CN111085237A - Catalyst for preparing chloroethylene from acetylene dichloroethane and preparation method and application thereof - Google Patents

Catalyst for preparing chloroethylene from acetylene dichloroethane and preparation method and application thereof Download PDF

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CN111085237A
CN111085237A CN201911398055.1A CN201911398055A CN111085237A CN 111085237 A CN111085237 A CN 111085237A CN 201911398055 A CN201911398055 A CN 201911398055A CN 111085237 A CN111085237 A CN 111085237A
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catalyst
activated carbon
acetylene
dichloroethane
melamine
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CN111085237B (en
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刘瑞艳
刘星
钟劲光
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Zhongke Yigong (Xiamen) Chemical Tech Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J37/0213—Preparation of the impregnating solution
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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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract

The invention relates to a catalyst for preparing vinyl chloride from acetylene dichloroethane, and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) adding activated carbon into an impregnation solution for impregnation, wherein the impregnation solution comprises aqueous solutions of melamine and phosphoric acid; 2) draining and drying the activated carbon obtained in the step 1); 3) activating the activated carbon obtained in the step 2) in an activating atmosphere to obtain the catalyst. The catalyst has the advantages of low production cost, simple and easy operation of the preparation method, stable quality, and good activity and stability in the reaction of preparing chloroethylene from acetylene dichloroethane.

Description

Catalyst for preparing chloroethylene from acetylene dichloroethane and preparation method and application thereof
Technical Field
The invention belongs to the field of chemical catalysis, particularly relates to a catalyst, and more particularly relates to a catalyst for preparing vinyl chloride from acetylene dichloroethane, and a preparation method and application thereof.
Background
One of the five general purpose polyvinyl chloride plastics is a synthetic resin obtained by polymerizing vinyl chloride monomer. Widely applied to building materials, industrial products, daily necessities and the like. Domestic polyvinyl chloride can be divided into two processes of a calcium carbide method and an ethylene method, and is restricted by resource distribution, wherein the calcium carbide method PVC accounts for 83 percent. However, the method for preparing vinyl chloride by calcium carbide uses mercury loaded activated carbon as a catalyst, and seriously pollutes the environment. The Water guarantee for Mercury requires that new primary mercury ores are prohibited from being mined from 8, 16 and 2017; newly built vinyl chloride monomer production processes are prohibited from using mercury, mercury compounds as catalysts or mercury-containing catalysts. Therefore, the mercury-free catalyst and the new mercury-free process become the technical problems which are urgently needed to be solved in the PVC industry of China.
A new process for preparing vinyl chloride by mercury-free catalytic reforming of acetylene dichloroethane, which is proposed by Keyi chemical science and technology limited in 2010, adopts barium chloride and a nitrogen-containing compound as effective components of a catalyst. At present, the technology becomes a research object of a plurality of scientific researchers, particularly develops a mercury-free catalyst suitable for the process route, and becomes a hotspot of industrial research.
Subsequent researches show that the nitrogen-doped active carbon is an effective component for catalyzing acetylene and dichloroethane to synthesize vinyl chloride. Thus, a series of catalyst studies surrounding nitrogen-doped activated carbon have emerged in recent years.
The patent application No. 201410532264.1 discloses a mercury-free catalyst and its application in the synthesis of vinyl chloride from acetylene dichloroethane. According to the preparation method of the mercury-free catalyst, a nitrogen-containing compound is loaded on the activated carbon after acid washing, dried at the temperature of 60-140 ℃, and calcined at the temperature of 400-800 ℃ for 4-6 hours. Wherein the nitrogen-containing compound is selected from one or more of ammonia water, ammonia gas, pyrrole, imidazole and acrylamide. Although this method avoids the use of metal salts as active ingredients, the nitrogen-containing compounds used have a low boiling point and are not subjected to nitrogen fixation treatment, and there is also a problem of serious nitrogen loss during the heat treatment. The prepared catalyst has few effective components and poor catalytic performance, and if the catalyst has low activity and the service life of only tens of hours, the catalyst can hardly meet the index of industrial application. Moreover, ammonia gas or the like is used as a nitrogen source, which causes environmental pollution.
The patent with application number 201510006148.0 discloses a polypyrrole activated carbon catalyst and its application in vinyl chloride synthesis. The preparation method of the polypyrrole activated carbon catalyst comprises the following steps: the method comprises the steps of dipping active carbon into pyrrole aqueous solution, adding an initiator, drying, and calcining at 500-900 ℃ in nitrogen atmosphere. In the preparation process, because the polypyrrole on the carrier is not solidified, the effective components are decomposed and lost in the high-temperature calcination process. The catalyst is used for a process for synthesizing vinyl chloride by hydrochlorinating acetylene, the catalytic activity of the catalyst is only 40-85%, the patent does not mention the stability of the catalyst, and the difference between the catalyst and the existing industrial requirements is far. In addition, the method adopts pyrrole as a nitrogen source catalyst, so that the cost is high and the method is uneconomical.
Patent No. 201711167819.7 discloses that an amino group-containing compound such as ethylenediamine or o-phenylenediamine is used as a nitrogen source, and a melamine resin or a macromolecular compound having more stable thermal stability and chemical properties is supported on activated carbon by a condensation reaction of an active carbonyl group-and/or hydroxyl group-containing compound such as formaldehyde with a nitrogen-containing compound. However, the nitrogen content of the nitrogen source adopted by the catalyst is low, the drying treatment is only carried out at 150-400 ℃, the calcination and activation are not carried out in a high-temperature activating atmosphere, the generated macromolecular substances easily block the pores of the catalyst, and the effective reaction area of the catalyst is small. Therefore, the prepared catalyst has better initial activity, but has poor stability due to less effective active sites. Moreover, the formaldehyde and the like used as nitrogen fixation solvents have high toxicity and pollute the environment.
Melamine has a nitrogen content and is inexpensive as compared with nitrogen-containing compounds such as acrylamide and o-phenylenediamine, and thus, melamine has been studied as a nitrogen source.
Patent application No. 201811591751.X mentions a method for preparing a nitrogen-doped carbon material for use in fixed bed acetylene hydrochlorination. The method adopts commercially available melamine formaldehyde resin as a precursor, and obtains the nitrogen-doped carbon catalyst by curing and temperature programming roasting in an inert atmosphere. The catalyst is applied to the reaction of preparing chloroethylene by hydrochlorinating acetylene in a fixed bed, and has certain catalytic activity and selectivity. Although the method can better fix the nitrogen on the melamine, the preparation process uses formaldehyde, so the method has high toxicity and is not friendly to the environment and the human health.
Wei Zhao et al have proposed the use of a catalyst prepared by subjecting coconut shell activated carbon to high temperature treatment using melamine as a nitrogen source to prepare nitrogen-doped activated carbon in the process of preparing vinyl chloride by catalytic cracking of dichloroethane, and have also investigated the differences in performance between catalysts prepared with different melamine contents and carbon carriers. The article uses melamine with high nitrogen content as nitrogen source, but no nitrogen fixation method and increased reactive sites have been studied in the article, and the obtained catalyst is only applied to dichloroethane cracking process.
In summary, nitrogen-doped activated carbon is an effective component for catalyzing acetylene dichloroethane to prepare vinyl chloride, and particularly, the nitrogen content in the nitrogen source and the number of active sites of the catalyst directly influence the performance of the catalyst. The nitrogen-doped carbon catalyst developed in the prior art has the defects that a nitrogen-containing compound is unstable, volatile, runs off and has poor nitrogen fixation effect in the preparation process, and the performance of the catalyst is not ideal; or toxic substances such as formaldehyde are adopted for nitrogen fixation, so that the method is not environment-friendly and has the requirement of further improvement.
Disclosure of Invention
The invention provides a catalyst for preparing vinyl chloride from acetylene dichloroethane, and a preparation method and application thereof, aiming at the problems in the prior art. The catalyst has the advantages of low production cost, simple and easy operation of the preparation method, stable quality, and good activity and stability in the reaction of preparing chloroethylene from acetylene dichloroethane.
The invention is realized by the following technical scheme:
the first aspect of the invention provides a preparation method of a catalyst for preparing vinyl chloride from acetylene dichloroethane, which comprises the following steps:
1) adding activated carbon into an impregnation solution for impregnation, wherein the impregnation solution comprises aqueous solutions of melamine and phosphoric acid;
2) draining and drying the activated carbon obtained in the step 1);
3) activating the activated carbon obtained in the step 2) in an activating atmosphere to obtain the catalyst.
Preferably, in step 1), melamine and water are mixed to obtain a mixed solution; phosphoric acid is then added to the mixed solution.
More preferably, the concentration of melamine in the mixed solution is 1-20 wt%, such as 1-3 wt%, 3-5 wt%, 5-10 wt%, 10-15 wt% or 15-20 wt%.
More preferably, the addition of phosphoric acid is followed by a constant temperature.
More preferably, the constant temperature is 20-100 deg.C, such as 20-60 deg.C, 60-80 deg.C or 80-100 deg.C.
Preferably, in step 1), the concentration of melamine in the dipping solution is 1.0-19.43 wt%, such as 1.0-2.95 wt%, 2.95-4.83 wt%, 4.83-9.71 wt%, 9.71-14.7 wt%, or 14.7-19.43 wt%.
Preferably, in the step 1), the surface area of the activated carbon is 700-1300 m2/g。
Preferably, in step 1), the volume ratio of the activated carbon to the impregnation liquid is 1: 1-5, such as 1: 1-1.5, 1: 1.5-2, 1: 2-3 or 1: 3 to 5.
Preferably, in step 1), the pH value of the impregnation liquid is 6-8, such as 6-7 or 7-8.
Preferably, in the step 1), the dipping temperature is 20-100 ℃, such as 20-60 ℃, 60-80 ℃ or 80-100 ℃.
Preferably, in the step 1), the dipping time is 2-24 hours, such as 2-4 hours, 4-6 hours or 6-24 hours.
Preferably, step 2) further comprises at least one of the following technical features:
1) the drying temperature is 120-200 ℃, such as 120-150 ℃, 150-180 ℃ or 180-200 ℃;
2) the drying time is 2-10 h, such as 2-4 h, 4-6 h, 6-8 h or 8-10 h.
Preferably, in step 3), the activation temperature is 400-900 ℃, such as 400-500 ℃, 500-600 ℃, 600-700 ℃, 700-800 ℃ or 800-900 ℃.
Preferably, in the step 3), the activation time is 2-10 h, such as 2-4 h, 4-6 h, 6-8 h or 8-10 h.
Preferably, in step 3), the activating atmosphere is selected from one or more of oxygen, carbon dioxide and water vapor.
Preferably, in the step 3), the amount of the activating atmosphere is 20-500 ml/min/100g of activated carbon, such as 20-100 ml/min/100g of activated carbon, 100-200 ml/min/100g of activated carbon, 200-250 ml/min/100g of activated carbon, 250-300 ml/min/100g of activated carbon, or 300-500 ml/min/100g of activated carbon.
The second aspect of the invention provides a catalyst for preparing vinyl chloride from acetylene dichloroethane, which is prepared by the preparation method.
The third aspect of the present invention provides the use of the above catalyst for the preparation of vinyl chloride from acetylene dichloride ethane.
Compared with the existing catalyst for preparing vinyl chloride from acetylene dichloroethane and the preparation method thereof, the catalyst and the preparation method thereof have the following characteristics:
1) the invention adopts melamine as nitrogen source, has high nitrogen content and low price, and has high economic feasibility when being used for preparing the catalyst;
2) according to the invention, nitrogen is fixed by phosphoric acid, on one hand, the phosphoric acid can catalyze the carbon material to react with melamine, N on the melamine is promoted to be more effectively retained on the activated carbon, and the fixing efficiency is improved, so that abundant carbon nitrogen compounds are generated, and the active sites on the catalyst are increased; on the other hand, the phosphoric acid has an activating effect on the surface of the activated carbon, so that the formed carbon nitrogen compound is more tightly combined with the carbon carrier and is not easy to run off, and the stability of the catalyst is improved.
3) Active gas is adopted to carry out high-temperature activation hole making on the catalyst, and the blocked pore channel on the surface of the catalyst is opened, so that the catalyst with high nitrogen content, rich surface area and concentrated pore diameter is obtained, and the quality and the stability of the catalyst are effectively improved.
The invention takes melamine as a nitrogen source, obtains the catalyst containing rich nitrogen-doped active carbon by formula optimization and technical improvement such as nitrogen fixation, hole making, activation and the like, is more environment-friendly compared with the prior catalyst, can greatly improve the catalytic performance of preparing chloroethylene by catalytic reforming of acetylene dichloroethane, has good activity and stability, and completely meets the requirement of industrial continuous production.
Drawings
FIG. 1 is a graph showing stability evaluation of a catalyst prepared in a comparative example.
FIG. 2 is a graph showing stability evaluation of the catalyst prepared in example 1.
FIG. 3 is a graph showing stability evaluation of the catalyst obtained in example 4.
Detailed Description
The technical solution of the present invention is illustrated by specific examples below. It is to be understood that one or more method steps mentioned in the present invention do not exclude the presence of other method steps before or after the combination step or that other method steps may be inserted between the explicitly mentioned steps; it should also be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Comparative example
(1) Weighing 20.0g of melamine and 380.0g of water, stirring to prepare a mixed solution, then regulating the pH value to 6.0 by using hydrochloric acid, and keeping the temperature at 80 ℃ to obtain an impregnation liquid, wherein the concentration of the melamine in the impregnation liquid is 4.95 wt%;
(2) the specific area is 700-1300 m2Adding activated carbon per gram into the prepared impregnation liquid, and controlling the volume ratio of the activated carbon to the impregnation liquid to be 1: 2, keeping the temperature of 80 ℃ for 4 hours;
(3) taking out the prepared active carbon, draining, and drying at 120 ℃ for 8 h;
(4) heating the dried catalyst to 600 ℃, and introducing oxygen gas at 300ml/min for activation for 6h to obtain the required catalyst A0;
(5) the catalyst is loaded into a tubular reactor and is introduced with acetylene and dichloroethane for reaction, and the reaction space velocity is controlled to be 40h-1The molar ratio of acetylene and dichloroethane is 1: 1.1, the reaction temperature is 240 ℃, the pressure is 0.08MPa, and the catalyst obtains the initial conversion rate of acetylene of 83.33 percent and the selectivity of vinyl chloride of 99.6 percent under the conditions.
Example 1
(1) Weighing 10.0g of melamine and 990.0g of water, stirring to prepare a mixed solution, then adjusting the pH value to 6.0 by using phosphoric acid, and keeping the temperature at 20 ℃ to obtain an impregnation liquid, wherein the concentration of the melamine in the impregnation liquid is 1.0 wt%;
(2) the specific area is 700-1300 m2Adding activated carbon per gram into the prepared impregnation liquid, and controlling the volume ratio of the activated carbon to the impregnation liquid to be 1: 5, keeping the temperature of 20 ℃ for 24 hours;
(3) taking out the prepared active carbon, draining, and drying at 150 deg.C for 6 h;
(4) heating the dried catalyst to 800 ℃, and introducing 500ml/min/100g of water vapor into the activated carbon for activating for 2 hours to obtain the required catalyst A1;
(5) the catalyst is loaded into a tubular reactor and is introduced with acetylene and dichloroethane for reaction, and the reaction space velocity is controlled to be 60h-1The molar ratio of acetylene and dichloroethane is 1: 1.05, the reaction temperature was 220 ℃ and the pressure was 0.05MPa, the catalyst gave an initial conversion of acetylene of 90.84% and a selectivity of vinyl chloride of 99.8% under the conditions described above.
Example 2
(1) Weighing 12.0g of melamine and 388.0g of water, stirring to prepare a mixed solution, then adjusting the pH value to 8.0 by using phosphoric acid, and keeping the temperature at 100 ℃ to obtain an impregnation liquid, wherein the concentration of the melamine in the impregnation liquid is 2.95 wt%;
(2) the specific area is 700-1300 m2Adding activated carbon per gram into the prepared impregnation liquid, and controlling the volume ratio of the activated carbon to the impregnation liquid to be 1: 1.5, keeping the temperature at 100 ℃ for 2 hours;
(3) taking out the prepared active carbon, draining, and drying at 120 deg.C for 10 h;
(4) heating the dried catalyst to 700 ℃, and activating with 100ml/min/100g of activated carbon mixed gas (1: 1) of water vapor and carbon dioxide for 4 hours to obtain the required catalyst A2;
(5) the catalyst is loaded into a tubular reactor and is introduced with acetylene and dichloroethane for reaction, and the reaction space velocity is controlled to be 60h-1The molar ratio of acetylene and dichloroethane is 1: 1.05, reaction temperature 240 ℃ and pressure 0.05MPa, the catalyst obtained an initial conversion of acetylene of 92.72% and a selectivity of vinyl chloride of 99.7% under the conditions described above.
Example 3
(1) Weighing 90.0g of melamine and 510.0g of water, stirring to prepare a mixed solution, then adjusting the pH value to 7.0 by using phosphoric acid, and keeping the temperature at 60 ℃ to obtain an impregnation liquid, wherein the concentration of the melamine in the impregnation liquid is 14.70 wt%;
(2) the specific area is 700-1300 m2Adding activated carbon per gram into the prepared impregnation liquid, and controlling the volume ratio of the activated carbon to the impregnation liquid to be 1: 3, keeping the temperature at 60 ℃ for 6 hours;
(3) taking out the prepared active carbon, draining, and drying at 180 deg.C for 4 h;
(4) heating the dried catalyst to 400 ℃, and introducing oxygen gas of 250ml/min/100g of activated carbon for activation for 10 hours to obtain the required catalyst A3;
(5) the catalyst is loaded into a tubular reactor and is introduced with acetylene and dichloroethane for reaction, and the reaction space velocity is controlled to be 60h-1The molar ratio of acetylene and dichloroethane is 1: 1.03 at a reaction temperature of 200 ℃ and a pressure of 0.08MPa, the catalyst obtained under the above conditions had an initial conversion of acetylene of 93.4% and a selectivity of vinyl chloride of 99.7%.
Example 4
(1) Weighing 20.0g of melamine and 380.0g of water, stirring to prepare a mixed solution, then adjusting the pH value to 6.0 by using phosphoric acid, and keeping the temperature at 80 ℃ to obtain an impregnation liquid, wherein the concentration of the melamine in the impregnation liquid is 4.83 wt%;
(2) the specific area is 700-1300 m2Adding activated carbon per gram into the prepared impregnation liquid, and controlling the volume ratio of the activated carbon to the impregnation liquid to be 1: 2, keeping the temperature of 80 ℃ for 4 hours;
(3) taking out the prepared active carbon, draining, and drying at 120 ℃ for 8 h;
(4) heating the dried catalyst to 600 ℃, and activating with 300ml/min/100g of activated carbon by water vapor for 6h to obtain the required catalyst A4;
(5) the catalyst is loaded into a tubular reactor and is introduced with acetylene and dichloroethane for reaction, and the reaction space velocity is controlled to be 40h-1The molar ratio of acetylene and dichloroethane is 1: 1.02, the reaction temperature is 220 ℃, the pressure is 0.03MPa, and the catalyst obtains the initial conversion rate of acetylene of 90.6 percent and the selectivity of vinyl chloride of 99.8 percent under the conditions.
Example 5
(1) Weighing 40.0g of melamine and 360.0g of water, stirring to prepare a mixed solution, then adjusting the pH value to 7.0 by using phosphoric acid, and keeping the temperature at 80 ℃ to obtain an impregnation liquid, wherein the concentration of the melamine in the impregnation liquid is 9.71 wt%;
(2) the specific area is 700-1300 m2Adding activated carbon per gram into the prepared impregnation liquid, and controlling the volume ratio of the activated carbon to the impregnation liquid to be 1: 3, keeping the temperature of 80 ℃ for 8 hours;
(3) taking out the prepared active carbon, draining, and drying at 200 deg.C for 2 h;
(4) heating the dried catalyst to 500 ℃, and activating with water vapor at a flow rate of 200ml/min/100g of activated carbon for 10 hours to obtain the required catalyst A5;
(5) the catalyst is loaded into a tubular reactor and is introduced with acetylene and dichloroethane for reaction, and the reaction space velocity is controlled to be 60h-1The molar ratio of acetylene and dichloroethane is 1: 1.1, the reaction temperature is 240 ℃, the pressure is 0.03MPa, and the catalyst obtains the initial conversion rate of acetylene of 91.62% and the selectivity of vinyl chloride of 99.8% under the conditions.
Example 6
(1) Weighing 40.0g of melamine and 160.0g of water, stirring to prepare a mixed solution, then adjusting the pH value to 8.0 by using phosphoric acid, and keeping the temperature at 100 ℃ to obtain an impregnation liquid, wherein the concentration of the melamine in the impregnation liquid is 19.43 wt%;
(2) the specific area is 700-1300 m2Adding activated carbon per gram into the prepared impregnation liquid, and controlling the volume ratio of the activated carbon to the impregnation liquid to be 1: keeping the temperature of 1,100 ℃ for 2 h;
(3) taking out the prepared active carbon, draining, and drying at 150 deg.C for 4 h;
(4) heating the dried catalyst to 900 ℃, and introducing carbon dioxide of 20ml/min/100g to activate for 8 hours to obtain the required catalyst A6;
(5) the catalyst is loaded into a tubular reactor and is introduced with acetylene and dichloroethane for reaction, and the reaction space velocity is controlled to be 40h-1The molar ratio of acetylene and dichloroethane is 1: 1.05, the reaction temperature is 180 ℃, the pressure is 0.03MPa, and the catalyst obtains the initial conversion rate of acetylene of 91.3 percent and the selectivity of vinyl chloride of 99.8 percent under the conditions.
In order to further research the reaction performance of the catalyst of the invention, the catalysts A0, A1 and A4 prepared by the methods of comparative example, example 1 and example 4 are respectively put into a tubular reactor, acetylene and dichloroethane are introduced for reaction, and the molar ratio of the acetylene to the dichloroethane is 1: 1.1, controlling the reaction temperature at 230 ℃ and the space velocity at 40h-1The reaction gauge pressure is 0.05MPa, the stability of the catalyst is evaluated, and the evaluation results are shown in Table 1, FIG. 2 and FIG. 3, and FIG. 1, FIG. 2 and FIG. 3 are pairsRatio, stability evaluation graphs of the catalysts prepared in example 1 and example 4.
Table 1 evaluation table of catalyst reaction performance
Figure BDA0002346835810000081
The results show that the catalyst prepared according to the invention has high reaction activity and good stability in the acetylene dichloroethane reforming reaction, and meets the requirements of industrialization.

Claims (10)

1. A preparation method of a catalyst for preparing vinyl chloride from acetylene dichloroethane is characterized by comprising the following steps:
1) adding activated carbon into an impregnation solution for impregnation, wherein the impregnation solution comprises aqueous solutions of melamine and phosphoric acid;
2) draining and drying the activated carbon obtained in the step 1);
3) activating the activated carbon obtained in the step 2) in an activating atmosphere to obtain the catalyst.
2. The method according to claim 1, wherein in step 1), the impregnation solution is obtained by: mixing melamine and water to obtain a mixed solution; phosphoric acid is then added to the mixed solution.
3. The method according to claim 2, wherein the melamine concentration in the mixed solution is 1 to 20 wt%.
4. The method according to claim 2, wherein the phosphoric acid is added and then the mixture is incubated.
5. The method according to claim 4, wherein the constant temperature is 20 to 100 ℃.
6. The method of claim 1, wherein step 1) further comprises any one or more of the following features:
1) the concentration of melamine in the dipping solution is 1.0-19.43 wt%;
2) the surface area of the activated carbon is 700-1300 m2/g；
3) The volume ratio of the activated carbon to the impregnating solution is 1: 1-5;
4) the pH value of the impregnation liquid is 6-8;
5) the dipping temperature is 20-100 ℃;
6) the dipping time is 2-24 h.
7. The method according to claim 1, wherein the step 2) further comprises at least one of the following technical features:
1) the drying temperature is 120-200 ℃;
2) the drying time is 2-10 h.
8. The method of claim 1, wherein step 3) further comprises any one or more of the following features:
1) the activation temperature is 400-900 ℃;
2) the activation time is 2-10 h;
3) the activating atmosphere is selected from one or more of oxygen, carbon dioxide and water vapor;
4) the amount of the activating atmosphere is 20-500 ml/min/100g of activated carbon.
9. A catalyst for preparing vinyl chloride from acetylene dichloride ethane, which is prepared by the preparation method of any one of claims 1 to 8.
10. The catalyst of claim 9 for use in the preparation of vinyl chloride from acetylene dichloroethane.
CN201911398055.1A 2019-12-30 2019-12-30 Catalyst for preparing chloroethylene from acetylene dichloroethane and preparation method and application thereof Active CN111085237B (en)

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