CN101274795A - Process for treating waste water in chlorfluazuron synthesis - Google Patents
Process for treating waste water in chlorfluazuron synthesis Download PDFInfo
- Publication number
- CN101274795A CN101274795A CNA2008100159864A CN200810015986A CN101274795A CN 101274795 A CN101274795 A CN 101274795A CN A2008100159864 A CNA2008100159864 A CN A2008100159864A CN 200810015986 A CN200810015986 A CN 200810015986A CN 101274795 A CN101274795 A CN 101274795A
- Authority
- CN
- China
- Prior art keywords
- bromine
- waste water
- chlorfluazuron
- chlorine
- ammonium chloride
- 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.)
- Pending
Links
Landscapes
- Physical Water Treatments (AREA)
Abstract
The invention provides a method for treating profenofos synthetic wastewater. A certain amount of chlorine is led into the wastewater produced in the synthesis process of profenofos, bromide ion in the wastewater is replaced by bromine and trimethyl ethyl ammonium chloride is generated, the generated bromine is separated with the wastewater, and then the wastewater after the bromine is separated is used for preparing the trimethyl ethyl ammonium chloride. The method can be used for treating the waste water produced in the synthesis process of the profenofos to recover valuable resource, thereby having better social and economic benefits.
Description
Technical field:
The method that the waste water that the present invention relates to be produced in a kind of Profenofos synthesis process is handled.
Background technology:
The Profenofos full name is O-ethyl-S-propyl group-O-(2-chloro-4-bromine)-phenyl phosphorothionate, is the pesticide new variety of the later stage seventies by the exploitation of Ciba-Geigy company, and the antagonism insect shows high activity, and special antagonism bollworm is remarkably productive.Its acute toxicity LD
50Be 358mg/kg (rat is oral).Profenofos crude oil is tawny liquid, and pure product are colourless transparent liquid, 110 ℃/0.001mmHg of boiling point, n
D 251.5511 the solubleness in the time of 20 ℃ in the water is 20ppm, can be dissolved in most of organic solvents.Kind was classified as one of kind of alternative riskiest pesticide by country in 2005, it is one of pesticide species that has development prospect, there are sizable potentiality in its outlet and internal trade market, at present domestic have ten surplus enterprise of family in production, and output increases with bigger amplitude year by year.In Profenofos final step synthetic production process, one ton of 90% Profenofos of every production can produce the waste water of 540～2700kg, the trimethylammonium ethyl brometo de amonio that contains the 405kg that has an appointment, chemical oxygen demand is high and have than niff, as not administered, can cause bigger pollution to environment, if administer and do not reclaim useful resources, then can cause the significant wastage of resource according to ordinary method.
Summary of the invention:
The purpose of this invention is to provide a kind of process for treating waste water in chlorfluazuron synthesis,, administer sewage and reach emission request by the recyclable useful resources of this method.
The objective of the invention is to realize as follows: feed quantitative chlorine in the waste water that in the Profenofos building-up process, produces, bromide anion in the waste water is replaced as bromine and generates the trimethylammonium ethyl ammonium chloride, the bromine that generates separates with waste water, and the waste water behind the utilization separation bromine prepares the trimethylammonium ethyl ammonium chloride then.
The temperature that feeds chlorine is 0～120 ℃, and the mol ratio of bromine is 1.05: 1 in the amount of feeding chlorine and the waste water, and feeding the chlorine reaction time is 3.0～3.5h.
Bromine and waste water separation method are following three kinds:
A. heating or bromine is steamed with water vapor with open steam, distillation temperature is 40～120 ℃.Water and bromine enter in the receptor after the condensation, the bromine sedimentation, and upper water returns in the still kettle, and there do not have in bromine look and the still waste water become in steam to be light yellow, and receptor lower floor gets bromine.
B. with rare gas element bromine is blown out, the bromine that blows out absorbs with soda ash solution and generates Sodium Bromide and sodium bromate, adds sour acidifying in the Sodium Bromide of generation and the sodium bromate, generates bromine; Blowing out temperature is 20～135 ℃, the rare gas element that uses as in air, nitrogen, three kinds of gases of carbonic acid gas one of or their mixture, the bromine that blows out absorbs with soda ash solution and generates Sodium Bromide and sodium bromate, add acidifying, the acid that adds is sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or these sour mixtures, and acidifying pH value is between 0.1～5.0; Preferred rare gas element is an air, blows out preferred 105 ± 5 ℃ of temperature, and the concentration of soda ash solution is saturated solution, and sulfuric acid is selected in acidifying for use, preferred 0～25 ℃ of souring temperature, acidifying pH value preferred 2; The bromine standing demix that generates, lower floor gets bromine.
C. with rare gas element bromine is blown out, blowing out temperature is 20～135 ℃, the rare gas element that uses as in air, nitrogen, three kinds of gases of carbonic acid gas one of or their mixture, the bromine that blows out absorb to form the organic solvent solution of bromine with organic solvent, and organic solvent solution is a kind of in benzene, chlorobenzene, toluene, tetracol phenixin, trichloromethane, dithiocarbonic anhydride, kerosene, ethanol, the ether.Preferred rare gas element is an air, blows out preferred 105 ± 5 ℃ of temperature, the preferred chlorobenzene of organic solvent.
Aqueous phase behind the separation bromine adds gac, through decoloration and deodorization, then gac is separated, and dewaters, and gets the trimethylammonium ethyl ammonium chloride after the cooling.The temperature of decoloration and deodorization is 10～120 ℃, 105 ± 5 ℃ of preferred temperature, and the weight ratio of activated carbon dosage and waste water is 1: 1000～1: 10, the decoloration and deodorization time is 0.1～10h.
Utilize bittern to produce the tower production unit of bromine, bromine production operation method according to routine realizes that logical chlorine prepares bromine and trimethylammonium ethyl ammonium chloride, the processing step of bromine is produced in the realization serialization, the mol ratio of bromide anion is 1.05: 1 in chlorine and the waste water, and the waste water of discharge prepares the trimethylammonium ethyl ammonium chloride by preceding method.
The invention has the beneficial effects as follows: adopt the present invention can administer the waste water that in the Profenofos building-up process, produces, reclaim useful resources, have good social benefit and economic benefit.
Embodiment:
Embodiment 1
3Na
2CO
3+3Br
2→5NaBr+NaBrO
3+3CO
2↑
5NaBr+NaBrO
3+3H
2SO
4→3Br
2+3Na
2SO
4+3H
2O
Feed quantitative chlorine and prepare bromine in waste water, and then extract the trimethylammonium ethyl ammonium chloride the water after separating bromine, chemical equation as above.
Add 2500kg waste water in the glassed steel reaction vessels of 3000L, under the stirring at room, with the flow feeding chlorine of 60kg/h, feeding chlorine weight is 156kg, continues reaction 0.5h after logical chlorine is finished.
In 1000L lass lining bromine absorption reaction still, add 30% sodium carbonate solution of 800kg and start and stir, add 30% sodium carbonate solution of 800kg in the tail gas tourie; With the waste water flow behind the logical chlorine is that the air of 50L/min carries out bubbling, heat up simultaneously, reach 105 ℃ until temperature, remain on that bubbling blows out bromine to the absorption reaction still under this temperature, in the sodium carbonate solution in the absorption reaction still expellant gas feeding tail gas tourie, the air that bloats behind about 4h becomes colorless and waste water becomes light yellowly, and substantially do not have bromine in the waste water this moment, puies forward the bromine step and finish.
Reactor is cooled to 70 ± 5 ℃, slowly drop into the 85kg gac, continue then under this temperature, to stir 30min, the mode of gac with vacuum filtration leached, water changes in the lass lining dehydration still of 3000L again, open vacuum system and feed water coolant to condenser, stir and intensification, rise to 85 ℃ until liquidus temperature, and anhydrous oozing in the condenser, while hot material is put to the scraping machine cooling and is made sheet, be put in the Paperboard bucket after packing immediately, trimethylammonium ethyl ammonium chloride 540kg.
In the lass lining bromine absorption reaction still chuck of 1000L, feed water coolant, from header tank, slowly splash into 92.5% sulfuric acid, remain neutral temperature and be no more than 30 ℃, surveying the pH value is 2 o'clock (92.5% sulfuric acid of about 240kg), standing demix, lower floor's bromine is put into packing porcelain altar, get bromine 330kg.The saturated bromine water in upper strata extracts the chlorobenzene solution for preparing bromine with chlorobenzene, and the aqueous phase after the extraction adds the mixing solutions of a small amount of urea and yellow soda ash, drains into purification tank for liquid waste after removing the bromine of trace and transferring pH=6～7.
30% sodium carbonate solution of 800kg in the tail gas absorption cell is moved in the 1000L lass lining bromine absorption reaction still, in the tail gas absorption cell, mend 30% sodium carbonate solution of new 800kg then, can carry out the processing of next batch 2500kg waste water.
Embodiment 2
Feed quantitative chlorine and prepare bromine in waste water, chemical equation as above and then is extracted the trimethylammonium ethyl ammonium chloride the water after separating bromine.
Add 2500kg waste water in the glassed steel reaction vessels of 3000L, under the stirring at room, with the flow feeding chlorine of 60kg/h, feeding chlorine weight is 156kg, continues reaction 0.5h after logical chlorine is finished.
In glass condenser, feed water coolant, in the glassed steel reaction vessels chuck of 3000L, feed steam, bromine is along with water vapor enters condenser, flow into after the condensation and divide in the water susceptor, bromine sinks to susceptor bottom, and water of condensation returns in the still, the water in still becomes yellow and the water of condensation that steams also become colourless substantially till, bromine in minute water susceptor is packed in the container, thick bromine 336kg.
Waste water is cooled to 70 ± 5 ℃ in the reactor, slowly drop into the 85kg gac, continue then under this temperature, to stir 30min, the mode of gac with vacuum filtration leached, water changes in the lass lining dehydration still of 3000L again, open vacuum system and feed water coolant to condenser, stir and intensification, rise to 85 ℃ until liquidus temperature, and anhydrous oozing in the condenser, while hot material is put to the scraping machine cooling and is made sheet, be put in the Paperboard bucket after packing immediately, trimethylammonium ethyl ammonium chloride 540kg.
Embodiment 3
With waste water from header tank with the flow of 300L/h from oxidizing tower inflow suitable for reading, chlorine feeds from the oxidizing tower bottom with the flow of 350L/h (0.2MPa), enter distillation tower from the oxidizing tower end opening after waste water and the oxidation of chlorine counter current contact, blown out by the water vapor that feeds from the distillation tower bottom, together enter condenser with a part of water vapor, become liquid after the condensation and enter bromine water-separating bottle, the thick bromine of separate and subside enters rectifying tower from the bromine water-separating bottle bottom, saturated bromine water is returned distillation tower, thick bromine obtains smart bromine after two-stage rectification, the waste water of discharging from distillation tower enters trimethylammonium ethyl ammonium chloride extraction element, prepares the trimethylammonium ethyl ammonium chloride by the method for embodiment 1 and 2.
Claims (7)
1, a kind of process for treating waste water in chlorfluazuron synthesis, it is characterized in that: feed quantitative chlorine in the waste water that in the Profenofos building-up process, produces, bromide anion in the waste water is replaced as bromine and generates the trimethylammonium ethyl ammonium chloride, the bromine that generates separates with waste water, and the waste water behind the utilization separation bromine prepares the trimethylammonium ethyl ammonium chloride then.
2, process for treating waste water in chlorfluazuron synthesis according to claim 1 is characterized in that: the temperature that feeds chlorine is 0～120 ℃, and the mol ratio of bromine is 1.05: 1 in the amount of feeding chlorine and the waste water, and feeding the chlorine reaction time is 3.0～3.5h.
3, process for treating waste water in chlorfluazuron synthesis according to claim 1 is characterized in that bromine and waste water separation method are: heating or bromine is steamed with water vapor with open steam, distillation temperature is 40～120 ℃.
4, process for treating waste water in chlorfluazuron synthesis according to claim 1, it is characterized in that bromine and waste water separation method are: bromine is blown out with rare gas element, the bromine that blows out absorbs with soda ash solution and generates Sodium Bromide and sodium bromate, add acidifying in Sodium Bromide that generates and the sodium bromate, generate bromine; Blowing out temperature is 20～135 ℃, the rare gas element that uses as in air, nitrogen, three kinds of gases of carbonic acid gas one of or their mixture, the bromine that blows out absorbs with soda ash solution and generates Sodium Bromide and sodium bromate, add acidifying, the acid that adds is sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or these sour mixtures, and acidifying pH value is between 0.1～5.0.
5, process for treating waste water in chlorfluazuron synthesis according to claim 1, it is characterized in that bromine and waste water separation method are: bromine is blown out with rare gas element, blowing out temperature is 20～135 ℃, the rare gas element that uses as in air, nitrogen, three kinds of gases of carbonic acid gas one of or their mixture, the bromine that blows out absorb to form the organic solvent solution of bromine with organic solvent, and organic solvent solution is a kind of in benzene, chlorobenzene, toluene, tetracol phenixin, trichloromethane, dithiocarbonic anhydride, kerosene, ethanol, the ether.
6, process for treating waste water in chlorfluazuron synthesis according to claim 1 is characterized in that: the aqueous phase behind the separation bromine adds gac, through decoloration and deodorization, then gac is separated, and dewaters, and gets the trimethylammonium ethyl ammonium chloride after the cooling; The temperature of decoloration and deodorization is 10～120 ℃, and the weight ratio of activated carbon dosage and waste water is 1: 1000～1: 10, and the decoloration and deodorization time is 0.1～10h.
7, process for treating waste water in chlorfluazuron synthesis according to claim 1, it is characterized in that: utilize bittern to produce the tower production unit of bromine, bromine production operation method according to routine realizes that logical chlorine prepares bromine and trimethylammonium ethyl ammonium chloride, the processing step of bromine is produced in the realization serialization, the mol ratio of bromide anion is 1.05: 1 in chlorine and the waste water, and the waste water of discharge prepares the trimethylammonium ethyl ammonium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100159864A CN101274795A (en) | 2008-05-07 | 2008-05-07 | Process for treating waste water in chlorfluazuron synthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100159864A CN101274795A (en) | 2008-05-07 | 2008-05-07 | Process for treating waste water in chlorfluazuron synthesis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101274795A true CN101274795A (en) | 2008-10-01 |
Family
ID=39994710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100159864A Pending CN101274795A (en) | 2008-05-07 | 2008-05-07 | Process for treating waste water in chlorfluazuron synthesis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101274795A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583864A (en) * | 2012-02-24 | 2012-07-18 | 山东科源化工有限公司 | Method for treating profenofos production wastewater |
| CN103253635A (en) * | 2013-05-23 | 2013-08-21 | 孟宪锋 | Process for extracting bromine from thiabendazole wastewater |
| CN105502296A (en) * | 2015-12-29 | 2016-04-20 | 河北合佳医药科技集团有限公司 | Method for preparing bromine from bromine-containing waste water produced during production of aminothiazoly loximate |
| CN106278802A (en) * | 2016-08-11 | 2017-01-04 | 山东科源化工有限公司 | A kind of method utilizing Profenofos by-product synthesis Profenofos raw material N-Propyl Bromide |
| CN109678115A (en) * | 2019-03-06 | 2019-04-26 | 山东科源化工有限公司 | A method of extracting bromine from the brominated waste of pesticide producing |
| CN112424114A (en) * | 2018-05-07 | 2021-02-26 | 科思创知识产权两合公司 | Storage medium and method for separating, storing and transporting chlorine from chlorine-containing gases |
| CN113736467A (en) * | 2021-09-27 | 2021-12-03 | 济宁市兖州区碧海化工有限公司 | Method for preparing soil conditioner by using waste bromide |
| CN115196598A (en) * | 2022-06-29 | 2022-10-18 | 天津长芦汉沽盐场有限责任公司 | Oxidation distillation tail gas treatment process and system in bromine production process |
-
2008
- 2008-05-07 CN CNA2008100159864A patent/CN101274795A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583864A (en) * | 2012-02-24 | 2012-07-18 | 山东科源化工有限公司 | Method for treating profenofos production wastewater |
| CN103253635A (en) * | 2013-05-23 | 2013-08-21 | 孟宪锋 | Process for extracting bromine from thiabendazole wastewater |
| CN105502296A (en) * | 2015-12-29 | 2016-04-20 | 河北合佳医药科技集团有限公司 | Method for preparing bromine from bromine-containing waste water produced during production of aminothiazoly loximate |
| CN106278802A (en) * | 2016-08-11 | 2017-01-04 | 山东科源化工有限公司 | A kind of method utilizing Profenofos by-product synthesis Profenofos raw material N-Propyl Bromide |
| CN106278802B (en) * | 2016-08-11 | 2019-04-30 | 山东科源化工有限公司 | A method of Profenofos raw material N-Propyl Bromide is synthesized using Profenofos by-product |
| CN112424114A (en) * | 2018-05-07 | 2021-02-26 | 科思创知识产权两合公司 | Storage medium and method for separating, storing and transporting chlorine from chlorine-containing gases |
| CN109678115A (en) * | 2019-03-06 | 2019-04-26 | 山东科源化工有限公司 | A method of extracting bromine from the brominated waste of pesticide producing |
| CN113736467A (en) * | 2021-09-27 | 2021-12-03 | 济宁市兖州区碧海化工有限公司 | Method for preparing soil conditioner by using waste bromide |
| CN113736467B (en) * | 2021-09-27 | 2023-08-04 | 济宁市兖州区碧海化工有限公司 | Method for preparing soil conditioner by utilizing waste bromide |
| CN115196598A (en) * | 2022-06-29 | 2022-10-18 | 天津长芦汉沽盐场有限责任公司 | Oxidation distillation tail gas treatment process and system in bromine production process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101274795A (en) | Process for treating waste water in chlorfluazuron synthesis | |
| CN108840310B (en) | Device and process for producing hydrogen chloride by deep analysis from dilute hydrochloric acid | |
| CN101525195A (en) | Method for treating profenofos synthetic wastewater by using hydrogen peroxide | |
| ES2968740T3 (en) | Procedure for the treatment of production wastewater from the preparation of propylene oxide by co-oxidation procedure | |
| CN104003422B (en) | Disposing mother liquor method new technology | |
| CN102502500A (en) | Device for producing hydrogen chloride by resolving hydrochloric acid | |
| CN104086362A (en) | Method for recycling organic solvents of wastewater generated in synthesis of hydrazine hydrate by ketazine method | |
| CN106699808A (en) | Acidolysis and solvent recycling process and device for producing glyphosate by using glycine method | |
| CN109134231A (en) | A kind of chloroacetic device and process of differential circulation continuous production | |
| CN106631684A (en) | Method for preparing SBA(sec-butyl alcohol) through hydrolysis with sec-butyl acetate | |
| WO2021129404A1 (en) | Device and method for recycling waste acid liquid for polycrystalline silicon texturing | |
| CN104311382B (en) | The method of monochloroethane is prepared by chlorination byproduct hydrogen chloride | |
| CN113003847B (en) | Treatment method for wastewater generated in production of preparing epoxypropane by co-oxidation method | |
| CN113620250B (en) | Bromine-containing waste gas recovery method | |
| CN104844414A (en) | Equipment and process for recovering glyphosate solvent during production with glycine method | |
| CN101657378A (en) | The technology of combination producing bromine and calcium chloride | |
| CN102887816B (en) | Method for preparing dichloropropanol with chemical reaction-pervaporation coupling method | |
| CN105417556B (en) | Preparation method of ammonium bifluoride | |
| CN100509786C (en) | Comprehensive process for tail gas in glyphosate production | |
| CN108273282B (en) | Vapor phase low-order heat recovery system of trioxymethylene synthetic distillation tower and recovery method thereof | |
| CN1504413A (en) | Reclamation process for waste water of rare earth extraction separation | |
| CN101254906B (en) | Method and device for vacuum nitric acid gas recovering during preparation of nitric acid | |
| CN104788304B (en) | The method that mineral acid acidified formates prepare high-pure anhydrous formic acid | |
| CN107777668A (en) | A kind of preparation method of demercuration bromide | |
| CN102040479B (en) | System for preparing dichloropropanol by autocatalytic reaction of glycerol and hydrogen chloride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20081001 |