CN110862413A - Glyphosate synthesis process and device - Google Patents
Glyphosate synthesis process and device Download PDFInfo
- Publication number
- CN110862413A CN110862413A CN201810981637.1A CN201810981637A CN110862413A CN 110862413 A CN110862413 A CN 110862413A CN 201810981637 A CN201810981637 A CN 201810981637A CN 110862413 A CN110862413 A CN 110862413A
- Authority
- CN
- China
- Prior art keywords
- glyphosate
- alcohol
- reaction
- catalyst
- mixed solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 75
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 124
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 108
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 68
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 44
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 42
- 239000011259 mixed solution Substances 0.000 claims abstract description 39
- 239000000243 solution Substances 0.000 claims abstract description 37
- 239000004471 Glycine Substances 0.000 claims abstract description 34
- 238000007259 addition reaction Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000006482 condensation reaction Methods 0.000 claims abstract description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims abstract description 23
- -1 alkoxy metal organic compound Chemical class 0.000 claims abstract description 16
- 230000007062 hydrolysis Effects 0.000 claims abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 13
- 238000007036 catalytic synthesis reaction Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000007792 addition Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 132
- 239000003814 drug Substances 0.000 claims description 19
- 230000035484 reaction time Effects 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 8
- 229920006324 polyoxymethylene Polymers 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 150000003138 primary alcohols Chemical class 0.000 claims description 2
- 150000003333 secondary alcohols Chemical class 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 2
- 235000009508 confectionery Nutrition 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- 150000002902 organometallic compounds Chemical class 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 238000012691 depolymerization reaction Methods 0.000 abstract description 19
- 230000008901 benefit Effects 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000036632 reaction speed Effects 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 description 18
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
- 125000003545 alkoxy group Chemical group 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 150000002373 hemiacetals Chemical class 0.000 description 8
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- YLGDTEYFAMCCEL-UHFFFAOYSA-N NCC(O)=O.COP(O)OC Chemical compound NCC(O)=O.COP(O)OC YLGDTEYFAMCCEL-UHFFFAOYSA-N 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 230000001476 alcoholic effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000010413 mother solution Substances 0.000 description 5
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000002585 base Substances 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
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 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
- 238000007086 side reaction Methods 0.000 description 2
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical group O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- LTRVAZKHJRYLRJ-UHFFFAOYSA-N lithium;butan-1-olate Chemical compound [Li+].CCCC[O-] LTRVAZKHJRYLRJ-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- MKNZKCSKEUHUPM-UHFFFAOYSA-N potassium;butan-1-ol Chemical compound [K+].CCCCO MKNZKCSKEUHUPM-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (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
A catalytic synthesis process of glyphosate uses alkoxy metal organic compound as catalyst to synthesize glyphosate, in particular to depolymerization and addition in the synthesis process of glyphosate, and comprises the following steps: mixing alcohol and paraformaldehyde, uniformly stirring, and adding the catalyst into the mixed solution, or directly adding the catalyst into the alcohol solution of formaldehyde to generate a transparent mixed solution; adding triethylamine and glycine into the mixed solution, stirring for addition reaction, and after the reaction is finished, adding dimethyl phosphite into the mixed solution for condensation reaction; 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. The technical scheme of the invention uses a specific catalyst to improve the reaction speed and selectivity of glyphosate synthesis, the depolymerization and addition reaction speed is high, the reaction is thorough, the final yield of the glyphosate product is improved by more than 3% compared with the traditional process, and the invention has the advantages of reaction advantage, energy saving advantage, cost advantage and environmental protection.
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 and a device thereof.
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 in Bombandon are basically produced by the iminodiacetic acid method. The glyphosate production in China began 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 alkoxy metal organic compound as catalyst for depolymerization and addition reaction. The catalyst mainly plays two roles: firstly, the catalyst plays a role in the depolymerization process, and promotes the paraformaldehyde 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.
The depolymerization catalyst is a series of alkoxy metal organic compounds such as lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide and the like generated by replacing hydroxyl hydrogen atoms of alcohols such as methanol, ethanol and the like by metal atoms such as lithium, sodium, potassium, magnesium, calcium and the like, and the structural general formula of the depolymerization catalyst is as follows: R-O-X. Wherein R is alkyl group of alcohol substance, O is hydroxyl oxygen atom of alcohol substance, and X is metal element. Other organic base compounds that provide alkoxy groups may also provide the same effect.
Preferably, the metallic element is a metallic element of the first and second main groups, and more preferably, the metallic element is an alkali metallic element (i.e. six metallic elements of the first main group I: lithium, sodium, potassium, rubidium, cesium, francium). The catalyst is alkoxy alkali metal compound such as sodium methoxide (lithium methoxide, potassium methoxide), sodium ethoxide (lithium ethoxide, potassium ethoxide), and sodium n-butoxide (lithium n-butoxide, potassium n-butoxide). Considering the factors of comprehensive cost and easy material acquisition, it is further preferable that the metal atoms are sodium, potassium and lithium, that is, the catalyst is selected from sodium alkoxide (potassium and lithium) compounds such as sodium methoxide (potassium and lithium), sodium ethoxide (potassium and lithium), sodium n-butoxide (potassium and lithium) and the like or alcohol solutions thereof.
Preferably, the alkali metal atom substitute (metal alkoxide) for 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 in the form of an alcoholic solution of the metal alkoxide (i.e., a series of solutions of sodium methoxide in methanol, sodium ethoxide in ethanol, sodium methoxide in ethanol, sodium ethoxide in methanol, etc.), and is used therewith. 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 implementation 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.
The catalyst can be added independently, or can be added into raw materials such as paraformaldehyde (or liquid formaldehyde alcohol solution), methanol, triethylamine and the like used in the processes of depolymerization and addition of glyphosate in advance, and then added into a 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.
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 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.
The presence of moisture can cause the catalyst to hydrolyze, which affects the activity of the catalyst. Therefore, it is preferable to dry and dehydrate paraformaldehyde, and then add methanol and a depolymerization catalyst to carry out a 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 30-90 ℃ for 10 s-120 min. After the dehydration, methanol and a depolymerization catalyst are added for depolymerization reaction.
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, carrying out 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: 0.05-0.8: 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.
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 liquor reaches about 85 percent, and the yield is also improved by 3 percent compared with the yield of the traditional glycine-dimethyl phosphite process.
Specifically, it states that: it should be understood that the catalyst, regardless of the manner in which it is synthesized, is within the scope of the present invention as long as the catalyst is used in the synthesis of glyphosate.
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 about 1 minute at normal temperature, has low reaction temperature, short reaction time (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 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 condensed water discharge pipe, 12, a steam inlet 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 30) 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 80 ℃. 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: 6.
the molar ratio of sodium methoxide to formaldehyde (the moles of paraformaldehyde are calculated as formaldehyde) is controlled: one hundred parts per million.
When the polymerization degree of the paraformaldehyde is 30, the molar number of the paraformaldehyde is 1000 × 96%/30.03 ═ 31.97mol, and the molar fraction of the paraformaldehyde is 31.97/30 ═ 1.07 mol.
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 8: 1) to 1.2.
The content of the glyphosate raw drug is 97.5 percent, the yield of the glyphosate raw drug calculated by glycine reaches 82 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 7.5 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 35) 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 70 ℃, adding ethanol (the molar ratio of methanol to paraformaldehyde is controlled to be 0.6:1) after dehydration is finished, stirring uniformly, adding a methanol solution of lithium methoxide into a mixed solution, and naturally reacting for 20 seconds at 30 ℃ to carry out depolymerization reaction to generate a high-activity ethanol solution of 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): two hundred 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, 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 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: ethanol: 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 95.5 percent, the yield of the glyphosate raw drug calculated by glycine reaches 80.4 percent, the total yield of the raw drug and the glyphosate in the mother solution reaches over 84.2 percent, and the yield is also improved by 5.9 percent compared with the yield of the traditional glycine-dimethyl phosphite process.
Example 3
1. Depolymerization reaction: taking a purchased methanol solution of anhydrous formaldehyde as a formaldehyde raw material, adding a methanol solution of catalyst potassium methoxide into the alcohol solution of the anhydrous formaldehyde, 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.
the molar ratio of the potassium methoxide to the formaldehyde (the mole number of the paraformaldehyde is calculated as the formaldehyde) is controlled as follows: 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 65 ℃, 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 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 materials in the glyphosate synthesis process is that paraformaldehyde (calculated by formaldehyde): glycine: dimethyl phosphite: methanol: triethylamine: hydrogen chloride was 1:0.4:0.35:2.2:0.3 (molar ratio of triethylamine in step 2 to triethylamine in step 3 was 5:1) to 1.4.
The content of the glyphosate raw drug is 95.0 percent, the yield of the glyphosate raw drug calculated by glycine reaches 79 percent, the total yield of the raw drug and the glyphosate in the mother solution reaches 82 percent, and the yield is improved by 4.5 percent compared with the yield of the traditional glycine-dimethyl phosphite process.
Example 4
1. Depolymerization reaction: mixing n-butanol and paraformaldehyde, stirring uniformly, and reacting at 30 deg.C for 30s to complete depolymerization reaction. The n-butanol and paraformaldehyde solutions are both added with ethanol solution of sodium ethoxide as catalyst. After the depolymerization is finished, ethanol is added until the molar ratio of polyformaldehyde to alcohol is 1: 7.5.
controlling the molar ratio of sodium ethoxide to formaldehyde (the mole number of paraformaldehyde is calculated as formaldehyde): parts per million; controlling the molar ratio of sodium ethoxide to methanol: ten 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 80 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: n-butanol: triethylamine: hydrogen chloride 1:0.65:0.38:7.5:0.8 (molar ratio of triethylamine in step 2 to triethylamine in step 3: 5:1) to 1.1.
The content of the glyphosate raw drug is 96.0 percent, the yield of the glyphosate raw drug calculated by glycine reaches 78.5 percent, the total yield of the raw drug and the glyphosate in the mother solution reaches 82.5 percent, and the yield is also improved by 4.0 percent compared with the yield of the traditional glycine-dimethyl phosphite process.
Example 5
1. Depolymerization reaction: taking a purchased methanol solution of anhydrous formaldehyde as a formaldehyde raw material, adding a catalyst lithium methoxide into the methanol solution of the anhydrous formaldehyde, 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: 2.4.
the molar ratio of the lithium methoxide to the formaldehyde (the mole number of the paraformaldehyde is calculated as the formaldehyde) is controlled as follows: 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 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 materials in the glyphosate synthesis process is that paraformaldehyde (calculated by formaldehyde): glycine: dimethyl phosphite: methanol: hydrogen chloride is 1:0.45:0.36:2.4: 1.8.
The content of the glyphosate raw drug is 95.0 percent, the yield of the glyphosate raw drug calculated by glycine reaches 78 percent, the total yield of the raw drug and the glyphosate in the mother solution reaches 82 percent, and the yield is improved by 3.5 percent compared with the yield of the traditional glycine-dimethyl phosphite process.
Claims (8)
1. A catalytic synthesis process of glyphosate is characterized in that: the method uses alkoxy metal organic compound or alcohol solution thereof as a catalyst for synthesizing glyphosate, and is particularly applied to depolymerization and addition in the glyphosate synthesis process, and comprises the following steps:
(1) mixing alcohol and paraformaldehyde, uniformly stirring, adding the catalyst into the mixed solution, or directly adding the catalyst into the alcohol solution of formaldehyde, and depolymerizing to generate a transparent mixed solution;
(2) adding triethylamine and glycine into the mixed solution obtained in the step (1) and stirring for addition reaction, and after the reaction is finished, adding dimethyl phosphite into the mixed solution for condensation reaction; 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.
2. The catalytic synthesis process of glyphosate according to claim 1, characterized in that: the molar ratio of materials in the glyphosate synthesis process is that paraformaldehyde: glycine: dimethyl phosphite: alcohol: triethylamine: hydrochloric acid =1: 0.4-0.8: 0.3-0.8: 2-8: 0.05-0.8: 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.
3. The catalytic synthesis process of glyphosate according to claim 1, characterized in that: the alkoxide metal organic compound alcohol solution catalyst in the step (1) is one or more of alkoxide metal compounds prepared from fresh anhydrous alcohol and anhydrous hydroxide or oxide of metal atoms, and exists in the form of alkoxide metal compound alcohol solution;
controlling the molar ratio of the catalyst to the paraformaldehyde: 1/10000000-1/100, wherein the molar weight of the paraformaldehyde is calculated by formaldehyde.
4. The catalytic synthesis process of glyphosate according to claim 1, characterized in that: the alcohol comprises primary alcohol, secondary alcohol, tertiary alcohol, and one or more of monohydric alcohol and polyhydric alcohol.
5. The catalytic synthesis process of glyphosate according to claim 1, characterized in that: in the step (2), the addition reaction temperature is 35-50 ℃, and the reaction time is 30-90 min; the condensation reaction temperature is 40-58 deg.C, and the reaction time is 30-120 min.
6. The catalytic synthesis unit of glyphosate according to any one of claims 1-5, characterized in that:
the catalyst pipeline and the methanol pipeline are respectively connected with the catalyst preparation tank, the catalyst preparation tank is connected with the upper part of the depolymerization kettle, and the lower part of the depolymerization kettle is connected with the synthesis kettle; synthetic cauldron passes through the pipeline and is connected with hydrolysis kettle upper portion, and hydrolysis kettle is connected with the crystallization kettle, and the crystallization kettle is connected with the former medicine drying device of sweet phosphine through washing the material device.
7. The catalytic synthesis plant of glyphosate of claim 6, wherein: the upper part of the depolymerization kettle is provided with a paraformaldehyde inlet pipeline and a methanol inlet pipeline.
8. The catalytic synthesis plant of glyphosate of claim 6, wherein: the upper part of the synthesis kettle is provided with a triethylamine inlet pipeline, a dimethyl phosphite inlet pipeline and a glycine inlet pipeline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810981637.1A CN110862413A (en) | 2018-08-27 | 2018-08-27 | Glyphosate synthesis process and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810981637.1A CN110862413A (en) | 2018-08-27 | 2018-08-27 | Glyphosate synthesis process and device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110862413A true CN110862413A (en) | 2020-03-06 |
Family
ID=69651034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810981637.1A Pending CN110862413A (en) | 2018-08-27 | 2018-08-27 | Glyphosate synthesis process and device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110862413A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112194677A (en) * | 2020-09-14 | 2021-01-08 | 镇江江南化工有限公司 | Novel process and synthesis device for preparing glyphosate by hydrolyzing by-product acid instead of hydrochloric acid |
| CN113582822A (en) * | 2021-07-31 | 2021-11-02 | 南通江山农药化工股份有限公司 | Continuous depolymerization method of paraformaldehyde and application thereof |
Citations (10)
| 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 |
| CN101993455A (en) * | 2010-12-13 | 2011-03-30 | 四川省乐山市福华通达农药科技有限公司 | Glyphosate synthesis process |
| 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 |
| CN104163832A (en) * | 2014-08-12 | 2014-11-26 | 湖北泰盛化工有限公司 | Glyphosate continuous production device and glyphosate continuous production method |
| 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 |
| CN106279273A (en) * | 2016-08-13 | 2017-01-04 | 安徽东至广信农化有限公司 | A kind of production technology of glyphosate technicals |
| CN106699536A (en) * | 2017-01-12 | 2017-05-24 | 湖北泰盛化工有限公司 | Preparation method of anhydrous formaldehyde alcohol solution and device |
| 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 |
| CN108329350A (en) * | 2018-04-20 | 2018-07-27 | 湖北泰盛化工有限公司 | A kind of glyphosate synthesis device |
| CN209128346U (en) * | 2018-08-27 | 2019-07-19 | 湖北泰盛化工有限公司 | A kind of glyphosate synthesis device |
-
2018
- 2018-08-27 CN CN201810981637.1A patent/CN110862413A/en active Pending
Patent Citations (10)
| 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 |
| CN101993455A (en) * | 2010-12-13 | 2011-03-30 | 四川省乐山市福华通达农药科技有限公司 | Glyphosate synthesis process |
| 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 |
| CN104163832A (en) * | 2014-08-12 | 2014-11-26 | 湖北泰盛化工有限公司 | Glyphosate continuous production device and glyphosate continuous production method |
| 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 |
| CN106279273A (en) * | 2016-08-13 | 2017-01-04 | 安徽东至广信农化有限公司 | A kind of production technology of glyphosate technicals |
| CN106699536A (en) * | 2017-01-12 | 2017-05-24 | 湖北泰盛化工有限公司 | Preparation method of anhydrous formaldehyde alcohol solution and device |
| 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 |
| CN108329350A (en) * | 2018-04-20 | 2018-07-27 | 湖北泰盛化工有限公司 | A kind of glyphosate synthesis device |
| CN209128346U (en) * | 2018-08-27 | 2019-07-19 | 湖北泰盛化工有限公司 | A kind of glyphosate synthesis device |
Non-Patent Citations (2)
| Title |
|---|
| 周锰飞: "草甘膦合成过程控制系统研究", 《浙江工业大学硕士学位论文》 * |
| 廖铁星主编: "《广西医药企业管理协会仓储管理养护技术研究会编. 化学试剂危险物品安全储存养护手册[M]》" * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112194677A (en) * | 2020-09-14 | 2021-01-08 | 镇江江南化工有限公司 | Novel process and synthesis device for preparing glyphosate by hydrolyzing by-product acid instead of hydrochloric acid |
| CN113582822A (en) * | 2021-07-31 | 2021-11-02 | 南通江山农药化工股份有限公司 | Continuous depolymerization method of paraformaldehyde and application thereof |
| CN113582822B (en) * | 2021-07-31 | 2023-06-06 | 南通江山农药化工股份有限公司 | Continuous depolymerization method of paraformaldehyde and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102775441B (en) | Continuous production method of glyphosate synthetic liquid | |
| CN114805314B (en) | Synthesis method of Entecavir | |
| CN110862413A (en) | Glyphosate synthesis process and device | |
| CN111825549B (en) | Synthesis method of n-butyl glycolate | |
| CN110860310B (en) | Organic catalyst for synthesizing glyphosate and glyphosate synthesis process | |
| CN103664923A (en) | Preparation method for nifuratel | |
| CN110862414B (en) | Process for catalytically synthesizing glyphosate | |
| CN109251153B (en) | Synthetic method of cinnamonitrile | |
| CN104072369B (en) | A kind of technique preparing Diisopropyl malonate | |
| CN115572272A (en) | Preparation method of febuxostat and aldehyde ester intermediate thereof | |
| CN102766160A (en) | Novel process for preparing glyphosate by utilizing glycine method | |
| CN112645815A (en) | Preparation method for catalytically synthesizing methyl cinnamate based on eutectic solvent | |
| CN209128346U (en) | A kind of glyphosate synthesis device | |
| CN113072441A (en) | Preparation method of 2-methoxy-6-methylbenzoic acid | |
| CN117466810B (en) | Industrial continuous production method of picloram | |
| CN114195638B (en) | Preparation method of phenyl o-hydroxybenzoate | |
| CN116162074B (en) | Purification method of 2, 5-furandicarboxylic acid | |
| CN103145562A (en) | N-ethyl aniline preparation method | |
| CN104262160A (en) | Method for preparing 2-nitro-2-methyl-1-propanol | |
| CN109232213A (en) | The method of hydroxy pivalin aldehyde is prepared under a kind of super critical condition | |
| CN115626893B (en) | Synthesis method of 2-hydroxy-5-hydroxymethylpyridine | |
| CN114605375B (en) | Synthetic method of 2-thiopheneacetic acid | |
| CN113121532B (en) | Preparation method of dye intermediate | |
| CN115746052B (en) | Process for hydrolyzing glyphosate by alkyl ester method | |
| CN114456048B (en) | Preparation method of penconazole intermediate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200306 |
|
| RJ01 | Rejection of invention patent application after publication |