CN110862414B - Process for catalytically synthesizing glyphosate - Google Patents
Process for catalytically synthesizing glyphosate Download PDFInfo
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- CN110862414B CN110862414B CN201810982642.4A CN201810982642A CN110862414B CN 110862414 B CN110862414 B CN 110862414B CN 201810982642 A CN201810982642 A CN 201810982642A CN 110862414 B CN110862414 B CN 110862414B
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- 239000005562 Glyphosate Substances 0.000 title claims abstract description 58
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 44
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 114
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 75
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 34
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004471 Glycine Substances 0.000 claims abstract description 28
- 238000007259 addition reaction Methods 0.000 claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006482 condensation reaction Methods 0.000 claims abstract description 19
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000012691 depolymerization reaction Methods 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 230000007062 hydrolysis Effects 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 100
- 239000000243 solution Substances 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 21
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 10
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 6
- 229920006324 polyoxymethylene Polymers 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- -1 alkoxy compound Chemical class 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052708 sodium Inorganic materials 0.000 abstract description 4
- 239000011734 sodium Substances 0.000 abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 3
- 150000001340 alkali metals Chemical class 0.000 abstract description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 3
- 230000036632 reaction speed Effects 0.000 abstract description 3
- 229910052700 potassium Inorganic materials 0.000 abstract 2
- 239000011591 potassium Substances 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 239000003814 drug Substances 0.000 description 12
- 229940079593 drug Drugs 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 150000002373 hemiacetals Chemical class 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- YLGDTEYFAMCCEL-UHFFFAOYSA-N NCC(O)=O.COP(O)OC Chemical compound NCC(O)=O.COP(O)OC YLGDTEYFAMCCEL-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 239000010413 mother solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 238000007036 catalytic synthesis reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- IXQYZUOOHQWOQL-UHFFFAOYSA-N potassium;methanol;methanolate Chemical compound [K+].OC.[O-]C IXQYZUOOHQWOQL-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- 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 ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
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 fresh absolute methanol, ethanol and the anhydrous hydroxide or oxide of potassium, sodium or potassium, sodium, or alkali metal, and one or more of them in the form of alcohol solution. A process for synthesizing glyphosate comprises the steps of carrying out depolymerization reaction after adding an organic catalyst into a methanol solution of paraformaldehyde or formaldehyde, 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 5%, 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
Quantitatively adding liquid caustic soda into the crystallization kettle, adjusting the pH value to an optimal range, and promoting 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 sodium and potassium metal atoms as a catalyst to be applied to glyphosate synthesis, and is particularly applied 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 the paraformaldehyde (the polymerization degree of the paraformaldehyde is 30-50) is promoted to be quickly and completely depolymerized; and secondly, a new alkoxy group with high activity and formaldehyde and hemiacetal molecules are generated in the depolymerization stage, so that the selectivity and the speed of the 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.
Further preferably, the catalyst is one or a combination of several of sodium methoxide, potassium methoxide, sodium ethoxide and potassium ethoxide generated by replacing hydroxyl hydrogen atoms of methanol and ethanol by sodium and potassium atoms.
Preferably, fresh anhydrous methanol, ethanol and anhydrous hydroxides (i.e., anhydrous solid bases) or oxides or alkali metal atom substitutes (metal alkoxides) of the above metal atom preparation alcohols may be used and present as an alcoholic solution of the metal alkoxide compound (i.e., a methanol solution of sodium methoxide, an ethanolic solution of potassium methoxide, a methanol solution of potassium methoxide, an ethanolic solution of potassium methoxide), followed by preparation.
Other metal alkoxide compounds and organic alkali metal compounds that can provide an alkoxy group can also provide 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 alcoholic solution of outsourced anhydrous formaldehyde as a formaldehyde source, the catalyst is directly added into the alcoholic solution of formaldehyde, so that the formaldehyde oligomer which is not fully depolymerized in the solution is completely depolymerized into formaldehyde single molecules, complete depolymerization is promoted, and meanwhile, new high-activity alkoxy groups, formaldehyde, hemiacetal and the like are generated.
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 maintain 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 the dehydration, methanol and a depolymerization catalyst are added for depolymerization reaction.
The mole ratio of the active ingredient (i.e. the alkoxy metal compound) of the depolymerization catalyst to formaldehyde (the mole number of paraformaldehyde is calculated by formaldehyde) is controlled as follows: 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 30-120 min.
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 is 1: 0.4-0.8: 0.3-0.8: 2-8: 0-0.8: 1-2; the molar ratio of the alcohol to the paraformaldehyde in the step (1) is controlled to be more than or equal to 0.3:1, and 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 is 1:0.5:0.6:6:0.5: 1.5.
The content of the glyphosate raw drug is more than 95.0 percent, the yield of the glyphosate raw drug calculated by glycine is more than 78 percent, the total yield of the raw drug and the glyphosate in the mother solution is 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, it states that: 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 according to 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 to be heated and controlled at about 50 ℃, takes 30-70 minutes, and has large amount of formaldehyde tail gas and strong 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 (3) adding methanol (the molar ratio of the methanol to the paraformaldehyde is controlled to be 0.5:1) after dehydration, uniformly stirring, adding a methanol solution of sodium methoxide into the mixed solution, quickly finishing depolymerization at normal temperature for 30 seconds to generate a methanol solution of high-activity anhydrous formaldehyde, and adding methanol until the molar ratio of the polyformaldehyde to the alcohol is 1: 7.
the molar ratio of sodium methoxide to formaldehyde (the moles of paraformaldehyde are calculated as formaldehyde) is controlled: 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: 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 70 min.
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 was 1:0.6:0.5:6:0.5 (molar ratio of triethylamine in step 2 to triethylamine in step 3 was 25:1) to 1.2.
The content of the glyphosate raw drug is 97.1 percent, the yield of the glyphosate raw drug calculated by glycine reaches 82.5 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 8 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 0.6:1) after dehydration is finished, stirring uniformly, adding potassium methoxide solid into a mixed solution, and naturally reacting for 20 seconds at 30 ℃ to carry out depolymerization reaction to generate a methanol solution of high-activity anhydrous formaldehyde; after the depolymerization is finished, ethanol is added until the molar ratio of polyformaldehyde to alcohol is 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, 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 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 50 ℃, preserving the heat for 20s, cooling to 43 ℃, 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, controlling the reaction temperature to be 45-58 ℃ and the reaction time to be 100 min.
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 was 1:0.55:0.45:7.8:0.2 (molar ratio of triethylamine in step 2 to triethylamine in step 3 was 6:1) to 1.3.
The content of the glyphosate raw drug is 94.6 percent, the yield of the glyphosate raw drug calculated by glycine reaches 82.0 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 7.6 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 the depolymerization is completed, methanol is added at most in a molar ratio of polyoxymethylene to alcohol of 1: 2.2;
controlling the molar ratio of the potassium methoxide to the 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 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 the heat for 18s, then cooling to about 38 ℃, and then adding dimethyl phosphite for condensation reaction.
3. Condensation reaction: and after the addition reaction is finished, adding dimethyl phosphite into the mixed solution, not supplementing a small amount of triethylamine, carrying out condensation reaction, and controlling the reaction temperature to be 52 ℃ and the reaction time to be 65 min.
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 is 1:0.4:0.35:2.2:0.4: 1.6.
The content of the glyphosate raw drug is 94.5 percent, the yield of the glyphosate raw drug calculated by glycine reaches 79.0 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 4.5 percent compared with the yield of the traditional glycine-dimethyl phosphite process.
Claims (4)
1. The process for synthesizing the glyphosate is characterized in that a methanol solution of paraformaldehyde or a methanol solution of formaldehyde is subjected to depolymerization reaction after an organic catalyst is added, the paraformaldehyde is heated and dehydrated for 2-3 minutes at 60 ℃, and the formaldehyde is anhydrous formaldehyde;
adding triethylamine and glycine after the reaction is finished, and stirring for 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 comprises one or a combination of more of sodium methoxide, potassium methoxide, a methanol solution of sodium methoxide, an ethanol solution of sodium methoxide, a methanol solution of potassium methoxide and an ethanol solution of potassium methoxide, and the molar ratio of the organic catalyst to paraformaldehyde is controlled as follows: 1/10000000-5/1000000, wherein the molar weight of the paraformaldehyde is calculated by formaldehyde.
2. The process for synthesizing glyphosate according to claim 1, wherein the organic catalyst is directly added into a mixed solution of paraformaldehyde and methanol, and the polymerization degree of the paraformaldehyde is 3-100.
3. The process for synthesizing glyphosate according to claim 1, wherein the addition reaction temperature is 35-50 ℃ and the reaction time is 30-90 min; the condensation reaction temperature is 40-58 ℃ and the reaction time is 30-120 min.
4. The process for synthesizing glyphosate according to claim 1, wherein the molar ratio of the materials in the glyphosate synthesis process is, based on the molar amount of formaldehyde: glycine: dimethyl phosphite: alcohol: triethylamine: hydrogen chloride =1: 0.4-0.8: 0.3-0.8: 2-8: 0-0.8: 1-2; the molar ratio of the methanol to the paraformaldehyde is controlled to be more than or equal to 0.3:1, and the methanol is supplemented at most when the molar ratio of the polyformaldehyde to the alcohol is 1: 2-8.
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