqueous solution into the product dipped in the step G, uniformly stirring the product by using a glass rod, placing the product in a 100 ℃ oven, drying the product for 4 hours, placing the product in a muffle furnace, and roasting the product for 4 hours;
I. and G and H are repeated, the obtained catalyst sample is subjected to tabletting and crushing, and is prepared into particles of 40-60 meshes for later use, wherein the metal active component Mo and the active auxiliary agent Ni are loaded on the carrier by adopting an isometric stepwise impregnation method. Mo in the prepared catalyst is MoO3The mass fraction is 11%; the mass fraction of Ni is 3.5 percent based on NiO, and the specific morphology of the obtained catalyst is shown in figures 1-2.
The activity evaluation of the Dibenzothiophene (DBT) hydrodesulfurization reaction is also carried out on a JQ-III type high-pressure fixed bed micro-reactor, and as shown in FIG. 3, the activity evaluation of the catalyst HDS takes a cyclohexane solution containing a sulfur model compound DBT as a reaction raw material, and the evaluation process is as follows: the catalyst loading used was 0.5g and was first presulfided, i.e. the catalyst was presulfided for 4h in a cyclohexane solution containing 2% CS 2. The prevulcanization conditions are as follows: temperature 360 deg.C, pressure 4.0MPa, H2the/Oil ratio (v/v) was 200 and the WHSV was 4.0h-1. After the pre-vulcanization is finished, the reaction is continued after the reaction raw material DBT is switched to. The DBT HDS reaction evaluation conditions were: the sulfur content in the cyclohexane solution is 500ppm, the reaction temperature is 320 ℃, the reaction pressure is 4MPa, and H is2The oil ratio (v/v) is 200, and the WHSV ranges from 10 to 200h–1Is adjustable. After the reaction system is stabilized, sampling for 3 times at each airspeed, and performing off-line analysis on the samples.
The total sulfur content of the DBT feedstock and the hydrogenated product was determined by analytical measurement using a sulfur-nitrogen analyzer (RPP-2000SN) manufactured by Tezhou Medium-Ring Analyzer, Inc., and the distribution of the hydrodesulfurization products was analyzed by a Thermo Finnigan DSQ gas chromatograph-mass spectrometer, having a HP-5MS elastoquartz capillary column (specification: 60 m. times.0.25 mm. times.0.25 m). The chromatographic test conditions were as follows: carrier gas: 99.999% helium; sample inlet temperature: 300 ℃; column temperature: 50 ℃; the temperature raising program is to raise the temperature from the column temperature of 20 ℃/min to 300 ℃ and keep the temperature for 10 min; the flow rate of the carrier gas was controlled to 1 mL/min. The mass spectrum adopts an EI source with the voltage of 70 eV; the filament current is 100A; multiplier voltage 1.2 KV; the mass range is 35-400 amu.
Comparative example 1
Preparation of spherical SBA-15 according to prior art methods
1. Weighing 2g P123 and 0.4g CTAB, adding into 45g HCl (2mol/L) and 15g H2O, placing in water bath 40 ℃, stirring and dissolving for about 4 h;
2. dropwise adding 5.8g of TEOS into the mixture 1, quickly stirring for 5min, and standing for 24h at 40 ℃;
3. then the mixture is transferred into a 100mL crystallization kettle and crystallized for 24 hours at the temperature of 100 ℃;
4. filtering, washing, drying at 80 deg.C for 12 hr, and calcining at 550 deg.C to remove surfactant.
With Al (NO)3)3·9H2O as aluminum source for modifying SBA-15
1. 0.2 of Al (NO)3)3·9H2Adding O into 50mL of water for dissolving;
2. then adding 0.5g of SBA-15 solid powder, and stirring and reacting for 12 hours at room temperature;
3. washed by deionized water filtration, dried at 100 ℃ for 12h, and then calcined at 550 ℃ for 6 h.
Load metal NiMo
1. And weighing ammonium molybdate in a certain mass according to the calculated Mo amount, and dissolving in a small amount of water. Adding an ammonium molybdate aqueous solution into an Al-SBA-15 carrier, uniformly stirring by using a glass rod, placing in a 100 ℃ oven, drying for 4h, placing in a muffle furnace, and roasting for 4h to obtain a product dipped for one time;
2. weighing a certain mass of nickel nitrate, dissolving the nickel nitrate in a proper amount of water, adding a nickel nitrate aqueous solution into the product dipped in the step G, uniformly stirring the product by using a glass rod, placing the product in a 100 ℃ oven, drying the product for 4 hours, placing the product in a muffle furnace, and roasting the product for 4 hours;
3. and (3) repeating the steps 1 and 2, tabletting and crushing the obtained catalyst sample to prepare particles of 40-60 meshes for later use, wherein the metal active component Mo and the active auxiliary agent Ni are loaded on the carrier by adopting an isometric stepwise impregnation method. Mo in the prepared catalyst is expressed as MoO3The mass fraction is 11%; the mass fraction of Ni, calculated as NiO, was 3.5%, and DBT deep desulfurization hydrogenation was performed under the same conditions as in example 1.
Comparative example 2
On the basis of the comparative example 1, the silicon source in the step A and the silicon source in the step B are both tetraethyl orthosilicate, other conditions are unchanged, and the obtained product is in a short column shape.
Comparative example 3
On the basis of the comparative example 1, the tetraethyl orthosilicate in the step A, the silicon source in the step B are sodium silicate, other conditions are unchanged, and the obtained product is long-strip-shaped.
Comparative example 4
On the basis of comparative example 1, the synthesized hollow spherical SBA-15 was replaced with the same mass of γ -Al2O3, and the other conditions were not changed.
The DBT HDS rate constant, TOF, HYD/DDS and other kinetic parameters of the catalysts in different embodiments are shown in Table 1, and as can be seen from Table 1, the hollow spherical catalyst disclosed by the application shows excellent deep hydrodesulfurization activity and has a good application prospect, and the morphology has a decisive influence on the rate constant, the TOF and other activity parameters.
Table 1: DBT deep hydrodesulfurization activity parameter for the catalysts of the above examples
Steps 1-7 in the reaction network for DBT hydrodesulfurization are typical reaction pathways for the NiMo/γ -Al2O3 catalyst to catalyze DBT hydrodesulfurization (as shown in FIG. 4), and some products will react further because the NiMo/Al-SBA-15 catalyst has more B, L acid sites. It is reported in the literature that more acidic sites contribute to the hydrocracking and isomerization performance of the catalyst. In the hydrogenation-followed-desulfurization reaction pathway, hydrogenation of the first benzene ring (THDBT) is the rate-controlling step, followed by further faster hydrogenation rates, resulting in lower yields of its intermediates (HHDBT and DHDBT). Although no DHDBT product is detected in the product, reaction steps 12 and 13 may still be present in the reaction network due to the faster rate of further reaction of DHDBT. The NiMo/Al-SBA-15 catalyst has a certain amount of B acid sites, and the products CHB and CHEB can further generate isomerization reaction to generate CPMB. The selectivity of the BP product was nearly unchanged with increasing reaction mass residence time, indicating a slower reaction rate for step 3. Additionally, due to the presence of the acidic site of B, DCH also isomerizes to form CPMCH.
Claims (5)
1. A preparation method of an oil product deep hydrodesulfurization catalyst comprises the following specific steps:
A. adding n-hexane solution containing tween 80 into sodium silicate solution, mixing to form W/O emulsion,
B. adding P123 into another aqueous solution, and then adding tetraethyl orthosilicate into the aqueous solution containing P123 to form a W/O emulsion;
C. adding the W/O emulsion obtained in the step B into the W/O emulsion formed in the step A, homogenizing for 11-20 min, finally forming W/O/W multiple emulsion by using the mixed solution, placing the W/O/W multiple emulsion in a water bath at 35 ℃, and stirring and dissolving for 60 min;
D. stirring for dissolving, aging for 24h under static state, transferring into crystallization kettle, and crystallizing for 24h at 100 deg.C;
E. filtering, washing, drying at 80 ℃ for 12h, and then calcining at 550 ℃ at high temperature to remove the surfactant;
F. a certain amount of Al (NO)3)3·9H2Adding O into water for dissolving; then adding 0.5g of SBA-15 solid powder obtained in the step E, and stirring and reacting for 12 hours at room temperature; filtering and washing with deionized water, drying at 100 deg.C for 12 hr, and roasting at 550 deg.C for 6 hr;
G. weighing ammonium molybdate with a certain mass according to the calculated Mo amount, placing the ammonium molybdate in a small amount of water for dissolving, adding an ammonium molybdate aqueous solution into the Al-SBA-15 carrier obtained in the step F, uniformly stirring the solution by using a glass rod, placing the solution in a drying oven at 100 ℃, drying the solution for 4 hours, placing the solution in a muffle furnace, and roasting the solution for 4 hours to obtain a product which is dipped for one time;
H. weighing a certain mass of nickel nitrate, dissolving the nickel nitrate in a proper amount of water, adding a nickel nitrate aqueous solution into the product dipped in the step G, uniformly stirring the product by using a glass rod, placing the product in a 100 ℃ oven, drying the product for 4 hours, placing the product in a muffle furnace, and roasting the product for 4 hours;
I. and repeating the step G and the step H to obtain the oil product deep hydrodesulfurization catalyst.
2. The method for preparing the oil product deep hydrodesulfurization catalyst according to claim 1, which is characterized by comprising the following steps: the volume ratio of the n-hexane to the Tween 80 in the step A is 15-20:1, and the mass ratio of the sodium silicate to the n-hexane solution containing the Tween 80 is 1-4: 10.
3. The preparation method of the oil product deep hydrodesulfurization catalyst according to claim 1 or 2, characterized by comprising the following steps: the mass ratio of the P123 to the water in the step B is 1: 8-18 percent of TEOS, and the mass percentage of TEOS is 10-30 percent.
4. The preparation method of the oil product deep hydrodesulfurization catalyst according to claim 1 or 2, characterized by comprising the following steps: and the mass ratio of the emulsion formed in the step B and the emulsion formed in the step A, which are added in the step C, is 2-3: 1.
5. The preparation method of the oil product deep hydrodesulfurization catalyst according to claim 1 or 2, characterized by comprising the following steps: al (NO) in step F3)3·9H2The amount of O added is 0.1-0.3 g.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5492870A (en) * | 1994-04-13 | 1996-02-20 | The Board Of Trustees Of The University Of Illinois | Hollow ceramic microspheres by sol-gel dehydration with improved control over size and morphology |
| CN1356265A (en) * | 2001-08-20 | 2002-07-03 | 复旦大学 | Process for preparing shape-controllable big-pore mesoporous molecular sieve |
| CN1693203A (en) * | 2005-04-13 | 2005-11-09 | 华东理工大学 | Process for preparing and controlling ordered pore structure of mesicpore molecular sieve |
| CN101298335A (en) * | 2008-03-21 | 2008-11-05 | 太原理工大学 | Hollow mesopore molecular sieve big ball and preparation thereof |
| CN106622308A (en) * | 2015-10-29 | 2017-05-10 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst, preparation method and applications thereof |
| CN107876072A (en) * | 2017-11-10 | 2018-04-06 | 中国石油大学(北京) | A kind of hydrogenation catalyst and its preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10252251B2 (en) * | 2015-08-28 | 2019-04-09 | Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada, Reno | Production of organic materials using solid catalysts |
-
2018
- 2018-04-26 CN CN201810382118.3A patent/CN108568309B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5492870A (en) * | 1994-04-13 | 1996-02-20 | The Board Of Trustees Of The University Of Illinois | Hollow ceramic microspheres by sol-gel dehydration with improved control over size and morphology |
| CN1356265A (en) * | 2001-08-20 | 2002-07-03 | 复旦大学 | Process for preparing shape-controllable big-pore mesoporous molecular sieve |
| CN1693203A (en) * | 2005-04-13 | 2005-11-09 | 华东理工大学 | Process for preparing and controlling ordered pore structure of mesicpore molecular sieve |
| CN101298335A (en) * | 2008-03-21 | 2008-11-05 | 太原理工大学 | Hollow mesopore molecular sieve big ball and preparation thereof |
| CN106622308A (en) * | 2015-10-29 | 2017-05-10 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst, preparation method and applications thereof |
| CN107876072A (en) * | 2017-11-10 | 2018-04-06 | 中国石油大学(北京) | A kind of hydrogenation catalyst and its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| "Synthesis of NiMo catalysts supported on mesoporous Al-SBA-15 with different morphologies and their catalytic performance of DBT HDS";Daowei Gao et al.;《Applied Catalysis B: Environmental》;20141018;第165卷;第269-284页 * |
| "Synthesis of Zr-containing SBA-15 with Hollow Spherical Morphology";Dong Liang et al.;《Chemistry Letters》;20090530;第38卷(第7期);第672-673页 * |
| "不同形貌SBA-15的控制合成";管冬冬 等;《广东化工》;20170115;第44卷(第1期);第21-22页 * |
| "不同形貌SBA-15的控制合成及应用";田旭庆 等;《化工生产与技术》;20141225;第 21 卷(第 6 期);第35-41页 * |
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