CN102766159B - Glyphosate alkaline mother liquor processing method - Google Patents
Glyphosate alkaline mother liquor processing method Download PDFInfo
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- CN102766159B CN102766159B CN201210222123.0A CN201210222123A CN102766159B CN 102766159 B CN102766159 B CN 102766159B CN 201210222123 A CN201210222123 A CN 201210222123A CN 102766159 B CN102766159 B CN 102766159B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a kind of glyphosate alkaline mother liquor processing method, its treatment process is: in this alkaline mother liquor, add hydrochloric acid conditioning solution pH value obtain solution A to 1-5; Solution A obtains solution B and sodium chloride solution through membrane sepn, and described sodium chloride solution obtains saturated solution through pervaporation, and saturated nacl aqueous solution obtains sodium carbonate through Hou's process for soda production and is recovered utilization; It is characterized in that: described solution B makes the concentration of solute in solution B be increased to 3-10 doubly through concentrated, ie in solution C, then in solution C, appropriate glycine and formaldehyde is added, glyphosate in solution C and phosphorous acid are reacted completely, namely the sweet phosphine of original increasing in the sweet phosphine of the increasing obtained and solution C, obtains increasing sweet phosphine solid through neutralization, suction filtration and drying step and is recovered utilization.Advantage of the present invention is: can to the glyphosate in glyphosate alkaline mother liquor, increase sweet phosphine, sodium phosphite, sodium-chlor fully recycles, cut the waste, reduce and pollute, improve the utilization ratio of alkaline mother liquor.
Description
Technical field
The present invention relates to a kind for the treatment of process of glyphosate mother solution, specifically, relate to a kind for the treatment of process of glyphosate alkaline mother liquor.
Background technology
Utilize dimethyl phosphate method to produce in glyphosate process, often produce one ton of glyphosate and probably have six tons of glyphosate mother solutions generations.The by product of the sodium phosphite of the glyphosate usually containing 0.8%-1% in glyphosate mother solution, the sweet phosphine of increasing of 3%-4%, 2%-3%, the glycine of 0.15%-0.3%, 1.5%-2%, the sodium-chlor of 10%-14%, the sodium hydroxide of 2.5%-3.5% and water.At present rear desalination (or concentrated after membrane sepn) is concentrated to method for processing mother solution of glyphosate, then the gyphosate solution of 30% is mixed with, the gyphosate solution of preparation 30% needs to consume a large amount of former powder of high-quality glyphosate (producing aqua inferior with the former powder of high-quality), and sodium phosphites a large amount of in this aqua, increase sweet phosphine and be not used, not only contaminate environment after discharge, but also cause waste.In addition, this aqua life-time service makes easily to cause soil compaction.Therefore, a kind of new technical scheme is needed to solve above-mentioned technical problem.
Summary of the invention
The object of this invention is to provide a kind for the treatment of process of glyphosate mother solution, the method can not only make full use of the sodium phosphite in alkali liquor, but also fully can recycle the sweet phosphine of increasing.
The technical scheme that the present invention solves the problems of the technologies described above employing is:
Glyphosate alkaline mother liquor processing method, described glyphosate alkaline mother liquor is the alkaline mother liquor of mother liquor remainder after adding in alkali and reclaiming triethylamine wherein of being produced glyphosate by dimethyl phosphate method; Its treatment process is: in this alkaline mother liquor, add hydrochloric acid conditioning solution pH value obtain solution A to 1-5; Solution A obtains solution B and sodium chloride solution through membrane sepn, and described sodium chloride solution obtains saturated solution through pervaporation, and saturated nacl aqueous solution obtains sodium carbonate through Hou's process for soda production and is recovered utilization; Described solution B makes the concentration of solute in solution B be increased to 3-10 doubly through concentrated, ie in solution C, then solution C sampling analysis is gone out to the content of each material in solution C, in solution C, appropriate glycine and formaldehyde is added according to analytical data, glyphosate in solution C and phosphorous acid are reacted completely, namely the sweet phosphine of original increasing in the sweet phosphine of the increasing obtained and solution C, obtains increasing sweet phosphine solid through neutralization, suction filtration and drying step and is recovered utilization.
Described solution A is separated out completely through being evaporated to sodium-chlor, then filters to obtain sodium-chlor and solution C, obtains sodium carbonate be recovered utilization after described sodium-chlor makes saturated solution through Hou's process for soda production.
In gained solution C, add appropriate iminodiethanoic acid one sodium salt and formaldehyde according to analytical data, the phosphorous acid in solution C is reacted completely, obtained pmida98, described pmida98 is recovered utilization through being oxidized obtained glyphosate.
Mother liquor remaining after being converted into glyphosate to described pmida98 carries out sampling analysis, adds appropriate formaldehyde and phosphorous acid makes the glyphosate in mother liquor react completely according to analytical results in remaining mother liquor, obtainedly increases sweet phosphine and is recovered utilization.
Also can add appropriate solution C in the mother liquor of above-mentioned remainder according to analytical results, formaldehyde makes the glyphosate in the mother liquor of above-mentioned remainder and formaldehyde reaction is complete, the sweet phosphine of obtained increasing is recovered utilization.
Described solution B must increase sweet phosphine and solution D after secondary membrane sepn, described solution D is after concentrated, solution D sampling analysis is gone out to the content of each material in solution D, then in solution D, appropriate iminodiethanoic acid one sodium salt and formaldehyde is added according to analytical data, phosphorous acid in solution D is reacted completely, obtained pmida98, described pmida98 is recovered utilization through being oxidized obtained glyphosate.
The aperture of described secondary film is less than the molecular diameter increasing sweet phosphine, is greater than the molecular diameter of glyphosate.
Advantage of the present invention is: can to the glyphosate in glyphosate alkaline mother liquor, increase sweet phosphine, sodium phosphite, sodium-chlor fully recycles, cut the waste, reduce and pollute, improve the utilization ratio of alkaline mother liquor.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Glyphosate alkaline mother liquor described in following examples is the alkaline mother liquor of mother liquor remainder after adding in alkali and reclaiming triethylamine wherein of being produced glyphosate by dimethyl phosphate method, and its gross weight is 2Kg.In this alkaline mother liquor of sampling and measuring, pH value is 12, and wherein containing the glyphosate of 0.8%, the sweet phosphine of increasing, the sodium phosphite of 3%, glycine, the sodium-chlor of 14%, the sodium hydroxide of 2.5% of 0.3% of 3%, other is water.
Embodiment 1
In above-mentioned alkaline mother liquor, add hydrochloric acid conditioning solution pH value obtain solution A to 1-5, now, the sodium phosphite in solution A is converted into phosphorous acid, sodium hydroxide is converted into sodium-chlor; Solution A obtains solution B and sodium chloride solution through membrane sepn, and sodium chloride solution obtains saturated solution through pervaporation, and saturated nacl aqueous solution obtains sodium carbonate through Hou's process for soda production and is recovered utilization; Solution B makes the concentration of solute in solution B be increased to 10 times through concentrated, ie in solution C, then in solution C, add the glycine 8.5 grams of 98% and 38.6 grams, the formaldehyde of 37%, glyphosate in solution C and phosphorous acid are reacted completely, namely the sweet phosphine of original increasing in the sweet phosphine of the increasing obtained and solution C, the sweet phosphine solid of increasing 98 grams obtaining 95% through neutralization, suction filtration and drying step is recovered utilization.The synthesis of glyphosate now in solution C, phosphorous acid and formaldehyde increases sweet phosphine, and its reaction equation is as follows:
React incomplete phosphorous acid to synthesize with glycine and formaldehyde again and increase sweet phosphine until phosphorous acid reacts completely, reaction equation is as follows:
Embodiment 2
In above-mentioned alkaline mother liquor, add hydrochloric acid conditioning solution pH value obtain solution A to 1-5, now, the sodium phosphite in solution A is converted into phosphorous acid, sodium hydroxide is converted into sodium-chlor; Solution A obtains solution B and sodium chloride solution through membrane sepn, and sodium chloride solution obtains saturated solution through pervaporation, and saturated nacl aqueous solution obtains sodium carbonate through Hou's process for soda production and is recovered utilization; Solution B makes the concentration of solute in solution B be increased to 6 times through concentrated, ie in solution C, then in solution C, add folding hundred iminodiethanoic acid one sodium salt 64 grams and 45 grams, 37% formaldehyde, phosphorous acid in solution C is reacted completely, obtained pmida98, described pmida98 is recovered utilization through being oxidized obtained glyphosate.
The reaction equation of obtained pmida98 is as follows:
Mother liquor remaining after being converted into glyphosate to pmida98 carries out sampling and testing, and can add appropriate formaldehyde and phosphorous acid or solution C and formaldehyde according to test toward mother liquor in, the glyphosate in mother liquor is reacted completely, and the sweet phosphine of obtained increasing is recovered utilization.
Embodiment 3
In above-mentioned alkaline mother liquor, add hydrochloric acid conditioning solution pH value obtain solution A to 1-5, now, the sodium phosphite in solution A is converted into phosphorous acid, sodium hydroxide is converted into sodium-chlor; Solution A is separated out completely through being evaporated to sodium-chlor, then filters to obtain sodium-chlor and solution C, obtains sodium carbonate be recovered utilization after described sodium-chlor makes saturated solution through Hou's process for soda production.
The treating processes embodiment 1 of solution C or embodiment 2.
Embodiment 4
In alkaline mother liquor, add hydrochloric acid conditioning solution pH value obtain solution A to 1-5, now, the sodium phosphite in solution A is converted into phosphorous acid, sodium hydroxide is converted into sodium-chlor; Solution A obtains solution B and sodium chloride solution through membrane sepn, and sodium chloride solution obtains saturated solution through pervaporation, and saturated nacl aqueous solution obtains sodium carbonate through Hou's process for soda production and is recovered utilization; Solution B must increase sweet phosphine and solution D after secondary membrane sepn, solution D makes the concentration of solute in solution D be increased to 8 times through concentrated, add folding hundred iminodiethanoic acid one sodium salt 64 grams and 45 grams, 37% formaldehyde, phosphorous acid in solution D is reacted completely, obtained pmida98, described pmida98 is recovered utilization through being oxidized obtained glyphosate.
Claims (1)
1. glyphosate alkaline mother liquor processing method, described glyphosate alkaline mother liquor is the alkaline mother liquor of mother liquor remainder after adding in alkali and reclaiming triethylamine wherein of being produced glyphosate by dimethyl phosphate method; Its treatment process is: in this alkaline mother liquor, add hydrochloric acid conditioning solution pH value obtain solution A to 1-5; Solution A obtains solution B and sodium chloride solution through membrane sepn, and described sodium chloride solution obtains saturated solution through pervaporation, and saturated nacl aqueous solution obtains sodium carbonate through Hou's process for soda production and is recovered utilization; It is characterized in that: described solution B makes the concentration of solute in solution B be increased to 3-10 doubly through concentrated, ie in solution C, then solution C sampling analysis is gone out to the content of each material in solution C, in solution C, appropriate glycine and formaldehyde is added according to analytical data, glyphosate in solution C and phosphorous acid are reacted completely, namely the sweet phosphine of original increasing in the sweet phosphine of the increasing obtained and solution C, obtains increasing sweet phosphine solid through neutralization, suction filtration and drying step and is recovered utilization.
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| CN105801426A (en) * | 2016-03-19 | 2016-07-27 | 安徽东至广信农化有限公司 | Method for recovering and treating triethylamine tail gas in glyphosate production |
| CN112062141A (en) * | 2020-08-25 | 2020-12-11 | 合众思(北京)环境工程有限公司 | Process for producing sodium chloride and phosphate from sodium hypochlorite wastewater |
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| US4486359A (en) * | 1979-07-09 | 1984-12-04 | Alkaloida Vegyeszeti Gyar | Process for the preparation of N-phosphonomethyl-glycine |
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| CN101659673A (en) * | 2009-09-24 | 2010-03-03 | 南京工业大学 | Processing technology for recovering and utilizing mother solution of glyphosate as resource |
| CN102127112A (en) * | 2010-01-19 | 2011-07-20 | 浙江新安化工集团股份有限公司 | Method for separating glyphosine solid from glyphosate mother liquor |
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