Preparation method and application of copper catalyst for acetylene hydrochlorination
阅读说明：本技术 一种用于乙炔氢氯化反应的铜催化剂的制备方法和应用 (Preparation method and application of copper catalyst for acetylene hydrochlorination ) 是由 赵佳 庞祥雪 王柏林 岳玉学 王赛赛 江曌 朱文锐 李小年 于 2020-12-22 设计创作，主要内容包括：本发明公开了一种用于乙炔氢氯化反应的铜催化剂的制备方法和应用。所述制备方法包括如下步骤：将含铜前驱体与贱金属助剂溶解在溶剂中,搅拌使其混合均匀,在20～30℃时,将所述混合液滴加到多孔固体载体上,并在高压脉冲电场的作用下采用等体积浸渍法,浸渍8～15小时,然后在40～110℃下干燥8～24小时,即得到铜催化剂；所述的贱金属助剂为Bi、Ba、Fe、Mn、Zn、K、Ca、Sn、Ni中的一种或多种金属的盐。本发明提供了所述的铜催化剂在乙炔氢氯化合成氯乙烯的反应中的应用。本发明将高压脉冲电场技术应用到催化剂制备过程中,有利于提高催化剂的活性,并且能够在长时间的反应过程中保持稳定。(The invention discloses a preparation method and application of a copper catalyst for acetylene hydrochlorination. The preparation method comprises the following steps: dissolving a copper-containing precursor and a base metal auxiliary agent in a solvent, stirring to uniformly mix the copper-containing precursor and the base metal auxiliary agent, dripping the mixed liquid onto a porous solid carrier at 20-30 ℃, soaking for 8-15 hours by adopting an isometric soaking method under the action of a high-voltage pulse electric field, and then drying for 8-24 hours at 40-110 ℃ to obtain a copper catalyst; the base metal auxiliary agent is one or more of Bi, Ba, Fe, Mn, Zn, K, Ca, Sn and Ni. The invention provides application of the copper catalyst in the reaction of synthesizing vinyl chloride by hydrochlorinating acetylene. The invention applies the high-voltage pulse electric field technology to the catalyst preparation process, is beneficial to improving the activity of the catalyst and can keep stable in the long-time reaction process.)
1. A preparation method of a copper catalyst for acetylene hydrochlorination comprises the following steps:
dissolving a copper-containing precursor and a base metal auxiliary agent in a solvent, stirring to uniformly mix the copper-containing precursor and the base metal auxiliary agent, dripping the mixed liquid onto a porous solid carrier at 20-30 ℃, soaking for 8-15 hours by adopting an isometric soaking method under the action of a high-voltage pulse electric field, and then drying for 8-24 hours at 40-110 ℃ to obtain a copper catalyst; the base metal auxiliary agent is one or more of Bi, Ba, Fe, Mn, Zn, K, Ca, Sn and Ni.
2. The method of claim 1, wherein: the porous solid carrier is subjected to microwave treatment.
3. The method of claim 2, wherein: the microwave treatment conditions are as follows: the output power is 500-900W, the frequency is 2000-2500 MHz, the processing time is 0.5-2 h, and the temperature is 20-30 ℃; the microwave treatment is carried out in N2Carried out under an atmosphere, N2The flow rate is 5-60 ml/min.
4. The method according to any one of claims 1 to 3, wherein: in the copper catalyst, the copper loading is 10-30 wt%; the loading capacity of the base metal additive is 0.1-2 wt%.
5. The method according to any one of claims 1 to 3, wherein: the copper-containing precursor is one of copper chloride, copper nitrate, copper sulfate, copper phosphate and copper pyrophosphate, and the base metal auxiliary agent is one or a mixture of bismuth chloride, barium chloride, ferric chloride, manganese chloride, zinc chloride, potassium chloride, calcium chloride, tin chloride, nickel chloride and the like.
6. The method according to any one of claims 1 to 3, wherein: the solvent is one or more of deionized water, absolute ethyl alcohol, tetrahydrofuran, methanol, acetone, diethyl ether, cyclohexane, carbon tetrachloride and benzene.
7. The method according to any one of claims 1 to 3, wherein: the high-voltage pulse electric field treatment conditions are as follows: the pulse voltage is 300-600V, the electric field intensity is 10-50 kv/cm, the pulse frequency is 1500-2000 Hz, and the processing time is 0.5-1.5 h.
8. The method according to any one of claims 1 to 3, wherein: the porous solid carrier is selected from one of activated carbon, mesoporous carbon, carbon nano tubes, graphene, silicon dioxide, aluminum oxide, titanium dioxide and molecular sieves.
9. The use of the copper catalyst prepared by the preparation method according to claim 1 in the reaction of synthesizing vinyl chloride by hydrochlorinating acetylene.
10. The use of claim 9, wherein: the application specifically comprises the following steps: the copper catalyst is filled in a fixed bed reactor, and raw material gases HCl and C are introduced2H2And reacting at the reaction temperature of 120-200 ℃ and the reaction pressure of 0.01-2 MPa to obtain the chloroethylene.
(I) technical field
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method and application of a copper catalyst for acetylene hydrochlorination.
(II) background of the invention
Vinyl chloride is a monomer of polyvinyl chloride (PVC) which is one of five synthetic resins in the world, and the PVC is widely applied to the important fields of national economy such as industry, agriculture, building materials and the like. The method is mainly characterized in that the chloroethylene is produced by a calcium carbide acetylene method, a dichloroethane cracking method and a petroleum ethylene method, the resource structure of 'rich coal, poor oil and less gas' in China determines that the method is to be the main process for producing chloroethylene in China in a long time in the future, namely, mercury chloride catalyzes acetylene and hydrogen chloride to react to generate chloroethylene, the catalyst has high activity and selectivity but poor thermal stability, and mercury loss of the catalyst can be caused in the using process, so that the activity is influenced, and more seriously, the highly toxic mercury chloride causes serious pollution to the environment. In 2016, 4 months, the twentieth conference of the twelfth national large convention of people in China decided to approve the Water Authority on Mercury, which requires that the contracting country forbid the production and import and export of products containing mercury since 2020. Therefore, the development of a non-mercury catalyst is necessary for the sustainable development of the industry for synthesizing vinyl chloride by the calcium carbide acetylene method.
At present, the industrially mature non-mercury catalysts are mainly noble metal catalysts, such as gold, palladium, ruthenium and the like, although the reaction activity has certain advantages, the catalysts are difficult to regenerate after being deactivated and the expensive price brings great cost pressure to the industrial production of vinyl chloride, and the development of the non-noble metal catalysts is imperative. Non-noble metal catalysts have the advantage of being relatively inexpensive, but their activity and stability are at a greater distance from noble metal catalysts.
Patent CN109821546A reports a composite copper-based catalyst, its preparation method and its application in the production of vinyl chloride. The acid treated active carbon is dipped in a solution containing copper salt and auxiliary agent, and the composite copper-based catalyst is prepared after drying and roasting. The catalyst has a space velocity of 300h-1Under the condition (2), the operation can only be stably carried out for 500 hours, and the problem of stability is not solved.
Patent CN201210575484.3 reports that copper chloride is used as an active component, and one or a mixture of any of non-noble metal elements, the chlorides of which are not easily volatilized, in alkali metal, alkaline earth metal and transition metal elements is used as a promoter metal element, and the copper chloride is prepared by equal volume impregnation, ultrasound and drying. The catalyst has low acetylene conversion rate and cannot meet the industrial requirement.
Patent CN201810775463.3 reports a copper complex catalyst for hydrochlorination of acetylene, the copper complex is formed by complexing copper salt and organic phosphoric acid ligand. Under the reaction conditions: the temperature is 180 ℃, and the space velocity of acetylene is 90h-1Flow rate ratio of V (HCl)/V (C)2H2) At 1.15, the catalyst was not significantly deactivated within 10h, and the long-term stability was not investigated.
Patent CN201710208643.9 reports a copper-based catalyst for acetylene hydrochlorination with high activity and stability, and a stabilizer with the advantages of low cost, low toxicity, good thermal stability, low vapor pressure and the like is introduced on the basis of the copper-based catalyst, so that the stability of the copper-based catalyst for acetylene hydrochlorination is remarkably improved. However, the initial conversion was not significantly increased compared to the comparative example without the addition of the stabilizer.
Patent CN101716528A adopts imidazole ionic liquid as solvent, and selects one or two of chlorides of mercury, copper, tin, platinum, palladium, gold and rhodium as catalyst active component, and the concentration is 0.02-1 mol/L; one or two of bismuth, cerium and potassium chlorides are selected as an auxiliary agent, and the concentration of the auxiliary agent is 0.0045-0.5 mol/L. The experimental result shows that the selectivity can reach more than 99.9 percent, and the conversion rate of the acetylene is 30 to 80 percent. Reference [ Green Chemistry 2011,13:1495-]Reported as ionic liquids [ Bmim [ ]]Cl is used as a solvent, the activity of different metal chlorides in the acetylene hydrochlorination reaction is tested, and the activity sequence of the different metal chlorides in the acetylene hydrochlorination reaction is consistent with that in the gas-solid phase reaction, wherein HAuCl with the highest activity is found4And H2PtCl6Close to 80%, all catalysts have high selectivity. The experimental result shows that the selectivity reaches 99 percent and the conversion rate is 62.5 percent under the conditions that the temperature t is 140 ℃, the concentration is 0.058mol/L, the acetylene gas velocity is 0.3L/h and the hydrogen chloride gas velocity is 0.4L/h, and the catalyst can still maintain the original activity after reacting for 3 days. Although the ionic liquid has good thermal stability and chemical stability, the ionic liquid is expensive, and cannot be used as a solvent to dissolve an active component, so that the ionic liquid has no economic applicability and cannot be industrialized.
In summary, it remains a great challenge to improve the activity and stability of copper-based catalysts in the hydrochlorination of acetylene. Although the activity can be improved by adding a metal additive, a stabilizer, or using an ionic liquid as an impregnation liquid, the problem of stability is difficult to solve. The dispersion degree of the active components of the catalyst determines the number of active sites exposed on the surface of the catalyst, and under the condition of the same content of the active components, the higher the dispersion degree is, the more the active components are exposed on the surface of the catalyst, and the better the catalytic performance of the catalyst is. In addition, the dispersity of the active components not only determines the utilization rate of the active components, but also influences the aggregation state of the catalytic active sites, thereby influencing the stability of the catalyst. The traditional impregnation method is influenced by an impregnation solvation effect and an active component clustering effect, the active component and the carrier have weak acting force and are not easy to highly disperse, and the active component and the carrier can migrate and agglomerate in the reaction process, so that the activity and the stability of the active component are seriously influenced. Therefore, the invention provides a method for improving the dispersion degree of copper on the surface of a carrier, and is significant in improving the activity and stability in the hydrochlorination reaction of acetylene.
Disclosure of the invention
The invention aims to solve the problems of poor acetylene conversion rate and poor stability of a copper catalyst in the reaction of synthesizing vinyl chloride by hydrochlorinating acetylene, and provides a preparation method and application of the copper acetylene hydrochlorination catalyst with high conversion rate and good stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a copper catalyst for acetylene hydrochlorination, comprising the steps of:
dissolving a copper-containing precursor and a base metal auxiliary agent in a solvent, stirring to uniformly mix the copper-containing precursor and the base metal auxiliary agent, dripping the mixed liquid onto a porous solid carrier at 20-30 ℃, soaking for 8-15 hours by adopting an isometric soaking method under the action of a high-voltage pulse electric field, and then drying for 8-24 hours at 40-110 ℃ to obtain a copper catalyst; the base metal auxiliary agent is one or more of Bi, Ba, Fe, Mn, Zn, K, Ca, Sn and Ni.
The invention adopts the combination of the traditional isometric impregnation method and the high-voltage pulse electric field technology (PEF), the interaction between the high-voltage pulse electric field with proper strength and the charged particles in the preparation system, under the action of the high-voltage pulse electric field, the charged particles carry out ordered orientation movement, which is beneficial to reducing agglomeration and better diffusing to the carrier, so that more active sites are exposed on the inner surface and the outer surface of the catalyst. By adopting the above technology, highly dispersed catalyst can be prepared, thereby facilitating the contact and interaction with reactants. The catalyst has the advantages of high activity and good stability in the hydrochlorination reaction of acetylene, and has good economic applicability and industrial application value.
Further, in the copper catalyst, the copper loading amount (relative to the mass of the carrier) is 10-30 wt%; the loading capacity (relative to the mass of the carrier) of the base metal auxiliary agent is 0.1-2 wt%.
Further, the copper-containing precursor is one of copper chloride, copper nitrate, copper sulfate, copper phosphate and copper pyrophosphate.
Further, the base metal auxiliary agent is one or a mixture of bismuth chloride, barium chloride, ferric chloride, manganese chloride, zinc chloride, potassium chloride, calcium chloride, tin chloride, nickel chloride and the like.
Further, the solvent is one or a mixture of deionized water, absolute ethyl alcohol, tetrahydrofuran, methanol, acetone, diethyl ether, cyclohexane, carbon tetrachloride and benzene.
Further, the high-voltage pulse electric field treatment conditions are as follows: the pulse voltage is 300-600V, the electric field intensity is 10-50 kv/cm, the pulse frequency is 1500-2000 Hz, and the processing time is 0.5-1.5 h.
The porous solid carrier is selected from one of activated carbon, mesoporous carbon, carbon nano tubes, graphene, silicon dioxide, aluminum oxide, titanium dioxide and molecular sieves. The activated carbon is preferably columnar carbon or spherical activated carbon, the particle size is 20-100 meshes, and the specific surface area is 500-1500 m2The pore volume is 0.25-1.5 mL/g. The mesoporous carbon is preferably processed into a columnar shape or a spherical shape, the particle size is 10-100 meshes, and the specific surface area is 500-1600 m2The pore volume is 0.25-2.5 mL/g. The carbon nano tube is preferably processed into a columnar shape or a spherical shape, the particle size is 10-100 meshes, and the specific surface is 250-1600 m2The pore volume is 0.25-2.5 mL/g. The graphene is preferably processed into a columnar shape or a spherical shape, the particle size is 10-100 meshes, and the specific surface area is 500-3000 m2The pore volume is 0.25-2.5 mL/g. The aluminum oxide is preferably gamma-Al2O3And processed into columnar or spherical shape with particle size of 10-100 meshes and specific surface area of 250-800 m2The pore volume is 0.1-1.5 mL/g. The silica is preferably processed into a columnar or spherical shapeParticle size of 10 to 100 mesh, specific surface area of 250 to 800m2The pore volume is 0.1-1.5 mL/g. The titanium dioxide is preferably processed into a columnar shape or a spherical shape, the particle size is 10-100 meshes, and the specific surface area is 250-800 m2The pore volume is 0.1-1.0 mL/g. The molecular sieve is preferably ZSM-5, a beta molecular sieve, a gamma molecular sieve, a 5A molecular sieve, a 10X molecular sieve or a 13X molecular sieve, the particle size is 10-100 meshes, and the specific surface area is 250-800 m2The pore volume is 0.1-1.8 mL/g. The porous solid carrier is particularly preferably activated carbon.
Further, the porous solid carrier is subjected to microwave treatment.
Furthermore, the microwave treatment conditions are as follows: the output power is 500-900W, the frequency is 2000-2500 MHz, the processing time is 0.5-2 h, and the temperature is 20-30 ℃; the microwave treatment is carried out in N2Carried out under an atmosphere, N2The flow rate is 5-60 ml/min.
The invention adopts microwave to pretreat the carrier, and the intrinsic activity of the active component is influenced by the interaction between the carrier and the active component. The carrier before pretreatment contains carboxyl, lactone acid, phenols, ethers and other groups with high electronegativity, and the existence of the groups can change the property of the carrier to different degrees, thereby greatly influencing the preparation and catalytic performance of the catalyst. The carrier is pretreated by adopting a microwave technology, so that groups with high electronegativity can be eliminated in a short time, the pore stability of the carrier can be improved, and the active components can be fully dispersed in the carrier.
The invention adopts an equal-volume impregnation method as the known technology in the field, namely, the dropwise added mixed solution is matched with the pore volume of the porous solid carrier. The dripped impregnation liquid completely enters the pore channels of the porous solid carrier.
In a second aspect, the invention provides the use of the copper catalyst in the reaction of synthesizing vinyl chloride by hydrochlorinating acetylene.
The application specifically comprises the following steps: the copper catalyst is filled in a fixed bed reactor, and raw material gases HCl and C are introduced2H2The reaction temperature is 120-200 ℃, the reaction pressure is 0.01-2 MPa, and the product is obtained by reactionVinyl chloride.
Further, the mass ratio of the raw material gas substances is n (HCl) to n (C)2H2) The volume space velocity of acetylene is 1: 1-1.2: 1, and the volume space velocity of acetylene is 5-500 h-1。
Compared with the prior art, the invention has the following innovation points and technical advantages:
(1) the invention applies the high-voltage pulse electric field technology (PEF) to the preparation process of the catalyst, the interaction between the high-voltage pulse electric field and the charged particles in the preparation system is beneficial to the high dispersion degree and effective anchoring of the active components of the catalyst on the surface of the carrier, reduces the agglomeration of the active components, exposes more active sites on the inner and outer surfaces of the catalyst, is beneficial to the contact and interaction between the active sites and reactants, exerts high activity, and can keep stable in the long-time reaction process.
(2) The invention adopts microwave to pretreat the carrier, can effectively eliminate high electronegativity groups in the carrier in a short time, has no obvious change in the specific surface area and pore volume of the carrier, improves the pore stability, and can prevent metal particles from sintering, thereby improving the stability of the catalyst.
(3) The copper-based catalyst prepared by the invention has the advantages of high catalytic activity, good stability and low cost.
(IV) detailed description of the preferred embodiments
The present invention will be described with reference to specific examples. It should be noted that the examples are only intended to illustrate the invention further, but should not be construed as limiting the scope of the invention, which is in no way limited thereto. Those skilled in the art may make insubstantial modifications and adaptations to the invention described above.
Example 1
Selecting columnar active carbon as carrier, with particle diameter of 20 mesh and specific surface area of 1000m2A pore volume of 1mL/g and a temperature of 5mL/min N at 20 DEG C2And (3) performing microwave treatment under the atmosphere, wherein the output power is 500W, the frequency is 2000MHz, and the microwave is taken out for standby after treatment for 0.5 h.
20.96g of chlorineDissolving copper and 0.21g ZnCl2Dissolving in methanol, stirring, adding the mixture at 30 deg.C to 100g of microwave-treated activated carbon carrier, treating under the action of high-voltage pulse electric field for 0.5h with pulse voltage of 300V, strength of 10kv/cm and frequency of 1500Hz, taking out from the high-voltage pulse electric field, soaking for 5h, and drying at 70 deg.C for 8h to obtain copper catalyst with copper loading of 10% and ZnCl2The loading was 0.1%.
5g of the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor under the following reaction conditions: the temperature is 120 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C)2H2)1:1, acetylene space velocity of 5h-1. At the initial stage of the reaction, the conversion rate of acetylene is 99.5 percent, and the selectivity of chloroethylene is 100 percent; after 1500 hours of reaction, the acetylene conversion was 99.12% and the vinyl chloride selectivity was 99.8%.
Example 2
Selecting spherical active carbon as carrier, with particle diameter of 80 mesh and specific surface area of 1500m2Per g, pore volume 0.25mL/g, and at 22 ℃ at 15mL/min N2And performing microwave treatment under the atmosphere, wherein the output power is 600W, the frequency is 2100MHz, and the microwave is taken out for standby after treatment for 1 h.
90g of copper nitrate and 2.25g of BiCl3Dissolving in deionized water, stirring, adding the mixture at 25 deg.C to 100g of microwave-treated activated carbon carrier, treating under the action of high-voltage pulse electric field for 0.6 hr with pulse voltage of 400V, strength of 20kv/cm and frequency of 1600Hz, taking out from the high-voltage pulse electric field, soaking for 10 hr, and drying at 110 deg.C for 8 hr to obtain copper catalyst with copper loading of 30% and BiCl3The loading was 2%.
5g of the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor under the following reaction conditions: the temperature is 140 ℃, the reaction pressure is 1MPa, n (HCl) is n (C)2H2)1.1:1, and the space velocity of acetylene is 200h-1. At the initial stage of the reaction, the conversion rate of acetylene is 99.28 percent, and the selectivity of chloroethylene is 100 percent; after 1500 hours of reaction, the acetylene conversion rate was 99.02% and the vinyl chloride selectivity was 99.5%.
Example 3
Mesoporous carbon is selected as a carrier, the particle size of the mesoporous carbon is 10 meshes, and the specific surface area is 1600m2Per g, pore volume 2.5mL/g, at 23 ℃ at 20mL/min N2And (3) performing microwave treatment under the atmosphere, wherein the output power is 700W, the frequency is 2200MHz, and the microwave is taken out for standby after treatment for 1.5 h.
37.5g of copper sulfate and 3.6g of FeCl3Dissolving in carbon tetrachloride, stirring to mix uniformly, dripping the mixture onto 100g of microwave-treated mesoporous carbon carrier at 30 ℃, treating for 0.7h under the action of a high-voltage pulse electric field, with the pulse voltage of 500V, the strength of 30kv/cm and the frequency of 1700Hz, taking out from the high-voltage pulse electric field, soaking for 15h, and drying for 15h at 80 ℃ to obtain the copper catalyst, wherein the copper loading is 15%, the FeCl is 15%3The loading was 1.2%.
5g of the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor under the following reaction conditions: the temperature is 160 ℃, the reaction pressure is 1.5MPa, n (HCl) is n (C)2H2)1.2:1, and the space velocity of acetylene is 300h-1. At the initial stage of the reaction, the conversion rate of acetylene is 99.56 percent, and the selectivity of chloroethylene is 100 percent; after 1500 hours of reaction, the acetylene conversion was 99.14% and the vinyl chloride selectivity was 99.21%.
Example 4
Selecting columnar carbon nano-tubes as a carrier, wherein the particle size of the columnar carbon nano-tubes is 50 meshes, and the specific surface area is 500m2Per g, pore volume 0.3mL/g, and at 25 deg.C, at 30mL/min N2And (3) performing microwave treatment under the atmosphere, wherein the output power is 800W, the frequency is 2200MHz, and the microwave is taken out for standby after treatment for 2 h.
56.4g of copper pyrophosphate and 0.345g of MnCl2Dissolving in benzene, stirring to mix uniformly, dripping the mixture onto 100g of microwave-treated carbon nanotube carrier at 22 ℃, treating for 0.8h under the action of a high-voltage pulse electric field, with pulse voltage of 600V, strength of 40kv/cm and frequency of 1800Hz, taking out from the high-voltage pulse electric field, soaking for 12h, and drying for 16h at 85 ℃ to obtain the copper catalyst, wherein the copper loading is 12%, and MnCl is added2The loading was 0.15%.
5g of the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor under the following reaction conditions: the temperature is 180℃,Reaction pressure 2MPa, n (HCl) n (C)2H2)1:1, acetylene space velocity 500h-1. At the initial stage of the reaction, the conversion rate of acetylene is 99.61%, and the selectivity of chloroethylene is 100%; after 1500 hours of reaction, the acetylene conversion rate was 99.02% and the vinyl chloride selectivity was 99.34%.
Example 5
Spherical graphene is selected as a carrier, the particle size of the spherical graphene is 60 meshes, and the specific surface area is 2500m2Per g, pore volume 1.5mL/g, at 30 ℃ at 60mL/min N2And (3) performing microwave treatment under the atmosphere, wherein the output power is 900W, the frequency is 2500MHz, and the microwave is taken out for standby after treatment for 1.25 h.
78g of copper phosphate and 0.28g of CaCl2Dissolving in diethyl ether, stirring to mix uniformly, dripping the mixed solution onto 100g of microwave-treated graphene carrier at 28 ℃, treating for 0.9h under the action of a high-voltage pulse electric field, with the pulse voltage of 350V, the strength of 50kv/cm and the frequency of 1800Hz, taking out from the high-voltage pulse electric field, soaking for 11h, and drying for 20h at 40 ℃ to obtain the copper catalyst, wherein the copper loading is 13 percent, CaCl is added2The loading was 0.1%.
5g of the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor under the following reaction conditions: the temperature is 200 ℃, the reaction pressure is 0.05MPa, n (HCl) n (C)2H2)1.1:1, and the space velocity of acetylene is 150h-1. At the initial stage of the reaction, the conversion rate of acetylene is 99.86 percent, and the selectivity of chloroethylene is 100 percent; after 1500 hours of reaction, the acetylene conversion was 99.25% and the vinyl chloride selectivity was 99.10%.
Example 6
Selecting columnar gamma-Al2O3Is a carrier with the particle size of 100 meshes and the specific surface area of 600m2Per g, pore volume 1.3mL/g, and at 28 ℃ at 50mL/min N2And (3) performing microwave treatment under the atmosphere, wherein the output power is 550W, the frequency is 2500MHz, and the microwave is taken out for standby after treatment for 1.6 h.
Dissolving 41.92g of copper chloride and 3.81g of KCl in tetrahydrofuran, stirring to mix uniformly, and dropwise adding the mixture to 100g of gamma-Al subjected to microwave treatment at 30 DEG2O3Treating the carrier for 1h under the action of a high-voltage pulse electric field, wherein the pulse voltage is 450V,the strength is 15kv/cm, the frequency is 2000Hz, then the catalyst is taken out from a high-voltage pulse electric field, the catalyst is soaked for 14h, and then the catalyst is dried for 24h at the temperature of 70 ℃, so that the copper catalyst is obtained, wherein the copper loading capacity is 20 percent, and the KCl loading capacity is 2 percent.
5g of the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor under the following reaction conditions: the temperature is 130 ℃, the reaction pressure is 0.15MPa, n (HCl) n (C)2H2)1.2:1, acetylene space velocity of 160h-1. At the initial stage of the reaction, the conversion rate of acetylene is 99.21 percent, and the selectivity of chloroethylene is 100 percent; after 1500 hours of reaction, the acetylene conversion was 99.01% and the vinyl chloride selectivity was 99.82%.
Example 7
Selecting columnar silicon dioxide as carrier, with particle diameter of 80 mesh and specific surface area of 750m2Per g, pore volume 0.25mL/g, at 30 ℃ at 60mL/min N2And (3) performing microwave treatment under the atmosphere, wherein the output power is 650W, the frequency is 2050MHz, and the microwave is taken out for standby after treatment for 1.6 h.
25g of copper sulfate and 3g of BaCl2Dissolving in acetone, stirring, adding the mixture at 25 deg.C to 100g of microwave-treated silica carrier, treating under the action of high-voltage pulse electric field for 1.2 hr with pulse voltage of 550V, intensity of 25kv/cm and frequency of 1550Hz, taking out from the high-voltage pulse electric field, soaking for 12 hr, and drying at 60 deg.C for 9.5 hr to obtain copper catalyst with copper loading of 10% and BaCl2The loading was 2%.
5g of the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor under the following reaction conditions: the temperature is 150 ℃, the reaction pressure is 1.2MPa, n (HCl) is n (C)2H2)1.2:1, acetylene space velocity 210h-1. At the initial stage of the reaction, the conversion rate of acetylene is 99.82%, and the selectivity of chloroethylene is 100%; after 1500 hours of reaction, the acetylene conversion rate was 99.15% and the vinyl chloride selectivity was 99.05%.
Example 8
Selecting columnar titanium dioxide as a carrier, wherein the particle size of the columnar titanium dioxide is 95 meshes, and the specific surface area of the columnar titanium dioxide is 300m2Per g, pore volume 0.8mL/g, at 21 ℃ at 60mL/min N2Performing microwave treatment under the atmosphere, wherein the output power is 750W and the frequency2150MHz, treating for 1.8h, and taking out.
56.4g of copper pyrophosphate and 3g of BiCl3Dissolving in diethylamine, stirring to mix uniformly, dripping the mixed solution onto 100g of microwave-treated titanium dioxide carrier at 25 ℃, treating for 1.5h under the action of a high-voltage pulse electric field, with pulse voltage of 310V, intensity of 35kv/cm and frequency of 1650Hz, taking out from the high-voltage pulse electric field, soaking for 14h, and drying for 22h at 65 ℃ to obtain the copper catalyst, wherein the copper loading is 12%, and the BiCl is3The loading was 2%.
5g of the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor under the following reaction conditions: the temperature is 170 ℃, the reaction pressure is 1.4MPa, n (HCl) is n (C)2H2)1.1:1, acetylene space velocity 220h-1. At the initial stage of the reaction, the conversion rate of acetylene is 99.85 percent, and the selectivity of chloroethylene is 100 percent; after 1500 hours of reaction, the acetylene conversion was 99.01% and the vinyl chloride selectivity was 99.26%.
Example 9
ZSM-5 molecular sieve is selected as a carrier, the particle size is 50 meshes, and the specific surface area is 800m2Per g, pore volume 1.8mL/g, and at 24 ℃ at 60mL/min N2And performing microwave treatment in the atmosphere, wherein the output power is 850W, the frequency is 2250MHz, and the microwave is taken out for standby after treatment for 1.85 h.
180g of copper phosphate and 0.525g of ZnCl2Dissolving in ether, stirring to mix uniformly, dripping the mixed solution onto 100g of ZSM-5 molecular sieve carrier subjected to microwave treatment at 28 ℃, treating for 1.25h under the action of a high-voltage pulse electric field, wherein the pulse voltage is 420V, the strength is 45kv/cm, the frequency is 1750Hz, taking out the mixed solution from the high-voltage pulse electric field, soaking for 10.5h, and drying for 10.5h at 45 ℃ to obtain the copper catalyst, wherein the copper loading is 30%, and ZnCl is obtained2The loading was 0.25%.
5g of the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor under the following reaction conditions: the temperature is 190 ℃, the reaction pressure is 1.8MPa, n (HCl) is n (C)2H2)1:1, acetylene space velocity 370h-1. At the initial stage of the reaction, the conversion rate of acetylene is 99.91 percent, and the selectivity of chloroethylene is 100 percent; after 1500 hours of reaction, the acetylene conversion was 9942% and vinyl chloride selectivity 99.35%.
Example 10
Selecting columnar active carbon as carrier, with particle diameter of 80 mesh and specific surface area of 1200m2A pore volume of 2.5mL/g at 23 ℃ at 45mL/min N2And (3) performing microwave treatment under the atmosphere, wherein the output power is 900W, the frequency is 2350MHz, and the microwave is taken out for standby after treatment for 1.9 h.
25.12g of copper chloride and 2.25g of BiCl3Dissolving in benzene, stirring, mixing, dripping the mixture onto 100g of microwave treated activated carbon carrier at 30 deg.C, treating for 1.5 hr under the action of high-voltage pulse electric field, pulse voltage 550V, strength 50kv/cm, frequency 1950Hz, taking out from high-voltage pulse electric field, soaking for 12 hr, and drying at 90 deg.C for 9 hr to obtain copper catalyst, wherein the copper loading is 12%, BiCl is3The loading was 1.5%.
5g of the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor under the following reaction conditions: the temperature is 200 ℃, the reaction pressure is 2MPa, n (HCl) is n (C)2H2)1.2:1, and the space velocity of acetylene is 50h-1. At the initial stage of the reaction, the conversion rate of acetylene is 99.58 percent, and the selectivity of chloroethylene is 100 percent; after 1500 hours of reaction, the acetylene conversion was 99.05% and the vinyl chloride selectivity was 99.42%.
Comparative example 1
Comparative example 1 illustrates the non-substitutability of high voltage pulsed electric field technology in the catalyst preparation process by comparison with example 1.
Selecting columnar active carbon as carrier, with particle diameter of 20 mesh and specific surface area of 1000m2A pore volume of 1mL/g and a temperature of 5mL/min N at 20 DEG C2And (3) performing microwave treatment under the atmosphere, wherein the output power is 500W, the frequency is 2000MHz, and the microwave is taken out for standby after treatment for 0.5 h.
20.96g of copper chloride and 0.21g of ZnCl were mixed2Dissolving in methanol, stirring, mixing, adding the mixture dropwise onto 100g of microwave-treated activated carbon carrier at 30 deg.C, soaking for 5h, and drying at 70 deg.C for 8h to obtain copper catalyst with copper loading of 10% and ZnCl2The loading was 0.1%.
5g of the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor under the following reaction conditions: the temperature is 120 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C)2H2)1:1, acetylene space velocity of 5h-1. At the initial stage of the reaction, the conversion rate of acetylene is 78.32%, and the selectivity of chloroethylene is 100%; after 1500 hours of reaction time, the acetylene conversion was 55.61% and the vinyl chloride selectivity was 99.8%.
Comparative example 2
Comparative example 2 illustrates the non-substitutability of the microwave-treated support during catalyst preparation by comparison with example 1.
Selecting columnar active carbon as carrier, with particle diameter of 20 mesh and specific surface area of 1000m2The pore volume is 1 mL/g. 20.96g of copper chloride and 0.21g of ZnCl were mixed2Dissolving in methanol, stirring, adding the mixture to 100g of activated carbon carrier at 30 deg.C, treating for 0.5h under the action of high-voltage pulse electric field with pulse voltage of 300V, strength of 10kv/cm and frequency of 1500Hz, taking out from the high-voltage pulse electric field, soaking for 5h, and drying at 70 deg.C for 8h to obtain copper catalyst with copper loading of 10% and ZnCl content2The loading was 0.1%.
5g of the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor under the following reaction conditions: the temperature is 120 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C)2H2)1:1, acetylene space velocity of 5h-1. At the initial stage of the reaction, the conversion rate of acetylene is 85.05 percent, and the selectivity of chloroethylene is 100 percent; after 1500 hours of reaction, the acetylene conversion was 65.43% and the vinyl chloride selectivity was 99.5%.
Comparative example 3
Comparative example 3 illustrates the non-substitutability of the combination of microwave technology and high-voltage pulsed electric field technology in the catalyst preparation process by comparison with example 1.
Selecting columnar active carbon as carrier, with particle diameter of 20 mesh and specific surface area of 1000m2The pore volume is 1 mL/g. 20.96g of copper chloride and 0.21g of ZnCl were mixed2Dissolving in methanol, stirring, adding the mixture dropwise onto 100g of activated carbon carrier at 30 deg.C, soaking for 5 hr, and oven drying at 70 deg.C for 8 hrObtaining the copper catalyst with the copper loading of 10 percent and ZnCl2The loading was 0.1%.
5g of the catalyst is applied to acetylene hydrochlorination in a fixed bed reactor under the following reaction conditions: the temperature is 120 ℃, the reaction pressure is 0.01MPa, n (HCl) n (C)2H2)1:1, acetylene space velocity of 5h-1. At the initial stage of the reaction, the conversion rate of acetylene is 71.62 percent, and the selectivity of chloroethylene is 100 percent; after 1500 hours of reaction time, the acetylene conversion was 51.24% and the vinyl chloride selectivity was 98.8%.