CN1193939C - Method of processing polybutadiene polymer industrial waste water - Google Patents
Method of processing polybutadiene polymer industrial waste water Download PDFInfo
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- CN1193939C CN1193939C CN 02123733 CN02123733A CN1193939C CN 1193939 C CN1193939 C CN 1193939C CN 02123733 CN02123733 CN 02123733 CN 02123733 A CN02123733 A CN 02123733A CN 1193939 C CN1193939 C CN 1193939C
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- polybutadiene
- waste water
- washing water
- kettle
- water
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Abstract
The present invention provides a treatment method of polybutadiene polymer technological waste water, particularly a treatment method of polybutadiene graft copolymer technological waste water in the production of ABS resin. In the treatment method of polybutadiene polymer technological waste water, polybutadiene polymerization kettle washing water and polybutadiene graft polymerization kettle washing water generated in the production of a polybutadiene graft copolymer are respectively treated, and the effective components of the two kinds of kettle washing water are recovered. Therefore, the present invention reduces waste, lowers the COD value of the waste water and lightens the load of subsequent waste water treatment. The present invention recovers useful materials in the waste water with high limit, and the present invention enhances production rate when the performance of a target product is kept.
Description
Technical field
The present invention relates to a kind of method of processing polybutadiene polymer industrial waste water, the method for processing polybutadiene graft copolymer industrial waste water in the particularly production ABS resin process.
Background technology
Polybutadiene graft copolymer is the intermediates of production ABS resin.Its production process and discharge of wastewater situation are: be raw material with the divinyl, letex polymerization makes polybutadiene latex (EBR latex), polybutadiene latex and vinylbenzene, vinyl cyanide are prepared the polyhutadiene graft latex with emulsion grafting polymerization, and the polyhutadiene graft latex makes polybutadiene graft copolymer through cohesion, centrifuge washing, drying.This graft copolymer and SAN blending make ABS resin.In the polybutadiene graft copolymer production process, there are four strands of waste water to discharge, are respectively centrifuge waste water and control of dust water that polyhutadiene polymeric kettle kettle washing water (comprising the degassing vessel washing water), polyhutadiene emulsion grafting polymerization still kettle washing water, polybutadiene graft copolymer and water sepn produce.At present polyhutadiene polymeric kettle kettle washing water (comprising the degassing vessel washing water), emulsion grafting polymerization still kettle washing water treatment process are in the ABS production equipment: at first remove by filter oversize material, again with directly be disposed to the one-level waste disposal plant after other operation waste water mixes and carry out coagulation, air supporting processing.Scum silica frost is with waste disposal, and waste water discharges behind multiple-stage treatment again.This treatment process makes the treatment capacity of waste water plant increase, load and increase, and processed waste water does not still reach the level of factory first discharge standard, and processing cost is higher.To produce 50000 tons of ABS resin devices per year is example, and in the polybutadiene graft copolymer production process, about 10 batches of the every polymerizations of polyhutadiene polymeric kettle need to clean once, about 2000 tons of year draining total amount, and its latex component content mean value is 0.8%; About 8 batches of the every graft polymerizations of grafting still need to clean once, about 4800 tons of year discharging, and latex composition mean value is 1.5%, contains recycling material in these waste water, directly emitting is a kind of waste.
Su Hong, Bai Cheng aim at " Jilin Institute of Chemical Technology journal " .-2000, in 17 (2) .-45-49 " research of the ABS wastewater processing technology method " literary composition, at Ji ABS production equipment C, B district waste water breakdown of emulsion, coagulating treatment have been proposed, E district waste water air supporting-hydrolysis-biochemical processing method, result shows: after the ABS wastewater treatment, all can reach the into requirement of Ji Hua company Sewage Plant.
Summary of the invention
The object of the present invention is to provide a kind of new method of processing polybutadiene graft copolymer industrial waste water, promptly the polyhutadiene polymeric kettle kettle washing water, the polyhutadiene graft polymerization still kettle washing water that produce in the production polybutadiene graft copolymer process are handled respectively, reuse effective constituent wherein, thereby cut the waste, reduce COD value of waste water, alleviate the subsequent wastewater treatment load, high limit reclaims useful material in the waste water, improves productive rate when keeping the target product performance.
The contriver finds by analysis, the performance of latex composition does not change in the kettle washing water that produces in the production polybutadiene graft copolymer process, do not polluted, its reuse can not caused the finished product changes of properties, promptly return the subsequent processing use so the material in the production polybutadiene graft copolymer waste water is carried out reuse.
Concrete grammar can be:
To the processing of (comprising polybutadiene latex degassing vessel washing water) of polyhutadiene polymeric kettle kettle washing water.With polyhutadiene polymeric kettle kettle washing water, deposit polybutadiene latex waste water storage tank in, measure the content of polybutadiene latex in this storage tank waste water.Carry out graft polymerization with polybutadiene latex, the water yield in polybutadiene latex, the water-content instead of part grafting process in the polyhutadiene polymeric kettle kettle washing water, making polyhutadiene polymeric kettle kettle washing water like this is zero blowdown, and the latex in the waste water and water are all utilized.
Processing to polyhutadiene graft polymerization still kettle washing water.Will be from the kettle washing water of graft polymerization still, deposit graft polymerization still waste water storage tank after filtering in, measure the content of polyhutadiene graft latex in this storage tank waste water, this strand waste water can be mixed into cohesion process with the graft copolymer from the graft polymerization still, and the graft copolymer after the cohesion obtains polybutadiene graft copolymer through centrifugal, drying.Be effective constituent in the recyclable kettle washing water like this, can reduce COD value of waste water again.
If measure by analysis, the equal no change of latex composition performance in polyhutadiene polymeric kettle kettle washing water and the polyhutadiene graft polymerization still kettle washing water, then can adopt above-mentioned two kinds of technical finesse method of processing polybutadiene graft copolymer industrial waste water simultaneously, can more effective processing waste water and recovered material.
Adopt polybutadiene graft copolymer method of wastewater treatment of the present invention, not only reduced wastewater discharge, reduced COD value in the waste water, and reuse the effective constituent in the waste water, when keeping the target product performance, improved productive rate.
Embodiment
Embodiment 1:
Polybutadiene latex polymeric kettle kettle washing water is used for the graft polymerization operation: polybutadiene latex polymeric kettle kettle washing water (comprising polybutadiene latex degassing vessel washing water) enters polybutadiene latex waste water storage tank, measures the content of polybutadiene latex in this storage tank waste water.Carry out graft polymerization with polybutadiene latex, the water yield in polybutadiene latex, the water-content instead of part grafting process in the kettle washing water.In the graft polymerization production process, latex content accounts for 1.0% of polybutadiene latex total amount in the waste water, and graftomer is through making ABS resin behind cohesion, the centrifugal drying with after APH-SAN, the auxiliary agent blending.Its melt flow rate (MFR) is 2.20g/10min, 96 ℃ of Vicat softening points, bend yield strength noted 64.3MPa, tensile yield strength 44.4MPa, cantilever beam impact strength 276.7J/m, Rockwell hardness (R scale) 104.5.Quality meets fully that the trade mark is ABS-1 among the GB 12672-90, GN, and the 095-15-150-2 standard, product performance do not change.
In 50,000 tons/year ABS production equipment, polybutadiene latex polymeric kettle kettle washing water year 2000 tons of total emission volumns, its active constituent content mean value is 0.8%, 16 tons of then annual recoverable materials.The polyhutadiene polymeric kettle kettle washing water COD value of solid content 0.8% is 24500mg/L, handles polyhutadiene polymeric kettle kettle washing water technology with grafting, makes the material fully recovering in polyhutadiene polymeric kettle kettle washing water and the water.
Embodiment 2:
Adopt the polybutadiene graft copolymer in the condensation technique recovery polyhutadiene graft polymerization still kettle washing water: the kettle washing water of graft polymerization still enters graft polymerization still waste water storage tank after filtering, in the cohesion production technique, condense with polyhutadiene graft latex, the water yield in polyhutadiene graft latex, the water-content instead of part agglomeration process in the kettle washing water, wherein add solid content 1.5% graft polymerization still kettle washing water, kettle washing water accounts for 3.0% of the total water of cohesion, 68 ℃ of condensation temperatures, 92 ℃ of curing temperatures.Its melt flow rate (MFR) of ABS resin of grafting powder after the cohesion and APH-SAN blending is 1.77g/10min, 96.5 ℃ of Vicat softening points, bend yield strength noted 63.3MPa, tensile yield strength 45.9MPa, cantilever beam impact strength 231.8J/m, Rockwell hardness (R scale) 103.5.Quality meets fully that the trade mark is ABS-1 among the GB 12672-90, GN, and the 095-15-150-2 standard, product performance do not change.
In 50,000 tons/year ABS production equipment, 4800 tons of polyhutadiene graft polymerization still kettle washing water year total emission volumns, grafting still kettle washing water solid content mean value is 1.5%, 72 tons of then annual recoverable materials.Solid content is that 1.7% grafting still kettle washing water COD is 25000mg/L, adopts condensation technique to handle grafting still kettle washing water, makes the material fully recovering in polyhutadiene grafting still kettle washing water and the water.
Embodiment 3:
Polybutadiene latex polymeric kettle kettle washing water is used for the graft polymerization operation: polybutadiene latex polymeric kettle kettle washing water (comprising polybutadiene latex degassing vessel washing water) enters polybutadiene latex waste water storage tank, measures the content of polybutadiene latex in this storage tank waste water.Carry out graft polymerization with polybutadiene latex, the water yield in polybutadiene latex, the water-content instead of part grafting process in the kettle washing water, in the graft polymerization production process, latex content accounts for 0.8% of polybutadiene latex total amount in the waste water.Adopt the polybutadiene graft copolymer in the condensation technique recovery polyhutadiene graft polymerization still kettle washing water simultaneously: the kettle washing water of graft polymerization still enters graft polymerization still waste water storage tank, in the cohesion production technique, condense with polyhutadiene graft latex, the water yield in polyhutadiene graft latex, the water-content instead of part agglomeration process in the kettle washing water, wherein add solid content 1.5% graft polymerization still kettle washing water, kettle washing water accounts for 2.7% of the total water of cohesion, 68 ℃ of condensation temperatures, 92 ℃ of curing temperatures.Its melt flow rate (MFR) of ABS resin of grafting powder after the cohesion and APH-SAN blending is 1.88g/10min, 97 ℃ of Vicat softening points, bend yield strength noted 64.1MPa, tensile yield strength 45.7MPa, cantilever beam impact strength 218.3J/m, Rockwell hardness (R scale) 105.5.Quality meets fully that the trade mark is ABS-1 among the GB 12672-90, GN, and the 095-15-150-2 standard, product performance do not change.
In 50,000 tons/year ABS production equipment, polybutadiene latex polymeric kettle kettle washing water is used for the graft polymerization operation, polyhutadiene graft polymerization still kettle washing water is used for two kinds of wastewater processing technologies of cohesion process and is used for the polybutadiene graft copolymer wastewater treatment simultaneously, about 88 tons of year recovered material, economize on water about 7000 tons, reduce COD value of waste water significantly.
Claims (9)
1. method of processing polybutadiene polymer industrial waste water, the performance of latex composition does not change, when not being subjected to polluting, entering subsequent processing by its contained latex amount, the water yield and use in the kettle washing water that it is characterized in that producing in the production polybutadiene graft copolymer process.
2. method of processing polybutadiene polymer industrial waste water according to claim 1 is characterized in that kettle washing water is a polyhutadiene polymeric kettle kettle washing water.
3. method of processing polybutadiene polymer industrial waste water according to claim 2 is characterized in that polyhutadiene polymeric kettle kettle washing water includes polybutadiene latex degassing vessel washing water.
4. method of processing polybutadiene polymer industrial waste water according to claim 3 is characterized in that depositing polyhutadiene polymeric kettle kettle washing water in polybutadiene latex waste water storage tank, measures the content of polybutadiene latex in this storage tank waste water; Carry out graft polymerization with polybutadiene latex, water in polybutadiene latex, the water instead of part grafting process in the polyhutadiene polymeric kettle kettle washing water.
5. method of processing polybutadiene polymer industrial waste water according to claim 1 is characterized in that kettle washing water is the kettle washing water of graft polymerization still.
6. method of processing polybutadiene polymer industrial waste water according to claim 5, it is characterized in that to deposit graft polymerization still waste water storage tank after filtering in from the kettle washing water of graft polymerization still, this strand waste water be mixed into cohesion process from the graft copolymer of graft polymerization still, the graft copolymer after the cohesion obtains polybutadiene graft copolymer through centrifugal, drying.
7. method of processing polybutadiene polymer industrial waste water according to claim 1 is characterized in that kettle washing water is the kettle washing water of polyhutadiene polymeric kettle kettle washing water and graft polymerization still.
8. method of processing polybutadiene polymer industrial waste water according to claim 7 is characterized in that polyhutadiene polymeric kettle kettle washing water includes polybutadiene latex degassing vessel washing water.
9. according to claim 7 or 8 described method of processing polybutadiene polymer industrial waste water, it is characterized in that depositing polyhutadiene polymeric kettle kettle washing water in polybutadiene latex waste water storage tank, measure the content of polybutadiene latex in this storage tank waste water; Carry out graft polymerization with polybutadiene latex, water in polybutadiene latex, the water instead of part grafting process in the polyhutadiene polymeric kettle kettle washing water; To deposit graft polymerization still waste water storage tank from the kettle washing water of graft polymerization still after filtering in, this strand waste water be mixed into cohesion process from the graft copolymer of graft polymerization still, the graft copolymer after the cohesion obtains polybutadiene graft copolymer through centrifugal, drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02123733 CN1193939C (en) | 2002-06-21 | 2002-06-21 | Method of processing polybutadiene polymer industrial waste water |
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| CN 02123733 CN1193939C (en) | 2002-06-21 | 2002-06-21 | Method of processing polybutadiene polymer industrial waste water |
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| CN1463930A CN1463930A (en) | 2003-12-31 |
| CN1193939C true CN1193939C (en) | 2005-03-23 |
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| CN 02123733 Expired - Fee Related CN1193939C (en) | 2002-06-21 | 2002-06-21 | Method of processing polybutadiene polymer industrial waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105712432B (en) * | 2016-02-23 | 2018-07-06 | 中国环境科学研究院 | Wastewater Pollutant reduction or control method in a kind of emulsion polymerization production of resins |
| CN111804253A (en) * | 2020-07-14 | 2020-10-23 | 山东京博中聚新材料有限公司 | Recycling process of styrene-butadiene latex reaction kettle washing water |
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