CN102153584A - Comprehensive treatment technique for recycling glyphosate mother liquor - Google Patents
Comprehensive treatment technique for recycling glyphosate mother liquor Download PDFInfo
- Publication number
- CN102153584A CN102153584A CN201110035621XA CN201110035621A CN102153584A CN 102153584 A CN102153584 A CN 102153584A CN 201110035621X A CN201110035621X A CN 201110035621XA CN 201110035621 A CN201110035621 A CN 201110035621A CN 102153584 A CN102153584 A CN 102153584A
- Authority
- CN
- China
- Prior art keywords
- glyphosate
- resin
- mother solution
- glyphosate mother
- formaldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Treating Waste Gases (AREA)
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 of treatment process of glyphosate mother solution.
Background technology
Because glyphosate has certain solubleness in water, so no matter adopt IDA method technology or glycine method technology, all can produce the rare mother liquor of a certain amount of glyphosate, glyphosate per ton produces 4～6 tons glyphosate mother solution approximately.Offshore company adopts and concentrates the buried treatment process in back, the manufacturing enterprise of China has then taked the rare mother liquor of glyphosate is concentrated back preparation 10% gyphosate solution, therefore the whole world has only China to produce and use 10% gyphosate solution at present, 1.0～1.5 tons of about by-product 10% gyphosate solutions simultaneously of glyphosate per ton.
Because 10% present gyphosate solution is with the mother liquor interpolation former powder of glyphosate basically or all prepares with mother liquor, and the unreacted starting material in the reaction process, by product all can accumulate in the mother liquor, simultaneously because glyphosate is a heat-sensitive materials, in concentration process, can decompose, cause the generation of impurity again.Therefore, be mingled with a large amount of inorganic salt and organic impurity in present 10% gyphosate solution.As the IDA method: this technology 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 concentrating, caused the accumulation of formaldehyde in mother liquor, the highest in 10% aqua formaldehyde can reach more than 6%, also contain the by product and the degradation production of reaction such as aminomethyl phosphonic acid, methyl glyphosate, nitroso-group glyphosate simultaneously.Regulation formaldehyde massfraction≤10g/kg among the standard GB 20684-2006, and present present situation be in IDA method 10% gyphosate solution formaldehyde content generally all more than 60g/kg, considerably beyond national standard control requirement.Because the formaldehyde excess with formic acid and glyphosate and impurity reaction generation carbonic acid gas thereof, " bottle rises " phenomenon often occurs, 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 formaldehyde when detecting content still exceed standard, 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 cancellation 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 to ratify active constituent content and is lower than 30% gyphosate solution and registers.Obtained the gyphosate solution of agricultural chemicals field test certificate of approval and approved registration, its active constituent content is lower than 30%, should announce the regulation of the 4th (), (three), (four) item according to phase approximately principle and this, before 31 days December in 2009, carry out the active constituent content change.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 can be sold and be used in its production assurance phase before changing." this just means that glyphosate 10% aqua will stop to produce in the end of this year, stops for the end of the year 2011 selling and using, we must resolve the handling problem of 10% aqua cancellation back glyphosate mother solution simultaneously.
In addition, even with glyphosate Separation and Recovery from mother liquor, the formaldehyde in the residual mother liquor is because its content is 1.5～7%, can not direct reuse in industrial production.If directly carry out biochemical treatment, because the existence meeting kill microorganisms of formaldehyde, and therefore be difficult to handle with traditional biochemical process.The direct discharging of waste water that contains formaldehyde does not only meet environmental requirement, and causes the waste of formaldehyde resource again, so must exploitation effectively contain the resource treatment technique of the waste water of rare formaldehyde.
China handles for glyphosate mother solution and has carried out big 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 handling problem of glyphosate mother solution, but burn the cost height, produce the mother liquor processing costs that glyphosate per ton produces and be at least 3800 yuan, general enterprise can't bear.Though every Study on Technology such as existing at present membrane concentration, multiple-effect evaporation, burning, advanced treatment, 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 emission and the exploitation of mother liquor recovery and utilization technology ", the target that glyphosate mother solution is recycled has been proposed, by multiple technologies combination and integrated, 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 objective of the invention is to: propose a kind of comprehensive process technology of new glyphosate mother solution, can the glyphosate in the glyphosate mother solution be separated with formaldehyde, thereby realize that resource utilization reclaims by the treatment process of gentleness.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 the formaldehyde-containing wastewater that can't carry out biochemical treatment originally reach the requirement of biochemical treatment simultaneously.
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 of treatment process of glyphosate mother solution is provided, described glyphosate mother solution prepares the process of glyphosate from IDA route air oxidation process, promptly 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 adsorption column that the described glyphosate mother solution of 10～15 times of resin packing volumes is filled through resin adsorbs: 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 an atmospheric operation; Described resin is a weak base anion-exchange resin;
2. resin desorption process: 1. step is adsorbed saturated resin absorption post, purge with pneumatics and remove residual glyphosate mother solution, add dipping by lye 30min again, desorption liquid is collected in extraction then, and desorption liquid contains glyphosate concentration greater than 6%;
3. formaldehyde removal process: the water outlet of the 1. described resin absorption process of step through malleation distillation carry dense recovery formalin, obtain 37% formalin, distillation tower still 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%.
The 1. described weak base anion-exchange resin of step, 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 the WDA918 macroreticular weakly base acrylic acid type anion exchange resin.
Described method of modifying is as follows:
A) under 30～40 ℃, wash described existing weak base anion-exchange resin 4～6hr with the alcohols of C1～C8 with the flow of 80～100ml/hr, washing finishes the back and with pneumatics the remaining alcohol in the resin is purged and do;
B) with steps A) resin that purge to do, under 50～90 ℃, soak 30min earlier, 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 with alkali lye;
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 organic amine solution of liquefied ammonia, ammoniacal liquor, alkali hydroxide soln, alkali-metal carbonate solution, sal volatile or C1～C8.
Preferred weak base anion-exchange resin of the present invention recycles the life-span and can surpass 2 years, and renewable.
The 1. described resin absorption temperature of step is 0～60 ℃.
The 2. described resin desorption temperature of step is 0～60 ℃.
The 2. described alkali lye of step is selected from any one in the organic amine solution 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 endpoint pH scope of the 2. described resin desorption of step is preferred 5.0～11.0, desorption liquid pH value scope preferred 4.0～8.5.
The 3. described malleation distillation temperature of step 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:
Glyphosate content is greater than 6% in the desorption liquid after 2. step adopts the alkaline matter desorption, 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, distillation back bottom product formaldehyde content reached the requirement that can directly carry out biochemical treatment less than 0.1%; The formalin concentration of proposing dense 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 market efficiency rapidly, 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, obvious social benefit.
Description of drawings
Fig. 1 is the schema of formaldehyde removal process in the method for the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail, so that 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, control 30～40 ℃, and employing ethanol washs.Washing with alcohol control enters washing time 4hr with the 100ml/hr flow; Washing with alcohol finishes, and with pneumatics the residual ethanol in the resin is purged and does; Adjustment and stable control hot water jacket 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, and control input and output material speed 100ml/hr.Advance alkali and finish, continue extraction, adopt deionized water wash resin to water outlet pH value to reach neutral, promptly obtain the weak base anion-exchange resin I of modification to doing.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, control 30～40 ℃, and employing methyl alcohol washs.Methanol wash control enters washing time 5hr with the 100ml/hr flow; Methanol wash finishes, and with pneumatics the residual methanol in the resin is purged and does; Adjustment and stable control hot water jacket 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, and control input and output material speed 100ml/hr.Advance alkali and finish, continue extraction, adopt deionized water wash resin to water outlet pH value to reach neutral, promptly obtain the weak base anion-exchange resin II of modification to doing.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, control 30～40 ℃, and employing ethanol washs.Washing with alcohol control enters washing time 6hr with the 80ml/hr flow; Washing with alcohol finishes, and with pneumatics the residual ethanol in the resin is purged and does; Adjustment and stable control hot water jacket 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, and control input and output material speed 100ml/hr.Advance alkali and finish, continue extraction, adopt the deionized water wash resin to reach neutral, promptly obtain the weak base anion-exchange resin III of modification to going out water ph value to doing.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 among the 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, control adsorption process glyphosate mother solution and adsorption system temperature are 0 ℃～10 ℃, absorption discharging time 2.5 hours, after the beginning water outlet, take out water sample middle control analysis glyphosate content in the adsorption process, all the time less than 100ppm every 30min.
2) step 1) is adsorbed saturated resin, purge with pneumatics and remove residual glyphosate mother solution, add 10% NaOH aqueous solution 10g immersion 30min then, desorption liquid, desorption liquid 56.2g, absorption effluent 452.5g are collected in extraction then.
Analyze:
Step 2) desorption liquid contains glyphosate 6.2%, formaldehyde 0.16%, formic acid 0.31%.
The 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 among the embodiment 2 to inhale, the effective stacking volume 50ml of resin in the attached column, the above-mentioned glyphosate mother solution of 600g is adsorbed through the two-stage series connection adsorption column, 30 ℃～40 ℃ of control adsorption process glyphosate mother solution and adsorption system temperature, absorption discharging time 4 hours, after the beginning water outlet, take out water sample middle control analysis glyphosate content in the adsorption process, all the time less than 100ppm every 30min.
2) step 1) is adsorbed saturated resin, purge with pneumatics and remove residual glyphosate mother solution, add 10%NaOH aqueous solution 12g then and soak 30min, desorption liquid, desorption liquid 59.8g, absorption effluent 551g are collected in extraction then.
Analyze:
Step 2) desorption liquid contains glyphosate 6.48%, formaldehyde 0.15%, formic acid 0.37%.
The 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 among the 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, 50 ℃～60 ℃ of control adsorption process glyphosate mother solution and adsorption system temperature, absorption discharging time 8 hours, after the beginning water outlet, take out water sample middle control analysis glyphosate content in the adsorption process, all the time less than 100ppm every 30min.
2) step 1) is adsorbed saturated resin, purge with pneumatics and remove residual glyphosate mother solution, add 10%NaOH aqueous solution 14g then and soak 30min, desorption liquid, desorption liquid 62.2g, absorption effluent 649.8g are collected in extraction then.
Analyze:
Step 2) desorption liquid contains glyphosate 7.24%, formaldehyde 0.17%, formic acid 0.30%.
The 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
Adopt the absorption effluent of step 1) among the embodiment 5, index is as follows: absorption effluent contains glyphosate 46ppm, formaldehyde 6.10%, formic acid 0.025%.
Continuous process is adopted in formaldehyde distillation: formaldehyde-containing wastewater after the resin absorption after being preheated to 100 ℃, is entered flash distillation in the flash tank, the flash tank 0.25MPa that keep-ups pressure, 120～130 ℃ of gas phase temperature controls, 170～180 ℃ of liquidus temperature controls.Through forming two bursts of logistics after the flash distillation: flash distillation formaldehyde steam, flash distillation formaldehyde waste water.This flash distillation formaldehyde waste water goes biochemical treatment after preheater economic benefits and social benefits heat exchange cooling, flash distillation formaldehyde steam stream enters low-pressure distillation tower and concentrates, control cat head working pressure and reflux ratio, and cat head can obtain 37% formaldehyde solution, and tower still 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%; Distillation back 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
Adopt the absorption effluent of step 1) among the embodiment 6, index is as follows: absorption effluent contains glyphosate 72ppm, formaldehyde 6.09%, formic acid 0.036%.
Continuous process is adopted in formaldehyde distillation: formaldehyde-containing wastewater after the resin absorption after being preheated to 100 ℃, is entered flash distillation in the flash tank, the flash tank 0.25MPa that keep-ups pressure, 110～120 ℃ of gas phase temperature controls, 160～170 ℃ of liquidus temperature controls.Through forming two bursts of logistics after the flash distillation: flash distillation formaldehyde steam, flash distillation formaldehyde waste water.This flash distillation formaldehyde waste water goes biochemical treatment after preheater economic benefits and social benefits heat exchange cooling, flash distillation formaldehyde steam stream enters low-pressure distillation tower and concentrates, control cat head working pressure and reflux ratio, and cat head can obtain 37% formaldehyde solution, and tower still 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%; Distillation back 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, promptly 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 adsorption column that the described glyphosate mother solution of 10～15 times of resin packing volumes is filled through resin adsorbs: 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 an atmospheric operation; Described resin is a weak base anion-exchange resin;
2. resin desorption process: 1. step is adsorbed saturated resin absorption post, purge with pneumatics and remove residual glyphosate mother solution, add dipping by lye 30min again, desorption liquid is collected in extraction then, and desorption liquid contains glyphosate concentration greater than 6%;
3. formaldehyde removal process: the water outlet of the 1. described resin absorption process of step through malleation distillation carry dense recovery formalin, obtain 37% formalin, distillation tower still waste water formaldehyde content is less than 0.1%.
2. the treatment process of the described glyphosate mother solution of claim 1 is characterized in that: described IDA route air oxidation process is the method that generates glyphosate with the oxidation of high density pmida98; Described pmida98 concentration is 25%～50%.
3. the treatment process of the described glyphosate mother solution of claim 2, it is characterized in that: described pmida98 concentration is 30%～40%.
4. the treatment process of the described glyphosate mother solution of claim 1, it is characterized in that: the 1. described weak base anion-exchange resin of step 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; 0.355-1.20m granularity 〉=95; Ooze mill rate of small round spheres 〉=90%.
5. the treatment process of the described glyphosate mother solution of claim 1, it is characterized in that: the 1. described resin absorption temperature of step is 0～60 ℃.
6. the treatment process of the described glyphosate mother solution of claim 1, it is characterized in that: the 2. described resin desorption temperature of step is 0～60 ℃.
7. the treatment process of the described glyphosate mother solution of claim 1 is characterized in that: the 2. described alkali lye of step is selected from any one in the organic amine solution of liquefied ammonia, ammoniacal liquor, alkali hydroxide soln, alkali-metal carbonate solution, sal volatile or C1～C8.
8. the treatment process of the described glyphosate mother solution of claim 7, it is characterized in that: described alkali lye is 8%～20% alkali metal hydroxide aqueous solution.
9. the treatment process of the described glyphosate mother solution of claim 1, it is characterized in that: the endpoint pH scope of the 2. described resin desorption of step is 5.0～11.0, desorption liquid pH value scope is 4.0～8.5.
10. the treatment process of the described glyphosate mother solution of claim 1, it is characterized in that: the 3. described malleation distillation temperature of step is 110～220 ℃, positive pressure pressure is 0.05MPa～0.4MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110035621 CN102153584B (en) | 2011-02-10 | 2011-02-10 | Comprehensive treatment technique for recycling glyphosate mother liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110035621 CN102153584B (en) | 2011-02-10 | 2011-02-10 | Comprehensive treatment technique for recycling glyphosate mother liquor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102153584A true CN102153584A (en) | 2011-08-17 |
| CN102153584B CN102153584B (en) | 2013-05-08 |
Family
ID=44435292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110035621 Active CN102153584B (en) | 2011-02-10 | 2011-02-10 | Comprehensive treatment technique for recycling glyphosate mother liquor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102153584B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2011
- 2011-02-10 CN CN 201110035621 patent/CN102153584B/en active Active
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 |
|---|
| 《安徽化工》 20080630 茆庆文 "草甘膦生产工艺综述及其发展趋势" 第5-7，16页 1-10 第34卷, 第3期 * |
| 《精细化工中间体》 20101231 张小宏 等 "草甘膦母液处理技术进展" 第8-10，15页 1-10 第40卷, 第6期 * |
| 张小宏 等: ""草甘膦母液处理技术进展"", 《精细化工中间体》, vol. 40, no. 6, 31 December 2010 (2010-12-31) * |
| 茆庆文: ""草甘膦生产工艺综述及其发展趋势"", 《安徽化工》, vol. 34, no. 3, 30 June 2008 (2008-06-30) * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102153584B (en) | 2013-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104591465B (en) | A kind of circuitboard etching waste liquid reclaims industry nitrogen-containing wastewater recycling and the method for processing | |
| CN104211244B (en) | Renewable and the gaseous state embrane method process of by-product strong aqua of a kind of absorption agent is containing the method for ammonia feed liquid or waste water | |
| CN102060406A (en) | Efficient stripping and closed-loop treatment integrated process for recycling ammonia nitrogen wastewater from tail gas | |
| CN204918230U (en) | Ammonia nitrogen blows and takes off, absorbs synthetic urotropine equipment | |
| CN102828192A (en) | Resourceful treatment method for pickling waste liquor in steel industry | |
| CN102730894A (en) | Method for treating waste alkaline liquor produced in butanol and octanol production device | |
| CN104725238B (en) | A kind of trimethylamine retracting device and recovery process thereof | |
| CN102816091A (en) | Aqueous solution full-cycle urea energy-saving production process | |
| CN101648970B (en) | Pretreatment method for membrane technology resource recovery of glyphosate mother liquor | |
| CN102167412B (en) | High-efficiency composite urea waste liquid deep hydrolysis desorption tower | |
| CN104628224B (en) | A kind of process technique of glycine condensation waste water | |
| CN101549898A (en) | Resource recycling technique of low-concentration formaldehyde wastewater and formaldehyde tail gas | |
| CN101591084B (en) | Method for treating glyphosate waste water and reducing the emission of carbon dioxide | |
| CN102153584B (en) | Comprehensive treatment technique for recycling glyphosate mother liquor | |
| CN101665428B (en) | Method for extracting succinic acid from succinic acid fermentation liquor | |
| CN104788321A (en) | Recycling device and recycling technology of dimethylamine | |
| CN104513144A (en) | Method of recycling methanol in formaldehyde production through silver method | |
| CN102530990A (en) | Method for recovering hydrogen and ammonia from synthetic ammonia purge gas by membrane separation-rectification integrated technology and device | |
| CN105777540B (en) | A kind of methylvinyl acetate synthetic method | |
| CN103613107A (en) | Biogas slurry deamination and ammonia recovery method | |
| CN201280447Y (en) | Circulating air lift deoxidization apparatus | |
| CN102992951B (en) | Method for preparing high-purity refined methanol by three-tower rectification | |
| CN101691383A (en) | Method for processing PMIDA synthesis mother liquor | |
| CN109503360A (en) | A kind of technique for spirit of vinegar recycling | |
| CN100408485C (en) | Method of circulation utilizing phenol containing waste water in novolac epoxy preparing process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |