CN111346662B - Preparation method, product and application of nitrogen-doped activated carbon-loaded ultralow-mercury catalyst - Google Patents
Preparation method, product and application of nitrogen-doped activated carbon-loaded ultralow-mercury catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a nitrogen-doped activated carbon loaded ultra-low mercury catalyst and a product prepared by the method, and the preparation method comprises the following steps: 1) Preparing nitrogen-doped activated carbon: dipping the activated carbon in amino resin dipping solution, drying and carbonizing to obtain nitrogen-doped activated carbon; the amino resin impregnation liquid is prepared by reacting an amino compound with an aldehyde compound; 2) Preparation of ultra-low mercury catalyst: loading the nitrogen-doped activated carbon in the step 1) with mercuric chloride and an auxiliary agent, and drying to obtain the product. The preparation method is simple to operate, economical and practical, the nitrogen doping and carbonization process is realized in the atmosphere furnace, and the preparation of the catalyst does not need to modify the existing production equipment; compared with a low-mercury catalyst, the catalyst has the advantages that the content of mercuric chloride is greatly reduced, the loss rate of the mercuric chloride is reduced, the catalytic activity is excellent, and the product selectivity is good.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation and application, and particularly relates to a preparation method, a product and application of a nitrogen-doped activated carbon supported ultralow-mercury catalyst.
Background
Polyvinyl chloride (PVC) is one of five common plastics and is widely applied to buildings, agriculture, industrial utilities and daily life. China is the largest PVC producing country in the world, and more than 80% of chloroethylene is prepared by an addition reaction of acetylene and hydrogen chloride under the action of a catalyst by adopting a calcium carbide method. Industrially, the reaction uses the activated carbon-supported high-mercury catalyst (the mercury chloride supported amount is 10-12%) at first, and the low-mercury catalyst (the mercury chloride supported amount is 4-6.5%) gradually becomes the mainstream catalyst after 2010. However, mercury chloride belongs to a highly toxic compound, and can be sublimated and lost at the hydrochlorination reaction temperature, so that the activity and the service life of the catalyst are reduced. With the continuous exhaustion of mercury resources and the effective policy of "water conservation for mercury" in China, the development of solid mercury catalysts and non-mercury catalysts with ultra-low mercury content becomes a major factor restricting the development of the chlor-alkali industry.
In recent years, under the active research of chlor-alkali enterprises, colleges and scientific research institutions on substitute products, various types of catalysts have come into play, and mainly include five major types, namely noble metal catalysts represented by gold trichloride, ruthenium chloride and the like, non-noble metal catalysts represented by copper, bismuth, tin, cobalt and the like, non-metal catalysts represented by nitrogen-doped carbon, liquid catalysts represented by ionic liquid and ultra-low mercury catalysts.
Hutchings et al investigated the catalytic activity of various metal chlorides on the hydrochlorination of acetylene and determined that noble metals (gold, platinum, palladium, ruthenium) have excellent catalytic activity on this reaction. Patent CN109876864A discloses an ultra-low content precious metal composite catalyst and a preparation method thereof, wherein the catalyst uses precious metal comprehensive cysteine and other amino acids and cobalt chloride and other metal chlorides as active components. Patent CN109847802A discloses a catalyst in which gold is mixed with heteroatoms such as phosphorus and nitrogen, and the stability and catalytic activity of gold are improved by using gold as an active component and various heteroatoms. Patents CN109622036A and CN109622016A combine the properties of gold catalysts and coordination atoms, and disclose catalysts in which complexes formed by gold and nitrogen-containing ligands are the main active components.
Although the activity and the service life of the gold catalyst for the hydrochlorination of acetylene can be effectively ensured and the gold catalyst is industrially tested, the expensive cost still limits the market promotion process. In a short time, the low-mercury and ultra-low-mercury catalysts still occupy the dominant position, and how to effectively reduce the volatilization of mercuric chloride, reduce the surface carbon deposition and prolong the service life of the catalysts is a problem to be solved urgently. The patent CN105195224A applies for a preparation method of a low-mercury catalyst with good thermal stability by using mercuric chloride, zinc chloride, palladium chloride, platinum chloride, tetrabutyl ammonium chloride and potassium triphenylphosphine sulfonate, and the loss rate of mercuric chloride is only 0.39%, but the preparation process is complicated (including ultrasonic-assisted adsorption, microwave-assisted adsorption and vacuum permeation adsorption), and is difficult to popularize and use in a large area. Patent CN105582967A disclosesA nano-class low-mercury catalyst is prepared from nano-carbon powder, nano-graphite powder or graphene as carrier through immersing active component in mercuric chloride, adding gamma-Al 2 O 3 And the mixture of the low-mercury catalyst and zirconium silicate is subjected to secondary impregnation, the low-mercury catalyst has stronger anti-toxicity and anti-carbon deposition capabilities, the service life of the catalyst can be effectively prolonged, and the powder form cannot meet the industrial application.
Disclosure of Invention
The invention aims to provide a preparation method, a product and application of a nitrogen-doped activated carbon supported ultralow-mercury catalyst.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of a nitrogen-doped activated carbon-loaded ultralow-mercury catalyst comprises the following steps:
1) Preparing nitrogen-doped activated carbon: dipping the activated carbon in amino resin dipping solution, drying and carbonizing to obtain nitrogen-doped activated carbon; the amino resin impregnation liquid is obtained by reacting an amino compound with an aldehyde compound;
2) Preparation of ultra-low mercury catalyst: the nitrogen-doped activated carbon obtained in the step 1) is loaded with mercuric chloride and an auxiliary agent and is obtained through drying treatment.
In the step 1), the amino compound is one or a mixture of more than two of melamine, dicyandiamide and urea; the aldehyde compound is one of formaldehyde, trioxymethylene, paraformaldehyde, acetaldehyde and glutaraldehyde; the molar ratio of the aldehyde compound to the amino compound is (1-3) to 1; the load capacity of the amino compound is 1-10% of the mass of the active carbon.
In step 1), isovolumetric impregnation is adopted: adding the amino resin impregnation liquid into active carbon, preserving heat for 6-12 h at 10-60 ℃, and drying at 115-125 ℃; the carbonization process comprises the following steps: heating to 550-850 ℃ at the heating rate of 2-5 ℃/min under the protection of nitrogen or argon in an atmosphere furnace, and preserving the heat for 2-6 h.
In the step 2), the temperature of the load is 60-80 ℃, the time of the load is 4-12 h, gradient drying is adopted, the temperature is firstly preserved for 1-2 h at 80 ℃, then preserved for 1-2 h at 100 ℃, and then drying is carried out at 105-125 ℃; the addition amount of the mercuric chloride is 1-3% of that of the nitrogen-doped activated carbon; the addition amount of the auxiliary agent is 1-20% of the nitrogen-doped activated carbon; the auxiliary agent is a mixture of one or more of chlorides of copper, bismuth, zinc, cerium and potassium and triethylamine hydrochloride, tetraalkylammonium chloride, pyridine hydrochloride and guanidine hydrochloride.
In the step 2), the loading method comprises the following steps of sequentially loading mercuric chloride and an auxiliary agent, and specifically comprises the following steps: putting the nitrogen-doped activated carbon into a mercuric chloride solution, preserving the heat for 4-12h at the temperature of 60-80 ℃, and drying at the temperature of 80-105 ℃ to obtain the mercuric chloride-loaded nitrogen-doped activated carbon; adding the nitrogen-doped activated carbon loaded with mercuric chloride into the auxiliary agent solution, and preserving the heat for 4-12 h at the temperature of 60-80 ℃ to finish the loading;
in the step 2), the loading method is to load mercury chloride and an auxiliary agent at the same time, and the specific steps are as follows: adding nitrogen-doped activated carbon into an impregnation liquid prepared from mercuric chloride and an auxiliary agent, and preserving the heat for 4-12 h at the temperature of 60-80 ℃ to finish the loading.
In the step 2), the loading method comprises the steps of loading mercuric chloride and part of the auxiliary agent and then loading the rest of the auxiliary agent, and comprises the following specific steps: adding nitrogen-doped activated carbon into impregnation liquid prepared from mercuric chloride and part of auxiliary agents, preserving the heat at the temperature of between 60 and 80 ℃ for 4 to 12h, and drying at the temperature of between 80 and 105 ℃ to obtain the mercuric chloride-loaded nitrogen-doped activated carbon; and then adding the nitrogen-doped activated carbon loaded with mercuric chloride and part of the auxiliary agents into impregnation liquid prepared by the rest of the auxiliary agents, and preserving the heat for 4-12 h at the temperature of 60-80 ℃ to finish the loading.
The nitrogen-doped activated carbon load ultra-low mercury catalyst product prepared by the preparation method.
The nitrogen-doped activated carbon-loaded ultralow-mercury catalyst product is applied to the reaction of synthesizing vinyl chloride by hydrochlorinating acetylene, the catalytic reaction is carried out in a fixed bed reactor, and the space velocity of the acetylene is 20-300 h -1 The molar ratio of the reaction gas is n (C2H2) :n (HCl) 1.05-1.2, and the reaction temperature is 90-140 ℃.
Compared with the prior art, the invention has the advantages that:
1) The preparation method of the nitrogen-doped activated carbon-loaded ultralow-mercury catalyst is simple to operate, economical and practical, the nitrogen-doped carbonization process is realized in an atmosphere furnace, and the preparation of the catalyst does not need to modify the existing production equipment;
2) Compared with a low-mercury catalyst, the catalyst has the advantages that the content of mercuric chloride is greatly reduced, the loss rate of the mercuric chloride (1-2.5%, and the content of the low-mercury catalyst GB/T31530-2015 for synthesizing vinyl chloride is regulated to be less than or equal to 3%) is also reduced, the catalytic activity is excellent, and the product selectivity is good.
Detailed Description
The invention is further described in connection with several specific embodiments, but the scope of the invention is not limited to the examples, which are set forth in the claims.
In the following examples, the concentration of the hydrochloric acid solution was 1mol/L.
Example 1
A preparation method of a nitrogen-doped activated carbon-loaded ultralow-mercury catalyst comprises the following steps:
1) Preparing nitrogen-doped activated carbon: diluting 1.8mL of formaldehyde solution (the mass fraction is 37-40%, the same applies below) to 10-12 mL, regulating the pH value to 9.5 by triethanolamine, adding 1g of melamine, stirring and dissolving in water bath at 60 ℃, adding into 10g of activated carbon, keeping the temperature at 60 ℃ for 10h, drying at 125 ℃, heating to 850 ℃ at the heating rate of 2-5 ℃/min under the protection of nitrogen in an atmosphere furnace, and calcining for 2h to obtain nitrogen-doped activated carbon;
2) Preparation of ultra-low mercury catalyst: weighing 5g of nitrogen-doped activated carbon, adding the nitrogen-doped activated carbon into an impregnation liquid prepared by dissolving 0.075g of mercuric chloride, 0.5g of zinc chloride, 0.5g of copper chloride and 0.1g of potassium chloride in 7.5-9 mL of hydrochloric acid solution, quickly stirring for 10min, standing for 6h at 80 ℃, pouring off excessive water, keeping the temperature of an oven at 80 ℃ for 2h, keeping the temperature at 100 ℃ for 2h, and drying at 115 ℃ to obtain the ultralow-mercury catalyst.
In addition, in the embodiment, walnut shell activated carbon, coal-based activated carbon, coconut shell activated carbon and wood activated carbon (the mesh number of the activated carbon is 2-8 meshes, the iodine value is 850-1350, and the mechanical strength is more than 95%) are respectively selected as the activated carbon, and different activated carbon-supported ultralow-mercury catalysts are prepared.
Acetylene hydrochlorination activity evaluation was performed on ultra-low mercury catalysts prepared from different activated carbons: at the reaction temperature of 125 ℃ and the space velocity of acetylene of 30h -1 、n (C2H2) :n (HCl) The catalytic activity under the conditions of = 1.1 is shown in table 1.
TABLE 1 catalytic Activity of different activated carbon-loaded ultra-low mercury catalysts
Example 2
A preparation method of an ultra-low mercury catalyst comprises the following steps:
1) Preparing nitrogen-doped activated carbon: diluting 0.9mL of formaldehyde solution to 10mL, adjusting the pH value to 9.1 by ammonia water, adding 0.5g of dicyandiamide, stirring at 10 ℃ for 2h to obtain a clear solution, adding the clear solution into 10g of coconut shell activated carbon, keeping the temperature at 60 ℃ for 6h, drying at 115 ℃, heating to 550 ℃ at the heating rate of 2-5 ℃/min under the protection of nitrogen in an atmosphere furnace, and calcining for 4h to obtain nitrogen-doped activated carbon;
2) Preparation of ultra-low mercury catalyst: weighing 5g of nitrogen-doped activated carbon, adding the nitrogen-doped activated carbon into an impregnation solution prepared by dissolving 0.15g of mercury chloride, 0.25g of zinc chloride, 0.75g of copper chloride and 0.1g of potassium chloride in 7.5mL of hydrochloric acid solution, standing at 80 ℃ for 12h, pouring off excessive water, preserving the heat at 80 ℃ for 2h, preserving the heat at 100 ℃ for 2h in an oven, and drying at 115 ℃ to obtain the ultralow-mercury catalyst.
Evaluation of acetylene hydrochlorination Activity: the space velocity of acetylene is 30h -1 ，n (C2H2) :n (HCl) 1.1, and the catalytic activities at different reaction temperatures are shown in table 2.
TABLE 2 catalytic activity at different reaction temperatures
Example 3
A preparation method of an ultra-low mercury catalyst comprises the following steps:
1) Preparing nitrogen-doped activated carbon: regulating the pH value of 10mL of deionized water to 9.8 by triethanolamine, adding 0.38g of trioxymethylene, 0.4g of dicyandiamide, 0.05g of melamine and 0.1g of urea, stirring for 3h at 45 ℃ to obtain a clear solution, adding the clear solution into 10g of coconut shell activated carbon, keeping the temperature at 60 ℃ for 6h, drying at 115 ℃, heating to 600 ℃ at the heating rate of 2-5 ℃/min under the protection of nitrogen in an atmosphere furnace, and calcining for 2h to obtain nitrogen-doped activated carbon;
2) Preparation of ultra-low mercury catalyst: weighing 5g of nitrogen-doped activated carbon, adding the nitrogen-doped activated carbon into an impregnation solution prepared by dissolving 0.15g of mercuric chloride, 0.25g of zinc chloride, 0.75g of copper chloride and 0.1g of potassium chloride in 7.5mL of hydrochloric acid solution, standing at 80 ℃ for 12h, pouring off excessive water, keeping the temperature in an oven at 80 ℃ for 2h, keeping the temperature at 100 ℃ for 2h, and drying at 115 ℃ to obtain the ultralow-mercury catalyst.
Evaluation of acetylene hydrochlorination Activity: the space velocity of the acetylene is 100h -1 ，n (C2H2) :n (HCl) 1.1, a reaction temperature of 125 ℃, an acetylene conversion rate of 91.46% and a vinyl chloride selectivity of 99.86%.
Example 4
A preparation method of an ultra-low mercury catalyst comprises the following steps:
1) Preparing nitrogen-doped activated carbon: diluting 1mL of formaldehyde solution to 10mL, adjusting the pH value to 9.3 by triethanolamine, adding 0.4g of dicyandiamide, 0.05g of melamine and 0.1g of urea, stirring for 2h at 25 ℃ to obtain a clear solution, dropwise adding the clear solution into 10g of coconut shell activated carbon, keeping the temperature at 60 ℃ for 6h, drying at 115 ℃, heating to 600 ℃ at the heating rate of 2-5 ℃/min under the protection of nitrogen in an atmosphere furnace, and calcining for 2h to obtain nitrogen-doped activated carbon;
2) Preparation of ultra-low mercury catalyst: weighing 5g of nitrogen-doped activated carbon, adding the nitrogen-doped activated carbon into an impregnation liquid prepared by dissolving 0.125g of mercuric chloride and 0.1g of potassium chloride in 7.5mL of water, standing for 4h at 60 ℃, pouring off excessive water, and drying for 10h at 105 ℃ in an oven; then adding the mixture into an impregnation liquid prepared by dissolving 0.6g of copper chloride and 0.2g of bismuth chloride in 7mL of hydrochloric acid solution, standing for 12h at 80 ℃, pouring off excessive water, keeping the temperature of an oven for 2h at 80 ℃, keeping the temperature of 100 ℃ for 2h, and drying at 125 ℃ to obtain the ultralow-mercury catalyst.
Evaluation of acetylene hydrochlorination Activity: the space velocity of acetylene is 60h -1 ，n (C2H2) :n (HCl) 1.15, at a reaction temperature of 125 ℃, the acetylene conversion rate is 95.25%, and the vinyl chloride selectivity is 99.82%.
Example 5
A preparation method of an ultra-low mercury catalyst comprises the following steps:
1) Preparing nitrogen-doped activated carbon: diluting 0.6mL of formaldehyde solution to 10mL, adjusting the pH value to 9.1 with ammonia water, adding 0.2g of dicyandiamide and 0.3g of urea, stirring for 2h at 10 ℃ to obtain a clear solution, dropwise adding the clear solution into 10g of coconut shell activated carbon, keeping the temperature at 60 ℃ for 6h, drying at 115 ℃, heating to 550 ℃ at the heating rate of 2-5 ℃/min under the protection of argon in an atmosphere furnace, and calcining for 2h to obtain nitrogen-doped activated carbon;
2) Preparation of ultra-low mercury catalyst: weighing 5g of nitrogen-doped activated carbon, adding the nitrogen-doped activated carbon into an impregnation liquid prepared by dissolving 0.05g of mercuric chloride and 0.05g of guanidine hydrochloride in 7.5mL of deionized water, standing for 4h at 80 ℃, pouring off excessive water, and drying for 10h at 80 ℃ in an oven; adding the mixture into a steeping liquor prepared by dissolving 1g of copper chloride, 0.05g of cerium chloride and 0.1g of potassium chloride in 7.5mL of hydrochloric acid solution, standing for 12h at 80 ℃, pouring off excessive water, keeping the temperature of an oven for 2h at 80 ℃, keeping the temperature of 100 ℃ for 2h, and drying at 125 ℃ to obtain the ultralow-mercury catalyst.
Evaluation of acetylene hydrochlorination Activity: the space velocity of the acetylene is 30h -1 ，n (C2H2) :n (HCl) 1.15, at a reaction temperature of 125 ℃, the acetylene conversion is 85.38%, and the vinyl chloride selectivity is 99.84%.
In other embodiments, in the step 1), the loading amount of the amino compound is 1-10% of the mass of the activated carbon. In the step 2), the temperature of the load is 60-80 ℃, and the time of the load is 4-12 h; the adding amount of the mercuric chloride is 1 to 3 percent of the nitrogen-doped active carbon; the addition amount of the auxiliary agent is 1-20% of the nitrogen-doped activated carbon.
Claims (7)
1. A preparation method of a nitrogen-doped activated carbon-loaded ultralow-mercury catalyst is characterized by comprising the following steps of:
1) Preparing nitrogen-doped activated carbon: the preparation method comprises the following steps:
a, diluting 1.8mL of formaldehyde solution to 10-12mL, adjusting the pH value to 9.5 by triethanolamine, adding 1g of melamine, stirring and dissolving in a water bath at 60 ℃, adding into 10g of activated carbon, keeping the temperature at 60 ℃ for 10h, drying at 125 ℃, heating to 850 ℃ at the heating rate of 2-5 ℃/min under the protection of nitrogen in an atmosphere furnace, and calcining for 2h to obtain nitrogen-doped activated carbon;
diluting 0.9mL of formaldehyde solution to 10mL, adjusting the pH value to 9.1 by ammonia water, adding 0.5g of dicyandiamide, stirring at 10 ℃ for 2h to obtain a clear solution, adding the clear solution into 10g of coconut shell activated carbon, keeping the temperature at 60 ℃ for 6h, drying at 115 ℃, heating to 550 ℃ at the heating rate of 2-5 ℃/min under the protection of nitrogen in an atmosphere furnace, and calcining for 4h to obtain nitrogen-doped activated carbon;
c: regulating the pH value of 10mL of deionized water to 9.8 by triethanolamine, adding 0.38g of trioxymethylene, 0.4g of dicyandiamide, 0.05g of melamine and 0.1g of urea, stirring for 3h at 45 ℃ to obtain a clear solution, adding the clear solution into 10g of coconut shell activated carbon, keeping the temperature at 60 ℃ for 6h, drying at 115 ℃, heating to 600 ℃ at the heating rate of 2 to 5 ℃/min under the protection of nitrogen in an atmosphere furnace, and calcining for 2h to obtain nitrogen-doped activated carbon;
d: diluting 1mL of formaldehyde solution to 10mL, adjusting the pH value to 9.3 by triethanolamine, adding 0.4g of dicyandiamide, 0.05g of melamine and 0.1g of urea, stirring for 2h at 25 ℃ to obtain a clear solution, dropwise adding the clear solution into 10g of coconut shell activated carbon, keeping the temperature at 60 ℃ for 6h, drying at 115 ℃, heating to 600 ℃ at the heating rate of 2-5 ℃/min under the protection of nitrogen in an atmosphere furnace, and calcining for 2h to obtain nitrogen-doped activated carbon;
diluting 0.6mL of formaldehyde solution to 10mL, adjusting the pH value to 9.1 by ammonia water, adding 0.2g of dicyandiamide and 0.3g of urea, stirring for 2h at 10 ℃ to obtain a clear solution, dropwise adding the clear solution into 10g of coconut shell activated carbon, keeping the temperature at 60 ℃ for 6h, drying at 115 ℃, heating to 550 ℃ at the heating rate of 2-5 ℃/min under the protection of argon in an atmosphere furnace, and calcining for 2h to obtain nitrogen-doped activated carbon;
A. in the B, the D and the E, the mass fraction of the formaldehyde solution is 37 to 40 percent;
2) Preparation of ultra-low mercury catalyst: loading mercury chloride and an auxiliary agent on the nitrogen-doped activated carbon obtained in the step 1), and drying to obtain the nitrogen-doped activated carbon; the adding amount of the mercuric chloride is 1 to 3 percent of the mass of the nitrogen-doped activated carbon;
the addition amount of the auxiliary agent is 1 to 20 percent of the mass of the nitrogen-doped activated carbon; the auxiliary agent is a mixture of one or more of chlorides of copper, bismuth, zinc, cerium and potassium and triethylamine hydrochloride, tetraalkylammonium chloride, pyridine hydrochloride and guanidine hydrochloride.
2. The method for preparing the nitrogen-doped activated carbon-supported ultralow-mercury catalyst according to claim 1, wherein in the step 2), the loading temperature is 60-80 ℃, the loading time is 4-12h, gradient drying is adopted, the temperature is firstly preserved for 1-2h at 80 ℃, then preserved for 1-2h at 100 ℃, and then drying is carried out at 105-125 ℃.
3. The preparation method of the nitrogen-doped activated carbon-supported ultralow-mercury catalyst according to claim 1, wherein the loading method in the step 2) is to sequentially load mercury chloride and an auxiliary agent, and the specific steps are as follows: putting the nitrogen-doped activated carbon into a mercuric chloride solution, preserving the heat for 4-12h at the temperature of 60-80 ℃, and drying at the temperature of 80-105 ℃ to obtain the mercuric chloride-loaded nitrogen-doped activated carbon; and adding the nitrogen-doped activated carbon loaded with mercury chloride into an auxiliary agent solution, and keeping the temperature at 60 to 80 ℃ for 4 to 12h to complete loading.
4. The preparation method of the nitrogen-doped activated carbon supported ultralow-mercury catalyst according to claim 1, wherein the loading method in the step 2) is to load mercury chloride and an auxiliary agent at the same time, and the specific steps are as follows: and adding nitrogen-doped activated carbon into an impregnation liquid prepared from mercuric chloride and an auxiliary agent, and carrying out heat preservation at 60-80 ℃ for 4-12h to finish loading.
5. The preparation method of the nitrogen-doped activated carbon-supported ultralow-mercury catalyst as claimed in claim 1, wherein in the step 2), the loading method comprises the steps of loading mercury chloride and part of the auxiliary agent and then loading the rest of the auxiliary agent, and comprises the following specific steps: adding nitrogen-doped activated carbon into an impregnation liquid prepared from mercuric chloride and a part of auxiliary agent, preserving heat for 4-12h at the temperature of 60-80 ℃, and drying at the temperature of 80-105 ℃ to obtain the mercuric chloride-loaded nitrogen-doped activated carbon; and adding the nitrogen-doped activated carbon loaded with mercuric chloride and part of the auxiliary agent into an impregnation liquid prepared from the rest auxiliary agents, and preserving the heat for 4-12h at the temperature of 60-80 ℃ to complete the loading.
6. The nitrogen-doped activated carbon-supported ultra-low mercury catalyst product prepared by the preparation method of any one of claims 1 to 5.
7. The application of the nitrogen-doped activated carbon-loaded ultralow-mercury catalyst product in the reaction of synthesizing vinyl chloride through acetylene hydrochlorination, which is disclosed by claim 6, is characterized in that the catalytic reaction is carried out in a fixed bed reactor, and the space velocity of acetylene is 20-300h -1 The molar ratio of the reaction gas isn (C2H2) :n (HCl) 1.05 to 1.2, and the reaction temperature is 90 to 140 ℃.
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