CN102874983B - Method for treating N-Phosphonomethyl iminodiacetic acid (PMIDA) mother liquid - Google Patents
Method for treating N-Phosphonomethyl iminodiacetic acid (PMIDA) mother liquid Download PDFInfo
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- CN102874983B CN102874983B CN201210384858.3A CN201210384858A CN102874983B CN 102874983 B CN102874983 B CN 102874983B CN 201210384858 A CN201210384858 A CN 201210384858A CN 102874983 B CN102874983 B CN 102874983B
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Abstract
The invention relates to a method for treating an N-Phosphonomethyl iminodiacetic acid (PMIDA) mother liquid which is obtained by producing glyphosate by an iminodiacetic acid method. The method includes adding alkaline substances into the PMIDA mother liquid, adjusting potential of hydrogen (pH) of the mother liquid to be in a range from 9 to 12, subjecting the mother liquid to multiple-effect evaporation and concentration, filtering to obtain a filter cake and a filter liquid, washing the filter cake to remove organic matters to obtain inorganic salt, and burning the filter liquid to obtain pyrophosphate. The method for treating the PMIDA mother liquid has the advantages that chlorine containing substances and phosphorus containing substances in the mother liquid can be recycled in a high yield coefficient mode, the process is simple, the environment-friendly benefit is remarkable, and the method is suitable for popularization and usage in industrial mass production.
Description
Technical field
The present invention relates to a kind for the treatment of process of pmida98 mother liquor, the treatment process of the pmida98 mother liquor that particularly a kind of iminodiacetic acid (salt) acid system production glyphosate obtains.
Technical background
Glyphosate is as the steriland herbicide of a kind of efficient, wide spectrum, low toxicity, range of application is more and more extensive, become the current weedicide of consumption maximum in the world, the method that Present Domestic is prepared glyphosate is a lot, dialkyl phosphite method and the iminodiacetic acid (salt) acid systems of adopting more, while adopting iminodiethanoic acid route to prepare glyphosate, can produce the acid mother liquid of the Multiple components such as chloride ion-containing, sodium ion, pmida98, in current production process, process comparatively difficulty of this kind of mother liquor, usually used as wastewater treatment, fall, not only waste resource, but also contaminate environment.
In the patent application of Chinese patent CN1422275A and CN1837105A, only the sodium-chlor in waste water is recycled, pmida98 is utilized; In the patent application of Chinese patent CN101041527A, recycled the pmida98 in waste water, but complex process wastes time and energy; Chinese patent CN101348266A adopts nanofiltration membrane concentrated mother liquor, reclaim the pmida98 in concentrated solution, light liquid is through evaporative crystallization, roasting, and dephosphorization is processed and is obtained refining sodium-chlor, although reclaimed pmida98 and byproduct sodium chloride, but the rate of recovery is also not bery high, from the data of embodiment 1, it is only 91.2% that pmida98 reclaims, and the sodium-chlor rate of recovery does not reach 90%.And treatment step is comparatively loaded down with trivial details, processing cost is not low yet.
Now, find a kind of can be high yield reclaim Recyclable in mother liquor, can reduce again waste water and discharge, alleviate environmental protection pressure, the treatment process that can produce higher secondary benefit and the simple pmida98 mother liquor of technique is simultaneously an industry problem urgently to be resolved hurrily.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides the treatment process that a kind of iminodiacetic acid (salt) acid system is produced the PMIDA synthesis mother liquor that glyphosate obtains.The present invention can effectively reclaim the material in pmida98 mother liquor, and technique is simple, easy to operate.
Concrete technical scheme of the present invention is as follows:
A treatment process for pmida98 mother liquor, comprises the following steps:
(1) in pmida98 mother liquor, add alkaline matter, make mother liquor pH regulator to 9-12, concentrated through multiple-effect evaporation, filter, obtain filter cake and filtrate;
(2) get filter cake, through washing, remove organic substance, obtain inorganic salt;
(3) get filtrate, through burning, obtain pyrophosphate salt.Further, also comprise waste heat and the solid reclaiming in incineration flue gas.
Described pmida98 mother liquor is while adopting iminodiethanoic acid legal system for glyphosate, the acid mother liquid of synthetic pmida98 gained.
In above-mentioned steps (1), alkaline matter is sodium hydroxide, potassium hydroxide, calcium hydroxide or calcium oxide.Inventing alkaline matter used is pH adjusting agent, and its state, concentration are not particularly limited, for considering of wastewater flow rate and processing cost, and preferred solid sodium hydroxide.
In above-mentioned steps (3), multiple-effect evaporation is concentrated into 60 ~ 90% of former weight.
In above-mentioned steps (3), incineration temperature is 600 ~ 900 ℃.
Adopting the present invention to process PMIDA synthesis mother liquor has the following advantages:
(1) technique is simple, efficient, chlorion transformation efficiency is more than 98%, step (2) gained waste water is after biochemical system is processed, the waste water COD of discharging is less than 20mg/L, TP is less than 0.5mg/L, and ammonia nitrogen is less than 10mg/L, has substantially realized the zero release of waste water, efficiently solve the processing problem of pmida98 mother liquor, environmental benefit of the present invention is outstanding;
(2) gained pyrophosphate salt content is more than 95%, and phosphorus containg substances transformation efficiency reaches more than 98%;
(3) gained Industrial Salt can be used for the industries such as chemical industry, papermaking, building, and the trisodium phosphate of gained can be used for chemical industry, plating, wool spinning, paper industry, so economic benefit of the present invention is outstanding.
Embodiment
Below by specific embodiment, the present invention is further elaborated, should be understood that, following explanation is only in order to explain the present invention, its particular content is not limited.
Embodiment 1
Get pmida98 mother liquor 1000g, have after testing chlorion 13.8%, total phosphorus 0.9%, add 30wt% sodium hydroxide solution, make after mother liquor pH regulator to 9, multiple-effect evaporation is concentrated into 60% of former weight, filter, filter cake is removed organism through washing, obtains sodium-chlor 223.12g, chlorion transformation efficiency is 98.1%, and waste water is COD 18mg/L after biochemical treatment, TP 0.4mg/L, ammonia nitrogen 8mg/L, filtrate, through 600 ℃ of burnings, obtains trisodium phosphate 38.5g, content 98.3%, phosphorus containg substances transformation efficiency 98.0%.Reclaim waste heat and solid in incineration flue gas simultaneously.
Embodiment 2
To containing chlorion 13.8%, in the pmida98 mother liquor 1000g of total phosphorus 0.9%, add 40wt% sodium hydroxide solution, make after mother liquor pH regulator to 10, multiple-effect evaporation is concentrated into 70% of former weight, filters, and filter cake is removed organism through washing, obtain sodium-chlor 223.92g, chlorion transformation efficiency is 98.5%, and waste water is COD 17mg/L after biochemical treatment, TP 0.3mg/L, ammonia nitrogen 7mg/L, filtrate, through 700 ℃ of burnings, obtains trisodium phosphate 38.4g, content 98.6%, phosphorus containg substances transformation efficiency 98.1%.Reclaim waste heat and solid in incineration flue gas simultaneously.
Embodiment 3
To containing chlorion 13.8%, in the pmida98 mother liquor 1000g of total phosphorus 0.9%, add 50wt% sodium hydroxide solution, make after mother liquor pH regulator to 11, multiple-effect evaporation is concentrated into 80% of former weight, filters, and filter cake is removed organism through washing, obtain sodium-chlor 224.4g, chlorion transformation efficiency is 98.7%, and waste water is COD 12mg/L after biochemical treatment, TP 0.3mg/L, ammonia nitrogen 6mg/L, filtrate, through 800 ℃ of burnings, obtains trisodium phosphate 38.5g, content 98.7%, phosphorus containg substances transformation efficiency 98.4%.Reclaim waste heat and solid in incineration flue gas simultaneously.
Embodiment 4
To containing chlorion 13.8%, in the pmida98 mother liquor 1000g of total phosphorus 0.9%, add sodium hydroxide, make after mother liquor pH regulator to 12, multiple-effect evaporation is concentrated into 90% of former weight, filters, and filter cake is removed organism through washing, obtain sodium-chlor 227.04g, chlorion transformation efficiency is 99.8%, and waste water is COD 10mg/L after biochemical treatment, TP 0.1mg/L, ammonia nitrogen 5mg/L, filtrate, through 900 ℃ of burnings, obtains trisodium phosphate 38.6g, content 99.6%., phosphorus containg substances transformation efficiency 99.6%.Waste heat and solid in while recovered flue gas.
Embodiment 5
To containing chlorion 13.8%, in the pmida98 mother liquor 1000g of total phosphorus 0.9%, add solid potassium hydroxide, make after mother liquor pH regulator to 10.5, multiple-effect evaporation is concentrated into 75% of former weight, filters, and filter cake is removed a small amount of organism through washing, obtain Repone K 284.4g, chlorion transformation efficiency is 98.1%, and waste water is COD 12mg/L after biochemical treatment, TP 0.4mg/L, ammonia nitrogen 8mg/L, filtrate, through 750 ℃ of burnings, obtains potassium pyrophosphate 47.8g, content 98.3%, phosphorus containg substances transformation efficiency 98.1%.Waste heat and solid in while recovered flue gas.
Embodiment 6
To containing chlorion 13.8%, in the pmida98 mother liquor 1000g of total phosphorus 0.9%, add solid hydrogen calcium oxide, make after mother liquor pH regulator to 10.5, multiple-effect evaporation is concentrated into 75% of former weight, filters, and filter cake is removed a small amount of organism through washing, obtain calcium chloride 211.8g, chlorion transformation efficiency is 98.2%, and waste water is COD 15mg/L after biochemical treatment, TP 0.3mg/L, ammonia nitrogen 7mg/L, filtrate, through 650 ℃ of burnings, obtains Calcium Pyrophosphate 36.8g, content 98.4%, phosphorus containg substances transformation efficiency 98.1%.Waste heat and solid in while recovered flue gas.
Embodiment 7
To containing chlorion 13.8%, in the pmida98 mother liquor 1000g of total phosphorus 0.9%, add solid oxidation calcium, make after mother liquor pH regulator to 10.5, multiple-effect evaporation is concentrated into 75% of former weight, filters, and filter cake is removed a small amount of organism through washing, obtain calcium chloride 212.4g, chlorion transformation efficiency is 98.4%, and waste water is COD 17mg/L after biochemical treatment, TP 0.4mg/L, ammonia nitrogen 8mg/L, filtrate, through 850 ℃ of burnings, obtains Calcium Pyrophosphate 36.9g, content 98.3%, phosphorus containg substances transformation efficiency 98.3%.Waste heat and solid in while recovered flue gas.
Claims (5)
1. a treatment process for pmida98 mother liquor, is characterized in that comprising the following steps:
Get pmida98 mother liquor, add alkaline matter, make mother liquor pH regulator to 9-12, concentrated through multiple-effect evaporation, filter, obtain filter cake and filtrate;
Get filter cake, through washing, remove organism, obtain inorganic salt;
Get filtrate, through burning, obtain pyrophosphate salt;
Described pmida98 mother liquor is while adopting iminodiethanoic acid legal system for glyphosate, the acid mother liquid of synthetic pmida98 gained.
2. treatment process according to claim 1, is characterized in that: described alkaline matter is sodium hydroxide, potassium hydroxide, calcium hydroxide or calcium oxide.
3. treatment process according to claim 1, is characterized in that: in step (1), multiple-effect evaporation is concentrated into 60 ~ 90% of former weight.
4. treatment process according to claim 1, is characterized in that: in step (3), incineration temperature is 600 ~ 900 ℃.
5. treatment process according to claim 1, is characterized in that, in step (3), also comprises waste heat and solid in recovered flue gas.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103342398B (en) * | 2013-07-17 | 2015-03-25 | 山东潍坊润丰化工股份有限公司 | Method for recovering high-purity organic salt from phosphorous-containing industrial wastewater |
| CN104591424B (en) * | 2014-03-14 | 2017-05-10 | 山东潍坊润丰化工股份有限公司 | IDA method glyphosate wastewater resource treatment method |
| CN104150668B (en) * | 2014-07-30 | 2016-01-13 | 常州市康瑞化工有限公司 | The method of chemistry mother liquor waste water multiple-effect evaporation process |
| CN105440074B (en) * | 2014-09-30 | 2018-05-22 | 北京紫光英力化工技术有限公司 | A kind of method that pmida Recycling Mother Solution is applied mechanically |
| CN105016515B (en) * | 2015-06-18 | 2017-07-28 | 浙江新安化工集团股份有限公司 | A kind of processing method of the phosphorous waste material produced in glufosinate-ammonium production process |
| CN108059140B (en) * | 2018-01-23 | 2020-02-18 | 浙江新安化工集团股份有限公司 | Method for preparing industrial trisodium phosphate by using glyphosate production waste through one-step method |
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| US6641741B2 (en) * | 2001-04-13 | 2003-11-04 | Dow Agrosciences Llc | Removal and recovery of chloride from phosphonomethyliminodiacetic acid process brine |
| CN101428935A (en) * | 2008-11-28 | 2009-05-13 | 四川贝尔实业有限责任公司 | Treatment process for wastewater from N-(Phosphonomethyl)iminodiacetic acid production |
| CN102079605A (en) * | 2010-12-23 | 2011-06-01 | 北京拓峰科技开发有限责任公司 | Novel process for zero discharge of glyphosate production waste water |
| CN102616914A (en) * | 2011-01-31 | 2012-08-01 | 浙江新安化工集团股份有限公司 | Treatment method of phosphorus-containing waste from pesticide production and product obtained thereby |
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Patent Citations (5)
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| CN1422275A (en) * | 2000-04-14 | 2003-06-04 | 美国陶氏益农公司 | Removal of chloride from phosphonomethyliminodiacetic acid process |
| US6641741B2 (en) * | 2001-04-13 | 2003-11-04 | Dow Agrosciences Llc | Removal and recovery of chloride from phosphonomethyliminodiacetic acid process brine |
| CN101428935A (en) * | 2008-11-28 | 2009-05-13 | 四川贝尔实业有限责任公司 | Treatment process for wastewater from N-(Phosphonomethyl)iminodiacetic acid production |
| CN102079605A (en) * | 2010-12-23 | 2011-06-01 | 北京拓峰科技开发有限责任公司 | Novel process for zero discharge of glyphosate production waste water |
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Address after: Haiyuan Binhai Economic Development Zone, Shandong province Weifang city 262737 Street No. 600 Applicant after: Shandong Weifang Rainbow Chemical Co., Ltd. Address before: Haiyuan Binhai Economic and Technological Development Zone in Shandong province Weifang City 600 street 262737 No. 1 ranked No. 1 Applicant before: Shandong Weifang Rainbow Chemical Co., Ltd. |
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Address after: No. 03001, chlor alkali Road, Weifang Coastal Economic Development Zone, Shandong, Shandong Patentee after: Shandong Weifang Rainbow Chemical Co.,Ltd. Address before: Haiyuan Binhai Economic Development Zone, Shandong province Weifang city 262737 Street No. 600 Patentee before: Shandong Weifang Rainbow Chemical Co.,Ltd. |
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