CN102874961A - Method for treating wastewater of rubber vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) - Google Patents
Method for treating wastewater of rubber vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) Download PDFInfo
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- CN102874961A CN102874961A CN201210362012XA CN201210362012A CN102874961A CN 102874961 A CN102874961 A CN 102874961A CN 201210362012X A CN201210362012X A CN 201210362012XA CN 201210362012 A CN201210362012 A CN 201210362012A CN 102874961 A CN102874961 A CN 102874961A
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Abstract
The invention discloses a method for treating wastewater of rubber vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS). The method comprises the following steps of: performing acid-base flocculation on the wastewater, filtering, conveying the wastewater into an electrolytic tank with a microelectrolysis filler, and performing microelectrolysis at temperature of between 60 and 80 DEG C for 2 to 5 hours; filtering the wastewater which is subjected to the microelectrolysis, adding the filtered wastewater into 30 percent of hydrogen peroxide, regulating the pH value to be 2 to 4, and treating for 2 to 5 hours, wherein 10 to 30 milliliters of hydrogen peroxide is added into each liter of wastewater; adding a flocculant polymeric aluminum chloride (PAC) into the wastewater for flocculating, regulating the pH value to be 8 to 10, and settling for 1 to 2 hours, wherein 200 to 500 milligrams of flocculant is added into each liter of wastewater; and after settling, filtering, and adsorbing the filtered wastewater by active carbon and resin, so that the removal rate of chemical oxygen demand (CODcr) is over 98 percent, and the emission standard is reached. The method is simple and good in treatment effect; equipment is small in investment and low in energy consumption; the removal rate of COD is high and is over 98 percent; and industrialization is easy to realize.
Description
Technical field
The present invention relates to the treatment process of a kind of vulcanization accelerator N cyclohexyl 2 benzothiazole sulfenamide (CBS, CZ) factory effluent, belong to environmental technology field.
Background technology
Accelerant CZ is the active aftereffect of a kind of height half ultra fast accelerator, and scorching quality is good, process safety, and curing time is short.Produce a large amount for the treatment of high-concentration saline organic wastewaters in the production process of accelerant CZ, be difficult to process, because the very large restriction that its production of environmental protection pressure and development are subject to.Waste water in the CZ production process is mainly derived from mother liquor distillation and washing process, and its salinity and COD concentration are higher, with color and smell, contains the multiple heterocycles organism in the water simultaneously, is difficult to it to be processed with methods such as biochemistry.Less to the improvement research report of such waste water at present, mostly be the techniques such as evaporative distillation, energy consumption is large, and treatment effect is relatively poor.Document (Nanjing Normal University's journal (engineering version), 2002,2:66) report is processed the accelerator CBS factory effluent with the method for evaporation concentration, this method is simple, but energy consumption is high, and the clearance of COD is general, and the high density still of generation is residual more difficult, and easily stop up vaporizer, cause equipment scrapping.Document (environmental engineering, 2007,4:78) reported the treatment process design of rubber accelerant wastewater, this article adopts and first highrank fuel salinity water is carried out the desalination pre-treatment with method of evaporating, and high-concentration waste water adopts little electrolysis～Fenton oxidation, flocculation precipitation method is processed, enter biochemical treatment again with after middle concentration waste water mixes, this complex process, long flow path through pretreated waste water, investment is large, and treatment effect is general.Patent (201010128489.2) has been mentioned the method for processing this waste water with electrolytic process, the method utilizes the high salt concentration ion in the water to conduct electricity, need not to add ionogen, the inferior sodium that anode produces is organism in the oxidizing water further, and its agglomerate is separated out again, but this method adopts noble metal electrode, investment is large, and resin easily is bonded on the electrode in the operational process, causes electrode to scrap, running cost is very high, long processing period.
Present method provides a kind of method of wastewater treatment, and facility investment is little, and treatment cycle is short, and treatment effect is better, and the waste water after the processing reaches emission request.
Summary of the invention
The object of the present invention is to provide a kind of method of processing the accelerator CZ factory effluent, the method facility investment is little, and process is simple, and energy consumption is low, and the clearance of COD is high, is easy to industrialization.
For achieving the above object, the present invention is realized by following technical proposals: a kind of with the soda acid flocculating settling, and little electrolysis, Fenton, flocculating settling, charcoal absorption, the method that resin absorption combines is processed, and treated waste water reenters the production system recycling.
Technical scheme of the present invention is as follows:
A kind of rubber vulcanizing accelerator CBS method of wastewater treatment: at first waste water is carried out the soda acid flocculation, the rear waste water of filtration enters the electrolyzer that micro-electrolysis stuffing is housed and carries out electrolysis and filtration, waste water after the filtration adds hydrogen peroxide again and carries out the Fenton oxidation, waste water after the oxidation flocculates, sedimentation, filtration, waste water after the filtration successively passes through gac and resin absorption, its COD
CrClearance reach more than 98%, reach emission standard.
A kind of rubber vulcanizing accelerator CBS method of wastewater treatment, waste water is carried out the soda acid flocculation, waste water enters the electrolyzer that micro-electrolysis stuffing is housed after filtering, at 60～80 ℃, little electrolysis 2～5 hours, waste water after little electrolysis filters, every liter of adding of waste water after the filtration 10～30ml hydrogen peroxide, the adding hydrogen peroxide concentration is 30% hydrogen peroxide, regulate pH=2～4, processed 2～5 hours, then the ratio adding flocculation agent PAC in 200～500mg/L waste water flocculates, regulate pH=8～10, the settling time is 1～2 hour; Filter first after the sedimentation, the waste water after the filtration successively passes through gac and resin absorption, its COD
CrClearance reach more than 98%.
Adopt the one-piece type micro-electrolysis stuffing of regular type Fe-C, make waste water submergence micro-electrolysis stuffing.
Adopt 20-40 purpose fruit tree gac, operation scheme is double-column series absorption, and the absorption flow rate control is at 1BV/h～1.5BV/h.
Adopting styrene-divinylbenzene copolymer is the nonpolar macroporous adsorption resin of skeleton.
The used acid of adjusting pH value that the present invention mentions is the acid such as the hydrochloric acid, sulfuric acid, nitric acid of conventional usefulness in the industry.
The used alkali of adjusting pH value that the present invention mentions is the alkali such as the sodium hydroxide, calcium hydroxide of conventional usefulness in the industry.
The gac of the use that the present invention mentions and resin can utilize conventional solvent to activate, for example hydrochloric acid, methyl alcohol equal solvent.
The invention has the advantages that: the method process is simple, and facility investment is little, and energy consumption is low, and the clearance of COD is high, can reach more than 98%, and treatment effect is better, reaches emission standard, is easy to industrialization.
Figure of description
Fig. 1: process flow sheet of the present invention.
Embodiment
Embodiments of the invention carry out according to the step of Fig. 1, are described as follows:
1. acid adjustment alkali filtration process: waste water is after grille well is removed wherein foreign material, enter equalizing tank, because the filtrate after the distillation is alkaline, add the polymerize aluminum chloride 1～2h that flocculates by 200-500mg/L waste water first, the material that is insoluble to alkali in the waste water is separated out, carry out single filter.After acid adding is regulated pH=3～4 again, add the polyacrylamide 1～2h that flocculates by 100-200mg/L waste water, the material that is insoluble to acid in the waste water is separated out, carry out cascade filtration.
2. little electrolysis process: the micro cell that waste water enters micro-electrolysis stuffing after filtering carries out microelectrolysis processing, make just submergence micro-electrolysis stuffing of waste water, temperature is 60～80 ℃, little electrolysis 2～5h, waste water after little electrolysis filters, and little electrolysis process can efficiently be removed COD, reduce colourity.
3.Fenton oxidizing process: the waste water behind little electrolytic filter enters the Fenton oxidation pond, adds 30% hydrogen peroxide with 10～30ml/L waste water, and acid adding is regulated pH=2～4, processes 2～5h.The Fenton oxidizing process can make most of organic matter degradations become small organic molecule, greatly reduces the difficulty of subsequent disposal.
4. flocculating settling technique: the waste water behind the Fenton is squeezed into the flocculating settling pond carry out flocculating settling, used flocculation agent is polymerize aluminum chloride, and additional proportion is 200～500ppm, adds alkali and regulates pH=8～10, and the settling time is 1～2h.The floss that this technique organism is flocculated precipitation is taken away, and greatly reduces the COD of waste water.
5. active carbon absorption technology: waste water enters active carbon adsorption column and carries out adsorption treatment after filtering, and reduces organic composition in the waste water, and the absorption flow rate control is at 1BV/h～1.5BV/h, and operation scheme is double-column series absorption.The colourity that greatly reduces waste water and the COD of this technique.
6. resin absorption technique: waste water enters resin absorbing column and carries out adsorption treatment after filtering, and reduces organic composition in the waste water, and the resin after the absorption adopts the blowback of methyl alcohol adverse current to carry out desorption and regeneration; Selecting styrene-divinylbenzene copolymer is the nonpolar macroporous adsorption resin of skeleton, and the absorption flow rate control is at 1BV/h～1.5BV/h, and operation scheme is double-column series absorption.After the resin absorption in the waste water organic CODcr further reduce (COD
CrAbout 60mg/L).
Embodiment 1:
In the soda acid flocculation basin, add CBS factory effluent 1000mL, add 200mg flocculant poly aluminum chloride and flocculate, filter behind the sedimentation 1h, add again dilute sulphuric acid and regulate pH=3, add 100mg flocculation agent polyacrylamide and flocculate, filter behind the sedimentation 1h.Waste water after the filtration joins in the integrated micro-electrolysis stuffing of 1700gFe-C, filters behind 60 ℃ of little electrolysis 2h.Waste water after the filtration enters the Fenton pond, adds the H of 10ml30%
2O
2, adding dilute sulphuric acid and regulate pH=2, reaction 2h adds 200mg flocculant poly aluminum chloride, regulates PH=8 with diluted sodium hydroxide solution and flocculates, and filters behind the sedimentation 1h.Waste water after the filtration successively enters the nonpolarity macroporous adsorptive resins chromatographic column that gac pillar that 20-40 order gac dresses up and styrene-divinylbenzene copolymer be skeleton and adsorbs, and the absorption flow rate control is at 1BV/h.The clearance of its COD can reach 98.1%, and the waste water after the processing reaches emission standard.
Embodiment 2:
Add CBS factory effluent 1000mL in the soda acid flocculation basin, add 300mg flocculant poly aluminum chloride and flocculate, sedimentation 1 rear filtration adds dilute hydrochloric acid again and regulates pH=3, adds 100mg flocculation agent polyacrylamide and flocculates, and filters behind the sedimentation 1h.Waste water after the filtration joins in the integrated micro-electrolysis stuffing of 1700gFe-C, filters behind 70 ℃ of little electrolysis 3h.Waste water after the filtration enters the Fenton pond, adds the H of 20ml30%
2O
2, adding again dilute hydrochloric acid and regulate pH=3, reaction 3h adds 400mg flocculant poly aluminum chloride, regulates PH=8.5 with rare aqua calcis and flocculates, and filters behind the sedimentation 1.5h.Waste water after the filtration successively enters the nonpolarity macroporous adsorptive resins chromatographic column that gac pillar that 20-40 order gac dresses up and styrene-divinylbenzene copolymer be skeleton and adsorbs, and the absorption flow rate control is at 1BV/h.The clearance of its COD can reach 98.3%, and the waste water after the processing reaches emission standard.
Embodiment 3:
In the soda acid flocculation basin, add CBS factory effluent 1000mL, add 400mg flocculant poly aluminum chloride and flocculate, filter behind the sedimentation 1h, add again rare nitric acid and regulate pH=3, add 200mg flocculation agent polyacrylamide and flocculate, filter behind the sedimentation 1h.Waste water after the filtration joins in the integrated micro-electrolysis stuffing of 1700gFe-C, filters behind 65 ℃ of little electrolysis 2.5h.Waste water after the filtration enters the Fenton pond, adds the H of 10ml30%
2O
2, adding again rare nitric acid and regulate pH=2, reaction 2.5h adds 300mg flocculant poly aluminum chloride, regulates PH=9 with dilute sodium hydroxide and flocculates, and filters behind the sedimentation 1h.Waste water after the filtration successively enters the nonpolarity macroporous adsorptive resins chromatographic column that gac pillar that 20-40 order gac dresses up and styrene-divinylbenzene copolymer be skeleton and adsorbs, and the absorption flow rate control is at 1.5BV/h.The clearance of its COD can reach 98.9%, and the waste water after the processing reaches emission standard.
Embodiment 4:
In the soda acid flocculation basin, add CBS factory effluent 1000mL, add 500mg flocculant poly aluminum chloride and flocculate, filter behind the sedimentation 2h, add again dilute sulphuric acid and regulate pH=4, add 200mg flocculation agent polyacrylamide and flocculate, filter behind the sedimentation 2h.Waste water after the filtration joins in the integrated micro-electrolysis stuffing of 1700gFe-C, filters behind 80 ℃ of little electrolysis 5h.Waste water after the filtration enters the Fenton pond, adds the H of 30ml30%
2O
2, adding again rare nitric acid and regulate pH=4, reaction 5h adds 500ppm flocculant poly aluminum chloride, regulates PH=10 with diluted sodium hydroxide solution and flocculates, and filters behind the sedimentation 2h.Waste water after the filtration successively enters the nonpolarity macroporous adsorptive resins chromatographic column that gac pillar that 20-40 order gac dresses up and styrene-divinylbenzene copolymer be skeleton and adsorbs, and the absorption flow rate control is at 1.5BV/h.The clearance of its COD can reach 98.6%, and the waste water after the processing reaches emission standard.
Claims (5)
1. rubber vulcanizing accelerator CBS method of wastewater treatment, it is characterized in that: at first waste water is carried out the soda acid flocculation, the rear waste water of filtration enters the electrolyzer that micro-electrolysis stuffing is housed and carries out electrolysis and filtration, waste water after the filtration adds hydrogen peroxide again and carries out the Fenton oxidation, waste water after the oxidation flocculates, sedimentation, filtration, waste water after the filtration successively passes through gac and resin absorption, its COD
CrClearance reach more than 98%.
2. rubber vulcanizing accelerator CBS method of wastewater treatment, it is characterized in that waste water is carried out the soda acid flocculation, waste water enters the electrolyzer that micro-electrolysis stuffing is housed after filtering, at 60～80 ℃, little electrolysis 2～5 hours, waste water after little electrolysis filters, every liter of adding of waste water after the filtration 10～30ml hydrogen peroxide, the adding hydrogen peroxide concentration is 30% hydrogen peroxide, regulate pH=2～4, processed 2～5 hours, then the ratio adding flocculation agent PAC in 200～500mg/L waste water flocculates, regulate pH=8～10, the settling time is 1～2 hour; Filter first after the sedimentation, the waste water after the filtration successively passes through gac and resin absorption, its COD
CrClearance reach more than 98%.
3. method as claimed in claim 1 or 2 is characterized in that adopting the one-piece type micro-electrolysis stuffing of regular type Fe-C, makes waste water submergence micro-electrolysis stuffing.
4. method as claimed in claim 1 or 2 is characterized in that adopting 20-40 purpose fruit tree gac, and operation scheme is double-column series absorption, and the absorption flow rate control is at 1BV/h～1.5BV/h.
5. method as claimed in claim 1 or 2, it is characterized in that adopting styrene-divinylbenzene copolymer is the nonpolar macroporous adsorption resin of skeleton.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529061A (en) * | 2014-12-13 | 2015-04-22 | 山东永泰化工有限公司 | Treatment process for rubber accelerator production wastewater |
| CN106673275A (en) * | 2017-02-24 | 2017-05-17 | 湖南瑞寰环境科技有限公司 | Method and device for treating biological organic wastewater containing ethylene oxide derivatives |
| CN113023972A (en) * | 2021-03-12 | 2021-06-25 | 南通寰宇博新化工环保科技有限公司 | High-salt organic wastewater treatment method based on electrochemical coupling hydrogen peroxide |
| CN114620852A (en) * | 2020-12-11 | 2022-06-14 | 圣奥化学科技有限公司 | Treatment method of wastewater from process for producing rubber vulcanization accelerator CBS by oxidation method |
| CN114620854A (en) * | 2020-12-11 | 2022-06-14 | 圣奥化学科技有限公司 | Treatment method of process wastewater generated in production of rubber vulcanization accelerator by oxidation method |
| CN116573816A (en) * | 2023-07-12 | 2023-08-11 | 东营巨宝工贸有限公司 | Treatment process of wastewater produced by vulcanization accelerator |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529061A (en) * | 2014-12-13 | 2015-04-22 | 山东永泰化工有限公司 | Treatment process for rubber accelerator production wastewater |
| CN104529061B (en) * | 2014-12-13 | 2016-02-17 | 山东永泰化工有限公司 | Rubber accelerant wastewater treatment process |
| CN106673275A (en) * | 2017-02-24 | 2017-05-17 | 湖南瑞寰环境科技有限公司 | Method and device for treating biological organic wastewater containing ethylene oxide derivatives |
| CN114620852A (en) * | 2020-12-11 | 2022-06-14 | 圣奥化学科技有限公司 | Treatment method of wastewater from process for producing rubber vulcanization accelerator CBS by oxidation method |
| CN114620854A (en) * | 2020-12-11 | 2022-06-14 | 圣奥化学科技有限公司 | Treatment method of process wastewater generated in production of rubber vulcanization accelerator by oxidation method |
| CN114620854B (en) * | 2020-12-11 | 2024-03-15 | 圣奥化学科技有限公司 | Treatment method of process wastewater from rubber vulcanization accelerator production by oxidation method |
| CN113023972A (en) * | 2021-03-12 | 2021-06-25 | 南通寰宇博新化工环保科技有限公司 | High-salt organic wastewater treatment method based on electrochemical coupling hydrogen peroxide |
| CN116573816A (en) * | 2023-07-12 | 2023-08-11 | 东营巨宝工贸有限公司 | Treatment process of wastewater produced by vulcanization accelerator |
| CN116573816B (en) * | 2023-07-12 | 2023-09-19 | 东营巨宝工贸有限公司 | Treatment process of wastewater produced by vulcanization accelerator |
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