CN109647523B - Preparation method and use method of metal-free catalyst for preparing vinyl chloride by hydrochlorinating acetylene in fixed bed - Google Patents
Preparation method and use method of metal-free catalyst for preparing vinyl chloride by hydrochlorinating acetylene in fixed bed Download PDFInfo
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Abstract
The invention discloses a preparation method and a use method of a metal-free catalyst for preparing vinyl chloride by hydrochlorinating acetylene in a fixed bed. The method adopts imidazole compounds as active species, and obtains the metal-free catalyst by coordination bonding with zinc oxide species uniformly deposited on the surface of active carbon. The method is characterized in that the active species in the catalyst are imidazole compounds, complex nitrogen element introduction and subsequent carbonization steps are not needed, and the loading capacity of the imidazole compounds can be adjusted by controlling the deposition thickness of zinc oxide species on the surface of the active carbon. 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
Technical Field
The invention provides a preparation method and a use method of a metal-free catalyst for preparing vinyl chloride by hydrochlorinating acetylene in a fixed bed, belonging to the technical field of material synthesis. The method takes imidazole compounds as active species, and obtains the metal-free catalyst by coordination bonding with zinc oxide species uniformly deposited on the surface of active carbon. 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 one of the most widely used general resins in the world, and is widely applied to household industries such as tableware, buildings and the like. Vinyl Chloride (VCM) is a monomer for PVC synthesis, and there are three main methods for its synthesis: acetylene (calcium carbide), ethylene and ethane processes. Because the energy structure of rich coal, poor oil and less gas in China and the competitive advantages of mature technology, less water consumption, low production cost and the like of the PVC production by the calcium carbide method in China, the calcium carbide method route taking coal as the raw material is the mainstream process of the PVC production in China. At present, the process relies mainly on the use of mercury catalysts. However, the catalyst has the problem of mercury loss in the high-temperature reaction process, seriously pollutes the environment and threatens the health of human beings. In order to realize the efficient and clean production of the chloroethylene, the research and development of the novel mercury-free catalyst have important theoretical and practical significance.
To date, research on mercury-free catalysts has focused primarily on non-mercury metal catalysts. In 1985, in the study of acetylene hydrochlorination, professor Huctings et al of cadiov university in england first reported the relationship between the potential of a metal standard electrode and its catalytic activity, and predicted the high activity of a gold catalyst. The high activity of gold catalysts was verified in subsequent studies. But its higher price limits its further industrial spread and application in view of cost. Researchers have attempted to reduce the cost of the catalyst by incorporating a second metal into the gold-based catalyst, for example, the Au-ba (ii)/AC catalyst obtained by professor tsujin university zuki introducing barium metal into the gold-based catalyst, and the experimental results have found that the catalyst performs best when the ratio of barium to gold is 1: 1. The preparation of a Ru-Co (III) -Cu (II)/SAC catalyst free of gold was also carried out after the teaching of Zhang Jinli.
While developing metal catalysts, metal-free catalysts are another focus of research, wherein nitrogen-containing materials are particularly widely studied. In 2014, Weifei et al, Qinghua university report that a nitrogen-doped carbon nanotube as a catalyst for acetylene hydrochlorination for the first time, and an excellent activity result is obtained; and g-C prepared by professor et al3N4the/AC catalyst shows good catalytic activity in the hydrochlorination reaction of acetylene; the SiC @ C-N and h-BN catalysts prepared by the research of Bauncil and academy and the like show excellent catalytic performance in the reaction, and the experimental results show that the metal-free catalyst has a prospect in the acetylene hydrochlorination reaction. However, the preparation of the catalyst also has the disadvantages of complicated preparation steps and strict requirements on conditions. Patents CN201310518594.0 and CN201711367823.8 disclose a metal-free catalyst for fixed bed hydrochlorination of acetylene. The preparation of the catalyst in the patent is mainly to dip the active component precursor on porous carriers such as active carbon, molecular sieve and the like, or directly carry out high-temperature calcination treatment on the active precursor to obtain a nitrogen-containing material, and the preparation method and the formula of the catalyst are in the aspects ofThe difference with the patent is larger. The catalyst is a metal-free catalyst obtained by taking an imidazole compound as an active species and performing coordination bonding with a zinc oxide species uniformly deposited on the surface of active carbon. The preparation process of the catalyst does not involve high-temperature calcination of an active precursor, and meanwhile, the type and the content of the imidazole compound in the catalyst are controllable.
Disclosure of Invention
The invention aims to provide a preparation method and a using method of a metal-free catalyst for preparing vinyl chloride by hydrochlorinating acetylene in a fixed bed. The preparation process of the catalyst does not involve high-temperature calcination of an active precursor, and meanwhile, the type and the content of an active imidazole compound in the catalyst are controllable, so that the catalyst has certain catalytic activity and selectivity when being applied to the reaction of preparing vinyl chloride by hydrochlorinating acetylene in a fixed bed.
The specific technical scheme of the invention is as follows:
scheme 1, a method for preparing a metal-free catalyst for preparing vinyl chloride by fixed bed hydrochlorination of acetylene, characterized by comprising the following steps:
(1) adding activated carbon into a sulfuric acid solution with the mass concentration of 10%, stirring for at least 6 h at the temperature of 60-90 ℃, then carrying out suction filtration and separation on the activated carbon, washing the activated carbon to be neutral by using deionized water, and drying the obtained filter cake at the temperature of 100-120 ℃ to obtain a sample A, wherein the activated carbon is one or more of wood carbon, coal carbon, coconut shell carbon or bamboo charcoal, and the mass of the sulfuric acid solution is 3-10 times that of the activated carbon;
(2) adopting an Atomic Layer Deposition (ALD) technology, sequentially and alternately passing deionized water and diethyl zinc precursor vapor through an ALD reaction tube filled with a sample A at the temperature of 120-150 ℃, and uniformly depositing 5-20 atomic layers of Zn (OH) on the surface of the sample A2A thin layer; then roasting at least 1 h at the temperature of 300-450 ℃ in an inert atmosphere to obtain Zn (OH)2Converting the ZnO into ZnO, and cooling to room temperature to obtain a sample B;
(3) placing the sample B into a high-pressure reaction kettle containing a polytetrafluoroethylene lining, simultaneously placing an imidazole compound, sealing the reaction kettle, performing heat treatment at the temperature of 160-200 ℃ for 12-48 h, washing the obtained sample with water, and drying at the temperature of 100-120 ℃ to obtain a sample C, wherein the imidazole compound is one or more of imidazole or benzimidazole;
(4) placing the sample C in a quartz reaction tube, introducing flowing hydrogen chloride gas, treating for at least 6 h at the temperature of 160-200 ℃, then switching to flowing inert gas, and purging for at least 8 h to obtain the metal-free catalyst, wherein the space velocity of the hydrogen chloride gas is 15-30 h–1The space velocity of the inert gas is 100-180 h–1。
Scheme 2, a method for preparing a metal-free catalyst for preparing vinyl chloride by fixed bed hydrochlorination of acetylene, characterized by comprising the steps of:
(1) adding activated carbon into a sulfuric acid solution with the mass concentration of 10%, stirring for at least 6 h at the temperature of 60-90 ℃, then carrying out suction filtration and separation on the activated carbon, washing the activated carbon to be neutral by using deionized water, and drying the obtained filter cake at the temperature of 100-120 ℃ to obtain a sample A, wherein the activated carbon is one or more of wood carbon, coal carbon, coconut shell carbon or bamboo charcoal, and the mass of the sulfuric acid solution is 3-10 times that of the activated carbon;
(2) adopting an Atomic Layer Deposition (ALD) technology, sequentially and alternately passing deionized water and diethyl zinc precursor vapor through an ALD reaction tube filled with a sample A at the temperature of 120-150 ℃, and uniformly depositing 5-20 atomic layers of Zn (OH) on the surface of the sample A2A thin layer; then roasting at least 1 h at the temperature of 300-450 ℃ in an inert atmosphere to obtain Zn (OH)2Converting the ZnO into ZnO, and cooling to room temperature to obtain a sample B;
(3) placing the sample B into a high-pressure reaction kettle containing a polytetrafluoroethylene lining, simultaneously placing an imidazole compound, sealing the reaction kettle, performing heat treatment at the temperature of 160-200 ℃ for 12-48 h, washing the obtained sample with water, and drying at the temperature of 100-120 ℃ to obtain a sample C, wherein the imidazole compound is one or more of 1-methylimidazole, 2-methylimidazole or 4-methylimidazole;
(4) placing the sample C in a quartz reaction tube, introducing flowing hydrogen chloride gas, treating for at least 6 h at the temperature of 160-200 ℃, then switching to flowing inert gas, and purging for at least 8 h to obtain the metal-free catalyst, wherein the space velocity of the hydrogen chloride gas is 15-30 h–1The space velocity of the inert gas is 100-180 h–1。
Scheme 3, a method for preparing a metal-free catalyst for preparing vinyl chloride by fixed bed hydrochlorination of acetylene, characterized by comprising the steps of:
(1) adding activated carbon into a sulfuric acid solution with the mass concentration of 10%, stirring for at least 6 h at the temperature of 60-90 ℃, then carrying out suction filtration and separation on the activated carbon, washing the activated carbon to be neutral by using deionized water, and drying the obtained filter cake at the temperature of 100-120 ℃ to obtain a sample A, wherein the activated carbon is one or more of wood carbon, coal carbon, coconut shell carbon or bamboo charcoal, and the mass of the sulfuric acid solution is 3-10 times that of the activated carbon;
(2) adopting an Atomic Layer Deposition (ALD) technology, sequentially and alternately passing deionized water and diethyl zinc precursor vapor through an ALD reaction tube filled with a sample A at the temperature of 120-150 ℃, and uniformly depositing 5-20 atomic layers of Zn (OH) on the surface of the sample A2A thin layer; then roasting at least 1 h at the temperature of 300-450 ℃ in an inert atmosphere to obtain Zn (OH)2Converting the ZnO into ZnO, and cooling to room temperature to obtain a sample B;
(3) placing the sample B into a high-pressure reaction kettle containing a polytetrafluoroethylene lining, simultaneously placing an imidazole compound, sealing the reaction kettle, performing heat treatment at the temperature of 160-200 ℃ for 12-48 h, washing the obtained sample with water, and drying at the temperature of 100-120 ℃ to obtain a sample C, wherein the imidazole compound is one or more of 2-aminoimidazole or 4-aminoimidazole;
(4) placing the sample C in a quartz reaction tube, introducing flowing hydrogen chloride gas, treating for at least 6 h at the temperature of 160-200 ℃, then switching to flowing inert gas, and purging for at least 8 h to obtain the metal-free catalyst, wherein the space velocity of the hydrogen chloride gas is 15-30 h–1The space velocity of the inert gas is 100-180 h–1。
Scheme 4, a method for preparing a metal-free catalyst for preparing vinyl chloride by fixed bed hydrochlorination of acetylene, characterized by comprising the steps of:
(1) adding activated carbon into a sulfuric acid solution with the mass concentration of 10%, stirring for at least 6 h at the temperature of 60-90 ℃, then carrying out suction filtration and separation on the activated carbon, washing the activated carbon to be neutral by using deionized water, and drying the obtained filter cake at the temperature of 100-120 ℃ to obtain a sample A, wherein the activated carbon is one or more of wood carbon, coal carbon, coconut shell carbon or bamboo charcoal, and the mass of the sulfuric acid solution is 3-10 times that of the activated carbon;
(2) adopting an Atomic Layer Deposition (ALD) technology, sequentially and alternately passing deionized water and diethyl zinc precursor vapor through an ALD reaction tube filled with a sample A at the temperature of 120-150 ℃, and uniformly depositing 5-20 atomic layers of Zn (OH) on the surface of the sample A2A thin layer; then roasting at least 1 h at the temperature of 300-450 ℃ in an inert atmosphere to obtain Zn (OH)2Converting the ZnO into ZnO, and cooling to room temperature to obtain a sample B;
(3) placing the sample B into a high-pressure reaction kettle containing a polytetrafluoroethylene lining, simultaneously placing an imidazole compound, sealing the reaction kettle, performing heat treatment at the temperature of 160-200 ℃ for 12-48 h, washing the obtained sample with water, and drying at the temperature of 100-120 ℃ to obtain a sample C, wherein the imidazole compound is one or more of 2-nitroimidazole or 4-nitroimidazole;
(4) placing the sample C in a quartz reaction tube, introducing flowing hydrogen chloride gas, treating for at least 6 h at the temperature of 160-200 ℃, then switching to flowing inert gas, and purging for at least 8 h to obtain the metal-free catalyst, wherein the space velocity of the hydrogen chloride gas is 15-30 h–1The space velocity of the inert gas is 100-180 h–1。
Scheme 5, a metal-free catalyst for the fixed bed hydrochlorination of acetylene to vinyl chloride characterized in that it is prepared using the preparation method described in any of schemes 1-4.
Scheme 6, a method of using the metal-free catalyst described in scheme 5, is characterized by comprising the following steps:
(1) putting the catalyst in a fixed bed reactor, heating to 140 ℃ and 260 ℃ under flowing inert gas and keeping the temperature for at least 1 h, 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 1 h, wherein the volume space velocity of the hydrogen chloride is 15-45 h–1；
(3) Acetylene gas is introduced, and the volume space velocity of the acetylene is 15 to 45 hours–1The molar ratio of the hydrogen chloride to the acetylene is 1.05-1.3: 1;
(4) the application temperature range of the metal-free catalyst is 140-300 ℃;
(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, a metal-free catalyst is mostly focused on research and development of nitrogen-containing materials, an active species precursor is generally soaked on carriers such as active carbon, a molecular sieve and the like with large specific surface in the preparation process, subsequent high-temperature calcination treatment is needed, and the content and the type of active nitrogen species in the obtained catalyst are difficult to control. Compared with the prior art, the invention has the following remarkable innovation:
(1) the invention synthesizes the metal-free catalyst for preparing chloroethylene by fixed bed acetylene hydrochlorination, the active species of the catalyst is imidazole compound, the structure is clear, and the content can be regulated and controlled according to the thickness of zinc oxide deposited on the surface of the active carbon;
(2) the metal-free catalyst is prepared by taking imidazole compounds as active species and performing coordination bonding with zinc oxide species uniformly deposited on the surface of active carbon. The preparation process of the catalyst does not involve the high-temperature calcination process of the active precursor, thereby greatly simplifying the preparation process of the catalyst and reducing the production cost.
Drawings
FIG. 1: SEM picture of metal-free catalyst Cat-1 prepared in example 1.
FIG. 2: SEM picture of metal-free catalyst Cat-2 prepared in example 2.
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.
Example 1
(1) Adding 10 g of coal carbon into 100 g of 10% sulfuric acid solution, stirring for 8 hours at 85 ℃, then carrying out suction filtration and separation on the activated carbon, fully washing the activated carbon with deionized water to be neutral, and drying the obtained filter cake for 24 hours at 100 ℃ to obtain a sample A;
(2) adopting an Atomic Layer Deposition (ALD) technology, sequentially and alternately passing deionized water and diethyl zinc precursor vapor through an ALD reaction tube filled with a sample A at 120 ℃, and uniformly depositing 5 atomic layers of Zn (OH) on the surface of the sample A2Thin layer, baking at 400 deg.C under argon atmosphere for 1.5 h to deposit Zn (OH) on the surface of activated carbon2Converting the ZnO into ZnO, and cooling to room temperature to obtain a sample B;
(3) placing 2 g of the sample B into a 50 mL high-pressure reaction kettle containing a polytetrafluoroethylene lining, simultaneously placing 5 g of imidazole, sealing the reaction kettle, then placing the reaction kettle at 180 ℃ for heat treatment for 24 hours, and then washing the obtained sample with water and drying the sample at 120 ℃ to obtain a sample C;
(4) placing the sample C in a quartz reaction tube, introducing flowing hydrogen chloride gas, treating for 6 h at 160 ℃, then switching to flowing nitrogen, and purging for at least 8 h to obtain the metal-free catalyst Cat-1, wherein the airspeed of the hydrogen chloride gas is 15 h–1The space velocity of the inert gas is 180 h–1。
Example 2
(1) Adding 10 g of coconut shell carbon into 30 g of sulfuric acid solution with the mass concentration of 10%, stirring for 8 hours at the temperature of 85 ℃, then carrying out suction filtration and separation on the activated carbon, fully washing the activated carbon with deionized water to be neutral, and drying the obtained filter cake for 24 hours at the temperature of 100 ℃ to obtain a sample A;
(2) adopting an Atomic Layer Deposition (ALD) technology, sequentially and alternately passing deionized water and diethyl zinc precursor vapor through an ALD reaction tube filled with a sample A at 120 ℃, and uniformly depositing 15 atomic layers of Zn (OH) on the surface of the sample A2Thin layer, baking at 400 deg.C under argon atmosphere for 1.5 h to deposit Zn (OH) on the surface of activated carbon2Converting the ZnO into ZnO, and cooling to room temperature to obtain a sample B;
(3) placing 2 g of the sample B into a 50 mL high-pressure reaction kettle containing a polytetrafluoroethylene lining, simultaneously placing 5 g of benzimidazole, sealing the reaction kettle, then placing the reaction kettle at 200 ℃ for heat treatment for 24 hours, and then washing the obtained sample with water and drying the sample at 120 ℃ to obtain a sample C;
(4) placing the sample C in a quartz reaction tube, introducing flowing hydrogen chloride gas, treating for 6 h at 160 ℃, then switching to flowing nitrogen, and purging for at least 8 h to obtain the metal-free catalyst Cat-2, wherein the airspeed of the hydrogen chloride gas is 15 h–1The space velocity of the inert gas is 180 h–1。
Example 3
(1) Adding 10 g of coal carbon into 50 g of 10% sulfuric acid solution, stirring for 8 hours at 85 ℃, then carrying out suction filtration and separation on the activated carbon, fully washing the activated carbon to be neutral by using deionized water, and drying the obtained filter cake for 24 hours at 100 ℃ to obtain a sample A;
(2) adopting an Atomic Layer Deposition (ALD) technology, sequentially and alternately passing deionized water and diethyl zinc precursor vapor through an ALD reaction tube filled with a sample A at 120 ℃, and uniformly depositing 5 atomic layers of Zn (OH) on the surface of the sample A2Thin layer, baking at 400 deg.C under argon atmosphere for 1.5 h to deposit Zn (OH) on the surface of activated carbon2Converting the ZnO into ZnO, and cooling to room temperature to obtain a sample B;
(3) placing 2 g of the sample B into a 50 mL high-pressure reaction kettle containing a polytetrafluoroethylene lining, simultaneously placing 5 g of 1-methylimidazole, sealing the reaction kettle, then placing the reaction kettle at 180 ℃ for heat treatment for 24 hours, washing the obtained sample with water, and drying the sample at 120 ℃ to obtain a sample C;
(4) placing the sample C in a quartz reaction tube, introducing flowing hydrogen chloride gas, treating for 6 h at 160 ℃, then switching to flowing nitrogen, and purging for at least 8 h to obtain the metal-free catalyst Cat-3, wherein the airspeed of the hydrogen chloride gas is 15 h–1The space velocity of the inert gas is 180 h–1。
Example 4
(1) Adding 10 g of coal carbon into 100 g of 10% sulfuric acid solution, stirring for 8 hours at 85 ℃, then carrying out suction filtration and separation on the activated carbon, fully washing the activated carbon with deionized water to be neutral, and drying the obtained filter cake for 24 hours at 100 ℃ to obtain a sample A;
(2) adopting an Atomic Layer Deposition (ALD) technology, sequentially and alternately passing deionized water and diethyl zinc precursor vapor through an ALD reaction tube filled with a sample A at 120 ℃, and uniformly depositing 5 atomic layers of Zn (OH) on the surface of the sample A2Thin layer, baking at 400 deg.C under argon atmosphere for 1.5 h to deposit Zn (OH) on the surface of activated carbon2Converting the ZnO into ZnO, and cooling to room temperature to obtain a sample B;
(3) placing 2 g of the sample B into a 50 mL high-pressure reaction kettle containing a polytetrafluoroethylene lining, simultaneously placing 5 g of 2-methylimidazole, sealing the reaction kettle, then placing the reaction kettle at 180 ℃ for heat treatment for 24 hours, washing the obtained sample with water, and drying the sample at 120 ℃ to obtain a sample C;
(4) placing the sample C in a quartz reaction tube, introducing flowing hydrogen chloride gas, treating for 6 h at 160 ℃, then switching to flowing nitrogen, and purging for at least 8 h to obtain the metal-free catalyst Cat-4, wherein the airspeed of the hydrogen chloride gas is 15 h–1The space velocity of the inert gas is 180 h–1。
Example 5
(1) Adding 10 g of wood charcoal into 100 g of 10% sulfuric acid solution, stirring for 8 hours at 85 ℃, then carrying out suction filtration and separation on the activated charcoal, fully washing the activated charcoal with deionized water to be neutral, and drying the obtained filter cake for 24 hours at 100 ℃ to obtain a sample A;
(2) adopting an Atomic Layer Deposition (ALD) technology, sequentially and alternately passing deionized water and diethyl zinc precursor vapor through an ALD reaction tube filled with a sample A at 120 ℃, and uniformly depositing 10 atomic layers of Zn (OH) on the surface of the sample A2Thin layer, baking at 400 deg.C under argon atmosphere for 1.5 h to deposit Zn (OH) on the surface of activated carbon2Converting the ZnO into ZnO, and cooling to room temperature to obtain a sample B;
(3) placing 2 g of the sample B into a 50 mL high-pressure reaction kettle containing a polytetrafluoroethylene lining, simultaneously placing 5 g of 2-aminoimidazole, sealing the reaction kettle, then placing the reaction kettle at 180 ℃ for heat treatment for 24 hours, and then washing the obtained sample with water and drying the sample at 120 ℃ to obtain a sample C;
(4) placing the sample C in a quartz reaction tube, introducing flowing hydrogen chloride gas, treating for 6 h at 160 ℃, then switching to flowing nitrogen, and purging for at least 8 h to obtain the metal-free catalyst Cat-5, wherein the airspeed of the hydrogen chloride gas is 15 h–1The space velocity of the inert gas is 180 h–1。
Example 6
(1) Adding 10 g of wood charcoal into 100 g of 10% sulfuric acid solution, stirring for 8 hours at 85 ℃, then carrying out suction filtration and separation on the activated charcoal, fully washing the activated charcoal with deionized water to be neutral, and drying the obtained filter cake for 24 hours at 100 ℃ to obtain a sample A;
(2) adopting an Atomic Layer Deposition (ALD) technology, sequentially and alternately passing deionized water and diethyl zinc precursor vapor through an ALD reaction tube filled with a sample A at 120 ℃, and uniformly depositing 10 atomic layers of Zn (OH) on the surface of the sample A2Thin layer, baking at 400 deg.C under argon atmosphere for 1.5 h to deposit Zn (OH) on the surface of activated carbon2Converting the ZnO into ZnO, and cooling to room temperature to obtain a sample B;
(3) placing 2 g of the sample B into a 50 mL high-pressure reaction kettle containing a polytetrafluoroethylene lining, simultaneously placing 5 g of 4-aminoimidazole, sealing the reaction kettle, then placing the reaction kettle at 180 ℃ for heat treatment for 24 hours, and then washing the obtained sample with water and drying the sample at 120 ℃ to obtain a sample C;
(4) placing the sample C in a quartz reaction tube, introducing flowing hydrogen chloride gas, treating for 6 h at 160 ℃, then switching to flowing nitrogen, and purging for at least 8 h to obtain the metal-free catalyst Cat-6, wherein the airspeed of the hydrogen chloride gas is 15 h–1The space velocity of the inert gas is 180 h–1。
Example 7
(1) Adding 10 g of bamboo charcoal into 100 g of a 10% sulfuric acid solution, stirring for 8 hours at 85 ℃, then carrying out suction filtration and separation on the activated carbon, fully washing the activated carbon to be neutral by using deionized water, and drying the obtained filter cake for 24 hours at 100 ℃ to obtain a sample A;
(2) adopting an Atomic Layer Deposition (ALD) technology, sequentially and alternately passing deionized water and diethyl zinc precursor vapor through an ALD reaction tube filled with a sample A at 120 ℃, and uniformly depositing 10 atomic layers of Zn (OH) on the surface of the sample A2Thin layer, baking at 400 deg.C under argon atmosphere for 1.5 h to deposit Zn (OH) on the surface of activated carbon2Converting the ZnO into ZnO, and cooling to room temperature to obtain a sample B;
(3) placing 2 g of the sample B into a 50 mL high-pressure reaction kettle containing a polytetrafluoroethylene lining, simultaneously placing 5 g of 2-nitroimidazole, sealing the reaction kettle, then placing the reaction kettle at 200 ℃ for heat treatment for 48 hours, and then washing the obtained sample with water and drying the sample at 120 ℃ to obtain a sample C;
(4) placing the sample C in a quartz reaction tube, introducing flowing hydrogen chloride gas, treating for 6 h at 160 ℃, then switching to flowing nitrogen, and purging for at least 8 h to obtain the metal-free catalyst Cat-7, wherein the airspeed of the hydrogen chloride gas is 15 h–1The space velocity of the inert gas is 180 h–1。
Example 8
(1) Adding 10 g of bamboo charcoal into 100 g of a 10% sulfuric acid solution, stirring for 8 hours at 85 ℃, then carrying out suction filtration and separation on the activated carbon, fully washing the activated carbon to be neutral by using deionized water, and drying the obtained filter cake for 24 hours at 100 ℃ to obtain a sample A;
(2) adopting an Atomic Layer Deposition (ALD) technology, sequentially and alternately passing deionized water and diethyl zinc precursor vapor through an ALD reaction tube filled with a sample A at 120 ℃, and uniformly depositing 10 atomic layers of Zn (OH) on the surface of the sample A2Thin layer, baking at 400 deg.C under argon atmosphere for 1.5 h to deposit Zn (OH) on the surface of activated carbon2Converting the ZnO into ZnO, and cooling to room temperature to obtain a sample B;
(3) placing 2 g of the sample B into a 50 mL high-pressure reaction kettle containing a polytetrafluoroethylene lining, simultaneously placing 5 g of 4-nitroimidazole, sealing the reaction kettle, then placing the reaction kettle at 200 ℃ for heat treatment for 48 hours, and then washing the obtained sample with water and drying the sample at 120 ℃ to obtain a sample C;
(4) placing the sample C in a quartz reaction tube, introducing flowing hydrogen chloride gas, treating for 6 h at 160 ℃, then switching to flowing nitrogen, and purging for at least 8 h to obtain the metal-free catalyst Cat-8, wherein the airspeed of the hydrogen chloride gas is 15 h–1The space velocity of the inert gas is 180 h–1。
Comparative example 1
The loading mode of imidazole on the activated carbon is changed, and the ALD zinc oxide deposition process is removed, so that compared with example 1, the effect of the zinc oxide atomic layer deposited on the surface of the activated carbon on the activity of the catalyst is achieved.
The preparation process was identical to example 1, with only the ALD process removed, and the specific operation was as follows:
(1) adding 10 g of coal carbon into 100 g of 10% sulfuric acid solution, stirring for 8 hours at 85 ℃, then carrying out suction filtration and separation on the activated carbon, fully washing the activated carbon with deionized water to be neutral, and drying the obtained filter cake for 24 hours at 100 ℃ to obtain a sample A;
(2) placing 2 g of the sample A into a 50 mL high-pressure reaction kettle containing a polytetrafluoroethylene lining, simultaneously placing 5 g of imidazole, sealing the reaction kettle, then placing the reaction kettle at 180 ℃ for heat treatment for 24 hours, and then washing the obtained sample with water and drying the sample at 120 ℃ to obtain a sample B;
(3) sample B was placed in a quartz reaction tube and flowing hydrogen chloride gas was bubbled through it at 160 deg.CTreating at 6 deg.C for 6 hr, switching to flowing nitrogen, purging for at least 8 hr to obtain catalyst named Cat-9 with hydrogen chloride gas space velocity of 15 hr–1The space velocity of the inert gas is 180 h–1。
The evaluation process and conditions of the catalyst were:
(1) 1 mL of catalyst is placed in a fixed bed reactor, the temperature is raised to 200 ℃ under flowing inert gas and the temperature is kept for 1 h, wherein the volume space velocity of the inert gas is 30 h–1；
(2) The inert gas is closed, the flowing hydrogen chloride gas is switched, the temperature is kept for 1 h, wherein the volume space velocity of the hydrogen chloride is 30 h–1；
(3) Acetylene gas is introduced, and the volume space velocity of the acetylene is 40 h–1The molar ratio of hydrogen chloride to acetylene is 1.2: 1;
qualitative and quantitative analysis is carried out on the reacted gas by using a gas chromatograph, sampling is carried out once every 1 h, the product composition is analyzed by using the gas chromatograph, sampling analysis is carried out at the point of reaction for 2 h, and the comparison data of the acetylene conversion rate and the chloroethylene selectivity of different metal-free catalysts are shown in the table:
Claims (6)
1. a preparation method of a metal-free catalyst for preparing vinyl chloride by fixed bed acetylene hydrochlorination is characterized by comprising the following steps:
(1) adding activated carbon into a sulfuric acid solution with the mass concentration of 10%, stirring for at least 6 h at 60-90 ℃, then carrying out suction filtration and separation on the activated carbon, washing the activated carbon to be neutral by using deionized water, and drying the obtained filter cake at the temperature of 100-120 ℃ to obtain a sample A, wherein the activated carbon is one or more of wood carbon, coal carbon, coconut shell carbon or bamboo charcoal, and the mass of the sulfuric acid solution is 3-10 times that of the activated carbon;
(2) adopting an Atomic Layer Deposition (ALD) technology to mix deionized water and the precursor at the temperature of 120-The vapor of diethyl zinc is sequentially and alternately passed through an ALD reaction tube containing the sample A, and 5 to 20 atomic layers of Zn (OH) are uniformly deposited on the surface of the sample A2A thin layer; then roasting at least 1 h at 300-450 ℃ in an inert atmosphere to obtain Zn (OH)2Converting the ZnO into ZnO, and cooling to room temperature to obtain a sample B;
(3) placing the sample B into a high-pressure reaction kettle containing a polytetrafluoroethylene lining, simultaneously placing an imidazole compound, sealing the reaction kettle, then placing the reaction kettle into a temperature range of 160-;
(4) placing the sample C in a quartz reaction tube, introducing flowing hydrogen chloride gas, treating for at least 6 h at the temperature of 160-200 ℃, then switching to flowing inert gas, and purging for at least 8 h to obtain the metal-free catalyst, wherein the space velocity of the hydrogen chloride gas is 15-30 h–1The space velocity of the inert gas is 100-180 h–1。
2. A preparation method of a metal-free catalyst for preparing vinyl chloride by fixed bed acetylene hydrochlorination is characterized by comprising the following steps:
(1) adding activated carbon into a sulfuric acid solution with the mass concentration of 10%, stirring for at least 6 h at 60-90 ℃, then carrying out suction filtration and separation on the activated carbon, washing the activated carbon to be neutral by using deionized water, and drying the obtained filter cake at the temperature of 100-120 ℃ to obtain a sample A, wherein the activated carbon is one or more of wood carbon, coal carbon, coconut shell carbon or bamboo charcoal, and the mass of the sulfuric acid solution is 3-10 times that of the activated carbon;
(2) adopting an Atomic Layer Deposition (ALD) technology, sequentially and alternately passing deionized water and diethyl zinc precursor vapor through an ALD reaction tube filled with a sample A at the temperature of 120-150 ℃, and uniformly depositing 5-20 atomic layers of Zn (OH) on the surface of the sample A2A thin layer; then roasting at least 1 h at 300-450 ℃ in an inert atmosphere to obtain Zn (OH)2Converting the ZnO into ZnO, and cooling to room temperature to obtain a sample B;
(3) placing the sample B into a high-pressure reaction kettle containing a polytetrafluoroethylene lining, simultaneously placing an imidazole compound, sealing the reaction kettle, performing heat treatment at the temperature of 160-200 ℃ for 12-48 h, washing the obtained sample with water, and drying at the temperature of 100-120 ℃ to obtain a sample C, wherein the imidazole compound is one or more of 1-methylimidazole, 2-methylimidazole or 4-methylimidazole;
(4) placing the sample C in a quartz reaction tube, introducing flowing hydrogen chloride gas, treating for at least 6 h at the temperature of 160-200 ℃, then switching to flowing inert gas, and purging for at least 8 h to obtain the metal-free catalyst, wherein the space velocity of the hydrogen chloride gas is 15-30 h–1The space velocity of the inert gas is 100-180 h–1。
3. A preparation method of a metal-free catalyst for preparing vinyl chloride by fixed bed acetylene hydrochlorination is characterized by comprising the following steps:
(1) adding activated carbon into a sulfuric acid solution with the mass concentration of 10%, stirring for at least 6 h at 60-90 ℃, then carrying out suction filtration and separation on the activated carbon, washing the activated carbon to be neutral by using deionized water, and drying the obtained filter cake at the temperature of 100-120 ℃ to obtain a sample A, wherein the activated carbon is one or more of wood carbon, coal carbon, coconut shell carbon or bamboo charcoal, and the mass of the sulfuric acid solution is 3-10 times that of the activated carbon;
(2) adopting an Atomic Layer Deposition (ALD) technology, sequentially and alternately passing deionized water and diethyl zinc precursor vapor through an ALD reaction tube filled with a sample A at the temperature of 120-150 ℃, and uniformly depositing 5-20 atomic layers of Zn (OH) on the surface of the sample A2A thin layer; then roasting at least 1 h at 300-450 ℃ in an inert atmosphere to obtain Zn (OH)2Converting the ZnO into ZnO, and cooling to room temperature to obtain a sample B;
(3) placing the sample B into a high-pressure reaction kettle containing a polytetrafluoroethylene lining, simultaneously placing an imidazole compound, sealing the reaction kettle, then placing the reaction kettle into a temperature range of 160-;
(4) placing the sample C in a quartz reaction tube, introducing flowing hydrogen chloride gas, treating for at least 6 h at the temperature of 160-200 ℃, then switching to flowing inert gas, and purging for at least 8 h to obtain the metal-free catalyst, wherein the space velocity of the hydrogen chloride gas is 15-30 h–1The space velocity of the inert gas is 100-180 h–1。
4. A preparation method of a metal-free catalyst for preparing vinyl chloride by fixed bed acetylene hydrochlorination is characterized by comprising the following steps:
(1) adding activated carbon into a sulfuric acid solution with the mass concentration of 10%, stirring for at least 6 h at 60-90 ℃, then carrying out suction filtration and separation on the activated carbon, washing the activated carbon to be neutral by using deionized water, and drying the obtained filter cake at the temperature of 100-120 ℃ to obtain a sample A, wherein the activated carbon is one or more of wood carbon, coal carbon, coconut shell carbon or bamboo charcoal, and the mass of the sulfuric acid solution is 3-10 times that of the activated carbon;
(2) adopting an Atomic Layer Deposition (ALD) technology, sequentially and alternately passing deionized water and diethyl zinc precursor vapor through an ALD reaction tube filled with a sample A at the temperature of 120-150 ℃, and uniformly depositing 5-20 atomic layers of Zn (OH) on the surface of the sample A2A thin layer; then roasting at least 1 h at 300-450 ℃ in an inert atmosphere to obtain Zn (OH)2Converting the ZnO into ZnO, and cooling to room temperature to obtain a sample B;
(3) placing the sample B into a high-pressure reaction kettle containing a polytetrafluoroethylene lining, simultaneously placing an imidazole compound, sealing the reaction kettle, then placing the reaction kettle into a temperature range of 160-;
(4) placing the sample C in a quartz reaction tube, introducing flowing hydrogen chloride gas, treating for at least 6 h at the temperature of 160-200 ℃, then switching to flowing inert gas, and purging for at least 8 h to obtain the metal-free catalyst, wherein the space velocity of the hydrogen chloride gas is 15-30 h–1Inert gas (es)The space velocity is 100-180 h–1。
5. A metal-free catalyst for the fixed bed hydrochlorination of acetylene to vinyl chloride, characterized in that it is prepared using the preparation method of any one of claims 1 to 4.
6. The method for using the metal-free catalyst according to claim 5, comprising the following steps:
(1) putting the catalyst in a fixed bed reactor, heating to 140 ℃ and 260 ℃ under flowing inert gas and keeping the temperature for at least 1 h, 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 1 h, wherein the volume space velocity of the hydrogen chloride is 15-45 h–1；
(3) Acetylene gas is introduced, and the volume space velocity of the acetylene is 15 to 45 hours–1The molar ratio of the hydrogen chloride to the acetylene is 1.05-1.3: 1;
(4) the application temperature range of the metal-free catalyst is 140-300 ℃;
(5) the reacted gas was qualitatively and quantitatively analyzed using gas chromatography.
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