CN108187721B - Preparation method and use method of nitrogen-doped carbon catalyst for preparing vinyl chloride through fixed bed acetylene hydrochlorination - Google Patents

Preparation method and use method of nitrogen-doped carbon catalyst for preparing vinyl chloride through fixed bed acetylene hydrochlorination Download PDF

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CN108187721B
CN108187721B CN201810022904.2A CN201810022904A CN108187721B CN 108187721 B CN108187721 B CN 108187721B CN 201810022904 A CN201810022904 A CN 201810022904A CN 108187721 B CN108187721 B CN 108187721B
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李伟
乔贤亮
关庆鑫
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Nankai University
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Abstract

The invention discloses a preparation method and an application method of a nitrogen-doped carbon catalyst for preparing vinyl chloride through fixed bed acetylene hydrochlorination, and belongs to the technical field of material synthesis. The method adopts natural silkworm cocoon shells with high nitrogen content as precursors, and obtains the nitrogen-doped carbon metal-free catalyst through carbonization and activation. The method has the characteristics that the catalyst takes natural biomass with high nitrogen content as a precursor, a complicated nitrogen element introducing step is not needed, the operation is simple, the cost is saved, and the nitrogen element can be uniformly distributed in the catalyst after carbonization and activation in the preparation process. The invention develops a novel metal-free catalyst and provides a preparation technology, and the catalyst is applied to the reaction of preparing chloroethylene by hydrochlorinating acetylene in a fixed bed and has certain catalytic activity and selectivity.

Description

Preparation method and use method of nitrogen-doped carbon catalyst for preparing vinyl chloride through fixed bed acetylene hydrochlorination
Technical Field
The invention provides a preparation method and an application method of a nitrogen-doped carbon catalyst for preparing vinyl chloride through fixed bed acetylene hydrochlorination, and belongs to the technical field of material synthesis. The method adopts the natural silkworm cocoon shell with high nitrogen content as a precursor, and obtains the nitrogen-doped carbon catalyst by carbonizing and activating in inert gas. The catalyst is applied to the reaction of preparing chloroethylene by hydrochlorinating acetylene in a fixed bed, and has certain catalytic activity and selectivity.
Background
Polyvinyl chloride is a resin material commonly used in the first and second world in China, and has wide application fields, and vinyl chloride is a main monomer for synthesizing polyvinyl chloride. In China, the production of vinyl chloride mainly takes acetylene as a raw material, and the reaction mainly takes mercury chloride loaded by active carbon as a catalyst. However, this catalyst has the following disadvantages: in the reaction process, the mercury-containing components in the catalyst are easy to volatilize and lose, so that the environment is seriously polluted, and the health of human beings is threatened. In order to realize the efficient and clean production of vinyl chloride, research and production of novel mercury-free catalysts instead of mercury-containing catalysts are urgent.
At present, the research of mercury-free catalysts is mainly based on noble metals. Huntings et al studied the performance of numerous metal chlorides in the hydrochlorination of acetylene and speculated that gold-containing catalysts should have optimal catalytic performance. Later, gold catalysts have been extensively studied and made a significant breakthrough. However, considering the cost problem of industrial application, the high price of the gold catalyst limits the further popularization and application of the gold catalyst. Recently, metal-free catalysts, particularly nitrogen-doped carbon materials, have become the focus of research. And g-C prepared by professor et al3N4a/AC catalyst which exhibits good catalytic activity in the hydrochlorination of acetylene; the SiC @ C-N and h-BN catalysts prepared by letters of institute of chemical and physical institute of Dalian and academia and the like show excellent catalytic performance in reaction, but the catalysts have more preparation steps and more strict requirements on conditions, and are not beneficial to mass production.
Patents CN201310518594.0 and CN201410532264.1 both disclose a metal-free catalyst for fixed bed acetylene hydrochlorination, and the preparation of the catalyst mainly adopts the method of impregnating active components on carriers such as activated carbon and molecular sieve, which is different from the present patent in terms of the formula and preparation method of the catalyst. This patent the catalyst has avoided complicated nitrogen element to introduce the step by natural high nitrogen content living beings as the precursor in the synthetic process, easy operation, easy bulk production.
Disclosure of Invention
The invention aims to provide a preparation method and a use method of a nitrogen-doped carbon catalyst for preparing vinyl chloride by fixed bed acetylene hydrochlorination.
The specific technical scheme of the invention is as follows:
scheme 1: a preparation method of a nitrogen-doped carbon catalyst for preparing vinyl chloride by fixed bed acetylene hydrochlorination is characterized by comprising the following steps:
1) shearing a certain mass of silkworm cocoon shells, soaking in deionized water at 30-50 ℃ for at least 6h, then carrying out suction filtration and separation on a sample, washing for a plurality of times by using the deionized water, and then drying at 80-100 ℃ to obtain a sample A;
2) placing the sample A in a tube furnace, heating to a target temperature at a heating rate of 5-10 ℃/min in a flowing air atmosphere for pre-carbonization, and keeping the temperature at the target temperature for at least 30min to obtain a sample B, wherein the air volume space velocity is 180h-1The pre-carbonization target temperature is 250-350 ℃;
3) and grinding the sample B into powder, placing the powder into a dilute hydrochloric acid solution, stirring at room temperature for at least 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and drying the obtained filter cake at 100-120 ℃ to obtain the nitrogen-doped carbon catalyst.
Scheme 2: a preparation method of a nitrogen-doped carbon catalyst for preparing vinyl chloride by fixed bed acetylene hydrochlorination is characterized by comprising the following steps:
1) shearing a certain mass of silkworm cocoon shells, soaking in deionized water at 30-50 ℃ for at least 6h, then carrying out suction filtration and separation on a sample, washing for a plurality of times by using the deionized water, and then drying at 80-100 ℃ to obtain a sample A;
2) placing the sample A in a tube furnace, heating to a target temperature at a heating rate of 5-10 ℃/min in a flowing air atmosphere for pre-carbonization, and keeping the temperature at the target temperature for at least 30min to obtain a sample B, wherein the air volume space velocity is 180h-1The pre-carbonization target temperature is 250-350 ℃;
3) grinding the sample B into powder, placing the powder into a dilute hydrochloric acid solution, stirring at room temperature for at least 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and drying the obtained filter cake at 100-120 ℃ to obtain a sample C;
4) mixing a sample C with KOH powder of a certain mass, sufficiently grinding, transferring the mixture into a tubular furnace, heating to 180-200 ℃ at a heating rate of 5-10 ℃/min under the atmosphere of flowing inert gas, keeping the temperature for at least 1h, continuously heating to a target temperature at a heating rate of 1-5 ℃/min, carrying out activation treatment, keeping the temperature for at least 2h at the target temperature, and then carrying out activation treatment on the mixture at the target temperatureNaturally cooling to room temperature under inert atmosphere purging to obtain a sample D, wherein the mass ratio of KOH to the sample C is 1-4, and the inert gas is N2One of He or Ar, wherein the activation target temperature is 450-1200 ℃;
5) and (3) placing the sample D in a dilute hydrochloric acid solution, stirring at room temperature for at least 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and finally drying the obtained filter cake at 100-120 ℃ to obtain the nitrogen-doped carbon material catalyst.
Scheme 3: a preparation method of a nitrogen-doped carbon catalyst for preparing vinyl chloride by fixed bed acetylene hydrochlorination is characterized by comprising the following steps:
1) shearing a certain mass of silkworm cocoon shells, soaking in deionized water at 30-50 ℃ for at least 6h, then carrying out suction filtration and separation on a sample, washing for a plurality of times by using the deionized water, and then drying at 80-100 ℃ to obtain a sample A;
2) placing the sample A in a tube furnace, heating to a target temperature at a heating rate of 5-10 ℃/min in a flowing inert atmosphere for pre-carbonization, and keeping the temperature at the target temperature for at least 30min to obtain a sample B, wherein the inert gas is N2One of He or Ar, and the volume space velocity is 180h-1The pre-carbonization target temperature is 250-450 ℃;
3) and grinding the sample B into powder, placing the powder into a dilute hydrochloric acid solution, stirring at room temperature for at least 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and drying the obtained filter cake at 100-120 ℃ to obtain the nitrogen-doped carbon catalyst.
Scheme 4: a preparation method of a nitrogen-doped carbon catalyst for preparing vinyl chloride by fixed bed acetylene hydrochlorination is characterized by comprising the following steps:
1) shearing a certain mass of silkworm cocoon shells, soaking in deionized water at 30-50 ℃ for at least 6h, then carrying out suction filtration and separation on a sample, washing for a plurality of times by using the deionized water, and then drying at 80-100 ℃ to obtain a sample A;
2) placing the sample A in a tube furnace, and heating to a target temperature at a heating rate of 5-10 ℃/min in a flowing inert atmospherePre-carbonizing, and keeping the temperature at the target temperature for at least 30min to obtain a sample B, wherein the inert gas is N2One of He or Ar, and the volume space velocity is 180h-1The pre-carbonization target temperature is 250-450 ℃;
3) grinding the sample B into powder, placing the powder into a dilute hydrochloric acid solution, stirring at room temperature for at least 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and drying the obtained filter cake at 100-120 ℃ to obtain a sample C;
4) mixing a sample C with KOH powder with a certain mass, sufficiently grinding, transferring the mixture into a tubular furnace, heating to 180-200 ℃ at a heating rate of 5-10 ℃/min under the flowing inert gas atmosphere, keeping the temperature constant for at least 1h, continuing heating to a target temperature at a heating rate of 1-5 ℃/min, carrying out activation treatment, keeping the temperature constant for at least 2h at the target temperature, and then naturally cooling to room temperature under the inert atmosphere purging to obtain a sample D, wherein the mass ratio of KOH to the sample C is 1-4, and the inert gas is N2One of He or Ar, wherein the activation target temperature is 450-1200 ℃;
5) and (3) placing the sample D in a dilute hydrochloric acid solution, stirring at room temperature for at least 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and finally drying the obtained filter cake at 100-120 ℃ to obtain the nitrogen-doped carbon material catalyst.
Scheme 5: a nitrogen-doped carbon catalyst for preparing vinyl chloride through a fixed bed acetylene hydrochlorination reaction is characterized by being prepared by the preparation method of any one of schemes 1-4.
Scheme 6: a method of using the nitrogen-doped carbon catalyst of scheme 5, comprising the steps of:
1) putting 1mL of catalyst in a fixed bed reactor, heating to 160-260 ℃ under flowing inert gas, and keeping the temperature for at least 1h, wherein the volume space velocity of the inert gas is 15-45 h-1；
2) Closing the inert gas, switching to flowing hydrogen chloride gas, and keeping the temperature for at least 1h, wherein the volume space velocity of the hydrogen chloride is 15-45 h-1；
3) Introducing into the secondAcetylene gas with the volume space velocity of 15-45 h-1The molar ratio of the hydrogen chloride to the acetylene is 1.05-1.3: 1;
4) the using temperature range of the nitrogen-doped carbon catalyst is 160-260 ℃;
5) the reacted gas was qualitatively and quantitatively analyzed using gas chromatography.
The existing catalyst for preparing vinyl chloride by acetylene hydrochlorination mainly takes a metal catalyst, active species are mostly soaked on carriers such as active carbon, molecular sieve and the like with large specific surface without the metal catalyst or are deposited on a SiC carrier in situ, the steps are complicated, and the requirements of test conditions are strict. Compared with the prior art, the invention has the following remarkable innovation:
(1) the novel nitrogen-doped carbon catalyst for preparing vinyl chloride by the hydrochlorination of acetylene in the fixed bed has certain catalytic activity and stability, is expected to partially replace the traditional metal catalyst, particularly the mercury-containing catalyst, and reduces the pollution to the environment;
(2) the catalyst takes natural high-nitrogen-content biomass silkworm cocoon shells as precursors, effectively avoids a complicated external nitrogen element doping step, greatly simplifies the preparation process of the catalyst, and can be prepared in batches;
(3) the catalyst precursor silkworm cocoon shell is composed of a large amount of micrometer-sized silk fibrin, has a certain spatial structure, can realize uniform distribution of nitrogen elements in the catalyst through subsequent carbonization and activation processes, is favorable for mass transfer and heat transfer in the catalysis process, and improves the catalysis efficiency;
(4) in view of the fact that a large amount of surplus biomass materials exist in China, the design and preparation of the catalyst can provide ideas and references for effectively utilizing waste biomass materials, and the development requirements of green chemistry and chemical engineering are met.
Drawings
FIG. 1: SEM image of nitrogen-doped carbon catalyst prepared in example 4.
FIG. 2: SEM image of nitrogen-doped carbon catalyst prepared in example 5.
Detailed Description
To better illustrate the patent, the following examples are now set forth. The following examples are intended to provide those skilled in the art with a more detailed understanding of the present invention, or to provide further insubstantial modifications and adaptations of the invention in light of the above teachings. However, the scope of the present invention is not limited by these examples. The scope of protection of the invention is set forth in the appended claims.
Example 1
1) Cutting about 10 g of silkworm cocoon shells into pieces, soaking the pieces in deionized water at 50 ℃ for more than 6 hours to remove impurities and soluble inorganic salts in the silkworm cocoons, then carrying out suction filtration and separation on samples, washing the samples with the deionized water for more than 5 times, and drying the samples at 100 ℃ to obtain a sample A;
2) placing the sample A in a tube furnace, heating to 250 ℃ at a heating rate of 5 ℃/min in a flowing air atmosphere for pre-carbonization, and keeping the temperature at 250 ℃ for 40 min to obtain a sample B, wherein the air volume space velocity is 180h-1The constant temperature at the lower temperature of 250 ℃ is to avoid excessive oxidation of surface groups of the material;
3) and grinding the sample B into powder, placing the powder into a 5% dilute hydrochloric acid solution, stirring at room temperature for 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and drying the obtained filter cake at 120 ℃ to obtain the nitrogen-doped carbon catalyst CAT-1.
Example 2
1) Cutting about 10 g of silkworm cocoon shells into pieces, soaking the pieces in deionized water at 50 ℃ for more than 6 hours to remove impurities and soluble inorganic salts in the silkworm cocoons, then carrying out suction filtration and separation on samples, washing the samples with the deionized water for more than 5 times, and drying the samples at 100 ℃ to obtain a sample A;
2) placing the sample A in a tube furnace, heating to 350 ℃ at a heating rate of 5 ℃/min in a flowing air atmosphere for pre-carbonization, and keeping the temperature at 350 ℃ for 40 min to obtain a sample B, wherein the air volume space velocity is 180h-1The constant temperature at the lower temperature of 350 ℃ is used for avoiding excessive oxidation of surface groups of the material;
3) and grinding the sample B into powder, placing the powder into a 5% dilute hydrochloric acid solution, stirring at room temperature for 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and drying the obtained filter cake at 120 ℃ to obtain the nitrogen-doped carbon catalyst CAT-2.
Example 3
1) Cutting about 10 g of silkworm cocoon shells into pieces, soaking the pieces in deionized water at 50 ℃ for 6 hours to remove impurities and soluble inorganic salts in the silkworm cocoons, then carrying out suction filtration and separation on samples, washing the samples with the deionized water for more than 5 times, and drying the samples at 100 ℃ to obtain a sample A;
2) placing the sample A in a tube furnace, heating to 350 ℃ at a heating rate of 5 ℃/min in a flowing air atmosphere for pre-carbonization, and keeping the temperature at 350 ℃ for 40 min to obtain a sample B, wherein the air volume space velocity is 180h-1；
3) Grinding the sample B into powder, placing the powder into a dilute hydrochloric acid solution, stirring the powder at room temperature for 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and drying the obtained filter cake at 120 ℃ to obtain a sample C;
4) 3g of sample C were mixed with 3g of KOH-powder, the mixture was transferred to a tube furnace after thorough grinding, under flowing N2Heating to 200 deg.C at a heating rate of 5 deg.C/min under atmosphere, maintaining the temperature for 1h, further heating to 450 deg.C at a heating rate of 5 deg.C/min for activating treatment, maintaining the temperature at 450 deg.C for 2h, and then maintaining the temperature in N2Naturally cooling to room temperature under atmosphere purging to obtain sample D, wherein N2The volume space velocity is 180h-1；
5) And (3) placing the sample D in a 5% dilute hydrochloric acid solution, stirring at room temperature for 12h, then carrying out suction filtration and separation on the powder, washing with deionized water to be neutral, and finally drying the obtained filter cake at 120 ℃ to obtain the nitrogen-doped carbon material catalyst CAT-3.
Example 4
1) Cutting about 10 g of silkworm cocoon shells into pieces, soaking the pieces in deionized water at 50 ℃ for 6 hours to remove impurities and soluble inorganic salts in the silkworm cocoons, then carrying out suction filtration and separation on samples, washing the samples with the deionized water for more than 5 times, and drying the samples at 100 ℃ to obtain a sample A;
2) place sample A in tubeIn a formula furnace, the temperature is raised to 350 ℃ at the temperature rise rate of 5 ℃/min in the flowing air atmosphere for pre-carbonization treatment, and the temperature is kept constant at 350 ℃ for 40 min to obtain a sample B, wherein the air volume space velocity is 180h-1；
3) Grinding the sample B into powder, placing the powder into a dilute hydrochloric acid solution, stirring the powder at room temperature for 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and drying the obtained filter cake at 120 ℃ to obtain a sample C;
4) 3g of sample C were mixed with 3g of KOH-powder, the mixture was transferred to a tube furnace after thorough grinding, under flowing N2Heating to 200 deg.C at a heating rate of 5 deg.C/min under atmosphere, keeping the temperature for 1h, further heating to 500 deg.C at a heating rate of 5 deg.C/min for activating treatment, keeping the temperature at 500 deg.C for 2h, and then maintaining the temperature at N2Naturally cooling to room temperature under atmosphere purging to obtain sample D, wherein N2The volume space velocity is 180h-1；
5) And (3) placing the sample D in a 5% dilute hydrochloric acid solution, stirring at room temperature for 12h, then carrying out suction filtration and separation on the powder, washing with deionized water to be neutral, and finally drying the obtained filter cake at 120 ℃ to obtain the nitrogen-doped carbon material catalyst CAT-4.
Example 5
1) Cutting about 10 g of silkworm cocoon shells into pieces, soaking the pieces in deionized water at 50 ℃ for 6 hours to remove impurities and soluble inorganic salts in the silkworm cocoons, then carrying out suction filtration and separation on samples, washing the samples with the deionized water for more than 5 times, and drying the samples at 100 ℃ to obtain a sample A;
2) placing the sample A in a tube furnace, heating to 350 ℃ at a heating rate of 5 ℃/min in a flowing air atmosphere for pre-carbonization, and keeping the temperature at 350 ℃ for 40 min to obtain a sample B, wherein the air volume space velocity is 180h-1；
3) Grinding the sample B into powder, placing the powder into a dilute hydrochloric acid solution, stirring the powder at room temperature for 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and drying the obtained filter cake at 120 ℃ to obtain a sample C;
4) 3g of sample C was mixed with 3g of KOH powder, and after sufficient grinding, the mixture was mixedThe compound was transferred to a tube furnace in flowing N2Heating to 200 deg.C at a heating rate of 5 deg.C/min under atmosphere, maintaining the temperature for 1h, further heating to 800 deg.C at a heating rate of 5 deg.C/min for activation treatment, maintaining the temperature at 800 deg.C for 2h, and then maintaining the temperature at N2Naturally cooling to room temperature under atmosphere purging to obtain sample D, wherein N2The volume space velocity is 180h-1；
5) And (3) placing the sample D in a 5% dilute hydrochloric acid solution, stirring at room temperature for 12h, then carrying out suction filtration and separation on the powder, washing with deionized water to be neutral, and finally drying the obtained filter cake at 120 ℃ to obtain the nitrogen-doped carbon material catalyst CAT-5.
Example 6
1) Cutting about 10 g of silkworm cocoon shells into pieces, soaking the pieces in deionized water at 50 ℃ for 6 hours to remove impurities and soluble inorganic salts in the silkworm cocoons, then carrying out suction filtration and separation on samples, washing the samples with the deionized water for more than 5 times, and drying the samples at 100 ℃ to obtain a sample A;
2) placing the sample A in a tube furnace, heating to 350 ℃ at a heating rate of 5 ℃/min in a flowing air atmosphere for pre-carbonization, and keeping the temperature at 350 ℃ for 40 min to obtain a sample B, wherein the air volume space velocity is 180h-1；
3) Grinding the sample B into powder, placing the powder into a dilute hydrochloric acid solution, stirring the powder at room temperature for 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and drying the obtained filter cake at 120 ℃ to obtain a sample C;
4) 3g of sample C were mixed with 3g of KOH-powder, the mixture was transferred to a tube furnace after thorough grinding, under flowing N2Heating to 200 deg.C at a heating rate of 5 deg.C/min under atmosphere, keeping the temperature for 1h, further heating to 1200 deg.C at a heating rate of 5 deg.C/min for activating treatment, keeping the temperature at 1200 deg.C for 2h, and then adding N2Naturally cooling to room temperature under atmosphere purging to obtain sample D, wherein N2The volume space velocity is 180h-1；
5) And (3) placing the sample D in a 5% dilute hydrochloric acid solution, stirring at room temperature for 12h, then carrying out suction filtration and separation on the powder, washing with deionized water to be neutral, and finally drying the obtained filter cake at 120 ℃ to obtain the nitrogen-doped carbon material catalyst CAT-6.
Example 7
1) Cutting about 10 g of silkworm cocoon shells into pieces, soaking the pieces in deionized water at 50 ℃ for more than 6 hours to remove impurities and soluble inorganic salts in the silkworm cocoons, then carrying out suction filtration and separation on samples, washing the samples with the deionized water for more than 5 times, and drying the samples at 100 ℃ to obtain a sample A;
2) placing the sample A in a tube furnace, heating to 400 ℃ at a heating rate of 5 ℃/min in flowing Ar atmosphere for pre-carbonization, and keeping the temperature at 400 ℃ for 40 min to obtain a sample B, wherein the airspeed of Ar is 180h-1；
3) And grinding the sample B into powder, placing the powder into a 5% dilute hydrochloric acid solution, stirring at room temperature for 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and drying the obtained filter cake at 120 ℃ to obtain the nitrogen-doped carbon catalyst CAT-7.
Example 8
1) Cutting about 10 g of silkworm cocoon shells into pieces, soaking the pieces in deionized water at 50 ℃ for more than 6 hours to remove impurities and soluble inorganic salts in the silkworm cocoons, then carrying out suction filtration and separation on samples, washing the samples with the deionized water for more than 5 times, and drying the samples at 100 ℃ to obtain a sample A;
2) placing the sample A in a tube furnace, heating to 400 ℃ at a heating rate of 5 ℃/min in flowing Ar atmosphere for pre-carbonization, and keeping the temperature at 400 ℃ for 40 min to obtain a sample B, wherein the airspeed of Ar is 180h-1；
3) Grinding the sample B into powder, placing the powder into a 5% dilute hydrochloric acid solution, stirring for 12 hours at room temperature, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and drying the obtained filter cake at 120 ℃ to obtain a sample C;
4) mixing 3g of sample C and 3g of KOH powder, fully grinding, transferring the mixture to a tubular furnace, heating to 200 ℃ at a heating rate of 5 ℃/min under a flowing Ar atmosphere, keeping the temperature for 1h, continuously heating to 500 ℃ at a heating rate of 5 ℃/min, carrying out activation treatment, keeping the temperature at 500 ℃ for 2h, and then adding the mixture to the mixtureNaturally cooling to room temperature under Ar atmosphere purging to obtain a sample D, wherein the Ar volume space velocity is 180h-1；
5) And (3) placing the sample D in a 5% dilute hydrochloric acid solution, stirring at room temperature for 12h, then carrying out suction filtration and separation on the powder, washing with deionized water to be neutral, and finally drying the obtained filter cake at 120 ℃ to obtain the nitrogen-doped carbon material catalyst CAT-8.
Comparative example 1
Preparation of NH3Sample activated in the atmosphere, aimed at a comparison with example 3, to understand NH3Effect of treatment on catalyst activity.
The procedure is the same as in example 3, except that "in flowing N" in step 42Heating to 200 deg.C at a heating rate of 5 deg.C/min under atmosphere, keeping the temperature for 1h, further heating to 500 deg.C at a heating rate of 5 deg.C/min for activating treatment, keeping the temperature at 500 deg.C for 2h, and then maintaining the temperature at N2Naturally cooling to room temperature under atmosphere purging to obtain sample D, wherein N2The volume space velocity is 180h-1"Change to" at 10% NH flow3/N2Heating to 200 deg.C at a heating rate of 5 deg.C/min under atmosphere, maintaining the temperature for 1h, further heating to 500 deg.C at a heating rate of 5 deg.C/min for activating treatment, maintaining the temperature at 500 deg.C for 2h, and adding 10% NH3/N2Naturally cooling to room temperature under atmosphere purging, and finally adding 10% NH3/N2Changed to flowing N2The atmosphere was purged for 2h to obtain sample D, 10% NH3/N2And N2The volume space velocity is all 180h-1", the catalyst obtained was numbered CAT-9.
The evaluation process and conditions of the catalyst were:
1) putting 1mL of catalyst in a fixed bed reactor, heating to 200 ℃ under flowing inert gas and maintaining for 1h, wherein the volume space velocity of the inert gas is 45h-1；
2) Then the inert gas is closed, the flowing hydrogen chloride gas is switched, and the flowing hydrogen chloride gas is maintained for 1h, wherein the volume space velocity of the hydrogen chloride is 45h-1；
3) Introducing acetylene gas, acetyleneThe volume space velocity is 40 h-1The molar ratio of hydrogen chloride to acetylene was 1.3: 1.
The reacted gas was qualitatively and quantitatively analyzed using gas chromatography. Sampling is carried out once every 1h, the composition of the product is analyzed by gas chromatography, sampling analysis is carried out at the point of reaction for 2h, and the comparison data of the acetylene conversion rate and the vinyl chloride selectivity of different nitrogen-doped carbon catalysts are shown as the following table:
Figure DEST_PATH_IMAGE001

Claims (6)

1. a preparation method of a nitrogen-doped carbon catalyst for preparing vinyl chloride by fixed bed acetylene hydrochlorination is characterized by comprising the following steps:
1) shearing a certain mass of silkworm cocoon shells, soaking in deionized water at 30-50 ℃ for at least 6h, then carrying out suction filtration and separation on a sample, washing for a plurality of times by using the deionized water, and then drying at 80-100 ℃ to obtain a sample A;
2) placing the sample A in a tube furnace, heating to a target temperature at a heating rate of 5-10 ℃/min in a flowing air atmosphere for pre-carbonization, and keeping the temperature at the target temperature for at least 30min to obtain a sample B, wherein the air volume space velocity is 180h-1The pre-carbonization target temperature is 250-350 ℃;
3) and grinding the sample B into powder, placing the powder into a dilute hydrochloric acid solution, stirring at room temperature for at least 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and drying the obtained filter cake at 100-120 ℃ to obtain the nitrogen-doped carbon catalyst.
2. A preparation method of a nitrogen-doped carbon catalyst for preparing vinyl chloride by fixed bed acetylene hydrochlorination is characterized by comprising the following steps:
1) shearing a certain mass of silkworm cocoon shells, soaking in deionized water at 30-50 ℃ for at least 6h, then carrying out suction filtration and separation on a sample, washing for a plurality of times by using the deionized water, and then drying at 80-100 ℃ to obtain a sample A;
2) placing the sample A in a tube furnace, heating to a target temperature at a heating rate of 5-10 ℃/min in a flowing air atmosphere for pre-carbonization, and keeping the temperature at the target temperature for at least 30min to obtain a sample B, wherein the air volume space velocity is 180h-1The pre-carbonization target temperature is 250-350 ℃;
3) grinding the sample B into powder, placing the powder into a dilute hydrochloric acid solution, stirring at room temperature for at least 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and drying the obtained filter cake at 100-120 ℃ to obtain a sample C;
4) mixing a sample C with KOH powder with a certain mass, sufficiently grinding, transferring the mixture into a tubular furnace, heating to 180-200 ℃ at a heating rate of 5-10 ℃/min under a flowing inert atmosphere, keeping the temperature constant for at least 1h, continuing heating to a target temperature at a heating rate of 1-5 ℃/min, carrying out activation treatment, keeping the temperature constant for at least 2h at the target temperature, and naturally cooling to room temperature under inert atmosphere purging to obtain a sample D, wherein the mass ratio of KOH to the sample C is 1-4, and the inert atmosphere is N2One of He or Ar, wherein the activation target temperature is 450-1200 ℃;
5) and (3) placing the sample D in a dilute hydrochloric acid solution, stirring at room temperature for at least 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and finally drying the obtained filter cake at 100-120 ℃ to obtain the nitrogen-doped carbon material catalyst.
3. A preparation method of a nitrogen-doped carbon catalyst for preparing vinyl chloride by fixed bed acetylene hydrochlorination is characterized by comprising the following steps:
1) shearing a certain mass of silkworm cocoon shells, soaking in deionized water at 30-50 ℃ for at least 6h, then carrying out suction filtration and separation on a sample, washing for a plurality of times by using the deionized water, and then drying at 80-100 ℃ to obtain a sample A;
2) placing the sample A in a tube furnace, heating to a target temperature at a heating rate of 5-10 ℃/min in a flowing inert atmosphere for pre-carbonization, and keeping the temperature at the target temperature for at least 30min to obtain a sampleProduct B in which the inert atmosphere is N2One of He or Ar, and the volume space velocity is 180h-1The pre-carbonization target temperature is 250-450 ℃;
3) and grinding the sample B into powder, placing the powder into a dilute hydrochloric acid solution, stirring at room temperature for at least 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and drying the obtained filter cake at 100-120 ℃ to obtain the nitrogen-doped carbon catalyst.
4. A preparation method of a nitrogen-doped carbon catalyst for preparing vinyl chloride by fixed bed acetylene hydrochlorination is characterized by comprising the following steps:
1) shearing a certain mass of silkworm cocoon shells, soaking in deionized water at 30-50 ℃ for at least 6h, then carrying out suction filtration and separation on a sample, washing for a plurality of times by using the deionized water, and then drying at 80-100 ℃ to obtain a sample A;
2) placing the sample A in a tube furnace, heating to a target temperature at a heating rate of 5-10 ℃/min in a flowing inert atmosphere for pre-carbonization, and keeping the temperature at the target temperature for at least 30min to obtain a sample B, wherein the inert atmosphere is N2One of He or Ar, and the volume space velocity is 180h-1The pre-carbonization target temperature is 250-450 ℃;
3) grinding the sample B into powder, placing the powder into a dilute hydrochloric acid solution, stirring at room temperature for at least 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and drying the obtained filter cake at 100-120 ℃ to obtain a sample C;
4) mixing a sample C with KOH powder with a certain mass, sufficiently grinding, transferring the mixture into a tubular furnace, heating to 180-200 ℃ at a heating rate of 5-10 ℃/min under a flowing inert atmosphere, keeping the temperature constant for at least 1h, continuing heating to a target temperature at a heating rate of 1-5 ℃/min, carrying out activation treatment, keeping the temperature constant for at least 2h at the target temperature, and naturally cooling to room temperature under inert atmosphere purging to obtain a sample D, wherein the mass ratio of KOH to the sample C is 1-4, and the inert atmosphere is N2One of He or Ar, wherein the activation target temperature is 450-1200 ℃;
5) and (3) placing the sample D in a dilute hydrochloric acid solution, stirring at room temperature for at least 12 hours, then carrying out suction filtration and separation on the powder, washing the powder to be neutral by using deionized water, and finally drying the obtained filter cake at 100-120 ℃ to obtain the nitrogen-doped carbon material catalyst.
5. A nitrogen-doped carbon catalyst for preparing vinyl chloride by a fixed bed acetylene hydrochlorination reaction, which is characterized by being prepared by the preparation method of any one of claims 1 to 4.
6. The method of using the nitrogen-doped carbon catalyst of claim 5, comprising the steps of:
1) putting 1mL of catalyst in a fixed bed reactor, heating to 160-260 ℃ under flowing inert gas, and keeping the temperature for at least 1h, wherein the volume space velocity of the inert gas is 15-45 h-1；
2) Closing the inert gas, switching to flowing hydrogen chloride gas, and keeping the temperature for at least 1h, wherein the volume space velocity of the hydrogen chloride is 15-45 h-1；
3) Introducing acetylene gas, wherein the volume space velocity of the acetylene is 15-45 h-1The molar ratio of the hydrogen chloride to the acetylene is 1.05-1.3: 1;
4) the using temperature range of the nitrogen-doped carbon catalyst is 160-260 ℃;
5) the reacted gas was qualitatively and quantitatively analyzed using gas chromatography.
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