CN115722219B - Granular carbon material supported gold catalyst, preparation method thereof and application thereof in reaction of preparing chloroethylene by hydrochlorination of acetylene - Google Patents

Granular carbon material supported gold catalyst, preparation method thereof and application thereof in reaction of preparing chloroethylene by hydrochlorination of acetylene Download PDF

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CN115722219B
CN115722219B CN202211421135.6A CN202211421135A CN115722219B CN 115722219 B CN115722219 B CN 115722219B CN 202211421135 A CN202211421135 A CN 202211421135A CN 115722219 B CN115722219 B CN 115722219B
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acetylene
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CN115722219A (en
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蓝国钧
周守杰
李瑛�
邱一洋
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses a granular carbon material supported gold catalyst, a preparation method thereof and application thereof in the reaction of preparing chloroethylene by hydrochlorination of acetylene. According to the catalyst disclosed by the invention, the active component is introduced into the catalyst by utilizing the powdery carbon material in the forming process, and through the interaction between the coordination functional group in the adhesive and gold in the forming process, gold species in the catalyst are well dispersed, so that active sites in the catalyst are increased, and the acetylene hydrochlorination activity and stability of the gold catalyst are further improved. According to the preparation method, the powdered carbon is directly prepared into the formed catalyst for acetylene hydrochlorination of a fixed bed, the operation of the production process is simple, the method can be used for continuous production, no waste liquid is generated in the production process, and the method is an environment-friendly process.

Description

Granular carbon material supported gold catalyst, preparation method thereof and application thereof in reaction of preparing chloroethylene by hydrochlorination of acetylene
Technical Field
The invention belongs to the technical field of catalyst preparation and application, and particularly relates to a granular carbon material supported gold catalyst, a preparation method thereof and application thereof in a reaction for preparing vinyl chloride by hydrochlorination of acetylene.
Background
Polyvinyl chloride is one of five general resin materials (polyethylene, polyvinyl chloride, ABS, polystyrene and polypropylene) in the world, and has wide application in industries such as industry, agriculture, packaging and the like. Because of the energy structure of rich coal, less oil and gas, the acetylene hydrochlorination method is a main production means of the chloroethylene industry. The catalyst of the current acetylene hydrochlorination method is an activated carbon supported mercury chloride catalyst, and the mercury chloride is easy to volatilize and run off and has high toxicity, thus bringing great threat to environmental protection and human health.
Gold catalyst is considered as a promising acetylene hydrogen chloride catalyst for replacing mercury chloride catalyst because of its high activity and non-toxicity. The activity of gold catalysts in vinyl chloride synthesis depends on the presence or absence of highly dispersed gold species of high valence in the catalyst. In order to obtain gold in a high valence state, a large amount of previous work has demonstrated that a high activity Au/C catalyst can be obtained using conventional aqua regia as an impregnating solvent. However, the preparation process has strong corrosiveness and high risk, and has serious influence on the production environment of the catalyst, thereby threatening the safety of the catalyst preparation process. Au/C catalysts prepared using aqua regia generally require about 500 kg aqua regia per ton of catalyst produced. The handling, recovery and disposal of these aqua regia would be a significant economic and technical challenge, which severely hampers the commercialization of gold catalysts. In order to find other schemes of green solvents capable of replacing aqua regia, extensive researches have been developed in recent years, for example, an organic aqua regia obtained by mixing N, N-dimethylformamide and thionyl chloride is used as a solvent to prepare a gold catalyst with a high gold proportion. However, the solvent such as thionyl chloride still has strong corrosiveness and strong toxicity, and the harsh conditions for preparing the gold catalyst are not improved. Complexing cationic gold with different ligands or ionic liquids to form a gold complex is another strategy to stabilize the gold valence state. Although gold catalysts with high gold ratios can be prepared using ionic liquids and organic ligands to stabilize gold complexes, the price and stability of the organic ligands remains a problem.
In addition, the reaction of acetylene with hydrogen chloride to produce vinyl chloride is a large tonnage industrial process, and a fixed bed reactor is currently used, and the acetylene hydrochlorination industrial catalyst is required to be granular and have certain crushing strength. Therefore, the current method for preparing the acetylene hydrochlorination catalyst mainly uses granular active carbon as a carrier, and adopts a soaking/dipping method to prepare the carbon material supported metal catalyst. However, as the diffusion speeds of the metal active component and the auxiliary agent on the millimeter-sized solid particles are different, and the solvent vapor can enrich the metal component on the surfaces of the particles in the drying process, the dispersity of the metal active component is low, and the metal utilization rate is low. In addition, the soaking/impregnating method of the solid particle catalyst is carried out intermittently, continuous production cannot be carried out, and the production efficiency is low. Chinese patent CN113976112B discloses a method for preparing a gold catalyst using a continuous flow device, however, the activated carbon carrier adopted in the patent is 200 mesh powdered activated carbon, which cannot be applied in actual industrial production of vinyl chloride.
In summary, the acetylene hydrochlorination catalyst loaded by the granular carbon material for obtaining the highly dispersed gold species is complex in preparation process, complex in steps, strong in corrosiveness of the used solvent and high in production cost. Therefore, it is especially important to develop a preparation method which can obtain high dispersion of metal active components, has simple process, green process and lower production cost.
Disclosure of Invention
The invention aims at providing a preparation method of a granular carbon material supported gold catalyst. The granular carbon material supported gold catalyst with highly dispersed metal components is prepared simply and efficiently by taking a powdery carbon material as a carbon carrier and taking an adhesive with chelating/coordination functions on metal ions as a dispersing aid. Active components are introduced into the powdered carbon during molding, and gold species are highly dispersed in granular active carbon by utilizing the interaction of rich chelating functional groups in the binder and gold. The water is used as a solvent, a highly corrosive solvent is not needed in the preparation process, and the acetylene hydrochlorination catalyst suitable for the fixed bed reactor is continuously prepared.
Another object of the present invention is to provide a gold catalyst prepared by the preparation method and its use in the reaction of hydrochlorination of acetylene to produce vinyl chloride, which has excellent activity of hydrochlorination of acetylene and extremely low deactivation rate during the reaction of 200 hours.
The preparation method of the granular carbon material supported gold catalyst comprises the following steps:
1) Dissolving gold precursor in water to obtain impregnating solution A, mixing adhesive in water to obtain adhesive solution B, and then mixing the impregnating solution A and the solution B to obtain solution C;
2) Uniformly mixing the solution C with the powdery carbon material, extruding, forming and drying to obtain a gold catalyst precursor D;
3) And carrying out heat treatment on the gold catalyst precursor D under the condition of inert gas, and finally cooling to room temperature to obtain the gold catalyst.
The preparation method of the granular carbon material supported gold catalyst is characterized in that the gold precursor is one or a mixture of a plurality of water-soluble gold salts such as chloroauric acid, potassium chloroaurate, sodium gold thiosulfate and the like.
The preparation method of the granular carbon material supported gold catalyst is characterized in that the organic ligand is one or a mixture of humic acid and salts thereof, alginic acid and salts thereof, tannic acid and salts thereof, carboxymethyl cellulose and salts thereof, sucrose, starch and maltodextrin, and the mass ratio of the adhesive to the gold precursor is 50-150:1, preferably 80-120:1. These binders have abundant coordinating groups that can undergo sufficient complexing coordination with the gold precursor to promote dispersion of the gold species in the catalyst; and secondly, the adhesives have large molecular weight, complex branched chains and rich oxygen-containing functional groups, have strong cohesive force, and can effectively bond the powdered carbon particles together after being fully mixed with the powdered carbon, so that the granular carbon material with macroscopic size is obtained after extrusion molding.
The preparation method of the granular carbon material supported gold catalyst is characterized in that the powdery carbon material is one or a mixture of more than 200 meshes of activated carbon, graphene, carbon nano tubes, carbon black and graphite, and the mass ratio of the powdery carbon material to gold precursor is 300-800:1, preferably 450-550:1. In the preparation process, as the mesh number of the carbon material is more than 200 meshes of powdery particles, compared with the impregnation with granular activated carbon, the gold precursor and the carbon material can be easily and uniformly mixed, so that the dispersion of gold species in the catalyst can be obviously improved; and secondly, the preparation process does not need an impregnation stage, no redundant waste liquid and no toxic or harmful solvent are generated, the production process can be continuously operated, and the process is simple, so that the preparation process is a green production process.
The preparation method of the granular carbon material supported gold catalyst is characterized in that the drying temperature in the step 2) is 50-200 ℃ and the drying time is 5-14 h.
The preparation method of the granular carbon material supported gold catalyst is characterized in that the roasting temperature in the step 3) is 400-1200 ℃, and the roasting treatment time is 1-5 h. After treatment at a certain temperature, the organic ligand can be converted into a porous carbon material, and the carbon material defect site anchors gold through heat treatment, so that chemical adsorption is formed, and the heat stability of the gold catalyst is improved; and the carbon skeleton formed by the adhesive after heat treatment in inert atmosphere and the powdery carbon material are mutually supported to form high-strength macroscopic particles, so that the adhesive has good strength and is suitable for a fixed bed reaction process of acetylene hydrochlorination.
The granular carbon material supported gold catalyst provided by the invention can be well applied to the reaction of preparing chloroethylene by hydrochlorination of acetylene, the hydrochlorination catalytic reaction of acetylene is carried out in a fixed bed continuous flow reactor, hydrogen chloride and acetylene gas are introduced after the catalyst is filled in the reactor and heated to the reaction temperature, the reaction temperature is 140-240 ℃, the space velocity of acetylene is 30-200 h -1, and the feeding volume ratio of the hydrogen chloride gas to the acetylene is 0.8-1.5:1.
Compared with the prior art, the invention has the following beneficial effects:
(1) Compared with a method of impregnating gold species with granular activated carbon, the method of the invention has the advantages that compared with the method of impregnating gold species with granular activated carbon, the method of using powdered carbon to introduce active components in the forming process of the catalyst can easily and uniformly mix gold precursors and carbon materials, thereby remarkably improving the dispersion of gold species on the activated carbon particles and further improving the acetylene hydrochlorination activity of the gold catalyst.
(2) According to the preparation method disclosed by the invention, the gold species and the carrier have strong interaction force through coordination complexing of rich coordination functional groups in the molecular structure of the adhesive in the forming process, so that the gold species are well dispersed on the pore channel surface of the carbon material, and the gold catalyst has excellent stability.
(3) The preparation method directly prepares the powdery carbon material into the formed catalyst for the fixed bed reaction of industrial acetylene hydrochlorination, has simple operation in the production process, can be used for continuous production, takes a small amount of water as a solvent, and has no waste liquid.
Drawings
FIG. 1 is a transmission electron microscope image of a gold catalyst of example 1;
FIG. 2 is a transmission electron microscope image of the gold catalyst of comparative example 1;
FIG. 3 is a graph showing the activity of the gold catalyst of example 1 in terms of acetylene hydrochlorination over time;
FIG. 4 is a graph showing the activity of the gold catalyst of comparative example 1 in terms of time for acetylene hydrochlorination;
FIG. 5 is a graph showing the time-dependent hydrochlorination activity of acetylene over the gold catalyst of comparative example 3.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
50G of chloroauric acid is weighed, and 5L of water is added to prepare 10g/L chloroauric acid solution.
Weighing 5kg of potassium humate, drying in a drying furnace at 120 ℃ for 2 hours, dispersing in 5L of water, and uniformly stirring. Slowly adding 5L of chloroauric acid solution into the prepared potassium humate solution, and uniformly stirring and mixing; weighing 25kg of powdery active carbon with the mesh number of more than 200 and the specific surface area of 1500m 2/g, drying for 2 hours in a drying furnace at 120 ℃, then uniformly mixing and stirring the mixed aqueous solution of chloroauric acid and potassium humate with the dried active carbon, and extruding for molding; drying the extruded catalyst precursor, setting the drying temperature to be 100 ℃, and drying for 9 hours; and (3) delivering the dried catalyst into a rotary furnace, roasting under the nitrogen condition, wherein the roasting temperature is 700 ℃, the heating rate is 6 ℃/min, heating from room temperature to the roasting temperature, carrying out constant-temperature heat treatment for 2 hours at the temperature, and naturally cooling to the room temperature to obtain the formed carbon-supported gold catalyst with the gold content of 0.1%.
A transmission electron microscope image of the gold catalyst prepared in example 1 is shown in FIG. 1. From the figure, it can be seen that gold in the gold catalyst is dispersed uniformly in the carbon support.
Example 2
50G of potassium chloroaurate was weighed and 5L of water was added to prepare a 10g/L potassium chloroaurate solution.
Weighing 5kg of potassium humate, drying in a drying furnace at 120 ℃ for 2 hours, dispersing in 5L of water, and uniformly stirring; slowly adding 5L of potassium chloroaurate solution into the prepared potassium humate solution, and uniformly stirring and mixing; weighing 25kg of powdery active carbon with the mesh number of more than 200 and the specific surface area of 1500m 2/g, drying for 2 hours in a drying furnace at 120 ℃, then mixing and stirring uniformly the mixed aqueous solution of potassium chloroaurate and potassium humate with the dried active carbon, and extruding for molding; drying the extruded catalyst precursor, setting the drying temperature to be 100 ℃, and drying for 9 hours; and (3) delivering the dried catalyst into a rotary furnace, roasting under the nitrogen condition, wherein the roasting temperature is 700 ℃, the heating rate is 6 ℃/min, heating from room temperature to the roasting temperature, carrying out constant-temperature heat treatment for 2 hours at the temperature, and naturally cooling to the room temperature to obtain the formed carbon-supported gold catalyst with the gold content of 0.1%.
Example 3
50G of potassium chloroaurate was weighed and 5L of water was added to prepare a 10g/L potassium chloroaurate solution.
Weighing 5kg of tannic acid, drying in a drying furnace at 120 ℃ for 2 hours, dispersing in 5L of water, and uniformly stirring; slowly adding 5L potassium chloroaurate solution into the prepared tannic acid solution, and stirring and mixing uniformly; weighing 25kg of powdery active carbon with the mesh number of more than 200 and the specific surface area of 1500m 2/g, drying for 2 hours in a drying furnace at 120 ℃, then mixing and stirring uniformly the mixed aqueous solution of potassium chloroaurate and tannic acid and the dried active carbon, and extruding for molding; drying the extruded catalyst precursor, setting the drying temperature to be 100 ℃, and drying for 9 hours; and (3) delivering the dried catalyst into a rotary furnace, roasting under the nitrogen condition, wherein the roasting temperature is 700 ℃, the heating rate is 6 ℃/min, heating from room temperature to the roasting temperature, carrying out constant-temperature heat treatment for 2 hours at the temperature, and naturally cooling to the room temperature to obtain the formed carbon-supported gold catalyst with the gold content of 0.1%.
Example 4
50G of potassium chloroaurate was weighed and 5L of water was added to prepare a 10g/L potassium chloroaurate solution.
Weighing 5kg of tannic acid, drying in a drying furnace at 120 ℃ for 2 hours, dispersing in 5L of water, and uniformly stirring; slowly adding 5L potassium chloroaurate solution into the prepared tannic acid solution, and stirring and mixing uniformly; weighing 25kg of powdery carbon black with the mesh number of more than 300 and the specific surface area of 500m 2/g, drying for 2 hours in a drying furnace at 120 ℃, then uniformly mixing and stirring the mixed aqueous solution of potassium chloroaurate and tannic acid with the dried carbon black, and extruding for molding; drying the extruded catalyst precursor, setting the drying temperature to be 100 ℃, and drying for 9 hours; and (3) delivering the dried catalyst into a rotary furnace, roasting under the nitrogen condition, wherein the roasting temperature is 700 ℃, the heating rate is 6 ℃/min, heating from room temperature to the roasting temperature, carrying out constant-temperature heat treatment for 2 hours at the temperature, and naturally cooling to the room temperature to obtain the formed carbon-supported gold catalyst with the gold content of 0.1%.
Example 5
50G of potassium chloroaurate was weighed and 5L of water was added to prepare a 10g/L potassium chloroaurate solution.
Weighing 5kg of potassium humate, drying in a drying furnace at 120 ℃ for 2 hours, dispersing in 5L of water, and uniformly stirring; slowly adding 5L of potassium chloroaurate solution into the prepared potassium humate solution, and uniformly stirring and mixing; weighing 25kg of powdery active carbon with the mesh number of more than 200 and the specific surface area of 1200m 2/g, drying for 2 hours in a drying furnace at 120 ℃, then mixing and stirring uniformly the mixed aqueous solution of potassium chloroaurate and potassium humate with the dried active carbon, and extruding for molding; drying the extruded catalyst precursor, setting the drying temperature to be 100 ℃, and drying for 9 hours; and (3) delivering the dried catalyst into a rotary furnace, roasting at the temperature of 900 ℃ and the heating rate of 6 ℃/min under the condition of nitrogen, heating from room temperature to the roasting temperature, carrying out constant-temperature heat treatment for 2 hours at the temperature, and naturally cooling to the room temperature to obtain the formed carbon-supported gold catalyst with the gold content of 0.1%.
Example 6
50G of potassium chloroaurate was weighed and 5L of water was added to prepare a 10g/L potassium chloroaurate solution.
Weighing 5kg of potassium humate, drying in a drying furnace at 120 ℃ for 2 hours, dispersing in 5L of water, and uniformly stirring; slowly adding 5L of potassium chloroaurate solution into the prepared potassium humate solution, and uniformly stirring and mixing; weighing 25kg of powdery active carbon with the mesh number of more than 200 and the specific surface area of 1200m 2/g, drying for 2 hours in a drying furnace at 120 ℃, then mixing and stirring uniformly the mixed aqueous solution of potassium chloroaurate and potassium humate with the dried active carbon, and extruding for molding; drying the extruded catalyst precursor, setting the drying temperature to be 150 ℃, and drying for 9 hours; and (3) delivering the dried catalyst into a rotary furnace, roasting under the nitrogen condition, wherein the roasting temperature is 700 ℃, the heating rate is 6 ℃/min, heating from room temperature to the roasting temperature, carrying out constant-temperature heat treatment for 2 hours at the temperature, and naturally cooling to the room temperature to obtain the formed carbon-supported gold catalyst with the gold content of 0.1%.
Comparative example 1
Weighing 5kg of potassium humate, drying in a drying furnace at 120 ℃ for 2 hours, dispersing in 10L of water, and uniformly stirring; weighing 25kg of powdery active carbon with the mesh number of more than 200 and the specific surface area of 1500m 2/g, drying for 2 hours in a drying furnace at 120 ℃, then uniformly mixing and stirring the aqueous solution of the potassium humate and the active carbon, and extruding for molding; drying the extruded catalyst precursor, setting the drying temperature to be 150 ℃, and drying for 9 hours; the dried catalyst is sent into a rotary furnace to be roasted under the condition of nitrogen, the roasting temperature is 700 ℃, the heating rate is 6 ℃/min, the temperature is raised from room temperature to the roasting temperature, the constant temperature heat treatment is carried out for 2 hours at the temperature, and the catalyst is naturally cooled to the room temperature, so as to obtain the active carbon carrier; then accurately weighing 21.28g of chloroauric acid, dissolving with water to prepare 10g/L of chloroauric acid solution, loading the solution onto 10kg of the prepared active carbon carrier by adopting an isovolumetric impregnation method, impregnating the carrier for 12 hours at room temperature, and drying the carrier for 8 hours at 120 ℃ to obtain the gold catalyst with the mass fraction of gold of 0.1%.
A transmission electron microscope image of the gold catalyst prepared in comparative example 1 is shown in FIG. 2. From fig. 2, it can be seen that gold particles in the gold catalyst are larger and the dispersibility is poor.
Comparative example 2
Taking 10kg of columnar activated carbon with the grain diameter of 3-5mm and the specific surface area of 1200m 2/g in the market as a catalyst carrier, sending the catalyst carrier into a drying furnace for drying, setting the drying temperature to 150 ℃, drying for 5h, naturally cooling, and storing in a closed container for later use; accurately weighing 21.28g of chloroauric acid, dissolving with water to prepare 10g/L of chloroauric acid solution, loading the solution onto 10kg of active carbon by adopting an isovolumetric impregnation method, impregnating the solution for 12 hours at room temperature, and drying the solution for 8 hours at 120 ℃ to obtain the commercial columnar active carbon-loaded gold catalyst with the gold mass fraction of 0.1%.
Comparative example 3
Taking 10kg of commercial powdery active carbon with the mesh number of more than 200 and the specific surface area of 1500m 2/g as a catalyst carrier, sending the catalyst carrier into a drying furnace for drying, setting the drying temperature to 150 ℃, drying for 5 hours, naturally cooling and then storing in a closed container for standby; accurately weighing 34.05g of chloroauric acid, dissolving with water to prepare 16g/L of chloroauric acid solution, loading the solution onto 10kg of active carbon by adopting an isovolumetric impregnation method, impregnating the solution for 12 hours at room temperature, and drying the solution for 8 hours at 120 ℃ to obtain the powdered carbon-loaded gold catalyst with the gold mass fraction of 0.16%.
Weighing 0.5kg of potassium humate, drying in a drying furnace at 120 ℃ for 2 hours, dispersing in 1L of water, and uniformly stirring; weighing 2.5kg of powdered carbon supported gold catalyst with the mass fraction of 0.16%, placing the powdered carbon supported gold catalyst in a drying furnace at 120 ℃ for drying for 2 hours, then uniformly mixing and stirring the aqueous solution of potassium humate and the powdered carbon supported gold catalyst, and extruding for molding; drying the extruded catalyst precursor, setting the drying temperature to be 150 ℃, and drying for 9 hours; and (3) sending the dried catalyst into a rotary furnace, roasting under the nitrogen condition, wherein the roasting temperature is 700 ℃, the heating rate is 6 ℃/min, heating from room temperature to the roasting temperature, carrying out constant-temperature heat treatment for 2 hours at the temperature, and naturally cooling to the room temperature to obtain the gold catalyst with the mass fraction of 0.1%.
The gold catalysts prepared in examples 1 to 6 and comparative examples 1 to 3 were used for the performance test and the mechanical strength test of vinyl chloride production by the acetylene method of calcium carbide, respectively. The catalytic performance of the acetylene hydrochlorination reaction was evaluated in a fixed bed continuous flow reactor. Before the reaction, the temperature is raised to 180 ℃ at 10 ℃/min under the protection of nitrogen, and the water and air in the catalyst are removed. Then switching to hydrogen chloride gas, and pretreating the catalyst through a reaction tube for 0.5h. Subsequently, acetylene and hydrogen chloride were simultaneously introduced into the reactor at a reaction temperature of 180℃and an acetylene space velocity of 100h -1, with a feed volume ratio V HCl/VC2H2 of 1.1. Finally, unreacted hydrogen chloride is removed from the reacted mixed gas through sodium hydroxide solution, and the tail gas is analyzed by adopting a gas chromatograph and being matched with an FID detector and a GDX-301 chromatographic column, wherein the specific data are shown in table 1.
TABLE 1
Deactivation rate [ a ] = (acetylene conversion for 5h reaction-acetylene conversion for 30h reaction)/25 h x 100%;
Acetylene conversion [a] = acetylene conversion for 5h of reaction.
Wherein, the time-dependent curve of the acetylene hydrochlorination activity of the gold catalyst of example 1 is shown in FIG. 3, the time-dependent curve of the acetylene hydrochlorination activity of the gold catalyst of comparative example 1 is shown in FIG. 4, and the time-dependent curve of the acetylene hydrochlorination activity of the gold catalyst of comparative example 3 is shown in FIG. 5.
After the binder is molded in comparative example 1, the carbon-supported gold catalyst is prepared by an impregnation method, and the active component gold of the prepared catalyst cannot be well dispersed on the carbon carrier due to diffusion influence, so that the stability of the catalyst is poor. Similar problems exist in the commercial char of comparative example 2. The carbon-supported gold catalyst prepared in comparative example 3 was impregnated and then molded, and the active component gold was heat-treated to cause agglomeration of gold particles due to weak force of the binder ligand with gold already supported in the powdery carbon material, and the active stability of comparative example 3 was poor due to direct coverage of the binder carbonized on the surface of the active center. Example 1 well solves the problems in the preparation process, and the high-activity high-stability carbon-supported gold catalyst is prepared.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.

Claims (8)

1. The preparation method of the granular carbon material supported gold catalyst is characterized by comprising the following steps of:
1) Dissolving gold precursor in water to obtain impregnating solution A, mixing adhesive in water to obtain adhesive solution B, and then mixing the impregnating solution A and the solution B to obtain solution C;
2) Uniformly mixing the solution C with the powdery carbon material, extruding, forming and drying to obtain a gold catalyst precursor D;
3) Carrying out heat treatment on the gold catalyst precursor D under the condition of inert gas, and finally cooling to room temperature to obtain the gold catalyst loaded by the granular carbon material;
the adhesive is one or a mixture of humic acid and salts thereof, alginic acid and salts thereof, tannic acid and salts thereof, and the mass ratio of the adhesive to the gold precursor is 50-150:1;
The powdery carbon material is one or a mixture of more than one of active carbon, graphene, carbon nano tube, carbon black and graphite, the mesh number of powdery particles is more than 200 meshes, and the mass ratio of the powdery carbon material to the gold precursor is 300-800:1;
And 3) roasting at 700-1200 ℃ for 1-5 hours.
2. The method for preparing the granular carbon material supported gold catalyst according to claim 1, wherein the gold precursor is one or a mixture of more of chloroauric acid, potassium chloroaurate, sodium chloroaurate and sodium gold thiosulfate.
3. The method for preparing the granular carbon material supported gold catalyst according to claim 1, wherein the mass ratio of the binder to the gold precursor is 80-120:1.
4. The method for preparing the granular carbon material supported gold catalyst according to claim 1, wherein the mass ratio of the powdery carbon material to the gold precursor is 450-550:1.
5. The method for preparing the granular carbon material supported gold catalyst according to claim 1, wherein the drying temperature in the step 2) is 50-200 ℃ and the drying time is 5-14 h.
6. A granular carbon material supported gold catalyst prepared by the method of any one of claims 1 to 5.
7. The use of a granular carbon material supported gold catalyst according to claim 6 in the hydrochlorination of acetylene to produce vinyl chloride.
8. The use according to claim 7, wherein the hydrochlorination of acetylene is carried out in a fixed bed continuous flow reactor, hydrogen chloride and acetylene gas are introduced after the catalyst is filled in the reactor and heated to a reaction temperature of 140-240 ℃, the space velocity of acetylene is 30-200 h -1, and the feed volume ratio of the hydrogen chloride gas to the acetylene is 0.8-1.5:1.
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Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB807581A (en) * 1955-11-23 1959-01-21 Fairweather Harold G C Production of alkynols and alkynediols
JP2008238161A (en) * 2007-02-27 2008-10-09 Sumitomo Chemical Co Ltd Method for manufacturing catalyst
CN103170363A (en) * 2011-12-21 2013-06-26 冯良荣 Catalyst for preparing chloroethylene by acetylene hydrochlorination
CN104801345A (en) * 2015-03-31 2015-07-29 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) Supported type mercury-free catalyst for chloroethylene production with acetylene hydrochlorination method
CN105107498A (en) * 2015-09-15 2015-12-02 浙江工业大学 Method for preparing carbon-loaded gold catalyst and application of catalyst
CN105126833A (en) * 2015-07-28 2015-12-09 浙江工业大学 Ruthenium-carbon catalyst and its use in acetylene hydrochlorination preparation of vinyl chloride
CN107115883A (en) * 2017-05-16 2017-09-01 浙江工业大学 A kind of starch base N doping mesopore forming charcoal and preparation method and application
CN107715883A (en) * 2017-10-26 2018-02-23 青岛大学 A kind of Ni3The preparation method of FeN@graphenes/marine alga aeroge elctro-catalyst
CN109364917A (en) * 2018-09-12 2019-02-22 浙江工业大学 A kind of N doping charcoal metal supported catalyst and its preparation method and application
CN109967125A (en) * 2019-03-20 2019-07-05 浙江大学 Monodispersed metal-tannic acid cladding activation carbon cloth catalyst and its preparation method and application
CN110116000A (en) * 2019-04-04 2019-08-13 杭州师范大学 A kind of sludge carbon-supported catalysts and its preparation method and application
CN110201663A (en) * 2019-05-28 2019-09-06 浙江大学 A kind of selective hydrocatalyst is in hydrogenation reaction as the application of catalyst
CN111203278A (en) * 2020-03-05 2020-05-29 石河子大学 Metal complex catalyst for catalyzing hydrochlorination of acetylene and preparation method and application thereof
CN111330621A (en) * 2020-03-18 2020-06-26 鄂尔多斯市瀚博科技有限公司 Supported mercury-free catalyst for synthesizing chloroethylene and preparation method thereof
CN111437807A (en) * 2020-02-29 2020-07-24 浙江工业大学 Preparation of porous heteroelement modified two-dimensional carbon material and application of porous heteroelement modified two-dimensional carbon material in vinyl chloride synthesis reaction
EP3793951A1 (en) * 2018-05-15 2021-03-24 Imperial College Of Science Technology And Medecine Catalytic materials for wastewater treatment
CN112547057A (en) * 2020-12-11 2021-03-26 浙江工业大学 Gold catalyst for producing vinyl chloride monomer by calcium carbide method and preparation method thereof
WO2021236586A1 (en) * 2020-05-18 2021-11-25 Archer-Daniels-Midland Company Processes for the hydrogenolysis of glycerol

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG11201607687WA (en) * 2014-04-29 2016-10-28 Rennovia Inc Carbon black based shaped porous products

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB807581A (en) * 1955-11-23 1959-01-21 Fairweather Harold G C Production of alkynols and alkynediols
JP2008238161A (en) * 2007-02-27 2008-10-09 Sumitomo Chemical Co Ltd Method for manufacturing catalyst
CN103170363A (en) * 2011-12-21 2013-06-26 冯良荣 Catalyst for preparing chloroethylene by acetylene hydrochlorination
CN104801345A (en) * 2015-03-31 2015-07-29 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) Supported type mercury-free catalyst for chloroethylene production with acetylene hydrochlorination method
CN105126833A (en) * 2015-07-28 2015-12-09 浙江工业大学 Ruthenium-carbon catalyst and its use in acetylene hydrochlorination preparation of vinyl chloride
CN105107498A (en) * 2015-09-15 2015-12-02 浙江工业大学 Method for preparing carbon-loaded gold catalyst and application of catalyst
CN107115883A (en) * 2017-05-16 2017-09-01 浙江工业大学 A kind of starch base N doping mesopore forming charcoal and preparation method and application
CN107715883A (en) * 2017-10-26 2018-02-23 青岛大学 A kind of Ni3The preparation method of FeN@graphenes/marine alga aeroge elctro-catalyst
EP3793951A1 (en) * 2018-05-15 2021-03-24 Imperial College Of Science Technology And Medecine Catalytic materials for wastewater treatment
CN109364917A (en) * 2018-09-12 2019-02-22 浙江工业大学 A kind of N doping charcoal metal supported catalyst and its preparation method and application
CN109967125A (en) * 2019-03-20 2019-07-05 浙江大学 Monodispersed metal-tannic acid cladding activation carbon cloth catalyst and its preparation method and application
CN110116000A (en) * 2019-04-04 2019-08-13 杭州师范大学 A kind of sludge carbon-supported catalysts and its preparation method and application
CN110201663A (en) * 2019-05-28 2019-09-06 浙江大学 A kind of selective hydrocatalyst is in hydrogenation reaction as the application of catalyst
CN111437807A (en) * 2020-02-29 2020-07-24 浙江工业大学 Preparation of porous heteroelement modified two-dimensional carbon material and application of porous heteroelement modified two-dimensional carbon material in vinyl chloride synthesis reaction
CN111203278A (en) * 2020-03-05 2020-05-29 石河子大学 Metal complex catalyst for catalyzing hydrochlorination of acetylene and preparation method and application thereof
CN111330621A (en) * 2020-03-18 2020-06-26 鄂尔多斯市瀚博科技有限公司 Supported mercury-free catalyst for synthesizing chloroethylene and preparation method thereof
WO2021236586A1 (en) * 2020-05-18 2021-11-25 Archer-Daniels-Midland Company Processes for the hydrogenolysis of glycerol
CN112547057A (en) * 2020-12-11 2021-03-26 浙江工业大学 Gold catalyst for producing vinyl chloride monomer by calcium carbide method and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Carbon-Supported Au Catalyst in Acetylene Hydrochlorination: Enhancing Catalytic Performance by Complexation of Dicarbonyl Ligands;Xianliang Qiao et al.;《ChemCatChem》(第14期);1-10 *
煤质柱状活性炭的尿素改性及其乙炔氢氯化性能;王言等;《化学反应工程与工艺》;第33卷(第4期);298-311 *

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