CN102583867B - Method for treating waste water in chloro pyrimidine combining process - Google Patents
Method for treating waste water in chloro pyrimidine combining process Download PDFInfo
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Abstract
The invention relates to a method for treating waste water in the production process of chloro pyrimidine, such as 4,6-dichloro-pyrimidine and 2-amino-4,6-dichloro-pyrimidine. The method finishes treatment of waste water by adopting a chemical method for treatment, adding water into products after recycling chloro reagent, dissolving the products, not controlling pH of material liquid in an extraction process, and then treating separated acid water and quick lime or Ca(OH)2, recycling and purifying organic amine, phosphate and chloridion in the waste water step by step. The method can treat waste water to enable the waste water to reach the standard and reduces treatment cost of three wastes.
Description
Technical field
The present invention relates to produce in the Chloropyrimide building-up process treatment process of waste water, described method reclaims respectively organic amine, subphosphate and calcium chloride by chemical process.
Background technology
Chloropyrimide is widely used in the organic synthesis field owing to having good reactive behavior, has application prospect very widely.As the critical materials of 4,6-dichloro pyrimidine as the sterilant Azoxystrobin, ADCP is as agricultural chemicals chlorimuronethyl important source material etc.The main flow synthesis technique adopts the chloro agent to be reacted under trimethylamine or the existence of nitrogen-containing hetero cyclammonium as phosphoryl chloride, phosphorus trichloride or phosphorus pentachloride at present.Because wastewater flow rate in the Chloropyrimide production process is too large, and complicated component, a large amount of phosphoric acid salt wherein contained and organic amine salt easily cause the eutrophication of water, destroy ecotope two and have limited greatly the industrial scale of Chloropyrimide.Therefore, the exploitation of method for treating waste water in chloro pyrimidine combining process is significant.
In industrial production, the waste water in the Chloropyrimide building-up process normally takes the method such as chemical precipitation to be processed after Chloropyrimide is reclaimed in extraction, obtains mixing salt, and filtrate is again through giving birth to, change processing, effluxes after up to standard.After treatment, although waste water can reach discharge index, before extraction, need to use the alkali such as ammoniacal liquor to carry out pH regulator, but this process is exothermic process, the ammonia soln volatilization, the workman can't be operated and be affected environment, even use other alkali also to need slowly to be processed, makes that the treatment time is long, cost is high, affect whole treatment cycle, in addition, process the bad processing of gained by-product mixed salt, and total processing costs is higher.
Goal of the invention
The invention provides the approach of the effective constituent in a kind of effective separation, recovery Chloropyrimide waste water, make wastewater treatment more economically, operability is stronger.
Technical scheme
The objective of the invention is to reach like this: after the Chloropyrimide hydrolysis, without regulating pH, directly under acidic conditions, with organic solvent, extracted.After extraction, remaining acid waste water adds unslaked lime or calcium hydroxide, and by the Distillation recovery organic amine, cooling, suction filtration reclaim alkali calcium phosphate afterwards, and filtrate obtains calcium chloride through decolouring, concentrated, crystallization.By chemical precipitation-distillation-centrifugal method, not only realized the recovery to organic amine in waste water, and reached the separation to Phosphorus From Wastewater acid group-chlorion.
In aforesaid method, handled waste water is regulated pH without alkaline matters such as ammoniacal liquor in extraction process;
In aforesaid method, unslaked lime or calcium hydroxide add-on by processing waste water quality 15～45%;
In aforesaid method, add the temperature of unslaked lime or calcium hydroxide at 30～60 ℃;
In aforesaid method, the recovered temperature of organic amine is at 50～100 ℃;
In aforesaid method, filtrate decolorization activated carbon dosage is between 0.5～5%;
In aforesaid method, the activated carbon decolorizing temperature is between 40～80 ℃.
In aforesaid method, organic solvent used is toluene.
Specifically, the treatment process that the present invention comprises comprises the steps:
1, will react complete and steam except the Chloropyrimide reaction material after a large amount of phosphorus oxychloride or phosphorus trichloride, phosphorus pentachloride is added to the water and be hydrolyzed, without neutralization, directly with organic solvent, being extracted separatory;
2, quantitative unslaked lime or calcium hydroxide are joined in the waste water of above-mentioned separatory gained and reacted;
3, will add the mixing after unslaked lime or calcium hydroxide after material heat up gradually, the Distillation recovery organic amine;
The material that 4, will reclaim organic amine is lowered the temperature, crystallization, and suction filtration, reclaim alkali calcium phosphate;
5, the filtrate that will reclaim after alkali calcium phosphate is decoloured, and removes organic impurity wherein;
6, will decolour after feed liquid concentrated, the calcium chloride solid is separated out in cooling.
The reaction equation related in treating processes:
CaO+H
2O→Ca(OH)
2
Ca(OH)2+2HCl→CaCl2+2H2O
3Ca(OH)2+2H3PO4→Ca3(PO4)2+6H2O
Ca(OH)2+2(CH3CH2)3N.HCl→CaCl2+2H2O+2(CH3CH2)3N
3Ca3(PO4)2+Ca(OH)2→2Ca5(OH)(PO4)3
Beneficial effect
In the present invention, owing to not carrying out pH regulator in extraction process, therefore avoided the pollution of other alkaline organics to organic amine, the organic amine content that recovery is obtained is more than 99%, and the rate of recovery is more than 90%; Process waste water with unslaked lime or calcium hydroxide, can accomplish phosphatic effective separation, the phosphate content in waste water is reduced to below 0.5mg/L; The centrifugal alkali calcium phosphate content obtained is more than 99% after treatment, can meet the service requirements in the field such as separant, biomaterial, water conditioner, dyestuff, rubber, pharmacy of resin anti-stick; The CaCl made after concentrated
2content can reach more than 99%, meets the industrial application requirement.
The unslaked lime or the calcium hydroxide that in the present invention, use are cheap and easy to get, the organic amine that recovery obtains, alkali calcium phosphate and calcium chloride have certain marketable value, therefore, adopt present method to process Chloropyrimide waste water, not only processing cost can be do not increased, and certain profit can be produced.The water that after processing, only residue steams, index reaches the service water emission request.
The accompanying drawing explanation
Fig. 1: processing flow chart of the present invention
Preferred forms
Below by example, mentality of designing of the present invention is described, but the present invention is not limited to following examples.
Embodiment 1,
Waste water produces: add 4,6-dihydroxy-pyrimidine 114g (1mol) in four-hole bottle, phosphorus oxychloride 465g (3mol), stirring and dissolving.Be warming up to 40～60 ℃, start to drip 256g (2.5mol) triethylamine, controlling temperature in the dropping process is 40-60 ℃, and 1h dropwises.Then, be warming up to 60～100 ℃, insulation 2h.Be down to room temperature, the reclaim under reduced pressure phosphoryl chloride.Add 1000g toluene, after mixing, feed liquid is slowly joined in the 1200g frozen water and is hydrolyzed.Keeping the frozen water temperature in the batch turning process is 0-10 ℃.After stirring hydrolysis 60min, pour feed liquid into separating funnel, standing separatory.Water extracts 3 times through toluene, standing separatory, and organic phase merges, and the gained water is acid waste water.
Acid waste water is processed: get acid waste water 900g, be warming up to 50～60 ℃, stir lower gradation and add unslaked lime 190g, insulation 30min, the Distillation recovery triethylamine that starts to heat up, intercept the cut between 60～100 ℃, stops distillation after detecting cut pH to 8～9, reclaim the pure 116g of triethylamine, the rate of recovery 90.6%.The cooling suction filtration obtains alkali calcium phosphate, dry weight 200g, content 98.5%.Filtrate with in hydrochloric acid and after add gac 3g, 50 ℃ of decolouring 30min, the suction filtration recovered carbon, filtrate is concentrated, drying obtains calcium chloride 154g, content 98.3%.Concentrated water outlet COD 480mg/L, NH
3-N 2mg/L, pH 7.1, can directly discharge.
Building-up process: with example 1.
Acid waste water is processed: get acid waste water 900g, be warming up to 60～70 ℃, stir lower gradation and add unslaked lime 180g, insulation 30min, the Distillation recovery triethylamine that starts to heat up, intercept the cut between 60～100 ℃, stops distillation after detecting cut pH to 8～9, reclaim the pure 101g of triethylamine, the rate of recovery 78.9%.The cooling suction filtration obtains alkali calcium phosphate, dry weight 201g, content 98.9%.Add gac 3g, 50 ℃ of decolouring 30min, the suction filtration recovered carbon, the filtrate concentrate drying obtains calcium chloride 133g, content 98.5%.Concentrated water outlet COD 880mg/L, NH3-N6mg/L, pH 7.8.
Embodiment 3,
Building-up process: with example 1.
Acid waste water is processed: get acid waste water 900g, be warming up to 40～50 ℃, stir lower gradation and add Ca (0H)
2286g, insulation 30min, the Distillation recovery triethylamine that starts to heat up, intercept the cut between 60～100 ℃, behind detection cut pH to 8～9, stops distillation, reclaims the pure 117g of triethylamine, the rate of recovery 91.4%.The cooling suction filtration obtains alkali calcium phosphate, dry weight 200g, content 99.5%.Filtrate with in hydrochloric acid and after add gac 3g, 50 ℃ the decolouring 30min, the suction filtration recovered carbon, the filtrate concentrate drying obtains calcium chloride 206g, content 99.3%.Concentrated water outlet COD350mg/L, NH3-N 1.4mg/L, pH 7.0.
Embodiment 4,
Building-up process: with example 1.
Acid waste water is processed: get acid waste water 900g, be warming up to 40～50 ℃, stir lower gradation and add Ca (0H)
2286g, insulation 30min, the Distillation recovery triethylamine that starts to heat up, intercept the cut between 75～101 ℃, behind detection cut pH to 8～9, stops distillation, reclaims the pure 115g of triethylamine, the rate of recovery 89.8%.The cooling suction filtration obtains alkali calcium phosphate, dry weight 197g, content 99.3%.Filtrate with in hydrochloric acid and after add gac 5g, 50 ℃ of decolouring 30min, the suction filtration recovered carbon, filtrate is concentrated, drying obtains calcium chloride 205g, content 99.1%.Concentrated water outlet COD 380mg/L, NH3-N 1.7mg/L, pH 7.2.
Above-described embodiment is only explanation technical conceive of the present invention and characteristics, and its purpose is to allow the person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences that spirit is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (3)
1. a separation, reclaim the method for the effective constituent in Chloropyrimide waste water, it is characterized in that: the method comprises the steps:
(1), will react complete and steam except the Chloropyrimide reaction material after a large amount of phosphorus oxychloride or phosphorus trichloride, phosphorus pentachloride is added to the water and be hydrolyzed, without neutralization, directly with organic solvent, extracted separatory;
(2), quantitative unslaked lime or calcium hydroxide are joined in the waste water of above-mentioned separatory gained and reacted;
(3), the mixed material that will add after unslaked lime or calcium hydroxide heats up gradually, the Distillation recovery organic amine;
(4), the material that will reclaim organic amine lowered the temperature, crystallization, suction filtration, reclaim alkali calcium phosphate;
(5), the filtrate that will reclaim after alkali calcium phosphate decoloured, and removes organic impurity wherein;
(6), the filtrate after decolouring is concentrated, the calcium chloride solid is separated out in cooling;
Wherein, organic solvent used is toluene; Handled waste water is regulated pH without the ammoniacal liquor alkaline matter in extraction process; 15～45% of the quality that unslaked lime or calcium hydroxide add-on are handled waste water, add the temperature of unslaked lime or calcium hydroxide at 30～60 ℃, and the recovered temperature of organic amine is at 50～100 ℃.
2. the method for the effective constituent in separation as claimed in claim 1, recovery Chloropyrimide waste water, is characterized in that filtrate decolorization activated carbon dosage is 0.5～5% of waste water weight.
3. the method for the effective constituent in separation as claimed in claim 1, recovery Chloropyrimide waste water, is characterized in that the activated carbon decolorizing temperature is between 40～80 ℃.
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| CN106976923A (en) * | 2017-04-14 | 2017-07-25 | 安徽广信农化股份有限公司 | A kind of process of salicylonitrile wastewater treatment |
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Inventor after: Yang Guozhong Inventor after: Wei Lihua Inventor after: Guo Tingting Inventor after: Chen Yinxia Inventor after: Chen Yujia Inventor after: Lin Guotao Inventor after: Zhang Haiyan Inventor after: Wang Shuoshuo Inventor after: Li Honglu Inventor after: Peng Yanli Inventor before: Yang Guozhong Inventor before: Liu Hongpan Inventor before: Wang Jin Inventor before: Guo Hongyan Inventor before: Han Sujuan Inventor before: Guo Tingting |
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