CN103288065A - Process for preparing disodium hydrogen phosphate from glyphosate - Google Patents
Process for preparing disodium hydrogen phosphate from glyphosate Download PDFInfo
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- CN103288065A CN103288065A CN2013101657745A CN201310165774A CN103288065A CN 103288065 A CN103288065 A CN 103288065A CN 2013101657745 A CN2013101657745 A CN 2013101657745A CN 201310165774 A CN201310165774 A CN 201310165774A CN 103288065 A CN103288065 A CN 103288065A
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- glyphosate
- sodium phosphate
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Abstract
The invention relates to a process for preparing disodium hydrogen phosphate from glyphosate. The process comprises the following steps: oxidization step: first, adding an acid and adjusting a glyphosate mother liquor till the liquor is acidic; then, in the condition of temperature range from 180 to 280 DEG C and pressure range from 3.0 to 9.0MPa, oxidizing organic phosphorus compounds and phosphorous acid in the glyphosate mother liquor to orthophosphate ions by using oxygen in air as an oxidant under the catalysis of a heterogeneous noble metal catalyst; extraction step: adding oxidized wastewater into the extraction liquor for extraction; layering; dividing upper extraction liquor to an extraction liquor separation tank; and neutralizing step: kalifying to neutralize the upper extraction liquor; carrying out solid-liquid separation under a certain temperature condition to obtain a disodium hydrogen phosphate product to be marketed; and after refining the extraction liquor, returning and applying mechanically.
Description
Technical field
The present invention relates to a kind of mother liquor that produces from glyphosate production process is the technology that raw material is produced Sodium phosphate dibasic.
Background technology
Glyphosate (glyphosate, C
3H
8NO
5P, CAS accession number 1071-83-6) be at the go out interior suction conductivity weedicide of natural disposition of a kind of efficient, low toxicity, the wide spectrum of nineteen seventies research and development by U.S. Monsanto Company, occupy the first place of world's agricultural chemicals sales volume for years, along with the establishing in large scale of transgenosis glyphosate resistant crops such as soybean, corn etc. in recent years, the whole world continues to increase the demand of glyphosate.
Present domestic glyphosate main flow production technique has two lines: glycine method and iminodiacetic acid (salt) acid system, and China's glyphosate output in 2010 is about 35-400,000 tons, and wherein glyphosate by using glycine output accounts for about 75% of ultimate production.All produce a large amount of high-concentration waste waters (being commonly referred to " glyphosate mother solution ") in the production process of two lines.Be example with the glycine route, one ton of glyphosate of every production can produce 4.5-8.0 tons of glyphosate mother solutions.The glyphosate mother solution water quality that certain glycine route glyphosate generation producer produces is as follows: pH is that 10.3, COD is 61000 mg/L, and total phosphorus is 24000 mg/L; Wherein based on glyphosate, methyl glyphosate, increase difficult degradation organic phosphine compounds such as sweet phosphine, total nitrogen is 5300 mg/L, sodium-chlor is 180 g/L.
Glyphosate mother solution has the feature of high COD, high content of phosphorus, difficult degradation, high bio-toxicity, and intractability is big, and processing cost is high.These phosphorus-containing wastewaters can cause serious environmental to pollute as without suitable processing, promote the eutrophication of water body.
The invention provides a kind of is the technology that raw material is produced Sodium phosphate dibasic with the glyphosate mother solution, when having cut down the phosphorus pollution, also phosphor resource has been realized efficient recovery, has alleviated the cost of sewage disposal.
Summary of the invention
The invention provides and a kind ofly produce the technology of Sodium phosphate dibasic from glyphosate mother solution, may further comprise the steps:
1, at first glyphosate mother solution is added acid for adjusting pH 2.5-5.0, adopt the method for heterogeneous catalysis atmospheric oxidation under specific pressure and temperature, the organo phosphorous compounds in the glyphosate mother solution and phosphorous acid to be oxidized into positive phosphorus acid ion then; Catalyzer is the solid ruthenium rhodium catalyst of special facture; Wherein support of the catalyst is titanium dioxide, and the composition of ruthenium is 0.5-5%, and the composition of rhodium is 0.5-5%, has advantages of high catalytic activity; Under the reaction conditions of the pressure range of 180 degrees centigrade-280 degrees centigrade temperature ranges and 3.0Mpa-9.0Mpa, as oxygenant, reach the purpose that the various organophosphoruss in the mother liquor and phosphorous acid is converted into the ortho-phosphoric acid root and removes waste water COD significantly with airborne molecular oxygen; Airborne oxygen participates in reaction as a kind of oxygenant, is that this reacts requisite a kind of material, and the amount of oxygen of supplying with in the reaction should be more than 0.7 times of glyphosate mother solution COD total amount of handling, and carries out to guarantee sufficient reacting.
2, waste water after step 1 oxidation is added extraction liquid, wherein extraction agent is tributyl phosphate, and thinner is kerosene, and the volume ratio of kerosene is 20-40%, carries out extracting operation, layering; The upper layer of extraction liquid that will contain inorganic phosphate salt material is diverted in the extraction liquid separator tank, and lower floor is waste water behind the dephosphorization, enters the subsequent disposal operation.
3, upper layer of extraction liquid hydro-oxidation sodium or the yellow soda ash that contains inorganic phosphate salt material is neutralized to pH7.0-pH10.0, through solid-liquid separation, obtains the Sodium phosphate dibasic solid phase prod in 10-30 degree centigrade temperature range; Extraction liquid returns to be applied mechanically.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
Present embodiment is example with the glyphosate alkaline mother liquor that glycine route technology produces.As follows as the waste water quality that certain factory produces: pH is that 10.3, COD is 61000 mg/L, and total phosphorus is 24000 mg/L, and total nitrogen is 5300 mg/L, and sodium-chlor is 180 g/L, and density is 1.2 tons/cubic metre.After adding hydrochloric acid is adjusted to pH2.5, adopt a cover treatment capacity be 2.5 tons of mother liquors/hour the heterogeneous catalytic oxidation device carry out continuous oxide treatment, temperature of reaction is 180 degree, reaction pressure is 3.0Mpa, the air feed rate is 10.0 cubic meters per minute, and the reaction time of mother liquor in reactor is 30 minutes.After waste water is operated through extraction (extraction agent is 70% tributyl phosphate+30% kerosene) after the oxidation, enter next process; The extraction liquids hydro-oxidation sodium that contains inorganic phosphorus is neutralized to pH7.5, at room temperature generates the Sodium phosphate dibasic solid crude product; Crude product Sodium phosphate dibasic 12 crystallines are adopted pure water washing one time, and centrifuging with gained crystal by adopting fluidised bed drying, obtains the product of higher degree.Detected result shows that quality product satisfies the industrial phosphoric acid disodium hydrogen standard among the national standard HG/T 2965-2009.
Embodiment 2
Glyphosate mother solution water quality in the present embodiment is identical with embodiment 1.After adding hydrochloric acid is adjusted to pH4, adopt a cover treatment capacity be 2.5 tons of mother liquors/hour the heterogeneous catalytic oxidation device carry out continuous oxide treatment, temperature of reaction is 230 degree, reaction pressure is 5.0Mpa, the air feed rate is 10.0 cubic meters per minute, and the reaction time of mother liquor in reactor is 30 minutes.After waste water is operated through extraction (extraction agent is 80% tributyl phosphate+20% kerosene) after the oxidation, enter next process.The extraction liquids hydro-oxidation sodium that contains inorganic phosphorus is neutralized to pH9.0, at room temperature generates the Sodium phosphate dibasic solid crude product.Crude product Sodium phosphate dibasic 12 crystallines are adopted pure water washing one time, and centrifuging with gained crystal by adopting fluidised bed drying, obtains the product of higher degree.Detected result shows that quality product satisfies the industrial phosphoric acid disodium hydrogen standard among the national standard HG/T 2965-2009.
Embodiment 3
Glyphosate mother solution water quality in the present embodiment is identical with embodiment 1.After adding hydrochloric acid is adjusted to pH4.5, adopt a cover treatment capacity be 2.5 tons of mother liquors/hour the heterogeneous catalytic oxidation device carry out continuous oxide treatment, temperature of reaction is 250 degree, reaction pressure is 6.0Mpa, the air feed rate is 10.0 cubic meters per minute, and the reaction time of mother liquor in reactor is 30 minutes.After waste water is operated through extraction (extraction agent is 60% tributyl phosphate+40% kerosene) after the oxidation, enter next process.The extraction liquids hydro-oxidation sodium that contains inorganic phosphorus is neutralized to pH8.0, at room temperature generates the Sodium phosphate dibasic solid crude product.Crude product Sodium phosphate dibasic 12 crystallines are adopted pure water washing one time, and centrifuging with gained crystal by adopting fluidised bed drying, obtains the product of higher degree.Detected result shows that quality product satisfies the industrial phosphoric acid disodium hydrogen standard among the national standard HG/T 2965-2009.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (5)
1. produce the technology of Sodium phosphate dibasic from glyphosate mother solution for one kind, it is characterized in that may further comprise the steps:
(1) oxidation operation, at first glyphosate mother solution is added acid and be adjusted to acidity, then under the reaction conditions of 180---280 degree centigrade and 3.0---9.0Mpa pressure range, under the catalysis of heterogeneous noble metal catalyst, be oxygenant with airborne oxygen, the organo phosphorous compounds in the glyphosate mother solution and phosphorous acid are oxidized into positive phosphorus acid ion;
(2) extraction process adds extraction liquid with waste water after the oxidation in the step 1 and carries out extracting operation, and layering contains inorganic phosphate salt material with the upper strata and is diverted in the extraction liquid separator tank;
(3) in and operation, upper layer of extraction liquid adds alkali and is neutralized to pH7.0-pH10.0, through solid-liquid separation, obtains the Sodium phosphate dibasic solid phase prod under 10-30 degree centigrade condition, returns after extraction liquid is refining and applies mechanically.
2. a kind ofly produce the technology of Sodium phosphate dibasic from glyphosate mother solution according to claim 1 is described, it is characterized in that the heterogeneous noble metal catalyst in the described step (1) is the ruthenium rhodium catalyst; Described ruthenium rhodium catalyst carrier is titanium dioxide, and the composition of ruthenium is 0.5-5%, and the composition of rhodium is 0.5-5%.
3. a kind ofly produce the technology of Sodium phosphate dibasic from glyphosate mother solution according to claim 1 is described, it is characterized in that the extraction liquid in the described step (2) is that tributyl phosphate adds kerosene; Described extraction agent is tributyl phosphate, and thinner is kerosene, and the volume ratio of kerosene is 20-40%.
4. a kind ofly produce the technology of Sodium phosphate dibasic from glyphosate mother solution according to claim 1 is described, it is characterized in that in the described step (1) glyphosate mother solution being added acid is adjusted to pH2.5-5.0.
5. a kind ofly produce the technology of Sodium phosphate dibasic from glyphosate mother solution according to claim 1 is described, it is characterized in that amount of oxygen should be more than 0.7 times of glyphosate mother solution COD total amount of handling in the described step (1).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098074A (en) * | 2014-05-09 | 2014-10-15 | 浙江悦瑞环保工程有限公司 | Process for preparing disodium hydrogen phosphate from phosphonomethyl aminodiacetic acid wastewater |
| CN106044731A (en) * | 2016-08-13 | 2016-10-26 | 安徽东至广信农化有限公司 | Method for preparing disodium hydrogen phosphate based on glyphosate mother solution |
| CN107188147A (en) * | 2017-07-18 | 2017-09-22 | 什邡圣地亚化工有限公司 | A kind of method that sodium ascorbyl phosphate is produced with glyphosate byproduct phosphoric acid disodium hydrogen |
| CN113698000A (en) * | 2021-09-15 | 2021-11-26 | 安徽东至广信农化有限公司 | Production process for preparing disodium hydrogen phosphate from glyphosate mother liquor by EOC method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101757761A (en) * | 2008-12-25 | 2010-06-30 | 浙江新安化工集团股份有限公司 | Method for treating glyphosate mother liquor by oxidation method |
| CN102344209A (en) * | 2010-08-06 | 2012-02-08 | 同济大学 | Method for treating glyphosate wastewater and recovering nitrogen and phosphor in wastewater |
| CN102728350A (en) * | 2012-07-10 | 2012-10-17 | 北京纬纶华业环保科技股份有限公司 | Catalyst for treating industrial waste water by catalytic wet air oxidation (CWAO) |
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2013
- 2013-05-08 CN CN2013101657745A patent/CN103288065A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101757761A (en) * | 2008-12-25 | 2010-06-30 | 浙江新安化工集团股份有限公司 | Method for treating glyphosate mother liquor by oxidation method |
| CN102344209A (en) * | 2010-08-06 | 2012-02-08 | 同济大学 | Method for treating glyphosate wastewater and recovering nitrogen and phosphor in wastewater |
| CN102728350A (en) * | 2012-07-10 | 2012-10-17 | 北京纬纶华业环保科技股份有限公司 | Catalyst for treating industrial waste water by catalytic wet air oxidation (CWAO) |
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| 杨民等: ""催化湿式氧化反应用贵金属催化剂的研究进展"", 《第2届全国工业催化技术及应用年会论文集》, vol. 13, 31 October 2005 (2005-10-31), pages 400 - 404 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098074A (en) * | 2014-05-09 | 2014-10-15 | 浙江悦瑞环保工程有限公司 | Process for preparing disodium hydrogen phosphate from phosphonomethyl aminodiacetic acid wastewater |
| CN106044731A (en) * | 2016-08-13 | 2016-10-26 | 安徽东至广信农化有限公司 | Method for preparing disodium hydrogen phosphate based on glyphosate mother solution |
| CN107188147A (en) * | 2017-07-18 | 2017-09-22 | 什邡圣地亚化工有限公司 | A kind of method that sodium ascorbyl phosphate is produced with glyphosate byproduct phosphoric acid disodium hydrogen |
| CN113698000A (en) * | 2021-09-15 | 2021-11-26 | 安徽东至广信农化有限公司 | Production process for preparing disodium hydrogen phosphate from glyphosate mother liquor by EOC method |
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