Glyphosate synthesis reaction device

Abstract

The utility model discloses a glyphosate synthesis reaction device. An extraction agent storage tank is connected with an extraction kettle through a pipeline and an extraction agent delivery pump; the upper part of the extraction kettle is connected with an extraction phase decompression separation tank through a pipeline; the bottom of the extraction phase decompression separation tank is connected with the upper part of the reaction kettle 2 through a pipeline and an extraction liquid transfer pump; the bottom of the reaction kettle 2 is connected with the upper part of the reaction kettle 3 through a pipeline, the bottom of the reaction kettle 3 is also connected with a crystallization kettle, and the crystallization kettle is connected with a glyphosate washing, drying and packaging device. Reaction and extraction coupling equipment is adopted, a glycine hydroxymethylation product is selectively separated, and directional conversion of glyphosate synthesis is improved through one-way selection and cyclic application, so that a glyphosate raw medicine with high purity is obtained.

Description

Technical Field

[0001] The utility model belongs to the field of glyphosate technical synthesis, in particular to a glycine method glyphosate technical 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] There are currently 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 glycine production process includes steps such as addition, condensation, and acid hydrolysis, among which addition and condensation are completed in a one-pot method in a synthesis reactor, and 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 in the original drug produced by this process is relatively high, reaching about 1.5%. The existing technology does not have a synthetic reaction device for reducing the content of glyphosate in glyphosate raw materials. Summary of the invention

[0004] The utility model aims to provide a novel glyphosate synthesis device, which provides a choice for the production of low-impurity and high-purity glyphosate technical.

[0005] A glyphosate synthesis reaction device, the bottom of the reaction kettle 1 is connected to the extraction kettle through a pipeline;

[0006] The extractant storage tank is connected to the extraction kettle via a pipeline and an extractant delivery pump; the upper part of the extraction kettle is connected to the extraction phase decompression separation tank via a pipeline;

[0007] The bottom of the extraction phase decompression separation tank is connected to the upper part of the reaction kettle 2 through a pipeline and an extraction liquid transfer pump;

[0008] The bottom of the reactor 2 is connected to the upper part of the reactor 3 through a pipeline, and the bottom of the reactor 3 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 the reactor 1 is connected to the formaldehyde solution storage tank, the methanol storage tank, the glycine storage tank and the triethylamine storage tank through pipelines P1, P2, P3 and P19 respectively.

[0010] The lower part of the extraction kettle is connected to the raffinate phase decompression separation tank through a pipeline.

[0011] The bottom of the extraction phase decompression separation tank is connected to the upper part of the reactor 2 through a pipeline and an extraction liquid transfer pump. The top of the reactor 2 is also connected to the methanol material storage tank, the triethylamine material storage tank, and the dimethyl phosphite material storage tank through pipelines P20, P21, and P23 respectively; the upper part of the reactor 3 is also connected to the hydrochloric acid pipeline P22.

[0012] The bottom of the raffinate phase decompression separation tank is connected to the upper part of the reactor 1 through a pipeline and a raffinate transfer pump;

[0013] The tops of the raffinate phase decompression separation tank and the extraction phase decompression separation tank are respectively connected to the extractant storage tank after passing through pipelines and compressors.

[0014] A glyphosate synthesis reaction process comprises the following process steps:

[0015] (1) adding paraformaldehyde, alcohol solution, glycine and catalyst into a reaction vessel 1 for reaction;

[0016] (2) After the reaction is completed, the reaction liquid is transferred to an extraction kettle, and carbon dioxide liquid is injected into the extraction kettle, and the components in the reaction liquid are selectively and continuously extracted and separated using carbon dioxide as an extractant;

[0017] (3) During the extraction process, the upper extract phase is continuously transferred to the extract phase decompression separation tank for decompression analysis, and the analyzed solution is transferred to the reactor 2 for use as a raw material;

[0018] (4) Continue to add measured amounts of methanol, triethylamine and dimethyl phosphite to reactor 2 to obtain a glyphosate intermediate through reaction. The intermediate is transferred to reactor 3 and hydrochloric acid is added for acid hydrolysis to obtain glyphosate. The intermediate is then transferred to a crystallization reactor for crystallization to obtain glyphosate.

[0019] The catalyst in step (1) is one or more of trimethylamine, triethylamine and triethanolamine; the alcohol solution is selected from a C1-C5 monohydric alcohol solution. The catalyst is preferably triethylamine, and the alcohol solution is preferably methanol.

[0020] In some embodiments, the molar ratio of paraformaldehyde (molar amount is formaldehyde), catalyst (for example triethylamine), and glycine is (0.8-1.2):(0.6-0.8):1, the molar ratio of alcohol solvent (preferably methanol) to glycine is (6-10):1, the addition reaction temperature is 0-45°C, and the reaction time is 40-120 min.

[0021] As a preferred solution, the paraformaldehyde is heated and depolymerized in a methanol solvent in advance, or the paraformaldehyde is depolymerized in a methanol solvent under the catalysis of triethylamine or other alkaline substances to obtain a methanol solution of formaldehyde, or a commercially available alcoholic formaldehyde solution is directly used.

[0022] The extraction temperature in step (2) is 31-45°C and the extraction pressure is 7-30MPa; the separation temperature after extraction in step (3) is 45-48°C and the extraction time is 5-120min.

[0023] The addition flow rate of carbon dioxide is matched with the feed amount, feed amount and processing amount of other raw materials in the reactor, and can be increased or decreased in proportion to the addition reaction liquid. In the embodiment, the carbon dioxide flow rate is 20-50 L / h.

[0024] Temperature during the extraction process refers to the temperature and pressure inside the extraction kettle; the separation temperature after extraction refers to the temperature of the extraction phase separation tank and the residual phase separation tank.

[0025] Extraction is a process in which carbon dioxide is continuously injected into and removed from a reaction solution. The extraction time refers to the time from the start of continuous injection and removal of carbon dioxide to the end.

[0026] After the extraction is completed, the raffinate phase at the lower layer is transferred to the raffinate phase decompression separation tank for decompression analysis, and the carbon dioxide analyzed is separated, compressed and recycled, and the solution obtained after analysis is transferred to the reactor 1 for use as a raw material;

[0027] In some embodiments, the extract (mixed solution A) can also be cooled below 10°C for 30 min-8 h, crystals are precipitated and filtered out, and then transferred to reactor 2 (E6), and methanol, triethylamine, and dimethyl phosphite are added to carry out condensation reaction.

[0028] During the extraction process, the upper extraction phase is continuously transferred to the extraction phase decompression 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 2 for use as a raw material.

[0029] In some embodiments, after extraction, methanol is added to the extract phase in a molar ratio of (0.5-1.5) to the initial glycine feed, and the molar ratio of the amount of triethylamine added to glycine is (0.3-0.5) to 1. 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) to 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) to 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.

[0030] The glyphosate synthesis reaction process described in the utility model is a reaction process carried out by adopting the device described.

[0031] According to the glycine-based glyphosate synthesis method disclosed in the utility model, the content of glyphosate impurities in the glyphosate technical crystal produced is reduced from about 1.5% in the traditional method to less than 0.8%, and further reduced to 0.6-0.7%; further reduced to 0.4-0.5%, with a reduction of more than 50%. The method provides a new process route for glyphosate production enterprises using the glycine method to reduce the glyphosate limit impurities. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is a process flow chart of the utility model, wherein E1 is a reactor 1, E2 is an extraction reactor, E3 is an extractant storage tank, E4 is a raffinate phase decompression separation tank, E5 is an extract phase decompression separation tank, E6 is a reactor 2, E7 is a reactor 3, E8 is a crystallization reactor, E9 is an extractant delivery pump, E10 is a raffinate transfer pump, E11 is an extract transfer pump, and E13 is a compressor. DETAILED DESCRIPTION

[0033] The present invention is further described in detail below according to the drawings and specific embodiments of the specification, but the present invention is not limited to the following specific embodiments, nor is it limited to the present invention by these embodiments:

[0034] Example 1

[0035] The top of the reactor 1 E1 is connected to the formaldehyde solution, methanol, glycine, and triethylamine storage tanks via pipelines P1, P2, P3, and P19, respectively; the bottom of the reactor 1 E1 is connected to the extraction reactor E2 via a pipeline;

[0036] The extractant storage tank E3 is connected to the extraction kettle E2 via a pipeline and an extractant delivery pump E9; the upper part of the extraction kettle E2 is connected to the extraction phase decompression separation tank E5 via a pipeline; and the lower part is connected to the raffinate phase decompression separation tank E4 via a pipeline;

[0037] The bottom of the extraction phase decompression separation tank E5 is connected to the upper part of the reactor 2 E6 through a pipeline and an extraction liquid transfer pump E11; the top of the reactor 2 E6 is also connected to the methanol, triethylamine, and dimethyl phosphite material storage tanks through pipelines P20, P21, and P23 respectively; the bottom of the reactor 2 E6 is connected to the upper part of the reactor 3 E7 through a pipeline, the upper part of the reactor 3 E7 is also connected to the hydrochloric acid pipeline P23, the bottom of the reactor 3 E7 is also connected to the crystallization kettle E8, and the crystallization kettle E8 is connected to the glyphosate washing material drying and packaging device.

[0038] The bottom of the extract phase decompression separation tank E5 is connected to the upper part of the reactor 2 E6 through a pipeline and an extract liquid transfer pump E11; the bottom of the raffinate phase decompression separation tank E4 is connected to the upper part of the reactor 1 E1 through a pipeline and a raffinate transfer pump E10.

[0039] The tops of the raffinate phase decompression separation tank E4 and the extraction phase decompression separation tank E5 respectively enter through pipelines and compressor E13 and are connected to the extractant storage tank E3, thereby realizing separation, compression and recycling of the extractant.

[0040] Example 2

[0041] The following process is carried out using the device described in Example 1:

[0042] Solid paraformaldehyde, methanol and triethylamine are respectively introduced into the reaction kettle 1 E1 through pipelines P1, P2 and P19, wherein the molar ratio of paraformaldehyde (calculated as formaldehyde), methanol and triethylamine is 1:8:0.78 (calculated as 1 with glycine).

[0043] The temperature of the reactor was controlled at 50°C and kept warm for 60 minutes; then the temperature was lowered to 20°C, 120 kg of glycine was injected from the P3 pipeline, and the reaction was kept warm at 25-35°C for 100 minutes to obtain an addition reaction liquid;

[0044] The addition reaction liquid is pumped into the extraction kettle, and the carbon dioxide in the extractant storage tank is pumped into the extraction kettle. The extraction is carried out at an extraction temperature of 38°C and an extraction pressure of 26MPa for 90 minutes. An extraction phase and a raffinate phase are generated during the reaction. The raffinate phase is retained at the bottom of the extraction kettle, and the extraction phase rises to the top of the extraction kettle. The separation temperature of the extraction phase and the raffinate phase is 46°C. The extraction is stopped after the extraction time is 90 minutes.

[0045] The raffinate phase obtained by the extraction reaction is recycled into the reactor 1 E1 again through the raffinate transfer pump E10 and the raffinate phase decompression separation tank E4;

[0046] The extract phase obtained by the extraction reaction is transferred into the reaction kettle 2E6 via the extract phase decompression separation tank E5 and the extract liquid transfer pump E11;

[0047] Immediately add 50kg of methanol, 30kg of triethylamine and 210kg of dimethyl phosphite into the extract of reactor 2 E6, raise the temperature to 50-52°C and carry out condensation reaction for 90min; after the condensation reaction is completed, transfer to reactor 3 and add concentrated hydrochloric acid for acidification and hydrolysis, raise the temperature to 117-118°C and keep warm for 30min, then transfer to a crystallization kettle for cooling and crystallization, cool to room temperature and filter, wash and dry to obtain glyphosate technical dry powder, with a glyphosate content of 96.02%; the glyphosate content is 0.66% as determined by chemical analysis.

Claims

1. A glyphosate synthesis reaction device, characterized in that: The bottom of the reaction kettle 1 (E1) is connected to the extraction kettle (E2) via a pipeline; The extractant storage tank (E3) is connected to the extraction kettle (E2) via a pipeline and an extractant delivery pump (E9); the upper part of the extraction kettle (E2) is connected to the extraction phase decompression separation tank (E5) via a pipeline; The bottom of the extract phase decompression separation tank (E5) is connected to the upper part of the reaction kettle 2 (E6) through a pipeline and an extract transfer pump (E11); The bottom of the reactor 2 (E6) is connected to the upper part of the reactor 3 (E7) through a pipeline. The bottom of the reactor 3 (E7) is also connected to the crystallization reactor (E8). The crystallization reactor (E8) is connected to the glyphosate washing material drying and packaging device.

2. The glyphosate synthesis reaction device according to claim 1, characterized in that: The top of the reactor 1 (E1) is connected to the formaldehyde solution storage tank, the methanol storage tank, the glycine storage tank and the triethylamine storage tank through pipelines P1, P2, P3 and P19 respectively.

3. The glyphosate synthesis reaction device according to claim 1, characterized in that: The lower part of the extraction kettle (E2) is connected to the raffinate phase decompression separation tank (E4) via a pipeline.

4. The glyphosate synthesis reaction device according to claim 1, characterized in that: The top of the reactor 2 (E6) is also connected to the methanol material storage tank, the triethylamine material storage tank, and the dimethyl phosphite material storage tank via pipelines P20, P21, and P23, respectively; the upper part of the reactor 3 (E7) is also connected to the hydrochloric acid pipeline P22.

5. The glyphosate synthesis reaction device according to claim 1, characterized in that: The bottom of the raffinate phase decompression separation tank (E4) is connected to the upper part of the reaction kettle 1 (E1) through a pipeline and a raffinate transfer pump (E10).

6. The glyphosate synthesis reaction device according to claim 1, characterized in that: The tops of the raffinate phase decompression separation tank (E4) and the extraction phase decompression separation tank (E5) are connected to the extractant storage tank (E3) after passing through pipelines and compressors (E13).

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