CN101684128A - Process for preparing glyphosate - Google Patents
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- CN101684128A CN101684128A CN200810079524A CN200810079524A CN101684128A CN 101684128 A CN101684128 A CN 101684128A CN 200810079524 A CN200810079524 A CN 200810079524A CN 200810079524 A CN200810079524 A CN 200810079524A CN 101684128 A CN101684128 A CN 101684128A
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Abstract
The invention discloses a process for preparing glyphosate, which is an improvement on the treatment process after foming crystal in the current glyphosate synthetic process. The process is suitable for dialkyl phosphate flow and also for IDA flow. The following steps are added in original process: a. adding an organic solvent after generating glyphosate from the crystal, b. adding alkali for neutralization until the pH value is 0.1-2, and washing the filtration matters with water until crystal qualification, and c. recovering the organic solvent in the process b. The process of the inventionnot only enhances the yield of the glyphosate initial powder, but also decreases resource wastage caused by recovering and processing mother liquid.
Description
Technical field
The present invention relates to a kind of process for producing of glyphosate.
Background technology
Glyphosate is a kind of organophosphorus herbicide, and formal name used at school N～(adjacent acyl group methyl) glycine belongs to the weedicide of non-selective, efficient, low toxicity, interior absorption wide spectrum.Can be widely used in preventing and kill off of crop weeds such as tea place, orchard, rubber plantation, corn, sugarcane and forest.At present, the synthetic route that adopts on industrial production mainly contains 2 both at home and abroad, i.e. IDA route and dialkyl phosphite route.Especially the dialkyl phosphite route is now adopted by domestic most of manufacturer.This route generally includes depolymerization, addition, condensation, acidolysis, Crystallization Procedure.Its processing step generally is a, Paraformaldehyde 96, methyl alcohol and triethylamine placing response still is stirred; B, the reactant water-bath is heated to certain temperature, is incubated to reactant and dissolves fully; C, a certain amount of glycine of adding carry out addition reaction; D, adding dimethylphosphite carry out condensation reaction; E, react certain hour at a certain temperature, and be chilled to cooling bath and add hydrochloric acid after the certain temperature and carry out acidolysis; F, acidolysis post-heating reaction solution. after steaming low-boiling-point substances such as methylal and methyl alcohol, cool off, leave standstill, allow its spontaneous nucleation.Through suction filtration, oven dry, get the former powder of white glyphosate again.All there is the low problem of the former powder yield of glyphosate in above-mentioned two kinds of processing methodes.For this reason, the scientific research personnel has carried out long-term and unremitting effort.As Mr. Wu Meining in order to improve the yield of the former powder of glyphosate, amount of water, hydrolysis temperature, acidolysis temperature in the existing technological reaction body process have all been carried out optimization experiment, the process for synthesizing glyphosate that draws an optimization thus (sees Wu Meining for details, process for synthesizing glyphosate optimization is inquired into, Zhejiang Normal University journal (natural science edition) 1998,21 (2): 48～52).Though this technology has improved the yield of the former powder of glyphosate than original technology, its effect is still not ideal enough.
Summary of the invention
Purpose of the present invention just provides a kind of novel process that significantly improves the former powder yield of glyphosate.
The object of the present invention is achieved like this:
The preparation technology of a kind of glyphosate provided by the present invention is a kind of improvement with general character at the treatment process after the formation crystallization in the existing process for synthesizing glyphosate.It is both applicable to the dialkyl phosphite route, also applicable to the IDA route.
Specifically, it is when being applicable to the dialkyl phosphite route, and it includes depolymerization, addition, condensation, acidolysis, Crystallization Procedure, and its innovation part is that it is further comprising the steps of:
After a, crystallization generate glyphosate, add organic solvent;
B, adding alkali again, to be neutralized to pH value be 0.1～2, filters; Filtrate wash with water to crystallization qualified till;
Organic solvent in c, the recovery b operation in the filtrate.
More than said organic solvent, can be any one organic solvent theoretically.
The selected organic solvent of the present invention can be the straight or branched fatty alcohol or the organic solvents such as ketone, ethers, ester class, halogenated hydrocarbon, hydro carbons and aromatic hydrocarbons of 1～5 carbon atom.
For example: the straight or branched fatty alcohol of 1～5 carbon atom can be selected methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol etc. for use.Lower ketones can be selected acetone, butanone, mibk etc. for use; Ethers can be selected ether, methyl tertiary butyl ether, tetrahydrofuran (THF), dioxane etc. for use; The ester class can be selected methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate for use, n-butyl acetate, sec-butyl acetate, isobutyl acetate, phenylacetate; Halogenated hydrocarbon can be selected methylene dichloride, chloroform, tetracol phenixin, monochloroethane, monobromethane, 1,2～ethylene dichloride, chlorobenzene for use; Hydro carbons and aromatic hydrocarbons can be selected normal hexane, hexanaphthene, benzene,toluene,xylene etc. for use.
If consider that from the difficulty or ease angle of cost and solvent recuperation methyl alcohol, ethanol, propyl alcohol, butanols, acetone, butanone, ether, methyl acetate, chloroform, normal hexane be preferred solvent the most.
Its consumption of above-described organic solvent no matter what, can improve the yield of the former powder of glyphosate, but be that 50%～150% of crystal solution is a preferable range with the consumption.
More than pH value preferred 0.5～1 in the said b operation.
Adding alkali in the said b operation, to be neutralized to pH value be 0.1～2, and after the filtration, time of repose is length no matter, also can improve the yield of the former powder of glyphosate, but be preferable range to leave standstill 1～24 hour.
When leaving standstill 1～24 hour in the said b operation, temperature does not have absolute influence to the yield that improves the former powder of glyphosate, but is preferable range to be controlled at 2～30 ℃.
The present invention is when being applicable to the IDA route, and it comprises hydrolysis, oxidation, crystallization, and it is further comprising the steps of:
After a, crystallization generate glyphosate, add organic solvent;
B, adding alkali again, to be neutralized to pH value be 0.1～2, filters; Filtrate wash with water to crystallization qualified till;
Organic solvent in c, the recovery b operation in the filtrate.
Other optimum conditions are all identical when being applicable to the dialkyl phosphite route, that is:
Above-described organic solvent can be any one organic solvent theoretically.Concrete selection can be identical with above-mentioned dialkyl phosphite route.
If from cost, and the difficulty or ease angle of solvent recuperation consider that any one in methyl alcohol, ethanol, propyl alcohol, butanols, acetone, butanone, ether, methyl acetate, chloroform, the normal hexane be preferred solvent the most.
The consumption of above-described organic solvent no matter what, can improve the yield of the former powder of glyphosate, but be that 50%～150% of crystal solution is a preferable range with the consumption.
PH value preferred 0.5～1 in the above-described said b operation.
Adding alkali in the said b operation, to be neutralized to pH value be 0.1～2, and after the filtration, time of repose is length no matter, also can improve the yield of the former powder of glyphosate, but be preferable range to leave standstill 1～24 hour.
When leaving standstill 1～24 hour in the said b operation, temperature does not have absolute influence to the yield that improves the former powder of glyphosate, but is preferable range to be controlled at 2～30 ℃.
The inventive method can significantly improve the yield of the former powder of glyphosate, reduces the glyphosate crystalline content in the technology mother liquor, reduces the growing amount of mother liquor.
Beneficial effect of the present invention obtains proof by following experiment contrast.
Beneficial effect contrast of the present invention sees table 1, table 2 for details.
Table 1:
Table 2
From above data contrast as can be seen, adopt the yield of the former powder of the inventive method glyphosate to be much higher than prior art, and the mother liquor that 1 ton of former powder of glyphosate of every production is produced is significantly less than prior art.Also effectively reduce the glyphosate content in the mother liquor simultaneously.Therefore, inventive method of the present invention has not only improved the yield of the former powder of glyphosate, has also reduced recovery, has handled the wasting of resources that mother liquor caused.
Specific embodiment:
Used raw material and the specification wanted among the embodiment:
Paraformaldehyde 96: technical grade, content＞91%; Glycine: technical grade, content 〉=95%; Dimethylphosphite: technical grade, content 〉=95%, triethylamine: technical grade, content 〉=97; Methyl alcohol: technical grade. content 〉=99%; Hydrochloric acid: technical grade, content 〉=30%., two sweet technical grades of seeing, content＞91% hydrogen peroxide technical grade, content＞20%.
Embodiment 1
Proportioning according to Paraformaldehyde 96 1.93mol, methyl alcohol 12mol and triethylamine 1mol takes by weighing Paraformaldehyde 96, methyl alcohol and triethylamine, mixes and stirs.The reactant water-bath is heated to 33～40 ℃, is incubated to reactant and dissolves fully.Add the 1mol glycine, insulated and stirred is to the reaction solution clear.The dimethylphosphite that adds calculated amount then reacts certain hour under 50～60 ℃ of temperature, and is added dropwise to hydrochloric acid 3.4mol after being chilled to 40 ℃ with cooling bath.Dropwise, use oil bath reacting by heating liquid instead. steam low-boiling-point substances such as methylal and methyl alcohol, when reaction solution rises to 110～115 ℃ of temperature, change distillation into the negative pressure depickling then that refluxes, when distillate obviously reduces till.Cooling, leave standstill, allow its spontaneous nucleation.Carry out according to following steps then:
After a, crystallization generate glyphosate, add ethanol (its consumption is 1.5 times of crystal solution);
It is 0.5～1 that b, repeated hydrogenation sodium oxide are neutralized to pH value, filters; Filtrate wash with water to crystallization qualified till; Filtrate gets the former powder of white glyphosate again through suction filtration, oven dry.Water lotion is handled through film, removes the salinity in the water lotion, and last filtrate being used to prepares hydrochloric acid.
Ethanol in c, the recovery b operation in the filtrate (is in the container of the first road filtrate placement in the b operation, with still kettle ethanol distillation is wherein separated, reclaim ethanol.The ethanol that reclaims can be applied mechanically again).
Weigh, survey content at last, calculate the former powder yield of glyphosate.Content is weighed, surveyed to flaxen mother liquor again after neutralization and reclaiming triethylamine.Calculate the total recovery of glyphosate at last.The former powder yield of its glyphosate is 80.2%, and total recovery is 81.1%.
Embodiment 2
Proportioning according to Paraformaldehyde 96 1.93mol, methyl alcohol 12mol and triethylamine 1mol takes by weighing Paraformaldehyde 96, methyl alcohol and triethylamine, mixes and stirs.The reactant water-bath is heated to 33～40 ℃, is incubated to reactant and dissolves fully.Add the 1mol glycine, insulated and stirred is to the reaction solution clear.The dimethylphosphite that adds calculated amount then reacts certain hour under 50～60 ℃ of temperature, and is added dropwise to hydrochloric acid 3.4mol after being chilled to 40 ℃ with cooling bath.Dropwise, use oil bath reacting by heating liquid instead. steam low-boiling-point substance to reaction solutions such as methylal and methyl alcohol and change distillation into the negative pressure depickling then that refluxes when rising to 110-115 ℃ of temperature, when distillate obviously reduces till.Cooling, leave standstill, allow its spontaneous nucleation.Carry out according to following steps then:
After a, crystallization generate glyphosate, add propyl alcohol (its consumption is 1 times of crystal solution);
It is 0.5～1 that b, repeated hydrogenation sodium oxide are neutralized to pH value, filters; Temperature is controlled at 2～30 ℃, leaves standstill 24 hours; Filtrate wash with water to crystallization qualified till; Filtrate gets the former powder of white glyphosate again through suction filtration, oven dry.Water lotion is handled through film, removes the salinity in the water lotion, and last filtrate being used to prepares hydrochloric acid.
Propyl alcohol in c, the recovery b operation in the filtrate (is in the container of the first road filtrate placement in the b operation, with still kettle general propyl alcohol fractionation by distillation wherein, reclaims propyl alcohol.The propyl alcohol that reclaims can be applied mechanically again).
Weigh, survey content at last, calculate the former powder yield of glyphosate.Content is weighed, surveyed to flaxen mother liquor again after neutralization and reclaiming triethylamine.Calculate the total recovery of glyphosate at last.The former powder yield of its glyphosate is 82.2%, and total recovery is 82.6%.
Embodiment 3
Proportioning according to Paraformaldehyde 96 1.93mol, methyl alcohol 12mol and triethylamine 1mol takes by weighing Paraformaldehyde 96, methyl alcohol and triethylamine, mixes and stirs.The reactant water-bath is heated to 33～40 ℃, is incubated to reactant and dissolves fully.Add the 1mol glycine, insulated and stirred is to the reaction solution clear.The dimethylphosphite that adds calculated amount then reacts certain hour under 50～60 ℃ of temperature, and is added dropwise to hydrochloric acid 3.4mol after being chilled to 40 ℃ with cooling bath.Dropwise, use oil bath reacting by heating liquid instead. steam low-boiling-point substance to reaction solutions such as methylal and methyl alcohol and change distillation into the negative pressure depickling then that refluxes when rising to 110-115 ℃ of temperature, when distillate obviously reduces till.Cooling, leave standstill, allow its spontaneous nucleation.Carry out according to following steps then:
After a, crystallization generate glyphosate, add isopropylcarbinol (its consumption is 0.5 times of crystal solution);
It is 0.3～0.4 that b, repeated hydrogenation sodium oxide are neutralized to pH value, filters; Temperature is controlled at 2～8 ℃, leaves standstill 2 hours; Filtrate wash with water to crystallization qualified till; Filtrate gets the former powder of white glyphosate again through suction filtration, oven dry.Water lotion is handled through film, removes the salinity in the water lotion, and last filtrate being used to prepares hydrochloric acid.
Isopropylcarbinol in c, the recovery b operation in the filtrate (is in the container of the first road filtrate placement in the b operation, with still kettle general isopropylcarbinol fractionation by distillation wherein, reclaims isopropylcarbinol.The isopropylcarbinol that reclaims can be applied mechanically again).
Weigh, survey content at last, calculate the former powder yield of glyphosate.Content is weighed, surveyed to flaxen mother liquor again after neutralization and reclaiming triethylamine.Calculate the total recovery of glyphosate at last.The former powder yield of its glyphosate is 83.2%, and total recovery is 83.5%.
Embodiment 4
Proportioning according to Paraformaldehyde 96 1.93mol, methyl alcohol 12mol and triethylamine 1mol takes by weighing Paraformaldehyde 96, methyl alcohol and triethylamine, mixes and stirs.The reactant water-bath is heated to 33～40 ℃, is incubated to reactant and dissolves fully.Add the 1mol glycine, insulated and stirred is to the reaction solution clear.The dimethylphosphite that adds calculated amount then reacts certain hour under 50～60 ℃ of temperature, and is added dropwise to hydrochloric acid 3.4mol after being chilled to 40 ℃ with cooling bath.Dropwise, use oil bath reacting by heating liquid instead. steam low-boiling-point substance to reaction solutions such as methylal and methyl alcohol and change distillation into the negative pressure depickling then that refluxes when rising to 110-115 ℃ of temperature, when distillate obviously reduces till.Cooling, leave standstill, allow its spontaneous nucleation.Carry out according to following steps then:
After a, crystallization generate glyphosate, add acetone (its consumption is 1 times of crystal solution);
It is 1.5～2 that b, repeated hydrogenation sodium oxide are neutralized to pH value, filters; Temperature is controlled at 18～24 ℃, leaves standstill 12 hours; Filtrate wash with water to crystallization qualified till; Filtrate gets the former powder of white glyphosate again through suction filtration, oven dry.Water lotion is handled through film, removes the salinity in the water lotion, and last filtrate being used to prepares hydrochloric acid.
Acetone in c, the recovery b operation in the filtrate (is in the container of the first road filtrate placement in the b operation, with acetone separation wherein, reclaims acetone.The acetone that reclaims can be applied mechanically again).
Weigh, survey content at last, calculate the former powder yield of glyphosate.Content is weighed, surveyed to flaxen mother liquor again after neutralization and reclaiming triethylamine.Calculate the total recovery of glyphosate at last.The former powder yield of its glyphosate is 81.3%, and total recovery is 81.6%.
Embodiment 5
Proportioning according to Paraformaldehyde 96 1.93mol, methyl alcohol 12mol and triethylamine 1mol takes by weighing Paraformaldehyde 96, methyl alcohol and triethylamine, mixes and stirs.The reactant water-bath is heated to 33～40 ℃, is incubated to reactant and dissolves fully.Add the 1mol glycine, insulated and stirred is to the reaction solution clear.The dimethylphosphite that adds calculated amount then reacts certain hour under 50～60 ℃ of temperature, and is added dropwise to hydrochloric acid 3.4mol after being chilled to 40 ℃ with cooling bath.Dropwise, use oil bath reacting by heating liquid instead. steam low-boiling-point substance to reaction solutions such as methylal and methyl alcohol and change distillation into the negative pressure depickling then that refluxes when rising to 110-115 ℃ of temperature, when distillate obviously reduces till.Cooling, leave standstill, allow its spontaneous nucleation.Carry out according to following steps then:
After a, crystallization generate glyphosate, add ether (its consumption is 1 times of crystal solution);
It is 0.2～0.8 that b, repeated hydrogenation sodium oxide are neutralized to pH value, filters; Temperature is controlled at 18～24 ℃, leaves standstill 12 hours; Filtrate wash with water to crystallization qualified till; Filtrate gets the former powder of white glyphosate again through suction filtration, oven dry.Water lotion is handled through film, removes the salinity in the water lotion, and last filtrate being used to prepares hydrochloric acid.
(being in the container of the first road filtrate placement in the b operation,, reclaiming ether in c, the recovery b operation in the filtrate with ether fractionation by distillation wherein.The ether that reclaims can be applied mechanically again).
Weigh, survey content at last, calculate the former powder yield of glyphosate.Content is weighed, surveyed to flaxen mother liquor again after neutralization and reclaiming triethylamine.Calculate the total recovery of glyphosate at last.The former powder yield of its glyphosate is 83.3%, and total recovery is 83.4%.
Embodiment 6
According to the proportioning of two sweet 1mol that see, hydrogen peroxide 1.5moll, take by weighing two sweet 1mol of seeing, hydrogen peroxide, mix and stir, the reactant water-bath is heated to 60～90 ℃, and insulation was reacted 2～4 hours, cooled off, left standstill, and allowed its spontaneous nucleation.Carry out according to following steps then:
After a, crystallization generate glyphosate, add ethanol (its consumption is 10 times of crystal solution);
It is 0.4 that b, repeated hydrogenation sodium oxide are neutralized to pH value, filters; Temperature is controlled at 18～24 ℃, leaves standstill 2 hours; Filtrate wash with water to crystallization qualified till; Filtrate gets the former powder of white glyphosate again through suction filtration, oven dry.Water lotion is handled through film, removes the salinity in the water lotion, and last filtrate being used to prepares hydrochloric acid.
(being in the container of the first road filtrate placement in the b operation, ethanol distillation wherein being separated, reclaiming ethanol in c, the recovery b operation in the filtrate with still kettle.The ethanol that reclaims can be applied mechanically again).
Through suction filtration, oven dry, get the former powder of white glyphosate again.Weigh, survey content, calculate the former powder yield of glyphosate.Content is weighed, surveyed to flaxen mother liquor again through reclaiming.Calculate the total recovery of glyphosate at last.The former powder yield of its glyphosate is 78.4%, and total recovery is 79.5%.
Embodiment 7
According to the proportioning of two sweet 1mol that see, hydrogen peroxide 1.5moll, take by weighing two sweet 1mol of seeing, hydrogen peroxide, mix and stir, the reactant water-bath is heated to 60～90 ℃, and insulation was reacted 2～4 hours, cooled off, left standstill, and allowed its spontaneous nucleation.Carry out according to following steps then:
After a, crystallization generate glyphosate, add butanols (its consumption is 2 times of crystal solution);
It is 0.3～0.5 that b, repeated hydrogenation sodium oxide are neutralized to pH value, filters; Temperature is controlled at 0 ℃, leaves standstill 10 minutes; Filtrate wash with water to crystallization qualified till; Filtrate gets the former powder of white glyphosate again through suction filtration, oven dry.Water lotion is handled through film, removes the salinity in the water lotion, and last filtrate being used to prepares hydrochloric acid.
(being in the container of the first road filtrate placement in the b operation,, reclaiming butanols in c, the recovery b operation in the filtrate with still kettle general butanols fractionation by distillation wherein.The butanols that reclaims can be applied mechanically again).
Through suction filtration, oven dry, get the former powder of white glyphosate again.Weigh, survey content, calculate the former powder yield of glyphosate.Content is weighed, surveyed to flaxen mother liquor again through reclaiming.Calculate the total recovery of glyphosate at last.The former powder yield of its glyphosate is 82.4%, and total recovery is 83.5%.
Embodiment 8
According to the proportioning of two sweet 1mol that see, hydrogen peroxide 1.5moll, take by weighing two sweet 1mol of seeing, hydrogen peroxide, mix and stir, the reactant water-bath is heated to 60～90 ℃, and insulation was reacted 2～4 hours, cooled off, left standstill, and allowed its spontaneous nucleation.Carry out according to following steps then:
After a, crystallization generate glyphosate, add chloroform (its consumption is 0.02 times of crystal solution);
It is 4 that b, repeated hydrogenation sodium oxide are neutralized to pH value, filters; Temperature is controlled at 18～24 ℃, leaves standstill 2 hours; Filtrate wash with water to crystallization qualified till; Filtrate gets the former powder of white glyphosate again through suction filtration, oven dry.Water lotion is handled through film, removes the salinity in the water lotion, and last filtrate being used to prepares hydrochloric acid.
(being in the container of the first road filtrate placement in the b operation,, reclaiming chloroform in c, the recovery b operation in the filtrate with chloroform separation wherein.The chloroform that reclaims can be applied mechanically again).
Through suction filtration, oven dry, get the former powder of white glyphosate again.Weigh, survey content, calculate the former powder yield of glyphosate.Content is weighed, surveyed to flaxen mother liquor again through reclaiming.Calculate the total recovery of glyphosate at last.The former powder yield of its glyphosate is 83.4%, and total recovery is 84.2%.
Embodiment 9
According to the proportioning of two sweet 1mol that see, hydrogen peroxide 1.5moll, take by weighing two sweet 1mol of seeing, hydrogen peroxide, mix and stir, the reactant water-bath is heated to 60～90 ℃, and insulation was reacted 2～4 hours, cooled off, left standstill, and allowed its spontaneous nucleation.Carry out according to following steps then:
After a, crystallization generate the hydrochloride of glyphosate, add ethyl acetate (its consumption is 1 times of crystal solution);
It is 0.8 that b, repeated hydrogenation sodium oxide are neutralized to pH value, filters; Temperature is controlled at 5 ℃, leaves standstill 8 hours; Filtrate wash with water to crystallization qualified till; Filtrate gets the former powder of white glyphosate again through suction filtration, oven dry.Water lotion is handled through film, removes the salinity in the water lotion, and last filtrate being used to prepares hydrochloric acid.
(being in the container of the first road filtrate placement in the b operation, ethyl acetate wherein separated, reclaiming ethyl acetate in c, the recovery b operation in the filtrate.The ethyl acetate that reclaims can be applied mechanically again).
Through suction filtration, oven dry, get the former powder of white glyphosate again.Weigh, survey content, calculate the former powder yield of glyphosate.Content is weighed, surveyed to flaxen mother liquor again through reclaiming.Calculate the total recovery of glyphosate at last.The former powder yield of its glyphosate is 83.5%, and total recovery is 84.5%.
Embodiment 10
According to the proportioning of two sweet 1mol that see, hydrogen peroxide 1.5moll, take by weighing two sweet 1mol of seeing, hydrogen peroxide, mix and stir, the reactant water-bath is heated to 60～90 ℃, and insulation was reacted 2～4 hours, cooled off, left standstill, and allowed its spontaneous nucleation.Carry out according to following steps then:
After a, crystallization generate glyphosate, add normal hexane (its consumption is 0.02 times of crystal solution);
It is 0.4 that b, repeated hydrogenation sodium oxide are neutralized to pH value, filters; Temperature is controlled at 28 ℃, leaves standstill 30 minutes; Filtrate wash with water to crystallization qualified till; Filtrate gets the former powder of white glyphosate again through suction filtration, oven dry.Water lotion is handled through film, removes the salinity in the water lotion, and last filtrate being used to prepares hydrochloric acid.
(being in the container of the first road filtrate placement in the b operation,, reclaiming normal hexane in c, the recovery b operation in the filtrate with normal hexane separation wherein.The normal hexane that reclaims can be applied mechanically again).
Through suction filtration, oven dry, get the former powder of white glyphosate again.Weigh, survey content, calculate the former powder yield of glyphosate.Content is weighed, surveyed to flaxen mother liquor again through reclaiming.Calculate the total recovery of glyphosate at last.The former powder yield of its glyphosate is 81.4%, and total recovery is 82.2%.
Reference examples 1
Proportioning according to Paraformaldehyde 96 1.9mol, methyl alcohol 12mol and triethylamine 1mol takes by weighing Paraformaldehyde 96, methyl alcohol and triethylamine, mixes and stirs.The reactant water-bath is heated to 33～40 ℃, is incubated to reactant and dissolves fully.Add the 1mol glycine, insulated and stirred is to the reaction solution clear.The dimethylphosphite that adds calculated amount then reacts certain hour under 60～70 ℃ of temperature, and is added dropwise to hydrochloric acid 3.4mol after being chilled to 40 ℃ with cooling bath.Dropwise, use oil bath reacting by heating liquid instead. steam low-boiling-point substance to reaction solutions such as methylal and methyl alcohol and change distillation into the negative pressure depickling then that refluxes when rising to 110 ℃ of temperature, when distillate obviously reduces till.Cooling, leave standstill, allow its spontaneous nucleation.Through suction filtration, oven dry, get the former powder of white glyphosate again.Weigh, survey content, calculate the former powder yield of glyphosate.Content is weighed, surveyed to flaxen mother liquor again after neutralization and reclaiming triethylamine.Calculate the total recovery of glyphosate at last.The former powder yield of its glyphosate is 68.4%, and total recovery is 77.1%.
Reference examples 2
According to the proportioning of two sweet 1mol that see, hydrogen peroxide 1.5mol, take by weighing two sweet 1mol of seeing, hydrogen peroxide, mix and stir, the reactant water-bath is heated to 60～90 ℃, and insulation was reacted 2～4 hours, cooled off, left standstill, and allowed its spontaneous nucleation.Through suction filtration, oven dry, get the former powder of white glyphosate again.Weigh, survey content, calculate the former powder yield of glyphosate.Content is weighed, surveyed to flaxen mother liquor again through reclaiming.Calculate the total recovery of glyphosate at last.The former powder yield of its glyphosate is 56.4%, and total recovery is 82.5%.
Claims (10)
1, a kind of preparation technology of glyphosate, it comprises depolymerization, addition, condensation, acidolysis, Crystallization Procedure, it is characterized in that it also comprises step:
After a, crystallization generate glyphosate, add organic solvent,
B, adding alkali again, to be neutralized to pH value be 0.1～2, filters; Filtrate wash with water to crystallization qualified till, filtrate is again through suction filtration, oven dry, the former powder of white glyphosate;
Organic solvent in c, the recovery b operation in the filtrate.
2, the preparation technology of glyphosate according to claim 1 is characterised in that said organic solvent is any one in methyl alcohol, ethanol, propyl alcohol, butanols, acetone, butanone, ether, methyl acetate, chloroform, the normal hexane.
3, the preparation technology of glyphosate according to claim 1 and 2, the consumption that is characterised in that said organic solvent is 50%～150% of a crystal solution.
4, the preparation technology of glyphosate according to claim 1 and 2 is characterised in that pH value is 0.5～1 in the said b operation.
5, the preparation technology of glyphosate according to claim 1 and 2 is characterised in that to add alkali in the said b operation to be neutralized to pH value be 0.1～4, after the filtration, leaves standstill 1～24 hour.
6, the preparation technology of glyphosate according to claim 5 is characterised in that temperature is controlled at 2～30 ℃ when leaving standstill 1～24 hour in the said b operation.
7, a kind of preparation technology of glyphosate, it comprises hydrolysis, oxidation, crystallization, it is characterized in that it also comprises step:
After a, crystallization generate glyphosate, add organic solvent,
B, adding alkali again, to be neutralized to pH value be 0.1～2, filters; Filtrate wash with water to crystallization qualified till, filtrate is again through suction filtration, oven dry, the former powder of white glyphosate;
Organic solvent in c, the recovery b operation in the filtrate.
8, the preparation technology of glyphosate according to claim 7 is characterised in that said organic solvent is any one in methyl alcohol, ethanol, propyl alcohol, the butanols.
9, according to the preparation technology of claim 7 or 8 described glyphosates, the consumption that is characterised in that said organic solvent is 50%～150% of a crystal solution.
10,, be characterised in that pH value is 0.5～1 in the said b operation according to the preparation technology of claim 7 or 8 described glyphosates.
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| CN113185548A (en) * | 2021-05-10 | 2021-07-30 | 浙江新安化工集团股份有限公司 | Glyphosate synthesis method for improving utilization rate of dimethyl phosphite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185548A (en) * | 2021-05-10 | 2021-07-30 | 浙江新安化工集团股份有限公司 | Glyphosate synthesis method for improving utilization rate of dimethyl phosphite |
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