CN110229186A - The method of glyphosine and glyphosate is recycled in glyphosate mother solution - Google Patents
The method of glyphosine and glyphosate is recycled in glyphosate mother solution Download PDFInfo
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- CN110229186A CN110229186A CN201910644105.3A CN201910644105A CN110229186A CN 110229186 A CN110229186 A CN 110229186A CN 201910644105 A CN201910644105 A CN 201910644105A CN 110229186 A CN110229186 A CN 110229186A
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- Prior art keywords
- glyphosate
- glyphosine
- mother solution
- level
- colloid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
Abstract
The invention discloses a kind of methods that glyphosine and glyphosate are recycled in glyphosate mother solution, the step of method in include: isolate sodium chloride crude product from glyphosate mother solution, obtain quenching mother liquor；Excessive acid is added into quenching mother liquor, carries out acidification reaction；The product of acidification reaction is separated, acidification isolate is obtained, being acidified includes acidified mother liquor in isolate；Acidified mother liquor is dehydrated to remove water, organic admixture is obtained；Gelatinizing agent is added into organic admixture, is formed by curing colloid, and isolate colloid；Colloid is dissolved in after water, solvent is added, isolated glyphosine and glyphosate.The present invention can green, efficiently, economically recycle glyphosate mother solution in sodium chloride crude product, glyphosine and glyphosate, realize organic matter value maximization in glyphosate mother solution, with glycine, glyphosate and the yield of glyphosine, which add up to, can increase by 25% or more, greatly improve the economic benefit of glyphosate by using glycine manufacturing enterprise.
Description
Technical field
The present invention relates to a kind of methods that glyphosine and glyphosate are recycled in glyphosate mother solution.
Background technique
Glyphosate (N- ((phosphonomethyl)) glycine) is the current maximum pesticide species of sales volume in the world, China
It is the global maximum country of glyphosate yield.
Domestic glyphosate corporate boss will use glycine method production technology, and the technique glyphosate yield is generally 75%
Left and right (with glycine).Glycine method has many advantages, such as that raw material is easy to get, process costs are low, economy is high and develops into China
Prevailing technology.In glyphosate production, a large amount of waste water can be generated, glyphosate per ton generates 5 tons or so of glyphosate mother solution.
Can be used as the raw material of soda ash and chlorine industry after sodium chloride purification recycling in mother liquor is still rich in high value organic matter
Main mother liquor how to recycle be long-standing problem glyphosate industry problem.Glyphosate per ton generates about 5 tons of mother liquors, in mother liquor
Mainly contain: sodium chloride, glyphosate, glyphosine, glycine, orthophosphite and a small amount of level-one residue cause a large amount of height
Concentration organism P wastewater (organic matter mother liquor).
Currently, glyphosate by using glycine mother liquid disposal, which generally uses after adding excessive alkali process recycling triethylamine, is used as waste
Processing.The processing method not only additionally increases the processing cost of mother liquor, also will cause mother liquor glyphosate, glyphosine, glycine
Etc. the whole waste of valuable material.Present part of the manufacturer using deep oxidization technique by it is organic phosphorus be converted into Phos after realize
The recycling of phosphor resource；Also there is the method for taking mother liquor to burn, the organic phosphorus sodium salt for being converted into Phos is recycled into benefit
With.
According to known to current data, although China as the world's largest glyphosate production state, has no that domestic glyphosate is raw
There is the report of glyphosine production at producer.
Glyphosine is important agricultural chemicals, as plant growth regulator, accelerate the ripening, increase sugared significant effect, toxicity it is low,
It remains low, may act on the growth regulating of the crops such as sugarcane, beet, sweet potato, fruit and soybean, cotton.In addition, glyphosine has
Methylenephosphonic acid structure meets the structure of phosphonic acid corrosion inhibiter, can also be used as metal inhibitor use.Nitrogenous alkyl phosphonic acids has
The structure of similar amino acid, has metal preferable sequestering, has good corrosion-mitigation scale-inhibition effect.Utilize the association between corrosion inhibiter
Same effect can be compounded with other corrosion inhibiter, and the synergistic effect between compounding agent can increase adsorption coverage and absorption is steady
It is qualitative, change the rate of adsorption, to improve inhibition efficiency, it is possible thereby to reduce inhibiter consumption, reduces production cost, expand slow
Lose agent application range.
So glyphosine is turned into the essential important agricultural chemicals of industry, market potential as Modern Agricultural Machine
It is huge；Meanwhile glyphosine can be used as efficient corrosion inhibiter, in intermetallic composite coating, protection and application aspect, before there is broad mass market
Scape.
Such as 200910114938.5, the invention of entitled " a method of original glyphosate powder is recycled from glyphosate mother solution "
Patent application, patented method desalination under strongly acidic conditions, can only extract the glyphosate of 20-30%, and original powder quality is obvious
Decline；A large amount of existing glyphosines can not recycle.
Such as 201010186170.5, the invention of entitled " a method of original glyphosate powder is recycled from glyphosate mother solution "
Patent application, since mother liquor glyphosate product and raw material and its by-product existence form are complicated, only by the crystallization water is added,
Glyphosate molecule in mother liquor can not mass crystallization precipitation；Moreover, a large amount of chlorinations will be contained in a small amount of glyphosate being precipitated
Sodium influences the quality of glyphosate.
In conclusion the country there is no the recycling technique of ideal glyphosate by using glycine mother liquor organic matter at present, urgently
Reliable, the economic and efficient integrated treatment from mother liquor to be developed and the technique for recycling organic matter.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of existing technologies, provides and recycled in a kind of glyphosate mother solution
The method of glyphosine and glyphosate, it can green, efficiently, economically recycle glyphosate mother solution in sodium chloride crude product, glyphosine
And glyphosate, organic matter value maximization in glyphosate mother solution is realized, with glycine, the yield of glyphosate and glyphosine is closed
Meter can increase by 25% or more, not only solve the glyphosate mother solution dangerous waste problem of long-standing problem manufacturing enterprise, and can substantially mention
The economic benefit of high glyphosate by using glycine manufacturing enterprise, there is wide promotion prospect in glyphosate by using glycine production industry.
In order to solve the above-mentioned technical problem, the technical scheme is that in a kind of glyphosate mother solution recycle glyphosine and
Include in the step of method of glyphosate, method:
After glyphosate mother solution isolates sodium chloride crude product by quenching method, quenching mother liquor is obtained；
Acid is added in quenching mother liquor, carries out acidification reaction；
Product after acidification reaction is separated, it is isolated the corresponding sodium salt crude product of acid to be added and in addition to sodium salt crude product
Acidified mother liquor；
Acidified mother liquor is dehydrated under vacuum conditions, obtains organic admixture, wherein includes that increasing is sweet in organic admixture
Phosphine and glyphosate；
Gelatinizing agent is added in organic admixture, the glyphosine and glyphosate in organic admixture are formed by curing colloid, separation
Obtain colloid and the level-one residue in addition to colloid；
Add water in colloid, the glyphosine in colloid is dissolved in water, and the glyphosate in colloid is precipitated, isolated glyphosate and glyphosine
Solution；
Glyphosine solution vacuum dehydration obtains melting glyphosine；Glyphosine sheeting is melted, glyphosine is obtained.
Further, level-one residue dehydrated under vacuum, then separates, and obtains phosphorous acid and the second level in addition to phosphorous acid remains
Excess.
Further, second level residue is dehydrated under vacuum conditions, is then separated, and obtains glycine and in addition to glycine
Three-level residue.
Further, three-level residue returns to acidification reaction process recycled.
Further, glyphosine solution vacuum dehydration also obtains level-one condensate liquid；It is dehydrated under level-one residue vacuum condition,
Also obtain B-grade condensation liquid；Second level residue is dehydrated under vacuum conditions, also obtains three-level condensate liquid；
It include water and gelatinizing agent in level-one condensate liquid, B-grade condensation liquid and three-level condensate liquid；
Level-one condensate liquid, B-grade condensation liquid and three-level condensate liquid are recycled through gelatinizing agent recovery system, obtain gelatinizing agent and water, gained
Gelatinizing agent returns to the curing process recycled of colloid, and obtained water is returned into colloid plus water conservancy project sequence is applied.
Further, the glyphosate mother solution is the mother liquor of glycine dimethylphosphite or diethyl phosphite method.
Further, the glyphosate mother solution is after glycine dimethyl phosphate method produces the recovered triethylamine of glyphosate
Mother liquor.
Further, it after glyphosate mother solution isolates sodium chloride crude product by quenching method, obtains wrapping in the method for quenching mother liquor
Contain:
Glyphosate mother solution obtains dehydration liquid by being dehydrated at least once；
After being dehydrated fluid dewatering to critical concentration, quenching medium is added, obtains mixture；Wherein, when critical concentration, dehydration liquid has wax
Phenomenon occurs；
Mixture is separated, quenching mother liquor and sodium chloride crude product are obtained.
Further, the quenching mother liquor is to contain glyphosate and its sodium salt, glyphosine and its sodium salt, glycine and its sodium
The mixture of salt, phosphorous acid and its sodium salt, methyl glyphosate and its sodium salt and methylamino phosphorous acid and its sodium salt.
Further, the PH range of glyphosate mother solution is 1 ~ 14.
Further, the acid in acidification reaction is organic acid or inorganic acid；
And/or the reaction temperature of acidification reaction is 20 ~ 200 DEG C；
And/or the PH range of acidification reaction is 0.01 ~ 6.5；
And/or the reaction time of acidification reaction is 0.1 ~ 12h.
Further, the acidification reaction carries out in acidification kettle；
And/or the separation of the product of the acidification reaction carries out in centrifuge；
And/or the dehydration of acidified mother liquor takes off in light kettle in vacuum and carries out；
And/or being solidificated in gelatinization kettle for the colloid carries out；
And/or water is added in the colloid and is carried out in molten-bath；
And/or the separation of glyphosate and glyphosine solution carries out in centrifuge；
And/or glyphosine solution vacuum dehydration carries out in vacuum kettle；
And/or melting glyphosine sheeting carries out in flaker.
Further, the water content of quenching mother liquor is 10 ~ 50%；
And/or the water content of the acidified mother liquor is 1 ~ 40%.
Further, the gelatinizing agent is chain growth initiator, and the gelatinizing agent includes azo-initiator, organic or nothing
At least one of machine class peroxide initiator, organic or inorganic reducing agent.
Further, in colloid plus when water, the quality of the water of addition is the 40 ~ 50% of colloid quality.
Further, the sodium chloride crude product recycles to obtain purification sodium chloride through sodium chloride recovery system；And/or the sodium salt
Crude product recycles to obtain purification sodium salt through sodium salt recycling system.
After above-mentioned technical proposal, obtain after glyphosate mother solution recycling sodium chloride crude product containing organic matter and its sodium salt
Quenching mother liquor；Excessive acid is added in the acidified kettle of quenching mother liquor, converts the sodium salt of organic matter under special reaction condition
Sodium salt and the isolated sodium salt crude product of organic matter and acidified mother liquor corresponding to acid is added in generation by organic matter；Acidified mother liquor
Water is removed through vacuum dehydration, obtains the organic admixture for containing a small amount of glyphosate ingredient based on glyphosine, organic matter mixing
Object enters gelatinization kettle, adds gelatinizing agent, and glyphosine and glyphosate are formed by curing colloid, plastic emitting separated from organic admixture
Body then obtains level-one residue, and after adding water in colloid, glyphosine is all dissolved in water, and glyphosate is precipitated, and after separation of solid and liquid, obtains
Glyphosate GP2 and glyphosine solution, glyphosine solution use vacuum dehydration, sheeting, obtain glyphosine, and level-one residue vacuum is de-
Phosphorous acid can simply be recycled by being separated by solid-liquid separation after water sedimentation, after the second level residue in addition to phosphorous acid continues vacuum dehydration, separation
Glycine can be precipitated after gelatinizing agent, and obtain three-level residue, three-level residue contains micro glyphosate, glyphosine, Asia
The unconverted or incomplete organic matter of conversion, returns to the synthesizing glyphosate of leading portion main reaction in phosphoric acid, glycine and acid hemolysis process
The acidification reaction process recycled of hydrolysis procedure or this method, the present invention can have been recycled effectively in glyphosate mother solution
Effective component, and it is easy to operate, separation efficiently, can recycle preparation high-purity glyphosine and glyphosate from quenching mother liquor, meanwhile,
Can efficiently recycle phosphorous acid and glycine, present invention green, efficiently, economically recycle in glyphosate mother solution it is effective at
Point, organic matter value maximization in glyphosate mother solution is realized, with glycine, the yield of glyphosate and glyphosine is total to be increased
Add 25% or more, the present invention not only solves the glyphosate mother solution dangerous waste problem of long-standing problem manufacturing enterprise, and can substantially mention
The economic benefit of high glyphosate by using glycine manufacturing enterprise, there is wide promotion prospect in glyphosate by using glycine production industry.
Detailed description of the invention
Fig. 1 is the flow chart that the method for glyphosine and glyphosate is recycled in glyphosate mother solution of the invention.
Specific embodiment
The present invention provides a kind of methods that glyphosine and glyphosate are recycled in glyphosate mother solution, and those skilled in the art can
To use for reference present disclosure, it is suitably modified realization of process parameters.In particular, it should be pointed out that all similar substitutions and modifications are to this
It is for the technical staff of field it will be apparent that they shall fall within the protection scope of the present invention.Method and application of the invention is
Through being described by preferred embodiment, related personnel obviously can not depart from the content of present invention, in spirit and scope to this
The methods and applications of text are modified or appropriate changes and combinations, carry out implementation and application the technology of the present invention.
As shown in Figure 1, a kind of method for recycling glyphosine and glyphosate in glyphosate mother solution, the step of method in include:
After glyphosate mother solution M0 isolates sodium chloride crude product SA1 by quenching method, quenching mother liquor M1 is obtained；
Acid is added in quenching mother liquor M1, carries out acidification reaction；
Product after acidification reaction is separated, it is isolated the corresponding sodium salt crude product SA2 of acid to be added and except sodium salt crude product
Acidified mother liquor M2 outside SA2；
Acidified mother liquor M2 is dehydrated under vacuum conditions, obtains organic admixture M3, wherein is wrapped in organic admixture M3
Include glyphosine GP1 and glyphosate GP2；
Gelatinizing agent HK3 is added in organic admixture M3, glyphosine GP1 and glyphosate GP2 solidification in organic admixture M3
Form colloid CD, isolated colloid CD and the level-one residue M4 in addition to colloid CD；
Add water in colloid CD, the glyphosine GP1 in colloid CD is dissolved in water, and the glyphosate GP2 in colloid CD is precipitated, isolated grass
Sweet phosphine GP2 and glyphosine solution；
The dehydration of glyphosine solution high-temperature vacuum obtains melting glyphosine；Glyphosine sheeting is melted, glyphosine GP1 is obtained.
Specifically, level-one residue M4 dehydrated under vacuum, then separates, and obtains phosphorous acid GP3 and in addition to phosphorous acid GP3
Second level residue M5.
Specifically, second level residue M5 is dehydrated under vacuum conditions, is then separated, and obtains glycine GP4 and except glycine
Three-level residue M6 other than GP4.
Specifically, three-level residue M6 returns to acidification reaction process recycled.Wherein, three-level residue M6 is containing micro-
It is unconverted or conversion is incomplete has in the glyphosate GP2 of amount, glyphosine GP1, phosphorous acid GP3, glycine GP4 and acid hemolysis process
The mixture of machine object.
Specifically, glyphosine solution vacuum dehydration also obtains level-one condensate liquid CW6；Under level-one residue M4 vacuum condition
Dehydration, also obtains B-grade condensation liquid CW7；Second level residue M5 is dehydrated under vacuum conditions, also obtains three-level condensate liquid CW8；
It include water and gelatinizing agent HK3 in level-one condensate liquid CW6, B-grade condensation liquid CW7 and three-level condensate liquid CW8；
Level-one condensate liquid CW6, B-grade condensation liquid CW7 and three-level condensate liquid CW8 are recycled through gelatinizing agent recovery system, obtain gelatinizing agent
HK3 and water, gained gelatinizing agent HK3 return to the curing process recycled of colloid CD, and obtained water is returned into colloid CD plus water
Process is applied.
Specifically, the glyphosate mother solution M0 is the mother liquor of glycine dimethylphosphite or diethyl phosphite method.
Specifically, the glyphosate mother solution M0 is after glycine dimethyl phosphate method produces the recovered triethylamine of glyphosate
Mother liquor.
Specifically, after glyphosate mother solution M0 isolates sodium chloride crude product SA1 by quenching method, the side of quenching mother liquor M1 is obtained
Include in method:
Glyphosate mother solution M0 obtains dehydration liquid by being dehydrated at least once；
After being dehydrated fluid dewatering to critical concentration, quenching medium QA is added, obtains mixture；Wherein, when critical concentration, dehydration liquid has wax
Change phenomenon；
Mixture is separated, quenching mother liquor M1 and sodium chloride crude product SA1 are obtained.
Specifically, the quenching mother liquor M1 is to contain glyphosate GP2 and its sodium salt, glyphosine GP1 and its sodium salt, glycine
GP4 and its sodium salt, phosphorous acid GP3 and its sodium salt, methyl glyphosate and its sodium salt and methylamino phosphorous acid and its sodium salt it is mixed
Close object.
Specifically, the PH range of glyphosate mother solution M0 is 1 ~ 14, and preferred PH range is 8 ~ 13, and preferred PH range is
10~12。
Specifically, the acid in acidification reaction is organic acid or inorganic acid, the preferably for example various benzene sulfonic acid classes of strong acid, methylbenzene sulphur
Acid, the sulfuric acid that mass concentration is 20% -60%, the concentrated hydrochloric acid that mass concentration is 15% -35%, more preferable mass concentration are 30%
The concentrated hydrochloric acid that sulfuric acid or mass concentration are 35%.
The reaction temperature of acidification reaction is 20 ~ 200 DEG C, preferably 60 ~ 150 DEG C, more preferable 110 ~ 130 DEG C；
The PH range of acidification reaction is 0.01 ~ 6.5, preferably 0.01 ~ 3, more preferable 0.1 ~ 1；
The reaction time of acidification reaction be 0.1 ~ 12h, preferably 0.2 ~ 3 hour, more preferable 1 ~ 2 hour.
Specifically, the acidification reaction carries out in acidification kettle RA1, and the acidification kettle RA1 is preferably by being resistant to acid used
Material manufacture 2.0MPa pressure vessel, and equipped with reflux cooling device, can be heated and be cooled down by heat transferring medium
Carry out temperature control, the agitating device equipped with the adjustable speed of agitator of speed reducer, the pumped vacuum systems equipped with vacuum pump set；
Under the conditions of high temperature and strong acid (HAc), the sodium salt of organic matter is converted into organic matter, phosphorous acid therein, glycine, methyl
The reactions such as amino phosphorous acid, methyl glyphosate, glyphosate generate the organic matter based on glyphosine, and the reaction mechanism is as follows:
Na3PO3 + 3 HAc —— H3PO3+3 NaAc
The sodium salt of sodium phosphite strong acid phosphorous acid strong acid
NH2CH2COONa + HAc —— NH2CH2COOH + NaAc
The sodium salt of Sodium Glycinate strong acid glycine strong acid
NH2CH2COOH + 2 HCHO + 2 H3PO3 --- (CH2PO(OH)2)2NCH2COOH + 2 H2O
Glycine formaldehyde phosphorous acid glyphosine water
PO(OH)2 CH2NHCH2COOH + HCHO + H3PO3 - ((CH2PO(OH)2)2NCH2COOH + H2O
Glyphosate formaldehyde phosphorous acid glyphosine water
The sodium salt of organic matter is converted into corresponding organic matter under high temperature and strong acid condition in above-mentioned reaction, and formaldehyde is mainly from grass
The decomposition of methylamino phosphorous acid and methyl glyphosate under the conditions of acidic high-temperature in sweet phosphine mother liquor M0；
After acidification reaction, acidification kettle RA1 starts its pumped vacuum systems, and vacuum degree control range is 0.1-80KPa, preferably
5-60KPa, more preferable 1-10KPa, are dehydrated, and are then separated to the product after acidification reaction；
The separation of the product of the acidification reaction carries out in centrifuge CM2；
The dehydration of acidified mother liquor M2 takes off in light kettle VC1 in vacuum to be carried out；
Being solidificated in gelatinization kettle RG1 for the colloid CD carries out；
Water is added in the colloid CD to carry out in molten-bath RG2, be added in colloid CD be equivalent to colloid CD mass 40 ~
50% water, at this point, glyphosine GP1 is completely soluble, glyphosate GP2 is precipitated, and passes through conventional solid-liquid separation such as centrifuge CM3, band
Filter is dry after separating glyphosate GP2；
The vacuum dehydration of glyphosine solution carries out in vacuum kettle RG4, and the water content of control melting glyphosine is no more than 0.5%, temperature
Control range is 100 ~ 200 DEG C, preferably 120 ~ 180 DEG C, more preferable 130 ~ 150 DEG C；
Melting glyphosine is transferred to steel band or rotating cylinder flaker FM1 sheeting, and flaker FM1 is equipped with dehumidifying and cooling system, temperature
Control range is 0 ~ 30 DEG C, and preferably 0 ~ 10 DEG C, more preferable 2 ~ 7 DEG C, humid control is no more than 25%.
Specifically, the water content of quenching mother liquor M1 is 10 ~ 50%, preferably 15 ~ 45%, more preferable 35 ~ 40%；
The water content of the acidified mother liquor M2 is 1 ~ 40%, preferably 2 ~ 20%, more preferable 15 ~ 17%；
Specifically, acidified mother liquor M2 is mainly organized as glyphosine GP1 and glyphosate GP2, while containing micro phosphorous acid GP3, sweet
The mixture for the organic matter not converted completely in propylhomoserin GP4 and acidification reaction；
Specifically, the gelatinizing agent HK3 is chain growth initiator, and the gelatinizing agent HK3 includes azo-initiator such as azo two
Isobutyl cyanogen, the different cyanogen in heptan of azo two etc., organic or inorganic peroxide initiator such as dialkyl peroxide, peroxidating diformazan
Benzoyl, persulfate, hydrogen peroxide, organic or inorganic reducing agent such as amine, tertiary amine, oxalic acid, glucose, alcohol or Fe2+, Cu+,
NaHSO3, Na2SO3, Na2S2O3 etc..
Specifically, the sodium chloride crude product SA1 recycles to obtain purification sodium chloride RSA1 through sodium chloride recovery system；The sodium
Salt crude product SA2 recycles to obtain purification sodium salt RSA2 through sodium salt recycling system.
Specifically, sodium chloride crude product SA1 recycles to obtain the method and step of purification sodium chloride RSA1 through sodium chloride recovery system
In include:
At least one level adverse current is carried out to the sodium chloride crude product SA1 isolated to dissolve and wash away to obtain sodium chloride crystal solution, the sodium chloride knot
Brilliant liquid passes through isolated sodium chloride transition product, and sodium chloride transition product carry out at least one level adverse current again and elute, and obtains purification chlorination
Sodium RSA1.
Specifically, also obtain dissolveing and washing away mother liquor every time after dissolveing and washing away, it is described dissolve and wash away mother liquor formed through organic matter removal agent processing it is heavy
It is separated by solid-liquid separation again behind shallow lake, the liquid after separation, which is back to, dissolves and washes away recycled in process.
Specifically, the solid of the mother liquor after processing and separation that dissolve and wash away is phosphorus-containing matter, the phosphorus-containing matter
Incinerator is sent burn or be converted into inorganic phosphorous compound by advanced oxidation processes being recycled.
Specifically, rinsing mother liquor is also obtained after elution every time, it is heavy that the rinsing mother liquor is formed through organic matter removal agent processing
It removes organic matter behind shallow lake to be separated by solid-liquid separation again, the liquid after separation is back to recycled in elution process.
Specifically, solid of the rinsing mother liquor after processing and separation is phosphorus-containing matter, the phosphorus-containing matter
Incinerator is sent burn or be converted into inorganic phosphorous compound by advanced oxidation processes being recycled.
Specifically, sodium salt crude product SA2 recycles to obtain method and step and the chlorination of purification sodium salt RSA2 through sodium salt recycling system
The method and step that sodium crude product SA1 recycles to obtain purification sodium chloride RSA1 through sodium chloride recovery system is same or like.
In order that the present invention can be more clearly and readily understood, right below according to specific embodiment and in conjunction with attached drawing
The present invention is described in further detail.
Embodiment one
Pump 5M3Glyphosate by using glycine mother liquor M0, glyphosate mother solution M0 are that glyphosate factory recycles the alkalinity after triethylamine
It is female to obtain 1266KG sodium chloride crude product SA1 and 1400KG quenching after quenching method recycles sodium chloride crude product SA1 by mother liquor, PH 10
Liquid M1；Sodium chloride crude product SA1 obtains 911KG purification sodium chloride RSA1 after sodium chloride recovery system conventional treatment；By quenching mother
After liquid M1 is moved in acidification kettle RS1,35% concentrated hydrochloric acid, 0.62 M is added3, in 120 DEG C of conditions with stirring and reflux cooler
After lower reaction 75 minutes, stop reflux cooler, start vacuum system, after control dehydration rate reaches 50%, be cooled to after 40 DEG C with
Centrifuge CM2 is separated by solid-liquid separation, and is obtained 1250KG sodium salt crude product SA2 and 773KG and is mainly contained glyphosate GP2, glyphosine
The acidified mother liquor M2 of GP1, glycine GP4, sodium salt crude product SA2 obtain 902KG purification sodium after sodium salt recycling system conventional treatment
Salt RSA2；Acidified mother liquor M2 obtains 362KG organic admixture M3 in 120 DEG C of vacuum dehydrations, and water content 18% is then organic
Object mixture M 3 enters in gelatinization kettle RG1, adds 200KG gelatinizing agent HK3, glyphosine GP1 and glyphosate GP2 and is formed by curing
430KG colloid CD, colloid CD is isolated from organic matter mixture M 3, then obtains 132KG level-one residue M4, and colloid CD is dissolved in
Water, glyphosate GP2 and glyphosine GP1 realization obtain glyphosine GP1 and the 21KG content that 232KG content is 95% after efficiently separating
For 95% glyphosate GP2, be separated by solid-liquid separation after level-one residue M4 vacuum dehydration sedimentation can simply recycle to obtain 23KG content be
Second level residue M5 is obtained after 96% phosphorous acid GP3, level-one residue M4 recycling phosphorous acid GP3, second level residue M5 is further continued for
After vacuum dehydration, 21KG content can be precipitated as 97% glycine GP4 after separating gelatinizing agent HK3, and it is remaining to obtain 15KG three-level
Object M6, three-level residue M6 contain micro glyphosate GP2, glyphosine GP1, phosphorous acid GP3, glycine GP4 and acid hemolysis process
In the unconverted or incomplete organic matter of conversion, can return to the synthesizing glyphosate hydrolysis procedure or this method of leading portion main reaction
Acidification reaction process recycled.
Embodiment two
Pump 5M3Glyphosate by using glycine mother liquor M0, glyphosate mother solution M0 are that glyphosate factory recycles the alkalinity after triethylamine
It is female to obtain 1266KG sodium chloride crude product SA1 and 1400KG quenching after quenching method recycles sodium chloride crude product SA1 by mother liquor, PH 10
Liquid M1；Sodium chloride crude product SA1 obtains 911KG purification sodium chloride RSA1 after sodium chloride recovery system conventional treatment；By quenching mother
After liquid M1 is moved in acidification kettle RS1,30% 0.41 M of sulfuric acid is added3, in 120 DEG C of conditions with stirring and reflux cooler
After lower reaction 90 minutes, stop reflux cooler, start vacuum system, after control dehydration rate reaches 50%, be cooled to after 40 DEG C with
Centrifuge CM2 is separated by solid-liquid separation, obtain 1215KG sodium sulphate crude product and 782KG mainly contain glyphosate GP2, glyphosine GP1,
The acidified mother liquor M2 of glycine GP4, sodium sulphate crude product obtain 1051KG refined sulfuric acid after the processing of conventional sodium salt recycling system
Sodium, acidified mother liquor M2 obtain 371KG organic admixture M3, water content 20%, then organic matter is mixed in 120 DEG C of vacuum dehydrations
It closes object M3 to enter in gelatinization kettle RG1, adds 210KG gelatinizing agent HK3, glyphosine GP1 and glyphosate GP2 and be formed by curing 441KG
Colloid CD, colloid CD is isolated from organic matter mixture M 3, then obtains 140KG level-one residue M4, colloid CD and be dissolved in water, grass
It is 95% that sweet phosphine GP2 and glyphosine GP1 realization, which obtains glyphosine GP1 and the 20KG content that 238KG content is 95% after efficiently separating,
Glyphosate GP2, it is 96% that being separated by solid-liquid separation after level-one residue M4 vacuum dehydration sedimentation, which can simply recycle to obtain 22KG content,
Second level residue M5 is obtained after phosphorous acid GP3, level-one residue M4 recycling phosphorous acid GP3, second level residue M5 is further continued for vacuum
After dehydration, 19KG content can be precipitated as 97% glycine GP4 after separating gelatinizing agent HK3, and obtain 12KG three-level residue
M6, three-level residue M6 contain in micro glyphosate GP2, glyphosine GP1, phosphorous acid GP3, glycine GP4 and acid hemolysis process
The unconverted or incomplete organic matter of conversion, can return to the synthesizing glyphosate hydrolysis procedure of leading portion main reaction or the acid of this method
Change reaction process recycled.
Embodiment three
Pump 5M3Glyphosate by using glycine mother liquor M0, glyphosate mother solution M0 are that glyphosate factory recycles the alkalinity after triethylamine
It is female to obtain 1266KG sodium chloride crude product SA1 and 1400KG quenching after quenching method recycles sodium chloride crude product SA1 by mother liquor, PH 10
Liquid M1；Sodium chloride crude product SA1 obtains 911KG purification sodium chloride RSA1 after sodium chloride recovery system conventional treatment；By quenching mother
After liquid M1 is moved in acidification kettle RS1,35% concentrated hydrochloric acid, 0.62 M is added3, in 130 DEG C of conditions with stirring and reflux cooler
After lower reaction 90 minutes, stop reflux cooler, start vacuum system, after control dehydration rate reaches 50%, be cooled to after 50 DEG C with
Centrifuge CM2 is separated by solid-liquid separation, and is obtained 1232KG sodium salt crude product SA2 and 775KG and is mainly contained glyphosate GP2, glyphosine
The acidified mother liquor M2 of GP1, glycine GP4, sodium salt crude product SA2 obtain 917KG purification sodium after sodium salt recycling system conventional treatment
Salt RSA2；Acidified mother liquor M2 obtains 370KG organic admixture M3 in 120 DEG C of vacuum dehydrations, and water content 20% is then organic
Object mixture M 3 enters in gelatinization kettle RG1, adds 300KG gelatinizing agent HK3, glyphosine GP1 and glyphosate GP2 and is formed by curing
480KG colloid CD, colloid CD is isolated from organic matter mixture M 3, then obtains 190KG level-one residue M4, and colloid CD is dissolved in
Water, glyphosate GP2 and glyphosine GP1 realization obtain glyphosine GP1 and the 20KG content that 235KG content is 95% after efficiently separating
For 95% glyphosate GP2, be separated by solid-liquid separation after level-one residue M4 vacuum dehydration sedimentation can simply recycle to obtain 18KG content be
Second level residue M5 is obtained after 96% phosphorous acid GP3, level-one residue M4 recycling phosphorous acid GP3, second level residue M5 is further continued for
After vacuum dehydration, 16KG content can be precipitated as 97% glycine GP4 after separating gelatinizing agent HK3, and it is remaining to obtain 8KG three-level
Object M6, three-level residue M6 contain micro glyphosate GP2, glyphosine GP1, phosphorous acid GP3, glycine GP4 and acid hemolysis process
In the unconverted or incomplete organic matter of conversion, can return to the synthesizing glyphosate hydrolysis procedure or this method of leading portion main reaction
Acidification reaction process recycled.
Example IV
Pump 5M3Glyphosate by using glycine mother liquor M0, glyphosate mother solution M0M0 are that glyphosate factory recycles the alkalinity after triethylamine
It is female to obtain 1266KG sodium chloride crude product SA1 and 1400KG quenching after quenching method recycles sodium chloride crude product SA1 by mother liquor, PH 10
Liquid M1；Sodium chloride crude product SA1 obtains 911KG purification sodium chloride RSA1 after conventional treatment；Quenching mother liquor M1 is moved into acidification kettle
After in RS1,30% concentrated hydrochloric acid, 0.72 M is added3, under conditions of 110 DEG C with stirring and reflux cooler after reaction 90 minutes,
Stop reflux cooler, starts vacuum system and be cooled to after 40 DEG C and consolidated with centrifuge CM2 after control dehydration rate reaches 50%
Liquid separation, obtains the acid that 1241KG sodium salt crude product SA2 and 770KG mainly contain glyphosate GP2, glyphosine GP1, glycine GP4
Change mother liquor M2, sodium salt crude product SA2 obtains 915KG purification sodium salt RSA2 after sodium salt recycling system conventional treatment；Acidified mother liquor M2
In 120 DEG C of vacuum dehydrations, 364KG organic admixture M3 is obtained, water content 20%, then organic admixture M3 enters glue
Change in kettle RG1, add 350KG gelatinizing agent HK3, glyphosine GP1 and glyphosate GP2 and be formed by curing 451KG colloid CD, from organic
Colloid CD is isolated in object mixture M 3, then obtains 263KG level-one residue M4, and colloid CD is dissolved in water, and glyphosate GP2 and increasing are sweet
Phosphine GP1 is realized efficiently separate after obtain that glyphosine GP1 and 18KG content that 235KG content is 95% is 95% glyphosate GP2, one
Being separated by solid-liquid separation after grade residue M4 vacuum dehydration sedimentation can simply recycle to obtain the phosphorous acid GP3 that 22KG content is 96%, level-one
Second level residue M5 is obtained after residue M4 recycling phosphorous acid GP3, after second level residue M5 is further continued for vacuum dehydration, separates gelatinization
13KG content can be precipitated after agent HK3 and be 97% glycine GP4, and obtain 8KG three-level residue M6, three-level residue M6 contains
There is unconverted in micro glyphosate GP2, glyphosine GP1, phosphorous acid GP3, glycine GP4 and acid hemolysis process or conversion incomplete
Organic matter, can return to the synthesizing glyphosate hydrolysis procedure of leading portion main reaction or the acidification reaction process circulating sleeve of this method
With.
Working principle of the present invention is as follows:
The quenching mother liquor M1 containing organic matter and its sodium salt is obtained after glyphosate mother solution M0 recycling sodium chloride crude product SA1；Quenching mother liquor
Excessive acid is added in the acidified kettle RA1 of M1, converts organic matter for the sodium salt of organic matter under special reaction condition, will generate
Organic matter sodium salt and organic matter isolated sodium salt crude product SA2 and acidified mother liquor M2；Acidified mother liquor M2 is removed through vacuum dehydration
Water is removed, the organic admixture M3, organic admixture M3 that contain a small amount of glyphosate GP2 ingredient based on glyphosine GP1 are obtained
It into gelatinization kettle RG1, adds gelatinizing agent HK3, glyphosine GP1 and glyphosate GP2 and is formed by curing colloid CD, mixed from organic matter
Colloid CD is isolated in object M3, then obtains level-one residue M4, and after adding water in colloid CD, glyphosine GP1 is all dissolved in water, and grass is sweet
Phosphine GP2 is precipitated, and after separation of solid and liquid, obtains glyphosate GP2 and glyphosine solution, glyphosine solution uses vacuum dehydration, sheeting, obtains
To glyphosine GP1, phosphorous acid GP3 can simply be recycled by being separated by solid-liquid separation after level-one residue M4 vacuum dehydration sedimentation, remove phosphorous acid
After second level residue M5 outside GP3 is further continued for dehydration, glycine GP4 can be precipitated after separating gelatinizing agent HK3, and it is surplus to obtain three-level
Excess M6, three-level residue M6 contain micro glyphosate GP2, glyphosine GP1, phosphorous acid GP3, glycine GP4 and acidolysis
The unconverted or incomplete organic matter of conversion in journey returns to the synthesizing glyphosate hydrolysis procedure or this method of leading portion main reaction
Acidification reaction process recycled, the present invention can effectively recycle the effective component in glyphosate mother solution M0, and operate letter
Single, separation efficiently, can recycle preparation high-purity glyphosine GP1 and glyphosate GP2 from quenching mother liquor M1, meanwhile, it can be efficient
Ground recycle phosphorous acid GP3 and glycine GP4, the present invention green, efficiently, economically recycle glyphosate mother solution M0 in it is effective at
Point, organic matter value maximization in glyphosate mother solution M0 is realized, in terms of glycine GP4, glyphosate GP2 and glyphosine GP1's
Yield is total can to increase by 25% or more, and the present invention not only solves the glyphosate mother solution M0 dangerous waste problem of long-standing problem manufacturing enterprise,
And the economic benefit of glyphosate by using glycine manufacturing enterprise can be greatly improved, have extensively in glyphosate by using glycine production industry
Wealthy promotion prospect.
Particular embodiments described above, pair present invention solves the technical problem that, technical scheme and beneficial effects carry out
It is further described, it should be understood that the above is only a specific embodiment of the present invention, is not limited to this
Invention, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should be included in this hair
Within bright protection scope.
Claims (16)
1. recycling the method for glyphosine and glyphosate in a kind of glyphosate mother solution, which is characterized in that
Include in the step of method:
After glyphosate mother solution isolates sodium chloride crude product by quenching method, quenching mother liquor is obtained；
Acid is added in quenching mother liquor, carries out acidification reaction；
Product after acidification reaction is separated, it is isolated the corresponding sodium salt crude product of acid to be added and in addition to sodium salt crude product
Acidified mother liquor；
Acidified mother liquor is dehydrated under vacuum conditions, obtains organic admixture, wherein includes that increasing is sweet in organic admixture
Phosphine and glyphosate；
Gelatinizing agent is added in organic admixture, the glyphosine and glyphosate in organic admixture are formed by curing colloid, separation
Obtain colloid and the level-one residue in addition to colloid；
Add water in colloid, the glyphosine in colloid is dissolved in water, and the glyphosate in colloid is precipitated, isolated glyphosate and glyphosine
Solution；
Glyphosine solution vacuum dehydration obtains melting glyphosine；Glyphosine sheeting is melted, glyphosine is obtained.
2. recycling the method for glyphosine and glyphosate in glyphosate mother solution according to claim 1, which is characterized in that
Level-one residue dehydrated under vacuum, then separates, and obtains phosphorous acid and the second level residue in addition to phosphorous acid.
3. recycling the method for glyphosine and glyphosate in glyphosate mother solution according to claim 2, which is characterized in that
Second level residue is dehydrated under vacuum conditions, is then separated, and glycine and the three-level residue in addition to glycine are obtained.
4. recycling the method for glyphosine and glyphosate in glyphosate mother solution according to claim 3, which is characterized in that
Three-level residue returns to acidification reaction process recycled.
5. recycling the method for glyphosine and glyphosate in glyphosate mother solution according to claim 3, which is characterized in that
Glyphosine solution vacuum dehydration, also obtains level-one condensate liquid；It is dehydrated under level-one residue vacuum condition, it is cold also to obtain second level
Lime set；Second level residue is dehydrated under vacuum conditions, also obtains three-level condensate liquid；
It include water and gelatinizing agent in level-one condensate liquid, B-grade condensation liquid and three-level condensate liquid；
Level-one condensate liquid, B-grade condensation liquid and three-level condensate liquid are recycled through gelatinizing agent recovery system, obtain gelatinizing agent and water, gained
Gelatinizing agent returns to the curing process recycled of colloid, and obtained water is returned into colloid plus water conservancy project sequence is applied.
6. recycling the method for glyphosine and glyphosate in glyphosate mother solution according to claim 1, which is characterized in that
The glyphosate mother solution is the mother liquor of glycine dimethylphosphite or diethyl phosphite method.
7. recycling the method for glyphosine and glyphosate in glyphosate mother solution according to claim 1, which is characterized in that
The glyphosate mother solution is that glycine dimethyl phosphate method produces the mother liquor after the recovered triethylamine of glyphosate.
8. recycling the method for glyphosine and glyphosate in glyphosate mother solution according to claim 1, which is characterized in that
After glyphosate mother solution isolates sodium chloride crude product by quenching method, obtain include in the method for quenching mother liquor:
Glyphosate mother solution obtains dehydration liquid by being dehydrated at least once；
After being dehydrated fluid dewatering to critical concentration, quenching medium is added, obtains mixture；Wherein, when critical concentration, dehydration liquid has wax
Phenomenon occurs；
Mixture is separated, quenching mother liquor and sodium chloride crude product are obtained.
9. recycling the method for glyphosine and glyphosate in glyphosate mother solution according to claim 1, which is characterized in that
The quenching mother liquor be containing glyphosate and its sodium salt, glyphosine and its sodium salt, glycine and its sodium salt, phosphorous acid and its
The mixture of sodium salt, methyl glyphosate and its sodium salt and methylamino phosphorous acid and its sodium salt.
10. recycling the method for glyphosine and glyphosate in glyphosate mother solution according to claim 1, which is characterized in that
The PH range of glyphosate mother solution is 1 ~ 14.
11. recycling the method for glyphosine and glyphosate in glyphosate mother solution according to claim 1, which is characterized in that
Acid in acidification reaction is organic acid or inorganic acid；
And/or the reaction temperature of acidification reaction is 20 ~ 200 DEG C；
And/or the PH range of acidification reaction is 0.01 ~ 6.5；
And/or the reaction time of acidification reaction is 0.1 ~ 12h.
12. recycling the method for glyphosine and glyphosate in glyphosate mother solution according to claim 1, which is characterized in that
The acidification reaction carries out in acidification kettle；
And/or the separation of the product of the acidification reaction carries out in centrifuge；
And/or the dehydration of acidified mother liquor takes off in light kettle in vacuum and carries out；
And/or being solidificated in gelatinization kettle for the colloid carries out；
And/or water is added in the colloid and is carried out in molten-bath；
And/or the separation of glyphosate and glyphosine solution carries out in centrifuge；
And/or glyphosine solution vacuum dehydration carries out in vacuum kettle；
And/or melting glyphosine sheeting carries out in flaker.
13. recycling the method for glyphosine and glyphosate in glyphosate mother solution according to claim 1, which is characterized in that
The water content of quenching mother liquor is 10 ~ 50%；
And/or the water content of the acidified mother liquor is 1 ~ 40%.
14. recycling the method for glyphosine and glyphosate in glyphosate mother solution according to claim 1, which is characterized in that
The gelatinizing agent is chain growth initiator, and the gelatinizing agent includes azo-initiator, organic or inorganic peroxidating
At least one of object initiator, organic or inorganic reducing agent.
15. recycling the method for glyphosine and glyphosate in glyphosate mother solution according to claim 1, which is characterized in that
In colloid plus when water, the quality of the water of addition is the 40 ~ 50% of colloid quality.
16. recycling the method for glyphosine and glyphosate in glyphosate mother solution according to claim 1, which is characterized in that
The sodium chloride crude product recycles to obtain purification sodium chloride through sodium chloride recovery system；
And/or the sodium salt crude product recycles to obtain purification sodium salt through sodium salt recycling system.
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