POROUS INTERMETALLIC COMPOUNDS, PREPARATION METHOD AND APPLICATION THEREOF

Abstract

The invention discloses a porous intermetallic compound and preparation method and application thereof. The pore structure of the porous intermetallic compound includes micropores and mesopores, and the micropores and mesopores are distributed in disorder, wherein the content of the micropores accounts for 6-68%, and the content of mesopores accounts for 32-92%; the specific surface area of the porous intermetallic compound is 50-1600 m.sup.2/g, and the porous intermetallic compound is a porous copper silicide intermetallic compound or porous copper-chalcogen intermetallic compound. The invention provides preparation methods of the porous intermetallic compound, and also provides an application of the porous intermetallic compound as a catalyst in the reaction of acetylene hydrochlorination to synthesize vinyl chloride. The porous intermetallic compound catalyst prepared by the invention can carry out the acetylene hydrochlorination reaction in a wide space velocity range, and has good catalytic activity.

Claims

1. A porous intermetallic compound, wherein: the pore structure of the porous intermetallic compound includes micropores and mesopores, and the micropores and mesopores are distributed in disorder, wherein the content of the micropores accounts for 6-68%, and the content of mesopores accounts for 32-92%; the specific surface area of the porous intermetallic compound is 50-1600 m.sup.2/g; the porous intermetallic compound is a porous copper silicide intermetallic compound or porous copper-chalcogen intermetallic compound; in the porous copper silicide intermetallic compound, the molar ratio of copper to silicon is 0.425:1; in the porous copper-chalcogen intermetallic compound, the chalcogen is one or more of sulfur, selenium and tellurium, and the chemical formula of the porous copper-chalcogen intermetallic compound is Cu.sub.xS.sub.ySe.sub.mTe.sub.n, wherein x>0, y, m, n0, and the molar ratio of copper to chalcogen, i.e. x/(y+m+n)=1:0.015.

2. The porous intermetallic compound of claim 1, wherein: in the porous copper silicide intermetallic compound, the content of micropores accounts for 10-40%, and the content of mesopores accounts for 60-90%.

3. The porous intermetallic compound of claim 1, wherein: the molar ratio of copper to silicon in the porous copper silicide intermetallic compound is 0.4-5:1.

4. The porous intermetallic compound of claim 1, wherein: the specific surface area of the porous copper silicide intermetallic compound is 400-600 m.sup.2/g.

5. The porous intermetallic compound of claim 1, wherein: in the porous copper-chalcogen intermetallic compound, the molar ratio of copper to chalcogen is 1:0.2-5.

6. A preparation method of a porous intermetallic compound of claim 1, which comprises: 1) mixing a copper precursor with compound A, wherein the mass ratio of the precursor to the compound A is 1:0.81.55, placing the resulting mixture in an inert atmosphere or air atmosphere, and fully grinding it in a planetary ball mill; wherein the compound A is a silicon-containing compound or an inorganic or organic chalcogen-containing compound; 2) putting the ground material obtained in step 1) into a constant temperature microwave shaker for microwave digestion treatment, wherein the frequency of the microwave digestion treatment is 300 MHz300 GHz, and the treatment time is 0.124 h; 3) placing the mixture obtained in step 2) in a Joule heating furnace under an inert gas atmosphere for rapid heating and cooling treatment by carbon thermal shock method, in which the temperature of the carbon thermal shock is 2003200 C., the duration of the shock is 0.05-3 seconds, and the heating/cooling rate is 102000 C. per second; 4) placing the material obtained in step 3) in deionized water for ultrasonic washing, and then subjecting the material to vacuum drying to obtain the porous intermetallic compound.

7. The preparation method of claim 6, wherein: in step 1), the copper precursor is selected from at least one of copper powder, copper chloride, copper nitrate, copper sulfate, copper oxide, cuprous oxide, copper hydroxide, copper phosphide, copper sulfide, copper selenide, and copper acetate; the silicon-containing compound is selected from one or more of nano-silica powder, diatomaceous earth, silicon acetate, trimethylsilimidazole, silicon dioxide, silica, silicic acid, and boron silicide; and the chalcogen-containing compound is selected from one or more of inorganic and organic compounds containing sulfur, selenium and/or tellurium.

8. The preparation method of claim 7, wherein: the chalcogen-containing compound is selected from one or more of thioglycolic acid, thioacetamide, 1,3-bis(thioacetic acid-S-n-propyl) imidazolium bromide, propanethiol, 2-propylthiol, sodium methanethiolate, n-butyl mercaptan, allyl mercaptan, n-dodecane mercaptan, cyclohexane mercaptan, methyl sulfide, methyl ethyl sulfide, thiourea, sulfur tetrachloride, sulfuric acid, sodium sulfide, tin sulfide, tungsten sulfide, selenium disulfide, phosphorus pentasulfide, sublimated sulfur, silicon sulfide, tellurium disulfide, selenium telluride, dimethyl selenium, selenophene, dimethyl diselenide, selenium tetrachloride, selenophene, triphenylphosphine selenide, selenium powder, copper selenide, selenium dioxide, selenium acid solution, iron selenide, selenium disulfide, selenium telluride, di-tert-butyl tellurium, diphenyl tellurium, diethyl tellurium, tellurium tetrachloride, tellurium isopropanol, tellurium powder, tellurium oxide, copper telluride, ammonium tellurate, telluric acid, tellurium disulfide, and selenium telluride.

9. The preparation method of claim 6, wherein: the porous intermetallic compound is a porous copper silicide intermetallic compound, in step 1), the ball milling speed is 100-100,000 rpm, and the ball milling time is 0.5-24 h.

10. The preparation method of claim 6, wherein: the porous intermetallic compound is a porous copper-chalcogen intermetallic compound, in step 1), the ball milling speed is 100-12000 rpm, and the ball milling time is 0.5-5 h.

11. The preparation method of claim 10, wherein: the ball milling speed is 2000-12000 rpm, and the ball milling time is 1-5 h.

12. The preparation method of claim 6, wherein: the porous intermetallic compound is a porous copper-chalcogen intermetallic compound, in step 2), the frequency of the microwave digestion treatment is 300 MHz-300 GHz, and the treatment time is 1-5 h.

13. The preparation method of claim 6, wherein: the porous intermetallic compound is a porous copper-chalcogen intermetallic compound, in step 3), the temperature of the carbon thermal shock method is 500-3200 C., the shock duration is 0.1-3 seconds, and the heating/cooling rate is 100-2000 C. per second.

14. The preparation method of claim 6, wherein: the temperature of vacuum drying in step 4) is 80-120 C., and the time of vacuum drying is 2-12 h.

15. A method for preparing a porous copper silicide intermetallic compound of claim 1, comprising the following steps: a) mixing a copper-containing precursor with a silicon-containing compound, wherein the mass ratio of the precursor to the silicon-containing compound is 1:0.81.4, and then subjecting the obtained mixture to microwave digestion treatment to obtain a silicon-copper skeleton material, wherein the frequency of the microwave digestion treatment is 300 MHz300 GHz, and the treatment time is 0.1-24 h; b) subjecting the silicon-copper skeleton material to a solid-state electrolysis process in an electrolytic cell, and collecting the cathode deposits to obtain the porous copper silicide intermetallic compound; wherein the electrolyte is NASICON oxide solid electrolyte, the electrode anode is made of CW104C copper alloy, the cathode is made of carbon nanofibers, the electrolysis time of the solid-state electrolysis process is 0.53 h, and the current density is 10-500 mA.Math.cm.sup.2.

16. The preparation method of claim 15, wherein: in step a), the treatment time is 0.5-5 h.

17. The preparation method of claim 16, wherein: in step b), the electrolysis time is 0.5-3 h, and the current density is 100-500 mA.Math.cm.sup.2.

18. An application of the porous intermetallic compound of claim 1 as a catalyst in the reaction of acetylene hydrochlorination to synthesize vinyl chloride.

19. The application of claim 18, wherein: the application is as follows: introducing raw material gases hydrogen chloride and acetylene into a fixed-bed reactor loaded with the porous intermetallic compound of claim 1, and performing the reaction at a reaction temperature of 80-400 C. to generate vinyl chloride.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0049] FIG. 1: Scanning electron microscope image of the material prepared in Example 1.

[0050] FIG. 2: Scanning electron microscope image of the material prepared in Example 4.

[0051] FIG. 3: Reaction performance diagram of the materials prepared in Example 1, Example 3 and Example 5.

[0052] FIG. 4: Scanning electron microscope image of the material prepared in Example 6.

[0053] FIG. 5: Scanning electron microscope image of the material prepared in Example 9.

[0054] FIG. 6: Reaction performance diagram of the material prepared in Example 9.

DETAILED DESCRIPTION OF THE INVENTION

[0055] The present invention is described below with specific examples. It is necessary to point out that the examples are only used to further illustrate the present invention, but should not be construed as limiting the protection scope of the present invention, and the present invention is not limited thereto in any way. Those skilled in the art can make some non-essential improvements and adjustments based on the content of the above invention.

Example 1

[0056] 1) 22.6 g of nano-silicon powder were added to 22 g of copper powder, and the mixture was processed in a planetary ball mill under air atmosphere at a ball milling speed of 20,000 rpm for 1 hour to fully mix the copper powder and the silicon powder;

[0057] 2) the above mixture was placed in a microwave shaker for microwave digestion treatment, the frequency of the microwave digestion treatment was 1500 MHz, and the treatment time was 2 h;

[0058] 3) the above mixture was placed in a Joule heating furnace under nitrogen atmosphere, the temperature of the carbon thermal shock was 3200 C., the shock duration was 120 milliseconds and the heating/cooling rate was 500 C. per second.

[0059] 4) the above material was ultrasonically washed with deionized water, and vacuum dried at 80 C. for 12 hours to obtain a porous copper silicide intermetallic compound material. The physical parameters are shown in Table 1, and the scanning electron microscope image is shown in FIG. 1;

[0060] 5) evaluation of acetylene hydrochlorination reaction in a fixed bed reactor: the effects of temperature and space velocity on the catalytic performance of the catalyst were investigated respectively. Under the condition of acetylene space velocity of 30-740 h.sup.1, the effect of acetylene space velocity on the catalytic performance of the catalyst was investigated. Then, the effect of temperature on the catalytic activity of the catalyst was investigated at 120-300 C., and the results are shown in Table 1; it was found that the effect was the best when the reaction was carried out under the conditions that the reaction temperature was 220 C., the acetylene space velocity was 40 h.sup.1, and the molar ratio of hydrogen chloride to acetylene was 1.05:1, the reaction conversion rate was 98.3% and the selectivity of vinyl chloride was 99% when the reaction initially reached a stable state, and the stability of the catalyst is shown in FIG. 3.

Example 2

[0061] 1) 15.7 g of boron silicide and 5 ml of silicic acid were added to 15 g of cupric chloride dihydrate powder, and the mixture was processed in a planetary ball mill under nitrogen atmosphere at a ball milling speed of 100,000 rpm for 0.5 h to fully mix the copper source and the silicon source;

[0062] 2) the above mixture was placed in a microwave shaker for microwave digestion treatment, the frequency of the microwave digestion treatment was 300 GHz, and the treatment time was 0.5 h;

[0063] 3) the above mixture was placed in a Joule heating furnace under nitrogen atmosphere, the temperature of the carbon thermal shock was 2800 C., the shock duration was 2500 milliseconds, and the heating/cooling rate was 1000 C. per second.

[0064] 4) the above material was ultrasonically washed with deionized water, and vacuum dried at 120 C. for 12 hours to obtain a porous copper silicide intermetallic compound, whose physical parameters are shown in Table 1;

[0065] 5) evaluation of acetylene hydrochlorination reaction in a fixed bed reactor: the acetylene hydrochlorination reaction was carried out at 280 C., acetylene space velocity was 70 h.sup.1, and the molar ratio of hydrogen chloride:acetylene was 1:1. When the reaction initially reached a stable state, the reaction conversion rate was 92.7% and the selectivity of vinyl chloride was 99%.

Example 3

[0066] 1) 13.5 g of diatomite were added to 12 g of copper powder, and the mixture was placed in a microwave shaker for microwave digestion treatment, wherein the frequency of the microwave digestion was 10 GHz and treatment time was 4 h, to obtain a silicon copper skeleton material;

[0067] 2) the silicon-copper skeleton material was subjected to solid-state electrolysis treatment in an electrolytic cell, the electrolyte was NASICON type oxide solid electrolyte, the electrode anode was made of CW104C copper alloy, the cathode was made of carbon nanofibers, the current density was 100 mA.Math.cm.sup.2, the electrolysis time was 0.5 h, and finally a porous copper silicide intermetallic compound material was obtained, and its physical parameters are shown in Table 1;

[0068] 3) evaluation of acetylene hydrochlorination reaction in a fixed bed reactor: the acetylene hydrochlorination reaction was carried out at 210 C., acetylene space velocity was 100 h.sup.1, the molar ratio of hydrogen chloride:acetylene was 1:1.1, and when the reaction initially reached a stable state, the reaction conversion rate was 90.5% and the selectivity of vinyl chloride was 99%.

Example 4

[0069] 1) 17.5 g silicon acetate and 1.5 g silicic acid were added to 20 g copper acetate monohydrate powder, and the mixture was placed in a microwave shaker for microwave digestion treatment, wherein the frequency of the microwave digestion was 800 MHz, treatment time was 4 h, to obtain a silicon copper framework material;

[0070] 2) the silicon-copper skeleton material was subjected to solid-state electrolysis treatment in an electrolytic cell, the electrolyte was NASICON type oxide solid electrolyte, the electrode anode was made of CW104C copper alloy, the cathode was made of carbon nanofibers, the current density was 500 mA.Math.cm.sup.2, the electrolysis time was 0.5 h, and finally a porous copper silicide intermetallic compound material was obtained, and its physical parameters are shown in Table 1, and the scanning electron microscope image is shown in FIG. 2;

[0071] 3) evaluation of acetylene hydrochlorination reaction in a fixed bed reactor: the acetylene hydrochlorination reaction was carried out at 270 C., acetylene space velocity was 370 h.sup.1, and the molar ratio of hydrogen chloride:acetylene was 1:12, and when the reaction initially reached a stable state, the reaction conversion rate was 95% and the selectivity of vinyl chloride was 98%.

Example 5

[0072] 1) 20 g silicon dioxide powder were added to 20 g copper sulfide powder, and the mixture was placed in a microwave shaker for microwave digestion treatment, wherein the frequency of the microwave digestion treatment was 200 GHz, treatment time was 1 h, to obtain a silicon copper framework material;

[0073] 2) the silicon-copper skeleton material was subjected to solid-state electrolysis treatment in an electrolytic cell. The electrolyte was NASICON type oxide solid electrolyte, the electrode anode was made of CW104C copper alloy, the cathode was made of carbon nanofibers, the current density was 200 mA.Math.cm.sup.2, the electrolysis time was 3 h, and finally a porous copper silicide intermetallic compound material was obtained, and its physical parameters are shown in Table 1;

[0074] 3) evaluation of acetylene hydrochlorination reaction in a fixed bed reactor: the acetylene hydrochlorination reaction was carried out at 300 C., acetylene space velocity was 30 h.sup.1, and the molar ratio of hydrogen chloride:acetylene was 0.9:1.2, and when the reaction initially reached a stable state, the reaction conversion rate was 97.9% and the selectivity of vinyl chloride was 99%.

Comparative Example 1

[0075] The fixed bed reactor was charged with copper silicide purchased from Aladdin, and the acetylene hydrochlorination reaction was evaluated under the following conditions: the reaction temperature was at 230 C., the acetylene space velocity was 50 h.sup.1, and the molar ratio of hydrogen chloride:acetylene was 1:1.2. When the reaction initially reached a stable state, the reaction conversion rate was 12% and the selectivity of vinyl chloride was 99%.

Comparative Example 2

[0076] 1) 22.6 g of nano-silicon powder were added to 22 g of copper powder, and the mixture was processed in a planetary ball mill under air atmosphere at a ball milling speed of 20,000 rpm for 1 hour to fully mix the copper powder and the silicon powder;

[0077] 2) the above mixture was placed in a microwave shaker for microwave digestion treatment, the frequency of the microwave digestion treatment was 1500 MHz, and the treatment time was 2 h;

[0078] 3) the above mixture was irradiated with X-rays in nitrogen atmosphere, the frequency of the radiation was 30 EHz, the internal temperature of the mixture was 1100 C., and the treatment was performed for 3 hours;

[0079] 4) the above material was ultrasonically washed with deionized water, and vacuum dried at 80 C. for 12 hours, to obtain a porous copper silicide intermetallic compound;

[0080] 5) the acetylene hydrochlorination reaction was evaluated in a fixed bed reactor with reference to the method in Example 1: the acetylene hydrochlorination reaction was performed at 220 C., the acetylene space velocity was 40 h.sup.1, the molar ratio of hydrogen chloride:acetylene was 1.05:1, and when the reaction initially reached a stable state, the reaction conversion rate was 68% and the selectivity of vinyl chloride was 99%.

Comparative Example 3

[0081] 1) 22.6 g of nano-silicon powder were added to 22 g of copper powder, and the mixture was processed in a planetary ball mill under air atmosphere at a ball milling speed of 20,000 rpm for 1 hour to fully mix the copper powder and the silicon powder;

[0082] 2) the above mixture was placed in a microwave shaker for microwave digestion treatment, the frequency of the microwave digestion treatment was 1500 MHz, and the treatment time was 2 h;

[0083] 3) the above mixture was placed in a tube furnace under nitrogen atmosphere, and calcined at a high temperature of 900 C. for 3 hours under nitrogen atmosphere.

[0084] 4) the above material was ultrasonically washed with deionized water, and vacuum dried at 80 C. for 12 hours, to obtain a porous copper silicide intermetallic compound;

[0085] 5) according to the method of Example 1, the acetylene hydrochlorination reaction was evaluated in the fixed bed reactor: the acetylene hydrochlorination reaction was carried out at 220 C., the acetylene space velocity was 40 h.sup.1, the molar ratio of hydrogen chloride:acetylene was 1.05:1, and when the reaction initially reached a stable state, the reaction conversion rate was 47% and the selectivity of vinyl chloride was 99%.

[0086] The physical parameters of the materials prepared in the Examples 1-5 and Comparative Examples 1-3 were tested and analyzed, wherein the specific surface area and pore size distribution were measured using a specific surface area analyzer KuBox1000, the analysis method used for the specific surface area was BET, the micropore treatment method was HK method, the mesoporous treatment method is the BJH method, and elemental analysis was measured by XRF. The results are shown in Table 1.

TABLE-US-00001 TABLE 1 Physical parameters and catalytic performance evaluation of porous copper silicide intermetallic compound catalysts specific acetylene surface T for space area/ elemental ratio of ratio of evaluation/ velocity/ conversion Example m.sup.2g.sup.1 composition micropores/% mesopores/% C. h.sup.1 rate/% selectivity/% Example 1 382 Cu.sub.1.2Si.sub.2.9 12 88 120 30 33.2 98.7 140 30 55.9 98.3 160 30 70.5 98.7 180 30 79.5 99 220 30 97.7 99.2 260 30 86.8 99 300 30 61.6 99 220 60 91.1 99 220 90 85.9 99 220 180 75.3 99 220 370 60.2 99 Example 2 421 Cu.sub.3.3Si.sub.0.8 28 72 280 70 92.7 99 Example 3 500 Cu.sub.2.1Si.sub.3.5 18 72 210 100 90.5 99 Example 4 430 Cu.sub.2.4Si.sub.0.1 25 75 270 370 95 98 Example 5 456 Cu.sub.1.4Si.sub.3 21 79 300 30 97.8 98 Comparative 45 Cu.sub.5Si 10 90 230 50 12 99 Example 1

[0087] The above conditions of the acetylene hydrochlorination reaction with the catalyst prepared in Examples 2-5 or Comparative Example 1 were all optimal reaction conditions.

Example 6

[0088] 1) 24.6 g of sublimation sulfur were added to 20 g of copper powder, and the mixture was processed in a planetary ball mill under air atmosphere at a ball milling speed of 2000 rpm for 1 h to fully mix the copper source and the sulfur source;

[0089] 2) the above mixture was placed in a microwave shaker for microwave digestion treatment, the frequency of the microwave digestion treatment was 300 MHz, and the treatment time was 2 h;

[0090] 3) the above mixture was placed in a Joule heating furnace under nitrogen atmosphere, the temperature of the carbon thermal shock was 2200 C., the shock duration was 55 milliseconds, and the heating/cooling rate was 105 C. per second.

[0091] 4) the above materials were ultrasonically washed with deionized water, and vacuum dried at 80 C. for 4 hours to obtain a porous copper-sulfur intermetallic material. The physical parameters are shown in Table 1, and the scanning electron microscope image is shown in FIG. 4;

[0092] 5) evaluation of acetylene hydrochlorination reaction in a fixed bed reactor: the effects of temperature and space velocity on the catalytic performance of the catalyst were investigated respectively. Under the condition of acetylene space velocity of 40 h.sup.1, the effect of temperature on the catalytic activity of the catalyst was investigated. Then, the effect of acetylene space velocity on the catalytic activity of the catalyst was investigated at 180 C., and the results are shown in Table 2; it was found that when the acetylene hydrochlorination reaction was performed at 180 C., the acetylene space velocity was 40 h.sup.1, and the molar ratio of hydrogen chloride:acetylene was 1.05:1, the technical effect was the best, wherein the reaction conversion rate was 90.3% and the selectivity of vinyl chloride was 99% when the reaction initially reached a stable state.

Example 7

[0093] 1) 17.5 g of 1,3-bis(thioacetic acid-S-n-propyl)imidazolium bromide and 5 ml of thioglycolic acid were added to 16 g of copper chloride dihydrate powder, the mixture was processed in a planetary ball mill under nitrogen atmosphere at a ball milling speed of 12000 rpm for 1 h to fully mix the copper source and the sulfur source;

[0094] 2) the above mixture was placed in a microwave shaker for microwave digestion treatment, the frequency of the microwave digestion treatment was 800 MHz, and the treatment time was 2 h;

[0095] 3) the above mixture was placed in a Joule heating furnace under nitrogen atmosphere, the temperature of the carbon thermal shock was 3200 C., the shock duration was 2500 milliseconds, and the heating/cooling rate was 1600 C. per second;

[0096] 4) the above material was ultrasonically washed with deionized water, and vacuum dried at 100 C. for 12 hours to obtain a porous copper-sulfur intermetallic compound material, whose physical parameters are shown in Table 2;

[0097] 5) evaluation of acetylene hydrochlorination reaction in a fixed bed reactor: the acetylene hydrochlorination reaction was carried out at 180 C., acetylene space velocity was 70 h.sup.1, the molar ratio of hydrogen chloride:acetylene was 1:1, and when the reaction initially reached a stable state, the reaction conversion rate was 93.9% and the selectivity of vinyl chloride was 99%.

Example 8

[0098] 1) 15.2 g of selenium disulfide were added to 12 g of copper sulfide powder, and the mixture was processed in a planetary ball mill under argon atmosphere at a ball milling speed of 10000 rpm for 5 h, and thereby mixed thoroughly;

[0099] 2) the above mixture was placed in a microwave shaker for microwave digestion treatment, the frequency of the microwave digestion treatment was 1200 MHz, and the treatment time was 3 h;

[0100] 3) the above mixture was placed in a Joule heating furnace under nitrogen atmosphere, the temperature of the carbon thermal shock was 500 C., the shock duration was 150 milliseconds, and the heating/cooling rate was 500 C. per second;

[0101] 4) the above material was ultrasonically washed with deionized water, and vacuum dried at 120 C. for 8 hours to obtain a porous copper-sulfur-selenium dual-phase intermetallic compound material, whose physical parameters are shown in Table 2;

[0102] 5) evaluation of acetylene hydrochlorination reaction in a fixed bed reactor: the acetylene hydrochlorination reaction was carried out at 210 C., acetylene space velocity was 100 h.sup.1, the molar ratio of hydrogen chloride:acetylene was 1:1.1, and when the reaction initially reached a stable state, the reaction conversion rate was 95.2% and the selectivity of vinyl chloride was 99%.

Example 9

[0103] 1) 15.2 g of selenium telluride were added to 10 g of copper sulfate powder, and the mixture was processed in a planetary ball mill under argon atmosphere at a ball milling speed of 8000 rpm for 3 h, and thereby mixed thoroughly;

[0104] 2) the above mixture was placed in a microwave shaker for microwave digestion treatment, the frequency of the microwave digestion treatment was 5000 MHz, and the treatment time was 4 h;

[0105] 3) the above mixture was placed in a Joule heating furnace under nitrogen atmosphere, the temperature of the carbon thermal shock was 2500 C., the shock duration was 900 milliseconds, and the heating/cooling rate was 1000 C. per second.

[0106] 4) the above material was ultrasonically washed with deionized water, and vacuum dried at 50 C. for 8 hours to obtain a porous copper-sulfur-selenide-tellurium three-phase intermetallic compound, whose physical parameters are shown in Table 2, and scanning electron microscope image is shown in FIG. 5;

[0107] 5) evaluation of acetylene hydrochlorination reaction in a fixed bed reactor: the acetylene hydrochlorination reaction was carried out at 270 C., acetylene space velocity was 370 h.sup.1, the molar ratio of hydrogen chloride:acetylene was 1:12, and when the reaction initially reached a stable state, the reaction conversion rate was 95% and the selectivity of vinyl chloride was 98%, and the stability is shown in FIG. 6.

Example 10

[0108] 1) 11 g of selenium powder and 10 ml of 40 wt % selenic acid solution were added to 10 g of copper acetate powder, and the mixture was processed in a planetary ball mill under argon atmosphere at a ball milling speed of 100 rpm for 4 h, and thereby mixed thoroughly;

[0109] 2) the above mixture was placed in a microwave shaker for microwave digestion treatment, the frequency of the microwave digestion treatment was 300 GHz, and the treatment time was 1 h;

[0110] 3) the above mixture was placed in a Joule heating furnace under nitrogen atmosphere, the temperature of the carbon thermal shock was 1000 C., the shock duration was 3000 milliseconds, and the heating/cooling rate was 1500 C. per second;

[0111] 4) the above material was ultrasonically washed with deionized water, and vacuum dried at 90 C. for 8 hours to obtain a porous copper-selenium intermetallic compound, whose physical parameters are shown in Table 2;

[0112] 5) evaluation of acetylene hydrochlorination reaction in a fixed bed reactor: the acetylene hydrochlorination reaction was carried out at 300 C., acetylene space velocity was 30 h.sup.1, the molar ratio of hydrogen chloride:acetylene was 0.9:1.2, and when the reaction initially reached a stable state, the reaction conversion rate was 98.4% and the selectivity of vinyl chloride was 99%.

Example 11

[0113] 1) 11 g of selenium telluride powder were added to 12 g of cuprous oxide powder, and the mixture was processed in a planetary ball mill under helium atmosphere at a ball milling speed of 12000 rpm for 5 h and thereby mixed thoroughly;

[0114] 2) the above mixture was placed in a microwave shaker for microwave digestion treatment, the frequency of the microwave digestion treatment was 100 GHz, and the treatment time was 1.2 h;

[0115] 3) the above mixture was placed in a Joule heating furnace under nitrogen atmosphere, the temperature of the carbon thermal shock was 1200 C., the shock duration was 1500 milliseconds, and the heating/cooling rate was 1000 C. per second;

[0116] 4) the above material was ultrasonically washed with deionized water and vacuum dried at 120 C. for 8 hours to obtain a porous copper-selenide-tellurium dual-phase intermetallic compound, whose physical parameters are shown in Table 2;

[0117] 5) evaluation of acetylene hydrochlorination reaction in a fixed bed reactor: the acetylene hydrochlorination reaction was carried out at 150 C., acetylene space velocity was 60 h.sup.1, the molar ratio of hydrogen chloride:acetylene was 0.9:1, and the reaction conversion rate was 97.9% and the selectivity of vinyl chloride was 98% when the reaction initially reached a stable state.

Comparative Example 4

[0118] The fixed bed reactor was charged with copper sulfide purchased from Aladdin, and the acetylene hydrochlorination reaction was evaluated under the following conditions: the reaction temperature was 230 C., the acetylene space velocity was 50 h.sup.1, and the molar ratio of hydrogen chloride:acetylene was 1:1.2. When the reaction initially reached a stable state, the reaction conversion rate was 23% and the selectivity of vinyl chloride was 96.7%.

Comparative Example 5

[0119] The fixed bed reactor was charged with copper selenide purchased from Aladdin, and the acetylene hydrochlorination reaction was evaluated under the following conditions: the reaction temperature was 150 C., acetylene space velocity was 30 h.sup.1, and the molar ratio of hydrogen chloride:acetylene was 1:1.1. When the reaction initially reached a stable state, the reaction conversion rate was 13% and the selectivity of vinyl chloride was 98.8%.

Comparative Example 6

[0120] According to Example 1 of the patent CN 201910783911.9, a copper sulfide triangular nanosheet material was prepared and used as the catalyst of the acetylene hydrochlorination reaction, and the acetylene hydrochlorination reaction was evaluated in the fixed bed reactor under the following conditions: the reaction temperature was 180 C., the acetylene space velocity was 40 h.sup.1, and the molar ratio of hydrogen chloride:acetylene was 1.05:1. When the reaction initially reached a stable state, the reaction conversion rate was 19% and the selectivity of vinyl chloride was 89%.

Comparative Example 7

[0121] According to Example 1 of the patent CN 202010644330.X, a rod-shaped nano-copper sulfide material was prepared and used as the catalyst of the acetylene hydrochlorination reaction, and the acetylene hydrochlorination reaction was evaluated in the fixed bed reactor under the following conditions: the reaction temperature was 180 C., the acetylene space velocity was 40 h.sup.1, and the molar ratio of hydrogen chloride:acetylene was 1.15:1. When the reaction initially reached a stable state, the reaction conversion rate was 23% and the selectivity of vinyl chloride was 86%.

Comparative Example 8

[0122] 1) 11 g of selenium powder and 10 ml of 40 wt % selenic acid solution were added to 10 g of copper acetate powder, the mixture was processed in a planetary ball mill under argon atmosphere at a ball milling speed of 100 rpm for 4 h, and thereby mixed thoroughly;

[0123] 2) the above mixture was placed in a microwave shaker for microwave digestion treatment, the frequency of the microwave digestion treatment was 300 GHz, and the treatment time was 1 h;

[0124] 3) the above mixture was irradiated with X-rays in a nitrogen atmosphere, the frequency of the radiation was 30 EHz, the internal temperature of the mixture was 1100 C., and the treatment was performed for 3 hours.

[0125] 4) the above material was ultrasonically washed with deionized water, and vacuum dried at 90 C. for 8 hours to obtain a porous copper-selenium intermetallic compound, whose physical parameters are shown in Table 2;

[0126] 5) evaluation of acetylene hydrochlorination reaction in a fixed bed reactor: the acetylene hydrochlorination reaction was carried out at 300 C., acetylene space velocity was 30 h.sup.1, the molar ratio of hydrogen chloride:acetylene was 0.9:1.2, and when the reaction initially reached a stable state, the reaction conversion rate was 62% and the selectivity of vinyl chloride was 99%.

Comparative Example 9

[0127] 1) 11 g of selenium powder and 10 ml of 40 wt % selenic acid solution were added to 10 g of copper acetate powder, and the mixture was processed in a planetary ball mill under argon atmosphere at a ball milling speed of 100 rpm for 4 h, and thereby mixed thoroughly;

[0128] 2) the above mixture was placed in a microwave shaker for microwave digestion treatment, the frequency of the microwave digestion treatment was 300 GHz, and the treatment time was 1 h;

[0129] 3) the above mixture was placed in a tube furnace under nitrogen atmosphere, and calcined at a high temperature of 900 C. for 3 hours under nitrogen atmosphere.

[0130] 4) the above material was ultrasonically washed with deionized water, and vacuum dried at 90 C. for 8 hours to obtain a porous copper-selenium intermetallic compound, whose physical parameters are shown in Table 2;

[0131] 5) evaluation of acetylene hydrochlorination reaction in a fixed bed reactor: the acetylene hydrochlorination reaction was carried out at 300 C., acetylene space velocity was 30 h.sup.1, the molar ratio of hydrogen chloride:acetylene was 0.9:1.2, and when the reaction initially reached a stable state, the reaction conversion rate was 52% and the selectivity of vinyl chloride was 98%.

[0132] The physical parameters of the materials prepared in the examples 6-11 and comparative examples 4-7 were tested and analyzed, wherein the specific surface area and pore size distribution were measured using Beijing Biode specific surface area analyzer KuBox1000, the analysis method used for the specific surface area was BET, the micropore treatment method was the HK method, the mesoporous treatment method is BJH method, and elemental analysis was measured by XRF. The results are shown in Table 2.

TABLE-US-00002 TABLE 2 Physical parameters and catalytic performance evaluation of porous copper-chalcogen intermetallic compound catalysts specific acetylene surface T for space area/ elemental ratio of ratio of evaluation/ velocity/ conversion Example m.sup.2g.sup.1 composition micropores/% mesopores/% C. h.sup.1 rate/% selectivity/% Example 6 583 Cu.sub.2.2S.sub.1.9 66 34 100 40 63.9 98.7 130 40 75.2 98.3 160 40 80.3 98.7 180 40 90.3 99 220 40 85.7 99.2 260 40 68.8 98.4 300 40 61.6 98.8 180 30 87.6 98.2 180 90 81.1 98.5 180 180 75.9 98.1 180 360 73.5 98.3 180 740 70.1 98.1 Example 7 1321 Cu.sub.3.8S.sub.0.9 72 28 180 70 93.9 99 Example 8 891 Cu.sub.2.8S.sub.2.1Se.sub.2.8 68 32 210 100 95.2 99 Example 9 1600 Cu.sub.2.7S.sub.0.6Se.sub.0.9Te.sub.1.8 25 75 270 370 95 98 Example 10 1200 Cu.sub.1.4Se.sub.3 9 91 300 30 98.4 98 Example 11 1166 Cu.sub.1.2Se.sub.2.9Te.sub.2.7 52 48 150 60 97.9 98 Comparative 170 CuS 63 37 230 50 23 96.7 Example 4 Comparative 230 CuSe 21 79 180 40 13 97.2 Example 5 Comparative 99 Cu.sub.1.3S.sub.1.7 53 47 180 40 19 89 Example 6 Comparative 169 Cu.sub.1.5S.sub.2.1 12 88 180 40 23 86 Example 7

[0133] The above conditions of the acetylene hydrochlorination reaction with the catalyst prepared in Examples 7-11 or Comparative Examples 4-7 were all optimal reaction conditions.