CN1962672A - Process of glycine method for preparing glyphosate - Google Patents
Process of glycine method for preparing glyphosate Download PDFInfo
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- CN1962672A CN1962672A CN 200510115909 CN200510115909A CN1962672A CN 1962672 A CN1962672 A CN 1962672A CN 200510115909 CN200510115909 CN 200510115909 CN 200510115909 A CN200510115909 A CN 200510115909A CN 1962672 A CN1962672 A CN 1962672A
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Abstract
The invention discloses an after-disposing of glyphosate, which is characterized by the following: adopting glycine and phosphorous alkyl ester as raw material; dissolving the raw material; acidolyzing; improving the receiving rate, production and quality of glyphosate; reducing material consumption and cost greatly.
Description
Invention field
The present invention relates to a kind of New post processing method that adopts when being the preparation herbicide glyphosate (N-(phosphonomethyl) glycine) of raw material with glycine and alkyl phosphite.
Background of invention
Glyphosate has another name called the sweet acid of phosphine, and chemical name is N-(phosphonomethyl) glycine, English N-(phosphono methyl) glycine by name, and general glyphosate by name, commodity for example Roundup by name, chemical structural formula is (I):
Glyphosate is a kind of steriland herbicide of wide spectrum efficiently, find and development and use in 1972 by U.S. Monsanto Company, because of it has good interior suction conductive performance, control to multiple dark root malignant weed is very effective, sales volume increases rapidly in recent years, along with the popularization of some genetically modified crops, its range of application will further enlarge.
At present the industrial product route of synthesizing glyphosate is more, as chloromethyl phosphonic acids method, iminodiethanoic acid (IDA) method, dialkyl phosphite method and phosphorous test etc., but really realizes industrializedly mainly containing two.Article one, what be that U.S. Monsanto Company adopts is iminodiethanoic acid (IDA) route of starting raw material with prussic acid or diethanolamine, and what another was that China generally adopts is the dialkyl phosphite route of starting raw material with the glycine.These two lines all can obtain purity and be not less than 93.5% the former powder of glyphosate.
Till now, existing numerous research is around the IDA route unwind, and disclosing respectively with iminodiethanoic acid (IDA) as US5312973, US5023369 is that starting raw material prepares pmida98 and prepared the method for glyphosate by the pmida98 oxidation; ZL93120707, ZL96195765 also disclose respectively by the iminodiacetic acid (salt) acid alkali metal salt and have prepared pmida98 and prepare the method for glyphosate by the pmida98 hydrogen peroxide oxidation.
Then study lessly for the dialkyl phosphite route, application number is that to disclose a kind of be the glyphosate preparation technology of raw material with the dialkyl phosphite for 85102988 patent of invention; Application number is that 00125933 patent of invention discloses a kind of improvement to dialkyl phosphite technology, does not adopt Paraformaldehyde 96 but utilizes the by product methylal of self to come synthesizing glyphosate; " trimethyl phosphite synthesizing glyphosate technical study " in addition (" PESTICIDES " 1999,38 (6) P8) introduced trimethyl phosphite and the glycine method at the aqueous phase synthesizing glyphosate; Application number is the method for starting raw material synthesizing glyphosate with the glycine an alkali metal salt for the patent of invention of 03147313.X provides a kind of.
Because the factor of raw material, dialkyl phosphite technology obtains tremendous development in China, its year scale reached 80,000 tons/year.
Dialkyl phosphite process using Paraformaldehyde 96 obtains formal in the depolymerization of methyl alcohol triethylamine system, and then with the glycine condensation, again with the dialkyl phosphite condensation, last acidifying, separating methanol, depickling, crystallization, filtration, oven dry obtain the former powder of glyphosate.
Obtain methylal, hemiacetal and a small amount of hydration formaldehyde etc. after the Paraformaldehyde 96 depolymerization, methylal boiling point low (42 ℃), highly volatile, in the process that adds glycine, can part volatilize, cause proportioning deviation to occur, even glycine can not be fully and methylal carry out condensation reaction, influence the finished product total recovery.
Glycine with methylal or hemiacetal condensation course in can produce less water, this part water can destroy dimethylphosphite.A lot of enterprises are head it off, often add can more fully react with the acetal that guarantees glycine into dimethylphosphite, improve the finished product yield.But this mode often causes component complexity in the process, has a strong impact on product quality and gets brilliant rate, also causes raw materials cost to increase.
The dimethylphosphite condenses adds mineral acid (HCl, HNO
3Or H
2SO
4Deng) carrying out acidifying, the normal pressure that slowly heats up reclaims methyl alcohol, and temperature reaches 110 ℃ after 4-5 hour, and decompression depickling temperature rises to 110 ℃, is incubated to add water crystallization, suction filtration, oven dry behind about 10min and obtain the former powder of glyphosate.The methyl alcohol that normal pressure reclaims after the low temperature acidifying is moisture and be strongly-acid, can't directly apply mechanically, generally need to add in the alkali and after carry out rectifying again and obtain anhydrous methanol.To additionally increase alkali cost and energy consumption like this.We discover that under 100 ℃ of left and right sides high temperature and strong acidic condition serious the decomposition will appear in product, thereby cause total yield of products to reduce.Application number is that 200410099086.4 patent of invention adds the way that alkali is regulated pH value preparation glyphosate crystal and added the ammonia treatment glyphosate mother solution with mentioning after acidolysis finishes, but not mentioned temperature height having a strong impact on supplies consumption and yield also.
Summary of the invention
The invention provides a kind of is the novel process of feedstock production glyphosate (N-(phosphonomethyl) glycine) with glycine and alkyl phosphite.
Specifically, the present invention obtains glycine formaldehyde condensation products liquid by single step reaction with Paraformaldehyde 96, glycine, monohydroxy-alcohol and tertiary amine under the certain temperature condition, experiment show acetal that this process modification can guarantee that the Paraformaldehyde 96 depolymerization obtains quickly and effectively with the glycine reactant condensation, promote that depolymerization is complete, also can not cause variation, thereby improve the final yield of glyphosate because of acetal volatilization causing material proportion.The small amount of moisture that inorganic salt not only can absorption reaction produce, and the hydrolysis that can reduce raw material and product causes system acidity to increase and condensation is incomplete can more effective raising glyphosate products yield, less supplies consumption.
Among the present invention, glycine can be the purified glycine, can be the inorganic salt mixt of glycine also, is preferably glycine inorganic salt mixed crystal.The glycine inorganic salt can be by obtaining after aminoacetonitriles alkaline hydrolysis, neutralization, the separation and purification.The refining glycine of saliferous glycine has simpler treatment process, higher yield, lower cost are arranged, but the saliferous glycine that the direct alkaline hydrolysis acidifying oven dry of the aminoacetonitriles that application number is the patent of invention of 03147313.X to be narrated obtains also is not suitable for the directly synthetic of glyphosate, the cause directly content of alkaline hydrolysis iminodiethanoic acid is subjected to temperature, alkali number and mode reinforced, separation and purification to influence very big, mixture IDA content is much higher than 0.5% product index requirement, the purity drop that can cause glyphosate consumes higher.In addition, the introducing of too much salt also can strengthen aftertreatment burden and solvent consumption, causes refuse and production cost to increase.Therefore, the amount of inorganic salt is being advisable below 25%, and is more suitable in the scope of 5-20%.
Therefore not only discover that the solvability of glycine in reaction system also is the key that influences yield, allow glycine that longer dissolution time is arranged in system but also the process innovation that do not influence production capacity also is important.We discover, for example Paraformaldehyde 96, glycine, methyl alcohol, the disposable blended one kettle way of triethylamine are reflected under the constant situation of whole time, more can guarantee the dissolving and the reaction of Paraformaldehyde 96 and glycine, can better overcome large-scale condensation still and mix engineering problems such as efficient is poor, production capacity is low, to improve and stable yield, quality effect obvious.The converted in-situ rate can reach (in glycine) more than 90% after separating polycondensation, and more former technology can improve glyphosate yield about 5%.Among the present invention, described monohydroxy-alcohol is C
1-C
4Monohydroxy-alcohol is preferably methyl alcohol.
Described tertiary amine is Trimethylamine 99 or triethylamine, is preferably triethylamine.
Above-mentioned temperature of reaction is 20-80 ℃, is preferably 30-60 ℃.
Described glycine can be purified glycine or the glycine that contains inorganic salt-inorganic salt mixed crystal.Glycine purity is 30-99%, is preferably 70-95%.When adopting the glycine inorganic salt, described inorganic salt are preferably one or more in sodium-chlor, Repone K, sodium sulfate, vitriolate of tartar, SODIUMNITRATE and the saltpetre, are preferably sodium-chlor or sodium sulfate.The glycine inorganic salt also can be that aminoacetonitriles etc. is through the isolating mixture of chemosynthesis.In addition, the glycine inorganic salt also can adopt the form of the combination of glycine and inorganic salt to substitute.When adopting inorganic salt, no matter adopt which kind of form, inorganic salt should be controlled at below 25% with respect to the amount of glycine and be advisable, and are more suitable in the scope of 5-20%.
Paraformaldehyde 96: glycine: the mol ratio of tertiary amine is 0.6-4.0: 1.0: 0.1-3 is preferably 12-3.0: 1.0: 0.5-2.0.The amount of monohydroxy-alcohol is not crucial, and generally speaking, its amount can form the solvent system that is suitable for the present invention's reaction and get final product glycine: the mol ratio of monohydroxy-alcohol is about 1: 5-18.
The condensated liquid of glycine formaldehyde adds the dialkyl phosphite of certain proportioning at a certain temperature, and insulation reaction obtains N-dialkyl (phosphonomethyl) glycine, is referred to as the condensation esterifying liquid.
Above-mentioned temperature of reaction is 20-90 ℃, is preferably 40-70 ℃.
Described dialkyl phosphite is dimethylphosphite or diethyl phosphite, is preferably dimethylphosphite.
Described dialkyl phosphite/glycine proportioning is 0.7-2.0/1, is preferably 0.9-1.3/1.
When adopting the glycine inorganic salt as the glycine raw material, finish the inventive method step 2) after, with the glycine formaldehyde condensation products liquid filtration under diminished pressure that obtains, the inorganic salt that filtering is introduced by glycine, with an amount of methanol wash inorganic salt, washings and filtrate are mixed for the next step, can be used as the by-product commodity selling after the inorganic salt oven dry.
In specific embodiments, for example, the method that the present invention prepares glyphosate comprises the steps:
1) Paraformaldehyde 96, glycine, monohydroxy-alcohol and tertiary amine are dropped in the same reaction vessel, under the certain temperature condition, for example 20-80 ℃, be preferably 30-60 ℃, obtain glycine formaldehyde condensation products liquid by single step reaction;
2) glycine formaldehyde condensation products liquid at a certain temperature; for example; 20-90 ℃; be preferably 40-70 ℃, add the dialkyl phosphite of certain proportioning, insulation reaction; obtain N-dialkyl (phosphonomethyl) glycine; described proportioning is dialkyl phosphite/glycine proportioning, and ratio range is generally 0.7-2.0/1, is preferably 0.9-1.3/1.N-dialkyl (phosphonomethyl) glycine obtains glyphosate through post-processing steps such as acidifyings.
In the inventive method, described monohydroxy-alcohol is C
1-C
4Monohydroxy-alcohol is preferably methyl alcohol.
Described tertiary amine is Trimethylamine 99 or triethylamine, is preferably triethylamine.
Described glycine can be purified glycine or the glycine that contains inorganic salt-inorganic salt mixed crystal.Glycine purity is 30-99%, is preferably 70-95%; Described inorganic salt are preferably one or more in sodium-chlor, Repone K, sodium sulfate, vitriolate of tartar, SODIUMNITRATE and the saltpetre, are preferably sodium-chlor or sodium sulfate.The glycine inorganic salt also can be that aminoacetonitriles etc. is through the isolating mixture of chemosynthesis.In addition, the glycine inorganic salt also can adopt the form of the combination of glycine and inorganic salt to substitute.When adopting inorganic salt, no matter adopt which kind of form, inorganic salt should be controlled at below 25% with respect to the amount of glycine and be advisable, and are more suitable in the scope of 5-20%.
Paraformaldehyde 96: glycine: the mol ratio of tertiary amine is 0.6-4.0: 1.0: 0.1-3 is preferably 12-3.0: 1.0: 0.5-2.0.The amount of monohydroxy-alcohol is not crucial, and generally speaking, its amount can form the solvent system that is suitable for the present invention's reaction and get final product glycine: the mol ratio of monohydroxy-alcohol is about 1: 5-18.
Described dialkyl phosphite is dimethylphosphite or diethyl phosphite, is preferably dimethylphosphite.
Described dialkyl phosphite/glycine proportioning is 0.7-2.0/1, is preferably 0.9-1.3/1.
The condensation esterifying liquid that obtains can adopt traditional technology to carry out aftertreatment, obtains the glyphosate raw material.
What traditional technology was taked the acidolysis of condensation esterifying liquid is acid hydrolysis, the mixture to 110 ℃ that progressively heats up and steam methyl alcohol, acid, water, methylal etc., be decompressed to 110 ℃ again, the cooling that is dissolved in water again, crystallization, filtration, washing, oven dry obtain the former powder of glyphosate.Mother liquor adds alkali again and reclaims triethylamine, and concentrated precipitated sodium chloride is mixed with 10% liquid glyphosate sale again.The fatal shortcoming of this technology is that facility investment is big, is batch production entirely, and the finishing apparatus of depickling, dealcoholysis is numerous, the energy consumption material consumption is big, consumes a large amount of hydrochloric acid, caustic soda, the abraum salt that by-product is a large amount of, the a large amount of losses of methyl alcohol have the generation and the emptying of a large amount of methyl chloride, and environmental pollution is serious.The methyl alcohol that steams need neutralize, just can apply mechanically after the rectifying.The neutral triethylamine also needs dry, and the moisture and the free alkali of the methyl alcohol of applying mechanically, triethylamine etc. are bigger to the influence of yield.We discover that acidity and temperature controlling are huge to the influence of yield in the acidolysis process, can cause 20～30% yield losses.
Therefore, a further object of the present invention provides the post-treating method that glycine and dialkyl phosphite legal system are equipped with glyphosate, this method can effectively solve above-mentioned technology, engineering technology problem, for extensive, low-cost, the serialization cleaner production of glyphosate provides more advanced technology, engineer equipment and system integration technology, reduce the generation and the energy consumption material consumption of the three wastes as far as possible.
We are unexpected under study for action to find that the condensation esterifying liquid after reaction is finished can steam most methyl alcohol and triethylamine under normal pressure or decompression, this partial material can directly be applied mechanically without separating, condenses volume after the distillation greatly reduces, acidolysis speeds up, acid consumption reduces, and be that hydrolyzable is complete below 80 ℃, not only can effectively suppress the generation of methyl chloride in the hydrolytic process, reduce methyl alcohol and hydrochloric acid consumption, and the yield losses that can effectively avoid the decomposes in the condenses hydrolytic process and cause can improve production capacity and product yield greatly, reduces methyl alcohol significantly, the supplies consumption of liquid caustic soda etc., reduce facility investment, increase economic efficiency.
Post-treating method of the present invention is to reclaim monohydroxy-alcohol and tertiary amine under condensation esterifying liquid elder generation normal pressure (or decompression) certain temperature, recovery liquid can directly overlap to be used in the next batch reaction, esterifying liquid behind the precipitation adds quantitative mineral acid acidolysis by proportioning, acidolysis finishes back decompression depickling or directly adds in the alkali and adjusting pH value, concentrate and separate out product, filtration drying obtains the former powder of glyphosate, and filtrate being used to prepares the liquid glyphosate.The monohydroxy-alcohol that reclaims, tertiary amine can directly be applied mechanically after replenishing a little, and that has saved most of material adds operations such as alkali, drying, neutralization deacidification, rectifying, has saved starting material and equipment input greatly, has reduced production cost.And acidolysis is more complete at low temperatures, and product is reduced greatly by pyrolytic decomposition destructive probability, and the glyphosate products total recovery can improve 5-10%.
The condensation reaction mixture of phosphorous acid ester can reclaim for example methyl alcohol and tertiary amine triethylamine for example of most of monohydroxy-alcohol earlier at a certain temperature, carries out acidolysis again.Condenses can be under 0-150 ℃ of condition precipitation, be preferably 30-120 ℃.
Above-mentioned acidolysis temperature is 20-100 ℃, is preferably 40-80 ℃
The described acidolysis time is 1-10h, is preferably 3-6h.
Described mineral acid is hydrochloric acid, sulfuric acid or nitric acid etc., is preferably hydrochloric acid.
Described acid mole proportioning is counted 0.5-10 by glycine, is preferably 1-4.
Described neutralization back system pH is 0.7-3.0, is preferably 1.5-2.5.
In specific embodiments, post-treating method of the present invention comprises the steps:
A) will adopt glycine method; step 2 for example of the present invention) Zhi Bei N-dialkyl (phosphonomethyl) glycine liquid; promptly; under condensation esterifying liquid elder generation normal pressure/decompression certain temperature; for example precipitation under 0-150 ℃ of condition is preferably 30-120 ℃, reclaims monohydroxy-alcohol and tertiary amine; recovery liquid can directly overlap to be used in the next batch reaction
B) esterifying liquid behind the precipitation adds quantitative mineral acid acidolysis by proportioning, for example, described acid mole proportioning is counted 0.5-10 by glycine, be preferably 1-4, acidolysis finishes back decompression depickling or directly adds in the alkali and adjusting pH value, concentrate and separate out product, filtration drying obtains the former powder of glyphosate, and filtrate being used to prepares the liquid glyphosate.
When adopting glyphosate by using glycine of the present invention, under the situation of selecting for use the glycine inorganic salt as the glycine raw material, filter desalination and washing and desalting step, in steps A) finish before.
Above-mentioned acidolysis temperature is 20-100 ℃, is preferably 40-80 ℃; The described acidolysis time is 1-10h, is preferably 3-6h.
Described mineral acid is hydrochloric acid, sulfuric acid or nitric acid etc., is preferably hydrochloric acid.
Described neutralization back system pH is 0.7-3.0, is preferably 1.5-2.5.
Post-treating method of the present invention, for the big suitability for industrialized production of preparing glyphosate by glycin method provide may, and significantly reduced the generation and the energy consumption material consumption of the three wastes.
Embodiment
Hereinafter provide indefiniteness embodiment, be intended to illustrate the present invention but not limit content of the present invention by any way.
Embodiment 1-1
With Paraformaldehyde 96 16.1g (0.537mol), triethylamine 25.6g (0.253mol) and 120ml methyl alcohol place simultaneously takes back flow condenser, in the 500mL four-hole boiling flask of thermometer and stirring, be stirred to transparent after, add glycine 19g (0.25mol), continue to be stirred to and be warming up to 45 ℃ after transparent, add dimethylphosphite 33g (0.3mol), behind 45-65 ℃ of insulation reaction 2-5h, add hydrochloric acid (30%) 87.5g (0.863mol) acidifying, normal pressure steams methyl alcohol simultaneously, when temperature reaches 110 ℃, the decompression depickling, when temperature reaches 110 ℃ once more, stop decompression, add 40g water, crystallisation by cooling, the suction filtration drying obtains the former powder 32.12g of glyphosate (content 96%), former powder yield 73%, total recovery 78%.
Embodiment 1-2
With Paraformaldehyde 96 16.1g (0.537mol), triethylamine 25.6g (0.253mol), glycine 19g (0.25mol) and 120ml methyl alcohol place simultaneously takes back flow condenser, in the 500mL four-hole boiling flask of thermometer and stirring, be stirred to and be warming up to 45 ℃ after transparent, add dimethylphosphite 33g (0.3mol), behind 45-65 ℃ of insulation reaction 2-5h, add hydrochloric acid (30%) 87.5g (0.863mol) acidifying, normal pressure steams methyl alcohol simultaneously, when temperature reaches 110 ℃, the decompression depickling, when temperature reaches 110 ℃ once more, stop decompression, add 40g water, crystallisation by cooling, the suction filtration drying obtains the former powder 33.18g of glyphosate (content 95.5%), former powder yield 75%, total recovery 80%.
Embodiment 1-3
With Paraformaldehyde 96 16.1g (0.537mol), triethylamine 25.6g (0.253mol), glycine-sodium sulfate mixture 23.17g (glycine content 82%, 0.25mol) and 120ml methyl alcohol place the 500mL four-hole boiling flask of taking back flow condenser, thermometer and stirring simultaneously, be stirred to that organism is complete to be warming up to 45 ℃ after molten, add dimethylphosphite 33g (0.3mol), behind 45-65 ℃ of insulation reaction 2-5h, filter desalination, with about 30ml anhydrous methanol washing sodium sulfate, filtrate and washing lotion merge, the heavy 4.05g (rate of recovery 97.12%) in filter cake sodium sulfate oven dry back.Methanol solution adds hydrochloric acid (30%) 87.5g (0.863mol) acidifying, and subsequent operations gets the former powder 34.47g of glyphosate (content 95.6%), former powder yield 78%, total recovery 83% at last with embodiment 1-2.
Embodiment 1-4
With Paraformaldehyde 96 16.1g (0.537mol), triethylamine 25.6g (0.253mol), glycine-sodium chloride mixture 22.35g (glycine content 85%, 0.25mol) and 120ml methyl alcohol place the 500mL four-hole boiling flask of taking back flow condenser, thermometer and stirring simultaneously, subsequent operations is with embodiment 1-3, reclaim sodium-chlor 3.2g (rate of recovery 95.44%), get the former powder 34.31g of glyphosate (content 94.8%) at last, former powder yield 77%, total recovery 82.5%.
Embodiment 2-1
Paraformaldehyde 96 16.1g (0.537mol), triethylamine 25.6g (0.253mol) and 120ml methyl alcohol are placed the 500mL four-hole boiling flask of taking back flow condenser, thermometer and stirring simultaneously, be stirred to transparent after, add glycine 19g (0.25mol), continue to be stirred to and be warming up to 45 ℃ after transparent, add dimethylphosphite 33g (0.3mol), behind 45-65 ℃ of insulation reaction 2-5h, 100 ℃ of normal pressures reclaim the methyl alcohol 105ml (rate of recovery 87.5%, water content 0.1%), reclaim simultaneously and obtain triethylamine 20.5g (rate of recovery 80%, moisture content 0.09%).Esterifying liquid behind the precipitation adds (30%) hydrochloric acid 76g (0.625mol) acidifying, and temperature is controlled at the depickling of reducing pressure behind the 40-70 ℃ of insulation 2-5h, adds 40g water again, crystallisation by cooling, the suction filtration drying obtains the former powder 33g of glyphosate (content 96%), former powder yield 75%, total recovery 80%.
Embodiment 2-2
Paraformaldehyde 96 16.1g (0.537mol), triethylamine 25.6g (0.253mol), glycine 19g (0.25mol) and 120ml methyl alcohol are placed the 500mL four-hole boiling flask of taking back flow condenser, thermometer and stirring simultaneously, be stirred to and be warming up to 45 ℃ after transparent, add dimethylphosphite 33g (0.3mol), behind 45-65 ℃ of insulation reaction 2-5h, 40-60 ℃ reduces pressure down or the 70-100 ℃ of normal pressure recovery methyl alcohol 105ml (rate of recovery 87.5%, water content 0.1%), reclaim simultaneously and obtain triethylamine 20.5g (rate of recovery 80%, moisture content 0.1%).Subsequent operations obtains the former powder 34.03g of glyphosate (content 95.5%), former powder yield 77%, total recovery 81% at last with embodiment 2-1.
Embodiment 2-3
With Paraformaldehyde 96 16.1g (0.537mol), triethylamine 25.6g (0.253mol), glycine-sodium sulfate mixture 23.17g (glycine content 82%, 0.25mol) and 120ml methyl alcohol place the 500mL four-hole boiling flask of taking back flow condenser, thermometer and stirring simultaneously, be stirred to that organism is complete to be warming up to 45 ℃ after molten, add dimethylphosphite 33g (0.3mol), behind 45-65 ℃ of insulation reaction 2-5h, filter desalination, with about 30ml anhydrous methanol washing sodium sulfate, filtrate and washing lotion merge, the heavy 4.05g (rate of recovery 97.12%) in filter cake sodium sulfate oven dry back.Methanol solution 40-70 ℃ reduces pressure down or 70-100 ℃ of normal pressure recovery methyl alcohol 130ml (rate of recovery 86.7%, water content 0.07%), reclaims simultaneously and obtain triethylamine 20.5g (rate of recovery 80%, moisture content 0.08%).Subsequent operations obtains the former powder 34.84g of glyphosate (content 95.8%), former powder yield 79%, total recovery 84% at last with embodiment 2-1.
Embodiment 3-1
With Paraformaldehyde 96 16.1g (0.537mol), triethylamine 25.6g (0.253mol) and 120ml methyl alcohol place simultaneously takes back flow condenser, in the 500mL four-hole boiling flask of thermometer and stirring, be stirred to transparent after, add glycine 19g (0.25mol), continue to be stirred to and be warming up to 45 ℃ after transparent, add dimethylphosphite 33g (0.3mol), behind 45-65 ℃ of insulation reaction 2-5h, 40-60 ℃ reduces pressure down or the 70-100 ℃ of normal pressure recovery methyl alcohol 90ml (rate of recovery 75%, water content 0.1%), reclaim simultaneously and obtain triethylamine 13g (rate of recovery 51%, moisture content 0.09%).Esterifying liquid behind the precipitation adds (30%) hydrochloric acid 76g (0.625mol) acidifying, after temperature is controlled at 40-70 ℃ of insulation 2-5h, cooling, with 30%NaOH regulator solution pH=2.0, concentrate in right amount more subsequently, crystallisation by cooling, the suction filtration drying obtains the former powder 34.77g of glyphosate (content 96%), former powder yield 79%, total recovery 84%.
Embodiment 3-2
Paraformaldehyde 96 16.1g (0.537mol), triethylamine 25.6g (0.253mol), glycine 19g (0.25mol) and 120ml methyl alcohol are placed the 500mL four-hole boiling flask of taking back flow condenser, thermometer and stirring simultaneously, be stirred to and be warming up to 45 ℃ after transparent, add dimethylphosphite 33g (0.3mol), behind 45-65 ℃ of insulation reaction 2-5h, 40-60 ℃ reduces pressure down or the 70-100 ℃ of normal pressure recovery methyl alcohol 90ml (rate of recovery 75%, water content 0.1%), reclaim simultaneously and obtain triethylamine 13g (rate of recovery 51%, moisture content 0.1%).Esterifying liquid behind the precipitation adds (30%) hydrochloric acid 76g (0.625mol) acidifying, and subsequent operations obtains the former powder 35.84g of glyphosate (content 95.5%), former powder yield 81%, total recovery 85% at last with embodiment 3-1.
Embodiment 3-3
With Paraformaldehyde 96 16.1g (0.537mol), triethylamine 25.6g (0.253mol), glycine-sodium sulfate mixture 23.17g (glycine content 82%, 0.25mol) and 120ml methyl alcohol place the 500mL four-hole boiling flask of taking back flow condenser, thermometer and stirring simultaneously, be stirred to that organism is complete to be warming up to 45 ℃ after molten, add dimethylphosphite 33g (0.3mol), behind 45-65 ℃ of insulation reaction 2-5h, filter desalination, with about 30ml anhydrous methanol washing sodium sulfate, filtrate and washing lotion merge, the heavy 4.05g (rate of recovery 97.12%) in filter cake sodium sulfate oven dry back.40-60 ℃ of following methanol solution decompression or 70-100 ℃ of normal pressure reclaim methyl alcohol 114ml (rate of recovery 76%, water content 0.07%), reclaim simultaneously and obtain triethylamine 13g (rate of recovery 51%, moisture content 0.08%).Esterifying liquid behind the precipitation adds (30%) hydrochloric acid 76g (0.625mol) acidifying, and subsequent operations obtains the former powder 37.4g of glyphosate (content 96%), former powder yield 85%, total recovery 88% at last with embodiment 3-1.
Can confirm that by the foregoing description single stage method of the present invention can improve the yield and the total recovery of the former powder of glyphosate.And with embodiment 2-1 and embodiment 3-1 and embodiment 1-1 comparison, can confirm, adopt aftertreatment technology of the present invention can improve the yield and the total recovery of product.
One skilled in the art will appreciate that in the case of without departing from the spirit of the present invention, can make amendment or improve technical scheme of the present invention, and can not depart from marrow of the present invention.These modifications and improvement are all within the scope of protection of present invention.
Claims (9)
1, a kind of post-treating method that adopts when being the feedstock production glyphosate with glycine and alkyl phosphite, it comprises the steps:
A) with N-dialkyl (phosphonomethyl) glycine liquid, first normal pressure/decompression is precipitation down, reclaims monohydroxy-alcohol and tertiary amine, and recovery liquid can directly overlap to be used in the next batch reaction,
B) esterifying liquid behind the precipitation is by the acidolysis of proportioning adding mineral acid, and acidolysis finishes back decompression depickling or directly adds in the alkali and adjusting pH value, concentrates and separates out product, and filtration drying obtains the former powder of glyphosate, and filtrate being used to prepares the liquid glyphosate.
2, according to the process of claim 1 wherein, be hydrochloric acid, sulfuric acid or nitric acid.
3, according to the method for claim 2, wherein, described mineral acid is a hydrochloric acid.
4, precipitation temperature according to arbitrary method of claim 1-3, wherein, steps A) is 0-150 ℃; Step B) acidolysis temperature is 20-100 ℃, and the acidolysis time is 1-10h, and neutralization back system pH is 0.7-3.0.
5, precipitation temperature according to the method for claim 4, wherein, steps A) is 30-120 ℃; Step B) acidolysis temperature is 40-80 ℃, and the acidolysis time is 3-6h, neutralization back system pH 1.5-2.5.
6, according to arbitrary method of claim 1-5, wherein, described mineral acid mole proportioning is counted 0.5-10 by glycine.
7, according to the method for claim 6, wherein, described mineral acid mole proportioning is counted 1-4 by glycine.
8, according to arbitrary method of claim 1-7, wherein, described monohydroxy-alcohol is a methyl alcohol, and tertiary amine is a triethylamine.
9, according to arbitrary method of claim 1-8, wherein, when the method for preparing glyphosate adopts the glycine inorganic salt as the glycine raw material, filter desalination and washing and desalting step, in steps A) finish before.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591353B (en) * | 2008-05-28 | 2011-09-07 | 北京紫光英力化工技术有限公司 | Novel process for recycling mother solution of glyphosate prepared by glycin method |
| CN101671363B (en) * | 2009-09-30 | 2012-02-22 | 四川省乐山市福华通达农药科技有限公司 | Hydrolyzation post-processing technique during preparation of glyphosate through glycin method |
| CN101440106B (en) * | 2008-12-19 | 2012-02-29 | 安徽锦邦化工股份有限公司 | Novel process for recovering waste acid from glyphosate production |
-
2005
- 2005-11-11 CN CNB2005101159092A patent/CN100500678C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591353B (en) * | 2008-05-28 | 2011-09-07 | 北京紫光英力化工技术有限公司 | Novel process for recycling mother solution of glyphosate prepared by glycin method |
| CN101440106B (en) * | 2008-12-19 | 2012-02-29 | 安徽锦邦化工股份有限公司 | Novel process for recovering waste acid from glyphosate production |
| CN101671363B (en) * | 2009-09-30 | 2012-02-22 | 四川省乐山市福华通达农药科技有限公司 | Hydrolyzation post-processing technique during preparation of glyphosate through glycin method |
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| CN100500678C (en) | 2009-06-17 |
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