CN116393161A - Preparation method of liquefied petroleum gas sweetening and diene reducing catalyst - Google Patents

Preparation method of liquefied petroleum gas sweetening and diene reducing catalyst Download PDF

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Publication number
CN116393161A
CN116393161A CN202310184887.3A CN202310184887A CN116393161A CN 116393161 A CN116393161 A CN 116393161A CN 202310184887 A CN202310184887 A CN 202310184887A CN 116393161 A CN116393161 A CN 116393161A
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catalyst
carrier
drying
metal oxide
roasting
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肖寒
朱金剑
李子涵
宋国良
刘伟
张景成
许岩
胡毅
董科军
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China National Offshore Oil Corp CNOOC
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/12—Liquefied petroleum gas
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
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    • B01J29/00—Catalysts comprising molecular sieves
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/633—Pore volume less than 0.5 ml/g
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract

The invention relates to a preparation method of a liquefied petroleum gas sweetening and polydiene reducing catalyst, which is characterized by comprising the following steps of: the catalyst consists of a carrier, a main metal oxide, a auxiliary metal oxide and sulfur species. The catalyst has carrier weight content of 55.0-75.0%, main metal oxide weight content of 15.0-25.0%, auxiliary metal oxide weight content of 0.5-5.0% and sulfur species content of 4.0-10.0%. The preparation method of the catalyst comprises the following steps: 1) Forming a carrier; 2) Preparing a metal solution; 3) Loading of active metal; 4) Sulfide loading. The catalyst prepared by the invention is matched with the acid-base center and the hydrogenation center of the catalyst efficiently, and can realize the deep sweetening and diene removal of liquefied gas synchronously in cooperation with the hydro-conversion of mercaptan and the selective hydrogenation reaction process of diene.

Description

Preparation method of liquefied petroleum gas sweetening and diene reducing catalyst
Technical Field
The invention relates to the technical field of catalysts, in particular to a preparation method of a liquefied petroleum gas sweetening and diene reducing catalyst.
Background
Liquefied Petroleum Gas (LPG) is one of the important petroleum processing products, mainly from catalytic cracking, ethylene cracking, delayed coking, etc. units in refineries, and is a mixture of gaseous hydrocarbons. LPG from mixed C 3 、C 4 The hydrocarbon composition can be used as high-efficiency clean fuel, and can be used as chemical raw materials for producing high-added-value products after separation and purification. However, LPG contains some amount of hydrogen sulfide (H 2 S), sulfur Carbonyl (COS), sulfides such as mercaptan, thioether and the like and diolefins, in particular to mercaptan compounds and diolefins, and has stronger reactivity, and the sulfur carbonyl sulfide (COS), the mercaptan, the thioether and the diolefins are used as chemical raw materials, are easy to cause the deactivation of catalysts in downstream processes and the oxidation reaction of active hydrocarbons in LPG to generate colloid, and the deep desulfurization and diolefin reduction of liquefied petroleum gas are required to be carried out.
The refining of liquefied petroleum gas generally adopts the combination of the technology of hydrogen sulfide removal by an organic amine method and mercaptan removal by an inorganic alkali method. The existing process for removing the thiol of the liquefied petroleum gas mainly comprises a classical alkaline leaching technology for removing the thiol of the liquefied petroleum gas or light naphtha by the Merox company, and the fiber membrane contact technology developed by the Meriem company can improve the utilization rate of the alkali, reduce the emission of alkaline residues, but can not achieve the purpose of treating the root cause, the problems of superficiality of total sulfur and corrosion of copper sheets of the liquefied petroleum gas can occur, the superficiality of the total sulfur can be relieved by extracting oxidized catalyst alkali with the light oil, but the effect is not obvious, and the problem of superficiality of the total sulfur can not be solved at present especially for coking liquefied petroleum gas. Aiming at the defects of the existing mercaptan removal technology, a process technology for reducing mercaptan by utilizing unsaturated hydrocarbon and mercaptan in liquefied petroleum gas to carry out mercaptan thioetherification reaction is developed, and the key core of the technology is a mercaptan thioetherification catalyst.
Chinese patent No. CN202111106087.7 discloses a liquefied gas sweetening catalyst, its preparation method and application, the catalyst preparation method comprises the following steps: a) Adding dry gelatin, sesbania powder and pore-expanding agent into the aqueous solution of peptizing agent, uniformly mixing, extruding, forming, drying and roasting to obtain catalyst carrier; the pore-expanding agent is one or more components selected from polyethylene glycol, sodium stearate, phosphoric acid, carboxymethyl cellulose, soluble starch and C5 resin fine powder; b) Impregnating the impregnation liquid on the catalyst carrier by adopting an isovolumetric impregnation method, and drying and roasting after the impregnation is finished to obtain the liquefied gas sweetening catalyst; the impregnating solution is a solution prepared from a cobalt source, a molybdenum source, an auxiliary agent and water. The catalyst synthesized by the invention is applied to a fixed bed evaluation liquefied gas desulfurization process, has high mercaptan conversion rate and low olefin loss rate, and shows good catalytic selectivity and reaction activity.
Chinese patent No. CN1330132a discloses a method for converting the thiol contained in liquefied petroleum gas, which uses a fixed bed catalytic oxidation method to convert the thiol. The active components of the catalyst are nano transition metal element (1-6 in Co, mn, ni, cu, fe, cr) oxides, perovskite type rare earth composite oxides, spinel type oxides or iron calcium oxide Ca2Fe2O5, and the catalyst has a certain mercaptan conversion effect. However, the composition of the catalyst is complex, and the preparation process of the catalyst needs to be strictly controlled.
Chinese patent No. CN104971724a discloses a method for preparing a low-temperature thiol-sulfide catalyst. The method comprises the following steps: step one, uniformly mixing and kneading pseudo-boehmite, sesbania powder and aqueous nitric acid solution to prepare a molded product; standing the molded product obtained in the first step for 5-10 h at normal temperature, airing, then drying at 100-140 ℃ for 2-4 h, then heating to 500-600 ℃ at a heating rate of 1-3 ℃/min, roasting for 4-8 h, crushing and screening to obtain 3-6 mm short strip particles, and obtaining a catalyst carrier precursor; step three, immersing the catalyst carrier precursor into an aqueous solution of inorganic acid or organic acid according to the ratio of 6g/g to 12g/g for hydrothermal treatment and post-treatment to obtain the catalyst carrier; and step four, loading nickel-containing salt and iron-containing salt step by adopting an isovolumetric impregnation method, and drying and roasting to obtain the low-temperature mercaptan thioetherification catalyst loaded with the bimetallic active components containing nickel oxide and iron oxide. The catalyst prepared by the invention can be used for thioetherification under the low-temperature condition and efficiently removing mercaptan.
CN113522347a the present invention provides a catalyst for removing mercaptan, a preparation method thereof and a method for removing mercaptan. The sweetening catalyst comprises a carrier and an active component, wherein the carrier is a manganese oxide molecular sieve, the active component is an oxide of metal M, and the metal M is one or more of metals of group VIB, VIII, IB and IIB. The mercaptan removal catalyst provided by the invention can realize mercaptan purification by utilizing the special crystal structure of the active phase in a mode of combining adsorption and catalytic conversion, has the advantages of low cost, high desulfurization precision, high sulfur capacity and high single-pass conversion rate, and is favorable for industrial popularization.
The existing sweetening catalyst is in an oxidation state or a reduction state and has conversion effect on mercaptan in liquefied petroleum gas, so that the vulcanizing catalyst has low-temperature high-activity sweetening and diene reducing catalysts and has very important significance on the basis of the existing catalyst.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a liquefied petroleum gas sweetening and diene reducing catalyst, wherein the catalyst consists of a carrier, a main metal oxide, a co-metal oxide and sulfur species; wherein the carrier in the catalyst consists of modified alumina and a molecular sieve, the mass content is 65.0-75.0%, the mass content of main metal oxide is 15.0-25.0%, the mass content of auxiliary metal oxide is 0.5-5.0%, and the mass content of sulfur species is 4.0-10.0%;
the preparation method of the catalyst comprises the following steps:
1) Forming a carrier; uniformly mixing modified alumina, a molecular sieve and a binder according to a mass ratio, putting the mixture into a kneader, adding a peptized solution prepared from water and nitric acid, kneading the mixture into a plastic body, and obtaining a carrier after extrusion molding, granulating, shaping, drying and roasting;
2) Preparing a metal solution; sequentially adding an organic complex, a main metal oxide and a precursor salt of a metal oxide in deionized water, uniformly stirring until the organic complex, the main metal oxide and the precursor salt of the metal oxide are dissolved, and obtaining a stable metal solution after constant volume;
3) Loading of active metal: loading the metal solution prepared in the step 2) onto the carrier obtained in the step 1) by adopting an isovolumetric impregnation method, and drying and roasting the impregnated carrier to obtain a catalyst;
4) Sulfide loading: preparing sulfide into soluble solution, loading sulfide onto the catalyst prepared in the step 3) by adopting an equal volume impregnation method, and drying and activating under inert atmosphere to obtain the liquefied petroleum gas sweetening and polydiene reducing catalyst.
According to the technical scheme of the invention, the specific surface area of the catalyst is 200-400 m 2 Per g, the pore volume is 0.30-0.60 mL/g.
According to the technical scheme of the invention, the main metal oxide is NiO or MoO 3 And WO 3 One or more of the auxiliary metal oxides is Co 2 O 3 、Fe 2 O 3 、K 2 O, mgO, znO, baO.
According to the technical scheme of the invention, the modified alumina is B 2 O 3 -Al 2 O 3 、SiO 2 -Al 2 O 3 、TiO 2 -Al 2 O 3 、ZrO 2 -Al 2 O 3 、P 2 O 5 -Al 2 O 3 One or more of them; the molecular sieve is one or more of modified Y, beta, SAPO-5, MCM-22 and MCM-56, wherein the modified Y molecular sieve has the following properties: siO (SiO) 2 /Al 2 O 3 The molar ratio is 60.0-200.0, the sodium oxide content is less than or equal to 0.05wt percent, and the pyridine-infrared acid amount is 0.50-1.00 mmol/g; the Beta molecular sieve is in a hydrogen form and has the following properties: siO (SiO) 2 /Al 2 O 3 The molar ratio is 40.0-200.0, the sodium oxide content is less than or equal to 0.05wt%, the pyridine-infrared acid content is 0.30-1.00 mmol/g, and the specific surface area is 350-650 m 2 Per gram, the pore volume is 0.30-0.60 mL/g; the SAPO-5 molecular sieve is in a hydrogen form, the sodium oxide content is less than or equal to 0.05wt percent, and the specific surface area is 200-450 m 2 Per gram, the pore volume is 0.30-0.60 mL/g, and the pyridine-infrared acid amount is 0.20-0.60 mmol/g; the MCM-22 and MCM-56 molecular sieves SiO 2 /Al 2 O 3 The molar ratio is 20.0-120.0, and the specific surface area is 250-500 m 2 Per g, the pore volume is 0.60-1.0 mL/g, and the pyridine-infrared acid amount is 0.40-0.80 mmol/g.
According to the technical scheme of the invention, the drying temperature of the carrier in the catalyst preparation step 1) is 50-250 ℃, the drying time is 2-24 h, and the roasting temperature is 500-850 ℃; roasting for 2-12 h; wherein the preferable drying temperature is 120-180 ℃, the drying time is 4-12 h, the roasting temperature is 650-800 ℃ and the roasting time is 2-8 h.
According to the technical scheme of the invention, the organic complex in the catalyst preparation step 2) is one or more of tartaric acid, citric acid, malic acid, aminotriacetic acid, oxalic acid, maleic acid and ethylenediamine tetraacetic acid; the main metal oxide salt is one of molybdenum trioxide, ammonium tetramolybdate, ammonium heptamolybdate, ammonium metatungstate, nickel nitrate hexahydrate, basic nickel carbonate and nickel acetate tetrahydrate.
According to the technical scheme of the invention, the drying temperature of the catalyst in the catalyst preparation step 3) is 50-200 ℃, the drying time is 4-24 h, and the roasting temperature is 350-550 ℃; roasting for 2-12 h; wherein, the preferable roasting temperature is 400-500 ℃ and the roasting time is 2-8 h.
According to the technical scheme of the invention, sulfide in the catalyst preparation step 4) is one or more of thiourea, thiosemicarbazide, diethyl thiourea, ethylene thiourea, vinyl thiourea, thiosemicarbazide, bis (hydroxymethyl) ethylene thiourea, thioacetamide, dithioacetamide, 2' -thiodiethanol, ammonium thiosulfate and ammonium dithiocarbamate; the loading of the sulfide is determined according to the content of the main metal oxide in the catalyst; the inert gas is one or more of helium, nitrogen, neon, argon, methane, ethane, propane, butane and carbon dioxide; the volume space velocity of the inert gas is 500-5000 -1 The method comprises the steps of carrying out a first treatment on the surface of the The volume space velocity of the inert gas is 500-5000 -1 The method comprises the steps of carrying out a first treatment on the surface of the The activation drying temperature is 150-450 ℃, and the drying time is 2-24 hours; wherein the preferable active temperature is 200-300 ℃, and the roasting time is 6-12 h.
The invention also provides application of the liquefied petroleum gas sweetening and polydiene reducing catalyst, and the catalyst can be directly applied to liquefied petroleum gas hydrodesulphurisation and polydiene reducing.
According to the technical scheme of the invention, the catalyst can be directly applied to the hydrodesulphurisation of liquefied gas and the reduction of diolefin. The preparation method of the invention adopts the in-situ sulfur carrying and activating technology by efficiently matching the acid-base center, the hydrogenation center and the pore canal structure on the catalyst, and the prepared catalyst can cooperate with the processes of the hydro-conversion of mercaptan and the selective hydrogenation of diene to realize the synchronous removal of liquefied petroleum gas and diene.
Detailed Description
The following examples are presented to further illustrate the preparation of the catalyst for sweetening and lowering diolefins in liquefied petroleum gas.
Example-1
35.0g (SiO) of modified Y molecular sieve 2 /Al 2 O 3 Molar ratio 80, dry content 85%) to 243.0g SiO 2 -Al 2 O 3 Modified alumina, 4.0g methylcellulose, 4.0g fieldPreparing the cyanine powder into mixed raw powder, putting the mixed raw powder into a kneader, kneading the mixed raw powder into a plastic body, and then extruding, forming, granulating and shaping the obtained product to obtain a wet carrier; drying the obtained wet carrier in an oven at 160 ℃ for 4 hours, then placing the wet carrier in a muffle furnace, and programming the temperature to 650 ℃ for roasting for 4 hours to obtain the carrier ZT-1.
7.5g of basic nickel carbonate, 16.5g of molybdenum trioxide, 3.0g of citric acid, 2.6g of basic cobalt carbonate and 3.2g of phosphoric acid are added into deionized water at a time, stirred, heated and dissolved, then 2.1g of potassium nitrate is added, stirred and dissolved uniformly, and then the volume of the metal solution is fixed to 58mL. 71.0g of carrier ZT-1 is placed in an impregnating tank, a metal solution is poured into the impregnating tank, the impregnation tank is impregnated for 2 hours by equal volume, the drying is carried out for 6 hours in a baking oven at 120 ℃, and finally the catalyst CTA-1 is obtained after the drying is placed in a muffle furnace, the temperature of the drying procedure is increased to 480 ℃ and the baking is carried out for 3 hours.
6.0g of ammonium sulfide and 7.0g of thiourea are taken to prepare 48mL of sulfur-containing solution, the sulfur-containing solution is loaded on 100g of catalyst CTA-1 by adopting an equal volume impregnation method, and the liquefied gas sweetening and polydiene catalyst SCTA-1 is obtained after activation for 12 hours at 240 ℃ under nitrogen atmosphere.
Example-2
38.0g (SiO) 2 /Al 2 O 3 Molar ratio of 60, dry content 80%) to 243.0g P 2 O 5 -Al 2 O 3 Preparing modified alumina, 4.0g of methyl cellulose and 4.0g of sesbania powder into mixed raw powder, putting the mixed raw powder into a kneader, kneading the mixed raw powder into a plastic body, and then obtaining a wet carrier through extrusion molding, granulating and shaping; drying the obtained wet carrier in an oven at 120 ℃ for 6 hours, then placing the wet carrier in a muffle furnace, and roasting the wet carrier for 6 hours at the temperature of 600 ℃ to obtain the carrier ZT-2.
7.5g of basic nickel carbonate, 16.5g of molybdenum trioxide, 3.0g of aminotriacetic acid, 2.6g of basic cobalt carbonate and 3.2g of phosphoric acid are added into deionized water at a time, stirred, heated and dissolved, then 2.1g of potassium nitrate is added, stirred and dissolved uniformly, and the volume of the metal solution is fixed to 56mL. 71.0g of carrier ZT-2 is placed in an impregnating tank, a metal solution is poured into the impregnating tank, the impregnation tank is impregnated for 2 hours by equal volume, the drying is carried out for 6 hours in a baking oven at 120 ℃, and finally the catalyst CTA-2 is obtained after the drying is placed in a muffle furnace, the temperature of the drying procedure is increased to 480 ℃ and the baking is carried out for 3 hours.
6.0g of ammonium sulfide and 7.0g of thiourea are taken to prepare 50mL of sulfur-containing solution, the sulfur-containing solution is loaded on 100g of catalyst CTA-2 by adopting an equal volume impregnation method, and the catalyst is activated for 12 hours at 240 ℃ under nitrogen atmosphere to obtain liquefied gas sweetening and diene-reducing catalyst SCTA-2.
Example-3
45.0g (88% dry basis) of H-SAPO-5 molecular sieve was mixed with 229.0g P 2 O 5 -Al 2 O 3 Preparing modified alumina, 3.0g of methylcellulose and 3.0g of sesbania powder into mixed raw powder, putting the mixed raw powder into a kneader, kneading the mixed raw powder into a plastic body, and then obtaining a wet carrier through extrusion molding, granulating and shaping; drying the obtained wet carrier in an oven at 150 ℃ for 6 hours, then placing the wet carrier in a muffle furnace, and programming the temperature to 650 ℃ for roasting for 6 hours to obtain the carrier ZT-3.
7.5g of basic nickel carbonate, 16.5g of molybdenum trioxide, 4.0g of tartaric acid, 2.6g of basic cobalt carbonate and 3.2g of phosphoric acid are added into deionized water at a time, stirred, heated and dissolved, then 2.1g of potassium nitrate is added, stirred and dissolved uniformly, and then the volume of the metal solution is fixed to 60mL. 71.0g of carrier ZT-3 is taken to be placed in an impregnating tank, a metal solution is poured into the impregnating tank, the impregnation tank is impregnated for 2 hours by equal volume, the drying is carried out for 6 hours in a baking oven at 120 ℃, and finally the catalyst CTA-3 is obtained after the drying is placed in a muffle furnace, the temperature of the drying procedure is increased to 480 ℃ and the baking is carried out for 3 hours.
6.0g of ammonium sulfide and 7.0g of thiourea are taken to prepare 52mL of sulfur-containing solution, the sulfur-containing solution is loaded on 100g of catalyst CTA-3 by adopting an equal volume impregnation method, and the catalyst is activated for 10 hours at 260 ℃ under nitrogen atmosphere to obtain liquefied gas sweetening and diene-reducing catalyst SCTA-3.
Example-4
47.0g (dry basis content 85%) of MCM-22 molecular sieve and 229.0g of TiO 2 -Al 2 O 3 Preparing modified alumina, 3.0g of methylcellulose and 3.0g of sesbania powder into mixed raw powder, putting the mixed raw powder into a kneader, kneading the mixed raw powder into a plastic body, and then obtaining a wet carrier through extrusion molding, granulating and shaping; drying the obtained wet carrier in an oven at 150 ℃ for 6 hours, then placing the wet carrier in a muffle furnace, and programming the temperature to 650 ℃ for roasting for 6 hours to obtain the carrier ZT-4.
7.5g of basic nickel carbonate, 16.5g of molybdenum trioxide, 3.0g of citric acid, 2.6g of basic cobalt carbonate and 3.2g of phosphoric acid are added into deionized water at a time, stirred, heated and dissolved, then 2.1g of potassium nitrate is added, stirred and dissolved uniformly, and then the volume of the metal solution is fixed to 55mL. 71.0g of carrier ZT-4 is taken to be placed in an impregnating tank, a metal solution is poured into the impregnating tank, the impregnation tank is impregnated for 2 hours by equal volume, the drying is carried out for 6 hours in a baking oven at 120 ℃, and finally the catalyst CTA-4 is obtained after the drying is placed in a muffle furnace, the temperature of the drying procedure is increased to 480 ℃ and the baking is carried out for 3 hours.
6.0g of ammonium sulfide and 7.0g of thiourea are taken to prepare 45mL of sulfur-containing solution, the sulfur-containing solution is loaded on 100g of catalyst CTA-4 by adopting an equal volume impregnation method, and the catalyst is activated for 10 hours at the temperature of 260 ℃ under nitrogen atmosphere to obtain liquefied gas sweetening and diene-reducing catalyst SCTA-4.
Example-5
47.0g (dry basis content 85%) of MCM-56 molecular sieve and 229.0g of TiO 2 -Al 2 O 3 Preparing modified alumina, 3.0g of methylcellulose and 3.0g of sesbania powder into mixed raw powder, putting the mixed raw powder into a kneader, kneading the mixed raw powder into a plastic body, and then obtaining a wet carrier through extrusion molding, granulating and shaping; drying the obtained wet carrier in an oven at 150 ℃ for 6 hours, then placing the wet carrier in a muffle furnace, and programming the temperature to 650 ℃ for roasting for 6 hours to obtain the carrier ZT-5.
7.5g of basic nickel carbonate, 16.5g of molybdenum trioxide, 3.0g of ethylenediamine tetraacetic acid, 2.6g of basic cobalt carbonate and 3.2g of phosphoric acid are added into deionized water at a time, stirred, heated and dissolved, then 2.1g of potassium nitrate is added, stirred and dissolved uniformly, and then the volume of the metal solution is fixed to 55mL. 71.0g of carrier ZT-5 is taken to be placed in an impregnating tank, a metal solution is poured into the impregnating tank, the impregnation tank is impregnated for 2 hours by equal volume, the drying is carried out for 6 hours in a baking oven at 120 ℃, and finally the catalyst CTA-5 is obtained after the drying is placed in a muffle furnace, the temperature of the drying procedure is increased to 480 ℃ and the baking is carried out for 3 hours.
6.0g of ammonium sulfide and 7.0g of thiourea are taken to prepare 45mL of sulfur-containing solution, the sulfur-containing solution is loaded on 100g of catalyst CTA-5 by adopting an equal volume impregnation method, and the liquefied gas sweetening and polydiene catalyst SCTA-5 is obtained after activation for 12 hours at the temperature of 280 ℃ under the nitrogen atmosphere.
Example-6
47.0g (dry basis content 85%) of MCM-22 molecular sieve and 225.0g of ZrO 2 -Al 2 O 3 Modified alumina, 3.0g methyl cellulose and 3.0g sesbania powder are mixedAdding the raw powder into a kneader, kneading into a plastic body, and then extruding, forming, granulating and shaping to obtain a wet carrier; drying the obtained wet carrier in an oven at 150 ℃ for 6 hours, then placing the wet carrier in a muffle furnace, and programming the temperature to 650 ℃ for roasting for 6 hours to obtain the carrier ZT-6.
7.5g of basic nickel carbonate, 16.5g of molybdenum trioxide, 4.0g of citric acid and 3.2g of phosphoric acid are added into deionized water at a time, stirred, heated and dissolved, 20.2g of ferric nitrate nonahydrate is added, stirred and dissolved uniformly, and then the volume of the metal solution is fixed to 55mL. 70.0g of carrier ZT-6 is placed in an impregnating tank, a metal solution is poured into the impregnating tank, the impregnation tank is impregnated for 2 hours by equal volume, the drying is carried out for 6 hours in a baking oven at 120 ℃, and finally the catalyst CTA-6 is obtained after the drying is placed in a muffle furnace, the temperature of the drying procedure is increased to 480 ℃ and the baking is carried out for 3 hours.
Preparing 45mL of sulfur-containing solution from 7.0g of ammonium thiosulfate and 8.5g of thiosemicarbazide, loading the sulfur-containing solution onto 100g of catalyst CTA-6 by adopting an isovolumetric impregnation method, and activating for 12 hours at the temperature of 280 ℃ under nitrogen atmosphere to obtain liquefied gas sweetening and polydiene catalyst SCTA-6.
Example-7
47.0g (dry basis content 85%) of MCM-22 molecular sieve and 229.0g of TiO 2 -Al 2 O 3 Preparing modified alumina, 3.0g of methylcellulose and 3.0g of sesbania powder into mixed raw powder, putting the mixed raw powder into a kneader, kneading the mixed raw powder into a plastic body, and then obtaining a wet carrier through extrusion molding, granulating and shaping; drying the obtained wet carrier in an oven at 150 ℃ for 6 hours, then placing the wet carrier in a muffle furnace, and programming the temperature to 650 ℃ for roasting for 6 hours to obtain the carrier ZT-7.
7.5g of basic nickel carbonate, 16.5g of molybdenum trioxide, 2.0g of citric acid and 3.2g of phosphoric acid are added into deionized water at a time, stirred, heated and dissolved, 14.6g of zinc nitrate hexahydrate is added, stirred and dissolved uniformly, and then the volume of the metal solution is fixed to 55mL. 70.0g of carrier ZT-7 is placed in an impregnating tank, a metal solution is poured into the impregnating tank, the impregnation tank is impregnated for 2 hours by equal volume, the drying is carried out for 6 hours in a baking oven at 120 ℃, and finally the catalyst CTA-7 is obtained after the drying is placed in a muffle furnace, the temperature of the drying procedure is increased to 480 ℃ and the baking is carried out for 3 hours.
Preparing 45mL of sulfur-containing solution from 7.0g of ammonium thiosulfate and 8.5g of thiosemicarbazide, loading the sulfur-containing solution onto 100g of catalyst CTA-7 by adopting an isovolumetric impregnation method, and activating for 12 hours at 240 ℃ under nitrogen atmosphere to obtain liquefied gas sweetening and polydiene catalyst SCTA-7.
Example-8
47.0g (dry basis content 85%) of MCM-22 molecular sieve and 230.0g of SiO 2 -Al 2 O 3 Preparing modified alumina, 3.0g of methylcellulose and 3.0g of sesbania powder into mixed raw powder, putting the mixed raw powder into a kneader, kneading the mixed raw powder into a plastic body, and then obtaining a wet carrier through extrusion molding, granulating and shaping; drying the obtained wet carrier in an oven at 150 ℃ for 6 hours, then placing the wet carrier in a muffle furnace, and programming the temperature to 650 ℃ for roasting for 6 hours to obtain the carrier ZT-8.
7.5g of basic nickel carbonate, 16.5g of molybdenum trioxide, 3.0g of aminotriacetic acid and 3.2g of phosphoric acid are added into deionized water at a time, stirred, heated and dissolved, 25.4g of magnesium nitrate hexahydrate is added, stirred and dissolved uniformly, and then the volume of the metal solution is fixed to 55mL. 70.0g of carrier ZT-8 is placed in an impregnating tank, a metal solution is poured into the impregnating tank, the impregnation tank is impregnated for 2 hours by equal volume, the drying is carried out for 6 hours in a baking oven at 120 ℃, and finally the catalyst CTA-8 is obtained after the drying is placed in a muffle furnace, the temperature of the drying procedure is increased to 480 ℃ and the baking is carried out for 3 hours.
Preparing 45mL of sulfur-containing solution from 7.0g of ammonium thiosulfate and 8.5g of thiosemicarbazide, loading the sulfur-containing solution onto 100g of catalyst CTA-8 by adopting an isovolumetric impregnation method, and activating for 12 hours at 260 ℃ under nitrogen atmosphere to obtain liquefied gas sweetening and polydiene catalyst SCTA-8.
Examples-9
47.0g (dry basis content 85%) of MCM-22 molecular sieve and 230.0g of SiO 2 -Al 2 O 3 Preparing modified alumina, 3.0g of methylcellulose and 3.0g of sesbania powder into mixed raw powder, putting the mixed raw powder into a kneader, kneading the mixed raw powder into a plastic body, and then obtaining a wet carrier through extrusion molding, granulating and shaping; drying the obtained wet carrier in an oven at 150 ℃ for 6 hours, then placing the wet carrier in a muffle furnace, and programming the temperature to 650 ℃ for roasting for 6 hours to obtain the carrier ZT-9.
7.5g of basic nickel carbonate, 16.5g of molybdenum trioxide, 3.0g of aminotriacetic acid and 3.2g of phosphoric acid are added into deionized water at a time, stirred, heated and dissolved, 6.8g of barium nitrate is added, and after the solution is uniformly stirred and dissolved, the volume of the metal solution is fixed to 55mL. 70.0g of carrier ZT-9 is placed in an impregnating tank, a metal solution is poured into the impregnating tank, the impregnation tank is impregnated for 2 hours by equal volume, the drying is carried out for 6 hours in a baking oven at 120 ℃, and finally the catalyst CTA-9 is obtained after the drying is placed in a muffle furnace, the temperature of the drying procedure is increased to 480 ℃ and the baking is carried out for 3 hours.
Preparing 45mL of sulfur-containing solution from 7.0g of ammonium thiosulfate and 8.5g of thiosemicarbazide, loading the sulfur-containing solution onto 100g of catalyst CTA-9 by adopting an isovolumetric impregnation method, and activating for 8 hours at 300 ℃ under nitrogen atmosphere to obtain liquefied gas sweetening and polydiene catalyst SCTA-9.
Examples-10
47.0g (dry basis content 85%) of MCM-22 molecular sieve and 229.0g of SiO 2 -Al 2 O 3 Preparing modified alumina, 3.0g of methylcellulose and 3.0g of sesbania powder into mixed raw powder, putting the mixed raw powder into a kneader, kneading the mixed raw powder into a plastic body, and then obtaining a wet carrier through extrusion molding, granulating and shaping; drying the obtained wet carrier in an oven at 180 ℃ for 4 hours, then placing the wet carrier in a muffle furnace, and roasting the wet carrier for 4 hours at 680 ℃ through programmed temperature, thus obtaining the carrier ZT-10.
After adding 16.0g of nickel nitrate hexahydrate, 18.2g of ammonium metatungstate and 3.0g of ethylenediamine tetra-14.6 g of zinc nitrate hexahydrate into deionized water at a time and uniformly stirring and dissolving, the metal solution is fixed to 58mL. 70.0g of carrier ZT-10 is placed in an impregnating tank, a metal solution is poured into the impregnating tank, the impregnation tank is impregnated for 2 hours by equal volume, then the catalyst is dried for 4 hours in a baking oven at 150 ℃, and finally the catalyst is placed in a muffle furnace and is baked for 4 hours at the temperature of 450 ℃ by programming, thus obtaining the catalyst CTA-10.
Preparing 45mL of sulfur-containing solution from 7.0g of ammonium thiosulfate and 8.5g of thiosemicarbazide, loading the sulfur-containing solution onto 100g of catalyst CTA-10 by adopting an isovolumetric impregnation method, and activating for 8 hours at 300 ℃ under argon atmosphere to obtain liquefied gas sweetening and polydiene catalyst SCTA-10.
Example-11
47.0g (dry basis content 85%) of MCM-22 molecular sieve and 229.0g of SiO 2 -Al 2 O 3 Preparing modified alumina, 3.0g of methylcellulose and 3.0g of sesbania powder into mixed raw powder, putting the mixed raw powder into a kneader, kneading the mixed raw powder into a plastic body, and then obtaining a wet carrier through extrusion molding, granulating and shaping; drying the wet carrier in an oven at 180deg.C for 4 hr, and placing inAnd (3) programming in a muffle furnace to be heated to 680 ℃ and roasting for 4 hours to obtain the carrier ZT-11.
16.0g of nickel nitrate hexahydrate, 9.1g of ammonium meta-tungstate, 10.0g of ammonium heptamolybdate and 3.0g of ethylenediamine tetra-14.6 g of zinc nitrate hexahydrate are added into deionized water at a time, and after being uniformly stirred and dissolved, the metal solution is fixed to 58mL. 70.0g of carrier ZT-11 is placed in an impregnating tank, a metal solution is poured into the impregnating tank, the impregnation tank is impregnated for 2 hours by equal volume, the drying is carried out in a baking oven at 160 ℃ for 4 hours, and finally the catalyst CTA-11 is obtained after the drying is placed in a muffle furnace, the temperature of the drying procedure is increased to 465 ℃ and the baking is carried out for 8 hours.
Preparing 45mL of sulfur-containing solution from 7.0g of ammonium thiosulfate and 8.5g of thiosemicarbazide, loading the sulfur-containing solution onto 100g of catalyst CTA-11 by adopting an isovolumetric impregnation method, and activating for 8 hours at 300 ℃ under argon atmosphere to obtain liquefied gas sweetening and polydiene catalyst SCTA-11.
Examples-12
35.0g (SiO) of modified Y molecular sieve 2 /Al 2 O 3 Molar ratio 80, dry content 85%) with 243.0g SiO 2 -Al 2 O 3 Preparing modified alumina, 4.0g of methyl cellulose and 4.0g of sesbania powder into mixed raw powder, putting the mixed raw powder into a kneader, kneading the mixed raw powder into a plastic body, and then obtaining a wet carrier through extrusion molding, granulating and shaping; drying the obtained wet carrier in an oven at 160 ℃ for 4 hours, then placing the wet carrier in a muffle furnace, programming the temperature to 650 ℃ and roasting for 4 hours to obtain the carrier ZT-12.
7.5g of basic nickel carbonate, 20.2g of molybdenum trioxide, 4.0g of citric acid, 2.6g of basic cobalt carbonate and 3.2g of phosphoric acid are added into deionized water at a time, stirred, heated and dissolved, then 2.1g of potassium nitrate is added, stirred and dissolved uniformly, and then the volume of the metal solution is fixed to 58mL. 66.0g of carrier ZT-12 is placed in an impregnating tank, a metal solution is poured into the impregnating tank, the impregnation tank is impregnated for 2 hours by equal volume, the drying is carried out for 6 hours in a baking oven at 120 ℃, and finally the catalyst CTA-12 is obtained after the drying is placed in a muffle furnace, the temperature of the drying procedure is increased to 480 ℃ and the baking is carried out for 3 hours.
Preparing 42mL of sulfur-containing solution from 8.0g of ammonium sulfide and 9.6g of thiourea, loading the sulfur-containing solution onto 100g of catalyst CTA-12 by adopting an equal volume impregnation method, and activating for 12 hours at 260 ℃ under nitrogen atmosphere to obtain liquefied gas sweetening and diene-reducing catalyst SCTA-12.
Examples-13
35.0g (SiO) of modified Y molecular sieve 2 /Al 2 O 3 Molar ratio 80, dry content 85%) to 243.0gB 2 O 3 -Al 2 O 3 Preparing modified alumina, 4.0g of methyl cellulose and 4.0g of sesbania powder into mixed raw powder, putting the mixed raw powder into a kneader, kneading the mixed raw powder into a plastic body, and then obtaining a wet carrier through extrusion molding, granulating and shaping; drying the obtained wet carrier in an oven at 160 ℃ for 4 hours, then placing the wet carrier in a muffle furnace, and programming to be heated to 600 ℃ for 6 hours to obtain the carrier ZT-13.
3.7g of basic nickel carbonate, 14.1g of molybdenum trioxide, 2.0g of citric acid, 2.6g of basic cobalt carbonate and 3.2g of phosphoric acid are added into deionized water at a time, stirred, heated and dissolved, then 2.1g of potassium nitrate is added, stirred and dissolved uniformly, and then the volume of the metal solution is fixed to 62mL. Placing 76.0g of carrier ZT-13 into an impregnation tank, pouring a metal solution, adopting equal volume impregnation for 2h, drying in a baking oven at 150 ℃ for 4h, and finally placing in a muffle furnace, programming and heating to 450 ℃ for roasting for 4h to obtain the catalyst CTA-13.
8.0g of ammonium sulfide and 9.6g of thiourea are taken to prepare 50mL of sulfur-containing solution, the sulfur-containing solution is loaded on 100g of catalyst CTA-13 by adopting an equal volume impregnation method, and the liquefied gas sweetening and polydiene catalyst SCTA-13 is obtained after activation for 12 hours at 260 ℃ under nitrogen atmosphere.
Examples-14
This example demonstrates the evaluation of the activity of the liquefied gas sweetening and polydiene reducing catalysts prepared by the present invention. The raw materials are simulated liquefied gas (wherein, the methyl mercaptan content is 260 mu g/g, the ethyl mercaptan content is 40 mu g/g, and the butadiene content is 8500 mu g/g), and the reaction conditions are as follows: the reaction pressure is 2.5MPa, the volume ratio of hydrogen to oil is 8:1, the average reaction temperature of hydrogenation pretreatment is 90 ℃, and the volume space velocity is 3.0h -1 The evaluation results of the catalyst are shown in Table-1.
TABLE-1 evaluation of liquefied gas sweetening and polydiene-reducing catalyst results
Catalyst Methyl mercaptan content (μg/g) Methyl mercaptan content (μg/g) Butadiene Hydrocarbon content (μg/g)
SCTA-1 1.2 1.5 280
SCTA-2 0.8 1.4 280
SCTA-3 0.8 1.2 260
SCTA-4 0.6 1.5 240
SCTA-5 0.9 1.3 250
SCTA-6 1.0 1.2 230
SCTA-7 1.5 1.8 300
SCTA-8 1.2 1.3 240
SCTA-9 0.8 1.2 220
SCTA-10 1.2 1.5 230
SCTA-11 0.9 1.2 250
SCTA-12 1.0 1.0 220
SCTA-13 0.8 1.4 240

Claims (10)

1. A preparation method of a liquefied petroleum gas sweetening and diene reducing catalyst is characterized by comprising the following steps: the catalyst consists of a carrier, a main metal oxide, a auxiliary metal oxide and sulfur species; wherein the carrier in the catalyst consists of modified alumina and a molecular sieve, the mass content is 65.0-75.0%, the mass content of main metal oxide is 15.0-25.0%, the mass content of auxiliary metal oxide is 0.5-5.0%, and the mass content of sulfur species is 4.0-10.0%;
the preparation method of the catalyst comprises the following steps:
1) Forming a carrier; uniformly mixing modified alumina, a molecular sieve and a binder according to a mass ratio, putting the mixture into a kneader, adding a peptized solution prepared from water and nitric acid, kneading the mixture into a plastic body, and obtaining a carrier after extrusion molding, granulating, shaping, drying and roasting;
2) Preparing a metal solution; sequentially adding an organic complex, a main metal oxide and a precursor salt of a metal oxide in deionized water, uniformly stirring until the organic complex, the main metal oxide and the precursor salt of the metal oxide are dissolved, and obtaining a stable metal solution after constant volume;
3) Loading of active metal: loading the metal solution prepared in the step 2) onto the carrier obtained in the step 1) by adopting an isovolumetric impregnation method, and drying and roasting the impregnated carrier to obtain a catalyst;
4) Sulfide loading: preparing sulfide into soluble solution, loading sulfide onto the catalyst prepared in the step 3) by adopting an equal volume impregnation method, and drying and activating under inert atmosphere to obtain the liquefied petroleum gas sweetening and polydiene reducing catalyst.
2. The process according to claim 1, wherein the specific surface area of the catalyst is 200 to 400m 2 Per g, the pore volume is 0.30-0.60 mL/g.
3. The method according to claim 1, wherein the main metal oxide is NiO or MoO 3 And WO 3 One or more of the auxiliary metal oxides areCo 2 O 3 、Fe 2 O 3 One or more of K2O, mgO, znO, baO.
4. The method of claim 1, wherein the modified alumina is B 2 O 3 -Al 2 O 3 、SiO 2 -Al 2 O 3 、TiO 2 -Al 2 O 3 、ZrO 2 -Al 2 O 3 、P 2 O 5 -Al 2 O 3 One or more of the following; the molecular sieve is one or more of modified Y, beta, SAPO-5, MCM-22 and MCM-56, wherein the modified Y molecular sieve has the following properties: siO (SiO) 2 /Al 2 O 3 The molar ratio is 60.0-200.0, the sodium oxide content is less than or equal to 0.05wt percent, and the pyridine-infrared acid amount is 0.50-1.00 mmol/g; the Beta molecular sieve is in a hydrogen form and has the following properties: siO (SiO) 2 /Al 2 O 3 The molar ratio is 40.0-200.0, the sodium oxide content is less than or equal to 0.05wt%, the pyridine-infrared acid content is 0.30-1.00 mmol/g, and the specific surface area is 350-650 m 2 Per gram, the pore volume is 0.30-0.60 mL/g; the SAPO-5 molecular sieve is in a hydrogen form, the sodium oxide content is less than or equal to 0.05wt percent, and the specific surface area is 200-450 m 2 Per gram, the pore volume is 0.30-0.60 mL/g, and the pyridine-infrared acid amount is 0.20-0.60 mmol/g; the MCM-22 and MCM-56 molecular sieves are integrally SiO 2 /Al 2 O 3 The molar ratio is 20.0-120.0, and the specific surface area is 250-500 m 2 Per g, the pore volume is 0.60-1.0 mL/g, and the pyridine-infrared acid amount is 0.40-0.80 mmol/g.
5. The method according to claim 1, wherein the drying temperature of the carrier in the catalyst preparation step 1) is 50-250 ℃, the drying time is 2-24 hours, and the roasting temperature is 500-850 ℃; roasting time is 2-12 h.
6. The method according to claim 1, wherein the organic complex in the catalyst preparation step 2) is one or more of tartaric acid, citric acid, malic acid, aminotriacetic acid, oxalic acid, maleic acid and ethylenediamine tetraacetic acid; the main metal oxide salt is one of molybdenum trioxide, ammonium tetramolybdate, ammonium heptamolybdate, ammonium metatungstate, nickel nitrate hexahydrate, basic nickel carbonate and nickel acetate tetrahydrate.
7. The method according to claim 1, wherein the drying temperature of the catalyst in the catalyst preparation step 3) is 50-200 ℃, the drying time is 4-24 hours, and the roasting temperature is 350-550 ℃; roasting time is 2-12 h.
8. The method according to claim 1, wherein the sulfide in the catalyst preparation step 4) is one or more of thiourea, thiosemicarbazide, diethyl thiourea, ethylene thiourea, vinyl thiourea, thiosemicarbazide, bis (hydroxymethyl) ethylene thiourea, thioacetamide, dithioacetamide, 2' -thiodiethanol, ammonium thiosulfate and ammonium dithiocarbamate; the loading of the sulfide is determined according to the content of the main metal oxide in the catalyst; the inert gas is one or more of helium, nitrogen, neon, argon, methane, ethane, propane, butane and carbon dioxide; the volume space velocity of the inert gas is 500-5000 -1 The method comprises the steps of carrying out a first treatment on the surface of the The drying temperature is 80-200 ℃, the drying time is 4-24 h, the activating temperature is 250-450 ℃, and the roasting time is 4-24 h.
9. The method according to claim 1, wherein the drying temperature of the carrier in the catalyst preparation step 1) is 120-180 ℃, the drying time is 4-12 h, the roasting temperature is 650-800 ℃, and the roasting time is 2-8 h; the drying temperature of the catalyst in the catalyst preparation step 3) is 80-150 ℃, the drying time is 4-12 h, the roasting temperature is 400-500 ℃, and the roasting time is 2-8 h; the drying temperature in the catalyst preparation step 4) is 100-150 ℃, the drying time is 4-8 h, the activating temperature is 300-400 ℃, and the activating time is 8-12 h.
10. The use of the liquefied petroleum gas sweetening and polydiene reducing catalyst as claimed in any one of claims 1 to 9, characterized in that the catalyst is directly applied to liquefied gas hydrodesulphurisation and polydiene reducing.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103316705A (en) * 2013-06-24 2013-09-25 大连理工大学 Catalyst for removing mercaptan sulfur in catalytic gasoline at low temperature and preparation method of catalyst
CN105126883A (en) * 2015-08-26 2015-12-09 中国石油天然气集团公司 Phosphorous or boron-modified low-temperature thioetherification bimetallic catalyst, preparation method therefor and application thereof
WO2016029387A1 (en) * 2014-08-27 2016-03-03 中国石油天然气集团公司 Bimetallic mercaptan transfer catalyst used in low-temperature mercaptan removal of liquefied petroleum gas
CN106732637A (en) * 2016-11-24 2017-05-31 中国石油大学(北京) A kind of low temperature mercaptan etherification catalyst and preparation method and application
WO2018161952A1 (en) * 2017-03-09 2018-09-13 武汉凯迪工程技术研究总院有限公司 Method for preparing hydrotreating catalyst by impregnation method
CN109201072A (en) * 2018-09-11 2019-01-15 福州大学 A kind of catalytically cracked gasoline catalyst for pre-hydrogenation and preparation method
CN110860285A (en) * 2019-11-27 2020-03-06 中国石油天然气集团有限公司 Preparation method of catalyst for low-temperature thioetherification and diene selective hydrogenation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103316705A (en) * 2013-06-24 2013-09-25 大连理工大学 Catalyst for removing mercaptan sulfur in catalytic gasoline at low temperature and preparation method of catalyst
WO2016029387A1 (en) * 2014-08-27 2016-03-03 中国石油天然气集团公司 Bimetallic mercaptan transfer catalyst used in low-temperature mercaptan removal of liquefied petroleum gas
CN105126883A (en) * 2015-08-26 2015-12-09 中国石油天然气集团公司 Phosphorous or boron-modified low-temperature thioetherification bimetallic catalyst, preparation method therefor and application thereof
CN106732637A (en) * 2016-11-24 2017-05-31 中国石油大学(北京) A kind of low temperature mercaptan etherification catalyst and preparation method and application
WO2018161952A1 (en) * 2017-03-09 2018-09-13 武汉凯迪工程技术研究总院有限公司 Method for preparing hydrotreating catalyst by impregnation method
CN109201072A (en) * 2018-09-11 2019-01-15 福州大学 A kind of catalytically cracked gasoline catalyst for pre-hydrogenation and preparation method
CN110860285A (en) * 2019-11-27 2020-03-06 中国石油天然气集团有限公司 Preparation method of catalyst for low-temperature thioetherification and diene selective hydrogenation

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