CN111330585B - Preparation method and application of modified catalyst - Google Patents
Preparation method and application of modified catalyst Download PDFInfo
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- CN111330585B CN111330585B CN202010209304.4A CN202010209304A CN111330585B CN 111330585 B CN111330585 B CN 111330585B CN 202010209304 A CN202010209304 A CN 202010209304A CN 111330585 B CN111330585 B CN 111330585B
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a preparation method and application of a modified catalyst, and belongs to the field of catalyst modification technology and application. The catalyst is prepared by taking a carbon material as a main raw material and a mixture of nickel salt and an acid solution as a modifier through an impregnation method, and then the modified carbon material is applied to acetylene hydrochlorination reaction as a catalyst and supports a catalyst active component. The prepared catalyst has the temperature of T =100-300 ℃, normal pressure and C 2 H 2 (GHSV)＝30‑300h ‑1 、n(HCl):n(C 2 H 2 ) The hydrochlorination activity test is carried out in a fixed bed evaluation device under the evaluation condition of =1.05-1.45, the acetylene conversion rate is up to 95%, the initial conversion rate is improved by 62.2-93.3% compared with that of an unmodified sample, the selectivity is higher than 99.5%, and the catalyst performance is obviously improved.
Description
Technical Field
The invention belongs to the field of catalyst modification technology and application, and particularly relates to a preparation method and application of a modified catalyst.
Background
Polyvinyl chloride (PVC for short) is one of the largest plastic products consumed and produced in China, and is a high molecular compound polymerized by vinyl chloride monomer (VCM for short). The synthesis method of VCM is mainly calcium carbide method (acetylene method), but has the catalyst problem, mercury chloride is mainly taken as an effective component of the catalyst in industry, mercury is easy to sublimate and lose, and serious pollution is caused to the environment. In order to reduce the pollution of mercury chloride to the environment and reduce the harm degree to human bodies as much as possible, the mercury resource consumption must be reduced when the calcium carbide VCM production can survive and can be carried away for a longer time.
Whether the performance of the mercury-free catalyst or the low-mercury catalyst is further optimized, the modification of the catalyst carrier is an effective means for improving the performance of the catalyst. The active carbon material is carbon which is specially treated, and organic raw materials are made into the porous adsorbent through the processes of carbonization and activation. The activated carbon material has the characteristics of large specific surface area, good chemical stability and mechanical strength, excellent acid resistance, alkali resistance, heat resistance and the like, so that the activated carbon material is widely applied to the fields of food, industry, agriculture, medicine, health, military and the like.
Ling Sai (Ling Sai, wu Anwen, xiong Ji, hu ZhengpengAcid modification of activated carbon and its use in hydrochlorination of acetylene [ J]46-50) and the like, and characteristics of structures of samples before and after modification by means of BET, infrared spectrum, SEM and the like, find that the acid modification not only removes partial impurities in the activated carbon, but also the acid modified activated carbon can increase the total amount of acid functional groups on the surface of the activated carbon and change the pore structure. The modified carbon material is used as a carrier of a mercury-free catalyst to show good performance in acetylene hydrochlorination, and the activated carbon is treated by 5mol/L nitric acid at an acetylene airspeed of 90h -1 At a temperature of 130 ℃ V (HC 1)/V (C) 2 H 2 ) Under the condition of 1.05, the selectivity of vinyl chloride is close to 98%, and the initial conversion rate can reach 71.8%, but the catalytic activity of the catalyst is low.
CN104415794B discloses a phosphorus modified catalyst carrier, a preparation method and application thereof. The preparation method mainly comprises the steps of dissolving the modifier in ethanol to obtain an impregnation solution, immersing the catalyst carrier in the impregnation solution for impregnation, then drying, roasting and cooling to obtain the phosphorus modified catalyst carrier. The modifier is triphenylphosphine, pyrophosphoric acid or metaphosphoric acid. The phosphorus content of the prepared phosphorus modified catalyst carrier is 1-10%, and the catalyst carrier is applied to the hydrochlorination of acetylene, wherein the reaction temperature is 170 ℃, and the acetylene space velocity is 180h -1 Raw material gas ratio V C2H2 /V HC1 Under the condition of 1.15, the initial conversion rate of acetylene is improved by 26-86% compared with an unmodified sample, the selectivity of the generated vinyl chloride is more than 99%, but the catalyst is easy to deactivate, has short service life and is difficult to carry out industrial production.
CN110479330A discloses a preparation method of an ammonium oxalate and phosphoric acid modified acetylene hydrochlorination catalyst. The catalyst is prepared by an isometric impregnation method, a carrier is pretreated, then coal-based activated carbon is added into a diluted nitric acid solution, the mixture is filtered, the activated carbon is washed by deionized water to enable a washing solution to be neutral, and the catalyst carrier is obtained after drying. Configuration of RuCl 3 Dissolving ammonium oxalate and phosphoric acid in deionized water, and adding a certain amount of RuCl 3 Anhydrous secondAdding coal-based activated carbon into the alcoholic solution while stirring, soaking and drying to finally obtain the ammonium oxalate and phosphoric acid modified catalyst. Respectively preparing ammonium oxalate and phosphoric acid combined modified ultralow-content ruthenium-based acetylene hydrochlorination catalyst samples with ruthenium content accounting for 0.008% and 0.005% of the mass percent of the activated carbon carrier. Under normal pressure, the reaction temperature is 150 ℃, and the acetylene space velocity is 522h -1 Total space velocity 1122h -1 、V(HC1)/V(C 2 H 2 ) Testing the catalytic performance of acetylene hydrochlorination under the condition of =1.15, and the result shows that the conversion rate of acetylene is 75.9% optimally, the selectivity of vinyl chloride is 99.24% optimally, but the conversion rate of acetylene and the catalytic activity are not high.
In order to research out a catalyst with high catalytic activity and high catalyst stability, research personnel carry out a great deal of research, and the existing mercury-free catalyst also has the problems of short service life, low catalytic activity, poor catalyst stability and the like. Therefore, it is desirable to provide a method for preparing a carbon material catalyst having a simple production method, a high catalytic activity and a high catalyst stability.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a preparation method and application of a modified catalyst. The invention aims to overcome the problem of low catalytic activity of the existing mercury-free catalyst, and improve the final catalytic effect of the catalyst by modifying the catalyst. Therefore, a preparation method of the modified catalyst is provided. The second purpose of the invention is to provide an application of the modified catalyst in preparation of acetylene hydrochlorination reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a modified catalyst comprises the following steps:
(1) Drying the activated carbon, soaking the activated carbon by using a modifier, and washing the activated carbon by using deionized water until the activated carbon is neutral to obtain the acid modified activated carbon.
(2) Dissolving nickel nitrate in deionized water to obtain a nickel nitrate solution, then immersing the acid modified activated carbon obtained in the step (1) in the nickel nitrate solution, and then calcining to obtain the modified activated carbon.
(3) And (3) adding a metal salt into a hydrochloric acid solution, then carrying out vacuum impregnation on the modified activated carbon obtained in the step (2), evaporating and drying to finally obtain the modified catalyst.
Further, the activated carbon in the step (1) is one or more of wood activated carbon, coal activated carbon and coconut shell activated carbon, and the specific surface area is 1300-1600m 2 (ii)/g, the mass fraction of ash is less than or equal to 5%, preferably 3-5%.
Further, the mass of the activated carbon in the step (1) is 50 to 200g, preferably 80 to 150g, and more preferably 100g.
Further, the drying temperature in the step (1) is 80-120 ℃, and the drying time is 6-12h.
Further, the modifier in the step (1) is a mixture of a nickel salt and an acid solution, wherein the nickel salt is one or more of nickel chloride, nickel nitrate and nickel sulfate, the acid solution is one or more of citric acid, nitric acid, hydrochloric acid and phosphoric acid, and the acid solution is preferably phosphoric acid and/or nitric acid.
Further, the concentration ratio of the nickel salt to the acid solution in the modifier in the step (1) is 1:5-45.
Further, the concentration of the acid solution in the step (1) is 1-5mol/L.
Further, the volume of the modifier in the step (1) is 3-6 times that of the activated carbon, so that the activated carbon is completely immersed in the modifier.
Further, the soaking time in the step (1) is 6-18h.
Further, the mass of the nickel nitrate in the step (2) is 0.1-0.5g, and the volume of the deionized water is 300-500mL.
Further, the immersion time in the step (2) is 2-3h.
Further, the calcination in the step (2) is firstly calcination at the temperature of 180-200 ℃ for 1-2h, then calcination at the temperature of 80-120 ℃ for 0.5-1h, and calcination at the temperature of 220-300 ℃ for 2-3h, wherein the heating rate is 10 ℃/min, and the atmosphere is nitrogen.
Further, the metal salt in step (3) is one or more of gold, copper, tin, bismuth chloride, sulfate, phosphate, and ethylenediamine, preferably phosphate, gold, copper, tin, and bismuth chloride, and more preferably gold, copper, tin, and bismuth chloride.
Further, the mass of the metal salt in the step (3) is 10-100g.
Further, the volume of the hydrochloric acid solution in the step (3) is 50-500mL, and the concentration is 0.5-1.5mol/L.
Further, the mass of the modified activated carbon in the step (3) is 25-80g.
Further, the vacuum degree of the vacuum impregnation in the step (3) is 0.095-0.099Mpa, and the impregnation time is 5-10h, preferably 6-8h, and more preferably 6h.
Further, the vacuum impregnation method described in step (3) includes, but is not limited to, vacuum equal-volume impregnation, vacuum stepwise impregnation and vacuum excess impregnation, preferably vacuum excess impregnation.
Further, the temperature of the evaporation in the step (3) is 60-80 ℃, and the time is 5-8h.
Further, the drying temperature in the step (3) is 80-120 ℃, and the drying time is 8-12h.
The invention also provides the application of the catalyst prepared by the method in acetylene hydrochlorination.
Compared with the prior art, the invention has the beneficial effects that:
in the application of the modified catalyst prepared by the invention in the hydrochlorination of acetylene, the prepared catalyst has the reaction temperature of 100-300 ℃ and the reaction temperature of C 2 H 2 (GHSV)＝30-300h -1 、n(HCl):n(C 2 H 2 ) Under the condition of =1.05-1.45, the initial conversion rate of acetylene is improved by 62.2-93.3% compared with an unmodified sample, and the selectivity of vinyl chloride monomer is greater than or equal to 99.5%.
Detailed Description
For a better understanding of the present invention, the present invention is further described in conjunction with the following specific examples, wherein the terminology used in the examples is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
The raw material sources are as follows:
the coal-based activated carbon is purchased from Aladdin company, and the product number is C299291;
the other raw materials are common commercial products, so that the source of the raw materials is not particularly limited.
Example 1
A preparation method of a modified catalyst comprises the following steps:
(1) 100g of coal-based activated carbon is placed in an oven to be dried for 8 hours at the temperature of 90 ℃, and then is soaked for 10 hours by using 1.5mol/L nitric acid solution and 0.3mol/L nickel nitrate solution, wherein the volume of the solution is 3 times of that of the coal-based activated carbon, and the coal-based activated carbon is ensured to be completely immersed in the solution. And then washing the mixture with deionized water to be neutral to obtain the acid modified activated carbon.
(2) Dissolving 0.1g of nickel nitrate in 400mL of deionized water to obtain a nickel nitrate solution, then soaking the acid modified activated carbon obtained in the step (1) in the nickel nitrate solution for 2h, calcining at 200 ℃ for 1h under the nitrogen atmosphere, then calcining at 100 ℃ for 0.8h, and then calcining at 250 ℃ for 3h, wherein the heating rate is 10 ℃/min to obtain the modified activated carbon.
(3) Adding 10g of bismuth chloride into a round-bottom flask containing 100mL of 0.5mol/L hydrochloric acid solution, then carrying out vacuum impregnation on 50g of the modified activated carbon obtained in the step (2), wherein the impregnation time is 6h and the vacuum degree is 0.096MPa, finally placing the round-bottom flask in a rotary evaporator, evaporating at 60 ℃ for 5h, and drying at 120 ℃ for 12h to obtain the modified catalyst.
Example 2
A preparation method of a modified catalyst comprises the following steps:
(1) 50g of coal-based activated carbon is placed in an oven to be dried for 6 hours at the temperature of 80 ℃, and then is soaked for 6 hours by using 1mol/L phosphoric acid solution and 0.05mol/L nickel sulfate solution, wherein the volume of the solution is 6 times of that of the coal-based activated carbon, so that the coal-based activated carbon is completely immersed in the solution. And then washing the mixture with deionized water to be neutral to obtain the acid modified activated carbon.
(2) Dissolving 0.1g of nickel nitrate in 300mL of deionized water to obtain a nickel nitrate solution, then soaking the acid modified activated carbon obtained in the step (1) in the nickel nitrate solution for 2h, calcining at 190 ℃ for 2h in a nitrogen atmosphere, then calcining at 120 ℃ for 0.5h, and then calcining at 300 ℃ for 2h, wherein the heating rate is 10 ℃/min to obtain the modified activated carbon.
(3) Adding 30g of bismuth chloride into a round-bottom flask containing 200mL of 1.5mol/L hydrochloric acid solution, then carrying out vacuum impregnation on 25g of the modified activated carbon obtained in the step (2), wherein the impregnation time is 5h, and the vacuum degree is 0.095MPa, finally placing the round-bottom flask in a rotary evaporator, evaporating at 60 ℃ for 5h, and drying at 80 ℃ for 8h to obtain the modified catalyst.
Example 3
A preparation method of a modified catalyst comprises the following steps:
(1) 200g of coal-based activated carbon is placed in an oven to be dried for 12 hours at 120 ℃, and then is soaked in 5mol/L nitric acid and 0.2mol/L nickel nitrate solution for 18 hours, wherein the volume of the solution is 4 times of that of the coal-based activated carbon, so that the coal-based activated carbon is completely soaked in the solution. And then washing the mixture with deionized water to be neutral to obtain the acid modified activated carbon.
(2) Dissolving 0.5g of nickel nitrate in 500mL of deionized water to obtain a nickel nitrate solution, then soaking the acid modified activated carbon obtained in the step (1) in the nickel nitrate solution for 3h, calcining at 180 ℃ for 2h in a nitrogen atmosphere, then calcining at 120 ℃ for 1h, and then calcining at 280 ℃ for 3h at a heating rate of 10 ℃/min to obtain the modified activated carbon.
(3) Adding 100g of bismuth chloride into a round-bottom flask containing 500mL of 1.5mol/L hydrochloric acid solution, then vacuum-impregnating 80g of the modified activated carbon obtained in the step (2) for 10 hours at a vacuum degree of 0.099MPa, finally placing the round-bottom flask in a rotary evaporator, evaporating at 80 ℃ for 8 hours, and drying at 120 ℃ for 12 hours to obtain the modified catalyst.
Example 4
A preparation method of a modified catalyst comprises the following steps:
(1) 80g of coal-based activated carbon is placed in an oven to be dried for 8 hours at the temperature of 100 ℃, and then is soaked for 10 hours by using 3mol/L hydrochloric acid and 0.1mol/L nickel chloride solution, wherein the volume of the solution is 5 times of that of the coal-based activated carbon, so that the coal-based activated carbon is completely immersed in the solution. And then washing the mixture with deionized water to be neutral to obtain the acid modified activated carbon.
(2) Dissolving 0.2g of nickel nitrate in 450mL of deionized water to obtain a nickel nitrate solution, then soaking the acid modified activated carbon obtained in the step (1) in the nickel nitrate solution for 2 hours, calcining at 180 ℃ for 1 hour under the nitrogen atmosphere, then calcining at 80 ℃ for 1 hour, and then calcining at 300 ℃ for 3 hours at the heating rate of 10 ℃/min to obtain the modified activated carbon.
(3) Adding 60g of bismuth chloride into a round-bottom flask containing 300mL of 0.5mol/L hydrochloric acid solution, then carrying out vacuum impregnation on 45g of the modified activated carbon obtained in the step (2) for 8h under the vacuum degree of 0.096MPa, finally placing the round-bottom flask in a rotary evaporator to evaporate at 80 ℃ for 8h, and drying at 100 ℃ for 10h to obtain the modified catalyst.
Example 5
A preparation method of a modified catalyst comprises the following steps:
(1) 150g of coal-based activated carbon is placed in an oven to be dried for 10 hours at 120 ℃, and then is soaked for 15 hours by using 4mol/L citric acid and 0.089mol/L nickel chloride solution, wherein the volume of the solution is 6 times of that of the coal-based activated carbon, so that the coal-based activated carbon is completely immersed in the solution. And then washing the mixture to be neutral by using deionized water to obtain the acid modified activated carbon.
(2) Dissolving 0.4g of nickel nitrate in 350mL of deionized water to obtain a nickel nitrate solution, then soaking the acid modified activated carbon obtained in the step (1) in the nickel nitrate solution for 2 hours, then calcining at 180 ℃ for 1 hour under the nitrogen atmosphere, then calcining at 80 ℃ for 1 hour, and then calcining at 220 ℃ for 3 hours at the heating rate of 10 ℃/min to obtain the modified activated carbon.
(3) Adding 80g of bismuth chloride into a round-bottom flask containing 400mL of 1mol/L hydrochloric acid solution, then carrying out vacuum impregnation on 80g of the modified activated carbon obtained in the step (2) for 9h under the vacuum degree of 0.096MPa, finally putting the round-bottom flask into a rotary evaporator, evaporating at 80 ℃ for 8h, and drying at 110 ℃ for 10h to obtain the modified catalyst.
Comparative example 1
The difference from the example 5 of the application is that the coal-based activated carbon in the step (1) is not soaked by 4mol/L of citric acid and 0.089mol/L of nickel chloride solution.
Other raw material contents and preparation methods were the same as in example 5.
Comparative example 2
The difference from the example 5 of the present application is that the concentration ratio of the nickel chloride solution to the citric acid in the step (1) is 1:3, wherein the concentration of the citric acid is 0.5mol/L.
The other raw material contents and the preparation method are the same as those of example 5.
Comparative example 3
The difference from the example 5 of the present application is that the concentration ratio of the nickel chloride solution to the citric acid in the step (1) is 1.
Other raw material contents and preparation methods were the same as in example 5.
Comparative example 4
The difference from example 5 of the present application is that the calcination in step (2) was carried out at 220 ℃ for 5 hours under a nitrogen atmosphere.
Other raw material contents and preparation methods were the same as in example 5.
Comparative example 5
The difference from the present example 5 is that the calcination in step (2) is carried out under nitrogen atmosphere at 160 ℃ for 3h, at 130 ℃ for 0.5h, and at 310 ℃ for 1h, with a heating rate of 10 ℃/min.
Other raw material contents and preparation methods were the same as in example 5.
Comparative example 6
Ling Sai (Ling Sai, wu Anwen, xiong Ji, hu Zhengpeng acid modification of activated carbon and its use in acetylene hydrochlorination [ J ] test results using nitric acid activated carbon modification in petroleum refining and chemical industry (9 h): 46-50.).
Test experiment:
the application of the acid modified carbon material catalyst prepared by the acid modified carbon material catalyst carrier in the acetylene hydrochlorination reaction is provided.
Catalyst performance evaluation device
The performance of the catalyst was evaluated using a stainless steel fixed bed reactor having an inner diameter of 8 to 15 mm.
The raw material gas, namely hydrogen chloride and acetylene, are controlled by respective mass flow controllers, and nitrogen is introduced for 30-60min before reaction to sweep away moisture and air.
After the raw material gas is swept, the raw material gas passes through various mass flowmeters, is mixed and enters a fixed bed reaction tube for reaction, and the temperature in the fixed bed is detected by a thermocouple.
And (4) allowing the tail gas to flow through an absorption bottle, absorbing NaOH solution to remove hydrogen chloride, and analyzing by using a gas chromatograph.
The catalyst prepared in the comparative examples 1-7 in the examples 1-5 is activated by hydrogen chloride for 40min at an acetylene space velocity of 120h -1 The reaction temperature is 150 ℃, and the raw material gas ratio is n (HCl): n (C) 2 H 2 ) Evaluation under the condition of =1.15, initial conversion of acetylene, selectivity of vinyl chloride, and initial conversion improvement rate of acetylene of the catalyst prepared from the acid-modified activated carbon catalyst support of the present application, compared to the unmodified catalyst support of comparative example 1 of the present application, were respectively tested, and the results are shown in table 1.
Table 1:
| initial conversion of acetylene (%) | Vinyl chloride selectivity (%) | Initial acetylene conversion enhancement (%) | |
| Example 1 | 84 | >99.5 | 86.7 |
| Example 2 | 82 | >99.5 | 82.2 |
| Example 3 | 87 | >99.5 | 93.3 |
| Example 4 | 78 | >99.5 | 73.3 |
| Example 5 | 73 | >99.5 | 62.2 |
| Comparative example 1 | 45 | >99.5 | - |
| Comparative example 2 | 64 | >98.3 | 42.2 |
| Comparative example 3 | 65 | >99.1 | 44.4 |
| Comparative example 4 | 68 | >98.9 | 51.1 |
| Comparative example 5 | 66 | >98.5 | 46.7 |
| Comparative example 6 | 71.8 | >97.9 | ≈23.8 |
As can be seen from table 1, the modified catalysts prepared in the examples, the modified catalysts prepared with nitric acid solution and nickel nitrate as modifiers, had the highest initial conversion rate of acetylene in the acetylene hydrochlorination reaction (example 3), while the catalysts obtained in comparative example 1 using coal-based activated carbon not soaked with the modifiers had a lower conversion rate of acetylene in the acetylene hydrochlorination reaction (45%), and it can be seen that the concentration ratio of the acid solution to the nickel salt in the modifiers, the calcination conditions, and the mass ratio of the metal salt solution to the nickel nitrate all affect the catalytic effect of the modified catalysts.
The embodiments of the present invention are preferred, and not intended to limit the scope of the present invention, and those skilled in the art can make reasonable changes and modifications without departing from the spirit and scope of the present invention. It is to be understood that such changes and modifications are intended to fall within the scope of the present disclosure.
Claims (6)
1. A preparation method of a modified catalyst used in acetylene hydrochlorination is characterized by comprising the following steps:
(1) Drying the activated carbon, soaking the activated carbon by using a modifier, and washing the activated carbon to be neutral by using deionized water to obtain acid modified activated carbon;
(2) Dissolving nickel nitrate in deionized water to obtain a nickel nitrate solution, then immersing the acid modified activated carbon obtained in the step (1) in the nickel nitrate solution, and then calcining to obtain modified activated carbon;
(3) Adding metal salt into a hydrochloric acid solution, then vacuum-impregnating the modified activated carbon obtained in the step (2), evaporating and drying to finally obtain a modified catalyst;
the modifier in the step (1) is a mixture of nickel salt and acid solution, wherein the nickel salt is one or more of nickel chloride, nickel nitrate and nickel sulfate, and the acid solution is one or more of citric acid, nitric acid, hydrochloric acid and phosphoric acid;
the concentration ratio of nickel salt to acid solution in the modifier in the step (1) is 1:5-45, and the volume of the modifier is 3-6 times that of the activated carbon;
the calcination in the step (2) is firstly carried out at the temperature of 180-200 ℃ for 1-2h, then is carried out at the temperature of 80-120 ℃ for 0.5-1h, and is further carried out at the temperature of 220-300 ℃ for 2-3h, the heating rate is 10 ℃/min, and the atmosphere is nitrogen;
the metal salt in the step (3) is one or more of chloride, sulfate and phosphate of gold, copper, tin and bismuth.
2. The method of claim 1, wherein: the active carbon in the step (1) is one or more of wood active carbon, coal active carbon and coconut shell active carbon, and the specific surface area is 1300-1600m 2 G, the mass fraction of ash is less than or equal to 5 percent.
3. The method of claim 1, wherein: the mass of the activated carbon in the step (1) is 50-200g.
4. The method of claim 1, wherein: the mass of the metal salt in the step (3) is 10-100g.
5. The method of claim 1, wherein: the concentration of the hydrochloric acid solution in the step (3) is 0.5-1.5mol/L.
6. Use of the catalyst prepared by the preparation method according to any one of claims 1 to 5 in the hydrochlorination of acetylene.
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| JP2006176698A (en) * | 2004-12-24 | 2006-07-06 | Utsunomiya Univ | Magnetic abrasive grain, its manufacturing method, electroless plating method and electroless plating activator for activated carbon |
| CN103495416A (en) * | 2013-10-24 | 2014-01-08 | 新疆大学 | Carbon-material supported catalyst for acetylene hydrochlorinate reaction |
| CN104549143A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Activated carbon desulfurization adsorbent and preparation method thereof |
| WO2017024420A1 (en) * | 2015-08-12 | 2017-02-16 | 华北电力大学（保定） | Supported solid phase catalyst, and preparation method and use thereof |
| CN105921164A (en) * | 2016-05-20 | 2016-09-07 | 湘潭大学 | Preparation method and application of nitrogen-doped activated carbon supported alkali metal modified nickel-based catalyst |
| CN107876011A (en) * | 2017-11-07 | 2018-04-06 | 常州布奇纺织有限公司 | A kind of sulfur-bearing industrial waste gas processing method |
| CN109821546A (en) * | 2019-03-04 | 2019-05-31 | 鄂尔多斯市瀚博科技有限公司 | Compound copper-based catalysts and preparation method and its application in production vinyl chloride |
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