CN111921543A - Preparation method and application of efficient acetylene hydrochlorination catalyst - Google Patents
Preparation method and application of efficient acetylene hydrochlorination catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 28
- 238000007038 hydrochlorination reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 15
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 15
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 13
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 13
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims abstract description 13
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 13
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000007598 dipping method Methods 0.000 claims abstract description 7
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000011943 nanocatalyst Substances 0.000 abstract description 2
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- 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
- B01J27/122—Halides of copper
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- 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
- B01J37/343—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 ultrasonic wave energy
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- 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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Abstract
The invention discloses a preparation method and application of a high-efficiency acetylene hydrochlorination catalyst, belonging to the field of nano catalyst synthesisThe preparation method comprises three steps, firstly using Zn (NO)3)2The ZIF-8 template material is prepared by the reaction of a methanol solution and a 2-methylimidazole methanol solution, and then microporous carbon is obtained through a calcination washing process. And finally, dipping the microporous carbon, the carbon nano tube and the graphene into a prepared solution with chloroauric acid, copper chloride, cobalt chloride and lanthanum chloride as active components, and drying to obtain the catalyst. The obtained catalyst has a composite multi-stage structure and a larger specific surface area, the dispersion effect of metal in the carrier is better, the utilization rate of metal salt is high, and the cost is reasonable. The invention develops a novel mercury-free catalyst and provides a preparation technology, and the catalyst is applied to the reaction of preparing chloroethylene by hydrochlorinating acetylene and has good catalytic activity and selectivity.
Description
Technical Field
The invention belongs to the field of nano catalyst synthesis, and particularly relates to a method and application of a high-efficiency acetylene hydrochlorination catalyst.
Background
Polyvinyl chloride (PVC) is one of the five most widely used plastics in engineering applications, and the main processes for the synthesis of polyvinyl chloride (PVC) using Vinyl Chloride Monomer (VCM) are acetylene hydrochlorination and ethylene oxychlorination processes. Acetylene hydrochlorination is mainly used in areas with rich coal resources and occupies a leading position in China, but the use of a large amount of mercury chloride as a catalyst causes resource shortage of mercury resources, the activated carbon has low mechanical strength and is easy to crush, and mercury as a highly toxic substance can cause serious damage to workers and the environment. Therefore, new non-mercury catalysts are the subject of intense research in this field.
Through research and test of researchers on more than 20 metal salts, the initial activity sequence is Pd (II)>Hg(II)>Cu(II)，Cu(I)>Ag (i), the activity of the catalyst is related to the standard electrode potential of the cation. Subsequently, the same investigator studied the use of activated carbon and found that the noble metal gold had a high activity in the hydrochlorination of acetylene with an initial activity higher than other catalysts, including HgCl2The catalyst, and doping of some metals (Cu, Sn, Ni, La, Co, etc.) can suppress carbon deposition and valence change of gold to improve the stability of the catalyst. Therefore, it is a major problem in the art to develop a novel catalyst support and to explore an effective method for stabilizing the active metal salt.
Disclosure of Invention
The invention aims to provide a method for preparing a high-efficiency acetylene hydrochlorination catalyst aiming at the defects in the background technology. The preparation process is simple, environment-friendly and low in cost. The problem of low metal salt adsorption efficiency of the carrier catalyst in the existing preparation method is solved, and the prepared catalytic material has high catalytic performance and high stability.
The invention relates to a high-efficiency acetylene hydrochlorination catalyst, which has the following specific technical scheme.
A preparation method of a high-efficiency acetylene hydrochlorination catalyst is characterized in that particles are made of nano materials with the particle size of 50-1000 nanometers and have a multi-stage composite nano microstructure, and the catalyst is prepared by the following steps:
a. first, Zn (NO) is prepared at normal temperature3)2Methanol solution (0.05-1mol L)-1) And 2-methylimidazole (MeIM) in methanol (0.05-1mol L)-1)。
b. 250mL of Zn (NO) was taken3)2The methanol solution was added dropwise to 250mL of 2-methylimidazole (MeIM) in methanol and stirred magnetically at room temperature for 3 hours. After the reaction was completed, the resulting mixture was centrifuged (11000rpm, 1 minute) to precipitate ZIF-8 nanocubes.
c. Heating the prepared ZIF-8 nanocube at high temperature for 10 min under the protection of nitrogen-1Raising the temperature to 800-1000 ℃, and heating for 2 hours to obtain the microporous carbon.
d. Preparing a solution of an active component, wherein the active component is a mixture of four components, namely chloroauric acid, copper chloride, cobalt chloride and lanthanum chloride. Dipping microporous carbon, graphene with different specifications and carbon nano tubes into the mixed solution for ultrasonic dispersion for 10 ℃ min-1The temperature was raised to 100 ℃ and stirred for 5 hours. The weight ratio of the chloroauric acid to the carrier is 0.05-5%, the weight ratio of the copper chloride to the carrier is 0.05-10%, the weight ratio of the cobalt chloride to the carrier is 0.05-10%, the weight ratio of the lanthanum chloride to the carrier is 0.05-5%, the weight ratio of the graphene to the carrier is 0.01-1%, and the weight ratio of the carbon nanotube to the carrier is 0.1-2%.
The prepared catalyst is used for preparing chloroethylene by acetylene hydrochlorination, the catalyst is subjected to packing and tubing, and the airspeed of acetylene is 30/h, HCl/C2H2The reaction was carried out under 1.1 conditions, with the reaction temperature being controlled between 150 ℃ and 200 ℃. The temperature of 10 ℃ between 150 ℃ and 200 ℃ is taken as a section, and 6 sections are taken on average to examine the influence of different temperature sections on the acetylene conversion rate and the vinyl chloride selectivity.
Compared with the prior art, the invention has the beneficial effects that:
1. the mesoporous carbon prepared by the method has a high specific surface area and a multi-stage microstructure, can effectively adsorb a catalyst, increases the total adsorption amount and uniformity of each metal salt by adding the carbon nanotube and the graphene, and reduces the waste of the metal salt.
2. The prepared catalyst has good effect on selectivity, the conversion rate of acetylene is improved along with temperature, and the conversion rate can reach 93-99%. The catalyst has high adjustability, the particle size of the material, the proportion of the graphene to the carbon nano tube and the microstructure can be adjusted, the catalytic performance of the material is further optimized, and the catalyst is worthy of further research.
Detailed Description
The preparation of the catalyst material of the present invention is further illustrated by the following specific examples, which are only intended to better understand the content of the present invention and not to limit the scope of the present invention.
Example 1
a. First, Zn (NO) is prepared at normal temperature3)2Methanol solution (0.1mol L)-1) And 2-methylimidazole (MeIM) in methanol (0.1mol L)-1)。
b. 250mL of Zn (NO) was taken3)2The methanol solution was added dropwise to 250mL of 2-methylimidazole (MeIM) in methanol and stirred magnetically at room temperature for 3 hours. After the reaction was completed, the resulting mixture was centrifuged (11000rpm, 1 minute) to precipitate ZIF-8 nanocubes.
c. Heating the prepared ZIF-8 nanocube at high temperature for 10 min under the protection of nitrogen-1Raising the temperature to 1000 ℃, and heating for 2 hours to obtain the microporous carbon.
d. Preparing a solution of an active component, wherein the active component is a mixture of four components, namely chloroauric acid, copper chloride, cobalt chloride and lanthanum chloride. Dipping microporous carbon, graphene with different specifications and carbon nano tubes into the mixed solution for ultrasonic dispersion for 10 ℃ min-1The temperature was raised to 100 ℃ and stirred for 5 hours. The weight ratio of the chloroauric acid to the carrier is 1%, the weight ratio of the copper chloride to the carrier is 0.05%, the weight ratio of the cobalt chloride to the carrier is 0.1%, the weight ratio of the lanthanum chloride to the carrier is 0.05%, the weight ratio of the graphene to the carrier is 1%, and the weight ratio of the carbon nanotube to the carrier is 2%.
e. The prepared catalyst shows good effect in the aspect of selectivity, and the conversion rate of acetylene reaches 96.2%.
Example 2
a. Firstly, at normal temperatureZn (NO) is provided3)2Methanol solution (0.5mol L)-1) And 2-methylimidazole (MeIM) in methanol (0.5-1mol L)-1)。
b. 250mL of Zn (NO) was taken3)2The methanol solution was added dropwise to 250mL of 2-methylimidazole (MeIM) in methanol and stirred magnetically at room temperature for 3 hours. After the reaction was completed, the resulting mixture was centrifuged (11000rpm, 1 minute) to precipitate ZIF-8 nanocubes.
c. Heating the prepared ZIF-8 nanocube at high temperature for 10 min under the protection of nitrogen-1Raising the temperature to 800 ℃, and heating for 2 hours to obtain the microporous carbon.
d. Preparing a solution of an active component, wherein the active component is a mixture of four components, namely chloroauric acid, copper chloride, cobalt chloride and lanthanum chloride. Dipping microporous carbon, graphene with different specifications and carbon nano tubes into the mixed solution for ultrasonic dispersion for 10 ℃ min-1The temperature was raised to 100 ℃ and stirred for 5 hours. The weight ratio of the chloroauric acid to the carrier is 0.8%, the weight ratio of the copper chloride to the carrier is 0.1%, the weight ratio of the cobalt chloride to the carrier is 0.3%, the weight ratio of the lanthanum chloride to the carrier is 0.1%, the weight ratio of the graphene to the carrier is 1%, and the weight ratio of the carbon nanotube to the carrier is 2%.
e. The prepared catalyst shows good effect in the aspect of selectivity, and the conversion rate of acetylene reaches 97.1%.
Example 3
a. First, Zn (NO) is prepared at normal temperature3)2Methanol solution (0.5mol L)-1) And 2-methylimidazole (MeIM) in methanol (0.5-1mol L)-1)。
b. 250mL of Zn (NO) was taken3)2The methanol solution was added dropwise to 250mL of 2-methylimidazole (MeIM) in methanol and stirred magnetically at room temperature for 3 hours. After the reaction was completed, the resulting mixture was centrifuged (11000rpm, 1 minute) to precipitate ZIF-8 nanocubes.
c. Heating the prepared ZIF-8 nanocube at high temperature for 10 min under the protection of nitrogen-1Raising the temperature to 800 ℃, and heating for 2 hours to obtain the microporous carbon.
d. Preparing a solution of active components, wherein the active components are a mixture of four components,chloroauric acid, copper chloride, cobalt chloride, and lanthanum chloride. Dipping microporous carbon, graphene with different specifications and carbon nano tubes into the mixed solution for ultrasonic dispersion for 10 ℃ min-1The temperature was raised to 100 ℃ and stirred for 5 hours. The weight ratio of the chloroauric acid to the carrier is 1.2%, the weight ratio of the copper chloride to the carrier is 0.3%, the weight ratio of the cobalt chloride to the carrier is 0.3%, the weight ratio of the lanthanum chloride to the carrier is 0.5%, the weight ratio of the graphene to the carrier is 1%, and the weight ratio of the carbon nanotube to the carrier is 2%.
e. The prepared catalyst shows good effect in the aspect of selectivity, and the conversion rate of acetylene reaches 99.1%.
Example 4
a. First, Zn (NO) is prepared at normal temperature3)2Methanol solution (0.5mol L)-1) And 2-methylimidazole (MeIM) in methanol (0.5-1mol L)-1)。
b. 250mL of Zn (NO) was taken3)2The methanol solution was added dropwise to 250mL of 2-methylimidazole (MeIM) in methanol and stirred magnetically at room temperature for 3 hours. After the reaction was completed, the resulting mixture was centrifuged (11000rpm, 1 minute) to precipitate ZIF-8 nanocubes.
c. Heating the prepared ZIF-8 nanocube at high temperature for 10 min under the protection of nitrogen-1Raising the temperature to 800 ℃, and heating for 2 hours to obtain the microporous carbon.
d. Preparing a solution of an active component, wherein the active component is a mixture of four components, namely chloroauric acid, copper chloride, cobalt chloride and lanthanum chloride. Dipping microporous carbon, graphene with different specifications and carbon nano tubes into the mixed solution for ultrasonic dispersion for 10 ℃ min-1The temperature was raised to 100 ℃ and stirred for 5 hours. The weight ratio of the chloroauric acid to the carrier is 0.5%, the weight ratio of the copper chloride to the carrier is 0.4%, the weight ratio of the cobalt chloride to the carrier is 0.9%, the weight ratio of the lanthanum chloride to the carrier is 0.1%, the weight ratio of the graphene to the carrier is 1%, and the weight ratio of the carbon nanotube to the carrier is 2%.
e. The prepared catalyst shows good effect in the aspect of selectivity, and the conversion rate of acetylene reaches 99.5%.
Claims (9)
1. A preparation method of a high-efficiency acetylene hydrochlorination catalyst comprises the following specific steps:
1) first, Zn (NO) is prepared at normal temperature3)2Taking 250mL of Zn (NO) from methanol solution and 2-methylimidazole MeIM methanol solution3)2Dripping methanol solution into 250mL 2-methylimidazole MeIM methanol solution, magnetically stirring at room temperature for 3 hours, centrifugally precipitating the ZIF-8 nanocubes after the reaction is finished, heating the prepared ZIF-8 nanocubes at high temperature under the protection of nitrogen, and heating the mixture for 10 ℃ min-1Heating for 2 hours to obtain microporous carbon;
2) preparing a solution of an active component as a carrier, wherein the active component is a mixture of the following four components: chloroauric acid, copper chloride, cobalt chloride, and lanthanum chloride.
2. The method for preparing a high efficiency acetylene hydrochlorination catalyst according to claim 1, which comprises the following steps: the specific method of the step 2) is as follows: dipping microporous carbon, graphene with different specifications and carbon nano tubes into the mixed solution for ultrasonic dispersion for 10 ℃ min-1The temperature was raised to 100 ℃ and stirred for 5 hours.
3. The method for preparing the high efficiency acetylene hydrochlorination catalyst according to claim 2, which is characterized in that: in the step 2), the weight ratio of the chloroauric acid to the carrier is 0.05-5%, the weight ratio of the copper chloride to the carrier is 0.05-10%, the weight ratio of the cobalt chloride to the carrier is 0.05-10%, the weight ratio of the lanthanum chloride to the carrier is 0.05-5%, the weight ratio of the graphene to the carrier is 0.01-1%, and the weight ratio of the carbon nanotube to the carrier is 0.1-2%.
4. The method for preparing a high efficiency acetylene hydrochlorination catalyst according to claim 1, which comprises the following steps: step 1) the heating temperature is 800-.
5. The method for preparing the efficient catalyst for hydrochlorination of acetylene according to claim 1Characterized in that: step 1) said Zn (NO)3)2The concentration of the methanol solution is 0.05-1mol L-1。
6. The method for preparing a high efficiency acetylene hydrochlorination catalyst according to claim 1, which comprises the following steps: the concentration of the 2-methylimidazole MeIM methanol solution in the step 1) is 0.05-1mol L-1。
7. The method for preparing a high efficiency acetylene hydrochlorination catalyst according to claim 1, which comprises the following steps: and (3) after the reaction in the step 1) is finished, the centrifugal condition is 11000rpm for 1 minute.
8. Use of the catalyst obtained according to any one of claims 1 to 7, characterized in that: the method is used for preparing vinyl chloride by hydrochlorination of acetylene.
9. Use of a catalyst according to claim 8, characterized in that: packing and tubing the catalyst at acetylene airspeed of 30/h and HCl/C2H2The reaction was carried out under 1.1 conditions, with the reaction temperature being controlled between 150 ℃ and 200 ℃.
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