Chlorine recovery and cyclic catalysis system for DCP (dicumyl peroxide) condensation process

Abstract

The invention relates to the technical field of chlorine gas recovery and catalysis, and discloses a chlorine gas recovery and circulation catalysis system for a DCP condensation process, the system comprises a catalysis circulation end, a chlorine gas recovery end, a regeneration control end and a multi-stage alarm module, and a synergistic system of catalysis circulation, chlorine gas recovery and regeneration control is constructed; the cyclic utilization of the immobilized catalyst and the regulation and control of the reaction process are realized; reaction system parameters are monitored in real time, a regeneration program is automatically triggered, the service life of a catalyst is prolonged, meanwhile, an inert gas replacement termination reaction mechanism is adopted, by-product accumulation caused by excessive reaction is prevented, and the purity of a main product and reaction safety are guaranteed; chlorine is captured stage by stage through the multi-stage absorption tower and is directionally converted into chlorinated hydrocarbon by-products, so that the environmental hidden danger of chlorine emission in the traditional process is solved.

Description

Technical Field

[0001] This invention relates to the field of chlorine recovery and catalysis technology, specifically to a chlorine recovery and recycling catalytic system for DCP condensation process. Background Technology

[0002] Chlorine is an elemental form of chlorine. At room temperature and pressure, it is a yellow-green, highly toxic gas with a strong, pungent odor. It is suffocating, denser than air, soluble in water and alkaline solutions, readily soluble in organic solvents, sparingly soluble in saturated salt water, easily compressible, and can be liquefied into a yellow-green, oily liquid chlorine.

[0003] Currently, the DCP condensation process generally adopts an open chlorine addition mode and a one-time catalyst participation mode. During the reaction, excess chlorine is directly discharged into the tail gas treatment system, which wastes resources and poses environmental hazards.

[0004] Therefore, a chlorine recovery and recycling catalytic system for the DCP condensation process is proposed to solve the above problems. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a chlorine recovery and recycling catalytic system for DCP condensation processes, which solves the problem mentioned in the background technology of directly discharging excess chlorine into the tail gas treatment system, causing resource waste and environmental hazards.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a chlorine recovery and recycling catalytic system for DCP condensation process, the system comprising a catalytic recycling end, a chlorine recovery end, and a regeneration control end, wherein the catalytic recycling end, the chlorine recovery end, and the regeneration control end are jointly provided with a multi-level alarm module; The catalytic cycle end is used to catalyze the condensation reaction through an immobilized catalyst bed, monitors the chloride ion concentration and by-product generation in the reaction system in real time, automatically triggers the catalyst regeneration program according to the preset catalytic activity threshold, and terminates the reaction by replacing the catalyst with an inert gas at the reaction endpoint. The chlorine recovery unit is used to capture chlorine in the reaction tail gas through a multi-stage absorption tower, and to carry out staged chemical conversion according to the chlorine concentration gradient, converting gaseous chlorine into liquid chlorinated hydrocarbon byproducts; The regeneration control unit is used to automatically start the solvent flushing-hot nitrogen regeneration cycle process by monitoring the catalyst activity decay rate online, so as to restore the activity of the immobilized catalyst. The multi-level alarm module is used to trigger audible and visual alarms and link with the emergency shutdown device when there is abnormal system pressure, chlorine leakage, or catalyst deactivation.

[0007] Preferably, the catalytic cycle includes a reaction control module, a supported catalyst module, and an endpoint determination module; The reaction control module includes a raw material proportioning unit, a temperature gradient unit, and a pressure compensation unit; The raw material proportioning unit is used to control the molar ratio of cumene hydroperoxide to dimethyl benzyl alcohol within the range of 1:1.05-1.15, and achieves a metering accuracy of ±0.5% through a mass flow meter; The temperature gradient unit is used to establish a four-segment temperature control curve: the initial zone is maintained at 40-50℃ for 10 minutes to achieve homogeneous mixing, the reaction zone is maintained at 55-65℃ for 120 minutes to complete the main reaction, the equilibrium zone is maintained at 70-75℃ for 20 minutes to decompose by-products, and the termination zone is maintained at 30-35℃ to achieve rapid cooling. The pressure compensation unit is equipped with a two-way regulating valve to maintain a slightly positive pressure of 0.15-0.25MPa in the reaction system, with a pressure fluctuation range of ≤0.05MPa.

[0008] Preferably, the supported catalyst module includes a support unit and an acid regulation unit; The carrier loading unit uses a mesoporous silica carrier with a pore size of 10-15nm, and loads a perchloric acid active component with a concentration of 12-15wt% by vacuum impregnation. The specific surface area of ​​the carrier is controlled in the range of 450-550m² / g. The acidity control unit integrates an online pH sensor and a metering pump to detect the pH value of the system in real time and generate a dynamic adjustment curve. When the pH is greater than 3.2, 0.5 mol / L acetic acid solution is automatically added, and when the pH is less than 2.8, ammonia buffer solution is injected to maintain the optimal catalytic activity range. When the reaction is terminated, a 5% sodium bicarbonate solution is injected through a distributed spray system, and the residual acidity is neutralized within 10 minutes.

[0009] Preferably, the endpoint determination module includes a by-product monitoring unit and a displacement termination unit; The byproduct monitoring unit collects reaction solution samples every 5 minutes using online gas chromatography to detect the real-time trend of phenol concentration changes and establishes a product-byproduct concentration ratio model. The reaction endpoint is determined when the phenol / dicumyl peroxide ratio is ≥0.03. The displacement termination unit adopts a dual-mode operation: nitrogen gas is introduced into the main reactor through a ring distributor for displacement at a flow rate of 1.2-1.5 times the reactor volume per minute for 15 minutes; the auxiliary cooling system circulates ethylene glycol solution through the jacket and cools the product at a gradient of 5-8℃ per minute to prevent thermal decomposition. The exhaust gas is condensed and recovered by a condensation and recovery device to capture volatile organic compounds.

[0010] Preferably, the chlorine recovery unit includes a chlorine capture module and a resource recovery module; The chlorine capture module is equipped with a three-stage series absorption tower: the first-stage tower is filled with 10% sodium hydroxide solution to achieve primary chlorine absorption, the second-stage tower is filled with cyclohexane solvent to carry out chlorinated hydrocarbon synthesis reaction, and the third-stage tower is filled with iodine-modified activated carbon adsorbent to deeply remove residual chlorine. Each stage of the tower is equipped with a differential pressure sensor, which triggers an automatic backwashing program when the interstage pressure difference of the multi-stage absorption tower is ≥5kPa. The resource recovery module introduces the chlorocyclohexane produced in the secondary column into a thin-film evaporator, and obtains by-products with a purity of ≥98.5% through two-stage distillation. Unreacted cyclohexane is returned to the secondary column for recycling.

[0011] Preferably, the resource recovery module includes a product separation unit and a recycling unit; The product separation unit uses an alumina-based molecular sieve membrane module to separate chlorocyclohexane from unreacted feedstock under operating conditions of 60℃ and 0.3MPa, with the membrane flux remaining stable at 15-20L / m²·h. The recycling unit is equipped with a molecular sieve dehydration tower to reduce the moisture content of the separated raw material from 0.5% to ≤200ppm; The waste gas from the dehydration tower regeneration is treated by catalytic combustion to meet emission standards, and the heat energy is recovered and used in the raw material preheating system.

[0012] Preferably, the regeneration control terminal includes an activity monitoring module and a regeneration execution module; The activity monitoring module collects current signals through the built-in electrode array in the reactor, calculates the reaction rate constant k value by combining it with the Arrhenius equation, establishes a k value-time decay curve, and automatically triggers the regeneration program when the k value drops to 85% of the initial value. The Arrhenius equation is: ; in The reaction rate constant is... Pre-exponential factor, For activation energy, The gas constant is... Absolute temperature; The regeneration module executes three regeneration steps sequentially according to a preset program: first, it rinses with solvent for 30 minutes to dissolve carbon deposits; then, it purges with hot nitrogen at 120℃ for 90 minutes to remove volatile impurities; and finally, it activates under a vacuum of -0.095MPa for 60 minutes to restore the pore structure.

[0013] Preferably, the regeneration execution module includes a solvent selection unit and an activation parameter unit; The solvent selection unit uses an acetone-deionized water mixed solvent with a volume ratio of 3:1. A pulsating flow is generated by a vortex mixer, and the solvent circulation flow rate is controlled at 2-3 m / s. The activation parameter unit is equipped with a multi-segment temperature control system. During the hot nitrogen regeneration stage, a uniform temperature field of 110±5℃ is established in the catalyst bed. The purging time is adaptively adjusted to the range of 60-90 minutes according to the pressure drop. During the vacuum activation stage, the composition of the desorbed gas is monitored online using a mass spectrometer, and regeneration is terminated when the concentration of hydrocarbons is less than 50 ppm.

[0014] Preferably, the regeneration execution module further includes a lifetime prediction unit; The lifespan prediction unit collects the correlation between the cumulative number of regenerations X and the activity recovery rate Y through a big data platform, and establishes a second-order polynomial regression equation: ; The model parameters are automatically updated after each regeneration cycle. When the predicted Y ≤ 92%, the system generates a catalyst replacement early warning report. Simultaneously monitor the catalyst's mechanical strength decay rate. When the particle size breakage rate is ≥15%, the replacement procedure is forcibly initiated. The spent catalyst is safely disposed of after neutralization with alkali solution.

[0015] Preferably, the multi-level alarm module includes a three-level response mechanism: The Level 1 response activates an audible and visual alarm and simultaneously turns on the emergency ventilation system when the chlorine concentration is ≥10ppm. The secondary response interlocks the cooling system, injects polymerization inhibitor, and activates the pressure relief valve when the pressure fluctuation is ≥0.1MPa; A Level 3 response triggers an emergency shutdown of the entire system when the temperature exceeds 80°C, closing the raw material inlet valve and opening the emergency collection tank. All response actions are recorded in the security control log and uploaded to the central monitoring platform in real time.

[0016] Beneficial effects Compared with the prior art, the present invention provides a chlorine recovery and recycling catalytic system for DCP condensation process, which has the following beneficial effects: 1. In this invention, by constructing a synergistic system of catalytic cycle, chlorine recovery and regeneration control, the recycling of the immobilized catalyst and the regulation of the reaction process are realized; by real-time monitoring of reaction system parameters and automatic triggering of the regeneration program, the service life of the catalyst is improved; at the same time, an inert gas replacement reaction termination mechanism is adopted to prevent the accumulation of by-products caused by over-reaction, and to ensure the purity of the main product and the safety of the reaction.

[0017] 2. In this invention, chlorine gas is captured in stages by multi-stage absorption towers and directionally converted into chlorinated hydrocarbon by-products, thereby realizing the resource utilization of gaseous pollutants. Combined with the inter-stage pressure difference adaptive backwashing and solvent recycling mechanism, the loss of absorption medium is reduced, the purity of by-products is improved, and a closed-loop circulation system is formed, thus solving the environmental hazards of chlorine emissions in traditional processes.

[0018] 3. In this invention, an operational anomaly is handled in a graded manner through a three-level response mechanism. Based on the risk level of chlorine leakage, pressure fluctuation, and temperature exceeding the standard, corresponding protective measures are automatically activated, and all response actions are uploaded to the central monitoring platform in real time, so as to realize the controllability of risks throughout the entire process and improve the inherent safety level of high-risk chemical production scenarios. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of a chlorine recovery and recycling catalytic system for DCP condensation process according to the present invention. Detailed Implementation

[0020] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0021] Specific embodiment: A chlorine recovery and recycling catalytic system for DCP condensation process, the system includes a catalytic recycling end, a chlorine recovery end and a regeneration control end, and the catalytic recycling end, chlorine recovery end and regeneration control end are jointly equipped with a multi-level alarm module; The catalytic cycle end is used to catalyze the condensation reaction through an immobilized catalyst bed, monitors the chloride ion concentration and by-product generation in the reaction system in real time, automatically triggers the catalyst regeneration program according to the preset catalytic activity threshold, and terminates the reaction by replacing the catalyst with an inert gas at the reaction endpoint. The chlorine recovery unit is used to capture chlorine in the reaction tail gas through a multi-stage absorption tower, and to carry out staged chemical conversion according to the chlorine concentration gradient, converting gaseous chlorine into liquid chlorinated hydrocarbon byproducts; The regeneration control unit is used to automatically start the solvent flushing-hot nitrogen regeneration cycle process by monitoring the catalyst activity decay rate online, so as to restore the activity of the immobilized catalyst. The multi-level alarm module is used to trigger audible and visual alarms and link with the emergency shutdown device when there is abnormal system pressure, chlorine leakage, or catalyst deactivation.

[0022] The catalytic cycle includes a reaction control module, a supported catalyst module, and an endpoint determination module. The reaction control module includes a raw material proportioning unit, a temperature gradient unit, and a pressure compensation unit; The raw material proportioning unit is used to control the molar ratio of cumene hydroperoxide to dimethyl benzyl alcohol within the range of 1:1.05-1.15, and achieves a metering accuracy of ±0.5% through a mass flow meter; The temperature gradient unit is used to establish a four-segment temperature control curve: the initial zone is maintained at 40-50℃ for 10 minutes to achieve homogeneous mixing, the reaction zone is maintained at 55-65℃ for 120 minutes to complete the main reaction, the equilibrium zone is maintained at 70-75℃ for 20 minutes to decompose by-products, and the termination zone is maintained at 30-35℃ to achieve rapid cooling. The pressure compensation unit is equipped with a two-way regulating valve to maintain a slightly positive pressure of 0.15-0.25MPa in the reaction system, with a pressure fluctuation range of ≤0.05MPa.

[0023] The immobilized catalyst module includes a support unit and an acid regulation unit; The carrier loading unit uses a mesoporous silica carrier with a pore size of 10-15nm, and loads a perchloric acid active component with a concentration of 12-15wt% by vacuum impregnation. The specific surface area of ​​the carrier is controlled in the range of 450-550m² / g. The acid control unit integrates an online pH sensor and a metering pump to monitor the system pH in real time and generate a dynamic adjustment curve. ; in The current pH value of the system. For the target pH value, To adjust the rate constant, Reaction time; This formula indicates that the rate of change of pH value is proportional to the degree to which the current value deviates from the target value. When the pH is greater than 3.2, 0.5 mol / L acetic acid solution is automatically added, and when the pH is less than 2.8, ammonia buffer solution is injected to maintain the optimal catalytic activity range. When the reaction is terminated, a 5% sodium bicarbonate solution is injected through a distributed spray system, and the residual acidity is neutralized within 10 minutes.

[0024] The endpoint determination module includes a byproduct monitoring unit and a displacement termination unit; The byproduct monitoring unit collects reaction solution samples every 5 minutes using online gas chromatography to detect the real-time trend of phenol concentration changes and establishes a product-byproduct concentration ratio model. The reaction endpoint is determined when the phenol / dicumyl peroxide ratio is ≥0.03. The displacement termination unit adopts a dual-mode operation: nitrogen gas is introduced into the main reactor through a ring distributor for displacement at a flow rate of 1.2-1.5 times the reactor volume per minute for 15 minutes; the auxiliary cooling system circulates ethylene glycol solution through the jacket and cools the product at a gradient of 5-8℃ per minute to prevent thermal decomposition. The exhaust gas is condensed and recovered by a condensation and recovery device to capture volatile organic compounds.

[0025] The chlorine recovery unit includes a chlorine capture module and a resource recovery module; The chlorine capture module is equipped with a three-stage series absorption tower: the first-stage tower is filled with 10% sodium hydroxide solution to achieve primary chlorine absorption, the second-stage tower is filled with cyclohexane solvent to carry out chlorinated hydrocarbon synthesis reaction, and the third-stage tower is filled with iodine-modified activated carbon adsorbent to deeply remove residual chlorine. Each stage of the tower is equipped with a differential pressure sensor, which detects the inter-stage pressure difference in the multi-stage absorption tower. Automatic backwashing procedure is triggered when the pressure is ≥5 kPa; ; in Differential pressure value Inlet pressure, This refers to the outlet pressure. The resource recovery module introduces the chlorocyclohexane produced in the secondary column into a thin-film evaporator, and obtains by-products with a purity of ≥98.5% through two-stage distillation. Unreacted cyclohexane is returned to the secondary column for recycling.

[0026] The resource recovery module includes a product separation unit and a recycling unit; The product separation unit uses an alumina-based molecular sieve membrane module, which improves the separation efficiency of chlorocyclohexane and unreacted raw materials to over 99.2% under operating conditions of 60℃ and 0.3MPa, with the membrane flux remaining stable at 15-20L / m²·h. The recycling unit is equipped with a molecular sieve dehydration tower to reduce the moisture content of the separated raw material from 0.5% to ≤200ppm; The waste gas from the dehydration tower regeneration is treated by catalytic combustion to meet emission standards, and the heat energy is recovered and used in the raw material preheating system.

[0027] The regeneration control unit includes an activity monitoring module and a regeneration execution module; The activity monitoring module collects current signals through the built-in electrode array in the reactor, calculates the reaction rate constant k value by combining it with the Arrhenius equation, establishes a k value-time decay curve, and automatically triggers the regeneration program when the k value drops to 85% of the initial value. The Arrhenius equation is: ; in The reaction rate constant is... Pre-exponential factor, For activation energy, The gas constant is... Absolute temperature; k-time decay curve: ; in Let be the reaction rate constant at time t. The initial reaction rate constant is . The attenuation coefficient is... For continuous running time; The regeneration module executes three regeneration steps sequentially according to a preset program: first, it rinses with solvent for 30 minutes to dissolve carbon deposits; then, it purges with hot nitrogen at 120℃ for 90 minutes to remove volatile impurities; and finally, it activates under a vacuum of -0.095MPa for 60 minutes to restore the pore structure.

[0028] The regeneration execution module includes a solvent selection unit and an activation parameter unit; The solvent selection unit uses an acetone-deionized water mixed solvent at a volume ratio of 3:1. A pulsating flow is generated through a vortex mixer, and the solvent circulation velocity is controlled at 2-3 m / s. ≥95%; The solvent impurity removal efficiency is expressed by the Stokes equation: ; in For efficient cleaning, For impurity density, Solvent density, It is the acceleration due to gravity. For impurity particle size, Solvent viscosity The velocity of the eddy current; The activation parameter unit is equipped with a multi-segment temperature control system. During the hot nitrogen regeneration stage, a uniform temperature field of 110±5℃ is established in the catalyst bed. The purging time is adaptively adjusted to the range of 60-90 minutes according to the pressure drop. During the vacuum activation stage, the composition of the desorbed gas is monitored online using a mass spectrometer, and regeneration is terminated when the concentration of hydrocarbons is less than 50 ppm.

[0029] The regeneration execution module also includes a lifetime prediction unit; The lifespan prediction unit collects the correlation between the cumulative number of regenerations X and the activity recovery rate Y through a big data platform, and establishes a second-order polynomial regression equation: ; The model parameters are automatically updated after each regeneration cycle. When the predicted Y ≤ 92%, the system generates a catalyst replacement early warning report. Simultaneously monitor the catalyst's mechanical strength decay rate. When the particle size breakage rate is ≥15%, the replacement procedure is forcibly initiated. The spent catalyst is safely disposed of after neutralization with alkali solution.

[0030] The multi-level alarm module includes a three-level response mechanism: The Level 1 response activates an audible and visual alarm and simultaneously turns on the emergency ventilation system when the chlorine concentration is ≥10ppm. The secondary response interlocks the cooling system, injects polymerization inhibitor, and activates the pressure relief valve when the pressure fluctuation is ≥0.1MPa; A Level 3 response triggers an emergency shutdown of the entire system when the temperature exceeds 80°C, closing the raw material inlet valve and opening the emergency collection tank. All response actions are recorded in the security control log and uploaded to the central monitoring platform in real time.

[0031] The system operates as follows: Step 1: Catalytic Reaction Control Stage In the catalytic cycle, the system initiates the condensation reaction through a supported catalyst bed. First, the reaction control module adjusts the feed ratio of cumene hydroperoxide to dimethylbenzyl alcohol to ensure the molar ratio remains within the optimized range, while a mass flow meter achieves high-precision metering. A temperature gradient unit establishes a four-segment temperature control curve: the initial zone maintains a low temperature for homogeneous mixing; the reaction zone heats up to promote the main reaction; the equilibrium zone controls the decomposition of byproducts; and the termination zone rapidly cools to prevent side reactions. A pressure compensation unit maintains a slightly positive pressure state through a bidirectional regulating valve, reducing the impact of pressure fluctuations on reaction stability. The supported catalyst module utilizes a mesoporous silica support to load the active components, and an acid control unit monitors the system's pH value in real time, automatically adding buffer solution to maintain the optimal catalytic activity range, ensuring efficient reaction.

[0032] Step 2: Reaction Termination and Chlorine Collection Stage As the reaction nears its endpoint, the endpoint determination module uses online gas chromatography to monitor changes in byproduct concentration in real time, establishing a product-byproduct ratio model. Once a preset threshold is reached, the reaction endpoint is determined. The system automatically triggers the displacement termination unit: inert gas is introduced into the reactor through a ring distributor, and the displacement flow rate is precisely controlled to quickly terminate the reaction. Simultaneously, a jacketed circulating coolant achieves gradient cooling to prevent thermal decomposition of the products. The displacement exhaust gas is collected by a condensation recovery device to capture volatile organic compounds, ensuring environmental safety. Simultaneously, the chlorine recovery end activates a multi-stage absorption tower to capture chlorine in the reaction tail gas. The first-stage tower uses an alkaline solution for primary absorption, the second-stage tower synthesizes chlorinated hydrocarbons using a solvent, and the third-stage tower uses a modified adsorbent to deeply remove residual chlorine. Each tower stage is triggered by a differential pressure sensor to perform an adaptive backwashing program to prevent clogging.

[0033] Step 3: Resource Utilization and By-product Separation Stage In the resource recovery module at the chlorine recovery end, chlorinated hydrocarbons produced in the secondary tower are introduced into the separation unit. An alumina-based molecular sieve membrane module efficiently separates chlorocyclohexane from unreacted feedstock under mild operating conditions, improving separation efficiency and membrane flux stability. The separated feedstock undergoes a molecular sieve dehydration tower to reduce moisture content, forming a drying cycle system. The regeneration waste gas from the dehydration tower is treated by catalytic combustion to recover heat energy, which is then used in the preheating system, achieving energy reuse. Simultaneously, unreacted solvent is returned to the secondary tower for recycling, and byproducts are purified by distillation to achieve high purity standards, forming a closed-loop resource recovery process.

[0034] Step 4: Catalyst Regeneration and Lifetime Management Phase The regeneration control unit monitors the catalyst activity decay trend online, acquiring signals and calculating reaction rate changes through a built-in electrode array. When the activity drops to a preset threshold, the regeneration program is automatically triggered. The regeneration execution module performs a three-step process: first, it uses a mixed solvent to pulse and dissolve carbon deposits; second, it uses hot nitrogen to uniformly purge and remove volatile impurities; and finally, it activates and restores the catalyst's pore structure under vacuum. The lifetime prediction unit dynamically updates parameters based on a model relating the cumulative number of regenerations to the activity recovery rate. When the predicted activity is insufficient or the mechanical strength decay exceeds the limit, a replacement warning is generated, and a safe disposal procedure is forcibly initiated. The spent catalyst is then neutralized and treated.

[0035] Step 5: Safety Monitoring and Emergency Response Phase A multi-level alarm module runs throughout the entire system, implementing a three-level response mechanism: Level 1 response activates audible and visual alarms and emergency ventilation upon detecting a chlorine leak; Level 2 response interlocks the cooling system and pressure relief devices when abnormal pressure fluctuations occur; Level 3 response triggers a system-wide emergency shutdown, closes raw material valves, and opens the emergency collection tank when the temperature exceeds the limit. All response actions are recorded in real time and uploaded to the central monitoring platform, ensuring that operational risks are controllable and improving the level of inherent safety.

[0036] It should be noted that, in this document, relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes the element.

[0037] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A chlorine recovery and recycling catalytic system for DCP condensation process, characterized in that: The system includes a catalytic circulation end, a chlorine recovery end, and a regeneration control end, and the catalytic circulation end, chlorine recovery end, and regeneration control end are all equipped with a multi-level alarm module; The catalytic cycle end is used to catalyze the condensation reaction through the immobilized catalyst bed, monitor the chloride ion concentration and by-product generation in the reaction system in real time, automatically trigger the catalyst regeneration program according to the preset catalytic activity threshold, and terminate the reaction by replacing with inert gas at the reaction endpoint. The chlorine recovery end is used to capture chlorine in the reaction tail gas through a multi-stage absorption tower, and to carry out staged chemical conversion according to the chlorine concentration gradient, converting gaseous chlorine into liquid chlorinated hydrocarbon byproducts. The regeneration control terminal is used to automatically start the solvent flushing-hot nitrogen regeneration cycle process by monitoring the catalyst activity decay rate online, so as to restore the activity of the immobilized catalyst. The multi-level alarm module is used to trigger audible and visual alarms and link with the emergency shutdown device when the system pressure is abnormal, chlorine leaks, or catalyst deactivation occurs.

2. The chlorine recovery and recycling catalytic system for DCP condensation process according to claim 1, characterized in that: The catalytic cycle end includes a reaction control module, a supported catalyst module, and an endpoint determination module. The reaction control module includes a raw material proportioning unit, a temperature gradient unit, and a pressure compensation unit. The raw material proportioning unit is used to control the molar ratio of cumene hydroperoxide to dimethyl benzyl alcohol within the range of 1:1.05-1.15, and achieves a metering accuracy of ±0.5% through a mass flow meter; The temperature gradient unit is used to establish a four-segment temperature control curve: the initial zone is maintained at 40-50℃ for 10 minutes to achieve homogeneous mixing, the reaction zone is maintained at 55-65℃ for 120 minutes to complete the main reaction, the equilibrium zone is maintained at 70-75℃ for 20 minutes to decompose by-products, and the termination zone is maintained at 30-35℃ to achieve rapid cooling. The pressure compensation unit is equipped with a two-way regulating valve to maintain a slightly positive pressure of 0.15-0.25 MPa in the reaction system, with a pressure fluctuation range of ≤0.05 MPa.

3. The chlorine recovery and recycling catalytic system for DCP condensation process according to claim 2, characterized in that: The supported catalyst module includes a support unit and an acid regulation unit; The carrier loading unit uses a mesoporous silica carrier with a pore size of 10-15nm, and loads a perchloric acid active component with a concentration of 12-15wt% by vacuum impregnation. The specific surface area of ​​the carrier is controlled in the range of 450-550m² / g. The acidity control unit integrates an online pH sensor and a metering pump to detect the pH value of the system in real time and generate a dynamic adjustment curve. When the pH is greater than 3.2, 0.5 mol / L acetic acid solution is automatically added, and when the pH is less than 2.8, ammonia buffer solution is injected to maintain the optimal catalytic activity range. When the reaction is terminated, a 5% sodium bicarbonate solution is injected through a distributed spray system, and the residual acidity is neutralized within 10 minutes.

4. A chlorine recovery and recycling catalytic system for DCP condensation process according to claim 2, characterized in that: The endpoint determination module includes a by-product monitoring unit and a displacement termination unit; The byproduct monitoring unit collects reaction solution samples every 5 minutes via online gas chromatography to detect the real-time trend of phenol concentration changes, establishes a product-byproduct concentration ratio model, and determines the reaction endpoint when the phenol / dicumyl peroxide ratio is ≥0.

03. The displacement termination unit adopts a dual-mode operation: nitrogen gas is introduced into the main reactor through a ring distributor for displacement at a flow rate of 1.2-1.5 times the reactor volume per minute for 15 minutes; the auxiliary cooling system circulates ethylene glycol solution through the jacket and cools the product at a gradient of 5-8℃ / min to prevent thermal decomposition. The exhaust gas is condensed and recovered by a condensation and recovery device to capture volatile organic compounds.

5. A chlorine recovery and recycling catalytic system for DCP condensation process according to claim 1, characterized in that: The chlorine recovery unit includes a chlorine capture module and a resource recovery module; The chlorine capture module is equipped with a three-stage series absorption tower: the first-stage tower is filled with 10% sodium hydroxide solution to achieve primary chlorine absorption, the second-stage tower is filled with cyclohexane solvent to carry out chlorinated hydrocarbon synthesis reaction, and the third-stage tower is filled with iodine-modified activated carbon adsorbent to deeply remove residual chlorine. Each stage of the tower is equipped with a differential pressure sensor, which triggers an automatic backwashing program when the interstage pressure difference of the multi-stage absorption tower is ≥5kPa. The resource recovery module introduces the chlorocyclohexane produced in the secondary column into a thin-film evaporator, and obtains a byproduct with a purity of ≥98.5% through two-stage distillation. Unreacted cyclohexane is returned to the secondary column for recycling.

6. A chlorine recovery and recycling catalytic system for DCP condensation process according to claim 5, characterized in that: The resource recovery module includes a product separation unit and a recycling unit; The product separation unit uses an alumina-based molecular sieve membrane module to separate chlorocyclohexane from unreacted raw materials under operating conditions of 60℃ and 0.3MPa, with the membrane flux remaining stable at 15-20L / m²·h. The recycling unit is equipped with a molecular sieve dehydration tower to reduce the moisture content of the separated raw material from 0.5% to ≤200ppm; The waste gas from the dehydration tower regeneration is treated by catalytic combustion to meet emission standards, and the heat energy is recovered and used in the raw material preheating system.

7. A chlorine recovery and recycling catalytic system for DCP condensation process according to claim 1, characterized in that: The regeneration control terminal includes an activity monitoring module and a regeneration execution module; The activity monitoring module collects current signals through the built-in electrode array of the reactor, calculates the reaction rate constant k value by combining it with the Arrhenius equation, establishes a k value-time decay curve, and automatically triggers the regeneration program when the k value drops to 85% of the initial value. The Arrhenius equation is: ； in The reaction rate constant is... Pre-exponential factor, For activation energy, The gas constant is Absolute temperature; The regeneration execution module performs three regeneration steps according to a preset program: first, it washes with solvent for 30 minutes to dissolve carbon deposits; then, it purges with hot nitrogen at 120°C for 90 minutes to remove volatile impurities; and finally, it activates under a vacuum of -0.095MPa for 60 minutes to restore the pore structure.

8. A chlorine recovery and recycling catalytic system for DCP condensation process according to claim 7, characterized in that: The regeneration execution module includes a solvent selection unit and an activation parameter unit; The solvent selection unit uses an acetone-deionized water mixed solvent with a volume ratio of 3:

1. A pulsating flow is generated by a vortex mixer, and the solvent circulation flow rate is controlled at 2-3 m / s. The activation parameter unit is equipped with a multi-segment temperature control system. During the hot nitrogen regeneration stage, a uniform temperature field of 110±5℃ is established in the catalyst bed. The purging time is adaptively adjusted to the range of 60-90 minutes according to the pressure drop. During the vacuum activation stage, the composition of the desorbed gas is monitored online using a mass spectrometer, and regeneration is terminated when the concentration of hydrocarbons is less than 50 ppm.

9. A chlorine recovery and recycling catalytic system for DCP condensation process according to claim 7, characterized in that: The regeneration execution module also includes a lifetime prediction unit; The lifetime prediction unit collects the correlation between the cumulative number of regenerations X and the activity recovery rate Y through a big data platform, and establishes a second-order polynomial regression equation: ； The model parameters are automatically updated after each regeneration cycle. When the predicted Y ≤ 92%, the system generates a catalyst replacement early warning report. Simultaneously monitor the catalyst's mechanical strength decay rate. When the particle size breakage rate is ≥15%, the replacement procedure is forcibly initiated. The spent catalyst is safely disposed of after neutralization with alkali solution.

10. A chlorine recovery and recycling catalytic system for DCP condensation process according to claim 1, characterized in that: The multi-level alarm module includes a three-level response mechanism: The Level 1 response activates an audible and visual alarm and simultaneously turns on the emergency ventilation system when the chlorine concentration is ≥10ppm. The secondary response interlocks the cooling system, injects polymerization inhibitor, and activates the pressure relief valve when the pressure fluctuation is ≥0.1MPa; A Level 3 response triggers an emergency shutdown of the entire system when the temperature exceeds 80°C, closing the raw material inlet valve and opening the emergency collection tank. All response actions are recorded in the security control log and uploaded to the central monitoring platform in real time.

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