CN102153584B - Comprehensive treatment technique for recycling glyphosate mother liquor - Google Patents
Comprehensive treatment technique for recycling glyphosate mother liquor Download PDFInfo
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Abstract
The invention provides a treatment method of glyphosate mother liquor. The glyphosate mother liquor is from the glyphosate preparation process by an IDA (incremental dynamic analysis) route air oxidation method. The treatment method comprises the steps of resin adsorption, resin desorption and formaldehyde recovery. The method provided by the invention achieves the goal of recycling waste materials, implements circulation and economy, and has the advantages of energy consumption saving, environmental friendliness, lower production cost and the like.
Description
Technical field
The present invention relates to a kind of industrialization method of wastewater treatment, be specifically related to a kind for the treatment of process of glyphosate mother solution.
Background technology
Have certain solubleness due to glyphosate in water, so no matter adopt IDA method technique or glycine method technique, all can produce the rare mother liquor of a certain amount of glyphosate, glyphosate per ton approximately produces the glyphosate mother solution of 4～6 tons.Offshore company adopts concentrated rear buried treatment process, the manufacturing enterprise of China has taked the concentrated rear preparation of the rare mother liquor of glyphosate 10% gyphosate solution, therefore at present the whole world only has domestic product and uses 10% gyphosate solution, and glyphosate per ton is 1.0～1.5 tons of by-product 10% gyphosate solutions approximately simultaneously.
Because 10% present gyphosate solution is add the former powder of glyphosate or all prepare with mother liquor with mother liquor basically, and the unreacted starting material in reaction process, by product all can accumulate in mother liquor, simultaneously because glyphosate is heat-sensitive materials, can decompose in concentration process, cause again the generation of impurity.Therefore, be mingled with a large amount of inorganic salt and organic impurity in 10% present gyphosate solution.As the IDA method: this technique is to generate glyphosate by the pmida98 oxidation, in oxidising process, can produce formaldehyde and other side reaction impurity of a part, because the formaldehyde volatility is poor, formaldehyde can not be steamed fully in concentrated, caused the accumulation of formaldehyde in mother liquor, the highest in 10% aqua formaldehyde can reach more than 6%, also contain simultaneously by product and the degradation production of the reaction such as aminomethyl phosphonic acid, methyl glyphosate, nitroso-group glyphosate.Regulation formaldehyde massfraction≤10g/kg in standard GB/T 20684-2006, and present present situation is that in IDA method 10% gyphosate solution, formaldehyde content generally all more than 60g/kg, is controlled requirement considerably beyond national standard.Due to the formaldehyde excess, with formic acid and glyphosate and impurity reaction generation carbonic acid gas thereof, " bottle rises " phenomenon often appears, and especially summer is more serious.
Some enterprises adopt the method for regulating pH values, transfer formaldehyde to urotropine (vulkacit H), and " bottle rises " phenomenon is overcome, but content still exceeds standard during formaldehyde examination, and the precipitation generation is arranged.As running into acidic conditions, urotropine can resolve into formaldehyde again.
The problem that glyphosate 10% aqua exists has caused the concern of relevant department and pesticide industry.In August, 2008, department of crop cultivation of the Ministry of Agriculture has issued " about soliciting the letter of " Pesticidal products active constituent content gradient administrative provisions (draft) " suggestion " on the net in (No. the 76th, [2008] plantation (plant protection) letter), has formally proposed 10% aqua and has cancelled problem.Pesticide industry association also once plans glyphosate 10% aqua in last Sep and lists " high pollution, high environmental risk " product register in.No. 1158 bulletin of the February 25 this year Ministry of Agriculture, Ministry of Industry and Information clearly " from this bulletin date of promulgation, stops ratifying active constituent content and registers lower than 30% gyphosate solution.Obtained the gyphosate solution of agricultural chemicals field test certificate of approval and approved registration, its active constituent content is lower than 30%, should according to the regulation of phase approximately principle with this bulletin the 4th (one), (three), (four) item, carry out the active constituent content change before 31 days December in 2009.Exceed the time limit and no longer keep its agricultural chemicals field test certificate of approval, agriculture chemical registration card, the interim registration card of agricultural chemicals and pesticide producing certificate of approval." and regulation " Pesticidal products of approved registration carries out according to this bulletin regulation that active constituent content changes, the Pesticidal products of having produced by former agriculture chemical registration card, the interim registration card of agricultural chemicals, pesticide producing certificate of approval before changing can be sold and be used within its production assurance phase." this just means that glyphosate 10% aqua will stop producing in the end of this year, stops selling and using the processing problem of glyphosate mother solution after we must resolve 10% aqua and cancel simultaneously the end of the year 2011.
In addition, even with glyphosate Separation and Recovery from mother liquor, the formaldehyde in residual mother liquor is because its content is 1.5～7%, can not direct reuse in industrial production.If directly carry out biochemical treatment, due to the existence meeting kill microorganisms of formaldehyde, and therefore be difficult to process with traditional biochemical process.The direct discharging of waste water that contains formaldehyde does not only meet environmental requirement, and causes again the waste of formaldehyde resource, therefore must exploitation effectively contain the resource treatment technique of the waste water of rare formaldehyde.
China processes for glyphosate mother solution and has carried out large quantity research.From method of edge treatment, burn route and be undoubtedly reasonable method, pass through evaporation concentration, concentrated solution is burned, almost can solve the processing problem of glyphosate mother solution, but it is high to burn cost, produces the mother liquid disposal expense that glyphosate per ton produces and is at least 3800 yuan, and general enterprises can't bear.Although the research of every technology such as existing membrane concentration, multiple-effect evaporation, burning, advanced treatment at present, the underintegration of every treatment technology.The Ministry of Science and Technology has issued " 863 high-tech research evolutionary operation(EVOP) " in November, 2008, the row special topic carries out " glyphosate waste water low-discharging and the exploitation of mother liquor recovery and utilization technology ", the target that glyphosate mother solution is recycled has been proposed, make up with integrated by multiple technologies, reduce the mother liquor generation, strengthen mother liquor and reclaim, therefrom extract the former powder of glyphosate, remove sodium-chlor, formaldehyde fully utilizes, and forms recycling economy, the final processing up to standard of waste water.
Summary of the invention
The object of the invention is to: propose a kind of comprehensive process technology of new glyphosate mother solution, can the glyphosate in glyphosate mother solution be separated with formaldehyde by the treatment process of gentleness, thereby realize that resource utilization reclaims.Treating processes, input cost is low, and output benefit is obvious, does not produce secondary pollution.Not only can reclaim glyphosate and formaldehyde, but make simultaneously the formaldehyde-containing wastewater that originally can't carry out biochemical treatment reach the requirement of biochemical treatment.
Above-mentioned purpose of the present invention is achieved through the following technical solutions, and the percentage composition that adopts in this specification sheets is the quality percentage composition without special instruction:
A kind for the treatment of process of glyphosate mother solution is provided, described glyphosate mother solution prepares the process of glyphosate from IDA route air oxidation process, namely generated the process of glyphosate by pmida98 oxidation under catalyst action, wherein glyphosate content is 0.5%～1.5%, and formaldehyde content is 1.5%～7%; The treating method comprises following steps:
1. resin absorption process: the described glyphosate mother solution of 10～15 times of resin filling volumes adsorption column through resin filling is adsorbed: adsorption process keeps mother liquor input and output material balance, single batch of absorption input and output material time is controlled to be 2～8hr, and adsorption process is atmospheric operation; Described resin is weak base anion-exchange resin;
2. resin desorption process: 1. step is adsorbed saturated resin absorbing column, purge with pneumatics and remove residual glyphosate mother solution, then add dipping by lye 30min, then desorption liquid is collected in extraction, and desorption liquid contains glyphosate concentration greater than 6%;
3. formaldehyde removal process: the step 1. water outlet of described resin absorption process reclaims formalin through malleation distillation concentrate, obtains 37% formalin, and distillation tower reactor waste water formaldehyde content is less than 0.1%; Flow process as shown in Figure 1.
Described IDA route air oxidation process preferably generates the method for glyphosate with the oxidation of high density pmida98; Described pmida98 concentration preferred 25%～50%, further preferred 30%～40%.
Step is described weak base anion-exchange resin 1., and as the highly selective polymeric adsorbent, its adsorption effect to glyphosate is especially good; Further preferred weak base anion-exchange resin has following physico-chemical property: water content 55-63%; Complete exchange capacity (mmol/g does) 〉=7.9; Wet volume density (g/ml) 0.68-0.78; Wet true density (g/ml) 1.05-1.11; Granularity (0.355-1.20mm) 〉=95; Ooze mill rate of small round spheres % 〉=90.
Described weak base anion-exchange resin with above-mentioned physico-chemical property can be obtained through modification by existing multiple weak base anion-exchange resin; Described existing weak base anion-exchange resin is selected from a kind of in 331 weakly alkaline epoxy type anion exchange resins, D301 macroreticular weakly base polystyrene I type anionite-exchange resin, D318 macroreticular weakly base acrylic acid type anion exchange resin, D311 macroreticular weakly base acrylic acid type anion exchange resin or WDA918 macroreticular weakly base acrylic acid type anion exchange resin.
Described method of modifying is as follows:
A) under 30～40 ℃, use the alcohols of C1～C8 with the described existing weak base anion-exchange resin 4～6hr of flow washing of 80～100ml/hr, with pneumatics, the remnants alcohol in resin is purged after washing finishes and do;
B) with steps A) resin that purge to do, under 50～90 ℃, first soak 30min with alkali lye, and then with the described resin of identical alkali lye continous pouring and the extraction of 1.5 times of resin volumes, the flow velocity that keeps alkali lye to pass in and out is 100ml/hr;
C) with step B) extraction to the resin of doing adopts deionized water wash to water outlet pH value to reach neutrality.
Step B) described alkali lye is selected from any one in the By Amine Solutions of liquefied ammonia, ammoniacal liquor, alkali hydroxide soln, alkali-metal carbonate solution, sal volatile or C1～C8.
Preferred weak base anion-exchange resin service life cycle of the present invention can surpass 2 years, and renewable.
Step 1. described resin absorption temperature is 0～60 ℃.
Step 2. described resin desorption temperature is 0～60 ℃.
Step 2. described alkali lye is selected from any one in the By Amine Solutions of liquefied ammonia, ammoniacal liquor, alkali hydroxide soln, alkali-metal carbonate solution, sal volatile or C1～C8.
The alkali metal hydroxide aqueous solution of described alkali lye preferred 8%～20%.
The step 2. endpoint pH scope of described resin desorption is preferred 5.0～11.0, desorption liquid pH value scope preferred 4.0～8.5.
Step 3. described malleation distillation temperature is 110～220 ℃, and pressure is 0.05MPa～0.4MPa.
Method for processing mother solution of glyphosate of the present invention can obtain following treatment effect:
In desorption liquid after 2. step adopts the alkaline matter desorption glyphosate content is greater than 6%, but the gyphosate solution of direct evaporation configuration 30% above concentration also can carry out the former powder of acidizing crystal recovery glyphosate;
After 3. step distilled, after distillation, the bottom product formaldehyde content less than 0.1%, reached and can directly carry out the requirement of biochemical treatment; The formalin concentration of concentrate recovery simultaneously reaches 37%, can be back to the pmida98 building-up process.
In sum, treatment process of the present invention has obtained higher resource recovery, and wherein the glyphosate rate of recovery is greater than 98%, and the rate of recovery of formaldehyde is greater than 97%.
If implement treatment process of the present invention, can form rapidly market efficiency, calculate to produce glyphosate 10000t/a, annual resin absorption reclaims glyphosate: 325t/a, reclaims 37% formaldehyde 3700t/a, no longer produces 10% aqua simultaneously, make discharged wastewater met the national standard, social benefit is remarkable.
Description of drawings
Fig. 1 is the schema of formaldehyde removal process in method of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail, in order to better understand content of the present invention, specific as follows:
Embodiment 1: the preparation I of modified resin
With the 200mlD318 macroreticular weakly base acrylic acid type anion exchange resin ion exchange column of packing into, this ion exchange column adopts chuck hot water thermal insulating, controls 30～40 ℃, and employing ethanol washs.Washing with alcohol is controlled and is entered with the 100ml/hr flow, washing time 4hr; Washing with alcohol finishes, and with pneumatics, the residual ethanol in resin is purged and does; Adjust and stablize and control hot water jacket's temperature to 60～65 ℃, the 20% ammoniacal liquor 100ml that configured in advance is good pours resin-column into and soaks resin 30min; Soak and finish, keep 60～65 degree, continous-stable adds 20% ammoniacal liquor 300ml, simultaneously according to identical speed extraction, controls input and output material speed 100ml/hr.Advance alkali and finish, continue extraction to doing, adopt deionized water wash resin to water outlet pH value to reach neutral, namely obtain the weak base anion-exchange resin I of modification.Obtain following data through check: water content 60.5%; Complete exchange capacity (mmol/g does) 〉=8.1; Wet volume density (g/ml) 0.76; Wet true density (g/ml) 1.08; Granularity (0.355-1.20mm)=96.9; Ooze mill rate of small round spheres %=92.5.
Embodiment 2: the preparation II of modified resin
With the 200ml D311 macroreticular weakly base acrylic acid type anion exchange resin ion exchange column of packing into, this ion exchange column adopts chuck hot water thermal insulating, controls 30～40 ℃, and employing methyl alcohol washs.Methanol wash is controlled and is entered with the 100ml/hr flow, washing time 5hr; Methanol wash finishes, and with pneumatics, the residual methanol in resin is purged and does; Adjust and stablize and control hot water jacket's temperature to 55～60 ℃, the triethylamine 100ml that configured in advance is good pours resin-column into and soaks resin 30min; Soak and finish, keep 60～65 degree, continous-stable adds triethylamine 300ml, simultaneously according to identical speed extraction, controls input and output material speed 100ml/hr.Advance alkali and finish, continue extraction to doing, adopt deionized water wash resin to water outlet pH value to reach neutral, namely obtain the weak base anion-exchange resin II of modification.Obtain following data through check: water content 59%; Complete exchange capacity (mmol/g does) 〉=8.1; Wet volume density (g/ml) 0.74; Wet true density (g/ml) 1.08; Granularity (0.355-1.20mm)=96.7; Ooze mill rate of small round spheres %=91.5.
Embodiment 3: the preparation III of modified resin
With the 200ml D301 macroreticular weakly base polystyrene I type anionite-exchange resin ion exchange column of packing into, this ion exchange column adopts chuck hot water thermal insulating, controls 30～40 ℃, and employing ethanol washs.Washing with alcohol is controlled and is entered with the 80ml/hr flow, washing time 6hr; Washing with alcohol finishes, and with pneumatics, the residual ethanol in resin is purged and does; Adjust and stablize and control hot water jacket's temperature to 75～85 ℃, the 20% aqueous sodium hydroxide solution 100ml that configured in advance is good pours resin-column into and soaks resin 30min; Soak and finish, keep 60～65 degree, continous-stable adds 20% aqueous sodium hydroxide solution 300ml, simultaneously according to identical speed extraction, controls input and output material speed 100ml/hr.Advance alkali and finish, continue extraction to doing, adopt the deionized water wash resin to reach neutral to going out water ph value, namely obtain the weak base anion-exchange resin III of modification.Obtain following data through check: water content 61.3%; Complete exchange capacity (mmol/g does) 〉=8.3; Wet volume density (g/ml) 0.77; Wet true density (g/ml) 1.06; Granularity (0.355-1.20mm)=97.2; Ooze mill rate of small round spheres %=93.1.
Embodiment 4: glyphosate I is reclaimed in glyphosate mother solution absorption
The glyphosate mother solution source: high density oxidation method, pmida98 slurry concentration 35%, 90% oxygen is oxygenant.
Glyphosate mother solution index: glyphosate content 0.7%, formaldehyde content 5.65%, formic acid content 0.07%;
Treatment step is as follows:
1) modified resin in employing embodiment 1, the effective stacking volume 50ml of inner resin of adsorption column, the above-mentioned glyphosate mother solution of 500g is adsorbed through the two-stage series connection adsorption column, controlling adsorption process glyphosate mother solution and adsorption system temperature is 0 ℃～10 ℃, absorption discharging time 2.5 hours, take out water sample middle control analysis glyphosate content every 30min in adsorption process after the beginning water outlet, all the time less than 100ppm.
2) with step 1) the saturated resin of absorption, purge with pneumatics and remove residual glyphosate mother solution, then add 10% NaOH aqueous solution 10g to soak 30min, then desorption liquid, desorption liquid 56.2g, absorption effluent 452.5g are collected in extraction.
Analyze:
Step 2) desorption liquid contains glyphosate 6.2%, formaldehyde 0.16%, formic acid 0.31%.
Step 1) absorption effluent contains glyphosate 35ppm, formaldehyde 6.22%, formic acid 0.04%.
The glyphosate rate of recovery 99.55%, absorption effluent formaldehyde yield 99.63%.
Embodiment 5: glyphosate II is reclaimed in glyphosate mother solution absorption
The glyphosate mother solution source: high density oxidation method, pmida98 slurry concentration 35%, 90% oxygen is oxygenant.
Glyphosate mother solution index: glyphosate content 0.65%, formaldehyde content 5.62%, formic acid content 0.06%;
Treatment step is as follows:
1) adopt the modified resin in embodiment 2 to inhale, the effective stacking volume 50ml of resin in attached column, the above-mentioned glyphosate mother solution of 600g is adsorbed through the two-stage series connection adsorption column, control 30 ℃～40 ℃ of adsorption process glyphosate mother solution and adsorption system temperature, absorption discharging time 4 hours, take out water sample middle control analysis glyphosate content every 30min in adsorption process after the beginning water outlet, all the time less than 100ppm.
2) with step 1) the saturated resin of absorption, purge with pneumatics and remove residual glyphosate mother solution, then add 10%NaOH aqueous solution 12g to soak 30min, then desorption liquid, desorption liquid 59.8g, absorption effluent 551g are collected in extraction.
Analyze:
Step 2) desorption liquid contains glyphosate 6.48%, formaldehyde 0.15%, formic acid 0.37%.
Step 1) absorption effluent contains glyphosate 46ppm, formaldehyde 6.10%, formic acid 0.025%.
The glyphosate rate of recovery 99.36%, absorption effluent formaldehyde yield 99.67%.
Embodiment 6: glyphosate III is reclaimed in glyphosate mother solution absorption
The glyphosate mother solution source: high density oxidation method, pmida98 slurry concentration 35%, 90% oxygen is oxygenant.
Glyphosate mother solution index: glyphosate content 0.65%, formaldehyde content 5.67%, formic acid content 0.06%;
Treatment step is as follows:
1) modified resin in employing embodiment 3, the effective stacking volume 50ml of inner resin of adsorption column, the glyphosate mother solution that 700g is above-mentioned adsorbs through the two-stage series connection adsorption column, control adsorption process glyphosate mother solution and adsorption system temperature 50 C～60 ℃, absorption discharging time 8 hours, take out water sample middle control analysis glyphosate content every 30min in adsorption process after the beginning water outlet, all the time less than 100ppm.
2) with step 1) the saturated resin of absorption, purge with pneumatics and remove residual glyphosate mother solution, then add 10%NaOH aqueous solution 14g to soak 30min, then desorption liquid, desorption liquid 62.2g, absorption effluent 649.8g are collected in extraction.
Analyze:
Step 2) desorption liquid contains glyphosate 7.24%, formaldehyde 0.17%, formic acid 0.30%.
Step 1) absorption effluent contains glyphosate 72ppm, formaldehyde 6.09%, formic acid 0.036%.
The glyphosate rate of recovery 98.97%, absorption effluent formaldehyde yield 99.70%.
Embodiment 7: absorption effluent reclaims formaldehyde I
Step 1 in employing embodiment 5) absorption effluent, index is as follows: absorption effluent contains glyphosate 46ppm, formaldehyde 6.10%, formic acid 0.025%.
Continuous process is adopted in the formaldehyde distillation: formaldehyde-containing wastewater after resin absorption after being preheated to 100 ℃, is entered flash distillation in flash tank, and flash tank keeps pressure 0.25MPa, and gas phase temperature is controlled 120～130 ℃, and liquidus temperature is controlled 170～180 ℃.Through forming two bursts of logistics after flash distillation: flash distillation formaldehyde steam, flash distillation formaldehyde waste water.This flash distillation formaldehyde waste water goes biochemical treatment after the preheater double-effect heat exchange is cooling, it is concentrated that flash distillation formaldehyde steam stream enters low-pressure distillation tower, controls tower top working pressure and reflux ratio, and tower top can obtain 37% formaldehyde solution, and tower reactor waste water goes biochemical treatment.
Input and output material situation: water inlet 50Kg; Output formaldehyde 8.12Kg, waste water 41.85Kg
Analyze: concentrated formaldehyde content 37.02% contains formic acid 0.01%; After distillation, waste water contains formaldehyde 0.087%.
The formaldehyde rate of recovery: 98.55%, relative glyphosate waste water total yield 98.2%.
Embodiment 8: absorption effluent reclaims formaldehyde II
Step 1 in employing embodiment 6) absorption effluent, index is as follows: absorption effluent contains glyphosate 72ppm, formaldehyde 6.09%, formic acid 0.036%.
Continuous process is adopted in the formaldehyde distillation: formaldehyde-containing wastewater after resin absorption after being preheated to 100 ℃, is entered flash distillation in flash tank, and flash tank keeps pressure 0.25MPa, and gas phase temperature is controlled 110～120 ℃, and liquidus temperature is controlled 160～170 ℃.Through forming two bursts of logistics after flash distillation: flash distillation formaldehyde steam, flash distillation formaldehyde waste water.This flash distillation formaldehyde waste water goes biochemical treatment after the preheater double-effect heat exchange is cooling, it is concentrated that flash distillation formaldehyde steam stream enters low-pressure distillation tower, controls tower top working pressure and reflux ratio, and tower top can obtain 37% formaldehyde solution, and tower reactor waste water goes biochemical treatment.
Input and output material situation: water inlet 100Kg; Output formaldehyde 16.26Kg, waste water 83.7Kg
Analyze: concentrated formaldehyde content 36.85% contains formic acid 0.01%; After distillation, waste water contains formaldehyde 0.093%.
The formaldehyde rate of recovery: 98.03%, relative glyphosate waste water total yield 98.2%.
Claims (10)
1. the treatment process of a glyphosate mother solution, described glyphosate mother solution prepares the process of glyphosate from IDA route air oxidation process, namely generated the process of glyphosate by pmida98 oxidation under catalyst action, wherein glyphosate content is 0.5% ~ 1.5%, and formaldehyde content is 1.5% ~ 7%; The treating method comprises following steps:
1. resin absorption process: the described glyphosate mother solution of 10 ~ 15 times of resin filling volumes adsorption column through resin filling is adsorbed: adsorption process keeps mother liquor input and output material balance, single batch of absorption input and output material time is controlled to be 2 ~ 8hr, and adsorption process is atmospheric operation; Described resin is weak base anion-exchange resin;
2. resin desorption process: 1. step is adsorbed saturated resin absorbing column, purge with pneumatics and remove residual glyphosate mother solution, then add dipping by lye 30min, then desorption liquid is collected in extraction, and desorption liquid contains glyphosate concentration greater than 6%;
3. formaldehyde removal process: the step 1. water outlet of described resin absorption process reclaims formalin through malleation distillation concentrate, obtains 37% formalin, and distillation tower reactor waste water formaldehyde content is less than 0.1%.
2. the treatment process of glyphosate mother solution claimed in claim 1 is characterized in that: described IDA route air oxidation process is the method for glyphosate that generates with the oxidation of high density pmida98; Described pmida98 concentration is 25% ~ 50%.
3. the treatment process of glyphosate mother solution claimed in claim 2, it is characterized in that: described pmida98 concentration is 30% ~ 40%.
4. the treatment process of glyphosate mother solution claimed in claim 1, it is characterized in that: step 1. described weak base anion-exchange resin has following physico-chemical property: water content 55-63%; Do complete exchange capacity 〉=7.9mmol/g; Wet volume density 0.68-0.78g/ml; Wet true density 1.05-1.11g/ml; 0.355-1.20mm granularity 〉=95; Ooze mill rate of small round spheres 〉=90%.
5. the treatment process of glyphosate mother solution claimed in claim 1, it is characterized in that: step 1. described resin absorption temperature is 0 ~ 60 ℃.
6. the treatment process of glyphosate mother solution claimed in claim 1, it is characterized in that: step 2. described resin desorption temperature is 0 ~ 60 ℃.
7. the treatment process of glyphosate mother solution claimed in claim 1 is characterized in that: step 2. described alkali lye is selected from any one in the By Amine Solutions of liquefied ammonia, ammoniacal liquor, alkali hydroxide soln, alkali-metal carbonate solution, sal volatile or C1 ~ C8.
8. the treatment process of glyphosate mother solution claimed in claim 7, it is characterized in that: described alkali lye is 8% ~ 20% alkali metal hydroxide aqueous solution.
9. the treatment process of glyphosate mother solution claimed in claim 1, it is characterized in that: the step 2. endpoint pH scope of described resin desorption is 5.0 ~ 11.0, desorption liquid pH value scope is 4.0 ~ 8.5.
10. the treatment process of glyphosate mother solution claimed in claim 1, it is characterized in that: step 3. described malleation distillation temperature is 110 ~ 220 ℃, positive pressure pressure is 0.05MPa ~ 0.4MPa.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101648972A (en) * | 2009-09-08 | 2010-02-17 | 浙江新安化工集团股份有限公司 | Method for recycling glyphosate from glyphosate mother liquid |
| CN101704841A (en) * | 2009-04-27 | 2010-05-12 | 南通泰禾化工有限公司 | Method for recovering glyphosate mother liquor |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704841A (en) * | 2009-04-27 | 2010-05-12 | 南通泰禾化工有限公司 | Method for recovering glyphosate mother liquor |
| CN101648972A (en) * | 2009-09-08 | 2010-02-17 | 浙江新安化工集团股份有限公司 | Method for recycling glyphosate from glyphosate mother liquid |
Non-Patent Citations (4)
| Title |
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| "草甘膦母液处理技术进展";张小宏 等;《精细化工中间体》;20101231;第40卷(第6期);第8-10，15页 * |
| "草甘膦生产工艺综述及其发展趋势";茆庆文;《安徽化工》;20080630;第34卷(第3期);第5-7，16页 * |
| 张小宏 等."草甘膦母液处理技术进展".《精细化工中间体》.2010,第40卷(第6期),第8-10，15页. |
| 茆庆文."草甘膦生产工艺综述及其发展趋势".《安徽化工》.2008,第34卷(第3期),第5-7，16页. |
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