CN112570043B - Catalyst for hydrochlorination of acetylene and application thereof - Google Patents

Catalyst for hydrochlorination of acetylene and application thereof Download PDF

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CN112570043B
CN112570043B CN202011441893.5A CN202011441893A CN112570043B CN 112570043 B CN112570043 B CN 112570043B CN 202011441893 A CN202011441893 A CN 202011441893A CN 112570043 B CN112570043 B CN 112570043B
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acetylene
aqueous solution
gold
activated carbon
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CN112570043A (en
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曾利辉
李霖
金晓东
苏雅文
李小虎
曾永康
万克柔
张之翔
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Kaili Catalyst New Materials 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
    • B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/10—Chlorides
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • 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
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    • 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 catalyst for hydrochlorination of acetylene and application thereof. The catalyst takes a gold compound as a catalytic active component, a potassium or sodium compound as a promoting component, and pretreated activated carbon as a carrier. According to the preparation method of the catalyst, the active carbon carrier is pretreated by a microwave radiation nitrogen modification technology, and nitrogen elements on the surface of the active carbon are coordinated with gold, so that the active carbon is highly dispersed and firmly anchored on the surface of the carrier, and alkali metal elements improve the surface alkalinity and the reduction electrode potential of the gold, thereby facilitating the adsorption of hydrogen chloride on the surface of the gold. The catalyst has extremely high catalytic activity and selectivity in the reaction of synthesizing chloroethylene by hydrochlorination of acetylene, and has extremely great industrial application prospect.

Description

Catalyst for hydrochlorination of acetylene and application thereof
Technical Field
The invention belongs to the technical field of new chemical catalytic materials, and particularly relates to a catalyst for acetylene hydrochlorination and a preparation method thereof. The catalyst has extremely high catalytic activity and selectivity in the hydrochlorination of acetylene and has extremely great industrial application prospect.
Background
Polyvinyl chloride (PVC) has been successfully substituted for conventional materials such as plates, paints, metals, and the like due to its excellent properties, broad characteristics, and economical fire resistance. It is acknowledged that PVC will continue to play an increasingly important role in the future. PVC is mainly polymerized by Vinyl Chloride (VCM) monomers, and at present, 3 VCM production processes which are mature in the world and are most widely applied are mainly an ethane method which takes natural gas as a raw material, an ethylene method which takes petroleum resources as a raw material and an acetylene method which takes coal resources as a raw material. In abroad, because of the advantages of abundant petroleum resources, the ethylene method is mainly adopted to produce chloroethylene, while the main advantages of China in terms of energy are more coal mines, so the acetylene method based on coal chemical industry is more suitable for China's national conditions. At present, mercury chloride is mainly used as a catalyst for producing vinyl chloride by a calcium carbide acetylene method, and irreversible heavy metal pollution is caused to the environment. Mercury metal entering the natural environment is absorbed by humans through the respiratory tract, digestive tract, and the like and accumulated. The mercury metal absorbed by human body has affinity reaction with sulfur radical and disulfide radical in human body, thus seriously disturbing the operation of enzyme system in human body, causing mercury poisoning and endangering human health. Because of the difficult degradation and extremely toxic physical properties of mercury, the loss and discarding of mercury in the use process not only causes serious environmental pollution, but also endangers the health of human beings. Therefore, under the framework of united nations, the "water mercury control convention" for limiting mercury emissions was formally signed in 1 month 19 of 2013, and the production and trade of mercury-containing products were gradually reduced before 2020. Therefore, in severe cases of human life health safety and international, a mercury-free catalyst is needed to replace the existing mercury chloride catalyst to complete the industrial transformation of vinyl chloride production by acetylene method.
Disclosure of Invention
The invention aims to improve the surface distribution of a catalytic active component gold on the carrier active carbon, and provides a catalyst for acetylene hydrochlorination reaction, which has extremely high catalytic activity and selectivity in the reaction of synthesizing vinyl chloride by hydrochlorination of acetylene and has extremely great industrial application prospect by carrying out special pretreatment on the carrier and introducing an alkali metal compound in the loading process to regulate and control the impregnation process.
Aiming at the purposes, the catalyst adopted by the invention takes a gold compound as a catalytic active component, a potassium or sodium compound as a promoting component, and pretreated activated carbon as a carrier; the mass of the carrier is calculated as 100%, wherein the loading of gold is 0.03% -1.5%, and the loading of the auxiliary catalytic component is 2% -12%; the catalyst is prepared by the following steps:
1. the specific surface area is more than or equal to 750m 2 Adding/g active carbon into water solution of water-soluble nitride, radiating by microwave for 1-12 hours at 50-90 ℃, vacuum filtering the obtained mixed slurry, washing with deionized water until the pH value of the filtrate is neutral, and drying to obtain pretreated active carbon; wherein the mass-volume ratio of the active carbon to the water solution of the water-soluble nitride is 1 g:3-10 mL, and the water-soluble nitride is any one or more of ammonia water solution, ammonium chloride, ammonium bicarbonate, ammonium sulfate, ammonium hydrogen phosphate and urea.
2. At normal temperature, adding pretreated activated carbon into an alkali metal compound aqueous solution with the mass concentration of 0.5-15% by adopting an isovolumetric impregnation method, soaking for 30-60 minutes, then adding a gold trichloride hydrochloric acid aqueous solution, standing for 4-30 hours, removing redundant liquid, and drying the rest solid particles to obtain a catalyst; wherein the alkali metal compound is one or more of sodium sulfite, potassium persulfate, sodium persulfate and potassium thiosulfate.
In the catalyst, the loading of gold is preferably 0.1-0.5% and the loading of the auxiliary catalytic component is 5-10% based on 100% of the mass of the carrier.
In the above-mentioned method for preparing the catalyst, in step 1, activated carbon is preferably added to an aqueous solution of a water-soluble nitride, and microwave irradiation is performed at 60 to 80 ℃ for 5 to 8 hours.
In the above-mentioned method for producing a catalyst, in step 1, it is further preferable that the power of the microwave radiation is 200 to 800W.
In the step 1 of the preparation method of the catalyst, it is further preferable that the aqueous solution of the water-soluble nitride is any one or more of an aqueous ammonia solution with a mass concentration of 10% -25%, an aqueous ammonium chloride solution with a mass concentration of 10% -20%, an aqueous ammonium bicarbonate solution with a mass concentration of 5% -20%, an aqueous ammonium sulfate solution with a mass concentration of 5% -15%, an aqueous ammonium hydrogen phosphate solution with a mass concentration of 5% -10%, and an aqueous urea solution with a mass concentration of 5% -15%.
In the step 2 of the preparation method of the catalyst, the pretreated activated carbon is preferably added into an alkali metal compound aqueous solution with the mass concentration of 1-10% by adopting an equal volume impregnation method at normal temperature, soaked for 30-60 minutes, then added with a gold trichloride hydrochloric acid aqueous solution and kept stand for 5-25 hours.
The activated carbon is preferably a coconut shell carbon in the form of a sheet, a cylinder, a pellet or a pellet.
The method for catalyzing acetylene hydrochlorination reaction by adopting the catalyst comprises the following steps: adding the catalyst into a fixed bed tube reactor, and treating for 4-10 hours in a dry hydrogen chloride atmosphere at 120-150 ℃; then acetylene is introduced, and the airspeed of the acetylene is controlled to be 250h -1 The mol ratio of the hydrogen chloride to the acetylene is 1.10, the temperature of the catalyst bed layer is 150-225 ℃, and the acetylene hydrochlorination reaction is carried out to synthesize the chloroethylene.
The beneficial effects of the invention are as follows:
1. according to the invention, under the action of microwave radiation, the water-soluble nitride is used for carrying out modification pretreatment on the carrier, so that the active center site on the surface of the carrier is effectively increased, the dispersion and firm loading of oxidized gold can be promoted, and the activity and stability of the gold-based catalyst are improved.
2. According to the invention, aiming at the characteristics of a gold-based catalyst, firstly, an alkali metal compound is loaded on the surface of a carrier, and then, hydrochloric acid solution of gold trichloride is loaded on the outer surface of the carrier through an impregnation method, so that an eggshell catalyst is formed, the catalytic effect of active component gold is fully exerted, and under the condition of lower gold loading, the catalyst achieves high acetylene hydrochlorination activity and selectivity.
Drawings
FIG. 1 is the operational life of the catalysts of examples 1 and 8.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, but the scope of the present invention is not limited to these examples.
Example 1
1. Weighing 850m of specific surface area 2 50.0g of/g of flaky coconut shell activated carbon is added into a flask containing 250mL of 15% ammonia water solution by mass concentration, the flask is placed into a microwave radiator with the frequency of 2450MHz, the power is set to 650W, the temperature is controlled to be 85 ℃, the microwave radiation is carried out for 2.5 hours, then the obtained mixed slurry is subjected to vacuum filtration, deionized water is used for washing until the pH value of filtrate is neutral, and then a filter cake is placed into a blast drying box with the temperature of 120 ℃ for drying until the weight is constant, thus obtaining the pretreated activated carbon.
2. At normal temperature, 30.0g of pretreated activated carbon is added into 22mL of sodium sulfite aqueous solution with the mass concentration of 2.5%, soaking treatment is carried out for 45min, then 10mL of hydrochloric acid aqueous solution containing 0.3g of gold and gold trichloride is added, standing is carried out for 12h, redundant liquid is removed, and the rest solid particles are transferred to a blast drying box for drying at 120 ℃ to obtain the catalyst. The catalyst obtained was found to have a gold loading of 1.0% and a sodium sulfite loading of 1.5% based on 100% of the mass of the pretreated activated carbon.
Example 2
1. Weighing 850m of specific surface area 2 50.0g of/g flaky coconut shell activated carbon is added into a flask containing 500mL of ammonium bicarbonate aqueous solution with mass concentration of 10%, the flask is placed into a microwave radiator with frequency of 2450MHz, the power is set to be 750W, the temperature is controlled to be 75 ℃, the microwave radiation is carried out for 8 hours, then the obtained mixed slurry is subjected to vacuum suction filtration, deionized water is used for washing until the pH value of filtrate is neutral, and then a filter cake is placed into a blast drying box with 120 ℃ for drying until the weight is constant, so that the pretreated activated carbon is obtained.
2. At normal temperature, adding 40.0g of pretreated activated carbon into 28mL of 4% potassium persulfate aqueous solution by mass concentration, soaking for 35min, then adding 5mL of gold trichloride aqueous solution containing 0.05g of gold, standing for 10h, removing redundant liquid, transferring the residual solid particles to a blast drying oven and drying at 60 ℃ to obtain the catalyst. The catalyst obtained contained 0.125% gold and 2.5% potassium persulfate as the pretreated activated carbon by mass of 100%.
Example 3
1. Weighing 850m of specific surface area 2 50.0g of/g of flaky coconut shell activated carbon is added into a flask containing 500mL of aqueous ammonia hydrogen phosphate solution with mass concentration of 5%, the flask is placed into a microwave radiator with frequency of 2450MHz, the power is set to 850W, the temperature is controlled to be 95 ℃, the microwave radiation is carried out for 5.5 hours, then the obtained mixed slurry is subjected to vacuum filtration, deionized water is used for washing until the pH value of the filtrate is neutral, and then a filter cake is placed into a blast drying box with 120 ℃ for drying until the weight is constant, so that the pretreated activated carbon is obtained.
2. At normal temperature, adding 30.0g of pretreated activated carbon into 22mL of 2% potassium thiosulfate aqueous solution, soaking for 60min, then adding 10mL of gold trichloride aqueous solution containing 0.06g of gold, standing for 18h, removing redundant liquid, transferring the residual solid particles into a blast drying oven and drying at 90 ℃ to obtain the catalyst. The catalyst obtained contained 0.2% of gold and 1.2% of potassium thiosulfate, based on 100% of the pretreated activated carbon.
Example 4
1. Weighing 850m of specific surface area 2 50.0g of/g flaky coconut shell activated carbon is added into a flask containing 300mL of urea aqueous solution with mass concentration of 8%, the flask is placed into a microwave radiator with frequency of 2450MHz, the power is set to 800W, the temperature is controlled to 80 ℃, the microwave radiation is carried out for 1.5 hours, then the obtained mixed slurry is subjected to vacuum filtration, deionized water is used for washing until the pH value of the filtrate is neutral, and then a filter cake is placed into a blast drying box with 120 ℃ for drying until the weight is constant, so that the pretreated activated carbon is obtained.
2. At normal temperature, adding 40.0g of pretreated activated carbon into 28mL of aqueous solution of sodium sulfite with mass concentration of 4.5%, soaking for 60min, then adding 5mL of aqueous solution of hydrochloric acid containing gold trichloride with mass concentration of 0.6g, standing for 12h, removing redundant liquid, transferring the residual solid particles into a blast drying box and drying at 110 ℃ to obtain the catalyst. The catalyst obtained contained 0.15% of gold and 2.5% of sodium sulfite as the pretreated activated carbon by 100%.
Example 5
1. Weighing 850m of specific surface area 2 50.0g of/g flaky coconut shell activated carbon is added into a flask containing 200mL of 15% ammonium chloride aqueous solution by mass concentration, the flask is placed into a microwave radiator with the frequency of 2450MHz, the power is set to 450W, the temperature is controlled to 55 ℃, the microwave radiation is carried out for 4.5 hours, the obtained mixed slurry is subjected to vacuum filtration, deionized water is used for washing until the pH value of the filtrate is neutral, and then a filter cake is placed into a blast drying box with the temperature of 120 ℃ for drying until the weight is constant, so that the pretreated activated carbon is obtained.
2. At normal temperature, 20.0g of pretreated activated carbon is added into 14mL of sodium sulfite aqueous solution with the mass concentration of 1.0%, soaking treatment is carried out for 35min, then 10mL of hydrochloric acid aqueous solution containing 0.01g of gold and gold trichloride is added, standing is carried out for 18h, redundant liquid is removed, and the rest solid particles are transferred to a blast drying box for drying at 80 ℃ to obtain the catalyst. The catalyst obtained contained 0.05% of gold and 0.7% of sodium sulfite as the pretreated activated carbon by 100% of mass.
Example 6
1. Weighing 850m of specific surface area 2 50.0g of/g flaky coconut shell activated carbon is added into a flask containing 150mL of urea aqueous solution with mass concentration of 12%, the flask is placed into a microwave radiator with frequency of 2450MHz, the power is set to be 750W, the temperature is controlled to be 85 ℃, the microwave radiation is carried out for 4.5 hours, then the obtained mixed slurry is subjected to vacuum suction filtration, deionized water is used for washing until the pH value of the filtrate is neutral, and then a filter cake is placed into a blast drying box with 120 ℃ for drying until the weight is constant, so that the pretreated activated carbon is obtained.
2. At normal temperature, adding 40.0g of pretreated activated carbon into 22mL of sodium sulfite aqueous solution with mass concentration of 5%, soaking for 40min, then adding 10mL of hydrochloric acid aqueous solution containing 0.02g of gold and gold trichloride, standing for 18h, removing redundant liquid, transferring the residual solid particles into a blast drying box and drying at 120 ℃ to obtain the catalyst. The catalyst obtained contained 0.05% gold and 2.6% sodium sulfite as the active carbon for pretreatment, based on 100% of the active carbon.
Example 7
1. Weighing 850m of specific surface area 2 50.0g of/g flaky coconut shell activated carbon is added into a flask containing 350mL of ammonium bicarbonate aqueous solution with mass concentration of 10%, the flask is placed into a microwave radiator with frequency of 2450MHz, the power is set to 600W, the temperature is controlled to 80 ℃, the microwave radiation is carried out for 5.0h, then the obtained mixed slurry is subjected to vacuum filtration, deionized water is used for washing until the pH value of the filtrate is neutral, and then a filter cake is placed into a blast drying box with 120 ℃ for drying until the weight is constant, so that the pretreated activated carbon is obtained.
2. At normal temperature, 30.0g of pretreated activated carbon is added into 22mL of 4% potassium thiosulfate aqueous solution by mass concentration, soaking is carried out for 40min, then 10mL of gold trichloride aqueous solution containing 0.1g of gold is added, standing is carried out for 9h, redundant liquid is removed, and the rest solid particles are transferred to a blast drying oven for drying at 85 ℃ to obtain the catalyst. The catalyst obtained contained 0.3% of gold and 2.5% of potassium thiosulfate, based on 100% of the pretreated activated carbon.
Example 8
1. Weighing 850m of specific surface area 2 50.0g of/g flaky coconut shell activated carbon is added into a flask containing 250mL of ammonia water solution with mass concentration of 20%, the flask is placed into a microwave radiator with frequency of 2450MHz, the power is set to 750W, the temperature is controlled to 90 ℃, the microwave radiation is carried out for 1.5 hours, then the obtained mixed slurry is subjected to vacuum filtration, deionized water is used for washing until the pH value of the filtrate is neutral, and then a filter cake is placed into a blast drying box with 120 ℃ for drying until the weight is constant, so that the pretreated activated carbon is obtained.
2. At normal temperature, 20.0g of pretreated activated carbon is added into 14mL of sodium sulfite aqueous solution with the mass concentration of 2.5%, soaking treatment is carried out for 50min, then 10mL of hydrochloric acid aqueous solution containing 0.1g of gold and gold trichloride is added, standing is carried out for 10h, redundant liquid is removed, and the rest solid particles are transferred to a blast drying box for drying at 75 ℃ to obtain the catalyst. The catalyst obtained contained 0.5% of gold and 1.5% of sodium sulfite as the pretreated activated carbon by 100%.
Example 9
The catalysts prepared in examples 1 to 8 were respectively added into a fixed bed tube reactor and treated for 5 hours in a dry hydrogen chloride atmosphere at 150 ℃; then acetylene is introduced, and the airspeed of the acetylene is controlled to be 250h -1 The mol ratio of the hydrogen chloride to the acetylene is 1.10, the temperature of the catalyst bed layer is 180 ℃, and the acetylene hydrochlorination reaction is carried out to synthesize the vinyl chloride, wherein the reaction time is 30 hours. The reaction results are shown in Table 1.
TABLE 1
Catalyst numbering Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8
Acetylene conversion/% 95.77 73.24 78.33 75.94 64.22 68.41 82.34 89.32
Vinyl chloride selectivity/% 99.98 99.88 99.78 99.67 99.88 99.84 99.87 99.89
It can be seen from table 1 that the catalyst of the present invention achieves high acetylene hydrochlorination activity and vinyl chloride selectivity at lower gold loadings.
The inventors further evaluated the service lives of the catalysts prepared in examples 1 and 8 described above for catalyzing hydrochlorination of acetylene, and the results are shown in FIG. 1. As can be seen from FIG. 1, the catalyst of the present invention was used at a space velocity of 50h -1 The continuous operation is carried out for 4000 hours, and the acetylene conversion rate can still reach more than 90 percent.

Claims (6)

1. An application of a catalyst in catalyzing hydrochlorination of acetylene, which is characterized in that: the catalyst takes a gold compound as a catalytic active component, a potassium or sodium compound as a promoting component, and pretreated activated carbon as a carrier; the mass of the carrier is calculated as 100%, wherein the loading of gold is 0.1% -0.5%, and the loading of the auxiliary catalytic component is 5% -10%; the catalyst is prepared by the following steps:
(1) The specific surface area is more than or equal to 750m 2 Adding/g active carbon into water solution of water-soluble nitride, radiating by microwave for 1-12 hours at 50-90 ℃, vacuum filtering the obtained mixed slurry, washing with deionized water until the pH value of the filtrate is neutral, and drying to obtain pretreated active carbon; wherein the mass-volume ratio of the active carbon to the water-soluble nitride aqueous solution is 1 g:3-10 mL, and the water-soluble nitride aqueous solution is any one or more of 10-25% ammonia water solution, 10-20% ammonium chloride aqueous solution, 5-20% ammonium bicarbonate aqueous solution, 5-15% ammonium sulfate aqueous solution, 5-10% ammonium hydrogen phosphate aqueous solution and 5-15% urea aqueous solution;
(2) At normal temperature, adding pretreated activated carbon into an alkali metal compound aqueous solution with the mass concentration of 0.5-15% by adopting an isovolumetric impregnation method, soaking for 30-60 minutes, then adding a gold trichloride hydrochloric acid aqueous solution, standing for 4-30 hours, removing redundant liquid, and drying the rest solid particles to obtain a catalyst; wherein the alkali metal compound is one or more of sodium sulfite, potassium persulfate, sodium persulfate and potassium thiosulfate.
2. Use of the catalyst according to claim 1 for catalyzing hydrochlorination of acetylene, characterized in that: in the step (1), activated carbon is added into the water solution of the water-soluble nitride, and microwave radiation is carried out for 5-8 hours at the temperature of 60-80 ℃.
3. Use of a catalyst according to claim 1 or 2 for catalyzing hydrochlorination of acetylene, characterized in that: the power of the microwave radiation is 200-800W.
4. Use of the catalyst according to claim 1 for catalyzing hydrochlorination of acetylene, characterized in that: at normal temperature, the pretreated activated carbon is added into an alkali metal compound aqueous solution with the mass concentration of 1-10% by adopting an isovolumetric impregnation method, soaked for 30-60 minutes, then added with a hydrochloric acid aqueous solution of gold trichloride, and kept stand for 5-25 hours.
5. Use of the catalyst according to claim 1 for catalyzing hydrochlorination of acetylene, characterized in that: the activated carbon is coconut shell activated carbon in the shape of a sheet, a cylinder, a sand grain or a small sphere.
6. Use of the catalyst according to claim 1 for catalyzing hydrochlorination of acetylene, characterized in that: adding the catalyst into a fixed bed tube reactor, and treating for 4-10 hours in a dry hydrogen chloride atmosphere at 120-150 ℃; then acetylene is introduced, and the airspeed of the acetylene is controlled to be 250h -1 The mol ratio of the hydrogen chloride to the acetylene is 1.10, the temperature of the catalyst bed layer is 150-225 ℃, and the acetylene hydrochlorination reaction is carried out to synthesize the chloroethylene.
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CN114146730A (en) * 2021-11-25 2022-03-08 内蒙古鄂尔多斯电力冶金集团股份有限公司 Acetylene gold hydrochloride-based catalyst and preparation method thereof
CN114890864B (en) * 2022-05-25 2023-03-17 南京工业大学 Method for using ultralow-content gold-based catalyst in reaction of preparing vinyl chloride through fixed bed acetylene hydrochlorination
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