CN114146728A - Composite carrier Cu-based acetylene hydrochlorination catalyst and preparation method thereof - Google Patents

Composite carrier Cu-based acetylene hydrochlorination catalyst and preparation method thereof Download PDF

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CN114146728A
CN114146728A CN202111432954.6A CN202111432954A CN114146728A CN 114146728 A CN114146728 A CN 114146728A CN 202111432954 A CN202111432954 A CN 202111432954A CN 114146728 A CN114146728 A CN 114146728A
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composite carrier
acetylene hydrochlorination
catalyst
copper
composite
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CN114146728B (en
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牛强
朱瑞波
解荣永
赵长森
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Ordos Hanbo Technology Co ltd
Inner Mongolia Erdos Electric Power Metallurgy Group Co Ltd
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Ordos Hanbo Technology Co ltd
Inner Mongolia Erdos Electric Power Metallurgy Group Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0254—Nitrogen containing compounds on mineral substrates
    • 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
    • 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
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • 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
    • 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
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
    • B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
    • 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
    • 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
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a composite carrier Cu-based acetylene hydrochlorination catalyst and a preparation method thereof, wherein the composite carrier Cu-based acetylene hydrochlorination catalyst comprises an auxiliary agent, a copper metal salt and the balance of a composite carrier; the preparation method of the composite carrier comprises the following steps: pouring activated carbon into the cerium nitrate solution, stirring, dropwise adding an alkali solution into the cerium nitrate solution, aging, filtering, drying and roasting after dropwise adding is finished to obtain the composite carrier; the preparation method comprises the following steps: mixing the auxiliary agent and the metal salt of copper according to the formula ratio, adding the composite carrier, soaking at normal temperature in equal volume, standing and drying to obtain the composite carrier Cu-based acetylene hydrochlorination catalyst. The preparation method is simple, high in catalytic efficiency, long in service life and easy to industrialize, and can meet the requirements and standards of industrial converters on acetylene hydrochlorination catalysts.

Description

Composite carrier Cu-based acetylene hydrochlorination catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a Cu-based acetylene hydrochlorination catalyst with a composite carrier and a preparation method thereof.
Background
Polyvinyl chloride is the second most common type of synthetic resin worldwide, with very broad market demand. Vinyl chloride is a raw material for synthesizing polyvinyl chloride, and there are 3 kinds of methods for synthesizing vinyl chloride, namely an acetylene method, an ethylene method and an ethane method, and currently, the acetylene method using coal as a raw material and the ethylene method using petroleum as a raw material are mainly industrialized. About 80% of the polyvinyl chloride output in China comes from the acetylene method. Along with the increase of environmental protection, the mercury-free production of PVC becomes a necessary trend. Therefore, the research and development of the mercury-free catalyst to replace the mercury-containing catalyst have positive social benefits and environmental protection benefits.
The research and development of the metal mercury-free catalyst mainly comprise noble metals such as Au, Pd and Ru and non-noble metals such as Bi, Sn and Cu. For example, CN 103623837A discloses a Ru-Co-Cu catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene, which comprises an inert porous carrier and ruthenium salt, copper salt and cobalt salt loaded on the inert porous carrier, wherein the mass of Ru accounts for 0.01 per thousand-5% of the mass of the Ru-Co-Cu catalyst for synthesizing vinyl chloride by hydrochlorinating acetylene, and the molar ratio of Ru to Cu to Co is 1: 0.1-10. The catalyst of the invention can reduce the reaction temperature when acetylene is synthesized into vinyl chloride by hydrochlorination, so that the reaction temperature is lower than 180 ℃, and the reaction product has good selectivity, few byproducts and high reaction activity, so that the conversion rate of acetylene is more than 99%, and the selectivity of vinyl chloride reaches 99.9%, but the catalyst of the invention has poor stability.
CN111715253A discloses a copper-based catalyst for preparing vinyl chloride by hydrochlorination of acetylene. The carrier of the catalyst is boron and nitrogen heteroatom doped modified active carbon, and the main active component is a complex formed by copper chloride and a nitrogen-containing or carbonyl-containing ligand. The modified carrier can enhance the interaction with the copper complex, prevent the loss of the copper complex, regulate and control the adsorption performance of acetylene and hydrogen chloride gas, improve the activity of the catalyst under the synergistic action of the acetylene and hydrogen chloride gas, and improve the acetylene conversion rate to 92.6 percent, although the invention can improve the stability of the catalyst, the improvement degree of the stability is limited.
CN109821546A discloses a preparation method of a composite copper-based catalyst, which comprises the following steps: dipping the activated carbon after acid treatment in a solution containing copper salt and an auxiliary agent, and drying and roasting to obtain the composite copper-based catalyst; the auxiliary agent is one or more of ferric chloride, cerium chloride, tin chloride, barium chloride, manganese chloride, zinc chloride, cobalt chloride, lanthanum chloride, nickel chloride, bismuth chloride and potassium chloride; the mass ratio of the activated carbon subjected to acid treatment, the copper salt and the auxiliary agent is 100:5: 1-100: 10: 5. The catalyst provided by the invention shows higher activity and selectivity in the reaction of producing vinyl chloride by hydrochlorinating acetylene, and can be used at an airspeed of 300h-1Under the condition of (1), the catalyst can stably run for 500h and has good stability, but the acetylene conversion rate is lower and is less than 80%.
Disclosure of Invention
In order to solve the technical problems, the invention provides a composite carrier Cu-based acetylene hydrochlorination catalyst and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a Cu-based acetylene hydrochlorination catalyst with a composite carrier comprises an auxiliary agent, a copper metal salt and the balance of the composite carrier.
Preferably, the auxiliary agent is at least one of N-methylformamide, 2-pyrrolidone, pyrrolidone hydrochloride and 1-butyl 3-methylimidazole chloride salt.
Preferably, the metal salt of copper is at least one of copper sulfate, copper nitrate and copper chloride.
Preferably, the preparation method of the composite carrier comprises the following steps: and (2) pouring the activated carbon into the cerium nitrate solution, stirring, dropwise adding an alkali solution into the cerium nitrate solution, aging, filtering, drying and roasting after dropwise adding is finished, thus obtaining the composite carrier.
Further preferably, the activated carbon is wood activated carbon and/or coal activated carbon.
Further preferably, the alkali solution is a sodium hydroxide solution or a potassium hydroxide solution.
Further preferably, the mass ratio of the cerium nitrate to the activated carbon is 0.02-0.1: 1.
further preferably, the molar ratio of the cerium nitrate to the base is 1: 7.
Further preferably, the firing is: roasting for 3-5h at 400-600 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere.
Preferably, the composite carrier Cu-based acetylene hydrochlorination catalyst comprises the following components in percentage by mass: 1-10% of assistant, 5-35% of copper metal salt and the balance of composite carrier.
The invention also provides a preparation method of the Cu-based acetylene hydrochlorination catalyst, which comprises the following steps: mixing the auxiliary agent and the metal salt of copper according to the formula ratio, adding the composite carrier, soaking at normal temperature in equal volume, standing and drying to obtain the composite carrier Cu-based acetylene hydrochlorination catalyst.
Preferably, the drying is: drying at 80-120 deg.C for 24-48 h.
The invention also provides the application of the composite carrier Cu-based acetylene hydrochlorination catalyst in acetylene hydrochlorination.
The invention has the beneficial effects that:
the invention adopts a precipitation method to precipitate CeO2The composite active carbon is loaded on the active carbon to form the composite active carbon, so that the generation of carbon deposition in the reaction process can be inhibited, the interaction between the active component and the carrier is effectively improved, and the loss of the active component is prevented; by adding the auxiliary agent and utilizing the stronger bonding effect formed between the auxiliary agent and the active component, the adsorption of the catalyst on HCl is improved, and Cu is effectively inhibited2+Reduction of (2). Compared with the prior art, the preparation method of the composite carrier Cu-based acetylene hydrochlorination catalyst is simple, high in catalytic efficiency, long in service life and easy to industrialize, can meet the requirements and standards of an industrial converter on the acetylene hydrochlorination catalyst, and meets market requirements.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Before the present embodiments are further described, it is to be understood that the scope of the invention is not limited to the particular embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The sources of the raw materials used in the present invention are not limited, and the raw materials used in the present invention are all those commonly available in the art unless otherwise specified.
Example 1
Weighing 1.5g of cerous nitrate hexahydrate, stirring and dissolving in 200ml of deionized water, weighing 52g of wood activated carbon, immersing in the cerous nitrate solution, stirring, gradually dropwise adding 24ml of 1mol/L NaOH solution into the mixed solution, standing and aging for 12h after dropwise adding, filtering, drying at 120 ℃ for 5h, drying at 400 ℃ under a nitrogen atmosphere, heating at a rate of 5 ℃/min, and roasting for 5h to obtain the composite carrier.
Weighing 6g of copper chloride and 1.2g of N-methyl formamide, adding 48ml of deionized water, stirring and mixing uniformly, dripping the mixed solution onto the composite carrier while stirring, standing for 12h, and drying for 24h at 120 ℃ to obtain the catalyst.
Evaluation of catalyst: the temperature is 150 ℃, and the space velocity is 35h-1Original source ofFeed gas C2H2When HCl is 1:1.08, the initial acetylene conversion rate is 97.6%, the selectivity of chloroethylene is more than 99.5%, the reaction is operated for 500h, and the catalyst acetylene conversion rate is 87.8%.
Example 2
Weighing 3.2g of cerous nitrate hexahydrate, stirring and dissolving in 200ml of deionized water, weighing 46g of wood activated carbon, immersing in the cerous nitrate solution, stirring, gradually dropwise adding 51ml of 1mol/L NaOH solution into the mixed solution, standing and aging for 12h after dropwise adding, filtering, drying at 120 ℃ for 8h, drying at 600 ℃ under a nitrogen atmosphere, raising the temperature at the rate of 5 ℃/min, and roasting for 3h to obtain the composite carrier.
Weighing 12g of copper chloride and 2.4g of 2-pyrrolidone, adding 44ml of deionized water, stirring and mixing uniformly, dripping the mixed solution onto the composite carrier while stirring, standing for 12h, and drying for 36h at 120 ℃ to obtain the catalyst.
Evaluation of catalyst: the temperature is 150 ℃, and the space velocity is 40h-1The feed gas C2H2HCl 1:1.06, the initial acetylene conversion rate is 95.9%, the selectivity of chloroethylene is more than 99.5%, the reaction is operated for 500h, and the catalyst acetylene conversion rate is 93.5%.
Example 3
Weighing 5.4g of cerous nitrate hexahydrate, stirring and dissolving the cerous nitrate hexahydrate in 200ml of deionized water, weighing 45g of coal-based activated carbon, immersing the coal-based activated carbon in a cerous nitrate solution, stirring, gradually dropwise adding 86ml of 1mol/L NaOH solution into the mixed solution, standing and aging for 12h after the dropwise adding is completed, filtering, drying at 120 ℃ for 8h, heating at the temperature of 450 ℃ under a nitrogen atmosphere at the speed of 5 ℃/min, and roasting for 3.5h to obtain the composite carrier.
Weighing 12g of copper chloride and 2.4g of pyrrolidone hydrochloride, adding 43ml of deionized water, stirring and mixing uniformly, dripping the mixed solution onto the composite carrier while stirring, standing for 12h, and drying for 48h at 100 ℃ to obtain the catalyst.
Evaluation of catalyst: the temperature is 150 ℃, and the space velocity is 37h-1The feed gas C2H2The initial acetylene conversion rate is 98.3 percent, the vinyl chloride selectivity is more than 99.5 percent, the reaction is operated for 500 hours, and the catalyst acetylene conversion rate is 94.4 percent.
Example 4
Weighing 3.2g of cerous nitrate hexahydrate, stirring and dissolving in 200ml of deionized water, weighing 35.4g of wood activated carbon, immersing in the cerous nitrate solution, stirring, gradually dropwise adding 51ml of 1mol/L NaOH solution into the mixed solution, standing and aging for 12h after dropwise adding, filtering, drying at 120 ℃ for 8h, heating at 550 ℃ under nitrogen atmosphere at the heating rate of 5 ℃/min, and roasting for 4.5h to obtain the composite carrier.
Weighing 18g of copper chloride and 4.8g of 1-butyl 3-methylimidazolium chloride, adding 33ml of deionized water, uniformly stirring and mixing, dropwise adding the mixture onto the composite carrier while stirring, standing for 12h, and drying for 48h at 100 ℃ to obtain the catalyst.
Evaluation of catalyst: the temperature is 150 ℃, and the space velocity is 35h-1The feed gas C2H2The initial acetylene conversion rate is 98.6 percent, the vinyl chloride selectivity is more than 99.5 percent, the reaction is operated for 500 hours, and the catalyst acetylene conversion rate is 95.7 percent.
Example 5
Weighing 3.2g of cerous nitrate hexahydrate, stirring and dissolving in 200ml of deionized water, weighing 32g of wood activated carbon, immersing in the cerous nitrate solution, stirring, gradually dropwise adding 51ml of 1mol/L NaOH solution into the mixed solution, standing and aging for 12h after dropwise adding is finished, filtering, drying at 120 ℃ for 6h, heating at a rate of 5 ℃/min under a nitrogen atmosphere, and roasting for 4h to obtain the composite carrier.
Weighing 21g of copper chloride and 6g of N-methyl formamide, adding 28ml of deionized water, stirring and mixing uniformly, dripping the mixed solution onto the composite carrier while stirring, standing for 12h, and drying for 48h at 110 ℃ to obtain the catalyst.
Evaluation of catalyst: the temperature is 150 ℃, and the space velocity is 35h-1The feed gas C2H2The initial acetylene conversion rate is 99.2 percent, the vinyl chloride selectivity is more than 99.5 percent, the reaction is operated for 500 hours, and the catalyst acetylene conversion rate is 96.3 percent.
Example 6
Weighing 1.5g of cerous nitrate hexahydrate, stirring and dissolving the cerous nitrate hexahydrate in 200ml of deionized water, weighing 43g of wood activated carbon, immersing the wood activated carbon in the cerous nitrate solution, stirring, gradually dropwise adding 24ml of 1mol/L NaOH solution into the mixed solution, standing and aging for 12h after dropwise adding, filtering, drying at 120 ℃ for 6h, heating at a rate of 5 ℃/min under a nitrogen atmosphere, and roasting for 4.5h to obtain the composite carrier.
Weighing 12g of copper nitrate, 2.4g of N-methylformamide and 2.4g of 2-pyrrolidone, adding 41ml of deionized water, stirring and mixing uniformly, dripping the mixed solution onto the composite carrier while stirring, standing for 12h, and drying at 120 ℃ for 30h to obtain the catalyst.
Evaluation of catalyst: the temperature is 150 ℃, and the space velocity is 35h-1The feed gas C2H2The initial acetylene conversion rate is 97.8 percent, the vinyl chloride selectivity is more than 99.5 percent, the reaction is operated for 500 hours, and the catalyst acetylene conversion rate is 96.7 percent.
Example 7
Weighing 1.5g of cerous nitrate hexahydrate, stirring and dissolving the cerous nitrate hexahydrate in 200ml of deionized water, weighing 43g of wood activated carbon, immersing the wood activated carbon in the cerous nitrate solution, stirring, gradually dropwise adding 24ml of 1mol/L NaOH solution into the mixed solution, standing and aging for 12h after dropwise adding, filtering, drying at 120 ℃ for 6h, heating at a rate of 5 ℃/min under a nitrogen atmosphere, and roasting for 4.5h to obtain the composite carrier.
Weighing 12g of copper sulfate, 1.2g of N-methylformamide and 3.6g of pyrrolidone hydrochloride, adding 42ml of deionized water, stirring and mixing uniformly, dripping the mixture on the composite carrier while stirring, standing for 12h, and drying for 24h at 110 ℃ to obtain the catalyst.
Evaluation of catalyst: the temperature is 150 ℃, and the space velocity is 35h-1The feed gas C2H2The initial acetylene conversion rate is 97.5 percent, the vinyl chloride selectivity is more than 99.5 percent, the reaction is operated for 500 hours, and the catalyst acetylene conversion rate is 95.9 percent.
Example 8
Weighing 3.2g of cerous nitrate hexahydrate, stirring and dissolving in 200ml of deionized water, weighing 43g of wood activated carbon, immersing in the cerous nitrate solution, stirring, gradually dropwise adding 51ml of 1mol/L NaOH solution into the mixed solution, standing and aging for 12h after dropwise adding is finished, filtering, drying at 120 ℃ for 6h, heating at the rate of 5 ℃/min under the nitrogen atmosphere for 500 ℃, and roasting for 4.5h to obtain the composite carrier.
Weighing 12g of copper sulfate, 1.2g of 2-pyrrolidone and 4.8g of 1-butyl 3-methylimidazolium chloride, adding 42ml of deionized water, stirring and mixing uniformly, dripping the mixed solution onto a composite carrier while stirring, standing for 12h, and drying at 120 ℃ for 24h to obtain the catalyst.
Evaluation of catalyst: the temperature is 150 ℃, and the space velocity is 35h-1The feed gas C2H2The initial acetylene conversion rate is 98.2 percent, the vinyl chloride selectivity is more than 99.5 percent, the reaction is operated for 500 hours, and the catalyst acetylene conversion rate is 96.4 percent.
Comparative example 1
Weighing 3.2g of cerous nitrate hexahydrate, stirring and dissolving in 200ml of deionized water, weighing 44g of wood activated carbon, immersing in the cerous nitrate solution, stirring, gradually dropwise adding 52ml of 1mol/L NaOH solution into the mixed solution, standing and aging for 12h after dropwise adding, filtering, drying at 120 ℃ for 5h, heating at the rate of 5 ℃/min under the nitrogen atmosphere for 500 ℃, and roasting for 4.5h to obtain the composite carrier.
Weighing 12g of copper chloride, adding 42ml of deionized water, stirring and mixing uniformly, dropwise adding the solution onto the composite carrier while stirring, standing for 12h, and drying at 120 ℃ for 24h to obtain the catalyst.
Evaluation of catalyst: the temperature is 150 ℃, and the space velocity is 35h-1The feed gas C2H2The initial acetylene conversion is 87.5 percent, the vinyl chloride selectivity is more than 99.5 percent, the reaction is operated for 500 hours, and the catalyst acetylene conversion is 65.6 percent.
Comparative example 2
Weighing 18g of copper sulfate, 1.2g of 2-pyrrolidone and 4.8g of 1-butyl 3-methylimidazolium chloride, adding 34ml of deionized water, stirring and mixing uniformly, dripping the mixed solution onto 36g of wood activated carbon while stirring, standing for 12h, drying at 120 ℃ for 36h, heating at 500 ℃ under a nitrogen atmosphere at a heating rate of 5 ℃/min, and roasting for 4.5h to obtain the catalyst.
Evaluation of catalyst: the temperature is 150 ℃, and the space velocity is 35h-1The feed gas C2H21:1.08 with an initial acetylene conversion of 96.3% and a vinyl chloride selectivity greater than99.5 percent, the reaction is run for 500 hours, and the conversion rate of the catalyst acetylene is 55.2 percent.
Comparative example 3
Weighing 3.2g of cerium chloride, stirring and dissolving in 200ml of deionized water;
putting the wood activated carbon into 2mol/L phosphoric acid, reacting for 4h at 70 ℃, washing to neutrality and drying;
weighing 46g of dried wood activated carbon, immersing the wood activated carbon in a cerium chloride solution, adding 12g of copper chloride and 2.4g of 2-pyrrolidone, adding 44mL of deionized water, stirring and mixing uniformly, stirring, drying at 100 ℃, and roasting in 150mL/min helium flow for 4 hours at 500 ℃ to obtain the catalyst.
Evaluation of catalyst: the temperature is 150 ℃, and the space velocity is 40h-1The feed gas C2H2HCl 1:1.06, initial acetylene conversion 94.7%, vinyl chloride selectivity over 99.5%, reaction run 500h, catalyst acetylene conversion 71.2%.
Comparative example 4
Weighing 3.2g of cobalt chloride, stirring and dissolving in 200ml of deionized water, weighing 46g of wood activated carbon, immersing in the cobalt chloride solution, stirring, gradually dropwise adding 51ml of 1mol/L NaOH solution into the mixed solution, standing and aging for 12h after dropwise adding, filtering, drying at 120 ℃ for 8h, drying at 600 ℃ under a nitrogen atmosphere at a heating rate of 5 ℃/min, and roasting for 3h to obtain the composite carrier.
Weighing 12g of copper chloride and 2.4g of succinimide, adding 44ml of deionized water, stirring and mixing uniformly, dripping the mixed solution onto the composite carrier while stirring, standing for 12h, and drying at 120 ℃ for 36h to obtain the catalyst.
Evaluation of catalyst: the temperature is 150 ℃, and the space velocity is 40h-1The feed gas C2H2HCl 1:1.06, initial acetylene conversion 92.6%, vinyl chloride selectivity over 99.5%, reaction run 500h, catalyst acetylene conversion 63.5%.
Comparative example 5
Weighing 8g of cerous nitrate hexahydrate, stirring and dissolving the cerous nitrate hexahydrate in 200ml of deionized water, weighing 46g of wood activated carbon, immersing the wood activated carbon in the cerous nitrate solution, stirring, gradually dropwise adding 51ml of 1mol/L NaOH solution into the mixed solution, standing and aging for 12h after the dropwise adding is completed, filtering, drying at 120 ℃ for 8h, heating at a rate of 10 ℃/min under a nitrogen atmosphere, and roasting for 3h to obtain the composite carrier.
Weighing 40g of copper chloride and 2.4g of cyclopentanone, adding 44ml of deionized water, stirring and mixing uniformly, dripping the mixed solution onto the composite carrier while stirring, standing for 12h, and drying at 120 ℃ for 36h to obtain the catalyst.
Evaluation of catalyst: the temperature is 150 ℃, and the space velocity is 40h-1The feed gas C2H2HCl 1:1.06, initial acetylene conversion 95.7%, chloroethylene selectivity over 99.5%, reaction running 500h, catalyst acetylene conversion 82.2%.
The results are shown in Table 1.
TABLE 1
Vinyl chloride Selectivity% Conversion of acetylene/% After 500h acetylene conversion/%)
Example 1 ≥99.5 97.6 87.8
Example 2 ≥99.5 95.9 93.5
Example 3 ≥99.5 98.3 94.4
Example 4 ≥99.5 98.6 95.7
Example 5 ≥99.5 99.2 96.3
Example 6 ≥99.5 97.8 96.7
Example 7 ≥99.5 97.5 95.9
Example 8 ≥99.5 98.2 96.4
Comparative example 1 ≥99.5 87.5 65.6
Comparative example 2 ≥99.5 96.3 55.2
Comparative example 3 ≥99.5 94.7 71.2
Comparative example 4 ≥99.5 92.6 63.5
Comparative example 5 ≥99.5 95.7 82.2
The present invention has been further described with reference to specific embodiments, which are only exemplary and do not limit the scope of the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (10)

1. A composite carrier Cu-based acetylene hydrochlorination catalyst is characterized by comprising an auxiliary agent, a copper metal salt and the balance of a composite carrier;
the preparation method of the composite carrier comprises the following steps: and (2) pouring the activated carbon into the cerium nitrate solution, stirring, dropwise adding an alkali solution into the cerium nitrate solution, aging, filtering, drying and roasting after dropwise adding is finished, thus obtaining the composite carrier.
2. The composite supported Cu-based acetylene hydrochlorination catalyst according to claim 1, characterized in that the molar ratio of cerium nitrate to base is 1: 7.
3. The composite carrier Cu-based acetylene hydrochlorination catalyst according to claim 1, wherein the mass ratio of the cerium nitrate to the activated carbon is 0.02-0.1: 1.
4. the composite supported Cu-based acetylene hydrochlorination catalyst according to claim 1, wherein the calcination is: roasting for 3-5h at 400-600 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere.
5. The composite carrier Cu-based acetylene hydrochlorination catalyst according to claim 1, wherein the activated carbon is wood activated carbon and/or coal activated carbon.
6. The composite carrier Cu-based acetylene hydrochlorination catalyst according to claim 1, characterized in that the auxiliary agent is at least one of N-methylformamide, 2-pyrrolidone, pyrrolidone hydrochloride, and 1-butyl 3-methylimidazolium chloride.
7. The composite carrier Cu-based acetylene hydrochlorination catalyst according to claim 1, characterized in that the metal salt of copper is at least one of copper sulfate, copper nitrate and copper chloride.
8. The composite carrier Cu-based acetylene hydrochlorination catalyst according to claim 1, which is characterized by comprising the following components in percentage by mass: 1-10% of assistant, 5-35% of copper metal salt and the balance of composite carrier.
9. The method for preparing a composite supported Cu-based acetylene hydrochlorination catalyst according to any one of claims 1 to 8, characterized in that the method comprises: mixing the auxiliary agent and the metal salt of copper according to the formula ratio, adding the composite carrier, soaking at normal temperature in equal volume, standing and drying to obtain the composite carrier Cu-based acetylene hydrochlorination catalyst.
10. Use of the composite supported Cu-based acetylene hydrochlorination catalyst according to any one of claims 1 to 8 in acetylene hydrochlorination reactions.
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