CN101691382B - Method for recycling glyphosate from glyphosate mother liquor of IDA method - Google Patents
Method for recycling glyphosate from glyphosate mother liquor of IDA method Download PDFInfo
- Publication number
- CN101691382B CN101691382B CN 200910019582 CN200910019582A CN101691382B CN 101691382 B CN101691382 B CN 101691382B CN 200910019582 CN200910019582 CN 200910019582 CN 200910019582 A CN200910019582 A CN 200910019582A CN 101691382 B CN101691382 B CN 101691382B
- Authority
- CN
- China
- Prior art keywords
- glyphosate
- recovery
- concentrated solution
- ida
- solution
- 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.)
- Active
Links
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 98
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000012452 mother liquor Substances 0.000 title claims abstract description 12
- 238000004064 recycling Methods 0.000 title abstract 2
- 239000007787 solid Substances 0.000 claims abstract description 16
- 230000003750 conditioning effect Effects 0.000 claims abstract description 9
- 230000018044 dehydration Effects 0.000 claims abstract description 9
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000012528 membrane Substances 0.000 claims abstract description 4
- 238000002203 pretreatment Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 22
- 238000011084 recovery Methods 0.000 claims description 17
- 239000010413 mother solution Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000001953 recrystallisation Methods 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000006200 vaporizer Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 238000001728 nano-filtration Methods 0.000 claims description 2
- 238000009738 saturating Methods 0.000 claims description 2
- 230000008719 thickening Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 abstract description 12
- 238000001704 evaporation Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a method for recycling glyphosate from glyphosate mother liquor of IDA method. The method adopts the following steps: entering the glyphosate mother liquor of IDA method into a membrane concentration device after pre-treatment to obtain primary glyphosate concentrated liquor; adding alkali conditioning agent in the primary glyphosate concentrated liquor, and carrying out distillation, concentration and dehydration in an evaporator to obtain secondary glyphosate concentrated liquor; adding acid in the secondary glyphosate concentrated liquor for conditioning, crystallizing at normal temperature, filtering and washing with water to obtain glyphosate solid, and re-crystallizing the glyphosate solid to obtain glyphosate bulk drug. The method combines membrane method and evaporating concentration, so that the yield of glyphosate is high, rectificating is unnecessary, the production cost is lowered, energy consumption is saved, environment protection pressure is reduced, and higher economic value is obtained.
Description
Technical field
The present invention relates to the recovery method of glyphosate in a kind of aqueous solution, particularly a kind of novel method that from the glyphosate mother solution that the IDA method is produced, reclaims glyphosate.
Background technology
Glyphosate becomes sales volume and the fastest weedicide of rate of growth in the world at present as the steriland herbicide of a kind of efficient, wide spectrum, low toxicity, and current domestic preparation glyphosate adopts alkyl esterification method and iminodiacetic acid (salt) acid system more.
The a large amount of glyphosate content of generation are about 1% mother liquor in iminodiethanoic acid (IDA) the method production glyphosate process, and existing technology is that mother liquor is concentrated with steam raising dehydration or employing embrane method, obtains the aqua of glyphosate content 10%.Along with the progressively raising of country to environmental requirement, the Ministry of Agriculture, the Ministry of Industry and Information Technology unite issue bulletin, and regulation is from February 25th, 2009, stop to ratify the registration that active constituent content is lower than 30% gyphosate solution.For the gyphosate solution of obtaining the registration of agricultural chemicals field test certificate of approval and approved, its active constituent content is lower than 30%, should carry out the active constituent content change before 31 days December in 2009.This means the incompatible requirement at present of technology that present glyphosate enterprise handles mother liquor, must have some changes or upgrade.
Summary of the invention
The present invention is in order to overcome problem above-mentioned, adopted the series of process improvement, the method that reclaims glyphosate in a kind of IDA method glyphosate mother solution is provided, this method adopts embrane method and evaporation concentration to combine, glyphosate rate of recovery height, and need not rectifying, production cost reduces, energy efficient has reduced environmental protection pressure, and stronger economic worth is arranged.
The present invention is achieved by the following technical solutions:
Reclaim the method for glyphosate in a kind of IDA method glyphosate mother solution of the present invention, adopt following steps:
(1) IDA method glyphosate mother solution enters film condensing device through pre-treatment, obtains the primary glyphosate concentrated solution; Saturating film absorbs in the triethylamine process, and acid absorber circulates, and reaching capacity up to the absorption triethylamine just enters next step technology;
(2) the primary glyphosate concentrated solution adds the alkali conditioning agent, regulates pH to 4～7; In vaporizer, distill thickening, obtain the secondary glyphosate concentrated solution;
(3) the secondary glyphosate concentrated solution adds acid and mediates, and regulates pH to 0.8～1.5, and crystallization under the normal temperature refilters washing and obtains glyphosate;
(4) glyphosate obtains glyphosate technicals through recrystallization.
Described preprocessing process comprises: (1) IDA method glyphosate mother solution adds the alkali conditioning agent, regulates pH to 2.5～6; (2) IDA method glyphosate mother solution is filtered through strainer, remove solid impurity.
Described vaporizer vacuum pressure is 0.09～0.095MPa, and dehydration temperaturre is 50～80 ℃.Primary glyphosate concentrated solution content (weight) is 6%～10%, and secondary glyphosate concentrated solution content (weight) is 15%～25%.The alkali conditioning agent is NH
3, NaOH, KOH or their aqueous solution.Film condensing device is three grades or level Four nanofiltration membrane concentrating unit.The distillation dehydration concentration process adopts single-action, and two imitate or triple-effect evaporator.Glyphosate content (weight) 70%～80%, glyphosate technicals content (weight) is 95%～100%.Crystal solution that produces in the process and recrystallization liquid can be returned original nut liquid pond recycled.
Adopt the present invention to reclaim that glyphosate has following advantages in the glyphosate mother solution:
(1) because the method that adopts embrane method and evaporation concentration to combine has reduced energy consumption cost than independent employing evaporation concentration, improves the rate of recovery, also solved the problem that independent employing embrane method can't reach higher cycles of concentration simultaneously.
(2) the glyphosate content that adopts the present invention to reclaim can reach more than 95%, and the glyphosate rate of recovery reaches more than 70%, apparently higher than the rate of recovery of other technology glyphosates.
(3) adopting the present invention to reclaim crystal solution that glyphosate obtains and recrystallization liquid can recycled, has reduced subsequent wastewater treatment pressure.
(4) need not rectifying, production cost reduces, and energy efficient has stronger economic worth.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
Get glyphosate content and be 1.0% IDA method glyphosate mother solution waste water 5kg, add NH
3Regulate pH to 2.5, solids removed by filtration impurity then.With the film condensing device of packing into of the mother liquor after filtering, obtain glyphosate content and be 6.0% film dope 0.82kg.Add ammoniacal liquor and be adjusted to pH and equal 5 in the film dope, 50 ℃ of temperature, underpressure distillation dehydration under the vacuum tightness 0.09MPa obtains the secondary concentration liquid 0.25kg of glyphosate content 19.1%.Add hydrochloric acid and regulate pH to 1.0 in secondary concentration liquid, slowly reduce to normal temperature and carry out crystallization, filter after the crystallization and wash that to obtain glyphosate content be 75% solid 53g, carrying out recrystallization at last, to obtain glyphosate content be 95.5% solid 38g.In the whole process, the glyphosate rate of recovery reaches 72.6%.
Embodiment 2
Get glyphosate content and be 1.0% IDA method glyphosate mother solution waste water 5kg, add NaOHpH to 4, solids removed by filtration impurity then.With the film condensing device of packing into of the mother liquor after filtering, obtain glyphosate content and be 7.9% film dope 0.62kg, in the film dope, add ammoniacal liquor and be adjusted to pH and equal 6,60 ℃ of temperature, underpressure distillation is dewatered under the vacuum tightness 0.095MPa, obtains the secondary concentration liquid 0.22kg of glyphosate content 22%.Add hydrochloric acid and regulate pH to 1.2 in secondary concentration liquid, slowly reduce to normal temperature and carry out crystallization, it is 71% solid 59g that crystallization and filtration and washing obtain glyphosate content, and carrying out recrystallization at last, to obtain glyphosate content be 95.0% solid 37.5g.In the whole process, the glyphosate rate of recovery reaches 71.2%.
Embodiment 3
Get glyphosate content and be 1.0% IDA method glyphosate mother solution waste water 5kg, add KOH and regulate pH to 5, solids removed by filtration impurity then.With the film condensing device of packing into of the mother liquor after filtering, obtain glyphosate content and be 8.6% film dope 0.62kg.Add KOH and be adjusted to pH and equal 6 in coating solution, 80 ℃ of temperature, underpressure distillation dehydration under the vacuum tightness 0.095MPa obtains the concentrated solution 0.22kg of glyphosate content 22%.In secondary concentration liquid, add hydrochloric acid and regulate pH to 1.5, slowly reduce to normal temperature and carry out crystallization, it is 71% solid 59g that crystallization and filtration and washing obtain glyphosate content, the recovery method of glyphosate according to claim 1 and 2 is characterized in that: described alkali conditioning agent carries out recrystallization at last, and to obtain glyphosate content be 95.0% solid 37.5g.In the whole process, the glyphosate rate of recovery reaches 71.2%.
Embodiment 4
Get glyphosate content and be 1.0% IDA method glyphosate mother solution waste water 5kg, add ammoniacal liquor and regulate pH to 6, solids removed by filtration impurity then.With the film condensing device of packing into of the mother liquor after filtering, obtain glyphosate content and be 9.8% film dope 0.5kg.Adding ammoniacal liquor in coating solution is adjusted to pH and equals 7,70 ℃ of temperature, underpressure distillation dehydration under the vacuum tightness 0.095MPa, obtain the concentrated solution 0.20kg of glyphosate content 24%, add hydrochloric acid and regulate pH to 1.0, slowly reduce to normal temperature and carry out crystallization, it is 79.8% solid 58g that crystallization and filtration and washing obtain glyphosate content, and carrying out recrystallization at last, to obtain glyphosate content be 96.0% solid 41g.In the whole process, the glyphosate rate of recovery reaches 78.7%.
Claims (8)
1. reclaim the method for glyphosate in the IDA method glyphosate mother solution, it is characterized in that realizing by following steps:
(1) IDA method glyphosate mother solution enters film condensing device through pre-treatment, obtains the primary glyphosate concentrated solution; Saturating film absorbs in the triethylamine process, and acid absorber circulates, and reaching capacity up to the absorption triethylamine just enters next step technology; Described pre-treatment is: add the alkali conditioning agent in mother liquor, regulate mother liquor pH to 2.5～6, filtrated stock is removed solid impurity then;
(2) the primary glyphosate concentrated solution adds the alkali conditioning agent, regulates pH to 4～7; In vaporizer, distill thickening, obtain the secondary glyphosate concentrated solution;
(3) the secondary glyphosate concentrated solution adds acid and mediates, and regulates pH to 0.8～1.5, and crystallization under the normal temperature refilters washing and obtains glyphosate;
(4) glyphosate obtains glyphosate technicals through recrystallization.
2. the method for recovery glyphosate according to claim 1 is characterized in that: described vaporizer vacuum pressure is 0.09～0.095MPa, and dehydration temperaturre is 50～80 ℃.
3. the method for recovery glyphosate according to claim 1 is characterized in that: described primary glyphosate concentrated solution weight content is 6%～10%, and described secondary glyphosate concentrated solution weight content is 15%～25%.
4. the method for recovery glyphosate according to claim 1 is characterized in that: described alkali conditioning agent is NH
3, NaOH, KOH or their aqueous solution.
5. the method for recovery glyphosate according to claim 1 is characterized in that: described film condensing device is three grades or level Four nanofiltration membrane concentrating unit.
6. the method for recovery glyphosate according to claim 1 is characterized in that: described distillation dehydration concentration process adopts single-action, and two imitate or triple-effect evaporator.
7. the method for recovery glyphosate according to claim 1 is characterized in that: described glyphosate weight content 70%～80%, described glyphosate technicals weight content is 95%～100%.
8. the method for recovery glyphosate according to claim 1 is characterized in that: crystal solution that produces in the process and recrystallization liquid can be returned original nut liquid pond recycled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910019582 CN101691382B (en) | 2009-10-15 | 2009-10-15 | Method for recycling glyphosate from glyphosate mother liquor of IDA method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910019582 CN101691382B (en) | 2009-10-15 | 2009-10-15 | Method for recycling glyphosate from glyphosate mother liquor of IDA method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101691382A CN101691382A (en) | 2010-04-07 |
| CN101691382B true CN101691382B (en) | 2011-08-24 |
Family
ID=42080116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910019582 Active CN101691382B (en) | 2009-10-15 | 2009-10-15 | Method for recycling glyphosate from glyphosate mother liquor of IDA method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101691382B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101570547B (en) * | 2009-06-16 | 2012-07-04 | 吴伦飞 | Method for processing glyphosate mother liquor |
| CN113072580A (en) * | 2021-04-19 | 2021-07-06 | 浙江新安化工集团股份有限公司 | Method for recovering glyphosate from glyphosate acid mother liquor by glycine method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195639A (en) * | 2007-08-02 | 2008-06-11 | 湖州金电化学技术有限公司 | Method for processing mother solution of glyphosate |
| CN101348299A (en) * | 2008-09-05 | 2009-01-21 | 江苏扬农化工股份有限公司 | Glyphosate synthesized mother liquor processing method |
-
2009
- 2009-10-15 CN CN 200910019582 patent/CN101691382B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195639A (en) * | 2007-08-02 | 2008-06-11 | 湖州金电化学技术有限公司 | Method for processing mother solution of glyphosate |
| CN101348299A (en) * | 2008-09-05 | 2009-01-21 | 江苏扬农化工股份有限公司 | Glyphosate synthesized mother liquor processing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101691382A (en) | 2010-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101058586B (en) | Method of concentrating and separating glyphosate in high salt content glyphosate mother liquor by film technique | |
| CN103012474B (en) | A kind of circular production method of glyphosate | |
| CN103736384B (en) | The treatment process of glyphosate hydrolysis tail gas | |
| CN109319998A (en) | A kind of the near-zero release processing system and technique of ternary precursor material production waste water | |
| CN104944398B (en) | Glyphosate mother solution recoverying and utilizing method | |
| CN102557316B (en) | Pretreatment method of epoxy resin desalinization wastewater | |
| CN102442917A (en) | Energy-saving and environment-friendly method for producing glycin based on chloroacetic acid method | |
| CN104860988A (en) | Glufosinate separation and purification method | |
| CN102807497A (en) | Method for recovering chloroacetic acid method glycine catalyst methenamine | |
| CN111659330B (en) | Process and equipment for continuously producing glufosinate-ammonium | |
| CN202193691U (en) | Equipment for triple-effect waste water desalination process | |
| CN101691382B (en) | Method for recycling glyphosate from glyphosate mother liquor of IDA method | |
| CN105130079A (en) | Treatment process combining H acid mother solution and T acid mother solution | |
| CN101648982A (en) | Method for recycling gentamicin from waste active carbon generated by discoloring gentamycin sulfate | |
| CN103265443B (en) | Industrial production method of high-purity iminodiacetic acid | |
| CN202465422U (en) | Ammonia nitrogen wastewater recycling treatment equipment | |
| CN101445464B (en) | Method for preparing iminodiacetic acid from iminodiacetic acid disodium salt | |
| CN106044731B (en) | A method of based on glyphosate mother solution preparing phosphoric acid disodium hydrogen | |
| CN101429133B (en) | Production process for recycling glutamic acid from high-dense high-mixture solution | |
| CN100537580C (en) | Glyphosate mother liquid treating method | |
| CN103665035B (en) | A kind of processing method of glyphosate mother solution | |
| CN108129328B (en) | Preparation method of methyl triethyl ammonium chloride | |
| CN114230084A (en) | Ternary precursor wastewater treatment equipment and process | |
| CN103554182B (en) | Prepare the method for glyphosate | |
| CN100540521C (en) | A kind of gulonic acid mother solution of using reclaims the sour practical art of ancient dragon |
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 | ||
| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
Address after: Haiyuan Binhai Economic Development Zone, Shandong province Weifang city 262737 Street No. 600 Patentee after: Shandong Weifang Rainbow Chemical Co., Ltd. Patentee after: Shandong Herbicides Engineering Research Center Address before: 250101 Shandong city of Ji'nan province high tech Zone (Lixia District Shunhua Road No. 750) hi tech innovation service center room A-303 Patentee before: Shandong Weifang Rainbow Chemical Co., Ltd. Patentee before: Shandong Herbicides Engineering Research Center |
|
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: No. 03001, chlor alkali Road, Weifang Coastal Economic Development Zone, Shandong, Shandong Co-patentee after: SHANDONG RESEARCH CENTER OF HERBICIDES ENGINEERING TECHNOLOGY Patentee after: Shandong Weifang Rainbow Chemical Co.,Ltd. Address before: Haiyuan Binhai Economic Development Zone, Shandong province Weifang city 262737 Street No. 600 Co-patentee before: SHANDONG RESEARCH CENTER OF HERBICIDES ENGINEERING TECHNOLOGY Patentee before: Shandong Weifang Rainbow Chemical Co.,Ltd. |