CN111659409A - Hydrodesulfurization catalyst and preparation method and application thereof - Google Patents
Hydrodesulfurization catalyst and preparation method and application thereof Download PDFInfo
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- CN111659409A CN111659409A CN202010499553.1A CN202010499553A CN111659409A CN 111659409 A CN111659409 A CN 111659409A CN 202010499553 A CN202010499553 A CN 202010499553A CN 111659409 A CN111659409 A CN 111659409A
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- ionic liquid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 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 66
- 239000002608 ionic liquid Substances 0.000 claims abstract description 45
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 26
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 89
- 239000011259 mixed solution Substances 0.000 claims description 57
- 239000012265 solid product Substances 0.000 claims description 53
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 34
- -1 alkyl imidazole Chemical compound 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 26
- 238000010992 reflux Methods 0.000 claims description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- 239000004202 carbamide Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 150000002603 lanthanum Chemical class 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 150000002751 molybdenum Chemical class 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000006477 desulfuration reaction Methods 0.000 abstract description 12
- 230000023556 desulfurization Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 6
- 150000004706 metal oxides Chemical class 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 4
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 238000001816 cooling Methods 0.000 description 16
- 239000011148 porous material Substances 0.000 description 12
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 10
- SZTAAXUNQDBYJM-UHFFFAOYSA-N C.[N].[N] Chemical compound C.[N].[N] SZTAAXUNQDBYJM-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 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
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JBGWMRAMUROVND-UHFFFAOYSA-N 1-sulfanylidenethiophene Chemical class S=S1C=CC=C1 JBGWMRAMUROVND-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000012546 transfer 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8871—Rare earth metals or actinides
-
- B01J35/394—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2400/02—Gasoline
Abstract
The invention discloses a preparation method of a hydrodesulfurization catalyst on one hand, which comprises the following steps: synthesizing a mesoporous alumina carrier under the assistance of ionic liquid; method for preparing LaCo by citric acid mixing methodl‑ XMoXO3/Al2O3A composite material; the ionic liquid is used for treating the modified perovskite/alumina framework material. The invention also discloses the catalyst prepared by the preparation method and the application of the catalyst in gasoline hydrodesulfurization. In the preparation method provided by the invention, alumina is a good carrier, and diffusion channels of reactant molecules and product molecules are provided; the formation of the metal oxide active center with the perovskite structure improves the metal utilization rate and makes desulfurization easier; the ionic liquid has adjustable structure, uniform distribution of active centers and high activity and selectivity; the combined action of the three components ensures that the catalyst has good hydrodesulfurization catalytic activity and shows good gasoline HDS selectionAnd the octane number loss is small.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a hydrodesulfurization catalyst suitable for a gasoline hydrodesulfurization process and a preparation method and application thereof.
Background
In the finished gasoline in China, catalytic cracking (FCC) gasoline accounts for more than 70%, and the FCC gasoline in China has the characteristics of high sulfur content and high olefin content, so that the quality of the FCC gasoline needs to be further improved and the sulfur content of the FCC gasoline needs to be reduced to realize the upgrading of the quality of the oil products in China and meet the VI gasoline standard in China.
However, in the process of FCC gasoline Hydrodesulfurization (HDS), olefin saturation reaction occurs simultaneously, resulting in serious octane number loss, and therefore, it is a development direction of FCC gasoline hydro-upgrading to develop selective hydrodesulfurization technology, i.e., deep desulfurization while maintaining no or less octane number loss.
At present, gasoline hydrodesulfurization catalysts are mainly researched by focusing on the hydrogenation removal of thiophene sulfides at high temperature and high pressure, a common catalyst is a supported catalyst, Co (Ni) and Mo (W) are used as active metals, alumina is used as a carrier, the active metals are reasonably utilized, the metal action is furthest exerted to improve the activity potential of the catalyst, and the catalyst is the key for realizing the selective hydrodesulfurization of FCC gasoline.
The mesoporous alumina is a material with high scientific research value, wide application and a plurality of crystal structures. Mesoporous alumina is often used as a carrier and adsorbent for catalysts, especially in the chemical and petrochemical industries such as hydrocracking, hydrodesulfurization, automobile exhaust control, and the like. This is because the mesoporous alumina not only has good physical properties and structural characteristics, such as density, specific surface area, pore volume, pore size distribution, etc., but also has good hydrothermal stability and chemical properties. The design of the pore diameter and the pore structure is important for optimizing the pore diffusion transport mode and the selectivity of the product, and the design also shows that the characteristic of the pore structure has very important influence on whether the supported catalyst has higher activity under the conditions of high specific surface area and large pore volume.
The perovskite-type complex oxide ABOy is widely applied in various fields due to the special crystal structure and excellent physical and chemical properties, and is more and more paid attention by researchers. A is usually a lanthanide, located in the center of the cube, coordinated to 12O's; b is a metal element with a smaller ion radius than A, is positioned at the top corner of the cube and can coordinate with 6O. Doping or substituting different elements for A site and B site ions will result in ABO3The generated crystal lattice defect or the abnormal valence state of the B-site ion generates oxygen vacancy and cavity in the structure of the integral catalyst, and the perovskite catalyst has unique physical and chemical properties, so that the material is used in catalytic oxidation, environmental catalysis, catalytic hydrogenation, hydrocracking, photocatalysis, solid fuel cell and chemical reactionThe study of sensors and the like has been widely conducted. However, the supported perovskite metal oxide has less reports as a light oil hydrogenation catalyst.
Disclosure of Invention
The invention aims to provide a gasoline hydrogenation catalyst which has adjustable carrier pore structure, good dispersion degree of active components, adjustable acidity and more effective active surfaces of the catalyst, and a preparation method and application thereof, aiming at the requirements of the existing hydrodesulfurization technology.
In order to achieve the above object, the present invention provides a preparation method of a hydrodesulfurization catalyst, comprising the steps of:
1) mixing Al (NO)3)3·9H2Adding O and urea into the ionic liquid aqueous solution to form a mixed solution A, and placing the mixed solution A into a reaction kettle for reaction;
2) centrifugally separating the reacted mixed solution, washing and drying to obtain white powder; roasting the white powder to obtain an alumina product;
3) dissolving soluble lanthanum salt, soluble cobalt salt, soluble molybdenum salt and citric acid in water and ethylene glycol to form a mixed solution B;
4) adding the alumina product into the mixed solution B, and carrying out ultrasonic reaction;
5) after the ultrasonic reaction is finished, filtering to obtain a solid product C, and then drying and roasting the solid product C to obtain LaCol-XMoXO3/Al2O3A composite material;
6) subjecting the LaCo tol-XMoXO3/Al2O3And adding the composite material into a mixed solution of ionic liquid and toluene, carrying out reflux reaction, and separating a solid product D after the reflux reaction is finished to obtain the catalyst.
Alternatively, according to the preparation method of the hydrodesulfurization catalyst, in the ionic liquid, the cation is one or two of alkyl imidazole and quaternary ammonium ion, and the anion is one or more of halogen ion, tetrafluoroborate, hexafluorophosphate, borate, phosphate, carbonate and hydroxide.
Alternatively, according to the preparation method of the hydrodesulfurization catalyst, the mixed solution A is reacted at the temperature of 150 ℃ and 200 ℃ for 16-24 h.
Alternatively, according to the preparation method of the hydrodesulfurization catalyst, the ionic liquid and Al (NO)3)3·9H2The molar ratio of O to urea is 1:10: 30.
Alternatively, according to the preparation method of the hydrodesulfurization catalyst, the white powder is calcined at the temperature of 500-700 ℃ for 4-6 h.
Alternatively, according to the method for preparing a hydrodesulfurization catalyst of the present invention, x is 0.2 to 0.8.
Alternatively, according to the preparation method of the hydrodesulfurization catalyst, the ultrasonic reaction is performed at a frequency of 40 to 60kHz for 20 to 40 min.
Alternatively, according to the preparation method of the hydrodesulfurization catalyst, in the step 6), the reflux reaction is carried out at 90-110 ℃ for 24-36 h.
On the other hand, the invention also provides a hydrodesulfurization catalyst obtained by the preparation method of the hydrodesulfurization catalyst.
In another aspect, the invention also provides the application of the catalyst in the gasoline hydrodesulfurization reaction.
The invention has the beneficial effects that:
in the preparation method provided by the invention, alumina is a good carrier, and diffusion channels of reactant molecules and product molecules are provided; the formation of the metal oxide active center with the perovskite structure improves the metal utilization rate and makes desulfurization easier; the ionic liquid has adjustable structure, uniform distribution of active centers and high activity and selectivity; the combined action of the three components ensures that the catalyst has good hydrodesulfurization catalytic activity, presents good gasoline HDS selectivity and has small octane value loss.
Detailed Description
The invention is further described below with reference to specific embodiments.
In one aspect, the present invention provides a method for preparing a hydrodesulfurization catalyst, comprising the steps of:
1) mixing Al (NO)3)3·9H2Adding O and urea into the ionic liquid aqueous solution to form a mixed solution A, and placing the mixed solution A into a reaction kettle for reaction;
2) centrifugally separating the reacted mixed solution, washing and drying to obtain white powder; roasting the white powder to obtain an alumina product;
3) dissolving soluble lanthanum salt, soluble cobalt salt, soluble molybdenum salt and citric acid in distilled water and ethylene glycol to form a mixed solution B;
4) adding the alumina product into the mixed solution B, and carrying out ultrasonic reaction;
5) after the ultrasonic reaction is finished, filtering to obtain a solid product C, and then drying and roasting the solid product C to obtain LaCol-XMoXO3/Al2O3A composite material;
6) subjecting the LaCo tol-XMoXO3/Al2O3And adding the composite material into a mixed solution of ionic liquid and toluene, carrying out reflux reaction, and separating a solid product D after the reflux reaction is finished to obtain the catalyst.
The ionic liquid is a low-melting-point organic salt completely consisting of anions and cations, and compared with the conventional molecular liquid, the ionic liquid has many unique properties such as wide liquid phase range, high thermal stability, extremely low vapor pressure, high ionic conductivity, designability and the like. Under a liquid environment, the ionic liquid can form an expanded hydrogen bond system and electrostatic force interaction with reactants to form a highly-structured supermolecular structure, so that the oriented growth of nano crystal grains is induced. Meanwhile, the ionic liquid has high catalytic activity, the acidity and the alkalinity can be adjusted according to the requirements of different catalytic systems, and the ionic liquid can play double roles of a solvent and catalysis in the reaction. In the desulfurization of fuel oil, the ionic liquid is a novel green product which accords with the current sustainable development strategy, has excellent desulfurization effect on thiophene substances which are difficult to remove in the fuel oil, and has the application of the ionic liquid in various desulfurization technologies such as catalytic desulfurization, extraction desulfurization, complex desulfurization and the like.
In the preparation method, the alumina mesoporous material with the pore channel adjustable structure is synthesized by using the ionic liquid as an auxiliary material, the ionic liquid is used as a template and has a structure guiding effect, the controllable synthesis of alumina is realized by inducing the growth of crystals, the pore structure of a carrier can be improved, and a diffusion channel of reactant molecules and product molecules is provided. In addition, by virtue of the extraction and phase transfer effects of the ionic liquid, the catalyst has the effects of an extracting agent and a catalyst in a desulfurization system, so that the catalytic effect of the catalytic material in the catalytic desulfurization reaction is enhanced, and the olefin content is effectively reduced.
According to the preparation method, the perovskite is loaded on the alumina carrier, so that the perovskite has rich and adjustable surface properties, the redox performance of the catalyst is improved through the synergistic effect of B-site doping, the selectivity of the catalyst on the hydrogenation reaction is controlled by utilizing the characteristic that the perovskite contains other metals, and the polymerization of active olefin is effectively inhibited. At the same time, the modified perovskite/alumina (LaCo) is treated by using ionic liquidl-XMoXO3/Al2O3) The framework material has a high specific surface area, can promote high dispersion of metal components, can adsorb more hydrogen and efficiently realize hydrogen dissociation, so that the desulfurization performance of the material is greatly improved.
Specifically, in the step 1), the ionic liquid and Al (NO) are used3)3·9H2The molar ratio of O to urea is 1:10: 30. For example, 1mmol of ionic liquid is weighed and dissolved in 30mL of deionized water, and the solution is stirred at room temperature to be mixed uniformly. Sequentially adding 10mmol of Al (NO)3)3·9H2O and 1.8g of urea are added into the solution, and the solution is stirred for 10min to be completely dissolved, so that a mixed solution A is obtained. The mixed solution A is transferred to a 50ml polytetrafluoroethylene reaction kettle and reacted for 16-24h at the temperature of 150-.
Preferably, in the ionic liquid, the cation is one or two of alkyl imidazole and quaternary ammonium ion, the anion is one or more of halogen ion, tetrafluoroborate, hexafluorophosphate, borate, phosphate, carbonate and hydroxide, and the ionic liquid may be, for example, 1-propyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium hexafluorophosphate, etc.
In the step 2), the reacted mixed solution is centrifuged, the separated solid is washed with deionized water and absolute ethanol for a plurality of times (at least three times) and then dried at 50 to 70 ℃ (preferably 55 ℃, 60 ℃, 65 ℃) for 24 to 48 hours (preferably 30 hours, 36 hours, 42 hours) to obtain white powder. The white powder is then calcined in a muffle furnace at 500 ℃ and 700 ℃ (preferably 600 ℃) for 4-6h to obtain the alumina product. Preferably, the particle size of the alumina product is 40-60 mesh. Because the ionic liquid is used for improving the alumina, the alumina has high strength and highly dispersed active components when used as a catalyst carrier, and the activity is obviously improved.
In the step 3), the soluble lanthanum salt may be, for example, lanthanum nitrate or lanthanum sulfate, the soluble cobalt salt may be, for example, cobalt nitrate or cobalt sulfate, and the soluble lanthanum salt may be, for example, lanthanum nitrate or lanthanum sulfate. Soluble lanthanum salt, soluble cobalt salt and soluble molybdenum salt are mixed according to a molar ratio of 1: (1-X): and (3) preparing the mixture ratio of X (wherein X is 0.2-0.8), and dissolving the mixture and citric acid in a solvent to form a mixed solution B. For example, 5mmol of lanthanum nitrate, 1mmol of cobalt nitrate and 4mmol of molybdenum nitrate (i.e., X ═ 0.8), 12mmol of citric acid were dissolved in 20mL of distilled water and 12mmol of ethylene glycol to form a mixed solution B.
In the step 4), the ultrasonic reaction is carried out for 20-40min at the frequency of 40-60 kHz. For example, sonication is carried out at a frequency of 50kHz for 40 min.
In the above step 5), the solid product C may be dried at 50 ℃ for 3 hours to complete the drying process. Then roasting the dried solid product at 400 ℃ for 2-4h, and then roasting at 800 ℃ for 2-4h to obtain LaCol-XMoXO3/Al2O3A composite material.
In the step 6), the ionic liquid can be selectedSuch as 1-butyl-3-methylimidazolium hexafluorophosphate ([ Bmim)]PF 6). For example, 0.03g of [ Bmim ] is weighed]PF6 to round-bottom flask, 100mL of toluene was added followed by 1g of LaCol- XMoXO3/Al2O3And (3) carrying out reflux reaction on the composite material for 24-36h at the temperature of 90-110 ℃. After the reaction is finished, cooling to room temperature, and filtering to obtain a solid product D. And (3) refluxing and washing the solid product D in dinitrogen methane for 24-36h, filtering, and drying at 60-80 ℃ for 12-18h to obtain the hydrodesulfurization catalyst.
On the other hand, the invention also provides a hydrodesulfurization catalyst obtained by the preparation method of the hydrodesulfurization catalyst. In the prepared catalyst, the total weight of the catalyst is taken as a reference, the cobalt content is 3.0-25.0%, the molybdenum content is 5.0-25.0%, the preferred cobalt content is 5.0-15.0%, and the preferred molybdenum content is 10.0-20.0%. The catalyst is beneficial to ordered accumulation of perovskite type metal oxide into a layered structure, uniform dispersion, modification of ionic liquid on the surface of alumina, 150-350m of specific surface area2Per g, pore volume of 0.5-1.2mL/g, pore diameter of 10-25nm, and strength of 40-100N cm-1Preferably 60 to 80N cm-1。
In another aspect, the invention also provides the application of the catalyst in the gasoline hydrodesulfurization reaction. The catalyst has high hydrodesulfurization activity, good catalyst selectivity, low olefin saturation rate and low octane number loss, and has wide application prospect in gasoline hydrodesulfurization reaction.
In order to specifically describe the present invention, the applicant exemplifies the preparation method of the hydrodesulfurization catalyst of the present application with the following specific examples. It should be understood that the following specific examples are illustrative of specific implementations of the invention only and are not to be construed as limiting the scope of the invention.
Example 1
1mmol of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate is weighed and dissolved in 30mL of deionized water, and the mixture is stirred at room temperature to be uniformly mixed. Sequentially adding 10mmol of Al (NO)3)3·9H2O and 1.8g of urea were added to the above solution with stirringStirring for 10min to dissolve completely. And transferring the mixed solution into a 50ml polytetrafluoroethylene reaction kettle, reacting at 180 ℃ for 24h, and cooling to room temperature after the reaction is finished.
And (3) centrifugally separating the mixed solution after reaction, washing the solid obtained by separation for multiple times (at least three times) by using deionized water and absolute ethyl alcohol, and then drying at 60 ℃ for 40 hours to obtain white powder. The white powder was then calcined in a muffle furnace at 600 ℃ for 5h to give the alumina product.
Lanthanum nitrate 5mmol, cobalt nitrate 1mmol, and molybdenum nitrate 4mmol (i.e., X ═ 0.8), citric acid 12mmol were dissolved in distilled water 20mL and ethylene glycol 12mmol to form a mixed solution B.
Adding the alumina product into the mixed solution B, and carrying out ultrasonic reaction for 40min at the frequency of 50 kHz. And after the ultrasonic reaction is finished, filtering the obtained solid product C, and drying the solid product C at 50 ℃ for 3 hours to finish the drying process. Then roasting the dried solid product at 400 ℃ for 3h, and then roasting at 800 ℃ for 4h to obtain LaCo0.2Mo0.8O3/Al2O3A composite material.
0.03g of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate was weighed into a round bottom flask, 100mL of toluene was added, 1g of LaCo was added0.2Mo0.8O3/Al2O3And (3) carrying out reflux reaction on the composite material for 36h at 90 ℃. After the reaction is finished, cooling to room temperature, and filtering to obtain a solid product D. And (3) refluxing and washing the solid product D in dinitrogen methane for 24 hours, filtering, and drying at 60 ℃ for 18 hours to obtain the hydrodesulfurization catalyst No. 1.
Example 2
1mmol of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate is weighed and dissolved in 30mL of deionized water, and the mixture is stirred at room temperature to be uniformly mixed. Sequentially adding 15mmol of Al (NO)3)3·9H2O and 2.4g of urea were added to the above solution, and stirred for 10min to be completely dissolved. And transferring the mixed solution into a 50ml polytetrafluoroethylene reaction kettle, reacting at 150 ℃ for 20h, and cooling to room temperature after the reaction is finished.
The mixed solution after the reaction was centrifuged, the solid obtained by the separation was washed with deionized water and absolute ethanol several times (at least three times) and then dried at 55 ℃ for 45 hours to obtain a white powder. The white powder was then calcined in a muffle furnace at 600 ℃ for 5h to give the alumina product.
Lanthanum nitrate 5mmol, cobalt nitrate 2mmol, and molybdenum nitrate 3mmol (i.e., X ═ 0.6), citric acid 12mmol were dissolved in distilled water 20mL and ethylene glycol 12mmol to form a mixed solution B.
Adding the alumina product into the mixed solution B, and carrying out ultrasonic reaction for 40min at the frequency of 40 kHz. And after the ultrasonic reaction is finished, filtering the obtained solid product C, and drying the solid product C at 50 ℃ for 3 hours to finish the drying process. Then roasting the dried solid product at 400 ℃ for 4h, and then roasting at 800 ℃ for 2h to obtain LaCo0.4Mo0.6O3/Al2O3A composite material.
0.03g of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate was weighed into a round bottom flask, 100mL of toluene was added, 1g of LaCo was added0.4Mo0.6O3/Al2O3And (3) carrying out reflux reaction on the composite material for 30h at 95 ℃. After the reaction is finished, cooling to room temperature, and filtering to obtain a solid product D. And (3) refluxing and washing the solid product D in dinitrogen methane for 36h, filtering, and drying at 80 ℃ for 15h to obtain the hydrodesulfurization catalyst No. 2.
Example 3
1mmol 1-butyl-3-methylimidazolium bromide was weighed and dissolved in 30mL deionized water, and stirred at room temperature to mix well. Sequentially adding 10mmol of Al (NO)3)3·9H2O and 1.8g of urea were added to the above solution, and stirred for 10min to be completely dissolved. And transferring the mixed solution into a 50ml polytetrafluoroethylene reaction kettle, reacting at 200 ℃ for 16h, and cooling to room temperature after the reaction is finished.
The mixed solution after the reaction is centrifugally separated, the solid obtained by the separation is washed for a plurality of times (at least three times) by deionized water and absolute ethyl alcohol, and then dried for 24 hours at 70 ℃ to obtain white powder. The white powder was then calcined in a muffle furnace at 700 ℃ for 4h to give the alumina product.
Lanthanum nitrate 5mmol, cobalt nitrate 3mmol, and molybdenum nitrate 2mmol (i.e., X ═ 0.4), citric acid 12mmol were dissolved in distilled water 20mL and ethylene glycol 12mmol to form a mixed solution B.
Adding the alumina product into the mixed solution B, and carrying out ultrasonic reaction for 20min at the frequency of 60 kHz. And after the ultrasonic reaction is finished, filtering the obtained solid product C, and drying the solid product C at 50 ℃ for 3 hours to finish the drying process. Then roasting the dried solid product at 400 ℃ for 4h, and then roasting at 800 ℃ for 3h to obtain LaCo0.6Mo0.4O3/Al2O3A composite material.
0.03g of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate was weighed into a round bottom flask, 100mL of toluene was added, 1g of LaCo was added0.6Mo0.4O3/Al2O3And (3) carrying out reflux reaction on the composite material at 110 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, and filtering to obtain a solid product D. And (3) refluxing and washing the solid product D in dinitrogen methane for 24 hours, filtering, and drying at 70 ℃ for 16 hours to obtain the hydrodesulfurization catalyst No. 3.
Example 4
1mmol of ionic liquid 1-butyl-3-methylimidazolium bromide is weighed and dissolved in 30mL of deionized water, and the mixture is stirred at room temperature to be uniformly mixed. Sequentially adding 5mmol of Al (NO)3)3·9H2O and 1.2g of urea were added to the above solution, and stirred for 10min to be completely dissolved. And transferring the mixed solution into a 50ml polytetrafluoroethylene reaction kettle, reacting at 160 ℃ for 18h, and cooling to room temperature after the reaction is finished.
The mixed solution after the reaction was centrifuged, the solid obtained by the separation was washed with deionized water and absolute ethanol several times (at least three times) and then dried at 65 ℃ for 36 hours to obtain a white powder. The white powder was then calcined in a muffle furnace at 500 ℃ for 4h to give the alumina product.
Lanthanum nitrate 5mmol, cobalt nitrate 4mmol, and molybdenum nitrate 1mmol (i.e., X ═ 0.2), citric acid 12mmol were dissolved in distilled water 20mL and ethylene glycol 12mmol to form a mixed solution B.
Adding the alumina product into the mixed solution B, and carrying out ultrasonic reaction for 30min at the frequency of 50 kHz. And after the ultrasonic reaction is finished, filtering the obtained solid product C, and drying the solid product C at 50 ℃ for 3 hours to finish the drying process. Then roasting the dried solid product at 400 ℃ for 3h, and then roasting at 800 ℃ for 4h to obtain LaCo0.8Mo0.2O3/Al2O3A composite material.
0.03g of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate was weighed into a round bottom flask, 100mL of toluene was added, 1g of LaCo was added0.8Mo0.2O3/Al2O3And (3) carrying out reflux reaction on the composite material for 30h at 100 ℃. After the reaction is finished, cooling to room temperature, and filtering to obtain a solid product D. And (3) refluxing and washing the solid product D in dinitrogen methane for 30h, filtering, and drying at 70 ℃ for 18h to obtain the hydrodesulfurization catalyst No. 4.
Comparative example 1:
in 30mL of deionized water, 10mmol of Al (NO) were added in sequence3)3·9H2O and 1.8g of urea were added to the above solution, and stirred for 10min to be completely dissolved. And transferring the mixed solution into a 50ml polytetrafluoroethylene reaction kettle, reacting at 180 ℃ for 24h, and cooling to room temperature after the reaction is finished.
And (3) centrifugally separating the mixed solution after reaction, washing the solid obtained by separation for multiple times (at least three times) by using deionized water and absolute ethyl alcohol, and then drying at 60 ℃ for 40 hours to obtain white powder. The white powder was then calcined in a muffle furnace at 600 ℃ for 5h to give the alumina product.
Lanthanum nitrate 5mmol, cobalt nitrate 1mmol, molybdenum nitrate 4mmol, and citric acid 12mmol were dissolved in distilled water 20mL and ethylene glycol 12mmol to form a mixed solution B.
Adding the alumina product into the mixed solution B, and carrying out ultrasonic reaction for 40min at the frequency of 50 kHz. And after the ultrasonic reaction is finished, filtering the obtained solid product C, and drying the solid product C at 50 ℃ for 3 hours to finish the drying process. Then the dried solid product is firstly baked at 400 DEG CFiring for 3h, then firing for 4h at 800 ℃ to obtain LaCo0.2Mo0.8O3/Al2O3A composite material.
1g of LaCo was added to 100mL of toluene0.2Mo0.8O3/Al2O3And (3) carrying out reflux reaction on the composite material for 36h at 90 ℃. After the reaction is finished, cooling to room temperature, and filtering to obtain a solid product D. And (3) refluxing and washing the solid product D in dinitrogen methane for 24h, filtering, and drying at 60 ℃ for 18h to obtain the comparative hydrodesulfurization catalyst No. 5. The catalyst was prepared analogously to example 1, with the addition of ionic liquid only being dispensed with.
Comparative example 2:
in 30mL of deionized water, 15mmol of Al (NO) was added3)3·9H2O and 2.4g of urea were added to the above solution, and stirred for 10min to be completely dissolved. And transferring the mixed solution into a 50ml polytetrafluoroethylene reaction kettle, reacting at 150 ℃ for 20h, and cooling to room temperature after the reaction is finished.
The mixed solution after the reaction was centrifuged, the solid obtained by the separation was washed with deionized water and absolute ethanol several times (at least three times) and then dried at 55 ℃ for 45 hours to obtain a white powder. The white powder was then calcined in a muffle furnace at 600 ℃ for 5h to give the alumina product.
Lanthanum nitrate 5mmol, cobalt nitrate 2mmol, molybdenum nitrate 3mmol, and citric acid 12mmol were dissolved in distilled water 20mL and ethylene glycol 12mmol to form a mixed solution B.
Adding the alumina product into the mixed solution B, and carrying out ultrasonic reaction for 40min at the frequency of 40 kHz. And after the ultrasonic reaction is finished, filtering the obtained solid product C, and drying the solid product C at 50 ℃ for 3 hours to finish the drying process. Then roasting the dried solid product at 400 ℃ for 4h, and then roasting at 800 ℃ for 2h to obtain LaCo0.4Mo0.6O3/Al2O3A composite material.
1g of LaCo was added to 100mL of toluene0.4Mo0.6O3/Al2O3And (3) carrying out reflux reaction on the composite material for 30h at 95 ℃. Inverse directionAfter completion, it was cooled to room temperature and filtered to give the solid product D. And (3) refluxing and washing the solid product D in dinitrogen methane for 36h, filtering, and drying at 80 ℃ for 15h to obtain the comparative hydrodesulfurization catalyst No. 6. The catalyst was prepared analogously to example 2, with the addition of ionic liquid only being dispensed with.
Comparative example 3:
in 30mL of deionized water, 10mmol of Al (NO) were added in sequence3)3·9H2O and 1.8g of urea were added to the above solution, and stirred for 10min to be completely dissolved. And transferring the mixed solution into a 50ml polytetrafluoroethylene reaction kettle, reacting at 200 ℃ for 16h, and cooling to room temperature after the reaction is finished.
The mixed solution after the reaction is centrifugally separated, the solid obtained by the separation is washed for a plurality of times (at least three times) by deionized water and absolute ethyl alcohol, and then dried for 24 hours at 70 ℃ to obtain white powder. The white powder was then calcined in a muffle furnace at 700 ℃ for 4h to give the alumina product.
Lanthanum nitrate 5mmol, cobalt nitrate 3mmol, molybdenum nitrate 2mmol, and citric acid 12mmol were dissolved in distilled water 20mL and ethylene glycol 12mmol to form a mixed solution B.
Adding the alumina product into the mixed solution B, and carrying out ultrasonic reaction for 20min at the frequency of 60 kHz. And after the ultrasonic reaction is finished, filtering the obtained solid product C, and drying the solid product C at 50 ℃ for 3 hours to finish the drying process. Then roasting the dried solid product at 400 ℃ for 4h, and then roasting at 800 ℃ for 3h to obtain LaCo0.6Mo0.4O3/Al2O3A composite material.
1g of LaCo was added to 100mL of toluene0.6Mo0.4O3/Al2O3And (3) carrying out reflux reaction on the composite material at 110 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, and filtering to obtain a solid product D. And (3) refluxing and washing the solid product D in dinitrogen methane for 24 hours, filtering, and drying at 70 ℃ for 16 hours to obtain the comparative hydrodesulfurization catalyst No. 7. The catalyst was prepared analogously to example 3, with the addition of ionic liquid only being dispensed with.
Comparative example 4:
in 30mL of deionized water, 5mmol of Al (NO) was added3)3·9H2O and 1.2g of urea were added to the above solution, and stirred for 10min to be completely dissolved. And transferring the mixed solution into a 50ml polytetrafluoroethylene reaction kettle, reacting at 160 ℃ for 18h, and cooling to room temperature after the reaction is finished.
The mixed solution after the reaction was centrifuged, the solid obtained by the separation was washed with deionized water and absolute ethanol several times (at least three times) and then dried at 65 ℃ for 36 hours to obtain a white powder. The white powder was then calcined in a muffle furnace at 500 ℃ for 4h to give the alumina product.
Lanthanum nitrate 5mmol, cobalt nitrate 4mmol, molybdenum nitrate 1mmol, and citric acid 12mmol were dissolved in distilled water 20mL and ethylene glycol 12mmol to form a mixed solution B.
Adding the alumina product into the mixed solution B, and carrying out ultrasonic reaction for 30min at the frequency of 50 kHz. And after the ultrasonic reaction is finished, filtering the obtained solid product C, and drying the solid product C at 50 ℃ for 3 hours to finish the drying process. Then roasting the dried solid product at 400 ℃ for 3h, and then roasting at 800 ℃ for 4h to obtain LaCo0.8Mo0.2O3/Al2O3A composite material.
1g of LaCo was added to 100mL of toluene0.8Mo0.2O3/Al2O3And (3) carrying out reflux reaction on the composite material for 30h at 100 ℃. After the reaction is finished, cooling to room temperature, and filtering to obtain a solid product D. And (3) refluxing and washing the solid product D in dinitrogen methane for 30h, filtering, and drying at 70 ℃ for 18h to obtain the comparative hydrodesulfurization catalyst No. 8. The catalyst was prepared analogously to example 4, with the addition of ionic liquid only being dispensed with.
In the hydrodesulfurization catalysts prepared in the above examples 1 to 4, the perovskite metal oxides can be orderly stacked to form a layered structure, the perovskite metal oxides are uniformly dispersed, and the ionic liquid is modified on the surface of the alumina. To better illustrate the catalytic activity of the catalysts prepared in examples 1-4 in gasoline hydrodesulfurization, the performance of the catalysts prepared in examples 1-4 and comparative examples 1-4 in catalyzing gasoline hydrodesulfurization was evaluated on a WFSM-3080 model fixed bed hydrogenation experimental unit. The gasoline used was FCC pyrolysis gasoline. And (2) carrying out pre-vulcanization treatment on the 8 catalysts before hydrogenation, wherein the treatment condition is that a vulcanizing agent dimethyl disulfide is introduced at 100-200 ℃, the airspeed is 1-8 h, the pressure is 0.1-5 MPa, the vulcanization temperature is 200-300 ℃, and the constant temperature is 1-10 h.
And carrying out hydrogenation reaction after vulcanization, wherein the reaction temperature is 110-. Gasoline sulfur content was measured by Shimadzu gas chromatograph GC2014C-FPD, and gasoline octane numbers before and after hydrogenation were measured by gasoline octane number determination (research method) GB/T5487-1995, and the results are shown in Table 1.
TABLE 1 catalyst gasoline hydrodesulfurization Performance
The above tests show that the catalysts prepared in examples 1-4 have high activity for catalyzing the hydrodesulfurization of FCC gasoline, and the octane number loss after hydrogenation is only 0.3-0.4 unit. In the comparative example, when no ionic liquid is used as a synthesis aid, the hydrogenation activity is low and the octane number loss is large.
It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be able to design alternative embodiments without departing from the scope of the appended claims. In the claims, any reference signs placed between parentheses shall not be construed as limiting the claim. The word "comprising" does not exclude the presence of elements or steps not listed in a claim. The usage of the words first, second and third, etcetera do not indicate any ordering and these words may be interpreted as names.
Claims (10)
1. A preparation method of a hydrodesulfurization catalyst comprises the following steps:
1) mixing Al (NO)3)3·9H2Adding O and urea into ionic liquid waterForming a mixed solution A in the solution, and placing the mixed solution A in a reaction kettle for reaction;
2) centrifugally separating the reacted mixed solution, washing and drying to obtain white powder; roasting the white powder to obtain an alumina product;
3) dissolving soluble lanthanum salt, soluble cobalt salt, soluble molybdenum salt and citric acid in water and ethylene glycol to form a mixed solution B;
4) adding the alumina product into the mixed solution B, and carrying out ultrasonic reaction;
5) after the ultrasonic reaction is finished, filtering to obtain a solid product C, and then drying and roasting the solid product C to obtain LaCol-XMoXO3/Al2O3A composite material;
6) subjecting the LaCo tol-XMoXO3/Al2O3And adding the composite material into a mixed solution of ionic liquid and toluene, carrying out reflux reaction, and separating a solid product D after the reflux reaction is finished to obtain the catalyst.
2. The method for producing a hydrodesulfurization catalyst according to claim 1, wherein the ionic liquid contains one or two of an alkyl imidazole and a quaternary ammonium ion as a cation, and one or more of a halogen ion, a tetrafluoroborate, a hexafluorophosphate, a borate, a phosphate, a carbonate, and a hydroxide as an anion.
3. The method for preparing a hydrodesulfurization catalyst as claimed in claim 2, wherein the mixed solution A is reacted at 150 ℃ and 200 ℃ for 16-24 h.
4. The method of preparing a hydrodesulfurization catalyst according to claim 1 wherein the ionic liquid, Al (NO)3)3·9H2The molar ratio of O to urea is 1:10: 30.
5. The method for preparing a hydrodesulfurization catalyst as claimed in claim 1, wherein the white powder is calcined at 500-700 ℃ for 4-6 h.
6. The method of producing a hydrodesulfurization catalyst according to claim 1, wherein X is 0.2 to 0.8.
7. The method for preparing a hydrodesulfurization catalyst according to claim 1, wherein the ultrasonic reaction is carried out at a frequency of 40 to 60kHz for 20 to 40 min.
8. The method for preparing a hydrodesulfurization catalyst according to any one of claims 1 to 7, wherein in step 6) the reaction is carried out at 90 to 110 ℃ for 24 to 36h under reflux.
9. A hydrodesulfurization catalyst obtained by the production method according to any one of claims 1 to 8.
10. Use of the catalyst according to claim 9 in the hydrodesulphurization reaction of gasoline.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4055513A (en) * | 1976-04-13 | 1977-10-25 | Exxon Research & Engineering Co. | Perovskite catalysts and process for their preparation |
| CN104549524A (en) * | 2014-12-26 | 2015-04-29 | 燕山大学 | Preparation method of catalytically cracked gasoline hydrodesulfurization catalyst containing nanocrystalline multi-stage duct ZSM-5 molecular sieve |
| US20150275111A1 (en) * | 2012-10-31 | 2015-10-01 | Thermochem Recovery International, Inc. | System and Method for Processing Raw Gas with In-Situ Catalyst Regeneration |
| CN106238073A (en) * | 2016-07-15 | 2016-12-21 | 温州泓呈祥科技有限公司 | A kind of MoS2the preparation method and application of/LDHS Hydrobon catalyst |
| CN107638882A (en) * | 2017-05-08 | 2018-01-30 | 中国科学院大连化学物理研究所 | A kind of catalyst for selective hydrodesulfurizationof of gasoline and its preparation and application |
-
2020
- 2020-06-04 CN CN202010499553.1A patent/CN111659409A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4055513A (en) * | 1976-04-13 | 1977-10-25 | Exxon Research & Engineering Co. | Perovskite catalysts and process for their preparation |
| US20150275111A1 (en) * | 2012-10-31 | 2015-10-01 | Thermochem Recovery International, Inc. | System and Method for Processing Raw Gas with In-Situ Catalyst Regeneration |
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