CN110860310B - Organic catalyst for synthesizing glyphosate and glyphosate synthesis process - Google Patents
Organic catalyst for synthesizing glyphosate and glyphosate synthesis process Download PDFInfo
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
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Abstract
An organic catalyst for synthesizing glyphosate is composed of the alkoxy compound of alkali metal in the first main group, the alkoxy compound prepared from the anhydrous alcohol and the anhydrous hydroxide or oxide of alkali metal in the first main group, or the alkali metal reaction, and one or more of alcohol solutions of said alkoxy compound. A process for synthesizing glyphosate comprises the steps of adding an organic catalyst into a methanol solution of paraformaldehyde or formaldehyde, carrying out depolymerization reaction, adding triethylamine and glycine after the reaction is finished, and stirring for addition reaction; after the reaction is finished, dimethyl phosphite is added for condensation reaction, hydrochloric acid is added for hydrolysis after the reaction is finished, and glyphosate is obtained after crystallization, material washing and drying. The specific catalyst is used for improving the reaction speed and the reaction selectivity of the synthesis of the glyphosate, the depolymerization reaction speed is high, the reaction is thorough, the addition reaction selectivity is high, the yield of the glyphosate product is higher than 3%, and the method has the advantages of reaction superiority, energy saving superiority, cost superiority and environmental protection superiority.
Description
Technical Field
The invention belongs to the technical field of glyphosate production, and particularly relates to a catalytic synthesis method of glyphosate by a glycine method.
Background
Glyphosate is a systemic conduction type herbicide with high efficiency, low toxicity, broad spectrum and biocidal activity, and 2 main production methods are available, namely a production method taking iminodiacetic acid (IDA) as a raw material and a production method taking glycine and alkyl phosphite as raw materials. Foreign companies mainly Bombardau are basically produced by the iminodiacetic acid method. The glyphosate production in China started in the 80 th century. In 1987, shenyang chemical research institute introduced a process for synthesizing glyphosate by using glycine-alkyl ester method using glycine and dimethyl phosphite as main raw materials, and after 30 years of development, the method is mature continuously, and the yield (calculated by glycine) of glyphosate is increased from 65% which is stable at the beginning to about 75%. The glyphosate process with glycine method uses methanol as solvent and triethylamine as catalyst, firstly synthesizes synthetic liquid with organic phosphine intermediate as main component, then hydrolyzes under acidic condition to obtain glyphosate, which can be divided into several reaction procedures of depolymerization, addition, condensation, hydrolysis and crystallization, and the main reaction is as follows:
(1) Depolymerization reaction
The paraformaldehyde is depolymerized in a methanol solution to produce substances such as formaldehyde, hemiacetal and the like.
(2) Addition reaction
Glycine is added into the depolymerization liquid, and the glycine, formaldehyde and hemiacetal are added in the environment of catalyst triethylamine and solvent methanol to generate an intermediate.
(3) Condensation reaction
Dimethyl phosphite is added to the mono-substituent and the di-substituent generated in the addition reaction to carry out esterification (condensation) reaction.
(4) Acidolysis reaction
(5) Crystallization of
And (3) quantitatively adding liquid caustic soda into the crystallization kettle, and adjusting the pH value to an optimal range to promote the glyphosate in the slurry to be fully crystallized and separated out.
In this conventional process, only triethylamine is used as a catalyst. The yield can reach about 75 percent by the glycine (namely about 25 percent of glycine generates side reaction in the production process), and if the yield of the glyphosate is only about 65 percent by the phosphorus (namely 35 percent of phosphorus generates side reaction), the by-product enters the process wastewater of mother liquor and the like. The traditional process method has low yield, not only influences economic benefits, but also increases the production of mother liquor and increases the environmental protection pressure.
Disclosure of Invention
The catalytic synthesis method of glyphosate provided by the invention uses one or more of alkoxy metal organic compounds generated by substituting hydroxyl hydrogen atoms of alcohol substances by alkali metal atoms such as lithium, sodium, potassium and the like as a catalyst to be applied to glyphosate synthesis, in particular to depolymerization and addition procedures in the glyphosate synthesis process. The catalyst mainly plays two roles: firstly, the catalyst plays a role in the depolymerization process, and promotes the paraformaldehyde (the polymerization degree of the paraformaldehyde is 30-50) to be quickly and completely depolymerized; and secondly, a new alkoxy group with high activity, formaldehyde and hemiacetal molecules are generated in the depolymerization stage, so that the selectivity and the rate of addition reaction are improved, the forward and reverse reactions of the addition of the formaldehyde and the glycine are promoted, and the yield and the quality of the glyphosate are improved.
More preferably, the organic base catalyst is one or a combination of more of lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide and potassium ethoxide generated by replacing hydroxyl hydrogen atoms of methanol and ethanol by alkali metal atoms such as lithium, sodium, potassium and the like.
Further preferably, the organic base catalyst comprises one or more of lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide and potassium ethoxide.
Preferably, the alkali metal atom substitute (alkoxide compound) of the alcohol is formulated using fresh anhydrous alcohol and an anhydrous hydroxide (i.e., anhydrous solid base) or oxide of the above alkali metal atom and is present as an alcoholic solution of the alkoxide compound (i.e., a methanol solution of sodium methoxide, a methanol solution of lithium methoxide, and a methanol solution of potassium methoxide), followed by addition. The alcohol includes primary alcohol, secondary alcohol, tertiary alcohol, including monohydric alcohol and dihydric alcohol, specifically including one or more of methanol, ethanol, propanol, butanol, isopropanol, isobutanol, n-butanol, and ethylene glycol. The alcoholic solution of the alkoxy metal compound comprises one or more of a series of alcoholic solutions of alkoxy metal compounds, such as a methanol solution of lithium methoxide, an ethanol solution of lithium methoxide, a methanol solution of sodium methoxide, an ethanol solution of potassium methoxide, an ethanol solution of lithium ethoxide, a methanol solution of sodium ethoxide, an ethanol solution of potassium ethoxide and the like.
Other alkali metal organyls which provide alkoxy groups may also be used to the same effect.
The specific reaction steps are as follows:
1. depolymerization reaction: and (2) mixing methanol and paraformaldehyde (adding methanol into solid paraformaldehyde or adding solid paraformaldehyde into methanol), uniformly stirring, adding the catalyst into the mixed solution, and rapidly depolymerizing at normal temperature to generate the high-activity methanol solution of anhydrous formaldehyde.
In the case of using an alcohol solution of outsourced anhydrous formaldehyde as a formaldehyde source, the catalyst is directly added into the alcohol solution of formaldehyde to completely depolymerize the formaldehyde oligomer which is not fully depolymerized in the solution into formaldehyde single molecules, so as to promote complete depolymerization and generate new high-activity alkoxy groups, formaldehyde, hemiacetal and the like.
After the depolymerization catalyst is added into the mixed solution system, an external heat source is not needed for heating, the solution is gradually clear after the material system naturally reacts for about 15 seconds at normal temperature, and is completely clear within 1 minute, so that depolymerization is completed. If the ambient temperature is too low, the depolymerization reaction temperature can be properly controlled by heating to be kept at about 30 ℃.
The presence of moisture can cause the catalyst to hydrolyze, which affects the activity of the catalyst. Therefore, it is preferable that paraformaldehyde is dried and dehydrated, and then methanol and a depolymerization catalyst are added to carry out depolymerization reaction. The specific implementation method comprises the following steps: firstly, adding paraformaldehyde into a depolymerization kettle, opening a pipeline valve of a tail gas receiving system of the depolymerization kettle, introducing steam into a jacket, and heating and dehydrating at 30-80 ℃ for 10 s-120 min. After dehydration, methanol and a depolymerization catalyst are added for depolymerization reaction.
The molar ratio of the effective component of the depolymerization catalyst (i.e., the metal alkoxide compound) to formaldehyde (the moles of paraformaldehyde are based on formaldehyde) is controlled by: 1/10000000-1/100.
2. Addition reaction: and after depolymerization, adding triethylamine and glycine into the mixed solution, uniformly stirring, controlling the reaction temperature to be 35-50 ℃ and the reaction time to be 30-90min, and carrying out addition reaction on the mixed system under the action of the high-activity nascent alkoxy group initiated by the catalyst, formaldehyde and hemiacetal molecules. Preferably, after the addition reaction is finished, the mixed solution is quickly heated to about 55 ℃, the temperature is kept for about 15s, then the temperature is reduced to about 40 ℃, and then dimethyl phosphite is added for condensation reaction.
3. Condensation reaction: after the addition reaction is finished, adding dimethyl phosphite into the mixed solution, adding a small amount of triethylamine, performing condensation reaction, and controlling the reaction temperature to be 40-58 ℃ and the reaction time to be 30-120min.
4. And after the condensation reaction is finished, adding hydrochloric acid into the mixed solution for hydrolysis, and then crystallizing, washing and drying to obtain the glyphosate.
5. The molar ratio of materials in the glyphosate synthesis process is that paraformaldehyde (calculated by formaldehyde): glycine: dimethyl phosphite: alcohol: triethylamine: hydrogen chloride =1, 0.4 to 0.8; the molar ratio of the alcohol to the paraformaldehyde in the step (1) is controlled to be more than or equal to 0.3, the alcohol is supplemented at most when the molar ratio of the polyformaldehyde to the alcohol is 1:2-8.
Further preferably, the molar ratio of the materials in the glyphosate synthesis process is that paraformaldehyde (calculated by formaldehyde): glycine: dimethyl phosphite: alcohol: triethylamine: hydrogen chloride = 1.6.
The content of the glyphosate raw drug is more than 95.0 percent, the yield of the glyphosate raw drug calculated by glycine reaches more than 78 percent, the total yield of the raw drug and the glyphosate in the mother solution reaches more than 82 percent, and the yield is improved by at least 3 percent compared with the yield of the traditional glycine-dimethyl phosphite process.
Specifically stated: it should be understood that the catalyst is synthesized in whatever manner, so long as the catalyst is used in the synthesis of glyphosate
The synthesis of which is within the scope of the present patent.
It is specifically stated that it is understood that the catalyst, regardless of the manner in which it is added to the reaction system, is within the scope of the present invention, as long as the catalyst is used in the synthesis of glyphosate. The catalyst can be added into a depolymerization reaction system independently, or can be added into raw materials such as paraformaldehyde (or liquid formaldehyde alcohol solution), methanol, triethylamine, glycine and the like used in the processes of depolymerization and addition of the glyphosate in advance, and then added into the reaction system along with the raw materials. Furthermore, the recovered methanol can also be added in the glyphosate solvent recovery process (namely the methanol and methylal recovery process), and then the recovered methanol is recycled to enter a depolymerization reaction system in the glyphosate synthesis process. Further, the catalyst may be formulated from anhydrous hydroxides (i.e., anhydrous solid bases) or oxides of metal atoms in accordance with the foregoing scheme.
Specifically, it states that: it should be understood that the synthesis reaction is within the scope of the present invention regardless of the reaction temperature and time, as long as the catalyst is used in the synthesis of glyphosate.
The technical scheme of the invention has the following beneficial effects:
the method has the advantages of high depolymerization reaction speed, thorough reaction, high addition reaction selectivity, high final yield of the glyphosate product by 3 percent, reaction advantage, energy saving advantage, cost advantage and environmental protection advantage.
1. The traditional paraformaldehyde depolymerization method needs heating and temperature control at about 50 ℃, takes 30-70 minutes, and has large formaldehyde tail gas amount and thick smell due to high temperature in the process. The process can complete depolymerization in only about 1 minute at normal temperature, has low reaction temperature, short time consumption (rapid reaction), small tail gas amount, and has the characteristics of simple and convenient operation, energy conservation, environmental protection and high efficiency.
2. The depolymerization reaction is more thorough, and the quality of the generated depolymerization liquid is more stable, and the depolymerization liquid has the advantages of reaction, environmental protection, energy conservation and quality.
3. The selectivity of the addition reaction is high, and the final yield of the glyphosate product is improved by at least 3 percent.
Drawings
FIG. 1 is a process flow diagram of a catalytic synthesis method of glyphosate according to the present invention. 1. The device comprises a catalyst preparation tank, 2, a depolymerization kettle, 3, a synthesis kettle, 4, a hydrolysis kettle, 5, a crystallization kettle, 6, a washing device, 7, a drying device, 8, a paraformaldehyde pipeline, 9, an alcohol solution inlet pipe, 10, a tail gas pipe, 11, a steam inlet pipe, 12, a depolymerization liquid discharge pipe, 13, a triethylamine inlet pipe, 14, a glycine inlet pipe, 15, a dimethyl phosphite inlet pipe, 16, a hydrochloric acid inlet pipe, 17, a hydrolysis tail gas pipe and 18, a glyphosate mother liquor pipe.
Detailed Description
Example 1
1. Depolymerization reaction: firstly, putting paraformaldehyde (the polymerization degree of the paraformaldehyde is 38) into a depolymerization kettle, opening a pipeline valve of a tail gas system connected with the depolymerization kettle, introducing steam into a jacket, and heating and dehydrating for 2 minutes at 60 ℃. And (2) adding methanol (the molar ratio of the methanol to the paraformaldehyde is controlled to be 0.5: 6.
controlling the molar ratio of lithium methoxide to formaldehyde (the mole number of paraformaldehyde is calculated as formaldehyde): five parts per million.
2. Addition reaction: and after depolymerization, adding triethylamine and glycine into the mixed solution, uniformly stirring, controlling the reaction temperature to be 40 ℃ and the reaction time to be 50min, and carrying out addition reaction on the mixed system under the action of the high-activity nascent alkoxy group initiated by the catalyst and the formaldehyde and hemiacetal molecules. After the addition reaction is finished, quickly heating the mixed solution to 55 ℃, preserving the heat for 15s, and then cooling to 40 ℃.
3. Condensation reaction: and after the addition reaction is finished, adding dimethyl phosphite into the mixed solution, adding a small amount of triethylamine, performing condensation reaction, and controlling the reaction temperature to be 50 ℃ and the reaction time to be 70min.
4. And after the condensation reaction is finished, adding hydrochloric acid into the mixed solution for hydrolysis, and then crystallizing, washing and drying to obtain the glyphosate.
5. The molar ratio of materials in the glyphosate synthesis process is that paraformaldehyde (calculated by formaldehyde): glycine: dimethyl phosphite: methanol: triethylamine: hydrogen chloride = 1.
The content of the glyphosate raw drug is 97.1 percent, the yield of the glyphosate raw drug calculated by glycine reaches 81.5 percent, the total yield of the raw drug and the glyphosate in the mother solution reaches more than 93 percent, and the yield is also improved by 7 percent compared with the yield of the traditional glycine-dimethyl phosphite process.
Example 2
1. Depolymerization reaction:
firstly, putting paraformaldehyde (the polymerization degree of the paraformaldehyde is 50) into a depolymerization kettle, opening a pipeline valve of a tail gas system connected with the depolymerization kettle, introducing steam into a jacket, heating and dehydrating for 3 minutes at 60 ℃, adding methanol (the molar ratio of the methanol to the paraformaldehyde is controlled to be 0.6; after depolymerization is finished, ethanol is added, and the molar ratio of polyformaldehyde to alcohol is at most 1:7.8.
controlling the molar ratio of lithium methoxide to formaldehyde (the mole number of paraformaldehyde is calculated as formaldehyde): parts per million.
2. Addition reaction:
and after depolymerization is finished, adding triethylamine and glycine into the mixed solution, uniformly stirring, controlling the reaction temperature to be 45 ℃ and the reaction time to be 45min, and allowing the mixed system to perform addition reaction under the action of high-activity nascent alkoxy groups, formaldehyde and hemiacetal molecules initiated by the catalyst. After the addition reaction is finished, quickly heating the mixed solution to 50 ℃, preserving the heat for 20s, then cooling to 43 ℃, and then adding dimethyl phosphite for condensation reaction.
3. Condensation reaction: after the addition reaction is finished, adding dimethyl phosphite into the mixed solution, adding a small amount of triethylamine, carrying out condensation reaction, controlling the reaction temperature to be 45-58 ℃ and the reaction time to be 100min.
4. And after the condensation reaction is finished, adding hydrochloric acid into the mixed solution for hydrolysis, and then crystallizing, washing and drying to obtain the glyphosate.
5. The molar ratio of materials in the glyphosate synthesis process is that paraformaldehyde (calculated by formaldehyde): glycine: dimethyl phosphite: methanol: triethylamine: hydrogen chloride =1, 0.45 (molar ratio of triethylamine added in step 2 to triethylamine in step 3 is 6).
The content of the glyphosate raw drug is 94.6 percent, the yield of the glyphosate raw drug calculated by glycine reaches 81.8 percent, the total yield of the raw drug and the glyphosate in the mother solution reaches more than 83.5 percent, and the yield is also improved by 7.4 percent compared with the yield of the traditional glycine-dimethyl phosphite process.
Example 3
1. Depolymerization reaction: taking the purchased absolute formaldehyde alcohol solution as a formaldehyde raw material, adding a catalyst potassium methoxide methanol solution into the absolute formaldehyde alcohol solution, and reacting for 20 seconds; after depolymerization is finished, methanol is added, and the molar ratio of polyformaldehyde to alcohol is at most 1:2.2;
controlling the molar ratio of the potassium methoxide to the formaldehyde: fifty parts per million.
2. Addition reaction: and after depolymerization, adding triethylamine and glycine into the mixed solution, uniformly stirring, controlling the reaction temperature to be 50 ℃ and the reaction time to be 35min, and carrying out addition reaction on the mixed system under the action of the high-activity nascent alkoxy group initiated by the catalyst and the formaldehyde and hemiacetal molecules. After the addition reaction is finished, quickly heating the mixed solution to 60 ℃, preserving heat for 18s, cooling to about 38 ℃, and adding dimethyl phosphite for condensation reaction.
3. Condensation reaction: after the addition reaction is finished, adding dimethyl phosphite into the mixed solution, adding a small amount of triethylamine, carrying out condensation reaction, and controlling the reaction temperature to be 52 ℃ and the reaction time to be 65min.
4. And after the condensation reaction is finished, adding hydrochloric acid into the mixed solution for hydrolysis, and then crystallizing, washing and drying to obtain the glyphosate.
5. The molar ratio of the materials in the glyphosate synthesis process is as follows: glycine: dimethyl phosphite: methanol: triethylamine: hydrogen chloride = 1.4.
The content of the glyphosate raw drug is 94.5 percent, the yield of the glyphosate raw drug calculated by glycine reaches 78.8 percent, the total yield of the raw drug and the glyphosate in the mother solution reaches 80.8 percent, and the yield is also improved by 4.3 percent compared with the yield of the traditional glycine-dimethyl phosphite process.
Example 4
1. Depolymerization reaction: mixing methanol and paraformaldehyde (polymerization degree of paraformaldehyde is 70), stirring uniformly, reacting at 30 deg.C for 30s to complete depolymerization reaction. The methanol and paraformaldehyde solutions are both added with an ethanol solution of a catalyst sodium ethoxide. After depolymerization is finished, ethanol is added, and the molar ratio of polyformaldehyde to alcohol is at most 1:7.5.
controlling the molar ratio of sodium ethoxide to paraformaldehyde (the mole number of paraformaldehyde is calculated as formaldehyde): parts per million.
2. Addition reaction: after depolymerization is finished, triethylamine (sodium ethoxide is added in triethylamine; the molar ratio of triethylamine to methanol is controlled: one millionth) is added into the mixed solution, glycine is added and stirred uniformly, the reaction temperature is controlled at 50 ℃ and the reaction time is controlled at 70min, and the mixed system is subjected to addition reaction under the action of high-activity nascent alkoxy groups initiated by the catalyst, formaldehyde and hemiacetal molecules. After the addition reaction is finished, quickly heating the mixed solution to 55 ℃, preserving the heat for 15s, and then cooling to 40 ℃;
3. condensation reaction: after the addition reaction is finished, adding dimethyl phosphite into the mixed solution, adding a small amount of triethylamine, carrying out condensation reaction, and controlling the reaction temperature at 50 ℃ and the reaction time for 80min.
4. And after the condensation reaction is finished, adding hydrochloric acid into the mixed solution for hydrolysis, and then crystallizing, washing and drying to obtain the glyphosate.
5. The molar ratio of materials in the glyphosate synthesis process is that paraformaldehyde (calculated by formaldehyde): glycine: dimethyl phosphite: methanol: triethylamine: hydrogen chloride = 1.
The content of the glyphosate raw drug is 97.8 percent, the yield of the glyphosate raw drug calculated by glycine reaches 77.5 percent, the total yield of the raw drug and the glyphosate in the mother solution reaches more than 83.8 percent, and the yield is also improved by 3.08 percent compared with the yield of the traditional glycine-dimethyl phosphite process.
Example 5
1. Depolymerization reaction: adding a methanol solution of potassium methoxide and an ethanol solution of potassium ethoxide which are used as catalysts into an alcohol solution of anhydrous formaldehyde according to any proportion, and reacting for 20 seconds; after depolymerization is finished, methanol is added, and the molar ratio of polyformaldehyde to alcohol is at most 1:2.4.
controlling the molar ratio of the potassium methoxide to the potassium ethoxide to the formaldehyde: eight parts per million.
2. Addition reaction: after depolymerization is finished, glycine is added into the mixed solution, the mixed solution is stirred uniformly, the reaction temperature is controlled to be 50 ℃, the reaction time is controlled to be 35min, and the mixed system is subjected to addition reaction under the action of high-activity nascent alkoxy groups, formaldehyde and hemiacetal molecules, which are initiated by the catalyst. After the addition reaction is finished, quickly heating the mixed solution to 60 ℃, preserving the heat for 18s, then cooling to about 38 ℃, and then adding dimethyl phosphite for condensation reaction.
3. Condensation reaction: after the addition reaction is finished, adding dimethyl phosphite into the mixed solution, adding a small amount of triethylamine, carrying out condensation reaction, and controlling the reaction temperature to be 52 ℃ and the reaction time to be 65min.
4. And after the condensation reaction is finished, adding hydrochloric acid into the mixed solution for hydrolysis, and then crystallizing, washing and drying to obtain the glyphosate.
5. The molar ratio of each material in the process of synthesizing glyphosate is as follows: glycine: dimethyl phosphite: methanol: hydrogen chloride = 1.45.
The content of the glyphosate raw drug is 95.2 percent, the yield of the glyphosate raw drug calculated by glycine reaches 78.0 percent, the total yield of the raw drug and the glyphosate in the mother solution reaches 83.5 percent, and the yield is also improved by 3.4 percent compared with the yield of the traditional glycine-dimethyl phosphite process.
Claims (5)
1. The application of the organic catalyst in synthesizing glyphosate is characterized in that a methanol solution of paraformaldehyde or a methanol solution of formaldehyde is added with the organic catalyst and then naturally reacts for 20s at 30 ℃ to carry out depolymerization reaction, and after the depolymerization reaction is finished, triethylamine and glycine are added and stirred to carry out addition reaction; after the reaction is finished, adding dimethyl phosphite for condensation reaction, after the reaction is finished, adding hydrochloric acid for hydrolysis, and then crystallizing, washing and drying to obtain glyphosate;
the organic catalyst is an alcoholic solution of an alkoxy metal compound, and the alcoholic solution of the alkoxy metal compound comprises one or more of a methanol solution of lithium methoxide, an ethanol solution of lithium methoxide, a methanol solution of sodium methoxide, an ethanol solution of potassium methoxide, an ethanol solution of lithium ethoxide, a methanol solution of sodium ethoxide, an ethanol solution of sodium ethoxide and an ethanol solution of potassium ethoxide;
the molar ratio of the metal alkoxide compound to the paraformaldehyde is controlled by: 1/10000000-5/100000, wherein the molar quantity of the paraformaldehyde is calculated by formaldehyde.
2. The use according to claim 1, wherein the organic catalyst is directly added to a mixed solution of paraformaldehyde and methanol, and the polymerization degree of the paraformaldehyde is 3-100.
3. The use according to claim 1, wherein the addition reaction temperature is 35-50 ℃ and the reaction time is 30-90min; the condensation reaction temperature is 40-58 deg.C, and the reaction time is 30-120min.
4. The application of claim 1, wherein the molar ratio of the materials in the glyphosate synthesis process is as follows, wherein the molar ratio of paraformaldehyde is calculated by formaldehyde: glycine: dimethyl phosphite: alcohol: triethylamine: hydrogen chloride =1: 0.4-0.8: 0.3-0.8: 2-8: 0-0.8: 1-2; controlling the molar ratio of the alcohol to the paraformaldehyde to be more than or equal to 0.3, wherein the molar ratio of the polyformaldehyde to the alcohol is 1:2-8.
5. The application of claim 1, wherein the molar ratio of the materials in the glyphosate synthesis process is, calculated as formaldehyde: glycine: dimethyl phosphite: alcohol: triethylamine: hydrogen chloride =1:0.5:0.6:6:0.5:1.5.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4439373A (en) * | 1982-12-27 | 1984-03-27 | Stauffer Chemical Company | Process for preparing phosphonomethylated amino acids |
| US4486359A (en) * | 1979-07-09 | 1984-12-04 | Alkaloida Vegyeszeti Gyar | Process for the preparation of N-phosphonomethyl-glycine |
| CN102766160A (en) * | 2012-07-16 | 2012-11-07 | 江苏索普（集团）有限公司 | Novel process for preparing glyphosate by utilizing glycine method |
| CN102775441A (en) * | 2012-07-30 | 2012-11-14 | 浙江金帆达生化股份有限公司 | Continuous production method of glyphosate synthetic liquid |
| CN103242182A (en) * | 2012-02-03 | 2013-08-14 | 刘长飞 | Clean production technology of glycine |
| CN105693470A (en) * | 2016-02-18 | 2016-06-22 | 江苏苏博特新材料股份有限公司 | Continuous 3-methyl-3-buten-1-ol production method |
| CN107827713A (en) * | 2017-11-24 | 2018-03-23 | 陕西启源科技发展有限责任公司 | The preparation method of new polyphenol kind antioxidant |
-
2018
- 2018-08-27 CN CN201810982635.4A patent/CN110860310B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4486359A (en) * | 1979-07-09 | 1984-12-04 | Alkaloida Vegyeszeti Gyar | Process for the preparation of N-phosphonomethyl-glycine |
| US4439373A (en) * | 1982-12-27 | 1984-03-27 | Stauffer Chemical Company | Process for preparing phosphonomethylated amino acids |
| CN103242182A (en) * | 2012-02-03 | 2013-08-14 | 刘长飞 | Clean production technology of glycine |
| CN102766160A (en) * | 2012-07-16 | 2012-11-07 | 江苏索普（集团）有限公司 | Novel process for preparing glyphosate by utilizing glycine method |
| CN102775441A (en) * | 2012-07-30 | 2012-11-14 | 浙江金帆达生化股份有限公司 | Continuous production method of glyphosate synthetic liquid |
| CN105693470A (en) * | 2016-02-18 | 2016-06-22 | 江苏苏博特新材料股份有限公司 | Continuous 3-methyl-3-buten-1-ol production method |
| CN107827713A (en) * | 2017-11-24 | 2018-03-23 | 陕西启源科技发展有限责任公司 | The preparation method of new polyphenol kind antioxidant |
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