CN116159579A - Acetylene hydrochlorination low-temperature mercury-free catalyst and preparation method thereof - Google Patents

Acetylene hydrochlorination low-temperature mercury-free catalyst and preparation method thereof Download PDF

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CN116159579A
CN116159579A CN202211566380.6A CN202211566380A CN116159579A CN 116159579 A CN116159579 A CN 116159579A CN 202211566380 A CN202211566380 A CN 202211566380A CN 116159579 A CN116159579 A CN 116159579A
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catalyst
acetylene
gold
temperature
hydrochlorination
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王刚
赵长森
牛强
王振
白雪
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Ordos Hanbo Technology Co ltd
Inner Mongolia Erdos Electric Power Metallurgy Group Co Ltd
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Ordos Hanbo Technology Co ltd
Inner Mongolia Erdos Electric Power Metallurgy Group Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
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Abstract

The invention provides an acetylene hydrochlorination low-temperature mercury-free catalyst and a preparation method thereof, belonging to the technical field of catalyst preparation. The catalyst comprises a carrier, an active component and an auxiliary agent, wherein the carrier is a nitrogen-doped carbon nano tube, the active component is a gold precursor, copper salt and manganese salt, and the auxiliary agent is a boron precursor; the composite use of the nitrogen doped carbon nano tube, the gold precursor, the copper salt, the manganese salt and the boron auxiliary agent ensures that the catalyst has proper acetylene and hydrogen chloride adsorption strength in the hydrochlorination reaction of acetylene, enhances the structure and electronic performance of active sites, is beneficial to promoting the oxidation-reduction cycle of the active sites and inhibiting the coking deactivation of the catalyst, and can show excellent activity, selectivity and stability of vinyl chloride at lower reaction temperature. The catalyst provided by the invention is green, pollution-free and simple to prepare, is an effective reaction catalyst for preparing vinyl chloride by hydrochlorination of acetylene, and has good industrial application prospect.

Description

Acetylene hydrochlorination low-temperature mercury-free catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to an acetylene hydrochlorination low-temperature mercury-free catalyst and a preparation method thereof.
Background
Polyvinyl chloride (PVC) is one of five general plastics worldwide, has excellent performances in flame retardance, chemical resistance, mechanical strength and electrical insulation property, and is widely applied to industries of building materials, daily necessities, floor leathers, pipes, wires and cables, packaging films and the like. Industrial PVC is produced mainly by polymerization of Vinyl Chloride (VCM). Based on the energy structure of rich coal and lean oil in China, coal-based acetylene hydrochlorination is a key chemical process for VCM and PVC production in China. Currently, the industrial process employs activated carbon loaded mercury chloride (HgCl) 2 ) As a reaction catalyst, and international ' water with mercury ' convention on the issue of mercury ' in 2017, which takes effect, requires control and reduction of mercury emissions, brings great environmental pressure to the process, and development of a green catalyst is urgently needed to replace mercury-based catalysts.
Studies of mercury-free catalytic systems for hydrochlorination of acetylene include two classes of supported metal catalysts and non-metal catalysts, with activated carbon supported gold catalysts (Au/C) exhibiting higher VCM activity and selectivity, considered to be the most potential replacement for HgCl 2 The catalyst is applied to the catalyst for the industrial production of the VCM. It is worth noting that compared to HgCl 2 The catalyst, au/C, needs to be adopted to achieve the same acetylene conversion rate in practical applicationWith higher reaction temperatures, energy consumption is high and the catalyst tends to suffer from rapid deactivation under the reaction conditions. This is due in part to the high valence gold (Au 3+ 、Au + ) Has higher reactivity, and Au is prepared under the conditions of acetylene which is a reducing gas and high temperature 3+ And Au (gold) + Is easily reduced to zero-valent gold (Au 0 ) The deactivation is caused, and the agglomeration growth of Au species is promoted, so that the Au species are difficult to participate in further oxidation-reduction cycle; meanwhile, compared with hydrogen chloride, acetylene is easier to adsorb on the surface of the catalyst in the reaction process, and if the activated acetylene does not undergo addition reaction with the hydrogen chloride, polymerization reaction is easy to occur mutually, and coke is formed to cover a reaction active site to cause the deactivation of the catalyst; in addition, under the high temperature condition, the rate of producing dichloroethane by the serial side reaction of the VCM and the hydrogen chloride can be obviously accelerated, the selectivity of the VCM is reduced, the waste of acetylene is caused, the operation cost is increased for the subsequent separation section, and the factors bring challenges to the industrial application of the catalyst. Therefore, the reduction of the reaction temperature of the Au-based catalyst and the development of the acetylene hydrochlorination catalyst with low temperature are of great significance for saving energy consumption and improving catalytic reaction performance.
Chinese patent CN201510924992.1 discloses a method for preparing vinyl chloride by hydrochlorination of acetylene at low temperature, which uses an Au-Cu composite catalyst loaded with activated carbon, wherein the weight percentages of gold element and copper element and carrier are respectively 0.01-0.1% and 20-100%, and compared with gold catalyst, the reaction temperature and carbon deposition rate can be reduced, thereby prolonging the service life of the catalyst.
Chinese patent CN201210305820.2 discloses a Ru-Co-Cu catalyst for synthesizing chloroethylene by hydrochlorination of acetylene, chinese patent CN201210307780.5 discloses a Ru-Pt-Cu catalyst for synthesizing chloroethylene by hydrochlorination of acetylene, chinese patent CN201210305818.5 discloses a Ru-Pt-Ni catalyst for synthesizing chloroethylene by hydrochlorination of acetylene, and Chinese patent CN201210307816.X discloses a Ru-Ni-Cu catalyst for synthesizing chloroethylene by hydrochlorination of acetylene.
Thus, current Au-based catalysts require higher reaction temperatures to achieve higher acetylene conversion, which can lead to reduced vinyl chloride product selectivity and catalyst life, and development of a low temperature acetylene hydrochlorination mercury-free catalyst is highly desirable.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a low-temperature mercury-free catalyst for hydrochlorination of acetylene and a preparation method thereof. The innovation point of the method is that the nitrogen doped carbon nano tube is adopted to load active components, the addition of copper can improve the dispersity of gold, prevent the aggregation of gold species, strengthen the electron transfer in the reaction process by adding manganese salt, inhibit the reduction of oxidized gold species to zero-valent gold, thereby having higher activity, and the addition of boron auxiliary agent provides electrons for the active components to promote the adsorption of reactants and intermediate species. The catalyst prepared by the invention has excellent chloroethylene activity and selectivity at a lower temperature, avoids the excessive high temperature of a bed hot spot, accelerates the deactivation of the catalyst, and has good industrial application prospect.
In a first aspect of the invention, the invention provides a low-temperature mercury-free catalyst for hydrochlorination of acetylene, which comprises a carrier, an active component and an auxiliary agent, wherein the carrier is a nitrogen-doped carbon nanotube, and the active component comprises a gold precursor, a copper salt, a manganese salt and a boron precursor.
Wherein, in the mercury-free catalyst, the weight of gold accounts for 0.05 to 0.2 percent of the weight of the catalyst.
Wherein, in the mercury-free catalyst, the weight of copper accounts for 0.1 to 0.5 percent of the weight of the catalyst.
Wherein, in the mercury-free catalyst, the weight of manganese accounts for 0.05 to 0.5 percent of the weight of the catalyst.
Wherein, in the mercury-free catalyst, the weight of boron accounts for 0.05-1% of the weight of the catalyst.
Wherein the gold precursor is one of chloroauric acid, gold acetate, trimethylphosphine gold (I) chloride, bis (1, 2-ethylenediamine) gold chloride and sodium gold thiosulfate; the copper salt is one of copper chloride, copper nitrate and copper acetate; the manganese salt is one of manganese dichloride, manganese nitrate and manganese gluconate; the auxiliary agent is one or more of boric acid, 1, 3-phenyldiboronic acid, 4-diphenyl diboronic acid and dichlorobenzene borane.
In a second aspect of the invention, the invention provides a method for preparing a low-temperature mercury-free catalyst for hydrochlorination of acetylene, comprising the following steps:
1) To Fe/gamma-Al 2 O 3 Placing the catalyst in a quartz boat of a horizontal tube furnace, heating to 500-700 ℃ under an inert atmosphere, switching to a hydrogen atmosphere, and maintaining for several hours, and fully reducing the catalyst;
2) And (3) switching the atmosphere into a mixed gas of organic hydrocarbon, ammonia and hydrogen, keeping the temperature unchanged, switching the gas into inert gas after a few hours, cooling to room temperature, sequentially soaking in a sodium hydroxide solution, carrying out ultrasonic treatment and washing to neutrality, soaking in a hydrochloric acid solution, carrying out ultrasonic treatment and washing to neutrality, and drying to obtain the nitrogen-doped carbon nanotube.
3) Preparing a solution of a gold precursor, copper salt and manganese salt, loading Au, cu and Mn components onto the nitrogen-doped carbon nano tube by adopting an immersion method or a deposition precipitation method, and drying to obtain a solid A;
4) Preparing a solution of an auxiliary agent boron precursor, and carrying out impregnation, aging and drying on the solid A to obtain the catalyst.
Preferably, the Fe/gamma-Al in step 1) 2 O 3 The catalyst preparation steps are as follows: determination of gamma-Al 2 O 3 The FeCl is weighed according to the load capacity 3 And dissolve and react to gamma-Al 2 O 3 Dipping, aging, drying and roasting to obtain Fe/gamma-Al 2 O 3 A catalyst.
Preferably, the organic hydrocarbon in the step 2) is one or more of methane, ethane, ethylene, acetylene and propane, and the volume flow ratio of the organic hydrocarbon to the ammonia to the hydrogen is 1-10:1-4:1.
preferably, the precipitant used in the deposition and precipitation method in the step 3) is one of sodium hydroxide, urea or sodium carbonate, the temperature is 60-90 ℃, and the aging time is 3-9h.
Preferably, the temperature of the impregnation process in steps 3) and 4) is 20-35 ℃, the drying temperature is 100-120 ℃ and the drying time is 12 hours.
In a third aspect of the invention, there is provided the use of the above-described low temperature mercury-free catalyst for hydrochlorination of acetylene.
The application conditions are as follows: temperature t=110-180 ℃, normal pressure, GHSV (C 2 H 2 )＝40-300h -1 、n(HCl)：n(C 2 H 2 )＝1.05-1.2。
Compared with the prior art, the invention has the beneficial effects that:
(1) The nitrogen doped carbon nano tube is adopted to load active components, the addition of copper can improve the dispersity of gold, prevent the aggregation of gold species, strengthen the electron transfer in the reaction process, inhibit the reduction of oxidized gold species to zero-valent gold, thereby having higher activity, and the addition of boron auxiliary agent provides electrons for the active components to promote the adsorption of reactants and intermediate species. The catalyst prepared by the invention shows excellent activity and selectivity of vinyl chloride at lower temperature. Compared with other mercury-free catalysts, the catalyst has the function of reducing energy consumption in the reaction operation process.
(2) The catalyst provided by the invention is operated at a lower temperature, so that the coking carbon deposition of the catalyst and the loss of gold species can be slowed down, the service life of the catalyst is prolonged, and the use cost of the gold catalyst is reduced.
(3) The catalyst provided by the invention has the advantages of simple preparation process, no pollution and high catalytic activity, and is a green mercury-free catalyst.
Description of the drawings:
FIG. 1 is a nitrogen physisorption-desorption isotherm plot of the catalyst prepared in example 1;
FIG. 2 is an infrared spectrum of the catalyst prepared in example 1;
FIG. 3 is a transmission electron microscope image of the catalyst prepared in example 1;
FIG. 4 is an XPS spectrum of the catalyst prepared in example 1.
The specific embodiment is as follows:
it is to be noted that the raw materials used in the present invention are all common commercial products, and the sources thereof are not particularly limited.
The following is a more specific illustration of the catalyst:
basic examples: fe/gamma-Al 2 O 3 The preparation method of the catalyst comprises the following steps:
determination of gamma-Al 2 O 3 The FeCl is weighed according to the load capacity 3 And dissolve and react to gamma-Al 2 O 3 Dipping, aging, drying and roasting to obtain Fe/gamma-Al 2 O 3 A catalyst.
Example 1: acetylene hydrochlorination low-temperature mercury-free catalyst and preparation method thereof
1) 5g of Fe/gamma-Al 2 O 3 Placing a catalyst (Fe load of 8%) in a quartz boat of a horizontal tube furnace, heating to 600 ℃ at a speed of 5 ℃/min under an argon atmosphere, switching to a hydrogen atmosphere, and keeping for 4 hours, and fully reducing the catalyst;
2) The atmosphere is switched into a mixed gas of ethane, ammonia and hydrogen, and the ratio of the gas volume flow is 4:1:1, keeping the temperature unchanged, switching the gas into argon after 8 hours, cooling to room temperature, soaking for 4 hours by using a sodium hydroxide solution with the mass concentration of 10%, performing ultrasonic treatment and washing to be neutral, soaking for 4 hours by using a hydrochloric acid solution with the mass concentration of 10%, performing ultrasonic treatment and washing to be neutral, and drying at 110 ℃ for 12 hours to obtain the nitrogen-doped carbon nano tube;
3) Weighing 25g of nitrogen-doped carbon nanotube carrier, preparing 0.0025g/mL of gold sodium thiosulfate, 0.0025g/mL of cupric chloride and 0.003g/mL of manganese dichloride solution, dipping the nitrogen-doped carbon nanotube, aging for 8 hours, and drying at 110 ℃ for 12 hours;
4) Preparing a boric acid solution with the concentration of 0.003g/mL, soaking and aging the solid dried in the steps for 8 hours, and drying at the temperature of 110 ℃ for 12 hours to obtain the catalyst, wherein the loading amounts of gold, copper and manganese are respectively 0.12%, 0.11% and 0.08%, and the loading amount of auxiliary agent boron is 0.15%.
Example 2: acetylene hydrochlorination low-temperature mercury-free catalyst and preparation method thereof
1) Weighing 25g of the nitrogen-doped carbon nanotube carrier in the embodiment 1, placing the carrier in a beaker, adding 500mL of water, stirring, preparing and adding 2.8mL of chloroauric acid with the concentration of 0.012g/mL and 2.2mL of copper chloride solution with the concentration of 0.015g/mL, stirring for 30min, then dropwise adding 0.005g/mL of sodium carbonate solution, regulating the pH value of the solution to 5-6, stirring for 30min, heating to 70 ℃ in a water bath, aging for 8h, centrifuging, washing, and drying at 110 ℃ for 12h;
2) Preparing manganese dichloride solution with the concentration of 0.005g/mL and 1, 3-phenyldiboronic acid solution with the concentration of 0.006g/mL, soaking and aging the dried solid in the steps for 8 hours, and drying at 110 ℃ for 12 hours to obtain the catalyst, wherein the loading amounts of gold, copper and manganese are respectively 0.12%, 0.11% and 0.08%, and the loading amount of auxiliary boron is 0.15%.
Example 3: acetylene hydrochlorination low-temperature mercury-free catalyst and preparation method thereof
1) Weighing 25g of the nitrogen-doped carbon nanotube carrier in the embodiment 1, preparing 0.0025g/mL of gold acetate and 0.004g/mL of copper acetate solution, co-impregnating the nitrogen-doped carbon nanotubes, aging for 8 hours, and drying at 110 ℃ for 12 hours;
2) Preparing a manganese nitrate solution with the concentration of 0.0025g/mL and a 4, 4-diphenyl diboronic acid solution with the concentration of 0.006g/mL, dipping, aging for 8 hours and drying at the temperature of 110 ℃ for 12 hours to obtain a catalyst, wherein the loading amounts of gold, copper and manganese are respectively 0.12%, 0.10% and 0.15%, and the loading amount of boron is 0.08%;
example 4: acetylene hydrochlorination low-temperature mercury-free catalyst and preparation method thereof
1) Weighing 25g of the nitrogen-doped carbon nanotube carrier in the embodiment 1, preparing a solution of 0.0025g/mL of trimethylphosphine gold (I) chloride and 0.004g/mL of copper nitrate, dipping the nitrogen-doped carbon nanotube, aging for 8 hours, and drying at 110 ℃ for 12 hours;
2) Preparing a manganese gluconate solution with the concentration of 0.02g/mL and a dichlorobenzene borane solution with the concentration of 0.006g/mL, soaking and aging the dried solid in the steps, and drying at 110 ℃ for 12 hours to obtain a catalyst, wherein the loading amounts of gold, copper and manganese are respectively 0.12%, 0.12% and 0.10%, and the loading amount of boron is 0.06%;
comparative example 1:
1) Weighing 25g of the nitrogen-doped carbon nanotube carrier in the embodiment 1, preparing 0.0025g/mL of gold sodium thiosulfate solution and 0.003g/mL of manganese dichloride solution, dipping the nitrogen-doped carbon nanotube, aging for 8 hours, and drying at 110 ℃ for 12 hours;
2) Preparing a boric acid solution with the concentration of 0.003g/mL, soaking and aging the solid dried in the steps for 8 hours, and drying at the temperature of 110 ℃ for 12 hours to obtain the catalyst, wherein the gold loading is 0.12%, the manganese loading is 0.08% and the auxiliary boron loading is 0.15%.
Comparative example 2:
1) Weighing 25g of the nitrogen-doped carbon nanotube carrier in the embodiment 1, preparing 0.0025g/mL of gold sodium thiosulfate and 0.0025g/mL of copper chloride solution, dipping the nitrogen-doped carbon nanotube, aging for 8 hours, and drying at 110 ℃ for 12 hours;
2) Preparing a boric acid solution with the concentration of 0.003g/mL, soaking and aging the solid dried in the steps for 8 hours, and drying at the temperature of 110 ℃ for 12 hours to obtain the catalyst, wherein the loading amounts of gold and copper are respectively 0.12% and 0.11%, and the loading amount of auxiliary boron is 0.15%.
Comparative example 3:
1) Weighing 25g of the nitrogen-doped carbon nanotube carrier in the embodiment 1, preparing 0.0025g/mL of gold sodium thiosulfate, 0.0025g/mL of cupric chloride and 0.003g/mL of manganese dichloride solution, dipping the nitrogen-doped carbon nanotube, aging for 8 hours and drying at 110 ℃ for 12 hours; the gold, copper and manganese loadings were measured to be 0.12%, 0.11% and 0.08%, respectively.
Comparative example 4:
1) 5g of Fe/gamma-Al 2 O 3 Placing a catalyst (Fe load of 8%) in a quartz boat of a horizontal tube furnace, heating to 600 ℃ at a speed of 5 ℃/min under an inert atmosphere, switching to a hydrogen atmosphere, and keeping for 4 hours, and fully reducing the catalyst;
2) The atmosphere was switched to a mixed gas of ethane and hydrogen with a gas flow ratio of 4:1, keeping the temperature unchanged, switching the gas into inert gas after 8 hours, cooling to room temperature, soaking in 10%wt sodium hydroxide solution, carrying out ultrasonic treatment and washing to neutrality, soaking in 10%wt hydrochloric acid solution, carrying out ultrasonic treatment and washing to neutrality, and drying at 110 ℃ for 12 hours to obtain the carbon nanotube;
3) Weighing 25g of the carbon nanotube carrier, preparing 0.0025g/mL of gold sodium thiosulfate, 0.0025g/mL of cupric chloride and 0.003g/mL of manganese dichloride solution, dipping the carbon nanotube, aging for 8 hours and drying at 110 ℃ for 12 hours;
4) Preparing a boric acid solution with the concentration of 0.003g/mL, soaking and aging the solid dried in the steps for 8 hours, and drying at the temperature of 110 ℃ for 12 hours to obtain the catalyst, wherein the loading amounts of gold, copper and manganese are respectively 0.12%, 0.11% and 0.08%, and the loading amount of auxiliary agent boron is 0.15%.
Comparative example 5:
1) Weighing 25g of nitrogen-doped carbon nanotube carrier, preparing 0.0025g/mL of gold sodium thiosulfate and 0.007g/mL of manganese dichloride solution, dipping the nitrogen-doped carbon nanotube, aging for 8 hours, and drying at 110 ℃ for 12 hours;
2) Preparing a boric acid solution with the concentration of 0.003g/mL, soaking and aging the solid dried in the steps for 8 hours, and drying at the temperature of 110 ℃ for 12 hours to obtain the catalyst, wherein the loading amounts of gold and manganese are respectively 0.12 percent and 0.19 percent, and the loading amount of auxiliary boron is 0.15 percent.
Comparative example 6:
1) Weighing 25g of nitrogen-doped carbon nanotube carrier, preparing 0.0025g/mL of gold sodium thiosulfate and 0.006g/mL of copper chloride solution, dipping the nitrogen-doped carbon nanotube, aging for 8 hours and drying at 110 ℃ for 12 hours;
2) Preparing a boric acid solution with the concentration of 0.003g/mL, soaking and aging the solid dried in the steps for 8 hours, and drying at the temperature of 110 ℃ for 12 hours to obtain the catalyst, wherein the loading amounts of gold and copper are respectively 0.12% and 0.19%, and the loading amount of auxiliary boron is 0.15%.
For the above examples 1-4 and comparative examples
The catalyst in 1-6 is subjected to acetylene hydrochlorination performance evaluation under the conditions of 140 ℃ and 120h of airspeed -1 Feed gas C 2 H 2 : hcl=1: 1.1, the conversion of acetylene in the initial stage of the reaction is 88.7%, and the selectivity of chloroethylene is more than 99%After 500h of reaction run, the conversion of acetylene on the catalyst was 80.9%.
The results of the catalytic performance test are summarized in Table 1:
table 1 comparison of catalyst performances of examples 1-4 and comparative examples 1-6
Detecting items Initial conversion of acetylene (%) Vinyl chloride selectivity (%) Acetylene conversion after 500h (%)
Example 1 98.3 ＞99％ 97.2
Example 2 97.2 ＞99％ 95.5
Example 3 96.9 ＞99％ 94.1
Example 4 96.4 ＞99％ 93.8
Comparative example 1 83.5 ＞99％ 80.5
Comparative example 2 85.3 ＞99％ 81.4
Comparative example 3 88.2 ＞99％ 82.6
Comparative example 4 84.1 ＞99％ 77.8
Comparative example 5 87.2 ＞99％ 83.2
Comparative example 6 91.0 ＞99％ 86.9
The following conclusions can be drawn from comparative examples 1-4 and comparative examples 1-6:
comparison of examples 1-4 and comparative example 1 shows that in the absence of the metallic copper component, the hydrochlorination activity of acetylene is relatively low, and the activity of the catalyst is reduced more after 500 hours of reaction;
comparison of examples 1-4 with comparative example 2 shows that in the absence of the manganese metal component, the hydrochlorination activity of acetylene is relatively low, and the activity of the catalyst is reduced more after 500 hours of reaction;
comparison of examples 1-4 and comparative example 3 shows that in the absence of the auxiliary boron component, the hydrochlorination activity of acetylene is relatively low, and the activity of the catalyst is reduced more after 500 hours of reaction;
comparison of examples 1-4 and comparative example 4 shows that when carbon nanotubes without nitrogen doping are used as carriers to load active components and auxiliary agents, the hydrochlorination activity of acetylene is relatively low, and the activity of the catalyst is reduced more after 500 hours of reaction;
comparison of example 1 with comparative examples 5-6 shows that the reactivity with manganese alone or copper alone at the same loading is not as good as with manganese and copper simultaneously, demonstrating the synergistic effect between copper and manganese.
The technical scheme of the invention is not limited to the technical means disclosed by the technical means, and also comprises the technical scheme formed by any combination of the technical features. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, and such changes and modifications are intended to be included within the scope of the invention.

Claims (10)

1. The low-temperature mercury-free catalyst for hydrochlorination of acetylene is characterized in that: the acetylene hydrochlorination low-temperature mercury-free catalyst comprises a carrier, an active component and an auxiliary agent, wherein the carrier is a nitrogen-doped carbon nanotube, the active component comprises a gold precursor, a copper salt and a manganese salt, and the auxiliary agent is a boron precursor.
2. The acetylene hydrochlorination low temperature mercury-free catalyst of claim 1, wherein: the diameter of the nitrogen-doped carbon nano tube is 5-20nm, and the specific surface area is 200-800m 2 /g。
3. The acetylene hydrochlorination low temperature mercury-free catalyst of claim 1, wherein: in the mercury-free catalyst, the weight of gold is 0.05-0.2% of the weight of the catalyst, the weight of copper is 0.1-0.5% of the weight of the catalyst, the weight of manganese is 0.05-0.5% of the weight of the catalyst, and the weight of boron is 0.05-1% of the weight of the catalyst.
4. The acetylene hydrochlorination low temperature mercury-free catalyst of claim 1, wherein: the gold precursor is one of chloroauric acid, gold acetate, trimethylphosphine gold (I) chloride and bis (1, 2-ethylenediamine) gold chloride, and gold sodium thiosulfate; the copper salt is one of copper chloride, copper nitrate and copper acetate; the manganese salt is one of manganese dichloride, manganese nitrate and manganese gluconate; the auxiliary agent is one or more of boric acid, 1, 3-phenyldiboronic acid, 4-diphenyl diboronic acid and dichlorobenzene borane.
5. The method for preparing the acetylene hydrochlorination low-temperature mercury-free catalyst according to any one of claims 1 to 4, wherein: the method comprises the following steps:
1) To Fe/gamma-Al 2 O 3 Placing the catalyst in a quartz boat of a horizontal tube furnace, heating to 500-700 ℃ under an inert atmosphere, switching to a hydrogen atmosphere, and keeping for 3 hours, and fully reducing the catalyst;
2) Switching the atmosphere into a mixed gas of organic hydrocarbon, ammonia and hydrogen, keeping the temperature unchanged, switching the gas into inert gas after a few hours, cooling to room temperature, soaking in sodium hydroxide solution, performing ultrasonic treatment and washing to neutrality, soaking in hydrochloric acid solution, performing ultrasonic treatment and washing to neutrality, and drying to obtain the nitrogen-doped carbon nanotube;
3) Preparing a solution of a gold precursor, copper salt and manganese salt, loading Au, cu and Mn components onto the nitrogen-doped carbon nano tube by adopting an immersion method or a deposition precipitation method, and drying to obtain a solid A;
4) Preparing a solution of an auxiliary agent boron precursor, and carrying out impregnation, aging and drying on the solid A to obtain the catalyst.
6. The method of manufacturing according to claim 5, wherein: the organic hydrocarbon in the step 2) is one or more of methane, ethane, ethylene, acetylene and propane, and the volume flow ratio of the organic hydrocarbon to the ammonia to the hydrogen is 1-10:1-4:1.
7. the method of manufacturing according to claim 5, wherein: the precipitant used in the deposition precipitation method in the step 3) is one of sodium hydroxide, urea or sodium carbonate, the temperature is 60-90 ℃, and the aging time is 3-9h.
8. The method of manufacturing according to claim 5, wherein: the temperature of the dipping process in the steps 3) and 4) is 20-35 ℃, the drying temperature is 100-120 ℃ and the drying time is 12 hours.
9. The method of manufacturing according to claim 5, wherein: fe/gamma-Al as described in step 1) 2 O 3 The catalyst preparation steps are as follows: determination of gamma-Al 2 O 3 The FeCl is weighed according to the load capacity 3 And dissolve and react to gamma-Al 2 O 3 Dipping, aging, drying and roasting to obtain Fe/gamma-Al 2 O 3 A catalyst.
10. Use of the acetylene hydrochlorination low-temperature mercury-free catalyst prepared by the preparation method of any one of claims 1 to 4 or the acetylene hydrochlorination low-temperature mercury-free catalyst prepared by the preparation method of any one of claims 5 to 9 in acetylene hydrochlorination.
CN202211566380.6A 2022-12-07 2022-12-07 Acetylene hydrochlorination low-temperature mercury-free catalyst and preparation method thereof Pending CN116159579A (en)

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