Polymerization reaction device

Abstract

The utility model provides a polymerization reaction device. The polymerization reaction device comprises a tubular reaction cluster, the tubular reaction cluster comprises a plurality of groups of calandria to form a heating area and a constant temperature area; the heating area is provided with a reaction liquid inlet, and the constant temperature area is provided with a reaction product outlet; a feeding hole of the kettle type liquid exhauster is connected with the reaction product outlet; the kettle type liquid exhauster is of a jacket type structure, and a stirring device is arranged in the kettle type liquid exhauster. Compared with the prior art, the polymerization reaction device provided by the utility model adopts a specific structure and a specific connection relation, realizes better integral interaction, can ensure that the polymerization reaction temperature is constant, the particle size distribution is balanced, the product performance is stable, and the phenomena of wall sticking and even caking are reduced, so that the experiment repeatability and the product stability are improved.

Description

Technical Field

[0001] The utility model relates to the technical field of reaction devices, and more specifically to a polymerization reaction device. Background Art

[0002] Inverse suspension polymerization is a technology that disperses water-soluble monomers into fine droplets in an organic solvent and conducts polymerization reactions. Its notable feature is that the droplets in the system are oil-in-water. Inverse suspension polymerization is an ideal method for industrial production of water-soluble spherical polymers developed in the past 10 years. Compared with other polymerization methods, it has the following outstanding advantages: simple equipment and process requirements, mild reaction conditions, low system viscosity, easy removal of reaction heat, few side reactions, solvents can be directly distilled and recovered, no wastewater and environmental pollution, etc. At present, inverse suspension polymerization is widely used in the polymerization reaction of water-soluble monomers such as acrylic acid, acrylamide, methacrylic acid, N-vinyl pyrrolidone, β-hydroxyethyl acrylate, etc., mainly in the preparation of water-absorbing resins and alcohol-absorbing resins.

[0003] At present, polymerization reactions are generally carried out in a kettle with an agitator. The polymerization kettle is a jacket structure, and the interior of the kettle is a polymerization reaction chamber. The jacket contains a heat-conducting medium. The temperature in the kettle is provided by the heat-conducting medium. After the heat-conducting medium is heated to a certain temperature, the temperature of the reaction liquid in the kettle is increased by heat conduction. The thermocouple is inserted from the kettle cover below the liquid level of the reaction liquid in the kettle to measure the temperature in the kettle. The temperature of the polymerization reaction is a key factor in the success or failure of the polymerization reaction. The temperature in the kettle changes in a certain temperature gradient in the radial direction, which results in that only measuring the temperature of a certain point below the liquid surface cannot reflect the temperature of the entire system. Even if multiple thermocouples are used, the measured temperature also changes in a gradient, and the temperature of the entire system cannot be uniformly stabilized at a certain temperature. This causes the polymerization reaction to always agglomerate, resulting in experimental failure, difficulty in discharging, and frequent cleaning of the kettle. Even if the discharging is successful, the particle size distribution of the products obtained under the same conditions is inconsistent, and even the product performance varies greatly, and the experimental repeatability is poor. In addition, the preparation of super absorbent resin using a polymerization kettle requires a two-step process of polymerization and distillation. The raw materials in the polymerization stage are oil phase and water phase, and the oil phase and low-viscosity gel after the reaction. The low-viscosity viscose needs to remove water to obtain the final product; and the dehydration process usually adopts a distillation process. During the distillation process, the gel near the liquid surface tends to form a circle of dry SAP layer on the wall, which requires the preparation process to be completed and the kettle cover opened to clean the kettle, which brings trouble to the operator.

[0004] In summary, the polymerization reaction is carried out in a reactor, and the temperature at various places in the reactor changes in a gradient and cannot be kept constant. For reactions with a narrow polymerization temperature range, thermodynamic instability is likely to occur. During the polymerization process, particles tend to agglomerate, making particle size control and discharging difficult. At the same time, sticking to the wall during the distillation process can easily make cleaning difficult. Therefore, even if the same reaction conditions are repeated many times, the particle size distribution of the successfully discharged products will vary greatly, and the product performance will not be completely consistent. Utility Model Content

[0005] In view of this, the purpose of the utility model is to provide a polymerization reaction device that improves the repeatability and stability of the polymerization reaction. Through technical improvements, the polymerization reaction temperature is guaranteed to be constant, the particle size distribution is balanced, the product performance is stable, and the wall sticking and even agglomeration phenomena are reduced, thereby improving the experimental repeatability and product stability.

[0006] The utility model provides a polymerization reaction device, comprising:

[0007] Tubular reaction cluster; the tubular reaction cluster comprises a plurality of groups of tubes, forming a temperature rising zone and a constant temperature zone; the temperature rising zone is provided with a reaction liquid inlet, and the constant temperature zone is provided with a reaction product outlet;

[0008] A kettle type deliquidator with a feed inlet connected to the reaction product outlet; the kettle type deliquidator is a jacketed structure with a stirring device inside.

[0009] Preferably, the temperature rising zone includes 1 to 15 groups of pipes, each group of pipes includes 15 to 50 sections of pipelines; the constant temperature zone includes 20 to 100 groups of pipes, each group of pipes includes 51 to 100 sections of pipelines.

[0010] Preferably, the diameter of the pipeline is 10 mm to 100 mm; the length of each section of the pipeline is 5 m to 15 m.

[0011] Preferably, the pipeline is a sleeve-type structure, including a central tube and a sleeve; one end of the central tube is connected to the reaction liquid inlet, and the other end is connected to the reaction product outlet; the interior of the sleeve is filled with a heat-conducting medium.

[0012] Preferably, an inner tube is provided in the central tube; and the cross section of the inner tube in the central tube is in a grid shape.

[0013] Preferably, a heat-conducting medium is contained in the jacket of the jacketed structure.

[0014] Preferably, the reaction product outlet is connected to the feed inlet of the kettle type deliquidator through a heating pipeline.

[0015] The utility model provides a polymerization reaction device, including: a tubular reaction cluster; the tubular reaction cluster includes a plurality of groups of pipes, forming a temperature rise zone and a constant temperature zone; the temperature rise zone is provided with a reaction liquid inlet, and the constant temperature zone is provided with a reaction product outlet; a kettle type deliquidator connected with a feed inlet and the reaction product outlet; the kettle type deliquidator is a jacketed structure, and a stirring device is provided inside. Compared with the prior art, the polymerization reaction device provided by the utility model adopts a specific structure and connection relationship to achieve better overall interaction, can ensure a constant polymerization reaction temperature, a balanced particle size distribution, stable product performance, reduce wall sticking and even agglomeration, thereby improving experimental repeatability and product stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 A schematic diagram of the structure of a polymerization reaction device provided in an embodiment of the utility model;

[0017] Figure 2 This is a cross-sectional view of a single tube in a polymerization reaction device provided in an embodiment of the utility model. DETAILED DESCRIPTION

[0018] The following will be combined with the embodiments of the utility model to clearly and completely describe the technical solution of the utility model. Obviously, the described embodiments are only part of the embodiments of the utility model, not all of the embodiments. Based on the embodiments of the utility model, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the utility model.

[0019] The utility model provides a polymerization reaction device, comprising:

[0020] Tubular reaction cluster; the tubular reaction cluster comprises a plurality of groups of tubes, forming a temperature rising zone and a constant temperature zone; the temperature rising zone is provided with a reaction liquid inlet, and the constant temperature zone is provided with a reaction product outlet;

[0021] A kettle type deliquidator with a feed inlet connected to the reaction product outlet; the kettle type deliquidator is a jacketed structure with a stirring device inside.

[0022] In the utility model, the polymerization reaction device includes a tubular reaction cluster and a kettle type deliquidator. The utility model adopts a tubular reaction cluster and a kettle type deliquidator, which are respectively used for polymerization and distillation. The gel particle size can be regulated in the polymerization stage, and the deliquidation amount can be regulated in the distillation stage, so as to control the product particle size and product performance, thereby solving the technical problems of frequent agglomeration and difficulty in particle size control in the existing polymerization kettle during the polymerization process.

[0023] In the utility model, the tubular reaction cluster includes several groups of pipes, forming a temperature rising zone and a constant temperature zone; the temperature rising zone is provided with a reaction liquid inlet, and the constant temperature zone is provided with a reaction product outlet. The utility model adopts the above tubular reaction cluster to ensure that the polymerization reaction temperature is always constant, solving the technical problem that the temperature in the traditional polymerization kettle cannot be guaranteed to be uniform and constant everywhere.

[0024] In the present invention, the temperature rising zone preferably includes 1 to 15 groups of pipes, more preferably 5 to 10 groups, each group of pipes preferably includes 15 to 50 sections of pipes, more preferably 20 to 30 sections; the constant temperature zone preferably includes 20 to 100 groups of pipes, more preferably 70 to 80 groups, each group of pipes preferably includes 51 to 100 sections of pipes, more preferably 80 to 90 sections.

[0025] In the present invention, the diameter of the pipeline is preferably 10 mm to 100 mm, more preferably 20 mm to 30 mm; the length of each section of the pipeline is preferably 5 m to 15 m, more preferably 8 m to 12 m.

[0026] In the present invention, the pipeline is preferably a sleeve-type structure, including a central tube and a sleeve; one end of the central tube is connected to the reaction liquid inlet, and the other end is connected to the reaction product outlet; the interior of the sleeve is filled with a heat-conducting medium.

[0027] In the present invention, the central tube is preferably provided with an inner tube member; the cross section of the inner tube member in the central tube is preferably in a grid shape. In the present invention, the inner tube member is a 3D printed three-dimensional structure.

[0028] In the utility model, the polymerization reaction occurs in the above-mentioned tubular reaction cluster. The pipes in the tubular reaction cluster are of a sleeve-type structure, which is composed of two parts, a temperature rising zone and a constant temperature zone. The pipes are relatively thin (10mm to 100mm) and are cluster-shaped as a whole; the central tube contains the reaction liquid and the sleeve contains the heat-conducting medium; the above-mentioned sleeve-type structure can ensure that the polymerization temperature is constant, control the polymerization reaction speed, and ensure that there is no agglomeration and the like in the reaction.

[0029] In a preferred embodiment of the utility model, the inside of the pipe of the tubular reaction cluster is polished at submicron level to meet the requirements of gel flow.

[0030] In the utility model, the feed inlet of the kettle type deliquidator is connected to the reaction product outlet.

[0031] In the utility model, the kettle type deliquoring device is a jacketed structure, and a stirring device is arranged inside.

[0032] In the utility model, a heat-conducting medium is contained in the jacket of the jacket-type structure.

[0033] In the utility model, the distillation reaction takes place in a kettle type deliquidator, which is a jacketed structure, with a heat-conducting medium in the jacket, a reaction product in the kettle, and a stirring device in the kettle.

[0034] In the present invention, the reaction product outlet and the feed inlet of the kettle type deliquidator are preferably connected through a heating pipeline.

[0035] In a preferred embodiment of the utility model, submicron polishing is performed inside the kettle type deliquoring device and the connecting pipeline, and the reactants do not stick to the wall, and the kettle can be cleaned after repeated multiple times.

[0036] The utility model provides a polymerization reaction device, wherein: (1) the pipeline in the tubular reaction cluster is a sleeve-type structure, the polymerization temperature is constant, the polymerization reaction speed is controlled, and it is ensured that the reaction does not have agglomeration and other phenomena; in addition, the internal parts of the tubular reaction cluster are 3D printed three-dimensional structures, which play a role in separating and disturbing the reaction liquid in the polymerization reaction, so that the gel is maintained in a certain particle size range. (2) The kettle deliquidator is a jacketed structure, with an agitator in the kettle. When the kettle is raised to a certain temperature and the temperature no longer changes, it means that the deliquidation is completed. Different temperatures in the kettle correspond to the water content in the product, and various water content products can also be prepared according to the product performance requirements; the kettle deliquidator can prepare products with different deliquidation amounts, which is easy to control the product deliquidation amount and control the product performance.

[0037] The utility model also provides a polymerization reaction method, which adopts the polymerization reaction device described in the above technical solution, comprising the following steps:

[0038] The reaction liquid is sequentially passed through a temperature rising zone and a constant temperature zone for polymerization reaction to obtain a reaction product;

[0039] The reaction product is deliquored under stirring conditions to obtain a polymer product with a stable particle size range.

[0040] In the present invention, the reaction liquid is preferably a mixture of an oil phase, an aqueous phase and an initiator; the present invention has no special restrictions on the types and sources of the oil phase, aqueous phase and initiator, and commercially available conventional reaction raw materials for polymerization reactions well known to those skilled in the art can be used.

[0041] In the present invention, the volume ratio of the oil phase to the water phase is preferably (0.5-2):1, more preferably 1:1; the reaction liquid is a mixture of the oil phase and the water phase, wherein the water phase undergoes polymerization to generate a gel, and the oil phase plays a role in promoting the reactants.

[0042] In the utility model, the reaction liquid enters the tubular reaction cluster at a certain speed, the polymerization temperature in the constant temperature zone remains constant, and under the cutting and disturbance of the inner tube, the reaction liquid gradually becomes a gel with low viscosity and a certain particle size. The length of the tubular reaction cluster is related to the residence time of the polymerization reaction.

[0043] In the present invention, the flow rate of the reaction liquid is preferably 10 m / s to 50 m / s, more preferably 20 m / s to 30 m / s.

[0044] In the present invention, the polymerization reaction temperature is preferably 60° C. to 80° C., more preferably 70° C., and the residence time is preferably 0.5 h to 2 h, more preferably 1 h.

[0045] After the reaction product comes out of the tubular reaction cluster, it enters the kettle deliquidator through the heating pipe. The temperature in the kettle deliquidator gradually increases (the heating pipe maintains >70°C entering the kettle deliquidator, gradually rises to 80°C~100°C and maintains stability). The reactants are in a dehydrated state, transitioning from a gel state to a solid. When the temperature is constant and no longer increases, the distillation dehydration process is completed, and a solid with a stable particle size range (10μm~150μm) is obtained.

[0046] The polymerization reaction method provided by the utility model places the polymerization and distillation processes in a tubular reaction cluster and a kettle deliquidator respectively. The tubular reaction cluster is a sleeve-tube structure, which ensures a stable polymerization temperature. In addition, the tube internals adopt a 3D printed three-dimensional structure, which ensures that the reactant gel is controlled within a certain particle size range during the reaction stage. The deliquidation amount is regulated in the kettle deliquidator to better regulate the product particle size and product performance. The equipment and pipelines involved in the reactants are all polished at the submicron level, which ensures that the reactants are easy to fall off and do not stick to the wall. The kettle can be opened for cleaning after multiple uses, solving the problem that the existing products have serious wall sticking and need to be opened for cleaning every time. The polymerization reaction method provided by the utility model can be produced repeatedly, the product stability is improved, the product particle size is balanced, and the trouble of manual operation is reduced.

[0047] The utility model provides a polymerization reaction device and method; the polymerization reaction device comprises: a tubular reaction cluster; the tubular reaction cluster comprises a plurality of groups of pipes, forming a temperature rise zone and a constant temperature zone; the temperature rise zone is provided with a reaction liquid inlet, and the constant temperature zone is provided with a reaction product outlet; a kettle type deliquidator having a feed inlet connected to the reaction product outlet; the kettle type deliquidator is a jacketed structure, and a stirring device is provided inside. Compared with the prior art, the polymerization reaction device provided by the utility model adopts a specific structure and connection relationship to achieve better overall interaction, can ensure a constant polymerization reaction temperature, a balanced particle size distribution, stable product performance, reduce wall sticking and even agglomeration phenomena, thereby improving experimental repeatability and product stability.

[0048] In order to further illustrate the present invention, the following examples are used to explain the present invention in detail. Figure 1As shown, it is a combined structure of a tubular reaction cluster and a kettle type deliquidator, wherein 1 is a tubular reaction cluster, 101 is a temperature rising zone, 102 is a constant temperature zone, 2 is a kettle type deliquidator, 201 is a stirrer, 202 is a deliquidation chamber, and 203 is a kettle jacket; see the single tube cross-sectional view for details. Figure 2 As shown, 103 is a central tube, 104 is an inner tube, and 105 is a casing.

[0049] Example 1

[0050] The tubular reaction cluster is composed of a series of pipes with a diameter of 20mm. There are 10 groups of pipes in the heating zone, each group of pipes consists of 20 sections of pipes, and each section of pipes is 10 meters long; 80 groups of pipes are set in the constant temperature zone, each group of pipes consists of 90 sections of pipes, and each section of pipes is 10 meters long. The reaction liquid is composed of cyclohexane, sodium acrylate and a certain initiator, and the oil-water volume ratio is 1:1. It enters the tubular reaction cluster at a speed of 20m / s. The polymerization temperature is constant at 70℃, and the polymerization reaction residence time is 1h. The polymerization reactants enter the deliquidator through the heating pipeline to maintain >70℃, and gradually increase the temperature of the deliquidator to 80℃, and all water is separated to form a spherical resin product with an average particle size of 50μm.

[0051] The combination of tubular reaction cluster and deliquoring device makes the particle size controlled at about 50μm, no sedimentation occurs in the polymerization stage, the deliquoring efficiency in the distillation stage is increased by 10%, the wall sticking phenomenon is significantly improved, multiple post-cleaning of the kettle can be realized, and manual operation is reduced.

[0052] The polymerization reaction was carried out in a conventional polymerization reactor under the same conditions. The results are compared in Table 1 below.

[0053] Table 1

[0054] project Polymerization reactor Tubular reaction cluster + deliquator Particle size The average particle size is between 30 and 70 microns. The average particle size is between 50 microns Dehydration efficiency 80％ 90％ Kettle washing frequency 1 wash per experiment 10 experiments 1 wash Yield 80％ 95％ Repeatability Particle size distribution trends cannot be repeated Particle size distribution is 100% normal distribution stability The process is unstable and the product performance varies Stable process and stable product performance

[0055] Example 2

[0056] The tubular reaction cluster is composed of a series of pipes with a diameter of 20mm. There are 10 groups of pipes in the heating zone, each group of pipes consists of 20 sections of pipes, and each section of pipes is 10 meters long; 80 groups of pipes are set in the constant temperature zone, each group of pipes consists of 90 sections of pipes, and each section of pipes is 10 meters long. The reaction liquid is composed of n-heptane, sodium acrylate and a certain initiator, and the oil-water volume ratio is 1:1. It enters the tubular reaction cluster at a speed of 20m / s. The polymerization temperature is constant at 70℃, and the polymerization reaction residence time is 1h. The polymerization reactants enter the deliquidator through the heating pipeline to maintain >70℃, and gradually increase the temperature of the deliquidator to 98℃, and all water is separated to form a spherical resin product with an average particle size of 100μm.

[0057] The combination of tubular reaction cluster and deliquoring device makes the particle size controlled at about 100μm, no sedimentation occurs in the polymerization stage, the deliquoring efficiency in the distillation stage is increased by 10%, the wall sticking phenomenon is significantly improved, multiple post-cleaning of the kettle can be realized, and manual operation is reduced.

[0058] The polymerization reaction was carried out in a conventional polymerization reactor under the same conditions. The results are compared in Table 2 below.

[0059] Table 2

[0060] project Polymerization reactor Tubular reaction cluster + deliquator Particle size The average particle size is between 50 and 150 microns. The average particle size is about 100 microns Dehydration efficiency 80％ 90％ Kettle washing frequency 1 wash per experiment 10 experiments 1 wash Yield 75％ 95％ Repeatability Particle size distribution trends cannot be repeated Particle size distribution is 100% normal distribution stability The process is unstable and the product performance varies Stable process and stable product performance

[0061] Example 3

[0062] The tubular reaction cluster is composed of a series of pipes with a diameter of 20mm. There are 10 groups of pipes in the heating zone, each group of pipes consists of 20 sections of pipes, and each section of pipes is 10 meters long; 80 groups of pipes are set in the constant temperature zone, each group of pipes consists of 90 sections of pipes, and each section of pipes is 10 meters long. The reaction liquid is composed of oil phase (1:1 of n-heptane and cyclohexane), sodium acrylate and a certain initiator, and the oil-water volume ratio is 1:1. It enters the tubular reaction cluster at a speed of 20m / s. The polymerization temperature is constant at 70℃, and the polymerization reaction residence time is 1h. The polymerized reactants enter the deliquidator through the heating pipeline to maintain >70℃, and gradually increase the temperature of the deliquidator to 80℃, and all water is separated to form a spherical resin product with an average particle size of 80μm.

[0063] The combination of tubular reaction cluster and deliquoring device makes the particle size controlled at about 80μm, no sedimentation occurs in the polymerization stage, the deliquoring efficiency in the distillation stage is increased by 10%, the wall sticking phenomenon is significantly improved, multiple post-cleaning of the kettle can be realized, and manual operation is reduced.

[0064] The polymerization reaction was carried out in a conventional polymerization reactor under the same conditions. The results are compared in Table 3 below.

[0065] Table 3

[0066] project Polymerization reactor Tubular reaction cluster + deliquator Particle size The average particle size is between 50 and 100 microns. The average particle size is about 80 microns Dehydration efficiency 80％ 90％ Kettle washing frequency 1 wash per experiment 10 experiments 1 wash Yield 80％ 95％ Repeatability Particle size distribution trends cannot be repeated Particle size distribution is 100% normal distribution stability The process is unstable and product performance varies. The process is stable and the product performance is stable.

[0067] In summary, the utility model provides a polymerization reaction device and method, which can provide repeatability and stability of polymerization reaction. The polymerization reaction occurs in a tubular reaction cluster, and the distillation occurs in a kettle deliquidator, which ensures the balance and stability of the polymerization reaction temperature. In addition, an internal tube is set in the tubular reaction cluster, and the gel is cut during the polymerization reaction. The cut gel continues to flow under the drive of the oil phase. Polymerization in the tubular reaction cluster not only ensures the constant temperature of the polymerization reaction, but also ensures that the gel has completed the particle size shaping at the beginning of its formation, which avoids the occurrence of reaction agglomeration and difficulty in particle size control. The kettle deliquidator cavity is heated to a certain temperature, and the temperature no longer changes, which means that the deliquidation is completed. The kettle deliquidator can prepare products with different deliquidation amounts, which is easy to control the product deliquidation amount and product performance. The tubular reaction cluster, the kettle deliquidator and the reactant flow pipeline are all polished with submicron mirrors, and coupled with the oil phase environment, this makes it difficult for the kettle to stick to the wall, and the reactor can be cleaned after multiple experiments, reducing the difficulty of manual operation.

[0068] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A polymerization reaction device, characterized in that: include: Tubular reaction cluster; the tubular reaction cluster comprises a plurality of groups of tubes, forming a temperature rising zone and a constant temperature zone; the temperature rising zone is provided with a reaction liquid inlet, and the constant temperature zone is provided with a reaction product outlet; A kettle type deliquidator with a feed inlet connected to the reaction product outlet; the kettle type deliquidator is a jacketed structure with a stirring device inside.

2. The polymerization reaction device according to claim 1, characterized in that: The temperature rising zone includes 1 to 15 groups of pipes, each group of pipes includes 15 to 50 sections of pipelines; the constant temperature zone includes 20 to 100 groups of pipes, each group of pipes includes 51 to 100 sections of pipelines.

3. The polymerization reaction device according to claim 2, characterized in that: The diameter of the pipeline is 10 mm to 100 mm; the length of each section of the pipeline is 5 m to 15 m.

4. The polymerization reaction device according to claim 2, characterized in that: The pipeline is a sleeve-type structure, including a central tube and a sleeve; one end of the central tube is connected to the reaction liquid inlet, and the other end is connected to the reaction product outlet; the interior of the sleeve is filled with a heat-conducting medium.

5. The polymerization reaction device according to claim 4, characterized in that: An inner tube is arranged in the central tube; the cross section of the inner tube in the central tube is in a grid shape.

6. The polymerization reaction device according to claim 1, characterized in that: The jacket of the jacketed structure is filled with heat-conducting medium.

7. The polymerization reaction device according to claim 1, characterized in that: The reaction product outlet is connected to the feed inlet of the kettle type deliquidator through a heating pipeline.

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