A device for continuously synthesizing glyphosate
Patent Information
- Application Number
- CN202410496609.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-04-24
- Publication Date
- 2026-10-23
- Estimated Expiration
- 2044-04-24
AI Technical Summary
甘氨酸法草甘膦生产已有30余年生产历史,溶剂回收、三乙胺回收、氯甲烷回收等工序在工业上已实现连续化,但反应过程和结晶过程仍是用间歇釜式或者连续釜式,生产效率仍较低,连续化程度不够高,存在产品质量批次不稳定、三废排放较大等问题
[0017]草甘膦全连续化学合成装置中针对液固体系的连续稳定运行开发了旋转动态反应器,具有良好的平推流效果,解决了传统釜式反应器的返混带来的反应均一性差,副产物多等难题,同时换热面积是传统釜式反应器的8-10倍,保证了放大生产时产品收率和质量的一致性。针对液液体系开发了内置多个依次轴向排布的正方形混合构件的管式微反应器,该结构的微通道反应器是将流体分离再汇聚,次数为构件数量的2的n次方,为指数级混合次数,使物料混合均一性在尺寸放大时能够保持一致,避免了尺寸扩大带来的传质效率降低导致收率降低的问题。最后通过开发的高效连续结晶器,实现了原料到合格产品的端对端连续化生产,完成了草甘膦的集成式生产,避免了传统釜式生产的装置分布范围大、能耗高、耗时长、过程安全性控制难度高等问题。
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Figure CN118558262B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of fine chemical technology, specifically relating to an apparatus for the fully continuous synthesis of glyphosate. Background Technology
[0002] Glyphosate is a highly efficient, low-toxicity, broad-spectrum, non-selective, and non-selective herbicide with excellent biological properties, and it is the world's most produced herbicide. In my country, 70% of glyphosate production capacity is generated using the alkyl ester method, with glycine and dimethyl phosphite as the main raw materials. This method uses methanol as the reaction solvent, and in the presence of the catalyst triethylamine, glycine, paraformaldehyde, and dimethyl phosphite react to produce glyphosate. Glyphosate production using the glycine method has a history of over 30 years. Solvent recovery, triethylamine recovery, and chloromethane recovery processes have been industrially achieved as continuous processes. However, the reaction and crystallization processes still use batch or continuous reactors, resulting in relatively low production efficiency, insufficient continuity, and problems such as inconsistent product quality across batches and significant emissions of waste.
[0003] Although patents CN111205319A, CN216630779U, CN110862413A, and CN104163832B have developed continuous batch reactors and corresponding processes, they still require a large number of reactors to meet the needs of industrial production. This results in a large production area, large online reaction materials and solvent volumes, high process safety risks, and the crystallization and purification of the final product glyphosate is still carried out in the reactor, leading to low production efficiency and insufficient batch quality stability. Summary of the Invention
[0004] In view of the problems existing in the prior art, the purpose of this invention is to provide a glyphosate fully continuous synthesis device with high production efficiency, good and stable product quality, and low emissions of waste.
[0005] The glyphosate fully continuous synthesis apparatus provided by this invention, based on the characteristics of the reaction process, adopts a matching microchannel reactor, a rotating dynamic reactor, a continuous batch hydrolysis and alcoholysis reactor, and a continuous crystallizer in a coupled manner to achieve fully continuous manufacturing from raw material input to finished glyphosate product. This not only makes it easy to expand production capacity and avoids problems such as inconsistent product batch quality, but also improves the degree of process automation control, reduces reagent consumption and waste emissions. Compared with existing production technologies, the product yield and quality stability are significantly improved, and the production cost is reduced.
[0006] The glyphosate fully continuous synthesis apparatus provided by this invention comprises 7 feed pumps, 4 micromixers, 6 microchannel reactors, 3 stirred tanks, 1 buffer tank, 2 back pressure valves, and 1 continuous crystallizer connected sequentially according to the glyphosate synthesis route, forming a fully continuous chemical synthesis apparatus matched to the glyphosate synthesis route; wherein:
[0007] The prepared first and second materials are respectively pumped to the first micromixer by the first and second pumps for thorough mixing. After mixing, they enter the first microchannel reactor directly through a connected pipeline for paraformaldehyde depolymerization. The reaction liquid flowing out of the first microchannel reactor is thoroughly mixed with the third material pumped by the third pump in the second micromixer and then directly enters the second microchannel reactor for an addition reaction. The reaction liquid flowing out of the second microchannel reactor enters the buffer tank through a connected pipeline as the fourth material. The fourth material is pumped to the third micromixer by the fourth pump and mixed with the fifth material pumped by the fifth pump. After mixing, it enters the third microchannel reactor directly through a connected pipeline for esterification. The temperature in the fourth microchannel reactor is slightly higher than that in the third microchannel reactor to promote complete conversion of the reactants. The reaction liquid flowing out of the fourth microchannel reactor flows through the first back pressure valve, which regulates the reaction pressure in the third and fourth microchannel reactors. The reaction solution enters the fourth micromixer and is thoroughly mixed with the sixth material delivered by the sixth pump before entering the fifth microchannel reactor for neutralization. The reaction solution then enters the sixth microchannel reactor directly through a connected pipeline for hydrolysis, while simultaneously increasing the temperature of the reaction solution to improve the removal efficiency of low-boiling-point solvents and compounds after entering the first stirred tank in the continuous batch reactor. The effluent from the sixth microchannel reactor enters the first stirred tank from the bottom, where low-boiling-point solvents and compounds rapidly evaporate. The evaporated gases enter a condensation and collection device connected to the pipeline of the first stirred tank. The remaining reaction solution flows upward from the bottom of the first stirred tank, enters the upper outlet, and then enters the lower part of the second stirred tank through a connecting pipeline, continuously removing the generated chloromethane and some of the solvent water. The remaining reaction solution flows upward from the bottom of the second stirred tank, enters the upper outlet, and then enters the lower part of the third stirred tank through a connecting pipeline for continued hydrolysis and de-alcoholization reaction. Until complete conversion, the reaction solution enters the continuous crystallizer, where glyphosate is precipitated by cooling.
[0008] In this invention, the first and third pumps are peristaltic pumps for conveying slurry, and the second, fourth, fifth, sixth, and seventh pumps are plunger pumps for conveying solution.
[0009] In this invention, the first to fourth micromixers are micromixers composed of four diamond-shaped tubular mixing components connected in series, such as... Figure 2 As shown, the rhomboid tubing refers to circular or square fluid channels with dimensions of 100μm-20mm and lengths of 1-100cm, suitable for flow rates of 1-3000mL / min. A preferred length is 10-100cm, suitable for flow rates of 300-3000mL / min. This micromixer structure ensures uniform material mixing.
[0010] In this invention, the second microchannel reactor is a rotating dynamic reactor, such as... Figure 3As shown, the specific structure is as follows: it is a cylindrical cavity with a heat exchange fluid jacket on the cavity wall; the cylindrical cavity contains only a central shaft, on which multiple stirring paddles are connected to enhance mass and heat transfer. The central shaft is driven by a motor with a rotation speed of 50-500 rpm. The cavity is cylindrical with a diameter of 3-60 cm and a length of 20-500 cm, and the applicable throughput is 10-50000 mL / min. Preferably, the diameter is 10-60 cm and the length is 100-500 cm, and the applicable throughput is 500-50000 mL / min. This microchannel reactor structure is suitable for continuous and stable operation of liquid-solid systems, and its heat exchange area is 8-10 times that of a traditional batch reactor.
[0011] Preferably, the first, third, fourth, fifth, and sixth microchannel reactors are tubular microreactors containing multiple (e.g., 4-8) sequentially arranged square mixing components, such as... Figure 4 As shown, the fluid channel size is 2-500 mm, the length is 1-10000 m, and the applicable throughput is 10-50000 mL / min. Preferably, the fluid channel size is 50-500 mm, the length is 100-10000 m, and the applicable throughput is 500-50000 mL / min. This microchannel reactor structure separates and then re-converges the fluid, resulting in good material mixing uniformity, and especially avoiding the problem of reduced mass transfer efficiency caused by size expansion during scale-up.
[0012] Preferably, the first back pressure valve and the second back pressure valve are made of stainless steel or Hastelloy, the connecting pipe is 1.6mm-20mm in size, and the pressure condition range is 0.1-2.0MPa.
[0013] Preferably, the first, second, and third stirred tanks are stirred tanks equipped with a stirring paddle, a low-boiling-point distillate outlet, a heat exchange jacket, a heat exchange fluid inlet / outlet, and a material inlet / outlet, such as... Figure 5 As shown, three stirred tanks are connected in series by pipes to achieve the flow of heat exchange fluid and material. The inner diameter of the stirred tank is 5-1000cm and the height is 5-1000cm, preferably 100-1000cm. The material is one or a combination of glass, polytetrafluoroethylene, stainless steel, Hastelloy, tantalum, and zirconium.
[0014] Preferably, the continuous crystallizer is a tubular reactor with a mixing structure and jacketed heat exchange, such as... Figure 6As shown, the tubular reactor has an S-shaped pipe with a heat exchange jacket on the pipe wall through which the heat supply flow passes; several evenly distributed spherical baffles are installed inside the pipe. The tubular reactor has an inner diameter of 2-20 cm, a length of 1-1000 m, and an applicable throughput of 10-5000 mL / min, preferably an inner diameter of 8-20 cm, a length of 100-1000 m, and an applicable throughput of 200-5000 mL / min; the material is one or a combination of several of the following: glass, polytetrafluoroethylene, stainless steel, Hastelloy, tantalum, and zirconium.
[0015] In this invention, the first material is a solution or slurry obtained by dissolving or dispersing paraformaldehyde in a solvent; the second material is a solution of alkali without solvent feeding or dissolved in a solvent; the third material is a solution or slurry obtained by dissolving or dispersing glycine in a solvent; the fourth material is an intermediate solution generated in the second microchannel reactor; the fifth material is a solution of dimethyl phosphite without solvent feeding or dissolved in a solvent; and the sixth material is a solution of acid without solvent feeding or dissolved in a solvent.
[0016] The temperature of the first microchannel reactor is 30-60℃, and the reaction time is 1-9 min; the temperature of the second microchannel reactor is 45-80℃, and the reaction time is 6-12 min; the temperature of the third microchannel reactor is 50-80℃, and the reaction time is 1-8 min; the temperature of the fourth microchannel reactor is 60-90℃, and the reaction time is 5-15 min; the temperature of the fifth microchannel reactor is 0-30℃, and the reaction time is 0.5-3 min; the temperature of the sixth microchannel reactor is 90-190℃, and the reaction time is 0.5-3 min; the temperature of the first stirred tank is 80-150℃, and the reaction time is 5-40 min; the temperature of the second stirred tank is 80-150℃, and the reaction time is 5-40 min; the temperature of the third stirred tank is 90-160℃, and the reaction time is 5-60 min; the temperature of the continuous crystallizer is 0-80℃, and the residence time is 1-30 min.
[0017] In the glyphosate fully continuous chemical synthesis unit, a rotating dynamic reactor was developed for the continuous and stable operation of the liquid-solid system. This reactor exhibits excellent plug flow performance, solving the problems of poor reaction uniformity and numerous by-products caused by backmixing in traditional batch reactors. Simultaneously, its heat exchange area is 8-10 times that of traditional batch reactors, ensuring consistent product yield and quality during scale-up production. For the liquid-liquid system, a tubular microreactor with multiple sequentially arranged axially arranged square mixing components was developed. This microchannel reactor separates and re-converges the fluids at a rate of 2 to the power of n (the number of components), representing an exponential mixing frequency. This ensures consistent material mixing uniformity during scale-up, avoiding the yield reduction caused by decreased mass transfer efficiency due to size expansion. Finally, through the development of a high-efficiency continuous crystallizer, end-to-end continuous production from raw materials to qualified products was achieved, completing the integrated production of glyphosate. This avoids the problems of large equipment distribution, high energy consumption, long processing time, and high difficulty in process safety control associated with traditional batch production. Attached Figure Description
[0018] Figure 1 This is a flowchart of a fully continuous chemical synthesis apparatus for glyphosate.
[0019] Figure 2 This is a schematic diagram of a micromixer structure with diamond-shaped series connections.
[0020] Figure 3 This is a schematic diagram of a rotating dynamic reactor.
[0021] Figure 4 This is a schematic diagram of a tubular microreactor with a built-in square mixing component.
[0022] Figure 5 This is a schematic diagram of the first reactor with a distillation function.
[0023] Figure 6 This is a schematic diagram of a continuous crystallizer with a hybrid structure and jacketed heat exchange.
[0024] The diagram labels are as follows: 1-Heat exchange fluid outlet, 2-Heat exchange fluid jacket, 3-Coaxial multi-blade agitator, 4-Heat exchange fluid inlet, 5-Motor, 6-Base plate, 7-Support frame, 8-Reactant outlet, 9-Reactant inlet; 10-Heat exchange fluid outlet, 11-Heat exchange fluid inlet, 12-Reactant inlet, 13-Reactant outlet, 14-Square mixing component; 15-Heat exchange fluid inlet, 16-Heat exchange fluid outlet, 17-Reactant inlet, 18-Reactant outlet, 19-Cooling fluid inlet; 20-Cooling fluid outlet, 21-Condenser, 22-Material collection tank, 23-Crystallized material outlet, 24-Heat exchange fluid outlet, 25-Heat exchange fluid inlet, 26-Crystallized material inlet, 27-Spherical baffle inside the crystallizer. Detailed Implementation
[0025] The present invention will be further described below with reference to the embodiments and accompanying drawings. However, the scope of protection of the present invention is not limited to the following embodiments.
[0026] Example 1
[0027] The prepared feed 1 (paraformaldehyde 0.64 kg / L) and feed 2 (triethylamine, flow ratio 2:1, retention time 9 min) are pumped to mixer 1 (micro mixer 1) via pumps 1 and 2 for thorough mixing. After mixing, the mixture is directly fed into reactor 1 (reactor 1) through a connected pipeline for paraformaldehyde depolymerization at 55°C. The reaction liquid flowing out of reactor 1 is then thoroughly mixed with feed 3 (glycine 0.41 kg / L, flow ratio 1.1:1, retention time 12 min) pumped by pump 3 in mixer 2 and then directly fed into reactor 2 for addition reaction at 60°C. The reaction liquid flowing out of reactor 2 is then mixed with the connected pipeline... The feedwater flows into a buffer tank via a pipeline, and is then pumped by the fourth pump to mix with feed 5 (dimethyl phosphite, flow ratio 4:1, retention time 8 min) pumped by the fifth pump. After mixing, the feedwater directly enters reactor 3 via a connected pipeline for esterification at 60°C. The esterification reaction liquid flowing out of reactor 3 enters reactor 4 for further esterification at 75°C to ensure complete conversion of the reactants. The reaction liquid flowing out of reactor 4 passes through back pressure valve 1, which regulates the reaction pressure in reactors 3 and 4. The reaction liquid flowing out of back pressure valve 1 enters mix 4 and is mixed with feed 6 (35% hydrochloric acid, flow ratio 2:1, retention time 8 min) pumped by the sixth pump. After thorough mixing (retention time 2.5 min), the mixture enters reactor 5 for neutralization. The reaction solution is then directly fed into reactor 6 via a connected pipe, where a hydrolysis reaction occurs at 150°C for 2 min, while the temperature of the reaction solution is simultaneously increased. The reaction solution effluent from reactor 6 passes through back pressure valve 2, which regulates the reaction pressure in reactors 5 and 6, facilitating the removal efficiency of low-boiling-point solvents and compounds after entering reactor 1 in the continuous batch reactor. The effluent from reactor 6 enters reactor 1 from the bottom (temperature 110°C, retention time 35 min), where low-boiling-point solvents and compounds rapidly evaporate. The generated gas enters the condenser and collection device connected to reactor 1 via a pipeline. The remaining reaction liquid flows upward from the bottom of reactor 1, enters the upper outlet, and then enters the lower part of reactor 2 (temperature 130℃, retention time 40 min) through a connecting pipeline. The generated chloromethane and some of the solvent water are continuously removed. The remaining reaction liquid flows upward from the bottom of reactor 2, enters the upper outlet, and then enters the lower part of reactor 3 (temperature 140℃, retention time 50 min) through a connecting pipeline to continue the hydrolysis and deethanolination reaction until complete conversion. The reaction liquid enters a continuous crystallizer (temperature 65℃, retention time 15 min), where glyphosate is obtained by cooling and precipitation. The purity is greater than 96%. The glyphosate yield, expressed as glycine, is 83%.
[0028] Example 2
[0029] The prepared feed 1 (paraformaldehyde 0.32 kg / L) and feed 2 (triethylamine, flow ratio 2.5:1, retention time 6 min) are distributed and transported to mixer 1 (micro mixer 1) via pumps 1 and 2 for thorough mixing. After mixing, the mixture is directly fed into reactor 1 (reactor 1) through a connected pipeline for paraformaldehyde depolymerization reaction at 50°C. The reaction liquid flowing out of reactor 1 is thoroughly mixed with feed 3 (glycine 0.21 kg / L, flow ratio 1:1, retention time 10 min) transported by pump 3 in mixer 2 and then directly fed into reactor 2 for addition reaction at 65°C. The reaction liquid flowing out of reactor 2 is then mixed with the connected pipeline... The mixture flows into a buffer tank via a pipeline and is then pumped by the fourth pump to mix with material 5 (dimethyl phosphite, flow ratio 3.5:1, retention time 4 min) pumped by the fifth pump. After mixing, the mixture directly enters reactor 3 via a connected pipeline for esterification at 70°C. The esterification reaction liquid flowing out of reactor 3 enters reactor 4 for further esterification at 75°C to ensure complete conversion of the reactants. The reaction liquid flowing out of reactor 4 passes through back pressure valve 1, which regulates the reaction pressure in reactors 3 and 4. The reaction liquid flowing out of back pressure valve 1 enters mix 4 and mixes with material 6 (30.5% hydrochloric acid, flow ratio 2:1) pumped by the sixth pump. After thorough mixing (with a retention time of 2 min), the mixture enters reactor 5 for neutralization. The reaction solution is then directly fed into reactor 6 via a connected pipe, where a hydrolysis reaction occurs at 140°C for 1 min, while the temperature of the reaction solution is simultaneously increased. The reaction solution flowing out of reactor 6 passes through back pressure valve 2, which regulates the reaction pressure in reactors 5 and 6, facilitating the removal efficiency of low-boiling-point solvents and compounds after entering reactor 1 in the continuous batch reactor. The effluent from reactor 6 enters reactor 1 from the bottom (at a temperature of 100°C and a retention time of 30 min), where low-boiling-point solvents and compounds rapidly evaporate. The volatile gases enter the condenser and collection device connected to reactor 1 via a pipeline. The remaining reaction liquid flows upward from the bottom of reactor 1, enters the upper outlet, and then enters the lower part of reactor 2 (temperature 125℃, retention time 45min) through a connecting pipeline. Here, the generated chloromethane and some of the solvent water are continuously removed. The remaining reaction liquid flows upward from the bottom of reactor 2, enters the upper outlet, and then enters the lower part of reactor 3 (temperature 145℃, retention time 45min) through a connecting pipeline to continue the hydrolysis and deethanolination reaction until complete conversion. The reaction liquid enters a continuous crystallizer (temperature 70℃, retention time 12min), where glyphosate is obtained by cooling and precipitation. The purity is greater than 98%. The glyphosate yield, expressed as glycine, is 84%.
[0030] Example 3
[0031] The prepared feed 1 (paraformaldehyde 0.84 kg / L) and feed 2 (triethylamine, flow ratio 1.5:1, retention time 7 min) are distributed and transported to mixer 1 (micro mixer 1) via pumps 1 and 2 for thorough mixing. After mixing, the mixture is directly fed into reactor 1 (reactor 1) through a connected pipeline for paraformaldehyde depolymerization reaction at 55°C. The reaction liquid flowing out of reactor 1 is thoroughly mixed with feed 3 (glycine 0.45 kg / L, flow ratio 1.5:1, retention time 8 min) transported by pump 3 in mixer 2 and then directly fed into reactor 2 for addition reaction at 60°C. The reaction liquid flowing out of reactor 2 is then mixed with the connected pipeline... The feed flows into a buffer tank via a pipeline and is then pumped by the fourth pump to mix with feed 5 (dimethyl phosphite, flow ratio 3.0:1, retention time 8 min) pumped by the fifth pump. After mixing, the feed directly enters reactor 3 via a connected pipeline for esterification at 62°C. The esterification reaction liquid flowing out of reactor 3 enters reactor 4 for further esterification at 80°C, ensuring complete conversion of the reactants. The reaction liquid flowing out of reactor 4 passes through back pressure valve 1, which regulates the reaction pressure in reactors 3 and 4. The reaction liquid flowing out of back pressure valve 1 enters mix 4 and mixes with feed 6 (31.5% hydrochloric acid, flow ratio 2:1.3) pumped by the sixth pump. After thorough mixing (with a retention time of 1.5 min), the mixture enters reactor 5 for a neutralization reaction. The reaction solution is then directly fed into reactor 6 via a connected pipe, where a hydrolysis reaction occurs at 120°C for 0.8 min, simultaneously increasing the temperature of the reaction solution. The reaction solution effluent from reactor 6 passes through back pressure valve 2, which regulates the reaction pressure in reactors 5 and 6, facilitating the removal efficiency of low-boiling-point solvents and compounds after entering reactor 1 in the continuous batch reactor. The effluent from reactor 6 enters reactor 1 from the bottom (at 120°C with a retention time of 25 min), where low-boiling-point solvents and compounds rapidly evaporate. The volatile gases enter the condenser connected to reactor 1 via a pipeline. The remaining reaction liquid flows upward from the bottom of reactor 1, enters the upper outlet, and then enters the lower part of reactor 2 (temperature 135℃, retention time 40 min) through a connecting pipeline. The generated chloromethane and some of the solvent water are continuously removed. The remaining reaction liquid flows upward from the bottom of reactor 2, enters the upper outlet, and then enters the lower part of reactor 3 (temperature 150℃, retention time 42 min) through a connecting pipeline to continue the hydrolysis and deethanolination reaction until complete conversion. The reaction liquid enters a continuous crystallizer (temperature 68℃, retention time 15 min), where glyphosate is obtained by cooling and precipitation. The purity is greater than 97%. The glyphosate yield, expressed as glycine, is 83.5%.
[0032] Based on the innovative concept of this invention, any changes and modifications made to the embodiments, or equivalent structural or procedural transformations made using the content of this invention's specification and drawings, that directly or indirectly apply the above technical solutions to other related technical fields, are all included within the scope of protection of the claims of this invention.
Claims
1. A fully continuous glyphosate synthesis apparatus, characterized in that, A fully continuous chemical synthesis unit, consisting of 7 feed pumps, 4 micromixers, 6 microchannel reactors, 3 stirred tanks, 1 buffer tank, 2 back pressure valves, and 1 continuous crystallizer, is sequentially connected according to the glyphosate synthesis route to form a unit that matches the glyphosate synthesis route. The prepared first and second materials are respectively pumped to the first micro mixer for thorough mixing via the first and second pumps. After mixing, they are directly introduced into the first microchannel reactor via connecting pipes for depolymerization of paraformaldehyde. The reaction liquid flowing out of the first microchannel reactor is fully mixed with the third material delivered by the third pump in the second micro mixer and then directly enters the second microchannel reactor to carry out the addition reaction. The reaction liquid flowing out of the second microchannel reactor enters the buffer tank through the connecting pipe as the fourth material; the fourth material is transported to the third micro mixer by the fourth pump and mixed with the fifth material transported by the fifth pump. After mixing, it enters the third microchannel reactor and the fourth microchannel reactor in sequence through the connecting pipe to carry out the esterification reaction. The temperature in the fourth microchannel reactor is higher than that in the third microchannel reactor to promote the complete conversion of the reaction raw materials. The reaction liquid flowing out of the fourth microchannel reactor flows through the first back pressure valve, which regulates the reaction pressure in the third and fourth microchannel reactors. The reaction liquid flowing out of the first back pressure valve enters the fourth micro mixer and is fully mixed with the sixth material delivered by the sixth pump before entering the fifth microchannel reactor for neutralization reaction. The reaction solution flowing out of the fifth microchannel reactor directly enters the sixth microchannel reactor through the connecting pipe to carry out the hydrolysis reaction, while simultaneously increasing the temperature of the reaction solution; The effluent from the sixth microchannel reactor enters the first stirred tank through the second back pressure valve at the bottom. Low-boiling-point solvents and compounds evaporate rapidly, and the volatile gases enter a condensation and collection device connected to the pipeline of the first stirred tank. The remaining reaction liquid flows upward from the bottom of the first stirred tank, enters the upper outlet, and then enters the lower part of the second stirred tank through a connecting pipeline. The generated chloromethane and some of the solvent water are continuously removed. The remaining reaction liquid flows upward from the bottom of the second stirred tank, enters the upper outlet, and then enters the lower part of the third stirred tank through a connecting pipeline to continue the hydrolysis and alcohol decontamination reaction until complete conversion. The reaction liquid then enters the continuous crystallizer, where glyphosate is precipitated by cooling. The first and third pumps are peristaltic pumps for conveying slurry, while the second, fourth, fifth, sixth, and seventh pumps are plunger pumps for conveying solutions. The first to fourth micro mixers are micro mixers composed of four diamond-shaped tubular mixing components connected in series; the fluid channels of the diamond-shaped tubular components are circular or square, with a length of 1-100 cm and an applicable flow rate of 1-3000 mL / min; The second microchannel reactor is a rotating dynamic reactor. Its specific structure is as follows: it is a cylindrical cavity with a heat exchange fluid jacket on the cavity wall for heat flow; a central shaft is set inside the cylindrical cavity, and multiple stirring paddles are connected to the central shaft to enhance mass and heat transfer. The central shaft is driven by a motor with a rotation speed of 50-500 rpm. The cavity is cylindrical with a diameter of 3-60 cm and a length of 20-500 cm, and the applicable throughput is 10-50000 mL / min. The first, third, fourth, fifth, and sixth microchannel reactors are tubular microreactors containing multiple sequentially axially arranged square mixing components; the fluid channel length is 1-10000m, and the applicable throughput is 10-50000mL / min. The pressure range of the connecting pipelines for the first back pressure valve and the second back pressure valve is 0.1-2.0 MPa; The first, second, and third stirred tanks are stirred tanks equipped with a stirring paddle, a low-boiling-point distillate outlet, a heat exchange jacket, a heat exchange fluid inlet and outlet, and a material inlet and outlet. The three stirred tanks are connected in series by pipes to realize the flow of heat exchange fluid and material. The inner diameter of the stirred tank is 5-1000cm and the height is 5-1000cm. The continuous crystallizer is a tubular reactor with a mixing structure and jacketed heat exchange; the tubular reactor has an S-shaped pipe with a heat exchange jacket on the pipe wall for the heat exchange fluid to pass through; several evenly distributed spherical baffles are installed inside the pipe; the tubular reactor has an inner diameter of 2-20 cm, a length of 1-1000 m, and an applicable throughput of 10-5000 mL / min. The first material is a solution or slurry obtained by dissolving or dispersing paraformaldehyde in a solvent; the second material is a solution of alkali without solvent feeding or dissolved in a solvent; the third material is a solution or slurry obtained by dissolving or dispersing glycine in a solvent; the fourth material is an intermediate solution generated in the second microchannel reactor; the fifth material is a solution of dimethyl phosphite without solvent feeding or dissolved in a solvent; and the sixth material is a solution of acid without solvent feeding or dissolved in a solvent.
2. A synthesis method based on the glyphosate fully continuous synthesis apparatus according to claim 1, characterized in that, The specific steps are as follows: The prepared first and second materials are transported to the first micro mixer by the first pump and the second pump respectively for thorough mixing. After mixing, they are directly introduced into the first microchannel reactor through the connecting pipeline for depolymerization of paraformaldehyde. The reaction liquid flowing out of the first microchannel reactor is fully mixed with the third material delivered by the third pump in the second micro mixer and then directly enters the second microchannel reactor to carry out the addition reaction. The reaction liquid flowing out of the second microchannel reactor enters the buffer tank through the connecting pipe as the fourth material; the fourth material is transported to the third micro mixer by the fourth pump and mixed with the fifth material transported by the fifth pump. After mixing, it enters the third microchannel reactor directly through the connecting pipe to carry out the esterification reaction. The temperature in the fourth microchannel reactor is slightly higher than that in the third microchannel reactor to promote the complete conversion of the reaction raw materials. The reaction liquid flowing out of the fourth microchannel reactor flows through the first back pressure valve, which regulates the reaction pressure in the third and fourth microchannel reactors. The reaction liquid flowing out of the first back pressure valve enters the fourth micro mixer and is fully mixed with the sixth material delivered by the sixth pump before entering the fifth microchannel reactor for neutralization reaction. The reaction solution flowing out of the fifth microchannel reactor directly enters the sixth microchannel reactor through the connecting pipe to carry out the hydrolysis reaction, while simultaneously increasing the temperature of the reaction solution; The effluent from the sixth microchannel reactor enters the first stirred tank from the bottom. Low-boiling-point solvents and compounds evaporate rapidly. The volatile gases enter a condensation and collection device connected to the pipeline of the first stirred tank. The remaining reaction liquid flows upward from the bottom of the first stirred tank, enters the upper outlet, and then enters the lower part of the second stirred tank through a connecting pipeline. The generated chloromethane and some of the solvent water are continuously removed. The remaining reaction liquid flows upward from the bottom of the second stirred tank, enters the upper outlet, and then enters the lower part of the third stirred tank through a connecting pipeline to continue the hydrolysis and alcohol decontamination reaction. Until complete conversion, the reaction liquid enters the continuous crystallizer, where glyphosate is precipitated by cooling. Specifically, the temperature of the first microchannel reactor is controlled at 30-60℃ for a reaction time of 1-9 min; the temperature of the second microchannel reactor is controlled at 45-80℃ for a reaction time of 6-12 min; the temperature of the third microchannel reactor is controlled at 50-80℃ for a reaction time of 1-8 min; the temperature of the fourth microchannel reactor is controlled at 60-90℃ for a reaction time of 5-15 min; the temperature of the fifth microchannel reactor is controlled at 0-30℃ for a reaction time of 0.5-3 min; the temperature of the sixth microchannel reactor is controlled at 90-190℃ for a reaction time of 0.5-3 min; the temperature of the first stirred tank is controlled at 80-150℃ for a reaction time of 5-40 min; the temperature of the second stirred tank is controlled at 80-150℃ for a reaction time of 5-40 min; the temperature of the third stirred tank is controlled at 90-160℃ for a reaction time of 5-60 min; and the temperature of the continuous crystallizer is controlled at 0-80℃ for a residence time of 1-30 min.
Citation Information
Patent Citations
A continuous production apparatus and method for glyphosate
CN104163832B
Glyphosate synthesis technology and device
CN110862413A
Continuous synthesis method and system of glyphosate
CN111205319A
Continuous glyphosate reaction device
CN216630779U
Alkyl ester method glyphosate continuous production system and process
CN110922426A