CN114146728B - 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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CN114146728B
CN114146728B CN202111432954.6A CN202111432954A CN114146728B CN 114146728 B CN114146728 B CN 114146728B CN 202111432954 A CN202111432954 A CN 202111432954A CN 114146728 B CN114146728 B CN 114146728B
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composite carrier
acetylene hydrochlorination
catalyst
hydrochlorination catalyst
copper
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CN114146728A (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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    • 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, copper metal salt and the balance of composite carrier; the preparation method of the composite carrier comprises the following steps: pouring active carbon into cerium nitrate solution, stirring, dripping alkali solution into the cerium nitrate solution, aging, filtering, drying and roasting after the dripping is completed to obtain the composite carrier; the preparation method comprises the following steps: mixing the auxiliary agent with copper metal salt in the formula amount, adding the composite carrier, soaking in an equal volume at normal temperature, standing and drying to obtain the Cu-based acetylene hydrochlorination catalyst of the composite carrier. The preparation method provided by the invention is simple, has high catalytic efficiency and long service life, is easy to industrialize, and can meet the requirements and standards of an industrial converter on an acetylene hydrochlorination catalyst.

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 composite carrier Cu-based acetylene hydrochlorination catalyst and a preparation method thereof.
Background
Polyvinyl chloride is the second largest universal synthetic resin worldwide, with very broad market demands. Vinyl chloride is a raw material for synthesizing polyvinyl chloride, and methods for synthesizing the vinyl chloride mainly comprise 3 methods, namely an acetylene method, an ethylene method and an ethane method, and the current industrialization mainly comprises an acetylene method which takes coal as a raw material and an ethylene method which takes petroleum as a raw material. About 80% of polyvinyl chloride output in China is derived from the acetylene method. Along with the increase of environmental protection, the mercury-free PVC production becomes a necessary trend. Therefore, the research and development of the mercury-free catalyst to replace the mercury-containing catalyst has positive social benefit and environmental benefit.
The research and development of the metal mercury-free catalyst mainly comprises two metal catalysts of noble metals such as Au, pd, ru and the like and non-noble metals such as Bi, sn, cu and the like. For example, CN 103623837A discloses a Ru-Co-Cu catalyst for synthesizing chloroethylene by hydrochlorination of acetylene, which comprises an inert porous carrier, and ruthenium salt, copper salt and cobalt salt carried on the inert porous carrier, wherein the mass of Ru accounts for 0.01-5% of the mass of the Ru-Co-Cu catalyst for synthesizing chloroethylene by hydrochlorination of acetylene, and the molar ratio of Ru, cu and Co is 1:0.1-10:0.1-10. The catalyst of the invention can reduce the reaction temperature to be lower than 180 ℃ when catalyzing hydrochlorination of acetylene to synthesize chloroethylene, and has good selectivity of reaction products, few byproducts and high reaction activity, so that the conversion rate of acetylene is over 99%, and the selectivity of chloroethylene reaches 99.9%, but the catalyst of the invention has poor stability.
CN111715253a discloses a copper-based catalyst for the hydrochlorination of acetylene to vinyl chloride. 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 nitrogen-containing or carbonyl-containing ligand. The modified carrier can not only enhance the interaction with the copper complex and prevent the loss of the copper complex, but also regulate and control the adsorption performance on acetylene and hydrogen chloride gas, and promote the activity of the catalyst under the synergistic effect of the acetylene and the hydrogen chloride gas, and the conversion rate of the acetylene reaches 92.6 percent, so that the stability of the catalyst can be improved, but the improvement degree of the stability is limited.
CN109821546a discloses a preparation method of a composite copper-based catalyst, which comprises the following steps: immersing 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, stannic 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 after the acid treatment to the copper salt to the auxiliary agent is 100:5:1-100:10:5. The catalyst provided by the invention has higher activity and selectivity in the reaction of producing chloroethylene by hydrochlorination of acetylene, and can be used at the space velocity of 300h -1 Is stable for 500 hours under the condition of having goodBut the acetylene conversion of the invention is lower, less than 80%.
Disclosure of Invention
In order to solve the technical problems, the invention provides the composite carrier Cu-based acetylene hydrochlorination catalyst and the preparation method thereof, and the preparation method of the composite carrier Cu-based acetylene hydrochlorination catalyst is simple, has high catalytic efficiency and long service life, is easy to industrialize, and can meet the requirements and standards of industrial converters on the acetylene hydrochlorination catalyst.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a Cu-base catalyst for hydrochlorination of acetylene is composed of assistant, cu metal salt and composite carrier.
Preferably, the auxiliary agent is at least one of N-methyl formamide, 2-pyrrolidone, pyrrolidone hydrochloride and 1-butyl 3-methylimidazole chloride.
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: pouring active carbon into cerium nitrate solution, stirring, dripping alkali solution into the cerium nitrate solution, aging, filtering, drying and roasting to obtain 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 cerium nitrate to base is 1:7.
Further preferably, the firing is: roasting for 3-5h at 400-600 ℃ at a heating rate of 5 ℃/min under the nitrogen atmosphere.
Preferably, the composite carrier Cu-based acetylene hydrochlorination catalyst comprises the following components in percentage by mass: 1-10% of auxiliary agent, 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 with copper metal salt in the formula amount, adding the composite carrier, soaking in an equal volume at normal temperature, standing and drying to obtain the Cu-based acetylene hydrochlorination catalyst of the composite carrier.
Preferably, the drying is: drying at 80-120deg.C for 24-48 hr.
The invention also provides application of the composite carrier Cu-based acetylene hydrochlorination catalyst in acetylene hydrochlorination.
The beneficial effects of the invention are as follows:
the invention adopts a precipitation method to precipitate CeO 2 The active carbon is loaded on the active carbon to form composite active carbon, so that on one hand, the generation of carbon deposition in the reaction process can be inhibited, on the other hand, 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, the auxiliary agent and the active component form stronger bonding action, thereby improving the adsorption of the catalyst to HCl and effectively inhibiting Cu 2+ Is reduced by (a). Compared with the prior art, the preparation method of the composite carrier Cu-based acetylene hydrochlorination catalyst is simple, has higher catalytic efficiency and long service life, is easy to industrialize, can meet the requirements and standards of industrial converters on the acetylene hydrochlorination catalyst, and meets the market demands.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Before the embodiments of the invention are explained in further detail, it is to be understood that the invention is not limited in its scope to the particular embodiments described below; it is also to be understood that the terminology used in the examples of the invention is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention.
Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. 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 invention does not limit the sources of the adopted raw materials, and if no special description exists, the adopted raw materials are all common commercial products in the technical field.
Example 1
1.5g of cerium nitrate hexahydrate is weighed, stirred and dissolved in 200ml of deionized water, 52g of wood activated carbon is weighed and immersed in cerium nitrate solution, stirred, 24ml of NaOH solution with the concentration of 1mol/L is gradually added dropwise into the mixed solution, the mixture is left to stand and age for 12 hours after the dropwise addition is completed, the mixture is filtered, dried for 5 hours at 120 ℃, heated at 400 ℃ under nitrogen atmosphere at a speed of 5 ℃/min, and baked for 5 hours, thus obtaining the composite carrier.
6g of copper chloride and 1.2g of N-methyl formamide are weighed, 48ml of deionized water is added, stirring and mixing are carried out uniformly, the mixture is dripped on a composite carrier, stirring is carried out while dripping, standing is carried out for 12h, and drying is carried out at 120 ℃ for 24h, thus obtaining the catalyst.
Catalyst evaluation: temperature 150 ℃ and airspeed 35h -1 Feed gas C 2 H 2 Hcl=1:1.08, its initial acetylene conversion is 97.6%, vinyl chloride selectivity is greater than 99.5%, the reaction is run for 500h, and catalyst acetylene conversion is 87.8%.
Example 2
3.2g of cerium nitrate hexahydrate is weighed, stirred and dissolved in 200ml of deionized water, 46g of wood activated carbon is weighed and immersed in cerium nitrate solution, stirred, 51ml of NaOH solution with the concentration of 1mol/L is gradually added dropwise into the mixed solution, the mixture is left to stand and age for 12 hours after the dropwise addition is completed, the mixture is filtered, dried at 120 ℃ for 8 hours, the temperature is raised at the temperature of 600 ℃ under the nitrogen atmosphere at the speed of 5 ℃/min, and the mixture is baked for 3 hours 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 mixture on a composite carrier, stirring while dripping, standing for 12h, and drying at 120 ℃ for 36h to obtain the catalyst.
Catalyst evaluation: temperature 150 ℃ and airspeed 40h -1 Feed gas C 2 H 2 Hcl=1:1.06, its initial acetylene conversion is 95.9%, vinyl chloride selectivity is greater than 99.5%, the reaction is run for 500h, and catalyst acetylene conversion is 93.5%.
Example 3
Weighing 5.4g of cerium nitrate hexahydrate, stirring and dissolving in 200ml of deionized water, weighing 45g of coal activated carbon, immersing in cerium nitrate solution, stirring, gradually dropwise adding 86ml of 1mol/L NaOH solution into the mixed solution, standing and aging for 12h after the dropwise addition is completed, filtering, drying at 120 ℃ for 8h, heating at 450 ℃ under nitrogen atmosphere at a heating rate 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 mixture on a composite carrier, stirring while dripping, standing for 12h, and drying at 100 ℃ for 48h to obtain the catalyst.
Catalyst evaluation: temperature 150 ℃ and airspeed 37h -1 Feed gas C 2 H 2 Hcl=1:1.06, its initial acetylene conversion is 98.3%, vinyl chloride selectivity is greater than 99.5%, the reaction is run for 500h, and catalyst acetylene conversion is 94.4%.
Example 4
3.2g of cerium nitrate hexahydrate is weighed, stirred and dissolved in 200ml of deionized water, 35.4g of wood activated carbon is weighed and immersed in cerium nitrate solution, stirred, 51ml of NaOH solution with the concentration of 1mol/L is gradually added dropwise into the mixed solution, the mixture is left to stand and age for 12 hours after the dropwise addition is completed, the mixture is filtered, dried at 120 ℃ for 8 hours, and baked for 4.5 hours at the temperature rising rate of 5 ℃/min under the nitrogen atmosphere, so that the composite carrier is obtained.
18g of copper chloride and 4.8g of 1-butyl 3-methylimidazole chloride are weighed, 33ml of deionized water is added, stirring and mixing are carried out uniformly, the mixture is dripped on a composite carrier, stirring is carried out while dripping, standing is carried out for 12h, and drying is carried out at 100 ℃ for 48h, so that the catalyst is obtained.
Catalyst evaluation: temperature 150 ℃ and airspeed 35h -1 Raw materialsGas C 2 H 2 Hcl=1:1.06, its initial acetylene conversion is 98.6%, vinyl chloride selectivity is greater than 99.5%, the reaction is run for 500h, and catalyst acetylene conversion is 95.7%.
Example 5
3.2g of cerium nitrate hexahydrate is weighed, stirred and dissolved in 200ml of deionized water, 32g of wood activated carbon is weighed and immersed in cerium nitrate solution, stirred, 51ml of NaOH solution with the concentration of 1mol/L is gradually added dropwise into the mixed solution, the mixture is left to stand and age for 12 hours after the dropwise addition is completed, the mixture is filtered, dried for 6 hours at 120 ℃, and baked for 4 hours at the temperature of 500 ℃ and the heating rate of 5 ℃/min under nitrogen atmosphere, so that the composite carrier is obtained.
21g of copper chloride and 6g of N-methyl formamide are weighed, 28ml of deionized water is added, stirring and mixing are carried out uniformly, the mixture is dripped on a composite carrier, stirring is carried out while dripping, standing is carried out for 12h, and drying is carried out at 110 ℃ for 48h, thus obtaining the catalyst.
Catalyst evaluation: temperature 150 ℃ and airspeed 35h -1 Feed gas C 2 H 2 Hcl=1:1.06, its initial acetylene conversion is 99.2%, vinyl chloride selectivity is greater than 99.5%, the reaction is run for 500h, and catalyst acetylene conversion is 96.3%.
Example 6
1.5g of cerium nitrate hexahydrate is weighed, stirred and dissolved in 200ml of deionized water, 43g of wood activated carbon is weighed and immersed in cerium nitrate solution, stirred, 24ml of NaOH solution with the concentration of 1mol/L is gradually added dropwise into the mixed solution, the mixture is left to stand and age for 12 hours after the dropwise addition is completed, the mixture is filtered, dried for 6 hours at 120 ℃, and baked for 4.5 hours at the temperature of 500 ℃ and the heating rate of 5 ℃/min under nitrogen atmosphere, so that the composite carrier is obtained.
12g of copper nitrate, 2.4g of N-methyl formamide and 2.4g of 2-pyrrolidone are weighed, 41ml of deionized water is added, the mixture is stirred and mixed uniformly, the mixture is dripped on a composite carrier, the mixture is stirred while dripping, the mixture is kept stand for 12h, and the mixture is dried for 30h at 120 ℃ to obtain the catalyst.
Catalyst evaluation: temperature 150 ℃ and airspeed 35h -1 Feed gas C 2 H 2 Hcl=1:1.06, its initial acetylene conversion is 97.8%, vinyl chloride selectivity is greater than 99.5%, the reaction is run for 500h, and catalyst acetylene conversion is 96.7%.
Example 7
1.5g of cerium nitrate hexahydrate is weighed, stirred and dissolved in 200ml of deionized water, 43g of wood activated carbon is weighed and immersed in cerium nitrate solution, stirred, 24ml of NaOH solution with the concentration of 1mol/L is gradually added dropwise into the mixed solution, the mixture is left to stand and age for 12 hours after the dropwise addition is completed, the mixture is filtered, dried for 6 hours at 120 ℃, and baked for 4.5 hours at the temperature of 500 ℃ and the heating rate of 5 ℃/min under nitrogen atmosphere, so that the composite carrier is obtained.
12g of copper sulfate, 1.2g of N-methyl formamide and 3.6g of pyrrolidone hydrochloride are weighed, 42ml of deionized water is added, the mixture is stirred and mixed uniformly, the mixture is dripped on a composite carrier, the mixture is stirred while dripping, the mixture is kept stand for 12h, and the mixture is dried for 24h at 110 ℃ to obtain the catalyst.
Catalyst evaluation: temperature 150 ℃ and airspeed 35h -1 Feed gas C 2 H 2 Hcl=1:1.06, its initial acetylene conversion is 97.5%, vinyl chloride selectivity is greater than 99.5%, the reaction is run for 500h, and catalyst acetylene conversion is 95.9%.
Example 8
3.2g of cerium nitrate hexahydrate is weighed, stirred and dissolved in 200ml of deionized water, 43g of wood activated carbon is weighed and immersed in cerium nitrate solution, stirred, 51ml of NaOH solution with the concentration of 1mol/L is gradually added dropwise into the mixed solution, the mixture is left to stand and age for 12 hours after the dropwise addition is completed, the mixture is filtered, dried for 6 hours at 120 ℃, and baked for 4.5 hours at the temperature of 500 ℃ and the heating rate of 5 ℃/min under nitrogen atmosphere, so that the composite carrier is obtained.
12g of copper sulfate, 1.2g of 2-pyrrolidone and 4.8g of 1-butyl 3-methylimidazole chloride are weighed, 42ml of deionized water is added, the mixture is stirred and mixed uniformly, the mixture is dripped on a composite carrier, the mixture is stirred while dripping, the mixture is kept stand for 12h, and the mixture is dried at 120 ℃ for 24h, so that the catalyst is obtained.
Catalyst evaluation: temperature 150 ℃ and airspeed 35h -1 Feed gas C 2 H 2 Hcl=1:1.06, its initial acetylene conversion is 98.2%, vinyl chloride selectivity is greater than 99.5%, the reaction is run for 500h, and catalyst acetylene conversion is 96.4%.
Comparative example 1
3.2g of cerium nitrate hexahydrate is weighed, stirred and dissolved in 200ml of deionized water, 44g of wood activated carbon is weighed and immersed in cerium nitrate solution, stirred, 52ml of NaOH solution with the concentration of 1mol/L is gradually added dropwise into the mixed solution, the mixture is left to stand and age for 12 hours after the dropwise addition is completed, the mixture is filtered, dried for 5 hours at 120 ℃, and baked for 4.5 hours at the temperature of 500 ℃ and the heating rate of 5 ℃/min under nitrogen atmosphere, so that the composite carrier is obtained.
Weighing 12g of copper chloride, adding 42ml of deionized water, stirring and mixing uniformly, dropwise adding the solution onto a composite carrier, stirring while dropwise adding, standing for 12h, and drying at 120 ℃ for 24h to obtain the catalyst.
Catalyst evaluation: temperature 150 ℃ and airspeed 35h -1 Feed gas C 2 H 2 Hcl=1:1.08, its initial acetylene conversion is 87.5%, vinyl chloride selectivity is greater than 99.5%, the reaction is run for 500h, and catalyst acetylene conversion is 65.6%.
Comparative example 2
18g of copper sulfate, 1.2g of 2-pyrrolidone and 4.8g of 1-butyl 3-methylimidazole chloride are weighed, 34ml of deionized water is added, the mixture is stirred and mixed uniformly, the mixture is dripped onto 36g of wood activated carbon, the mixture is stirred while dripping, the mixture is kept stand for 12 hours, the mixture is dried at 120 ℃ for 36 hours, the temperature rising rate is 5 ℃/min at 500 ℃ under nitrogen atmosphere, and the mixture is roasted for 4.5 hours, so that the catalyst is obtained.
Catalyst evaluation: temperature 150 ℃ and airspeed 35h -1 Feed gas C 2 H 2 Hcl=1:1.08, its initial acetylene conversion is 96.3%, vinyl chloride selectivity is greater than 99.5%, the reaction is run for 500h, and catalyst acetylene conversion is 55.2%.
Comparative example 3
3.2g of cerium chloride is weighed and stirred to be dissolved in 200ml of deionized water;
placing wood activated carbon into 2mol/L phosphoric acid, reacting for 4 hours at 70 ℃, washing to be neutral, and drying;
weighing 46g of dried wood activated carbon, immersing in 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 at 500 ℃ in 150mL/min helium gas flow for 4 hours to obtain the catalyst.
Catalyst evaluation: temperature 150 ℃ and airspeed 40h -1 Feed gas C 2 H 2 Hcl=1:1.06, its initial acetylene conversion 94.7%, vinyl chloride selectivity greater than 99.5%, reaction run 500h, catalyst acetylene conversion 71.2%.
Comparative example 4
3.2g of cobalt chloride is weighed, stirred and dissolved in 200ml of deionized water, 46g of wood activated carbon is weighed and immersed in cobalt chloride solution, stirring is carried out, 1mol/L NaOH solution 51ml is gradually added dropwise into the mixed solution, standing and ageing are carried out for 12h after the dropwise addition is finished, filtering is carried out, drying is carried out for 8h at 120 ℃, the temperature is 600 ℃ under the nitrogen atmosphere, the heating rate is 5 ℃/min, and the composite carrier is obtained after roasting for 3 h.
Weighing 12g of copper chloride and 2.4g of succinimide, adding 44ml of deionized water, stirring and mixing uniformly, dripping the mixture on a composite carrier, stirring while dripping, standing for 12h, and drying at 120 ℃ for 36h to obtain the catalyst.
Catalyst evaluation: temperature 150 ℃ and airspeed 40h -1 Feed gas C 2 H 2 Hcl=1:1.06, its initial acetylene conversion 92.6%, vinyl chloride selectivity greater than 99.5%, reaction run 500h, catalyst acetylene conversion 63.5%.
Comparative example 5
8g of cerium nitrate hexahydrate is weighed, stirred and dissolved in 200ml of deionized water, 46g of wood activated carbon is weighed and immersed in cerium nitrate solution, and 51ml of NaOH solution with the concentration of 1mol/L is gradually dropwise added into the mixed solution, and after the dropwise addition is completed, the mixture is kept stand and aged for 12 hours, filtered, dried at 120 ℃ for 8 hours, and baked for 3 hours under the nitrogen atmosphere at 600 ℃ and the heating rate of 10 ℃/min to obtain the composite carrier.
40g of copper chloride and 2.4g of cyclopentanone are weighed, 44ml of deionized water is added, stirring and mixing are carried out uniformly, the mixture is dripped on a composite carrier, stirring is carried out while dripping, standing is carried out for 12h, and drying is carried out at 120 ℃ for 36h, thus obtaining the catalyst.
Catalyst evaluation: temperature 150 ℃ and airspeed 40h -1 Feed gas C 2 H 2 Hcl=1:1.06, its initial acetylene conversion is 95.7%, vinyl chloride selectivity is greater than 99.5%, the reaction is run for 500h, and catalyst acetylene conversion is 82.2%.
The results are shown in Table 1.
TABLE 1
Vinyl chloride selectivity% Acetylene conversion/% 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 invention has been further described above in connection with specific embodiments, which are exemplary only and do not limit the scope of the invention in any way. It will be understood by those skilled in the art that various changes and substitutions of details and forms of the technical solution of the present invention may be made without departing from the spirit and scope of the present invention, but these changes and substitutions fall within the scope of the present invention.

Claims (9)

1. A composite carrier Cu-based acetylene hydrochlorination catalyst is characterized by comprising an auxiliary agent, copper metal salt and the balance of a composite carrier;
the preparation method of the composite carrier comprises the following steps: pouring active carbon into cerium nitrate solution, stirring, dripping alkali solution into the cerium nitrate solution, aging, filtering, drying and roasting after the dripping is completed to obtain the composite carrier;
the auxiliary agent is at least one of N-methyl formamide, 2-pyrrolidone, pyrrolidone hydrochloride and 1-butyl 3-methylimidazole chloride.
2. The composite carrier Cu-based acetylene hydrochlorination catalyst according to claim 1, wherein 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 cerium nitrate to activated carbon is 0.02-0.1:1.
4. the composite support Cu-based acetylene hydrochlorination catalyst of claim 1, wherein the calcination is: roasting for 3-5h at 400-600 ℃ at a heating rate of 5 ℃/min under 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 of claim 1, wherein the metal salt of copper is at least one of copper sulfate, copper nitrate and copper chloride.
7. 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 auxiliary agent, 5-35% of copper metal salt and the balance of composite carrier.
8. The method for preparing the composite carrier Cu-based acetylene hydrochlorination catalyst according to any one of claims 1 to 7, wherein the preparation method is as follows: mixing the auxiliary agent with copper metal salt in the formula amount, adding the composite carrier, soaking in an equal volume at normal temperature, standing and drying to obtain the Cu-based acetylene hydrochlorination catalyst of the composite carrier.
9. Use of a composite carrier Cu-based acetylene hydrochlorination catalyst according to any one of claims 1 to 7 in acetylene hydrochlorination reactions.
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CN111774094A (en) * 2019-04-03 2020-10-16 南开大学 Copper-based mercury-free catalyst for producing chloroethylene by calcium carbide method and preparation and use methods thereof

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