Glyphosate active compound catalytic synthesis device

Abstract

The utility model discloses a glyphosate technical catalytic synthesis device. The bottom of a reaction kettle 1 is connected with a reaction kettle 2 through a pipeline; the bottom of the reaction kettle 2 is connected with the extraction kettle; the upper part of the extraction kettle is connected with an extraction phase analysis separation tank through a pipeline; the lower part of the extraction kettle is connected with a raffinate phase decompression separation tank through a pipeline; the bottom of the raffinate analysis separation tank is connected with the upper part of the reaction kettle 3 through a pipeline and a raffinate transfer pump; the bottom of the reaction kettle 3 is connected with the upper part of a reaction kettle 4 through a pipeline, the bottom of the reaction kettle 4 is also connected with a crystallization kettle, and the crystallization kettle is connected with a glyphosate washing, drying and packaging device. The method comprises the following steps: carrying out hydroxymethylation addition reaction on glycine and formaldehyde to generate a unit addition intermediate and a binary addition intermediate, carrying out reaction conversion on the binary addition intermediate under the action of a catalyst, and carrying out selective extraction separation on the reaction liquid by adopting a carbon dioxide extraction method, thereby overcoming the defects of the existing glyphosate production technology by adopting a glycine method. The reaction conversion per pass is improved, and the content of impurities in the glyphosate raw medicine is reduced.

Description

Technical Field

[0001] The utility model belongs to the field of glyphosate technical synthesis, in particular to a glycine method glyphosate technical catalytic synthesis device. Background Art

[0002] Glyphosate is a highly effective chemical herbicide. It is currently the most widely used and largest-volume excellent herbicide in the world. It can control more than 40 families of plants, including monocots and dicots, annuals and perennials, herbs and shrubs. It is widely used for weeding in non-agricultural fields, orchards, roads, forestry, etc. It has been popular since its commercialization in the 1970s, especially with the development of crop genetic modification technology since the 1990s, making it the world's number one herbicide variety. The annual global usage is about 800,000 tons, and the production capacity is about 1.1 million tons.

[0003] At present, there are two industrialized glyphosate production routes. One is the glycine-alkyl ester method using glycine as the starting material; the other is the IDA method using iminodiacetonitrile as the starting material. The glycine method has the advantages of mature production technology, good industrial supporting facilities, and relatively low investment costs, and is therefore widely adopted by glyphosate manufacturers in my country. The total production capacity of the glycine method is about 500,000 tons, accounting for about half of the global production capacity. The existing glyphosate production process includes addition, condensation, acid hydrolysis and other steps, among which addition and condensation are completed in a one-pot method in a synthesis reactor. Only triethylamine is used as a catalyst in the reaction process. It has the characteristics of mature technology and simple process, but the content of glyphosate produced by this process is relatively high, reaching about 1.5%. Utility Model Content

[0004] The utility model aims to overcome the shortcomings of the existing glycine method glyphosate production technology, provide a novel glyphosate catalytic synthesis equipment, and produce glyphosate technical with lower impurity content such as glyphosate.

[0005] The bottom of the reactor 1 is connected to the reactor 2 via a pipeline; the bottom of the reactor 2 is connected to the extraction kettle;

[0006] The upper part of the extraction kettle is connected to the extraction phase analysis separation tank through a pipeline; the lower part of the extraction kettle is connected to the raffinate phase decompression separation tank through a pipeline;

[0007] The bottom of the raffinate phase analysis separation tank is connected to the upper part of the reactor 3 through a pipeline and a raffinate transfer pump;

[0008] The bottom of the reactor 3 is connected to the upper part of the reactor 4 through a pipeline, and the bottom of the reactor 4 is also connected to the crystallization kettle, and the crystallization kettle is connected to the glyphosate washing material drying and packaging device.

[0009] The top of reactor 1 is connected to the formaldehyde solution storage tank, methanol storage tank, glycine storage tank and catalyst 1 storage tank via pipelines P15, P16, P17 and P18 respectively; the top of reactor 2 is connected to the catalyst 2 storage tank via pipeline P19.

[0010] The extractant storage tank is connected to the extraction kettle via a pipeline and an extractant delivery pump; the tops of the extraction phase analysis and separation tank and the raffinate phase analysis and separation tank are connected to the extractant storage tank via pipelines and compressors respectively.

[0011] The bottom of the extraction phase analysis separation tank is connected to the upper part of the reaction kettle 1 through a pipeline and an extraction liquid transfer pump;

[0012] The top of the reactor 3 is also connected to the methanol, triethylamine, and dimethyl phosphite material storage tanks via pipelines P20, P21, and P22 respectively; the upper part of the reactor 4 is also connected to the hydrochloric acid pipeline P23.

[0013] Another technical solution of the utility model is to use the above-mentioned device of the utility model to carry out the following process:

[0014] (1) putting paraformaldehyde, alcohol solution, glycine and catalyst 1 into a reaction vessel 1 for reaction;

[0015] (2) After the reaction is completed, the reaction liquid is transferred to the reaction kettle 2, and the catalyst 2 is added to react. After the reaction is completed, the reaction liquid is transferred to the extraction kettle, and carbon dioxide liquid is injected into the extraction kettle. The components in the reaction liquid are selectively and continuously extracted and separated using carbon dioxide as an extractant;

[0016] (3) After the extraction is completed, the raffinate phase at the lower layer is transferred to the raffinate phase analysis and separation tank for decompression analysis. The carbon dioxide analyzed is separated and compressed and then recycled. The solution obtained after analysis is transferred to the reactor 3;

[0017] (4) Methanol, triethylamine and dimethyl phosphite are continuously added to reactor 3 to obtain a glyphosate intermediate through reaction. The intermediate is transferred to reactor 4, hydrochloric acid is added for acid hydrolysis to obtain glyphosate, and the intermediate is transferred to a crystallization reactor for crystallization. The glyphosate technical is obtained through drying.

[0018] In some embodiments, it is a conventional operation in the art to put paraformaldehyde, alcohol solution, glycine and catalyst 1 into reactor 1 for reaction. Generally, paraformaldehyde is heated and depolymerized in methanol solvent in advance, or paraformaldehyde is depolymerized in methanol solvent under the catalysis of triethylamine or other alkaline substances to obtain a methanol solution of formaldehyde, and the effective components are formaldehyde and hemiacetal. For example, in patents CN 101704842 A or CN 110862414 B, it is disclosed that paraformaldehyde is first depolymerized in advance, and then added with glycine in methanol solvent with triethylamine as a catalyst.

[0019] In the present application, the obtained addition reaction liquid can also be obtained by simultaneously adding glycine and paraformaldehyde into a monohydric alcohol and a tertiary amine system to realize a one-step depolymerization and condensation reaction.

[0020] In step (1), the alcohol solution is selected from a monohydric alcohol solution of C1-C5; the catalyst 1 comprises trimethylamine, triethylamine or triethanolamine; the alcohol solution is preferably methanol, and the catalyst 1 is preferably triethylamine.

[0021] The molar ratio of paraformaldehyde (molar amount in formaldehyde) to glycine raw material is (1.7-2.1) : 1, the molar ratio of solvent alcohol solution (preferably methanol) to glycine is (7.6-12) : 1, and the molar ratio of the total amount of catalyst 1 (preferably triethylamine) added to glycine is (0.7-1.1) : 1.

[0022] The catalyst 2 described in step (2) is a phosphate or a polyphosphate, and the catalyst 2 is selected from one or a combination of sodium tripolyphosphate, sodium pyrophosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, and trisodium phosphate.

[0023] The molar ratio of catalyst 2 to glycine is (0.001-0.15): 1. In some preferred embodiments, the molar ratio of catalyst 2 to glycine is (0.01-0.15): 1. In some preferred embodiments, the molar ratio of catalyst 2 to glycine is (0.1-0.15): 1. In some preferred embodiments, the molar ratio of catalyst 2 to glycine is (0.1-0.15): 1.

[0024] The above-mentioned paraformaldehyde, glycine, solvent methanol, and catalyst 1 triethylamine are stirred and heated to 30°C-52°C to react until the reaction liquid is clear, and then catalyst 2 is added and mixed at 30-45°C. The reaction is terminated after reacting for 10-30 minutes until the reaction liquid turns slightly yellow; and then the reaction liquid is injected into the carbon dioxide extraction system for extraction.

[0025] The pH value is adjusted to 8.0-9.0 before adding phosphate or polyphosphate catalyst for reaction; the catalytic reaction temperature is 30-45° C., and the reaction time is 5-30 minutes; the molar ratio of the added amount of the phosphate or polyphosphate catalyst to glycine is (0.001-0.15):1.

[0026] In step (2), the extraction temperature is 31-43°C, the extraction pressure is 20-30 MPa, the separation temperature after extraction is 45-50°C, and the extraction time is 5-120 min.

[0027] During the extraction process, the upper extraction phase is continuously transferred to the extraction phase analysis separation tank for decompression analysis, the analyzed carbon dioxide is separated, compressed and recycled, and the remaining solution after analysis is transferred to the reactor 1 for recycling as a raw material.

[0028] In some embodiments, after extraction, methanol is added to the raffinate phase at a molar ratio of (5-8) to the initial glycine feed: 1, and triethylamine is added to adjust the pH value to 8.0-9.0. Then, dimethyl phosphite is added in a stoichiometric ratio to carry out a condensation reaction at 45-60°C for 60-120 minutes, and the molar ratio of dimethyl phosphite to the initial glycine feed is (0.8-1.25): 1. When the condensation reaction is completed, hydrochloric acid is added for acidification and hydrolysis, and the molar ratio of hydrochloric acid to glycine is (2.6-3.2): 1. The temperature is raised to 110°C -130°C within 1-7 hours to react and generate glyphosate, and then the glyphosate crystals are crystallized by cooling and precipitating, and the glyphosate technical product is obtained by washing and drying.

[0029] The glyphosate synthesis reaction process is a reaction process carried out using the device.

[0030] Beneficial effects: With the glycine-based glyphosate synthesis method disclosed in the utility model, the content of glyphosate impurities in the glyphosate technical crystals produced is reduced from about 1.5% in the traditional method to below 0.4%, and more preferably to below 0.36%. This method provides a new optimization idea for glyphosate production enterprises using the glycine method to reduce the glyphosate limit impurities. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is a process flow chart of the utility model, wherein E1 is a reactor 1, E2 is a reactor 2, E3 is an extraction reactor, E4 is a reactor 3, E5 is a reactor 4, E6 is a crystallization reactor, E11 is an extractant storage tank, E12 is an extract phase analysis and separation tank, E13 is an extract phase analysis and separation tank, E10 is an extractant delivery pump, E7 is an extract liquid transfer pump, E8 is a compressor, and E9 is an extract liquid transfer pump. DETAILED DESCRIPTION

[0032] The following is based on the attached Figure 1 The present invention is further described in detail with reference to the following specific embodiments, but the present invention is not limited to the following specific embodiments, nor is it limited to the present invention:

[0033] Example 1

[0034] The top of reactor 1 E1 is connected to the formaldehyde solution storage tank, methanol storage tank, glycine storage tank and catalyst 1 storage tank via pipelines P15, P16, P17 and P18 respectively; the bottom of reactor 1 E1 is connected to reactor 2 E2 via a pipeline; the top of reactor 2 E2 is connected to the catalyst 2 storage tank via pipeline P19, and the bottom of reactor 2 E2 is connected to the extraction kettle;

[0035] The extractant storage tank E11 is connected to the extraction kettle E3 via a pipeline and an extractant delivery pump E10; the upper part of the extraction kettle E3 is connected to the extraction phase analysis separation tank E12 via a pipeline; and the lower part is connected to the raffinate phase decompression separation tank E13 via a pipeline.

[0036] The bottom of the raffinate separation tank E13 is connected to the upper part of the reactor 3 E4 via a pipeline and a raffinate transfer pump E9; the bottom of the extract phase separation tank E12 is connected to the upper part of the reactor 1 E1 via a pipeline and an extract transfer pump E7.

[0037] The tops of the extraction phase analysis and separation tank E12 and the raffinate phase analysis and separation tank E13 respectively enter through pipelines and compressors E8 and are connected to the extraction agent storage tank E11, thereby realizing separation, compression and recycling of the extraction agent.

[0038] The top of reactor 3 E4 is also connected to methanol, triethylamine and dimethyl phosphite material storage tanks via pipelines P20, P21 and P22 respectively; the bottom of reactor 3 E4 is connected to the upper part of reactor 4 E5 via a pipeline, the upper part of reactor 4 E5 is also connected to the hydrochloric acid pipeline P23, the bottom of reactor 4 E5 is also connected to the crystallization kettle E6, and the crystallization kettle E6 is connected to the glyphosate washing material drying and packaging device.

[0039] Example 2

[0040] The following process is carried out using the device described in Example 1:

[0041] The formaldehyde solution, methanol, glycine and triethylamine are respectively introduced into the reactor 1 (E1) through pipelines P15, P16, P17 and P18, wherein the molar ratio of the formaldehyde solution (calculated as formaldehyde), methanol, glycine and triethylamine is 1.8:10:1.0:1 and the temperature is raised to 45°C for reaction.

[0042] After the reaction is completed, the reaction liquid is transferred to the reaction kettle 2 (E2), sodium tripolyphosphate (the molar ratio of sodium tripolyphosphate to glycine is (0.01:1)) is added for reaction, and after the reaction is completed, the reaction liquid is transferred to the extraction kettle (E3);

[0043] Liquid carbon dioxide (100 L / h) was injected into the extraction kettle, and the components in the reaction liquid were selectively and continuously extracted and separated at an extraction temperature of 35°C and a pressure of 20 MPa. The separation temperature was controlled at 48°C and the extraction time was 100 min.

[0044] During the extraction process, the upper extraction phase is continuously transferred to the extraction phase analysis separation tank (E12) for reduced pressure analysis (analysis conditions are: pressure ≤ 3.0 MPa, temperature ≤ 48°C), the analyzed carbon dioxide is separated, compressed and recycled, and the remaining solution after analysis is transferred to reactor 1 (E1) for recycling as raw material.

[0045] After the single batch extraction is completed, the raffinate phase at the lower layer is transferred to the raffinate phase analysis separation tank (E13) for decompression analysis (analysis conditions: pressure ≤ 3.0 MPa; temperature ≤ 48 ° C), the analyzed carbon dioxide is separated and compressed for recycling, and the solution obtained after analysis is transferred to the reactor 3 (E4) for use as a raw material. The measured methanol, triethylamine and dimethyl phosphite are continued to be added to the reactor 3, the molar ratio of methanol to the initial glycine is 5:1, and the amount of triethylamine is supplemented to adjust the pH value to about 8.2, and the temperature is raised to 42 ° C to react to obtain glyphosate intermediates, which are transferred to the reactor 4 (E5), and hydrochloric acid is added in a measured ratio, and the temperature is raised to 110-130 ° C for acid hydrolysis to obtain glyphosate, which is transferred to the crystallization kettle (E6) for crystallization (crystallization temperature is 10 ° C), and then transported to the glyphosate washing device for washing, and the glyphosate content is 96.96%; after drying, the glyphosate technical is obtained. The test results showed that the glyphosate content was 0.40%.

[0046] The above embodiments are only examples for clearly explaining the embodiments, and are not intended to limit the embodiments. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here, so the obvious changes or modifications derived are still within the protection scope of the invention of the utility model.

Claims

1. A catalytic synthesis device for glyphosate technical, characterized in that: The bottom of the reaction kettle 1 (E1) is connected to the reaction kettle 2 (E2) via a pipeline; the bottom of the reaction kettle 2 (E2) is connected to the extraction kettle (E3); The upper part of the extraction kettle (E3) is connected to the extraction phase analysis and separation tank (E12) via a pipeline; the lower part of the extraction kettle (E3) is connected to the raffinate phase analysis and separation tank (E13) via a pipeline; The bottom of the raffinate phase separation tank (E13) is connected to the upper part of the reaction kettle 3 (E4) via a pipeline and a raffinate transfer pump (E9); The bottom of the reactor 3 (E4) is connected to the upper part of the reactor 4 (E5) through a pipeline. The bottom of the reactor 4 (E5) is also connected to the crystallization reactor (E6). The crystallization reactor (E6) is connected to the glyphosate washing material drying and packaging device.

2. The glyphosate technical catalytic synthesis device according to claim 1, characterized in that: The top of reactor 1 (E1) is connected to the formaldehyde solution storage tank, methanol storage tank, glycine storage tank and catalyst 1 storage tank via pipelines P15, P16, P17 and P18 respectively; the top of reactor 2 (E2) is connected to the catalyst 2 storage tank via pipeline P19.

3. The glyphosate technical catalytic synthesis device according to claim 1, characterized in that: The extractant storage tank (E11) is connected to the extraction kettle (E3) via a pipeline and an extractant delivery pump (E10).

4. The glyphosate technical catalytic synthesis device according to claim 1, characterized in that: The tops of the extraction phase analysis and separation tank (E12) and the raffinate phase analysis and separation tank (E13) respectively enter through pipelines and compressors (E8) and are connected to the extraction agent storage tank (E11).

5. The glyphosate technical catalytic synthesis device according to claim 1, characterized in that: The bottom of the extraction phase analysis separation tank (E12) is connected to the upper part of the reaction kettle 1 (E1) through a pipeline and an extraction liquid transfer pump (E7).

6. The glyphosate technical catalytic synthesis device according to claim 1, characterized in that: The top of the reactor 3 (E4) is also connected to the methanol, triethylamine, and dimethyl phosphite material storage tanks via pipelines P20, P21, and P22, respectively; the upper part of the reactor 4 (E5) is also connected to the hydrochloric acid pipeline P23.

Images