Preparation method of modified activated carbon loaded bimetallic catalyst, prepared catalyst and application thereof

Abstract

The invention provides a preparation method of a modified activated carbon loaded bimetallic catalyst, the prepared catalyst and application thereof. The preparation method of the modified activated carbon loaded bimetallic catalyst comprises the following steps: firstly, modifying activated carbon serving as a carrier of the bimetallic catalyst, thereby enhancing the anchoring capability to a metal component, improving the stability of the catalyst component and prolonging the service life of the catalyst component; secondly, the double metals are tightly attached together through coordination of a complexing agent, and meanwhile the dispersity of the double metals is kept; in addition, the bimetallic catalyst is rapidly synthesized through flash drying and electromagnetic heating technologies, and the preparation method of the catalyst has the advantages of high efficiency, stability, high activity and the like. The catalyst prepared by the method has multiple functions when being used for dechlorination reaction of 1, 2-dichloroethane, and can generate ethane with high selectivity under a hydrogen condition and ethylene with high selectivity under a hydrogen-free condition while keeping a relatively high conversion rate.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysts, and specifically relates to a method for preparing a modified activated carbon-supported bimetallic catalyst, the prepared catalyst and application of the catalyst in catalytic dechlorination of 1,2-dichloroethane. Background Art

[0002] 1,2-Dichloroethane (1,2-DCE) is a colorless liquid that is slightly soluble in water and has a chloroform-like odor. It can be used as a raw material or intermediate, and is widely used in the production of fine chemicals such as medicines and pesticides. It can also be used to produce basic chemical products with higher added value, such as vinyl chloride, ethane, and ethylene.

[0003] At present, the main methods for catalytic dechlorination of 1,2-dichloroethane as raw material to prepare high value-added products such as ethylene or ethane include electrochemical method, catalytic oxidation method, catalytic hydrogenation method, etc. Among them, catalytic hydrodehalogenation is a relatively mature method for the safe and green treatment of chloroalkanes. This method has the advantages of clean process route, high atom economy, low production cost, and recyclable catalyst. Catalytic hydrodehalogenation is one of the best methods to convert 1,2-dichloroethane into higher value-added products such as ethylene, vinyl chloride, and ethane, but this type of catalyst is often used in a high temperature environment containing HCl. The harsh reaction conditions often lead to problems such as low catalyst conversion rate and easy deactivation. Therefore, solving the conversion rate and selectivity of this type of catalyst is still the focus of attention.

[0004] CN117654604A discloses a method for preparing a catalyst for preparing vinyl chloride by catalytic cracking of 1,2-dichloroethane with high selectivity, comprising the following steps: the pretreatment material is a silicon-containing or aluminum-containing material, firstly, 50g of SSZ-13 molecular sieve is added to 10ml of 20% methyl orthosilicate solution for impregnation, and the pretreatment temperature is 30°C. After pretreatment for 24 hours, it is placed at 60°C for drying for 24 hours, and then kept in a muffle furnace at 700°C for 4 hours. Evaluation process 1,2-dichloroethane is brought into a fluidized bed reactor by helium bubbling, and a 91% conversion rate and 87% vinyl chloride selectivity are obtained in an environment where the reactor temperature is 290°C and the mass space velocity is 4.6h-1.

[0005] CN105148907A discloses a catalyst for the selective hydrodechlorination reaction of 1,2-dichloroethane, and its preparation method and application. The catalyst uses oxide C as a carrier, wherein C is one of Al2O3, SiO2, TiO2 or ZrO2, metal A is one of Ag or Cu, and metal B is one of Pd or Pt. The catalyst preparation method is to add oxide C to a metal A salt solution for impregnation, evaporation, drying, and roasting to obtain A / C; then A / C is reduced by H2, and then in an inert gas, a replacement reaction is carried out with a deoxygenated metal B salt solution, and after stirring for 0.5 to 3 hours, filtering and drying, an AB / C catalyst is obtained. The AB / C catalyst is used for the selective hydrodechlorination reaction of 1,2-dichloroethane to obtain a product with a selectivity of more than 80% with ethylene as the main product.

[0006] CN102658127A discloses a bimetallic catalyst prepared by continuous photodeposition method and its application in selective hydrodechlorination degradation of 1,2-dichloroethane. 100 mg of pd-Pt(1.07)-Ag(1.05) / TiO2 catalyst is used in gas phase hydrogenation catalytic degradation of 1,2-dichloroethane, the reaction temperature is 200-250°C, the concentration of H2 is 30000-40000ppm, the concentration of 1,2-dichloroethane is 7000-7500ppm, the carrier gas is He, the flow rate of the mixed gas is 40-50mL / min, the reaction is carried out under normal pressure for 17-19h, and the selectivity of ethylene is 89.1-90.0%.

[0007] CN117732480A invention discloses a preparation of a hydrogenolysis dehalogenation catalyst and its application in the generation of ethylene from 1,2-dichloroethane. The preparation method of the catalyst is: first, a soluble salt of metal A and a soluble salt of metal B are uniformly dissolved in deionized water to prepare a bimetallic precursor solution, and then a surfactant is added and mixed to obtain a co-impregnation solution. Then the co-impregnation solution is mixed with activated carbon, adsorbed and impregnated, placed in a blast oven for drying, and then subjected to microwave heat treatment to obtain a hydrogenolysis dehalogenation catalyst. The activated carbon is loaded with 0.5wt% ruthenium and 2.0wt% zinc precursors under the conditions of 30mL / min nitrogen, 300W power, and a magnetron microwave emission frequency of 3GHz. The catalyst obtained by microwave treatment for 15min is used for the reaction. Under the reaction conditions of 280°C, n(H2):n(1,2-DCE)=6:1, and a space velocity of 1550h-1, the best performance of the catalyst shows a conversion rate of 94.2% and an ethylene selectivity of 95.9%.

[0008] CN113634275A invention discloses a method for preparing a catalytic hydrodechlorination catalyst and its application. The catalyst comprises a main active component Ru, an auxiliary element M and a carrier, wherein the auxiliary element M is at least one of B, N and P, and the auxiliary element M forms an amorphous state with the noble metal Ru and is loaded on the carrier, wherein the carrier is a mixture of one or two of activated carbon, carbon black and silicon carbide. The catalyst is used in the reaction of catalytic hydrodechlorination of 1,2-dichloroethane to prepare ethylene, in which the conversion rate can reach 90% and the selectivity for ethylene is 95%.

[0009] In summary, bimetallic catalysts are often used as active components in the catalysts used for the hydrodechlorination of 1,2-dichloroethane. The existing preparation methods of bimetallic catalysts have problems such as uneven dispersion and high economic cost. When used in the reaction, they have low conversion rate and low selectivity. Under high temperature and HCl conditions, the catalyst activity is deactivated and the selectivity is reduced. Summary of the invention

[0010] In view of the above problems, the present invention proposes a method for preparing a modified activated carbon-supported bimetallic catalyst, the prepared catalyst and its application in the catalytic dechlorination of 1,2-dichloroethane; the idea is to modify the activated carbon as a carrier of the bimetallic catalyst, thereby enhancing the anchoring ability for the metal component and improving the stability and service life of the catalyst component; secondly, the coordination of the complexing agent is used to make the bimetallic closely fit together while maintaining the dispersibility of the bimetallic; in addition, the bimetallic catalyst can be quickly synthesized through flash drying and electromagnetic heating technology, and the catalyst preparation method has the advantages of high efficiency, stability, and high activity. The catalyst prepared by this method is multifunctional for 1,2-dichloroethane. While maintaining a high conversion rate, it can generate ethane with high selectivity under hydrogen conditions and ethylene with high selectivity under hydrogen-free conditions.

[0011] In a first aspect, the present invention provides a method for preparing a modified activated carbon-supported bimetallic catalyst, the steps of which include:

[0012] A1. Crushed activated carbon and sieved it into 10-40 mesh granular activated carbon, washed it with ultrasonic water, filtered it and separated it, dried it and placed it in a microwave tube furnace at a power of 200-900W, a temperature of 300-900℃, N 2 Calcination treatment at a flow rate of 30-100 mL / min for 1-8 h;

[0013] A2. The activated carbon treated in step A1 is added to a 0.05-0.40 g / mL urea solution, refluxed at 100-140°C for 1-5 hours, the excess solution is filtered and separated, and the treated carrier is vacuum dried to obtain modified activated carbon;

[0014] A3. Mix potato starch and water, stir and dissolve at 20-90 ° C and 50-500 rpm, filter, and prepare a 0.05-0.20 g / mL complexing agent solution;

[0015] A4. First, prepare 0.001-0.01 g / mL of metal precursor I solution and 0.001-0.1 g / mL of metal precursor II solution, and add the metal precursor I solution and the metal precursor II solution to a container in a volume ratio of 1:1-15, and mix them, and obtain a uniformly mixed co-impregnation solution by ultrasonic treatment; take the complexing agent solution prepared in step A3 and add it to the co-impregnation solution, and stir it at 50-500 rpm for 2-30 min to prepare a colloidal solution containing a bimetallic; wherein the metal in the metal precursor I solution is selected from one of Pt, Pd, and Ru, and the metal in the metal precursor II solution is selected from one of Fe, Co, Ni, and Cu;

[0016] A5. Take the modified activated carbon treated in step A2 and add it to container 1, add the bimetallic colloid solution prepared in step A4, the feed ratio of the modified activated carbon to the bimetallic colloid solution is 1g:1-3mL, and add methanol, the volume ratio of methanol to the bimetallic colloid solution is 0.5-1.5:1, and stir and adsorb for 0.5-3h at 50-100°C and 50-500rpm;

[0017] A6. Take a container 2 with a larger capacity than container 1 and at least two openings, connect the opening of container 1 in step A5 to the opening of container 2 with a rubber tube, and connect the other opening of container 2 to a vacuum pump; close the connection between container 1 and container 2, evacuate container 2 to a vacuum using a vacuum pump, and heat and stir the mixture in the sealed container 1 under the conditions of heating and stirring at 60-200° C. and 50-500 rpm for 0.5-1 h, then open the connection between container 1 and container 2, evaporate the liquid in container 1 instantly, and continue at -0.1 MPa for 10-60 min;

[0018] A7. Dry the remaining material in container 1 and place it in a container filled with N 2 The sealed quartz tube is placed in a medium frequency furnace and heat treated for 5-50 seconds at 50 Hz, 500-1000 W, and 300-800° C. to prepare a modified activated carbon-supported bimetallic catalyst.

[0019] Preferably, in step A1, the calcination conditions in the microwave tube furnace are: calcination treatment for 1-5h at a power of 400-800W, a temperature of 400-800°C, and a N2 flow rate of 50-100mL / min.

[0020] Preferably, in step A1, the drying is carried out in a forced air oven at 60-120° C. for 3-9 hours; more preferably, the drying is carried out in a forced air oven at 80-120° C. for 3-9 hours.

[0021] Preferably, in step A2, the feed ratio of the activated carbon treated in step A1 to 0.05-0.40 g / mL urea solution is 1 g: 0.5-1.0 mL.

[0022] Preferably, in step A2, the concentration of the urea solution is 0.10-0.30 g / mL.

[0023] Preferably, in step A2, reflux is performed at 100-140° C. for 1-3 hours.

[0024] Preferably, in step A2, the vacuum drying is carried out in a vacuum oven at -0.1 MPa at 40-80°C for 1-8 h, and more preferably in a vacuum oven at -0.1 MPa at 50-80°C for 1-8 h.

[0025] Preferably, in step A3, potato starch and water are stirred and dissolved at 30-80° C. and 100-400 rpm, filtered, and configured into a 0.05-0.15 g / mL complexing agent solution.

[0026] Preferably, in step A4, 0.001-0.01 g / mL of metal precursor I solution and 0.01-0.1 g / mL of metal precursor II solution are prepared, and the metal precursor I solution and the metal precursor II solution are added to a beaker in a volume ratio of 1:1-10, and a uniformly mixed co-impregnation solution is obtained by ultrasonic treatment.

[0027] Preferably, in step A4, the complexing agent solution prepared in step A3 is added to the co-impregnation solution, and stirred at 50-500 rpm for 20 min to prepare a colloidal solution containing bimetallic compounds.

[0028] Preferably, in step A4, the volume ratio of the complexing agent solution to the co-impregnation solution is 0.5-1.5:1.

[0029] Preferably, in step A5, after adding methanol, stirring adsorption is carried out at 50-100° C. and 50-200 rpm for 0.5-1 h.

[0030] Preferably, in step A7, the drying refers to drying in a forced air oven at 60-120° C. for 1-6 hours.

[0031] Step A6 of the present invention is a flash evaporation step, which is designed to improve the flash evaporation effect of the mixture in container 1. It can be understood that the larger the capacity of container 2 is compared with container 1, the more helpful it is to improve the flash evaporation effect.

[0032] In a second aspect, the present invention provides a modified activated carbon-supported bimetallic catalyst prepared according to the preparation method described in the first aspect.

[0033] In a third aspect, the present invention provides an application of the modified activated carbon-supported bimetallic catalyst described in the second aspect in the catalytic dechlorination of 1,2-dichloroethane, wherein the modified activated carbon-supported bimetallic catalyst is firstly treated with NH 3 Carry out pre-activation.

[0034] As an embodiment, the application is for preparing ethylene, and the steps include:

[0035] B1. Load the modified activated carbon-supported bimetallic catalyst into a fixed bed reactor and 3 / N 2 The mixed gas is introduced into the fixed bed reactor at a ratio of 1:1-10, wherein NH 3 The catalyst is pre-activated after a certain period of ventilation at a flow rate of 5-10 mL / min, and the fixed bed reactor is heated to 180-500°C at 3-10°C / min and kept at a constant temperature for 1-6 hours to complete the pre-activation of the modified activated carbon-supported bimetallic catalyst;

[0036] B2. Raise the temperature of the fixed bed reactor to 220-450°C at 3-10°C / min, and turn off the NH 3 / N 2 Supply; Open the feed pump to introduce 1,2-dichloroethane as raw material into the vaporization chamber, vaporize the raw material at 70-160°C, mix it with nitrogen and introduce it into the fixed bed reactor to make n(N 2 ):n(C 2 H 4 Cl 2 )=5-1:1, the volume space velocity of the raw material is 200-2000h -1 , ethylene is produced under the action of modified activated carbon-supported bimetallic catalyst.

[0037] As another embodiment, the application is for preparing ethane, and the steps include:

[0038] C1. Load the modified activated carbon-supported bimetallic catalyst into a fixed bed reactor and 3 / N 2 The mixed gas is introduced into the fixed bed reactor at a volume ratio of 1:1-10, wherein NH 3 The catalyst is pre-activated after a certain period of ventilation at a flow rate of 5-10 mL / min, and the fixed bed reactor is heated to 180-500°C at 3-10°C / min and kept at a constant temperature for 1-6 hours to complete the pre-activation of the modified activated carbon-supported bimetallic catalyst;

[0039] C2. Raise the temperature of the fixed bed reactor to 220-440°C at 3-10°C / min, and turn off N 2 NH 3 Supply; open H 2 The feed pump is used to supply 1,2-dichloroethane as a raw material to the vaporization chamber, and the raw material is vaporized at 70-160°C, and then mixed with hydrogen and enters the reactor. The volume space velocity of the raw material is 500-2000h -1 , control the reaction material ratio to n(H 2 ):n(C 2 H 4 Cl 2 )=1-10:1, and ethane is generated under the action of modified activated carbon supported bimetallic catalyst.

[0040] The beneficial effects of the present invention are:

[0041] (1) The present invention first performs high-temperature calcination in a microwave tube furnace to remove organic matter and impurities on the activated carbon, and then impregnates the activated carbon with urea to increase the alkalinity of the activated carbon. At the same time, the adsorption capacity and adsorption order of the carrier for the bimetallic are adjusted to enhance the electron transmission capacity of the activated carbon, improve the reception and transfer of electrons by the active components of the catalyst, and help improve the adsorption of the catalyst to the substrate.

[0042] (2) The bimetallic complexing agent prepared by soluble potato starch is used to coordinate and complex the bimetallic, adjust the adsorption order and adsorption capacity of the bimetallic on the activated carbon, and enhance the co-coordination and synergistic effect of the bimetallic. Soluble starch as a complexing agent can enhance the stability of the bimetallic colloidal solution, make the metal ions form a complex, and maintain the uniformity and stability of the solution.

[0043] (3) By using flash drying and electromagnetic heating of the medium frequency furnace, the electromagnetic heating directly acts on the metal, quickly heating the metal to the required temperature, achieving uniform heating of the catalyst and accurately controlling the heating temperature, which is conducive to the precise control of high-efficiency catalysts. The heating requirements can be met in a short time, thereby avoiding the decomposition of N-doped activated carbon at high temperature for a long time, and effectively maintaining the actual N doping amount.

[0044] (4) The catalyst prepared by the present invention has a more efficient performance in the hydrodechlorination reaction of 1,2-dichloroethane, while maintaining the original conversion rate, improving the selectivity of the product ethane and increasing the service life; secondly, under hydrogen-free conditions, the 1,2-dichloroethane reaction still maintains a relatively efficient conversion rate and has a high selectivity for ethylene. DETAILED DESCRIPTION

[0045] The following examples are only used to further illustrate the present invention, but the protection scope of the present invention is not limited thereto.

[0046] If no specific conditions are specified in the examples of the present invention, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be obtained by conventional technical means or purchased commercially.

[0047] In the embodiments of the present invention, the raw materials are all 1,2-dichloroethane produced by Guangdong Guanghua Technology Co., Ltd., and the activated carbon is from Chengde Tianyuan Activated Carbon Co., Ltd. The columnar activated carbon has a particle size of 10-40 mesh and a specific surface area of ​​1000-1500m 2 / g, the pore size is between 2.0-5.0nm, and the average pore size is 2.7nm.

[0048] Example 1

[0049] A1, activated carbon pretreatment: The activated carbon was crushed and sieved into 10-20 mesh granular activated carbon, washed with ultrasonic water, filtered and separated, and dried in a blast oven at 110°C for 5 hours. 2 The flow rate was 50 mL / min and the calcination treatment was carried out for 3 h.

[0050] A2, activated carbon modification treatment: add 3g of the activated carbon pretreated in A1 to 3mL of 0.20g / mL urea solution, reflux at 120℃ for 3h, filter and separate the excess solution, and dry the treated carrier in a vacuum oven at -0.1MPa at 70℃ for 4h.

[0051] A3, preparation of complexing agent: potato starch and water were mixed, stirred at 200 rpm and 60° C. to dissolve, filtered, and prepared into a potato starch solution containing 0.10 g / mL.

[0052] A4, preparation of metal precursor: 3 ml of 0.005 g / mL platinum chloride and 3 mL of 0.04 g / mL copper nitrate solution were ultrasonically treated for 5 min to obtain a uniformly mixed co-impregnation solution, 6 mL of the complexing agent prepared in A3 above was added, and stirred at 200 rpm for 20 min to obtain a bimetallic colloid solution.

[0053] A5, impregnation: 6 g of activated carbon prepared in A2 was placed in a 50 mL round-bottom flask, and the bimetallic colloid solution prepared in A4 was added for impregnation. 12 mL of methanol was added, and the mixture was stirred at 50°C and 100 rpm for 1 h for adsorption.

[0054] A6, flash drying: connect the round-bottom flask of A5 to a 10L round-bottom flask with a rubber tube, and connect the other end of the 10L round-bottom flask to a vacuum pump; close the channel between the two round-bottom flasks, heat and stir the precursor in the 50mL round-bottom flask at 100°C and 100rpm for 0.5h, and evacuate the 10L round-bottom flask to vacuum; open the channel between the two round-bottom flasks instantly, evaporate the liquid in the 50mL round-bottom flask instantly, and continue to evacuate at -0.1MPa for 20min. The water content of the precursor is 28.32%.

[0055] A7, electromagnetic heat treatment: dry the remaining precursor in the 50 mL round-bottom flask at 80 °C in a forced air oven for 2 h; then move the precursor into a N 2 In a sealed quartz tube, heat treatment was carried out in a medium frequency furnace at 50 Hz, 800 W, and 600°C for 20 s to prepare an activated carbon-supported bimetallic catalyst. ICP detection showed that the loading amount of metal Pt was 0.24 wt% and the loading amount of metal copper was 1.96 wt%.

[0056] The specific application of the catalyst is as follows:

[0057] Pre-activation: The bimetallic catalyst prepared above was used in a fixed bed reactor with V N2 :V NH3 =3:1 ratio and then the catalyst was pre-activated after ventilation for 30 min, wherein NH 3 The flow rate was 7 mL / min. The fixed bed reactor was heated to 400°C at 5°C / min and kept at this temperature for 3 h to complete the pre-activation.

[0058] Application 1: Increase the temperature to 320℃ at 5℃ / min, turn off NH 3 , turn on the feed pump and start the reaction. The raw material is first vaporized in the vaporization chamber at 120°C, then mixed with nitrogen and enters the fixed bed reactor, n(N2):n(C2H4Cl2)=2:1, and the volume space velocity of the raw material is 1000h -1 , thereby catalyzing the dechlorination of 1,2-dichloroethane to produce ethylene.

[0059] Application 2: Increase temperature to 300°C at 5°C / min, turn off NH 3 、N 2 , open H 2 , feed pump, and react. The raw material is first gasified at 120℃ in the gasification chamber, and then mixed with hydrogen before entering the reactor. The volume space velocity of the raw material is 1500h -1 ,n(H 2 ):n(C 2 H 4 Cl 2 )=3:1, thereby catalyzing the dechlorination of 1,2-dichloroethane to produce ethane.

[0060] The catalyst of Example 1 was subjected to a 5-hour stability evaluation, and the product was analyzed by gas chromatography. The area normalization results showed that the catalyst of Example 1 exhibited a conversion rate of 93.45% and an ethylene selectivity of 91.94% in Application 1, and exhibited a conversion rate of 94.34% and an ethane selectivity of 96.43% in Application 2.

[0061] Example 2

[0062] Example 2 is different from Example 1 in that the pretreatment conditions of the activated carbon in A1 are changed. Here, the activated carbon is crushed and sieved into 30-40 mesh granular activated carbon, washed with ultrasonic water, filtered and separated, and dried in a blast oven at 120°C for 6h. 2 The flow rate was 100 mL / min and the calcination treatment was performed for 5 h, and the catalyst was taken out after cooling to room temperature. The rest of the catalyst preparation process and evaluation conditions were the same as those in Example 1.

[0063] The catalyst of Example 2 was subjected to a 5-hour stability evaluation, and the product was analyzed by gas chromatography. The area normalization results showed that the catalyst of Example 2 exhibited a conversion rate of 94.21% and an ethylene selectivity of 91.21% in Application 1; the catalyst of Example 2 exhibited a conversion rate of 94.13% and an ethane selectivity of 92.81% in Application 2.

[0064] Embodiment 3-4

[0065] Compared with Example 1, Examples 3 and 4 changed the conditions for modified activated carbon in A2. Example 3 refluxed at 140°C for 3 h in a 0.10 g / mL urea solution and dried at 100°C for 3 h in a -0.1 MPa vacuum oven; Example 4 refluxed at 100°C for 1 h in a 0.30 g / mL urea solution and dried at 50°C for 5 h in a -0.1 MPa vacuum oven. The rest of the catalyst preparation process and evaluation conditions were the same as Example 1.

[0066] After 5 hours of stable evaluation, the product was analyzed by gas chromatography. The area normalization results showed that the catalyst of Example 3 showed a conversion rate of 93.36% and an ethylene selectivity of 90.55% in Application 1; and a conversion rate of 93.22% and an ethane selectivity of 94.56% in Application 2. The catalyst of Example 4 showed a conversion rate of 94.25% and an ethylene selectivity of 95.35% in Application 1; and a conversion rate of 94.93% and an ethane selectivity of 96.73% in Application 2.

[0067] Embodiment 5-6

[0068] Compared with Example 1, Examples 5 and 6 change the concentration of the complexing agent in A3, that is, change the concentration of the soluble potato starch. Here, Example 5 uses 0.05 g / mL and Example 6 uses 0.15 g / mL starch solution.

[0069] After 5 hours of stable evaluation, the products were analyzed by gas chromatography. The area normalization results showed that the catalyst of Example 5 showed a conversion rate of 90.36% and an ethylene selectivity of 90.79% in Application 1; a conversion rate of 91.16% and an ethane selectivity of 93.73% in Application 2; the catalyst of Example 6 showed a conversion rate of 94.36% and an ethylene selectivity of 94.55% in Application 1; and a conversion rate of 93.74% and an ethane selectivity of 95.83% in Application 2.

[0070] Embodiment 7-8

[0071] In Examples 7 and 8, the ratio of platinum in metal component I to copper in metal component II in A4 was changed compared to Example 1, wherein Example 7 used 3 mL of 0.01 g / mL platinum chloride solution and 3 mL of 0.01 g / mL copper nitrate solution; Example 8 used 3 mL of 0.001 g / mL platinum chloride solution and 3 mL of 0.04 g / mL copper nitrate solution. The remaining catalyst preparation process and evaluation conditions were the same as in Example 1.

[0072] After 5 hours of stable evaluation, the products were analyzed by gas chromatography. The area normalization results showed that the catalyst of Example 7 showed a conversion rate of 92.86% and an ethylene selectivity of 92.55% in Application 1; a conversion rate of 93.22% and an ethane selectivity of 91.56% in Application 2; the catalyst of Example 8 showed a conversion rate of 94.68% and an ethylene selectivity of 93.45% in Application 1; and a conversion rate of 95.34% and an ethane selectivity of 95.73% in Application 2.

[0073] Examples 9-10

[0074] In Examples 9 and 10, the loading amount of the bimetal in A4 was changed compared to Example 1, wherein 3 mL of 0.0025 g / mL platinum chloride solution and 3 mL of 0.02 g / mL copper nitrate solution were used in Example 9; 3 mL of 0.01 g / mL platinum chloride solution and 3 mL of 0.08 g / mL copper nitrate solution were used in Example 10. The rest of the catalyst preparation process and evaluation conditions were the same as in Example 1.

[0075] After 5 hours of stable evaluation, the products were analyzed by gas chromatography. The area normalization results showed that the catalyst of Example 9 showed a conversion rate of 90.36% and an ethylene selectivity of 90.55% in Application 1; a conversion rate of 90.30% and an ethane selectivity of 90.93% in Application 2; the catalyst of Example 10 showed a conversion rate of 97.45% and an ethylene selectivity of 92.35% in Application 1; and a conversion rate of 98.49% and an ethane selectivity of 97.68% in Application 2.

[0076] Examples 11-12

[0077] Compared with Example 1, Examples 11 and 12 change the metal type in the metal component I in A4, and the specific experiments are as follows. Example 11 uses 3 mL of 0.005 g / mL palladium chloride solution and 3 mL of 0.04 g / mL copper nitrate solution; Example 12 uses 3 mL of 0.005 g / mL ruthenium chloride solution and 3 mL of 0.04 g / mL copper nitrate solution. The rest of the catalyst preparation process and evaluation conditions are the same as Example 1.

[0078] After 5 hours of stable evaluation, the products were analyzed by gas chromatography. The area normalization results showed that the catalyst of Example 11 showed a conversion rate of 93.34% and an ethylene selectivity of 90.55% in Application 1; a conversion rate of 93.81% and an ethane selectivity of 95.56% in Application 2; the catalyst of Example 12 showed a conversion rate of 92.36% and an ethylene selectivity of 91.15% in Application 1; and a conversion rate of 91.29% and an ethane selectivity of 93.33% in Application 2.

[0079] Examples 13-15

[0080] Compared with Example 1, Examples 13, 14, and 15 change the metal type in the metal component II in A4, and the specific experiments are as follows. Example 13 uses 3 mL of 0.005 g / mL platinum chloride solution and 3 mL of 0.04 g / mL ferric chloride solution; Example 14 uses 3 mL of 0.005 g / mL platinum chloride solution and 3 mL of 0.04 g / mL cobalt nitrate solution; Example 15 uses 3 mL of 0.005 g / mL platinum chloride solution and 3 mL of 0.04 g / mL nickel nitrate solution. The rest of the catalyst preparation process and evaluation conditions are the same as Example 1.

[0081] After 5 hours of stable evaluation, the product was analyzed by gas chromatography. The area normalization results showed that the catalyst of Example 13 showed a conversion rate of 91.01% and an ethylene selectivity of 94.55% in Application 1; and a conversion rate of 91.31% and an ethane selectivity of 90.09% in Application 2. The catalyst of Example 14 showed a conversion rate of 90.99% and an ethylene selectivity of 91.55% in Application 1; and a conversion rate of 90.69% and an ethane selectivity of 91.63% in Application 2. The catalyst of Example 15 showed a conversion rate of 96.36% and an ethylene selectivity of 91.95% in Application 1; and a conversion rate of 97.69% and an ethane selectivity of 98.63% in Application 2.

[0082] Examples 16-17

[0083] Compared with Example 1, Examples 16 and 17 changed the amount of complexing agent liquid in A4 and the adsorption time in A5, as follows. Example 16: In A4, 3 mL of complexing solution was added; 6 g of activated carbon was taken from A5 and placed in a 50 mL round-bottom flask of Device 1, and adsorbed at room temperature and 100 rpm for 0.5 h. Example 17: In A4, 9 mL of complexing solution was added; 6 g of activated carbon was taken from A5 and placed in a 50 mL round-bottom flask of Device 1, and adsorbed at room temperature and 100 rpm for 3 h.

[0084] After 5 hours of stable evaluation, the product was analyzed by gas chromatography. The area normalization results showed that the catalyst of Example 16 showed a conversion rate of 90.25% and an ethylene selectivity of 93.55% in Application 1; and a conversion rate of 91.53% and an ethane selectivity of 90.88% in Application 2. The catalyst of Example 17 showed a conversion rate of 92.72% and an ethylene selectivity of 96.00% in Application 1; and a conversion rate of 93.53% and an ethane selectivity of 94.32% in Application 2.

[0085] Embodiment 18

[0086] Compared with Example 1, the flash drying time in A6 was changed in Example 18. In Example 18, vacuum was continuously drawn in A6 for 40 minutes, at which time the water content of the precursor was 14.54%. The rest of the catalyst preparation process and evaluation conditions were the same as in Example 1.

[0087] After 5 hours of stable evaluation, the product was analyzed by gas chromatography. The area normalization results showed that the catalyst of Example 18 showed a conversion rate of 93.90% and an ethylene selectivity of 90.07% in Application 1, and a conversion rate of 95.11% and an ethane selectivity of 93.87% in Application 2.

[0088] Examples 19-20

[0089] Compared with Example 1, Examples 19 and 20 changed the power, temperature and heating time of electromagnetic heating in A7. Example 19 was treated in an intermediate frequency furnace at 50 Hz, 600 W, and 400° C. for 10 s; Example 20 was treated in an intermediate frequency furnace at 50 Hz, 1000 W, and 800° C. for 40 s.

[0090] After 5 hours of stable evaluation, the products were analyzed by gas chromatography. The area normalization results showed that the catalyst of Example 19 showed a conversion rate of 90.08% and an ethylene selectivity of 92.35% in Application 1; a conversion rate of 92.71% and an ethane selectivity of 90.09% in Application 2, and the catalyst of Example 20 showed a conversion rate of 90.54% and an ethylene selectivity of 92.46% in Application 1; and a conversion rate of 90.52% and an ethane selectivity of 97.43% in Application 2.

[0091] Comparative Example 1

[0092] Comparative Example 1 Compared with Example 15, untreated activated carbon and a co-impregnation solution without a complexing agent are used for impregnation, and the catalyst is prepared by air drying. The specific experimental process is as follows.

[0093] Catalyst preparation: 3 g of 10-20 mesh activated carbon was added to 3 mL of 0.005 g / mL platinum chloride solution and 3 mL of 0.04 g / mL nickel nitrate solution, and the mixture was ultrasonically treated for 5 min to obtain a uniformly mixed co-impregnation solution. The mixture was stirred and adsorbed at room temperature and 100 rpm for 2 h, and then dried in a blast oven at 80 ° C for 2 h and at 180 ° C for 5 h to obtain the catalyst required for Comparative Example 1. The catalyst evaluation process of Comparative Example 1 was the same as the evaluation conditions of Example 15.

[0094] After 5 hours of stable evaluation, the product was analyzed by gas chromatography. The area normalization results showed that the catalyst of comparative example 1 showed a conversion rate of 60.24% and an ethylene selectivity of 67.24% in application 1; and a conversion rate of 62.35% and an ethane selectivity of 64.55% in application 2. This comparative experiment proves that the pretreatment and modification of activated carbon and the complexing agent prepared by soluble potato starch solution can improve the performance of bimetallic supported catalysts.

[0095] Comparative Example 2

[0096] Compared with Example 15, in Comparative Example 2, the activated carbon was not pretreated, and the rest of the catalyst preparation and evaluation process were the same as in Example 15.

[0097] After 5 hours of stable evaluation, the product was analyzed by gas chromatography. The area normalization results showed that the catalyst of comparative example 2 showed 83.78% conversion and 85.71% ethylene selectivity in application 1; and 83.13% conversion and 87.87% ethane selectivity in application 2. This comparative experiment proves that activated carbon treated with nitric acid can increase the oxygen-containing groups on the activated carbon, which is beneficial to the improvement of catalyst performance.

[0098] Comparative Example 3

[0099] Compared with Example 15, in Comparative Example 3, the activated carbon was not subjected to urea modification treatment, and the rest of the catalyst preparation and evaluation process were the same as those of Example 15.

[0100] After 5 hours of stable evaluation, the product was analyzed by gas chromatography. The area normalization results showed that the catalyst of comparative example 3 showed a conversion rate of 76.88% and an ethylene selectivity of 78.64% in application 1; and a conversion rate of 77.95% and an ethane selectivity of 79.96% in application 2. This comparative experiment proves that the addition of N to activated carbon can give activated carbon more defects, which is beneficial to the anchoring and dispersion of metal components, thereby improving the catalytic activity.

[0101] Comparative Examples 4-5

[0102] Compared with Example 15, the temperature of reflux during urea modification was changed in Comparative Examples 4 and 5, where Comparative Example 4 used 180° C. reflux for 3 h, and Comparative Example 5 used 80° C. reflux for 3 h. The rest of the catalyst preparation process and evaluation process of Comparative Examples 4 and 5 were the same as those of Example 15.

[0103] After 5 hours of stable evaluation, the product was analyzed by gas chromatography. The area normalization results showed that the catalyst of comparative example 4 showed a conversion rate of 72.56% and an ethylene selectivity of 77.94% in application 1; and a conversion rate of 74.30% and an ethane selectivity of 76.52% in application 2. The catalyst of comparative example 5 showed a conversion rate of 71.08% and an ethylene selectivity of 70.08% in application 1; and a conversion rate of 72.32% and an ethane selectivity of 73.21% in application 2. This comparative experiment proves that reflux at a higher temperature may cause the urea acting on the activated carbon to decompose and fail to achieve the purpose of modification; the reflux effect at a lower temperature is not obvious, and most of the urea is physically adsorbed and combined with the activated carbon.

[0104] Comparative Example 6

[0105] Comparative Example 6 Compared with Example 15, soluble potato starch was not used as a complexing agent for the impregnation solution. That is, the soluble potato starch solution in A3 and A4 was replaced by an equal amount of deionized water, and the rest of the catalyst preparation process and evaluation process were the same as Example 15.

[0106] After 5 hours of stable evaluation, the product was analyzed by gas chromatography. The area normalization results showed that the catalyst of comparative example 6 showed a conversion rate of 78.36% and an ethylene selectivity of 74.14% in application 1; and a conversion rate of 78.98% and an ethane selectivity of 74.61% in application 2. This comparative experiment proves that the complexing agent prepared by using soluble potato starch solution can coordinate the bimetallic complex, make the bimetallic close together, and improve the catalytic performance of the bimetallic catalyst.

[0107] Comparative Example 7

[0108] Comparative Example 7 Compared with Example 15, the precursor after impregnation was not flash dried. That is, in A5, 6 g of the prepared activated carbon was added to the bimetallic colloid solution of A4 for impregnation, and stirred at 50°C and 100 rpm for 1 hour for adsorption. After that, it was dried at 80°C for 2 hours in a blast oven, and then subjected to electromagnetic heating treatment in a medium frequency furnace.

[0109] The rest of the catalyst preparation process and evaluation process are the same as Example 15.

[0110] After 5 hours of stable evaluation, the product was analyzed by gas chromatography. The area normalization results showed that the catalyst of comparative example 7 showed a conversion rate of 71.24% and an ethylene selectivity of 72.36% in application 1; and a conversion rate of 70.16% and an ethane selectivity of 72.34% in application 2. This comparative experiment proves that the use of flash drying can pre-dry the precursor, quickly increase the volatilization of the solvent, and improve the redispersion of the metal to a certain extent, thereby adjusting the catalyst results and improving the catalyst performance.

[0111] Comparative Example 8

[0112] Comparative Example 8 Compared with Example 15, the prepared catalyst was not subjected to electromagnetic heat treatment. That is, the precursor subjected to flash drying was not subjected to electromagnetic heat treatment, but was simply dried in a forced air oven at 80° C. for 5 h. The rest of the catalyst preparation process and evaluation process were the same as those of Example 15.

[0113] After 5 hours of stable evaluation, the product was analyzed by gas chromatography. The area normalization results showed that the catalyst of comparative example 8 showed a conversion rate of 67.13% and an ethylene selectivity of 70.12% in application 1; and a conversion rate of 68.24% and an ethane selectivity of 69.98% in application 2. This comparative experiment proves the high efficiency of electromagnetic heat treatment, which can synthesize catalysts in a shorter time and significantly improve the catalytic performance.

[0114] Comparative Example 9

[0115] Compared with Example 15, in Comparative Example 9, ammonia was not used for pre-activation in the catalyst application part, and the rest of the catalyst preparation process and evaluation process were the same as those of Example 15.

[0116] After 5 hours of stable evaluation, the product was analyzed by gas chromatography. The area normalization results showed that the catalyst of comparative example 9 showed a conversion rate of 71.75% and an ethylene selectivity of 61.25% in application 1; and a conversion rate of 72.90% and an ethane selectivity of 63.02% in application 2. This comparative experiment proves that ammonia pretreatment can effectively activate the catalyst, reduce the metal, and improve the catalyst's conversion rate for the reactants and the selectivity of the target products ethylene and ethane.

[0117] Examples 21-22

[0118] Compared with Example 15, Examples 21 and 22 changed the conditions in the catalyst pretreatment step a. The pretreatment conditions in Example 21 were NH 3 / N 2 =1:2 volume ratio, of which NH 3 The flow rate was 10 mL / min, and the catalyst was preactivated after ventilation for 20 min. The fixed bed reactor was heated to 330°C at 3°C / min and kept at this temperature for 2 h to complete the preactivation. The pretreatment conditions of Example 22 were NH 3 / N 2 =1:5 volume ratio, of which NH 3 The flow rate was 5 mL / min, and the catalyst was preactivated after ventilation for 40 min. The fixed bed reactor was heated to 300°C at 6°C / min and kept at this temperature for 5 h to complete the preactivation.

[0119] After 5 hours of stable evaluation, the product was analyzed by gas chromatography. The area normalization results showed that the catalyst of Example 21 showed a conversion rate of 92.24% and an ethylene selectivity of 92.35% in Application 1; and a conversion rate of 93.45% and an ethane selectivity of 94.32% in Application 2. The catalyst of Example 22 showed a conversion rate of 91.42% and an ethylene selectivity of 91.23% in Application 1; and a conversion rate of 92.01% and an ethane selectivity of 93.21% in Application 2.

[0120] Embodiment 23-24

[0121] Compared with Example 15, Examples 23 and 24 changed the conditions in Catalyst Application 2. Example 23: The temperature was raised to 330°C at 10°C / min, and the volumetric space velocity of the raw material was 2000h-1. -1 , control the reaction material ratio n(H 2 ):n(C 2 H 4 Cl2 )=5:1. Example 23 The temperature was raised to 280°C at 3°C / min, and the volumetric space velocity of the raw material was 1000h -1 , control the reaction material ratio n(H 2 ):n(C 2 H 4 Cl 2 )=3:1.

[0122] After 5 hours of stable evaluation, the product was analyzed by gas chromatography. The area normalization results showed that the catalyst of Example 21 showed a conversion rate of 99.43% and an ethane selectivity of 90.45% in Application 2; the catalyst of Example 22 showed a conversion rate of 91.66% and an ethane selectivity of 96.78% in Application 2.

[0123] Embodiment 25

[0124] Example 25 The catalyst prepared in Example 15 was used to carry out stability test. Here, only Application 2 evaluation was performed, wherein the evaluation conditions were: V N2 :V NH3 =3:1 ratio, of which NH 3 The flow rate was 5 mL / min, and the catalyst was preactivated after ventilation for 30 min. The fixed bed reactor was heated to 350 °C at 5 °C / min and kept at this temperature for 3 h. After the preactivation was completed, the temperature was raised to 330 °C at 5 °C / min and the NH 3 、N 2 , open H 2 , feed pump, and react. The raw material is first gasified at 120℃ in the gasification chamber, and then mixed with hydrogen before entering the reactor. The volume space velocity of the raw material is 1500h -1 , control the reaction material ratio n(H 2 ):n(C 2 H 4 Cl 2 )=3:1.

[0125] After stable evaluation, the product was analyzed by gas chromatography, and the area normalized results showed that: the catalyst of Example 25 showed a conversion rate of 99.87% and an ethane selectivity of 98.75% after a reaction of 10h; the catalyst showed a conversion rate of 99.12% and an ethane selectivity of 98.89% after a reaction of 50h; the catalyst showed a conversion rate of 98.99% and an ethane selectivity of 97.72% after a reaction of 100h; the catalyst showed a conversion rate of 99.07% and an ethane selectivity of 98.84% after a reaction of 300h; the catalyst showed a conversion rate of 99.13% and an ethane selectivity of 99.34% after a reaction of 500h; the catalyst showed a conversion rate of 98.32% and an ethane selectivity of 97.95% after a reaction of 800h; the catalyst showed a conversion rate of 96.36% and an ethane selectivity of 96.55% after a reaction of 1000h;

[0126] In summary, by treating activated carbon, urea-modified activated carbon, and soluble potato starch-prepared complexing agents at high temperatures to coordinate and complex bimetallic, and using flash drying and electromagnetic heating of a medium-frequency furnace, an efficient catalyst loaded with bimetallic activated carbon was prepared, which has more efficient dechlorination performance in the hydrogenation and dechlorination reaction of 1,2-dichloroethane, can efficiently produce ethane under hydrogenation conditions, and can efficiently and selectively generate ethylene under hydrogen-free conditions. In the stability experiment, the original conversion rate and selectivity can be maintained while the service life of the catalyst is increased.

[0127] Table 1. Catalyst performance of the examples and comparative examples

[0128]

[0129]

[0130] Table 2. Stability test table of Example 25

[0131] Time (h) Conversion rate (%) Ethane selectivity (%) 10 99.87 98.75 50 99.12 98.89 100 98.99 97.72 300 98.74 97.47 800 98.32 97.05 1000 97.36 96.55

Claims

1. A method for preparing a modified activated carbon-supported bimetallic catalyst, characterized in that: The preparation method comprises the following steps: A1. The activated carbon was crushed and sieved into 10-40 mesh granular activated carbon, washed with ultrasonic water, separated by filtration, dried and placed in a microwave tube furnace, and calcined for 1-8h at a power of 200-900W, a temperature of 300-900℃, and a N2 flow rate of 30-100mL / min; A2. The activated carbon treated in step A1 is added to a 0.05-0.40 g / mL urea solution, refluxed at 100-140°C for 1-5 hours, the excess solution is filtered and separated, and the treated carrier is vacuum dried to obtain modified activated carbon; A3. Mix potato starch and water, stir and dissolve at 20-90 ° C and 50-500 rpm, filter, and prepare a 0.05-0.20 g / mL complexing agent solution; A4. First, prepare 0.001-0.01 g / mL of metal precursor I solution and 0.001-0.1 g / mL of metal precursor II solution, and add the metal precursor I solution and the metal precursor II solution to a container in a volume ratio of 1:1-15, and mix them, and obtain a uniformly mixed co-impregnation solution by ultrasonic treatment; take the complexing agent solution prepared in step A3 and add it to the co-impregnation solution, and stir at 50-500 rpm for 2-30 min to prepare a colloidal solution containing a bimetallic compound; The metal in the metal precursor I solution is selected from one of Pt, Pd, and Ru, and the metal in the metal precursor II solution is selected from one of Fe, Co, Ni, and Cu; A5. Take the modified activated carbon treated in step A2 and add it to container 1, add the bimetallic colloid solution prepared in step A4, the feed ratio of the modified activated carbon to the bimetallic colloid solution is 1g:1-3mL, and add methanol, the volume ratio of methanol to the bimetallic colloid solution is 0.5-1.5:1, and stir and adsorb for 0.5-3h at 50-100°C and 50-500rpm; A6. Take a container 2 with a larger capacity than container 1 and at least two openings, connect the opening of container 1 in step A5 to the opening of container 2 with a rubber tube, and connect the other opening of container 2 to a vacuum pump; close the connection between container 1 and container 2, evacuate container 2 to a vacuum using a vacuum pump, and heat and stir the mixture in the sealed container 1 under the conditions of heating and stirring at 60-200° C. and 50-500 rpm for 0.5-1 h, then open the connection between container 1 and container 2, evaporate the liquid in container 1 instantly, and continue at -0.1 MPa for 10-60 min; A7. Dry the remaining material in container 1 and place it in a sealed quartz tube filled with N2. Put the quartz tube into a medium frequency furnace and heat treat it at 50 Hz, 500-1000 W, and 300-800°C for 5-50 seconds to prepare a modified activated carbon-loaded bimetallic catalyst.

2. The preparation method according to claim 1, characterized in that: In step A1, the calcination conditions in the microwave tube furnace are: calcination treatment for 1-5h at a power of 400-800W, a temperature of 400-800°C, and a N2 flow rate of 50-100mL / min.

3. The preparation method according to claim 1, characterized in that: In step A2, the feed ratio of the activated carbon treated in step A1 to 0.05-0.40 g / mL urea solution is 1 g:0.5-1.0 mL; the concentration of the urea solution is 0.10-0.30 g / mL; and reflux is performed at 100-140° C. for 1-3 hours.

4. The preparation method according to claim 1, characterized in that: In step A3, potato starch and water are stirred and dissolved at 30-80° C. and 100-400 rpm, filtered, and configured into a 0.05-0.15 g / mL complexing agent solution.

5. The preparation method according to claim 1, characterized in that: In step A4, 0.001-0.01 g / mL of metal precursor I solution and 0.01-0.1 g / mL of metal precursor II solution are prepared, and the metal precursor I solution and the metal precursor II solution are added to a beaker in a volume ratio of 1:1-10, and a uniformly mixed co-impregnation solution is obtained by ultrasonic treatment; The volume ratio of the complexing agent solution to the co-impregnation solution is 0.5-1.5:

1.

6. The preparation method according to claim 1, characterized in that: In step A5, after adding methanol, stirring adsorption is carried out at 50-100° C. and 50-200 rpm for 0.5-1 h.

7. A modified activated carbon-supported bimetallic catalyst prepared according to the preparation method according to any one of claims 1 to 6.

8. Use of the modified activated carbon-supported bimetallic catalyst as claimed in claim 7 in the catalytic dechlorination of 1,2-dichloroethane, wherein the modified activated carbon-supported bimetallic catalyst is pre-activated with NH3 before use.

9. The use according to claim 8, characterized in that: The application is for preparing ethylene, and the steps include: B1. The modified activated carbon-supported bimetallic catalyst is loaded into a fixed bed reactor, and a mixed gas of NH3 / N2 is introduced into the fixed bed reactor at a ratio of 1:1-10, wherein NH3 is introduced at a flow rate of 5-10 mL / min, and the catalyst is pre-activated after ventilation for a certain period of time, and the fixed bed reactor is heated to 180-500°C at 3-10°C / min and kept at a constant temperature for 1-6 hours to complete the pre-activation of the modified activated carbon-supported bimetallic catalyst; B2. Raise the temperature of the fixed bed reactor to 220-450°C at 3-10°C / min, turn off the NH3 / N2 supply; turn on the feed pump to introduce 1,2-dichloroethane as a raw material into the vaporization chamber, vaporize the raw material at 70-160°C, mix it with nitrogen and introduce it into the fixed bed reactor, so that n(N2):n(C2H4Cl2)=5-1:1, and the volume space velocity of the raw material is 200-2000h -1 , ethylene is produced under the action of modified activated carbon-supported bimetallic catalyst.

10. The use according to claim 8, characterized in that: The application is for preparing ethane, and the steps include: C1. The modified activated carbon-supported bimetallic catalyst is loaded into a fixed bed reactor, and a mixed gas of NH3 / N2 is introduced into the fixed bed reactor at a volume ratio of 1:1-10, wherein NH3 is introduced at a flow rate of 5-10 mL / min, and the catalyst is pre-activated after ventilation for a certain period of time, and the fixed bed reactor is heated to 180-500°C at 3-10°C / min and kept at a constant temperature for 1-6 hours to complete the pre-activation of the modified activated carbon-supported bimetallic catalyst; C2. Raise the temperature of the fixed bed reactor to 220-440℃ at 3-10℃ / min, turn off the supply of N2 and NH3; turn on the H2 supply and feed pump, and let the feed pump pass 1,2-dichloroethane as the raw material into the vaporization chamber, vaporize the raw material at 70-160℃, and then mix it with hydrogen before entering the reactor. The volume space velocity of the raw material is 500-2000h -1 , the reaction material ratio is controlled to be n(H2):n(C2H4Cl2)=1-10:1, and ethane is generated under the action of modified activated carbon-supported bimetallic catalyst.

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