Catalyst for catalyzing polychloropropane, preparation method and post-treatment method of reaction liquid of catalyst

Abstract

The invention relates to the field of catalysts for catalyzing polychloropropane, in particular to a catalyst for catalyzing polychloropropane, a preparation method of the catalyst and a post-treatment method of reaction liquid of the catalyst. The catalyst for catalyzing the polychloropropane reaction liquid comprises a carrier material and an active component loaded in the carrier material, the carrier material comprises a metal organic framework material, and the active component comprises any one of aluminum chloride or ferric chloride. According to the invention, a metal organic framework is used as a carrier, aluminum chloride or ferric chloride is loaded as an active component and introduced into a polychloropropane catalytic system, and uniform dispersion and confinement of the active component are realized through the high specific surface area and adjustable pore structure of MOFs; the problems that a traditional Lewis acid catalyst is prone to loss and poor in cycling stability, and a traditional reaction liquid aftertreatment process is large in waste liquid amount and high in energy consumption are solved.

Description

Technical Field

[0001] This invention relates to the field of catalysts for catalyzing polychlorinated propanes, and specifically to a catalyst for catalyzing polychlorinated propanes, a preparation method thereof, and a post-treatment method for the reaction solution. Background Technology

[0002] 1,1,1,3-Tetrachloropropane is an important organic intermediate. It can be converted to 1,1,1,2,3-pentachloropropane via a two-step reaction of dehydrochlorination and chlorination. Reaction with hydrogen fluoride yields 1-chloro-3,3,3-trifluoropropane and 3,3,3-trifluoropropene. Further dehydrochlorination of 1,1,1,2,3-pentachloropropane yields 1,1,2,3-tetrachloropropene, a crucial raw material for the preparation of the chemical herbicide chlorpyrifos, and an intermediate in the synthesis of the novel environmentally friendly refrigerants 2-chloro-333-trifluoropropene and 2,3,3,3-tetrafluoropropene. 1-chloro-3,3,3-trifluoropropane is an important clean solvent, while 3,3,3-trifluoropropene is a monomer for synthesizing high-performance polymers. Additionally, 3,3,3-trifluoropropene can be used as an intermediate in pesticide and pharmaceutical production, and as a substitute for Freon.

[0003] The traditional synthesis process of 1,1,1,2,3-pentachloropropane uses ferric chloride as a catalyst to first catalyze the dehydrochlorination of 1,1,1,3-tetrachloropropane to obtain trichloropropene, which then reacts with chlorine to obtain 1,1,1,2,3-pentachloropropane. Ferric chloride or aluminum chloride is used to catalyze the dehydrochlorination of polychloropropanes. Due to the high activity of these two catalysts, if the reaction liquid is directly distilled, the Lewis acid catalyst is more likely to cause coking of the material after concentration in the bottom of the distillation column, which affects the heat transfer efficiency of the heat exchanger and increases the cost of high boiling point and waste treatment. Therefore, in order to reduce the adverse effects of Lewis acid catalyst on the subsequent material separation, the dissolved Lewis acid catalyst needs to be removed from the reaction liquid before distillation.

[0004] Currently, the most commonly used methods for removing Lewis acid catalysts are direct distillation and water washing. In direct distillation, after the catalyst accumulates in the reboiler, a large amount of raw material and product is discharged as waste liquid to maintain the fluidity of the material, increasing hazardous waste treatment costs. Furthermore, the reboiler in the direct distillation reboiler is prone to coking, affecting heat exchange and requiring regular disassembly, cleaning, and slag removal, which does not meet occupational health requirements. Water washing easily generates wastewater containing salt and chlorinated organic matter, requiring supporting wastewater treatment devices such as neutralization, electro-oxidation, and evaporation, significantly increasing production costs. Moreover, the introduction of water into the reaction solution accelerates the corrosion of metal equipment, reducing its service life. Summary of the Invention

[0005] In view of the technical problems existing in the prior art, the present invention provides a catalyst for catalyzing polychlorinated propane, a preparation method thereof, and a post-treatment method for the reaction solution.

[0006] In a first aspect, this application provides a catalyst for catalyzing polychlorinated propane, employing the following technical solution: A catalyst for catalyzing polychlorinated propane reaction liquids includes a support material and an active component supported within the support material. The support material includes a metal-organic framework material, and the active component includes either aluminum chloride or ferric chloride.

[0007] Through the above technical solution, this application uses metal-organic frameworks as carriers, loads aluminum chloride or ferric chloride as active components and introduces them into polychlorinated propane catalytic systems. The high specific surface area and tunable pore structure of MOFs achieve uniform dispersion and confinement of active components, solving the problems of easy loss and poor cycle stability of traditional Lewis acid catalysts.

[0008] Furthermore, the catalyst for the catalytic reaction of polychlorinated propane also includes a coating layer, which is a 5-20 nm silica coating layer.

[0009] Through the above technical solution, this application defines the catalyst structure, forming a three-layer composite structure of "support-active component-coating layer". Utilizing the density and chemical inertness of the silica coating layer, the loss of the active component is further suppressed: the coating layer acts as a physical barrier, preventing the reaction solution from scouring the active component, while its nanoscale thickness balances mass transfer efficiency and protective effect, avoiding a decrease in catalytic activity due to excessive coating thickness. Compared to catalysts without a coating layer, this design significantly improves the structural stability of the catalyst during recycling, extends its service life, and reduces the amount of catalyst residue in the reaction solution, thus reducing the adsorption load on the subsequent simulated moving bed system.

[0010] Furthermore, the metal-organic framework material is manufactured using the following technical solution: Zirconium chloride and terephthalic acid were mixed and placed in DMF solvent. The mixture was heated and kept at that temperature for reaction. After washing and drying, metal-organic framework materials were prepared.

[0011] This application presents a solvothermal synthesis process using zirconium chloride and terephthalic acid as raw materials and DMF as solvent, employing the aforementioned technical solution. Through synergistic control of raw material ratios, solvent selection, and heat treatment processes, the integrity of the crystal structure and the uniformity of the pores in the MOF materials are ensured. Zirconium chloride, as a metallic node, provides Lewis acidic sites, forming a stable three-dimensional framework with terephthalic acid ligands through coordination bonds. The high boiling point of DMF is beneficial for crystal growth, enhancing the specific surface area and thermal stability of the MOFs. Compared to general MOF preparation methods, this process, through precise control of reaction conditions, can directionally regulate the pore size distribution and surface functional groups of MOFs, providing a structural basis for the efficient loading of active components.

[0012] Secondly, this application provides a method for preparing a catalyst for catalyzing polychlorinated propane reaction solutions, employing the following technical solution: A method for preparing a catalyst for catalyzing polychlorinated propane reaction solutions includes the following preparation steps: The metal-organic framework material was mixed with ferric chloride ethanol solution. After mixing, the mixture was filtered and dried to obtain dried particles. Take the dried particles and place them in an ethanol solution of tetraethyl orthosilicate. Adjust the pH and keep the reaction at a warm temperature for 5-8 hours. After filtration, wash and dry the particles, then heat them and calcine them at a warm temperature. After purification and cooling to room temperature, the catalyst for the catalytic reaction of polychlorinated propane can be prepared.

[0013] Through the above technical solution, this application employs a combined liquid-phase impregnation-sol-gel process. The liquid-phase impregnation method utilizes the polarity of the ethanol solvent to regulate the dispersion of active components within the MOF pores, preventing aggregation. The sol-gel method achieves uniform deposition of the silica coating layer by adjusting the pH value, ensuring a tight bond between the coating layer and the carrier. Compared to physical mixing methods, this method can precisely control the loading of active components and the thickness of the coating layer, achieving a balance between activity and stability. Furthermore, the calcination step removes residual organic matter, further enhancing the density of the coating layer.

[0014] Thirdly, this application provides a post-treatment method for a catalyst-catalyzed polychlorinated propane reaction solution, employing the following technical solution: A post-treatment method for polychlorinated propane reaction liquid using a catalyst includes the following steps: (1) Preheat the polychlorinated propane reaction solution to 120-160℃. After the preheating reaction is completed, add it to the simulated moving bed system. After the suspended particles are removed by the filter with a size of 60-100 mesh, the reaction solution is sent to the adsorption bed filled with activated carbon adsorption column to adsorb the catalyst dissolved in the reaction solution. The reaction solution after removing the catalyst is discharged from the simulated moving bed system. (2) When the online system detects that the catalyst content of the reaction liquid discharged after adsorption in step (1) is greater than 0.1 mg / kg, the reaction liquid is switched to another adsorption column, the adsorption column that is saturated with adsorption is switched to the desorption system, and the desorbent is used to desorb the adsorption column that is saturated with adsorption in step (1), and the desorption liquid is collected. (3) When the catalyst content in the desorbent discharged after desorption in step (2) of the online system is less than 0.1 mg / kg, the eluted adsorption column is switched to the regeneration system, the vacuum is turned on, and the desorbent is desorbed at a temperature of 40-80℃ and a pressure of 0.1~5 kPa to regenerate the adsorption column. The desorbent collected by the desorption is reused. (4) The desorbent collected in step (2) enters the recovery process, and the desorbent and reaction liquid are recovered by solvent distillation. The desorbent is reused, and the recovered reaction liquid is combined with the catalyst-free reaction liquid discharged from the simulated moving bed system in step (1) and then sent to the distillation system to finally obtain the product. (5) When the filtration pressure in step (1) rises to above 0.3 MPa, the filter is purged, cleaned and regenerated, and the reaction solution is switched to another filter.

[0015] Through the above technical solution, this application combines the catalyst with a post-treatment method for polychlorinated propane reaction liquid, constructing an integrated process of catalysis, separation, and regeneration. After the catalyst reaction, the reaction liquid enters a simulated moving bed system, where residual catalyst is removed by filtration and activated carbon adsorption columns, and the material is recovered through desorption and distillation. The synergistic optimization of the catalyst and the post-treatment system reduces the subsequent adsorption load through the low loss rate of the MOFs-based catalyst, while the high selectivity of the activated carbon adsorption column in the moving bed can deeply remove residual catalyst. The two form a synergistic effect of reducing the amount of catalyst and increasing the efficiency of the separation process. Compared with traditional post-treatment processes, this method eliminates the water washing or high-temperature distillation steps, reducing wastewater discharge and energy consumption. At the same time, the vacuum regeneration of the adsorption column can realize the recycling of the desorbent, reducing costs.

[0016] Furthermore, the polychloropropane mentioned in step (1) includes one of 1,1,1,3-tetrachloropropane or 1,1,1,2,3-pentachloropropane.

[0017] Through the above technical solutions, this application specifies the specific types of polychlorinated propanes and clarifies the applicable objects of the catalyst and post-treatment methods. Based on the molecular structural characteristics of these two types of polychlorinated propanes, the pore confinement effect of MOF catalysts suppresses side reactions, while simulating the mild processing conditions of a moving bed system reduces the decomposition of heat-sensitive materials. Compared to general polychlorinated propane treatment methods, the targeted selection of these two types of feedstocks enhances the process's specificity: the dehydrochlorination reaction of 1,1,1,3-tetrachloropropane and the further conversion of 1,1,1,2,3-pentachloropropane both require highly efficient catalysts and low-loss separation processes; this solution meets these requirements through a synergistic material-method approach.

[0018] Furthermore, the desorbent used in step (2) includes one of methanol, ethanol, acetone, and diethyl propyl ether.

[0019] Through the above technical solutions, this application limits the types of desorbents and optimizes the desorption process of the simulated moving bed system. Low-boiling-point, highly polar organic solvents are selected as desorbents. Solvents such as methanol / ethanol can form complexes with ferric chloride adsorbed on the activated carbon adsorption column through hydrogen bonding, promoting the desorption of the catalyst from the adsorption column. Simultaneously, their low-boiling-point characteristics facilitate subsequent distillation and recovery, reducing energy consumption. Compared to traditional water-based desorbents, organic solvents avoid equipment corrosion caused by the introduction of moisture and have good compatibility with polychlorinated propane reaction solutions, reducing product contamination. This clause, by limiting the type of desorbent, ensures desorption efficiency and material recovery rate, further improving the closed-loop design of the post-treatment process and forming a resource recycling system of "desorption-regeneration-reuse".

[0020] In summary, this application has the following beneficial effects: First, this application addresses the core issues of easy loss and poor stability of traditional Lewis acid catalysts in polychlorinated propane reactions by employing a three-layer composite structure design of metal-organic framework (MOF) support / active component / coating layer. The MOF support, with its high specific surface area and tunable pore structure, achieves uniform dispersion and molecular-level confinement of the active component, and its pore effect enhances the contact efficiency between reactants and active sites. Simultaneously, the chemical stability of the MOFs themselves reduces the dissolution of the active component during the reaction. The silica coating layer, acting as a physical barrier, further inhibits the loss of the active component. Its nanoscale thickness balances mass transfer efficiency and protection, preventing a decrease in catalytic activity due to excessive coating thickness. This structural innovation allows the catalyst to maintain a stable distribution of active sites during recycling, extending its lifespan while reducing the amount of catalyst residue in the reaction solution, laying the foundation for low-load processing in subsequent simulated moving bed systems. Compared to supportless or traditional inorganic supported catalysts, this design achieves a dual improvement in activity and stability through material synergy, providing a highly efficient and sustainable catalytic system for polychlorinated propane catalytic reactions.

[0021] Secondly, this application constructs a synergistic process of "catalytic reaction-filtration-adsorption-desorption-regeneration" through deep coupling of catalyst design and a simulated moving bed post-treatment system, significantly improving the continuity and separation efficiency of polychlorinated propane production. The low leaching characteristics of the catalyst directly reduce the concentration of residual catalyst in the reaction solution, alleviating the load on the subsequent separation system. The application of activated carbon adsorption columns in the simulated moving bed system utilizes their high selective adsorption performance to deeply remove residual catalyst, avoiding the problems of limited adsorption capacity and easy clogging of traditional activated carbon. The process design of the desorption and regeneration stages enables efficient regeneration of the adsorption column and recycling of the desorbent, ensuring continuous and stable operation of the adsorption-desorption process. The online switching and cleaning / regeneration mechanism of the filter further ensures the uninterrupted treatment of the reaction solution, avoiding production interruptions due to equipment maintenance. This synergistic optimization not only shortens the process flow but also improves the overall automation level and processing efficiency of the process through seamless connection of each unit operation.

[0022] Third, this application implements the concept of green chemistry throughout the entire chain, from material selection and process design to resource recycling, significantly reducing energy consumption and environmental impact in the polychlorinated propane (PCB) production process. Improved catalyst cycle stability reduces the amount of fresh catalyst required, and the chemical inertness of the MOF support and coating reduces the generation of spent catalyst. The simulated moving bed system employs organic solvent desorption and vacuum regeneration technologies, achieving efficient recovery of the desorbent and reaction liquid, avoiding wastewater discharge problems caused by traditional water washing processes. The recycling of the desorbent and the distillation recovery of the reaction liquid further improve resource utilization, forming a closed-loop resource system of catalyst recycling, solvent reuse, and material recovery. Furthermore, the design of N2 purging and cleaning of filters and low-energy regeneration of adsorption columns in the process contributes to reducing overall energy consumption. Compared to traditional processes, this solution achieves a synergistic improvement in economic benefits and environmental performance by reducing solid waste emissions, lowering organic solvent consumption, and optimizing energy efficiency. It aligns with the trend of sustainable development in the modern chemical industry and provides a scalable technological paradigm for the industry's green transformation. Detailed Implementation

[0023] The present application will be further described in detail below with reference to the embodiments.

[0024] Example 1 Zirconium chloride and terephthalic acid were placed in a reaction vessel at a molar ratio of 1:1.2. N,N-dimethylformamide was added as a solvent, and the mixture was stirred until completely dissolved. The temperature was raised to 120°C and maintained for 24 hours. After the reaction was completed, the product was washed three times with DMF and ethanol, and then dried under vacuum at 80°C for 12 hours to obtain a metal-organic framework material. 10g of the above metal-organic framework material was taken and 50mL of 8% ferric chloride ethanol solution was added. The mixture was stirred in a constant temperature water bath at 60°C for 8 hours. The solid particles were collected by filtration and dried at 100°C for 6 hours to obtain catalyst 1.

[0025] Example 2 Take 5g of the catalyst prepared in Example 1 and disperse it in an 8% tetraethyl orthosilicate-ethanol mixed solution at a mass ratio of 1:10. Adjust the pH of the system to 4 with dilute hydrochloric acid and stir the reaction at 30°C for 6 hours to allow the tetraethyl orthosilicate to hydrolyze and form a silica coating layer. After the reaction is completed, filter and collect the particles, wash them twice with ethanol, dry them at 80°C for 8 hours, and then calcine them in a muffle furnace at 500°C for 2 hours. After natural cooling to room temperature, catalyst 2 is obtained.

[0026] Example 3 (1) Add catalyst 1 and 1,1,1,2,3-pentachloropropane reaction solution at an addition rate of 0.5% and preheat to 120°C. After the preheating reaction is completed, add 0.5m 3 The reaction solution is added to the simulated moving bed system at a flow rate of / h. After the suspended particles are removed by a 100-mesh filter, it is fed into a column containing 10 φ3*6 columnar activated carbons. Before use, the activated carbons are soaked in 0.1mol / L sodium hydroxide solution at 80℃ for 12h, then washed with deionized water until pH < 8. After vacuum drying, they are packed into an adsorption column of φ200*2500. In the adsorption bed of the adsorption column, the activated carbon adsorbs the catalyst dissolved in the reaction solution. The reaction solution after removing the catalyst is discharged from the simulated moving bed system. (2) When the catalyst content in the reaction liquid discharged after adsorption in step (1) of the online system is greater than 0.1 mg / kg, the reaction liquid is switched to another adsorption column. The adsorption column that is saturated with adsorption is switched to the desorption system, and 0.05 m 3 A methanol desorbent at a flow rate of / h is used to desorb the bed that has been saturated with adsorption in step (1), and the desorbed liquid is collected. (3) When the catalyst content in the desorbent discharged after desorption in step (2) of the online system is less than 0.1 mg / kg, the eluted bed is switched to the regeneration system, the vacuum is turned on, and the desorbent is desorbed at 60℃ and 2.3 kPa pressure to regenerate the adsorption column. The desorbent collected by the desorption is reused. (4) The desorbent collected in step (2) enters the recovery process, and the desorbent and reaction liquid are recovered by solvent distillation. The desorbent is reused, and the recovered reaction liquid is combined with the catalyst-free reaction liquid discharged from the simulated moving bed system in step (1) and then sent to the distillation system. (5) When the filtration pressure in step (1) rises to above 0.3 MPa, the filter is purged, cleaned and regenerated, and the reaction solution is switched to another filter.

[0027] Example 4 (1) Add catalyst 2 and 1,1,1,2,3-pentachloropropane reaction solution at an addition rate of 1.0% and preheat to 140°C. After the preheating reaction is completed, spray with 0.5m 3 The reaction solution is added to the simulated moving bed system at a flow rate of / h. After the suspended particles are removed by a 100-mesh filter, it is fed into a column containing 10 φ3*6 columnar activated carbons. Before use, the activated carbons are soaked in 0.1mol / L sodium hydroxide solution at 80℃ for 12h, then washed with deionized water until pH < 8. After vacuum drying, they are packed into an adsorption column of φ200*2500. In the adsorption bed of the adsorption column, the activated carbon adsorbs the catalyst dissolved in the reaction solution. The reaction solution after removing the catalyst is discharged from the simulated moving bed system. (2) When the catalyst content in the reaction liquid discharged after adsorption in step (1) of the online system is greater than 0.1 mg / kg, the reaction liquid is switched to another adsorption column. The adsorption column that is saturated with adsorption is switched to the desorption system, and 0.05 m 3 A methanol desorbent at a flow rate of / h is used to desorb the bed that has been saturated with adsorption in step (1), and the desorbed liquid is collected. (3) When the catalyst content in the desorbent discharged after desorption in step (2) of the online system is less than 0.1 mg / kg, the eluted bed is switched to the regeneration system, the vacuum is turned on, and the desorbent is desorbed at 60℃ and 2.3 kPa pressure to regenerate the adsorption column. The desorbent collected by the desorption is reused. (4) The desorbent collected in step (2) enters the recovery process, and the desorbent and reaction liquid are recovered by solvent distillation. The desorbent is reused, and the recovered reaction liquid is combined with the catalyst-free reaction liquid discharged from the simulated moving bed system in step (1) and then sent to the distillation system. (5) When the filtration pressure in step (1) rises to above 0.3 MPa, the filter is purged, cleaned and regenerated, and the reaction solution is switched to another filter.

[0028] Example 5 The difference between this embodiment and embodiment 3 is that the preheating temperature in step 1) is 160°C and the filter size is 60 mesh; the desorbent in step 2) is ethanol; and the regeneration temperature in step 3) is 80°C and the pressure is 0.1 kPa.

[0029] Example 6 The difference between this embodiment and Example 3 is that in step 1), the amount of catalyst 1 added to the reaction solution is 0.2%, the preheating temperature of the reaction solution for the synthesis of 1,1,1,2,3-pentachloropropane by chlorination of 1,1,1,3-tetrachloropropane by catalyst 1 is 70°C, and the filter size is 80 mesh; the desorbent in step 2) is acetone; and the regeneration temperature in step 3) is 40°C and the pressure is 5 kPa.

[0030] Example 7 The difference between this embodiment and Example 3 is that in step 1), the reaction solution is preheated at 140°C for the reaction solution of catalyst 1 catalyzing the dehydrochlorination of 1,1,1,2,3-pentachloropropane to synthesize 1,1,2,3-tetrachloropropene; in step 2), the desorbent is diethyl propyl ether; and in step 3), the regeneration temperature is 80°C and the pressure is 1 kPa.

[0031] Comparative Example 1 The difference between this embodiment and Example 7 is that ferric chloride is used as a catalyst to catalyze the dehydrochlorination of 1,1,1,2,3-pentachloropropane to synthesize 1,1,2,3-tetrachloropropene, and the catalyst is removed by direct vacuum distillation.

[0032] Performance testing Product purity: The mass fraction of the target product was analyzed by gas chromatography (GC-9790, equipped with SE-30 nonpolar column), in units of %.

[0033] Catalyst recovery rate: calculated as the ratio of catalyst content in the desorption solution to the initial input amount, in units of %.

[0034] Yield: The actual yield of the target products (1,1,2,3-tetrachloropropene and 1,1,1,2,3-pentachloropropane) in the reaction solution was determined by gas chromatography, and the yield was calculated in combination with the amount of raw materials input (Yield = Actual Yield / Theoretical Yield × 100%), in % %. Waste liquid volume ratio: Collect the waste liquid (including washing wastewater, distillation residue, etc.) generated during the entire post-treatment process and measure the proportion of the total volume to the reaction liquid volume; The specific results are shown in Table 1 below: Table 1 Performance Test Table

[0035] By comparing the test results of Examples 1-7 and Comparative Example 1 with those in Table 1, it can be found that: By comparing Examples 1-2 and Examples 3-4, this application further illustrates the solvothermal synthesis process using zirconium chloride and terephthalic acid as raw materials and DMF as solvent. Through the synergistic control of raw material ratios, solvent selection, and heat treatment processes, the integrity of the crystal structure and the uniformity of the pores in the MOF materials are ensured. Zirconium chloride, as a metal node, provides Lewis acidic sites and forms a stable three-dimensional framework with terephthalic acid ligands through coordination bonds. The high boiling point of DMF is beneficial for crystal growth, improving the specific surface area and thermal stability of the MOFs. Compared to general MOF preparation methods, this process, through precise control of reaction conditions, can directionally regulate the pore size distribution and surface functional groups of MOFs, providing a structural basis for the efficient loading of active components.

[0036] Further comparison with Examples 5-7 and Comparative Example 1 illustrates that the technical solution of this application combines the catalyst with the post-treatment method of the polychlorinated propane reaction solution to construct an integrated process of catalysis, separation, and regeneration. After the catalyst reaction, the reaction solution enters a simulated moving bed system, where residual catalyst is removed by filtration and activated carbon adsorption column, and the material is recovered by desorption and distillation. The synergistic optimization of the catalyst and the post-treatment system reduces the subsequent adsorption load through the low loss rate of the MOFs-based catalyst, while the high selectivity of the activated carbon adsorption column in the simulated moving bed can deeply remove residual catalyst. The two form a synergistic effect of reducing the amount of catalyst and increasing the efficiency of the separation process.

[0037] The present invention has been described in detail above with reference to specific embodiments and exemplary examples; however, these descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and embodiments of the present invention without departing from the spirit and scope of the invention, and all such modifications and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the appended claims.

[0038] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0039] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0040] In the context of this specification, except where expressly stated otherwise, any matters or issues not mentioned shall apply directly to those known in the art without any modification.

Claims

1. A catalyst for catalyzing polychlorinated propane reaction solutions, characterized in that, It includes a carrier material and an active component loaded within the carrier material, wherein the carrier material includes a metal-organic framework material, and the active component includes either aluminum chloride or ferric chloride.

2. The catalyst for catalyzing polychlorinated propane reaction solutions according to claim 1, characterized in that, The catalyst used for catalyzing polychlorinated propane reaction liquid also includes a coating layer, which is a 5-20 nm silica coating layer.

3. The catalyst for catalyzing polychlorinated propane reaction solutions according to claim 1, characterized in that, The metal-organic framework material is made using the following technical solution: Zirconium chloride and terephthalic acid were mixed and placed in DMF solvent. The mixture was heated and kept at that temperature for reaction. After washing and drying, metal-organic framework materials were prepared.

4. A method for preparing a catalyst for catalyzing polychlorinated propane reaction liquid according to any one of claims 1-3, characterized in that, The preparation steps include the following: The metal-organic framework material was mixed with ferric chloride ethanol solution. After mixing, the mixture was filtered and dried to obtain dried particles. Take the dried particles and place them in an ethanol solution of tetraethyl orthosilicate. Adjust the pH and keep the reaction at a warm temperature for 5-8 hours. After filtration, wash and dry the particles, then heat them and calcine them at a warm temperature. After purification and cooling to room temperature, the catalyst for the catalytic reaction of polychlorinated propane can be prepared.

5. A method for post-treatment of a polychlorinated propane reaction solution catalyzed by a catalyst prepared according to any one of claims 1-4, characterized in that, Includes the following steps: (1) Preheat the polychlorinated propane reaction solution to 120-160℃. After the preheating reaction is completed, add it to the simulated moving bed system. After the suspended particles are removed by the filter with a size of 60-100 mesh, the reaction solution is sent to the adsorption bed filled with activated carbon adsorption column to adsorb the catalyst dissolved in the reaction solution. The reaction solution after removing the catalyst is discharged from the simulated moving bed system. (2) When the online system detects that the catalyst content of the reaction liquid discharged after adsorption in step (1) is greater than 0.1 mg / kg, the reaction liquid is switched to another adsorption column, the adsorption column that is saturated with adsorption is switched to the desorption system, and the desorbent is used to desorb the adsorption column that is saturated with adsorption in step (1), and the desorption liquid is collected. (3) When the catalyst content in the desorbent discharged after desorption in step (2) of the online system is less than 0.1 mg / kg, the eluted adsorption column is switched to the regeneration system, the vacuum is turned on, and the desorbent is desorbed at a temperature of 40-80℃ and a pressure of 0.1~5 kPa to regenerate the adsorption column. The desorbent collected by the desorption is reused. (4) The desorbent collected in step (2) enters the recovery process, and the desorbent and reaction liquid are recovered by solvent distillation. The desorbent is reused, and the recovered reaction liquid is combined with the catalyst-free reaction liquid discharged from the simulated moving bed system in step (1) and then sent to the distillation system to finally obtain the product. (5) When the filtration pressure in step (1) rises to above 0.3 MPa, the filter is purged, cleaned and regenerated, and the reaction solution is switched to another filter.

6. The post-treatment method for a Lewis acid-catalyzed polychlorinated propane reaction solution according to claim 5, characterized in that, The polychloropropane mentioned in step (1) includes one of 1,1,1,3-tetrachloropropane or 1,1,1,2,3-pentachloropropane.

7. The post-treatment system and method for Lewis acid-catalyzed polychlorinated propane reaction liquid according to claim 5, characterized in that, The desorbent used in step (2) includes one of methanol, ethanol, acetone, and diethyl propyl ether.

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