CN102826696A - Rubber vulcanization accelerator TBBS (N-tert-butyl-2-benzothiazolesulfenamide) wastewater treatment method - Google Patents
Rubber vulcanization accelerator TBBS (N-tert-butyl-2-benzothiazolesulfenamide) wastewater treatment method Download PDFInfo
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- CN102826696A CN102826696A CN2012103624440A CN201210362444A CN102826696A CN 102826696 A CN102826696 A CN 102826696A CN 2012103624440 A CN2012103624440 A CN 2012103624440A CN 201210362444 A CN201210362444 A CN 201210362444A CN 102826696 A CN102826696 A CN 102826696A
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Abstract
The invention discloses a rubber vulcanization accelerator TBBS (N-tert-butyl-2-benzothiazolesulfenamide) wastewater treatment method which comprises the following steps: carrying out acid-alkali flocculation on wastewater, filtering, and sending the filtered wastewater into an electrolytic bath filled with a microelectrolysis filler; carrying out microelectrolysis at 60-80 DEG C for 2-5 hours, filtering, adding the filtered wastewater into 30% oxydol according to 10-30ml oxydol/L wastewater, regulating the pH value to 2-4, treating for 2-5 hours, adding 200-500 mg/L of flocculant PAC into every liter of wastewater to carry out flocculation, regulating the pH value to 8-10, and depositing for 1-2 hours; and after the deposition, filtering, sequentially passing the filtered wastewater through activated carbon and resin for adsorption. The CODcr (chemical oxygen demand) removal rate is up to higher than 98%, and satisfies the discharge standard. The method disclosed by the invention has the advantages of simple process, low equipment investment, low energy consumption, high COD removal rate (higher than 98%) and favorable treatment effect, satisfies the discharge standard and can easily implement industrialization.
Description
Technical field
The present invention relates to the treatment process of a kind of vulcanization accelerator N-tertiary butyl-2-benzothiazole sulfonamide (TBBS, NS) factory effluent, belong to environmental technology field.
Background technology
Accelerator NS is a kind of rubber moderate accelerator; It is one of important kind of sulfenamide vulcanization accelerator; Have anti-incipient scorch property and vulcanization rate fast two big advantages concurrently; Be the principal item of the novel promotor of instead of rubber vulcanizating accelerant NOBS, but its production technique produce a large amount of high-salt wastewaters that is difficult to administer, and has limited its development.Research (the pollution prevention technique of document Fenton reagent oxidation pretreatment of rubber accelerator NS factory effluent; The 22nd the 5th phase of volume); Mentioned method with the actual oxidation pretreatment of rubber of Fenton accelerator NS factory effluent; But the treatment effect of this method is relatively poor, and the clearance of COD has only more than 70%, does not reach the emission standard requirement far away.Process for treating waste water of rubber vulcanization accelerator NS production (CN101407344A) has proposed to handle with multiple-effect evaporation the method for promotor waste water; But this technological equipment investment is big; Power consumption is big, and factor such as easy blocking heat transfer tube has limited its widespread usage in industry in the operational process.
Present method provides a kind of method of wastewater treatment, and facility investment is little, and the processing cycle is short, and treatment effect is preferable, 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 handling the vulcanization accelerator NS factory effluent, this method facility investment is little, and process is simple, and energy consumption is low, and the clearance of COD is high, is easy to industriallization.
For achieving the above object, the present invention realizes through 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 handled, and treated waste water gets into the production system recycling again.
Technical scheme of the present invention is following:
A kind of rubber vulcanizing accelerator TBBS method of wastewater treatment: at first waste water is carried out the soda acid flocculation; Filtration back waste water gets into the electrolyzer that micro-electrolysis stuffing is housed and carries out electrolysis and filtration; Waste water after the filtration adds ydrogen peroxide 50 again and carries out the Fenton oxidation; Waste water after the oxidation flocculates, sedimentation, filtration, and the 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 TBBS method of wastewater treatment: waste water is carried out the soda acid flocculation, filter back waste water and get into the electrolyzer that micro-electrolysis stuffing is housed, at 60～80 ℃; Little electrolysis 2～5 hours, the waste water after little electrolysis filters, and the waste water after the filtration adds 10～30ml ydrogen peroxide 50 for every liter; The adding hydrogen peroxide concentration is 30% ydrogen peroxide 50; Regulate pH=2～4, handled 2～5 hours, the ratio adding flocculation agent PAC in 200～500mg/L waste water flocculates then; Regulate pH=8～10, the settling time is 1～2 hour; Filter earlier 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 the twin columns series adsorption, 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 mentioned is 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 mentioned is alkali such as the sodium hydroxide, calcium hydroxide of conventional usefulness in the industry.
The gac of the use that the present invention mentioned and resin can utilize conventional solvent to carry out activation, for example hydrochloric acid, methyl alcohol equal solvent.
The invention has the advantages that: this procedure 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 preferable, reaches emission standard, is easy to industriallization.
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, explain as follows:
1. acid adjustment alkali filtration process: waste water is after grille well is removed foreign material wherein; Get into equalizing tank,, add the Poly aluminum Chloride (PAC) 1～2h that flocculates by 200-500mg/L waste water earlier because the filtrating after the distillation is alkaline; The material that is insoluble to alkali in the waste water is separated out, carry out one-level and filter.After adding acid for adjusting pH=3～4 again, add the SEPIGEL 305 1～2h that flocculates, the material that is insoluble to acid in the waste water is separated out, carry out cascade filtration by 100-200mg/L waste water.
2. little electrolysis process: the micro cell that filters back waste water entering micro-electrolysis stuffing carries out little electrolysis treatment; 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 gets into the Fenton oxidation pond, and the ydrogen peroxide 50 with 10～30ml/L waste water adding 30% adds acid for adjusting pH=2～4, handles 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 technology: the waste water behind the Fenton is squeezed into the flocculating settling pond carry out flocculating settling, used flocculation agent is a Poly aluminum Chloride (PAC), and additional proportion is 200～500ppm, adds alkali and regulates pH=8～10, and the settling time is 1～2h.This technology organism is taken away by the floss of flocculation sediment, greatly reduces the COD of waste water.
5. active carbon absorption technology: filter back waste water and get into active carbon adsorption column and carry out adsorption treatment, reduce organic composition in the waste water, the absorption flow rate control is at 1BV/h～1.5BV/h, and operation scheme is the twin columns series adsorption.The colourity that greatly reduces waste water and the COD of this technology.
6. resin absorption technique: filter back waste water and get into the resin absorption post and carry out adsorption treatment, reduce organic composition in the waste water, 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 the twin columns series adsorption.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 TBBS factory effluent 1000mL, add 200mg flocculant poly aluminum chloride and flocculate, sedimentation 1h after-filtration adds dilute sulphuric acid again and regulates pH=3, adds 100mg flocculation agent SEPIGEL 305 and flocculates sedimentation 1h after-filtration.Waste water after the filtration joins in the incorporate micro-electrolysis stuffing of 1700gFe-C, 60 ℃ of little electrolysis 2h after-filtration.Waste water after the filtration gets into 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 sedimentation 1h after-filtration.Waste water after the filtration successively gets into 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:
In the soda acid flocculation basin, add TBBS factory effluent 1000mL, add 300mg flocculant poly aluminum chloride and flocculate, sedimentation 1 after-filtration adds Hydrogen chloride again and regulates pH=3, adds 100mg flocculation agent SEPIGEL 305 and flocculates sedimentation 1h after-filtration.Waste water after the filtration joins in the incorporate micro-electrolysis stuffing of 1700gFe-C, 70 ℃ of little electrolysis 3h after-filtration.Waste water after the filtration gets into the Fenton pond, adds the H of 20ml30%
2O
2, adding Hydrogen chloride again and regulate pH=3, reaction 3h adds 400mg flocculant poly aluminum chloride, regulates PH=8.5 with rare aqua calcis and flocculates sedimentation 1.5h after-filtration.Waste water after the filtration successively gets into 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 TBBS factory effluent 1000mL, add 400mg flocculant poly aluminum chloride and flocculate, sedimentation 1h after-filtration adds rare nitric acid again and regulates pH=3, adds 200mg flocculation agent SEPIGEL 305 and flocculates sedimentation 1h after-filtration.Waste water after the filtration joins in the incorporate micro-electrolysis stuffing of 1700gFe-C, 65 ℃ of little electrolysis 2.5h after-filtration.Waste water after the filtration gets into the Fenton pond, adds the H of 10ml30%
2O
2, adding rare nitric acid again and regulate pH=2, reaction 2.5h adds 300mg flocculant poly aluminum chloride, regulates PH=9 with dilute sodium hydroxide and flocculates sedimentation 1h after-filtration.Waste water after the filtration successively gets into 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 TBBS factory effluent 1000mL, add 500mg flocculant poly aluminum chloride and flocculate, sedimentation 2h after-filtration adds dilute sulphuric acid again and regulates pH=4, adds 200mg flocculation agent SEPIGEL 305 and flocculates sedimentation 2h after-filtration.Waste water after the filtration joins in the incorporate micro-electrolysis stuffing of 1700gFe-C, 80 ℃ of little electrolysis 5h after-filtration.Waste water after the filtration gets into the Fenton pond, adds the H of 30ml30%
2O
2, adding rare nitric acid again and regulate pH=4, reaction 5h adds 500ppm flocculant poly aluminum chloride, regulates PH=10 with diluted sodium hydroxide solution and flocculates sedimentation 2h after-filtration.Waste water after the filtration successively gets into 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 TBBS method of wastewater treatment; It is characterized in that: at first waste water is carried out the soda acid flocculation; Filter back waste water and get into the electrolyzer that micro-electrolysis stuffing is housed and carry out electrolysis and filter, the waste water after the filtration adds ydrogen peroxide 50 again and carries out the Fenton oxidation, and the 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.
2. a rubber vulcanizing accelerator TBBS method of wastewater treatment is characterized in that waste water is carried out the soda acid flocculation, filters back waste water and gets into the electrolyzer that micro-electrolysis stuffing is housed; At 60～80 ℃, little electrolysis 2～5 hours, the waste water after little electrolysis filters; Waste water after the filtration adds 10～30ml ydrogen peroxide 50 for every liter, and the adding hydrogen peroxide concentration is 30% ydrogen peroxide 50, regulates pH=2～4; Handled 2～5 hours; Ratio adding flocculation agent PAC in 200～500mg/L waste water flocculates then, regulates pH=8～10, and the settling time is 1～2 hour; Filter earlier after the sedimentation, the waste water after the filtration successively passes through gac and resin absorption, its COD
CrClearance reach more than 98%.
3. according to claim 1 or claim 2 method 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. according to claim 1 or claim 2 method is characterized in that adopting 20-40 purpose fruit tree gac, and operation scheme is the twin columns series adsorption, and the absorption flow rate control is at 1BV/h～1.5BV/h.
5. according to claim 1 or claim 2 method, it is characterized in that adopting styrene-divinylbenzene copolymer is the nonpolar macroporous adsorption resin of skeleton.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107698078A (en) * | 2017-11-13 | 2018-02-16 | 广州桑尼环保科技有限公司 | Pretreatment method and treatment system for explosive production wastewater |
| CN111925074A (en) * | 2020-09-07 | 2020-11-13 | 山东德利环保工程有限公司 | Novel landfill leachate treatment system and process |
| 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 |
| CN114620853A (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 DZ by sodium hypochlorite method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107698078A (en) * | 2017-11-13 | 2018-02-16 | 广州桑尼环保科技有限公司 | Pretreatment method and treatment system for explosive production wastewater |
| CN107698078B (en) * | 2017-11-13 | 2021-04-02 | 广州桑尼环保科技有限公司 | Pretreatment method and treatment system for explosive production wastewater |
| CN111925074A (en) * | 2020-09-07 | 2020-11-13 | 山东德利环保工程有限公司 | Novel landfill leachate treatment system and process |
| 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 |
| CN114620853A (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 DZ by sodium hypochlorite 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 |
| CN114620853B (en) * | 2020-12-11 | 2024-04-09 | 圣奥化学科技有限公司 | Treatment method of process wastewater for producing rubber vulcanization accelerator DZ by sodium hypochlorite method |
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Application publication date: 20121219 |