Au / hof-co0.5fe0.5 catalyst for acetylene hydrochlorination reaction and preparation method and application thereof

Abstract

The application discloses an Au / HOF-Co0.5Fe0.5 catalyst for acetylene hydrochlorination reaction and a preparation method and application thereof. The Au / HOF-Co0.5Fe0.5 catalyst comprises a carrier and a gold active component loaded on the carrier, and the carrier is a doped hydrogen-bonded organic framework HOF-Co0.5Fe0.5. The application provides application of the Au / HOF-Co0.5Fe0.5 catalyst in a reaction of synthesizing chloroethylene through acetylene hydrochlorination, and the catalyst has good stability and high activity.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of catalysts, and particularly relates to a supported gold catalyst for acetylene hydrochlorination reaction and a preparation method and application thereof. BACKGROUND

[0002] Polyvinyl chloride (PVC) is one of the five major engineering plastics in the world, and has a universal application in the chemical industry. Vinyl chloride (VCM) is a monomer for the synthesis of PVC, and the annual demand for PVC is 400 million tons, so that VCM is a very important chemical raw material, and about 90% of VCM is used to produce PVC. There are mainly three chemical synthesis processes for vinyl chloride, which are C2H2 method, C2H4 method and C2H6 method. The resource structure of "rich in coal, poor in oil and less gas" in China determines that the calcium carbide acetylene method will be the main process for the production of vinyl chloride in China for a long time in the future, that is, the reaction of acetylene and hydrogen chloride catalyzed by mercuric chloride to generate vinyl chloride. The activity and selectivity of the catalyst are relatively high, but the thermal stability is poor, and the use process will cause the loss of mercury in the catalyst, thereby affecting the activity, and more seriously, the high-toxicity mercuric chloride will cause serious pollution to the environment. At present, many scholars are actively exploring how to replace the mercury catalyst in the acetylene hydrochlorination reaction, and seeking a green and efficient technical route, and people gradually focus on mercury-free chlorides with metal chlorides as active components, among which, noble metal chlorides show the best catalytic activity, such as gold, palladium, ruthenium, copper and other metals as active components, which are reported to have higher catalytic activity than mercury.

[0003] In 1985, it was predicted that gold is the best catalyst for acetylene hydrochlorination reaction, and this prediction was later confirmed. This has triggered the development of many gold catalytic reactions. The supported gold catalyst is very stable and will not leach metal from the catalyst, which is completely opposite to the supported mercuric chloride catalyst. It is found that the gold catalyst contains gold nanoparticles, and early studies show that Au 3+ has high activity. However, this assumption is mainly based on the characterization and comparison of new catalysts and old catalysts. Recently, people's interest in finding a commercially viable mercury-free catalyst for this important industrial process has been rekindled, and these studies are mostly focused on using gold as a catalyst.

[0004] Many previous studies have shown that the presence of Au 3+ is important for observing high activity in acetylene hydrochlorination. In some catalysts, lanthanide elements are deliberately added to stabilize the high valence state of gold. The evidence supporting this guess comes from the x-ray photoelectron spectroscopy (XPS) of fresh and deactivated catalysts, in which Au 3+of the Au nanoparticles. Interestingly, transmission electron microscopy studies showed that after deactivation, the Au nanoparticles were almost free of sintering. Although Au 3+ is important in the initial stage, but to observe high activity, Au + must be present. During the reaction, the combination of acetylene and HCl creates an active Au 3+ -Au + pairs and propose that these pairs form and reform during the reaction, thus leading to long catalyst life for acetylene hydrochlorination with supported gold catalysts.

[0005] Therefore, it is of great industrial application prospect to develop a supported gold catalyst with stable active center for acetylene hydrochlorination reaction. SUMMARY

[0006] The purpose of the present application is to solve the problems of Au 3+ reduction at high temperature, carbon deposition at low temperature and the like of gold catalyst in catalytic reaction, and to provide a supported gold catalyst for acetylene hydrochlorination reaction, a preparation method and application thereof, which has good stability and high activity.

[0007] To achieve the above-mentioned purpose of the application, the technical scheme adopted by the present application is as follows:

[0008] In a first aspect, the present application provides an Au / HOF-Co0.5Fe0.5 catalyst for acetylene hydrochlorination reaction, comprising a carrier and a gold active component supported on the carrier, wherein the carrier is a doped hydrogen-bonded organic framework HOF-Co0.5Fe0.5, and the preparation method of the carrier is as follows:

[0009] Step one: 4,4'-dipyridyl, Na2S and S are added to deionized water, and mixed uniformly to form a mixed solution;

[0010] Step two: the mixed solution is transferred to a high-pressure kettle with a polytetrafluoroethylene lining, and is hydrothermally treated at 140-160℃ for 60-84h;

[0011] Step three: the mixed solution obtained in step two is cooled to 60-80℃, and is transferred to a sealed glass bottle;

[0012] Step four: divalent Fe compound and Co compound are added to the mixed solution obtained in step three, and are stirred for 1-3h and then filtered; the feeding ratio of the divalent Fe compound and Co compound is 1:1 in terms of the molar ratio of Fe and Co contained therein;

[0013] Step five: the filtrate obtained in step four is crystallized at 20-40℃ for 10-12h to obtain crystals, i.e. the doped hydrogen-bonded organic framework HOF-Co0.5Fe0.5.

[0014] Further, in step one, the molar ratio of 4,4'-bipyridine, Na2S, S, Fe+Co is 2.23:2.53:2.53:2.25, wherein Fe+Co represents the total moles of Fe contained in the divalent Fe compound and Co contained in the Co compound.

[0015] Further, in step one, the mixture is uniformly mixed by ultrasonic treatment followed by stirring to form a mixed solution.

[0016] Further, in step four, the Fe compound is at least one of FeSO4, FeCl2, FeC2O4, and the Co compound is at least one of CoCl2, Co(NO3)2, CoSO4, and (NH4)2C2O4.

[0017] In the Au / HOF-Co0.5Fe0.5 catalyst, the gold active component can be a gold active component of a conventional supported gold catalyst used in the hydrochlorination of acetylene, such as a gold atom, and the loading of the active component can also be a conventional loading, such as a loading (calculated as the mass ratio of gold element to support) of gold active component of 0.2-10 wt%.

[0018] In a second aspect, the application provides a preparation method of an Au / HOF-Co0.5Fe0.5 catalyst for the hydrochlorination of acetylene, comprising the following steps: dissolving a trivalent gold precursor in a solvent to obtain an active component solution; loading the trivalent gold precursor onto a doped hydrogen-bonded organic framework HOF-Co0.5Fe0.5 by a solution impregnation method; after vacuum drying treatment, performing treatment by a glow discharge method to improve the dispersion of the Au active component and inhibit the agglomeration thereof; and finally obtaining the Au / HOF-Co0.5Fe0.5 catalyst.

[0019] As a preference, the trivalent gold precursor is selected from HAuCl4.

[0020] As a preference, the solvent is concentrated hydrochloric acid (such as 32 wt% concentrated hydrochloric acid), concentrated HNO3 (such as 70 wt% concentrated nitric acid), aqua regia (3:1 HCl (32 wt%):HNO3 (70 wt%)), or deionized water.

[0021] As a preference, the specific operation of the solution impregnation method is that after the active component solution and the support are mixed, stirring is performed for 1-2 h, and the supernatant is removed by centrifugation to achieve loading of the trivalent gold precursor onto the support.

[0022] As a preference, the vacuum drying treatment condition is a temperature of 120-300°C and a time of 8-12 hours.

[0023] As preferred, the glow discharge plasma treatment condition is that the vacuum pump maintaining system is kept in vacuum state by using a vacuum pump with a power of 500 W, the pressure of the plasma chamber is kept at 100 Pa by adjusting the air flow, the plasma treatment intensity is adjusted by adjusting the discharge voltage value, the applied voltage is 80-300 V, and the treatment time is 0.5-2 h. Further preferably, the applied voltage is 80-100 V, and the treatment time is 1-2 h.

[0024] In a third aspect, the application provides application of the Au / HOF-Co0.5Fe0.5 catalyst in the reaction of catalytic hydrochlorination of acetylene to synthesize vinyl chloride.

[0025] The application specifically refers to that the Au / HOF catalyst is loaded in a fixed bed reactor, raw gas HCl and C2H2 are introduced, the reaction temperature is 120-200 ℃, the reaction pressure is 0.01-2 MPa, and vinyl chloride is obtained by reaction.

[0026] As preferred, the amount-of-substance ratio of the raw gas is n(HCl):n(C2H2)=1:1-1.2:1, the acetylene volume space velocity is 5-500 h-1, and the reaction time is 0.5-2 h. -1 .

[0027] Compared with the prior art, the application has the following innovations and technical advantages:

[0028] (1) The hydrogen-bonded organic framework material HOF is used to replace the traditional activated carbon as the catalyst carrier in the application, and the HOF material has the advantages of high crystallinity, large surface area and rich porosity. Compared with single-atom catalysts (SACs), the transition metal macrocycle HOF also has clear active sites, providing an ideal model system for exploring structure-property correlations. And the HOF structure optimizes the molecular structure to promote intrinsic catalytic activity or builds a porous framework to increase the surface exposure of active sites. As the preparation technology of HOF material gradually matures and the cost gradually decreases, the application has strong industrial application prospects.

[0029] (2) The HOF carrier is doped with Fe and Co in the application, and is further coordinated with Au, which enhances the activity and stability of the Au-based catalyst. And it can increase the dispersion of Au active components and the anti-carbon deposition capacity.

[0030] (3) The glow discharge plasma technology is used to replace the traditional calcination process in the application, which greatly enhances the dispersion of gold, is beneficial to reduce agglomeration, makes more active sites exposed on the inner and outer surfaces of the catalyst, plays a high activity, and can maintain stability in a long reaction process.

[0031] (4) The Au / HOF-Co0.5Fe0.5 catalyst prepared by the method has high conversion rate and high selectivity in the acetylene hydrochlorination reaction, has good stability, and has good economic applicability and industrial application value. DETAILED DESCRIPTION

[0032] The application will be further described in the following specific examples. It should be pointed out that the examples are only used to further illustrate the application, and cannot be understood as limiting the protection scope of the application. The application is not limited to the examples in any way. Those skilled in the art can make some non-essential improvements and adjustments according to the content of the above application.

[0033] Example 1

[0034] (1) Synthesis of Fe and Co doped hydrogen bond organic framework (HOF-Co0.5Fe0.5): 4,4'-dipyridyl (2.23 mmol), Na2S (2.53 mmol), S (2.53 mmol) were first added to 16.7 mL of deionized water, and ultrasonic treatment was performed for 20 min, and then room temperature stirring was performed in an electromagnetic stirrer for 5 h, and the magnetic field strength was set to 100 T. Then the mixed solution was added to a reaction kettle with a polytetrafluoroethylene liner, and the temperature was kept at 150℃ at a heating rate of 1℃ / min, and hydrothermal treatment was performed for 72 h. Then the temperature was cooled to 70℃ at a cooling rate of 1℃ / min to obtain a pink solution of the hydrogen bond framework product. After adding a total amount of 2.25 mmol of Co(NO3)2·6H2O and FeSO4·7H2O with a molar ratio of 0.5:0.5 to the above solution, room temperature stirring was performed in an electromagnetic stirrer for 2 h, and the magnetic field strength was set to 100 T. The obtained filtrate was crystallized at 30℃ for 12 h to obtain needle-like crystals, and the HOF-Co0.5Fe0.5 support material was obtained.

[0035] (2) Preparation of Au / HOF-Co0.5Fe0.5 catalyst: Take 10 g of HOF-Co0.5Fe0.5 material obtained in step (1) into a container. Take gold precursor HAuCl4xH2O (0.204 g, gold content is 49 wt%) and dissolve it in 4 ml aqua regia solution (3:1 HCl (32 wt%): HNO3 (70 wt%)), add it into the container after ultrasonic treatment for 10 min, stir for 2 hours, centrifuge, remove the supernatant, vacuum dry at 120°C for 10 hours, and then carry out glow discharge treatment, use a vacuum pump with a power of 500 W to keep the system in a vacuum state, adjust the air flow to keep the pressure in the plasma chamber at 100 Pa, adjust the plasma treatment intensity by adjusting the discharge voltage value, apply a voltage of 80 V, and the treatment time is 1.5 h. Thus, the Au / HOF-Co0.5Fe0.5 catalyst with a Au (III) loading of 1 wt% is obtained.

[0036] (3) The catalyst is tested for the ethyne hydrochlorination reaction in a fixed bed reactor, and the reaction conditions are: temperature 150°C, reaction pressure 0.01 MPa, n(HCl):n(C2H2) = 1:1, ethyne space velocity 30 h -1 -1. The ethyne conversion rate is 99.72% and the vinyl chloride selectivity is 100% at the beginning of the reaction; after 800 hours of reaction, the ethyne conversion rate is 99.55% and the vinyl chloride selectivity is 99.86%.

[0037] Example 2

[0038] (1) HOF-Co0.5Fe0.5 prepared according to Example 1.

[0039] (2) Preparation of Au / HOF-Co0.5Fe0.5 catalyst: Take 10 g of HOF-Co0.5Fe0.5 material obtained in step (1) into a container. Take gold precursor HAuCl4xH2O (0.204 g, gold content is 49 wt%) and dissolve it in 4 ml HCl (32 wt%), add it into the container after ultrasonic treatment for 10 min, stir for 2 hours, centrifuge, remove the supernatant, vacuum dry at 120°C for 10 hours, and then carry out glow discharge treatment, use a vacuum pump with a power of 500 W to keep the system in a vacuum state, adjust the air flow to keep the pressure in the plasma chamber at 100 Pa, adjust the plasma treatment intensity by adjusting the discharge voltage value, apply a voltage of 80 V, and the treatment time is 1.5 h. Thus, the Au / HOF-Co0.5Fe0.5 catalyst with a Au (III) loading of 1 wt% is obtained.

[0040] (3) The catalyst was tested in the hydrochlorination of acetylene in a fixed bed reactor. The reaction conditions were: temperature 150°C, reaction pressure 0.01 MPa, n(HCl):n(C2H2) = 1:1, acetylene space velocity 30 h -1 The conversion of acetylene was 99.28% and the selectivity of vinyl chloride was 99.82% at the beginning of the reaction. After 800 hours of reaction, the conversion of acetylene was 98.89% and the selectivity of vinyl chloride was 99.47%.

[0041] Example 3

[0042] (1) HOF-Co0.5Fe0.5was prepared as in Example 1.

[0043] (2) Preparation of Au / HOF-Co0.5Fe0.5catalyst: 10 g of HOF-Co0.5Fe0.5material obtained in step (1) was taken into a container. Gold precursor HAuCl4xH2O (0.204 g, gold content 49 wt%) was dissolved in 4 ml of HNO3(70 wt%) and added into the container after ultrasonic treatment for 10 min. The mixture was stirred for 2 hours, centrifuged, and the supernatant was removed. The material was vacuum dried at 120°C for 10 hours, and then subjected to glow discharge treatment. The system was kept in vacuum by a vacuum pump with a power of 500 W. The pressure in the plasma chamber was kept at 100 Pa by adjusting the air flow. The plasma treatment intensity was adjusted by adjusting the discharge voltage value. The applied voltage was 80 V, and the treatment time was 1.5 h. Thus, the Au / HOF-Co0.5Fe0.5catalyst with a Au(III) loading of 1 wt% was obtained.

[0044] (3) The catalyst was tested in the hydrochlorination of acetylene in a fixed bed reactor. The reaction conditions were: temperature 150°C, reaction pressure 0.01 MPa, n(HCl):n(C2H2) = 1:1, acetylene space velocity 30 h -1 The conversion of acetylene was 99.28% and the selectivity of vinyl chloride was 99.82% at the beginning of the reaction. After 800 hours of reaction, the conversion of acetylene was 98.89% and the selectivity of vinyl chloride was 99.47%.

[0045] Example 4

[0046] (1) Synthesis of Fe, Co doped hydrogen bonded organic framework (HOF-Co0.8Fe0.2): First, 4,4'-bipyridine (2.23 mmol), Na2S (2.53 mmol), S (2.53 mmol) were added to deionized water, ultrasonic treatment for 20 min, then stirred at room temperature in an electromagnetic stirrer for 5 h, the magnetic field intensity was set to 100 T. Then the mixed solution was added to the reaction kettle with a polytetrafluoroethylene liner, and kept at 150℃ with a heating rate of 1℃ / min, and hydrothermal treatment was carried out for 72 h. Then it was cooled to 70℃ at the same heating rate to obtain a pink solution of hydrogen bonded organic framework product. After adding a total of 2.25 mmol of Co(NO3)2·6H2O and FeSO4·7H2O with a molar ratio of 0.8:0.2 to the above solution, it was stirred at room temperature in an electromagnetic stirrer for 2 h, the magnetic field intensity was set to 100 T, and then filtered. The obtained filtrate was crystallized at 30℃ for 12 h to obtain needle-like crystals, i.e. a Co0.2Fe0.8 doped HOF support material.

[0047] (2) Preparation of Au / HOF-Co0.2Fe0.8 catalyst: 10 g of the HOF-Co0.2Fe0.8 material obtained in step (1) was taken into a container. A gold precursor HAuCl4·xH2O (0.204 g, gold content 49 wt%) was dissolved in 4 ml aqua regia solution (3:1 HCl (32 wt%):HNO3 (70 wt%)), and after ultrasonic treatment for 10 min, it was added to the container, stirred for 2 h, centrifuged, the supernatant was removed, vacuum dried at 120℃ for 10 h, and then subjected to glow discharge treatment, a vacuum pump was used to keep the system in a vacuum state with a power of 500 W, the pressure in the plasma chamber was kept at 100 Pa by adjusting the air flow, and the plasma treatment intensity was adjusted by adjusting the discharge voltage value, the applied voltage was 80 V, and the treatment time was 1.5 h. Thus, an Au / HOF-Co0.2Fe0.8 catalyst with an Au(III) loading of 1 wt% was obtained.

[0048] (3) The catalyst was tested for the ethyne hydrochlorination reaction in a fixed bed reactor, and the reaction conditions were: temperature 150℃, reaction pressure 0.01 MPa, n(HCl):n(C2H2) = 1:1, ethyne space velocity 30 h-1. -1 At the beginning of the reaction, the ethyne conversion rate was 98.72%, and the vinyl chloride selectivity was 99.73%; after 800 h of reaction, the ethyne conversion rate was 97.55%, and the vinyl chloride selectivity was 98.88%.

[0049] Comparative Example 1

[0050] Comparative Example 1 is used to illustrate the excellent performance of the hydrogen bonded organic framework support material in terms of catalytic stability by comparison with Example 1.

[0051] (1) Take 10 g of activated carbon (Fujian Xinsen SAC) into a container. Take the gold precursor HAuCl4xH2O (0.204 g, gold content of 49 wt%) and dissolve it in 4 ml of aqua regia solution (3:1 HCl (32 wt%): HNO3 (70 wt%)), add it into the container after ultrasonic treatment for 10 min, stir for 2 hours, centrifuge, remove the supernatant, vacuum dry at 120°C for 10 hours, and then perform glow discharge treatment, use a vacuum pump with a power of 500 W to keep the system in a vacuum state, adjust the air flow to keep the pressure in the plasma chamber at 100 Pa, adjust the plasma treatment intensity by adjusting the discharge voltage value, apply a voltage of 80 V, and the treatment time is 1.5 h. A gold-based catalyst with a Au(III) loading of 1 wt% is obtained.

[0052] (2) The catalyst is tested for the ethyne hydrochlorination reaction in a fixed bed reactor, and the reaction conditions are: temperature 150°C, reaction pressure 0.01 MPa, n(HCl): n(C2H2) = 1:1, ethyne space velocity 30 h -1 -1. The initial ethyne conversion rate is 83.66%, and the vinyl chloride selectivity is 93.57%; after 800 hours of reaction, the ethyne conversion rate is 70.38%, and the vinyl chloride selectivity is 87.92%.

[0053] Comparative Example 2

[0054] Comparative Example 2 is used to illustrate the excellent performance of the hydrogen-bonded organic framework carrier material in terms of catalytic stability by comparison with Example 2.

[0055] (1) Take 10 g of activated carbon fiber (Nantong Senyou SY-1000) into a container. Take the gold precursor HAuCl4xH2O (0.204 g, gold content of 49 wt%) and dissolve it in 4 ml of HCl (32 wt%), add it into the container after ultrasonic treatment for 10 min, stir for 2 hours, centrifuge, remove the supernatant, vacuum dry at 120°C for 10 hours, and then perform glow discharge treatment, use a vacuum pump with a power of 500 W to keep the system in a vacuum state, adjust the air flow to keep the pressure in the plasma chamber at 100 Pa, adjust the plasma treatment intensity by adjusting the discharge voltage value, apply a voltage of 100 V, and the treatment time is 1.5 h. A gold-based catalyst with a Au(III) loading of 1 wt% is obtained.

[0056] (2) The catalyst is tested for the ethyne hydrochlorination reaction in a fixed bed reactor, and the reaction conditions are: temperature 150°C, reaction pressure 0.01 MPa, n(HCl): n(C2H2) = 1:1, ethyne space velocity 30 h -1The conversion of acetylene was 80.46% and the selectivity of vinyl chloride was 93.37% at the beginning of the reaction. After 800 hours of reaction, the conversion of acetylene was 68.39% and the selectivity of vinyl chloride was 88.93%.

[0057] Comparative Example 3

[0058] Comparative Example 3 is used to illustrate the irreplaceability of glow discharge plasma in the preparation of catalysts by comparison with Example 3.

[0059] (1) HOF-Co0.5Fe0.5 was prepared as in Example 1.

[0060] (2) Preparation of Au / HOF-Co0.5Fe0.5 catalyst: 10 g of HOF-Co0.5Fe0.5 material obtained in step (1) was taken into a container. Gold precursor HAuCl4xH2O (0.204 g, gold content 49 wt%) was dissolved in 4 ml of HNO3(70 wt%) and added into the container after ultrasonic treatment for 10 min. The mixture was stirred for 2 hours, centrifuged, and the supernatant was removed. The Au / HOF-Co0.5Fe0.5 catalyst with a Au(III) loading of 1 wt% was obtained by vacuum drying at 120°C for 10 hours.

[0061] (3) The catalyst was tested in the acetylene hydrochlorination reaction in a fixed bed reactor. The reaction conditions were: temperature 150°C, reaction pressure 0.01 MPa, n(HCl):n(C2H2) = 1:1, acetylene space velocity 30 h -1 The conversion of acetylene was 85.84% and the selectivity of vinyl chloride was 93.92% at the beginning of the reaction. After 800 hours of reaction, the conversion of acetylene was 66.58% and the selectivity of vinyl chloride was 88.57%.

Claims

1. An Au / HOF-Co0.5Fe0.5 catalyst for the hydrochlorination of acetylene, comprising a support and a gold active component supported on the support, characterized in that: The carrier is a doped hydrogen-bonded organic framework HOF-Co0.5Fe0.5, and the preparation method of the carrier is as follows: Step one: 4,4'-dipyridyl, Na2S, and S are added to deionized water, and mixed uniformly to form a mixed solution; Step two: the mixed solution is transferred into a high-pressure kettle with a polytetrafluoroethylene lining, and is hydrothermally treated at 140-160 DEG C for 60-84 h; Step three: the mixed solution obtained in step two is cooled to 60-80 DEG C, and is transferred into a sealed glass bottle; Step four: divalent Fe compounds and Co compounds are added to the mixed solution obtained in step three, and are stirred for 1-3 h and then filtered; the feeding ratio of the divalent Fe compounds and Co compounds is 1:1 in terms of the molar ratio of Fe and Co contained therein; Step five: the filtrate obtained in step four is crystallized at 20-40 DEG C for 10-12 h to obtain crystals, i.e. the doped hydrogen-bonded organic framework HOF-Co0.5Fe0.5; The Au / HOF-Co0.5Fe0.5 catalyst is prepared by a preparation method comprising the following steps: a trivalent gold precursor is dissolved in a solvent to obtain an active component solution; the trivalent gold precursor is loaded on the doped hydrogen-bonded organic framework HOF-Co0.5Fe0.5 by a solution impregnation method, vacuum drying treatment is performed, and then a glow discharge method is used for treatment to improve the dispersion of the Au active component and inhibit the agglomeration thereof, and finally the Au / HOF-Co0.5Fe0.5 catalyst is obtained.

2. The Au / HOF-Co0.5Fe0.5 catalyst for the hydrochlorination of acetylene according to claim 1, characterized by: In step four, the Fe compounds are at least one of FeSO4, FeCl2, and FeC2O4, and the Co compounds are at least one of CoCl2, Co(NO3)2, and CoSO4.

3. The Au / HOF-Co0.5Fe0.5 catalyst for hydrochlorination of acetylene according to claim 1, characterized by: The treatment conditions of the glow discharge method are as follows: a vacuum pump with a power of 500 W is used to keep the system in a vacuum state, the pressure of the plasma chamber is kept at 100 Pa by adjusting the air flow, the plasma treatment intensity is adjusted by adjusting the discharge voltage value, the applied voltage is 80-300 V, and the treatment time is 0.5-2 h.

4. The Au / HOF-Co0.5Fe0.5 catalyst for the hydrochlorination of acetylene according to claim 3, characterized by: The applied voltage is 80-100 V, and the treatment time is 1-2 h.

5. A process for the preparation of Au / HOF-Co0.5Fe0.5 catalyst for the hydrochlorination of acetylene according to any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: a trivalent gold precursor is dissolved in a solvent to obtain an active component solution; the trivalent gold precursor is loaded on the doped hydrogen-bonded organic framework HOF-Co0.5Fe0.5 by a solution impregnation method, vacuum drying treatment is performed, and then a glow discharge method is used for treatment to improve the dispersion of the Au active component and inhibit the agglomeration thereof, and finally the Au / HOF-Co0.5Fe0.5 catalyst is obtained.

6. The production method according to claim 5, characterized by: The trivalent gold precursor is selected from HAuCl4.

7. The production method according to claim 5, wherein: The solvent is concentrated hydrochloric acid, concentrated HNO3, aqua regia, or deionized water.

8. The production method according to claim 5, wherein: The specific operation of the solution impregnation method is as follows: after the active component solution and the carrier are mixed, stirring is performed for 1-2 h, the supernatant is removed by centrifugation, and the trivalent gold precursor is loaded on the carrier.

9. The production method according to claim 5, wherein: The vacuum drying treatment conditions are as follows: the temperature is 120-300 DEG C, and the time is 8-12 h.

10. Use of the Au / HOF-Co0.5Fe0.5 catalyst according to any one of claims 1 to 4 in the reaction of catalytic hydrochlorination of acetylene to synthesize vinyl chloride.