A method for hydrolyzing and acidifying glyphosate

Abstract

The continuous reaction system of glyphosate raw materials, the glyphosate synthetic liquid storage tank is connected to the acid de-alcoholization reactor, the acid de-alcoholization reactor is provided with the first reaction functional section, the second reaction functional section, the third reaction functional section, and the fourth reaction functional section from top to bottom, the first reaction functional section is a packing section, and other adjacent reaction functional sections are separated by partitions, and the partitions cannot realize the up and down movement of materials. The top of the fourth reaction functional section is connected to the upper end of the third reaction functional section through a gas phase pipeline near the partition position; the top of the third reaction functional section is connected to the upper end of the second reaction functional section through a gas phase pipeline near the partition position. In each functional section, the gas phase of each level flows from bottom to top to the upper section by pressure difference, and maintains a certain height of gas-liquid contact in the upper section for mass transfer and heat transfer, and strengthens gas-liquid mass transfer and heat transfer through stripping and aeration, and plays a gas stripping role, and quickly removes formaldehyde, methylal, chloromethane and other materials in the material.

Description

Technical Field

[0001] The invention relates to the technical field of glyphosate production, in particular to a continuous reaction system for a glyphosate raw material drug in a continuous acid-dealcoholization process of glyphosate. Background Art

[0002] Glyphosate is a highly efficient, low-toxic, broad-spectrum, lethal, non-selective herbicide with excellent biological properties. It is the herbicide variety with the largest production volume in the world. At present, there are two mainstream production processes for glyphosate in China: the alkyl ester method (glycine method) and the iminodiacetic acid method (IDA method). The production process abroad is mainly the iminodiacetic acid method of Monsanto Company in the United States. 70% of my country's glyphosate production capacity is produced by the alkyl ester method with glycine and dimethyl phosphite as the main raw materials. This method uses methanol as the reaction solvent. In the presence of the catalyst triethylamine, glycine, polyformaldehyde, and dimethyl phosphite react to obtain a synthetic liquid (glyphosate synthetic liquid). After a certain proportion of the synthetic liquid is mixed with hydrochloric acid, steam is used to heat it to the reaction endpoint temperature. As the temperature rises, hydrolysis and acidolysis reactions occur to generate glyphosate and by-products methylal and chloromethane. Methylal, methanol, chloromethane and other steam are evaporated from the reactor. The remaining liquid phase after the acid hydrolysis reaction is glyphosate slurry, which is crystallized, separated, washed and dried to obtain glyphosate technical that meets national standards.

[0003] The gaseous tail gas of the acidolysis reaction (i.e., the light component extracted by the fan) is mainly composed of water, methylal, methanol, hydrogen chloride and methyl chloride mixture. The tail gas is sent to the gaseous tail gas recovery device for recovery and treatment. The recovery process is referred to as solvent recovery and methyl chloride recovery in the glyphosate industry: the distilled mixed gas is condensed in multiple stages, the condensate (diluted methanol) is sent to the solvent recovery device, and the non-condensable gas is treated by the methyl chloride recovery device; or the high-temperature tail gas is condensed or absorbed to recover dilute hydrochloric acid; or the distilled mixed gas is first neutralized in a neutralization tower, and the neutralized gas is used to recover methanol and methylal, and the non-condensable gas is treated by the methyl chloride recovery device. Methanol is reused as a solvent in the glyphosate synthesis process, and methylal and methyl chloride are sold as by-products.

[0004] The production of glyphosate by the glycine method has a history of more than 30 years. The processes of solvent recovery, triethylamine recovery, and methyl chloride recovery have been continuously realized in the industry. Due to the limitations of factors such as the characteristics of the glyphosate acidolysis reaction, the acidolysis dealcoholization process is still an intermittent stirred tank method.

[0005] The intermittent hydrolysis process of glyphosate has the following problems: 1. Low production efficiency, high comprehensive energy consumption, and high labor intensity of workers. 2. The capacity of a single set of equipment is small, the number of reactors per unit production capacity is large, and there are many instrument control points. There is a lack of effective continuity before and after, and there are problems such as unstable product quality caused by human factors in operation, which also restricts the expansion of production equipment and the improvement of intrinsic safety. Continuous production of glyphosate can completely overcome these shortcomings through automated control. Therefore, the development of a continuous acid-dehydrolysis device for glyphosate is one of the main research directions of glyphosate production enterprises.

[0006] Patent CN 111205319 A discloses a continuous synthesis method and system of glyphosate by glycine method, wherein the acidified liquid obtained by acidification of the synthetic liquid is subjected to primary hydrolysis reaction and secondary hydrolysis reaction, and the slurry after the secondary hydrolysis reaction is crystallized to obtain glyphosate. The primary hydrolysis reaction device comprises a primary hydrolysis reaction tower and a primary hydrolysis reaction kettle; the secondary hydrolysis reaction device comprises a secondary hydrolysis reaction kettle, and the gas outlet of the secondary hydrolysis reaction device is connected to a hydrolysis tail gas condenser. The tail gas of the primary hydrolysis reaction device and the condensate and tail gas of the primary hydrolysis reaction device are sent to a methanol recovery device for treatment. The hydrolysis reaction device of the method is divided into multiple stages, the device is complex, the process is long, the acidolysis reaction time is long, and the yield is not high. Moreover, the method still relies on an enamel kettle as a reactor. Summary of the invention

[0007] In view of the above technical problems, the present invention provides a continuous reaction system for glyphosate raw materials, wherein a glyphosate acidolysis liquid storage tank is connected to an acidolysis deethanolation reactor, and the acidolysis deethanolation reactor is provided with a first reaction functional section, a second reaction functional section, a third reaction functional section, and a fourth reaction functional section from top to bottom, wherein the first reaction functional section is a packing section, and other adjacent reaction functional sections are separated by partitions, and the partitions cannot realize the up and down movement of materials.

[0008] A method for hydrolyzing and acidifying glyphosate, wherein the material flow in the continuous hydrolyzing and acidifying process comprises the following steps:

[0009] After the glyphosate acid hydrolyzate enters the first reaction functional section of the acid de-alcoholization reactor, the liquid phase enters the second reaction functional section through the filler of the first reaction functional section;

[0010] 10-100% volume fraction of the liquid phase in the second reaction functional section is pumped into the middle of the second reaction functional section again by spraying through a circulation pump to achieve circulation;

[0011] After the reaction liquid reacts in the second reaction functional section, part of the liquid phase flows from the second functional reaction section to the Nth reaction functional section;

[0012] 10-100% volume fraction of the liquid phase in the Nth reaction functional section is pumped into the heater through a circulation pump for heating and then pumped into the middle of the Nth reaction functional section again in a spraying manner to achieve circulation;

[0013] After the reaction liquid reacts in the Nth reaction functional section, part of the liquid phase flows from the Nth reaction functional section to the N+1th reaction functional section, and 10-100% of the liquid phase by volume in the fourth reaction functional section is pumped into the second heater for heating through a circulation pump, and then is again pumped into the N+1th reaction functional section in a spraying manner to achieve circulation; a reaction is carried out in the N+1th reaction functional section to obtain a glyphosate slurry, wherein N is 2-10.

[0014] When N is 3, the material flow steps in the continuous hydrolysis acid dealcoholization process are:

[0015] After the glyphosate acid hydrolyzate enters the first reaction functional section of the acid de-alcoholization reactor, the liquid phase enters the second reaction functional section through the filler of the first reaction functional section;

[0016] 10-100% volume fraction of the liquid phase in the second reaction functional section is pumped into the middle of the second reaction functional section again by spraying through a circulation pump to achieve circulation;

[0017] After the reaction liquid reacts in the second reaction functional section, part of the liquid phase flows from the second functional reaction section to the third reaction functional section;

[0018] 10-100% volume fraction of the liquid phase in the third reaction functional section is pumped into the heater through a circulation pump for heating and then pumped into the middle of the third reaction functional section again in a spraying manner to achieve circulation, while controlling the reaction temperature of the third reaction functional section to be 85-115°C;

[0019] After the reaction liquid reacts in the third reaction functional section, part of the liquid phase flows from the third reaction functional section to the fourth reaction functional section, and 10-100% of the liquid phase by volume in the fourth reaction functional section is pumped into the second heater for heating through a circulation pump, and then pumped into the fourth reaction functional section again in a spraying manner to achieve circulation, while controlling the reaction temperature of the fourth reaction functional section to 115-140° C.; a reaction is carried out in the fourth reaction functional section to obtain a glyphosate slurry.

[0020] The specific gravity of glyphosate acid hydrolyzate is 0.92-1.12.

[0021] The gas phase of the fourth reaction functional section enters the middle of the third reaction functional section in the form of gas injection or directly; the gas phase of the third reaction functional section enters the middle of the second reaction functional section directly or in the form of injection.

[0022] The gas phase of the fourth reaction functional section enters the gas recovery device; the gas phase of the third reaction functional section enters the gas recovery device.

[0023] The gas phase of the fourth reaction functional section directly enters the middle of the third reaction functional section; the gas phase of the third reaction functional section enters the second reaction functional section in the form of gas injection.

[0024] The flow rate of glyphosate synthesis liquid entering the first reaction functional section of the acid dealcoholization reactor is a, and the flow rate range of a is from 1m 3 / h-150m 3 / h;

[0025] The flow rate of the reaction liquid entering the second reaction functional section through the filler of the first reaction functional section is b, and the flow rate of b is 10-100% of a;

[0026] After the reaction liquid reacts in the second reaction functional section, the liquid phase in the second reaction functional section enters the third reaction functional section through the liquid phase pipeline at a flow rate of c for reaction, and the flow rate of c is 10-90% of a;

[0027] After the reaction liquid reacts in the third reaction functional section, the liquid phase in the third reaction functional section enters the fourth reaction functional section through the liquid phase pipeline at a flow rate d for reaction, and the flow rate d is 10-70% of a.

[0028] The liquid phase in the second reaction functional section enters the third reaction functional section from the upper 1 / 5-1 / 8 of the second reaction functional section and the bottom of the second reaction functional section for reaction; wherein, the flow rate of the upper 1 / 5-1 / 8 of the second reaction functional section entering the third reaction functional section is e, and the flow rate of e is 10-100% of c; the flow rate of the bottom of the second reaction functional section entering the third reaction functional section is f, and the flow rate of f is 10-100% of c; and e+f=b.

[0029] The liquid phase in the third reaction functional section enters the fourth reaction functional section from the upper 1 / 5-1 / 8 of the third reaction functional section and the bottom of the third reaction functional section for reaction; wherein, the flow rate of the upper 1 / 5-1 / 8 of the third reaction functional section entering the fourth reaction functional section is g, and the flow rate of g is 10-100% of c, and the flow rate of the bottom of the third reaction functional section entering the fourth reaction functional section is h, and the flow rate of h is 10-100% of d, and g+h=c.

[0030] The temperature in the second reaction functional section is controlled at 55-85°C and the pressure is -10kpa~5kpa; the temperature in the third reaction functional section is controlled at 85-115°C and the pressure is -5~50kPa; the temperature in the fourth reaction functional section is controlled at 115-140°C and the pressure is -2-50kPa.

[0031] The continuous synthesis method of glyphosate provided by the present invention is achieved by the following specific technical scheme:

[0032] The synthetic liquid is fully mixed with a certain amount of acid in advance to obtain a mixed acid solution for standby use. The mixing process can be carried out in a stirred reactor (intermittent mixing) or continuously mixed by a pipeline mixer.

[0033] The mixed acid solution is continuously pumped into the reactor from the top feed port and enters the tower through the liquid distributor.

[0034] Preferably, the acid is a methanol solution of hydrochloric acid or hydrogen chloride.

[0035] Preferably, the stirred reactor (mixing reactor) is replaced by a static mixer, and the continuous and stable synthetic liquid feed and the hydrochloric acid added in proportion according to the process requirements enter the static mixer together for continuous mixing.

[0036] Preferably, the mixed acid liquid is preheated using a heat source such as steam condensed water produced as a byproduct of the heat exchanger in the third and fourth reaction functional sections of this scheme before entering the tower.

[0037] In each functional section, the liquid phase with the light components removed overflows from top to bottom to the next section by gravity. The material vapor from the second-stage reaction functional section at the bottom of the tower contacts the mixed acid liquid entering from the top of the tower in countercurrent in the first-stage reaction functional section for mass transfer, heat exchange, reaction and degassing. After preheating and preliminary dealcoholization in the first-stage reaction functional section, the liquid phase enters the second-stage reaction functional section. The temperature of this section is maintained by the heat energy brought in by the higher-temperature non-condensable gas and saturated steam generated in the next-stage reaction functional section, and is balanced with the heat energy consumed by the vaporization of methanol and water in this section. The volatile methylal and methanol components are vaporized and leave the reactor with the rising non-condensable gas. The reaction liquid then enters the third and fourth-stage reaction functional sections through overflow and underflow in turn for temperature reaction. The temperature of the third-stage reaction functional section is jointly maintained and controlled by the higher-temperature non-condensable gas and saturated steam generated in the fourth-stage reaction functional section and the heater on the external circulation pipeline; the temperature of the fourth-stage reaction functional section is maintained and controlled by the heater on the external circulation pipeline;

[0038] Alternatively, part of the liquid phase can flow to the next stage through the underflow pipe as an auxiliary liquid flow, and the flow rate can be adjusted by an automatic control valve to balance the liquid level and pressure of each reaction functional area. As a special case, when the underflow pipe valve opening is 0% or the reactor is not provided with an underflow passage at this stage, all the liquid flows through the overflow pipe into the next stage reaction functional section.

[0039] When sieve plates are used to divide functional areas, a small amount of liquid flows through the sieve holes of the tower plate to the next section.

[0040] In each functional section, the gas phase of each level flows from bottom to top to the upper section by pressure difference, and maintains a certain height of gas-liquid contact in the upper section for mass transfer and heat transfer. The gas-liquid mass transfer and heat transfer are enhanced through stripping and aeration, and the gas stripping effect is played to quickly remove formaldehyde, methylal, methyl chloride and other materials in the material.

[0041] The light components in the reaction liquid (methanol, water, hydrogen chloride, and methylal and chloromethane generated during the acidolysis reaction) form a gas phase and are discharged from the upper gas phase pipes of the first reaction functional section, the second reaction functional section, the third reaction functional section, and the fourth reaction functional section. Among them, the upper part of the first reaction functional section is the top of the tower. The gas phase tail gas generated in the second reaction functional section is discharged from the top of the tower after mass transfer and heat transfer in the first reaction functional section.

[0042] Alternatively, part of the gas phase can be directly sent to the gas phase main pipe through the gas phase pipeline as an auxiliary gas flow, and the flow rate can be adjusted by an automatic control valve to balance the pressure of each reaction functional zone. As a special case, when the valve opening of the auxiliary gas flow pipeline of the current reaction section is 0% or the reactor is not provided with an auxiliary gas flow passage, the gas flow all flows from bottom to top to the next reaction functional section by the pressure difference.

[0043] The gaseous tail gas of the above acidolysis reaction (i.e., the light component extracted by the fan) is mainly composed of water, methylal, methanol, hydrogen chloride and methyl chloride mixture, which is sent to the solvent recovery and methyl chloride recovery steps to recover methanol, methylal and methyl chloride.

[0044] In the second, third and fourth stage reaction functional sections, circulation pumps are respectively provided to force the reaction liquid to circulate, and microscopic mixing is achieved through nozzles and guide tube structures.

[0045] In the third and fourth reaction functional sections, an external heater is installed on the circulation pipeline, and the reaction liquid is heated by the heater before the circulation reflux to maintain the reaction liquid at the specified temperature. In the third reaction functional section, the reaction liquid is fully circulated. In the fourth reaction functional section, part of the material is refluxed and part of the material is extracted.

[0046] The reaction liquid is treated in a continuous acid dealcoholization tower to realize an acid dealcoholization reaction in a stirred tank process to generate glyphosate and obtain a glyphosate feed liquid.

[0047] In the process of acid dealcoholization, optionally, a certain amount of acid is added to any one or several of the second, third, and fourth reaction functional sections in the reactor to improve the hydrolysis and acidolysis efficiency. Optionally, a certain amount of process water is added to any one or several of the second, third, and fourth reaction functional sections in the reactor to adjust the viscosity and solid content of the reaction system. At the same time, the vaporization of water will produce a gas lift effect, further improving the dealcoholization and deacidification efficiency.

[0048] Functionally, the reactor described in this scheme realizes the composite functions of plug flow and full mixed flow reactor in one reactor. By designing different functional sections and optimizing the acidolysis and hydrolysis chemical reaction process, in each functional section, the gas phases of each level flow from bottom to top to the upper section by pressure difference, and maintain a certain height of gas-liquid countercurrent contact in the upper section for mass transfer and heat transfer, and the gas-liquid mass transfer and heat transfer are enhanced by stripping and aeration. In the last three reaction functional sections, macroscopic mixing is achieved by the large circulation of the pump and the microscopic mixing structure to produce a strong surface renewal effect, and microscopic mixing is achieved by the nozzle and guide tube structure to promote the mixing effect. Therefore, the "re-mixing" problem faced in the process of continuous intermittent stirring tank process improvement is solved, and the problems of incomplete reaction of the original continuous technology (appearance of raw materials) are solved. Therefore, the acidolysis and hydrolysis chemical reaction process is fully and thoroughly, the continuous operation is stable and reliable, and all acidolysis reactions are completed in one reactor, and no enamel kettle is required for further auxiliary reaction; compared with the original intermittent stirring process, the yield is high, the heat is stepped, and the steam energy consumption is low.

[0049] In the case of the sieve plate, the top of the fourth reaction functional section is connected to the gas recovery device via a gas phase pipeline near the partition; the top of the third reaction functional section is connected to the gas recovery device via a gas phase pipeline near the partition, and the first reaction functional section is connected to the gas recovery device via a gas phase pipeline.

[0050] In each functional section, the liquid phase with light components removed overflows from top to bottom to the next section by gravity. The material vapor from the second-stage reaction functional section at the bottom of the tower contacts the mixed acid liquid entering from the top of the tower in the first-stage reaction functional section in countercurrent to carry out mass transfer, heat exchange, reaction and degassing. After preheating and preliminary dealcoholization in the first-stage reaction functional section, the liquid phase enters the second-stage reaction functional section. The temperature of this section is maintained by the heat energy brought in by the higher temperature non-condensable gas and saturated steam generated in the next-stage reaction functional section, and is balanced with the heat energy consumed by the vaporization of methanol and water in this section. The volatile methylal and methanol components are vaporized and leave the reactor with the rising non-condensable gas. The reaction liquid then enters the third and fourth-stage reaction functional sections through overflow and underflow in turn to heat up and react. The temperature of the third-stage reaction functional section is jointly maintained and controlled by the higher temperature non-condensable gas and saturated steam generated in the fourth-stage reaction functional section and the heater on the external circulation pipeline; the temperature of the fourth-stage reaction functional section is maintained and controlled by the heater on the external circulation pipeline.

[0051] Alternatively, part of the liquid phase can flow to the next stage through the underflow pipe as an auxiliary liquid flow, and the flow rate can be adjusted by an automatic control valve to balance the liquid level and pressure of each reaction functional area. As a special case, when the underflow pipe valve opening is 0% or the reactor is not provided with an underflow passage at this stage, all the liquid flows through the overflow pipe into the next stage reaction functional section.

[0052] When sieve plates are used to divide functional areas, a small amount of liquid flows through the sieve holes of the tower plate to the next section.

[0053] In each functional section, the gas phase of each level flows from bottom to top to the upper section by pressure difference, and maintains a certain height of gas-liquid contact in the upper section for mass transfer and heat transfer. The gas-liquid mass transfer and heat transfer are enhanced through stripping and aeration, and the gas stripping effect is played to quickly remove formaldehyde, methylal, methyl chloride and other materials in the material.

[0054] The light components in the reaction liquid (methanol, water, hydrogen chloride, and methylal and chloromethane generated during the acidolysis reaction) form a gas phase and are discharged from the upper gas phase pipes of the first reaction functional section, the second reaction functional section, the third reaction functional section, and the fourth reaction functional section. Among them, the upper part of the first reaction functional section is the top of the tower. The gas phase tail gas generated in the second reaction functional section is discharged from the top of the tower after mass transfer and heat transfer in the first reaction functional section.

[0055] Alternatively, part of the gas phase can be directly sent to the gas phase main pipe through the gas phase pipeline as an auxiliary gas flow, and the flow rate can be adjusted by an automatic control valve to balance the pressure of each reaction functional zone. As a special case, when the valve opening of the auxiliary gas flow pipeline of the current reaction section is 0% or the reactor is not provided with an auxiliary gas flow passage, the gas flow all flows from bottom to top to the next reaction functional section by the pressure difference.

[0056] The "re-mixing" problem faced in the process of continuous batch stirring tank process improvement has been solved, and the problems of incomplete reaction (raw materials) of the original continuous technology have been solved. Therefore, the acid hydrolysis and hydrolysis chemical reaction process is fully and thoroughly, the continuous operation is stable and reliable, and the entire acid hydrolysis reaction is completed in one reactor, and no enamel kettle is required for further auxiliary reaction; compared with the original batch stirring process, the yield is high, the heat is cascaded, and the steam energy consumption is low. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 The present invention is a flow chart of the hydrolysis and acid dealcoholization method of glyphosate of Example 1, wherein: 1. a glyphosate synthesis liquid storage tank; 2. an acid dealcoholization reactor; 3. a first reaction functional section; 4. a second reaction functional section; 5. a third reaction functional section; 6. a fourth reaction functional section; 7. a heater one; 8. a heater two; 9. a gas recovery device; 10. a crystallizer; 11-1, 11-2, 11-3, 11-4, 11-5, and 11-6 are all circulation pumps; 12. a sieve plate; and 13. a spray device.

[0058] Figure 2The present invention is a flow chart of the hydrolysis and acid dealcoholization method of glyphosate of Example 2, wherein: 1'. glyphosate synthesis liquid storage tank; 2'. acid dealcoholization reactor; 3'. first reaction functional section; 4'. second reaction functional section; 5'. third reaction functional section; 6'. fourth reaction functional section; 7'. heater one; 8'. heater two; 9'. gas recovery device; 10'. crystallizer; 11-1', 11-2', 11-3', 11-4', 11-5', 11-6' are all circulation pumps; 12'. sieve plate; 13'. spray device.

[0059] Figure 3 This is the method for hydrolysis and acid dealcoholization of glyphosate of Example 3, wherein: 1". glyphosate synthesis liquid storage tank; 2". acid dealcoholization reactor; 3". first reaction functional section; 4". second reaction functional section; 5". third reaction functional section; 6". fourth reaction functional section; 7". heater one; 8". heater two; 9". gas recovery device; 10". crystallizer; 11-1", 11-2", 11-3", 11-4", 11-5", 11-6" are all circulation pumps; 12". sieve plate; 13". spray device; 14". acid storage tank. DETAILED DESCRIPTION

[0060] Glyphosate mixed acid solution is a mixed acid solution obtained by acidifying a synthetic liquid during the continuous synthesis of glyphosate by the glycine method. For example, references CN1037396A and CN111205319A all obtained glyphosate mixed acid solution. This glyphosate mixed acid solution is a mixed acid solution that is difficult to handle and is well known to those skilled in the art.

[0061] Example 1

[0062] The filler of the present invention includes metallic or non-metallic regular or irregular fillers. Specifically, regular corrugated fillers 350Y are used in this embodiment.

[0063] Glyphosate mixed acid solution at 10m 3 / h speed into the first reaction functional section of the acid dealcoholization reactor, in which the liquid phase operating temperature is controlled at 40°C; the liquid phase enters the second reaction functional section through the filler of the first reaction functional section, and enters the third and fourth reaction functional sections through the sieve plate. By controlling the sieve plate aperture, the reaction liquid flow rate through the sieve plate is about 10m 3 / h. At this time, by measuring the liquid level height of each section in the tower, the reaction liquid flow rate from the second reaction section to the third reaction section through the sieve plate is about 8m 3 / h, and the reaction liquid flow rate from the third reaction section to the fourth reaction section through the sieve plate is about 5m 3 / h; control the flow rate of the second, third and fourth stage circulation pumps to 9m 3 / h for the full circulation of the second, third and fourth stage reaction liquids, and the temperatures of the second, third and fourth stages are controlled at 70℃, 100℃ and 130℃; the reaction liquid stays in the acid de-alcoholization reactor for 8-10 hours; the gas phase of the fourth reaction functional section enters the third reaction functional section, the gas phase of the third reaction functional section enters the second reaction functional section, and the gas phase of the second reaction functional section is connected to the gas recovery device through the gas phase pipeline through the first reaction functional section. At 72h, the flow rate of the extracted glyphosate slurry is 3.5m 3 / h, the glyphosate content was 23.02% and the total yield was 86.25%.

[0064] Example 2

[0065] The filler described in the present invention includes metallic or non-metallic regular or irregular fillers. Specifically, regular corrugated fillers 350Y are used in this embodiment.

[0066] Glyphosate mixed acid solution at 10m 3 / h speed into the first reaction functional section of the acid dealcoholization reactor, in which the liquid phase operating temperature is controlled at 40°C; the liquid phase enters the second reaction functional section through the filler of the first reaction functional section, and enters the third and fourth reaction functional sections through the sieve plate. By controlling the sieve plate aperture, the reaction liquid flow rate through the sieve plate is about 10m 3 / h. At this time, by measuring the liquid level height of each section in the tower, the reaction liquid flow rate from the second reaction section to the third reaction section through the sieve plate is about 7.5m 3 / h, and the reaction liquid flow rate from the third reaction section to the fourth reaction section through the sieve plate is about 4.5m 3 / h; control the flow rate of the second, third and fourth stage circulation pumps to 9m 3 / h to carry out the full circulation of the second, third and fourth stage reaction liquids, and control the temperatures of the second, third and fourth stages to 75℃, 110℃ and 135℃; the reaction liquid stays in the acid de-alcoholization reactor for 8-10 hours; the gas phase of the fourth reaction functional section enters the third reaction functional section, the gas phase of the third reaction functional section enters the second reaction functional section, and the gas phase of the second reaction functional section is connected to the gas recovery device through the gas phase pipeline through the first reaction functional section. At 72h, the flow rate of the extracted glyphosate slurry is 3.2m 3 / h, the glyphosate content was 23.46%, and the total yield was 87.34%.

[0067] Example 3

[0068] The filler described in the present invention includes metallic or non-metallic regular or irregular fillers. Specifically, regular corrugated fillers 350Y are used in this embodiment.

[0069] Glyphosate mixed acid solution at 2.5m 3 / h speed into the first reaction functional section of the acid dealcoholization reactor, the liquid phase operating temperature in the first reaction functional section of the reactor is controlled at 40 ° C; the liquid phase enters the second reaction functional section through the filler of the first reaction functional section, and enters the third and fourth reaction functional sections through the sieve plate. By controlling the aperture of the sieve plate, the reaction liquid flow rate through the sieve plate is about 1m 3 / h. After the reaction liquid reacts in the second reaction section for about 2 hours, the liquid level rises to the overflow pipe and enters the third reaction functional section with a flow rate of 1.2m 3 / h; after the reaction liquid reacts in the third reaction section for about 4 hours, it enters the fourth reaction functional section through the overflow pipe, with a flow rate of 0.4m 3 / h; control the flow rate of the second, third and fourth stage circulation pumps to 1m 3 / h for the full circulation of the second, third and fourth stage reaction liquids, and the temperatures of the second, third and fourth stages are controlled at 70℃, 100℃ and 130℃; the reaction liquid stays in the acid de-alcoholization reactor for 8-10 hours; the gas phase of the fourth reaction functional section enters the third reaction functional section, the gas phase of the third reaction functional section enters the second reaction functional section, and the gas phase of the second reaction functional section is connected to the gas recovery device through the gas phase pipeline through the first reaction functional section. At 35 days, the flow rate of the extracted glyphosate slurry is 0.75m 3 / h, the glyphosate content was 23.75%, and the total yield was 88.62%.

[0070]

[0071]

[0072] Example 4

[0073] The method steps are the same as those in Example 2. If the heater temperature is too low, resulting in the temperature of the fourth functional stage being lower than the reaction endpoint temperature of 140°C, the glyphosate content in the reaction output is low, and the content can only reach 11.62%. The yield is as low as 42.55%, and the cost is too high.

[0074] The method steps are the same as those in Example 2. If the temperature of the heater is too high, causing the temperature of the fourth functional section to be higher than the reaction endpoint temperature of 140°C, the material in the fourth functional section will become gelatinous, causing the reaction tower to be blocked, the pressure in the tower to increase, and a safety accident to occur.

[0075] Example 5

[0076] The filler of the present invention includes metallic or non-metallic regular or irregular fillers. Specifically, regular corrugated fillers 350Y are used in this embodiment.

[0077] Glyphosate mixed acid solution at 2.5m 3 / h speed into the first reaction functional section of the acid dealcoholization reactor, the liquid phase operating temperature in the first reaction functional section of the reactor is controlled at 40 ° C; the liquid phase enters the second reaction functional section through the filler of the first reaction functional section, and enters the third and fourth reaction functional sections through the sieve plate. By controlling the aperture of the sieve plate, the reaction liquid flow rate through the sieve plate is about 1m 3 / h. After the reaction liquid reacts in the second reaction section for about 2 hours, the liquid level rises to the overflow pipe and enters the third reaction functional section with a flow rate of 1.2m 3 / h; after the reaction liquid reacts in the third reaction section for about 4 hours, it enters the fourth reaction functional section through the overflow pipe, with a flow rate of 0.5m 3 / h; control the flow rate of the second, third and fourth stage circulation pumps to 1m 3 / h for full circulation of the second, third and fourth stage reaction liquids, and control the temperatures of the second, third and fourth stages to 70°C, 100°C and 130°C. Control the fourth reaction stage gas phase to the third reaction stage and the tail gas recovery valve to be fully opened, and the measured flow rate of the fourth reaction functional stage gas phase entering the third reaction functional stage is 0.47m 3 / h, the flow rate connected to the tail gas recovery is about 0.53m 3 / h; control the third reaction stage gas phase to the second reaction stage and tail gas recovery valve to be fully opened, and the measured flow rate of the third reaction functional stage gas phase entering the second reaction functional stage is 0.14m 3 / h, the flow rate connected to the tail gas recovery is about 0.16m 3 / h; the flow rate of the first section of tail gas pipe at the top of the tower is 0.71m 3 / h. The reaction liquid stays in the acid de-alcoholization reactor for 8-10 hours. At 72h, the flow rate of glyphosate slurry produced is 0.78m 3 / h, the glyphosate content was 22.86%, and the total yield was 85.76%.

Claims

1. A method for hydrolyzing and acidifying glyphosate, characterized in that: The material flow in the continuous hydrolysis acid dealcoholization process includes the following steps: After the glyphosate acid hydrolyzate enters the first reaction functional section of the acid de-alcoholization reactor, the liquid phase enters the second reaction functional section through the filler of the first reaction functional section; 10-100% volume fraction of the liquid phase in the second reaction functional section is pumped into the middle of the second reaction functional section again by a circulation pump in a spraying manner to achieve circulation; After the reaction liquid reacts in the second reaction functional section, part of the liquid phase flows from the second functional reaction section to the third reaction functional section; 10-100% volume fraction of the liquid phase in the third reaction functional section is pumped into the heater through a circulation pump for heating, and then pumped into the middle of the third reaction functional section again in a spraying manner to achieve circulation; After the reaction liquid reacts in the third reaction functional section, part of the liquid phase flows from the third reaction functional section to the fourth reaction functional section, and 10-100% of the liquid phase by volume in the fourth reaction functional section is pumped into the second heater through a circulation pump for heating, and then pumped into the fourth reaction functional section again in a spraying manner to achieve circulation; react in the fourth reaction functional section to obtain glyphosate slurry; The temperature in the second reaction functional section is controlled at 55-85°C and the pressure is -10kpa~5kpa; the temperature in the third reaction functional section is controlled at 85-115°C and the pressure is -5~50 kPa; the temperature in the fourth reaction functional section is controlled at 115-140°C and the pressure is -2-50kPa; The glyphosate acidolysis liquid storage tank is connected to the acido dealcoholization reactor, and the acido dealcoholization reactor is provided with a first reaction functional section, a second reaction functional section, a third reaction functional section, and a fourth reaction functional section from top to bottom. The first reaction functional section is a packing section, and other adjacent reaction functional sections are separated by partitions, and the partitions cannot realize the up and down movement of materials.

2. The method for hydrolyzing and acidifying glyphosate according to claim 1, characterized in that: The specific gravity of the glyphosate acid hydrolyzate is 0.92-1.12, and the filler is a perforated plate corrugated structured filler 150Y, 250Y, 350Y, 450Y.

3. The method for hydrolyzing and acidifying glyphosate according to claim 1, characterized in that: The gas phase of the fourth reaction functional section enters the middle of the third reaction functional section in the form of gas injection or directly; the gas phase of the third reaction functional section enters the middle of the second reaction functional section directly or in the form of injection.

4. The method for hydrolyzing and acidifying glyphosate according to claim 1, characterized in that: The gas phase of the fourth reaction functional section enters the gas recovery device; the gas phase of the third reaction functional section enters the gas recovery device.

5. The method for hydrolyzing and acidifying deethanolation of glyphosate according to claim 1, characterized in that: Part of the gas phase of the fourth reaction functional section enters the middle of the third reaction functional section in the form of gas injection, and part enters the gas recovery device; part of the gas phase of the third reaction functional section enters the second reaction functional section, and part enters the gas recovery device.

6. The method for hydrolyzing and acidifying glyphosate according to claim 1, characterized in that: The flow rate of the glyphosate synthesis liquid entering the first reaction functional section of the acid de-alcoholization reactor is a, and the flow rate of a ranges from 10m3 / h to 150m3 / h; The flow rate of the reaction liquid entering the second reaction functional section through the filler of the first reaction functional section is b, and the flow rate of b is 10-100% of a; After the reaction liquid reacts in the second reaction functional section, the liquid phase in the second reaction functional section enters the third reaction functional section through the liquid phase pipeline at a flow rate of c for reaction, and the flow rate of c is 10-90% of a; After the reaction liquid reacts in the third reaction functional section, the liquid phase in the third reaction functional section enters the fourth reaction functional section through the liquid phase pipeline at a flow rate d for reaction, and the flow rate d is 10-70% of a.

7. The method for hydrolyzing and acidifying glyphosate according to claim 6, characterized in that: The liquid phase in the second reaction functional section enters the third reaction functional section from the upper 1 / 5-1 / 8 of the second reaction functional section and the bottom of the second reaction functional section for reaction; wherein, the flow rate of the upper 1 / 5-1 / 8 of the second reaction functional section entering the third reaction functional section is e, and the flow rate of e is 10-100% of c; the flow rate of the bottom of the second reaction functional section entering the third reaction functional section is f, and the flow rate of f is 10-100% of c; and e+f=c.

8. The method for hydrolyzing and acidifying glyphosate according to claim 7, characterized in that: The liquid phase in the third reaction functional section enters the fourth reaction functional section from the upper 1 / 5-1 / 8 of the third reaction functional section and the bottom of the third reaction functional section for reaction; wherein, the flow rate of the upper 1 / 5-1 / 8 of the third reaction functional section entering the fourth reaction functional section is g, and the flow rate of g is 10-100% of d, and the flow rate of the bottom of the third reaction functional section entering the fourth reaction functional section is h, and the flow rate of h is 10-100% of d, and g+h=d.

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