CN101486732A - Two-stage condensation crystallization method for recycling glyphosate from glyphosate production wastewater - Google Patents
Two-stage condensation crystallization method for recycling glyphosate from glyphosate production wastewater Download PDFInfo
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- CN101486732A CN101486732A CNA2009100250468A CN200910025046A CN101486732A CN 101486732 A CN101486732 A CN 101486732A CN A2009100250468 A CNA2009100250468 A CN A2009100250468A CN 200910025046 A CN200910025046 A CN 200910025046A CN 101486732 A CN101486732 A CN 101486732A
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- glyphosate
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Abstract
The invention relates to a two-phase concentration and crystallization method of the glyphosate in recycling glyphosate production sewage, which comprises the following steps: (1) the pH value of the sewage is adjusted to 5 to 6 with concentrated hydrochloric acid; (2) the sewage is distilled and concentrated under negative pressure until the glyphosate concentration reaches 40g/L to 50g/L and then filtered under vacuum; the liberated NaCl is eliminated; (3) the filtrate is distilled and concentrated again under the same conditions until the glyphosate concentration reaches 100g/L to 120g/L and then the hot filtrate is filtered to eliminate NaCl; (4) under stirring, the filtrate is acidified with concentrated hydrochloric acid until the pH value becomes 0.5 to 1 and then filtered to eliminate NaCl again; the concentration of the glyphosate in the filtrate is 70g/L to 75g/L now; (5) a few crystal seeds are added to the obtained filtrate and stirred under proper conditions for crystallization; and (6) after the crystallization is completed, suction filtration is conducted to obtain solid glyphosate; the content of glyphosate is more than 50 percent and the recovery rate thereof is higher than 50 percent. The method recycles the glyphosate product in sewage, thereby realizing the reclamation of three wastes (waste gas, waste water and waste residues).
Description
Technical field
The present invention relates to a kind of chemical industry method, be specifically related to a kind of two-stage condensation crystallization method that reclaims glyphosate in the glyphosate production wastewater.
Background technology
Glyphosate is a kind of efficient, low toxicity, wide spectrum steriland herbicide, is that the current whole world is most widely used, and one of pesticide species of output maximum expects global demand amount in 2010 and will reach 1,000,000 tons.
The industrial process of glyphosate mainly contains dialkyl phosphite method and IDA method at present at home and abroad, and in the production of dialkyl phosphite method, product per ton will produce 4～6 tons of waste water, and the pH value of waste water is between 11～14, and density is generally 1.16x10
3Kg/m
3, COD
CrAbout 50000mg/L, total phosphorus concentration is 22～26g/L, contains in the waste water about glyphosate products 20g/L, and NaCl is 15～20%, also contains phosphoric acid and phosphite and multiple compositions such as a spot of methyl alcohol, formaldehyde in addition.
Because this discharged waste water is big, the Pollutant levels height has seriously restricted the survival and development of glyphosate production enterprise.For many years, manufacturing enterprise and scientific research personnel have done unremitting effort to the utilization and the processing of this waste water.Mainly be this waste water to be carried out tentatively concentrated aspect utilizing, glyphosate content reaches about 5%, is mixed with 10% glyphosate emulsion supply market at the glyphosate dry powder that adds 95% content.Because this emulsion amount is too big, market can not all digest at all, emulsion organic impurity and inorganic salt content height that this in addition method obtains, and complicated component applies the herbicidal effect behind the farmland and the influence of soil is still waiting further demonstration.Mainly the research work of carrying out around the destructive oxidation degraded aspect processing, for example chemical oxidation, electrooxidation and biochemical treatment etc.Because NaCl concentration height in the waste water, treatment effect is all not ideal.
Summary of the invention
The purpose of this invention is to provide a kind of two-stage condensation crystallization method that reclaims glyphosate in the glyphosate production wastewater, this method basis is at present both at home and abroad to this Study on wastewater present situation, character and composition situation at this waste water, in line with reclaiming resource, save the principle of cost, adopt the glyphosate in the two-stage condensation crystallization method recovery glyphosate production wastewater, to overcome in the existing glyphosate production technology, discharged waste water is big, the Pollutant levels height, waste water is difficult to handle, the problem of the survival and development of restriction glyphosate production enterprise; Sweet phosphine produces the grass product that reclaim in the waste water, to reach the purpose of recycling "the three wastes" (water, gas and industrial residue).
The scheme of finishing the foregoing invention task is: a kind of two-stage condensation crystallization method that reclaims glyphosate in the glyphosate production wastewater is characterized in that step is as follows:
(1). with concentrated hydrochloric acid the pH value of waste water is adjusted to 5～6;
(2). distillation concentrates under condition of negative pressure, reaches 45～50g/L to glyphosate concentration, and vacuum suction filter is removed the NaCl that separates out;
(3). filtrate is carried out second distillation under the same conditions again and is concentrated, and glyphosate concentration is 100～120g/L in filtrate, takes advantage of heat filtering, removes desalt (NaCl);
(4). this filtrate is acidified to pH=0.5～1 with concentrated hydrochloric acid under stirring state, filters, desalt once more (NaCl), the glyphosate concentration in the filtrate is 70～75g/L at this moment;
(5). the filtrate that obtains more than inciting somebody to action adds a small amount of glyphosate crystal seed, under optimum conditions stirred crystallization;
(6). complete back to be crystallized suction filtration, the solid glyphosate that obtains reclaiming, glyphosate content are greater than 50%, and the rate of recovery of glyphosate is more than 50%.
Described crystalline " suitable condition " sees below.
Specific operation process and experiment condition are as follows:
One section distillation concentrates
(1). get 500mL glyphosate raw wastewater, regulate between pH to 5.5～6 with concentrated hydrochloric acid;
(2). in vacuum tightness is 0.095Mpa, and temperature is lower than under 80 ℃ the condition carries out underpressure distillation.The volume that is distilled to still liquid stops heating during for half left and right sides, and still liquid is carried out vacuum suction filter, and the result is as follows:
One section salt 74.06g
One section filtrate 190mL glyphosate concentration 47.32g/L
Two sections distillations concentrate
(3). one section distillation is concentrated the filtrate that obtains carry out two sections distillation concentration operations under above identical condition, the result is as follows:
Two sections salt 37.71g
Two sections filtrate 79.50mL glyphosate concentration 106.67g/L
(4). the filtrate acidifying: because the glyphosate in the concentrated solution is to exist with sodium-salt form, for the ease of the crystallization of glyphosate, filtrate is acidified to different pH values with concentrated hydrochloric acid, the solution after the acidifying filters desalination;
(5). every part of filtrate adds crystal seed, crystallization under static conditions;
(6) .48h after-filtration, the glyphosate quality and content such as the table 1 that obtain:
The pH value influences crystalline
Table 1 pH value influences crystalline
By the data of table 1 as can be seen, the pH of acidizing fluid is 0.5～1 comparatively suitable, and the crystalline glyphosate is maximum when 0.5 left and right sides.
The waste water concentrating degree influences crystalline
Get one section concentrated solution of equal volume and carry out two sections and concentrate, when reaching different glyphosate concentration, regulate pH=0.5, adds identical crystal seed amount with concentrated hydrochloric acid, crystallization 21h under static state, filtration, the glyphosate quality and the content of separating out see Table 2:
The different concentrating degree of table 2 influence crystalline
The result shows in the table 2, and two sections concentrated solution crystallizations influences to glyphosate in bigger concentration range are little, and promptly concentration ratio can reach 5.7～7.1 (concentration ratio refers to the ratio of raw wastewater volume and concentrated solution volume).The comparison of stationary crystallization and dynamic crystallization
Get 4 parts of two sections concentrated solutions of 40mL respectively, wherein glyphosate content is 8.64%, be adjusted to certain pH value with concentrated hydrochloric acid, after filtering desalination, add identical crystal seed amount in the filtrate, at ambient temperature, adopt dynamically and static two kinds of crystallization modes, behind the crystallization 22h, filter the quality and the content that obtain solid glyphosate and see Table 3:
Crystallization mode is to the influence of precipitate quality
Table 3 crystallization mode is to the influence of precipitate quality
By the data in the table 3 as can be seen, the crystallization that more helps glyphosate during dynamic crystallization is separated out.
Crystallization time is to the influence of the glyphosate rate of recovery
Get glyphosate content and be 7.66% concentrated solution, regulate pH=0.5 after, add the 0.1g crystal seed, dynamic crystallization different time at ambient temperature, filtration obtains the glyphosate filter cake of different amounts, and calculates the crystalline rate of recovery respectively by measuring glyphosate content, the results are shown in Table 4:
Table 4 crystallization time is to the influence of the glyphosate rate of recovery
From the data of table 4 as can be seen, the rate of recovery of glyphosate improves along with the increase of crystallization time, considers production efficiency, and generally can select crystallization time is to be advisable about 20h.
The crystal seed add-on is to the influence of the glyphosate rate of recovery
Get several parts of the concentrated solutions of same concentrations, regulate pH=0.52, in filtrate, add the crystal seed of different mass after, at room temperature dynamic crystallization 22h filters, and measures solid masses and glyphosate content, and calculate recovery rate, the results are shown in Table 5:
Table 5 adds the influence of crystal seed quality to the glyphosate rate of recovery
Data from table 5 as can be seen, the rate of recovery of glyphosate improves with the increase gradually of crystal seed amount, when the crystal seed add-on be in the concentrated solution glyphosate total amount 2% the time, the glyphosate rate of recovery in the concentrated solution has surpassed 50%.
Tc is to the influence of the glyphosate rate of recovery
Get 4 parts of the concentrated solutions of same concentrations, regulate pH=0.49, in filtrate, add the crystal seed of same amount after, dynamic crystallization 21h under differing temps filters, and measures solid masses and glyphosate content, and calculate recovery rate, the results are shown in Table 6:
Table 6 Tc is to the influence of the glyphosate rate of recovery
Data from table 6 as can be seen, the rate of recovery of glyphosate was more than 50% when Tc reached 20～30 ℃, the crystalline glyphosate rate of recovery is the highest in the time of 30 ℃.
According to above experimental result, glyphosate waste water is regulated certain pH value after concentrating by two sections underpressure distillation, adds an amount of crystal seed, under suitable crystallization condition, can reclaim out the glyphosate more than 50%, and the solid glyphosate content of recovery is greater than 50%.
The invention solves in the existing glyphosate production technology, discharged waste water is big, Pollutant levels height, the problem of the survival and development of restriction glyphosate production enterprise; Adopt the glyphosate in the two-stage condensation crystallization method recovery glyphosate production wastewater, reclaimed the glyphosate products in the waste water, reached " three wastes,, the purpose of resource utilization.
Embodiment
Embodiment 1, reclaims the two-stage condensation crystallization method of glyphosate in the glyphosate production wastewater, and the concrete operations step is:
One section distillation concentrates
(1). get 500mL glyphosate raw wastewater, regulate between pH to 5.5～6 with concentrated hydrochloric acid;
(2). in vacuum tightness is 0.095Mpa, and temperature is lower than under 80 ℃ the condition carries out underpressure distillation.The volume that is distilled to still liquid stops heating during for half left and right sides, and still liquid is carried out vacuum suction filter, and the result is as follows:
One section salt 74.06g
One section filtrate 190mL glyphosate concentration 47.32g/L
Two sections distillations concentrate
(3). one section distillation is concentrated the filtrate that obtains carry out two sections distillation concentration operations under above identical condition, the result is as follows:
Two sections salt 37.71g
Two sections filtrate 79.50mL glyphosate concentration 106.67g/L
After two sections distillations concentrated, the raw wastewater volume was 5.7～7.1 with the ratio of concentrated solution volume;
(4). the filtrate acidifying: because the glyphosate in the concentrated solution is to exist with sodium-salt form, for the ease of the crystallization of glyphosate, it is 0.5 that filtrate is acidified to pH with concentrated hydrochloric acid, and the solution after the acidifying filters desalination;
(5). every part of filtrate adds crystal seed, crystallization under dynamic or static conditions; The crystal seed add-on be in the concentrated solution glyphosate total amount 2%; Crystallization time is 20h; Tc is 30 ℃.
(6) the .48h after-filtration obtains glyphosate.
Embodiment 2, and is substantially the same manner as Example 1, but in (4) step, the pH of described acidizing fluid is 1; In (5) step, described Tc is 20 ℃; Described crystallization condition is static.
Embodiment 3, and is substantially the same manner as Example 1, but in (4) step, the pH of described acidizing fluid is 0.7; In (5) step, described Tc is 25 ℃.
Claims (4)
1, a kind of two-stage condensation crystallization method that reclaims glyphosate in the glyphosate production wastewater is characterized in that step is as follows:
(1). waste water is regulated pH=5～6 with concentrated hydrochloric acid;
(2). distillation concentrates under condition of negative pressure, reaches 45～50g/L to glyphosate concentration, and vacuum suction filter is removed the NaCl that separates out;
(3). filtrate is carried out second distillation under the same conditions again and is concentrated, and glyphosate concentration is 100～120g/L in filtrate, takes advantage of heat filtering, removes NaCl;
(4). this filtrate is acidified to pH=0.5～1 with concentrated hydrochloric acid under stirring state, filter, and removes NaCl once more, and the glyphosate concentration in the filtrate is 70～75g/L at this moment;
(5). the filtrate that obtains more than inciting somebody to action adds a small amount of glyphosate crystal seed, under optimum conditions stirred crystallization;
(6). complete back to be crystallized suction filtration, the solid glyphosate that obtains reclaiming, glyphosate content are greater than 50%, and the rate of recovery of glyphosate is more than 50%.
2, the two-stage condensation crystallization method of glyphosate in the recovery glyphosate production wastewater according to claim 1 is characterized in that specific operation process and condition are as follows:
One section distillation concentrates
(1). get 500mL glyphosate raw wastewater, regulate between pH to 5.5～6 with concentrated hydrochloric acid;
(2). in vacuum tightness is 0.095Mpa, and temperature is lower than under 80 ℃ the condition carries out underpressure distillation; The volume that is distilled to still liquid stops heating during for half left and right sides, and still liquid is carried out vacuum suction filter, and the result is as follows:
One section salt 74.06g
One section filtrate 190mL glyphosate concentration 47.32g/L
Two sections distillations concentrate
(3). one section distillation is concentrated the filtrate that obtains carry out two sections distillation concentration operations under above identical condition, the result is as follows:
Two sections salt 37.71g
Two sections filtrate 79.50mL glyphosate concentration 106.67g/L
(4). the filtrate acidifying
Because the glyphosate in the concentrated solution is to exist with sodium-salt form, for the ease of the crystallization of glyphosate, filtrate is acidified to different pH values with concentrated hydrochloric acid, the solution after the acidifying filters desalination;
(5). every part of filtrate adds crystal seed, crystallization under dynamic or static conditions;
(6) the .48h after-filtration obtains glyphosate.
3, the two-stage condensation crystallization method of glyphosate in the recovery glyphosate production wastewater according to claim 1 and 2 is characterized in that,
After two sections distillations concentrated, the raw wastewater volume was 5.7～7.1 with the ratio of concentrated solution volume;
In (4) step, the pH of described acidizing fluid is 0.5～1;
In (5) step, the crystal seed add-on be in the concentrated solution glyphosate total amount 2%; Described crystallization time is 20h; Described Tc is 20～30 ℃.
4, the two-stage condensation crystallization method of glyphosate in the recovery glyphosate production wastewater according to claim 3 is characterized in that, in (4) step, the pH of described acidizing fluid is 0.5; In (5) step, described Tc is 30 ℃; Described crystallization condition is dynamic.
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| CN2009100250468A CN101486732B (en) | 2009-02-17 | 2009-02-17 | Two-stage condensation crystallization method for recycling glyphosate from glyphosate production wastewater |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830928A (en) * | 2010-05-28 | 2010-09-15 | 吴伦飞 | Method for recovering glyphosate raw powder from glyphosate mother liquid |
| CN114287443A (en) * | 2021-12-10 | 2022-04-08 | 湖北泰盛化工有限公司 | Method for producing glyphosate potassium salt water agent by using glyphosate low-quality material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465111C (en) * | 2007-06-21 | 2009-03-04 | 山东潍坊润丰化工有限公司 | Process of treating glyphosate producing effluent |
| CN100551927C (en) * | 2007-08-27 | 2009-10-21 | 山东潍坊润丰化工有限公司 | The circulation recovery method of glyphosate mother solution |
| CN101348266B (en) * | 2008-09-05 | 2010-06-02 | 江苏扬农化工股份有限公司 | Comprehensive processing method of N-phosphonomethyliminodiacelic acid mother liquor |
-
2009
- 2009-02-17 CN CN2009100250468A patent/CN101486732B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830928A (en) * | 2010-05-28 | 2010-09-15 | 吴伦飞 | Method for recovering glyphosate raw powder from glyphosate mother liquid |
| CN101830928B (en) * | 2010-05-28 | 2016-01-20 | 吴伦飞 | A kind of method reclaiming the former powder of glyphosate from glyphosate mother solution |
| CN114287443A (en) * | 2021-12-10 | 2022-04-08 | 湖北泰盛化工有限公司 | Method for producing glyphosate potassium salt water agent by using glyphosate low-quality material |
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