CN102838238A - Wastewater treatment method for rubber vulcanization accelerator MBT (2-meraptobenzothiazole) - Google Patents
Wastewater treatment method for rubber vulcanization accelerator MBT (2-meraptobenzothiazole) Download PDFInfo
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- CN102838238A CN102838238A CN2012103633581A CN201210363358A CN102838238A CN 102838238 A CN102838238 A CN 102838238A CN 2012103633581 A CN2012103633581 A CN 2012103633581A CN 201210363358 A CN201210363358 A CN 201210363358A CN 102838238 A CN102838238 A CN 102838238A
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Abstract
The invention discloses a wastewater treatment method for rubber vulcanization accelerator MBT (2-meraptobenzothiazole). The wastewater treatment method comprises the following steps of: performing acidic and alkaline flocculation on wastewater; feeding filtered wastewater in an electrolytic cell filled with micro-electrolysis filler; performing micro-electrolysis for 2-5 hours at 60-80 DEG C; filtering the micro-electrolyzed wastewater; adding hydrogen peroxide with concentration into the filtered wastewater according to the proportion of 10-30 ml of hydrogen peroxide per every liter of filtered wastewater; adjusting pH (Potential of Hydrogen) to be 2-4; treating for 2-5 hours; adding flocculant PAC (Polymeric Aluminum Chloride) according to proportion of 200-500 mg of flocculant PAC per 1 L of wastewater for flocculation; adjusting pH to be 8-10; settling for 1-2 hours; and after settlement, firstly filtering and then adsorbing the filtered wastewater through active carbon and resin in sequence, wherein the removal rate of COD cr (Chemical Oxygen Demand cr) reaches over 98 percent to reach the emission standard. The method has the advantages of simple process, less equipment investment, low energy consumption, high COD removal rate, capability of reaching over 98 percent, good treatment effect, capability of reaching the emission standard and easiness in industrialization.
Description
Technical field
The present invention relates to the treatment process of a kind of vulcanization accelerator 2-thiol benzothiazole (MBT) factory effluent, belong to environmental technology field.
Background technology
Accelerant MBT is the universal promotor of a kind of rubber, is widely used in various rubber, natural gum is combined to glue with general sulphur has quick promoter action, also can be used as the chemical plasticizing agent.There is bitter taste not to be easy for making the rubber item with Food Contact.Be mainly used in and make the inner tube of a tyre, adhesive tape, rubber overshoes and mechanicals etc.Accelerant MBT also is a raw material of producing rubber accelerator TBBS, DCBS, MBTS etc., is one of important kind of sulfenamide vulcanization accelerator.Document " resin adsorption is handled the research of accelerator M wastewater " (Techniques and Equipment for Environmental Pollution Control; The 5th the 7th phase of volume), mentioned employing resin absorption-NaClO aeration oxidation second-stage treatment technology, substep is removed the method for organic pollutant and waste water sulfide; This kind method is simple to operate; Waste water after the processing can reach national grade one discharge standard, but this method consumption processing cost is quite high, has limited its widespread usage in industry.
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 accelerator M BT 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 vulcanization accelerant MBT 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 vulcanization accelerant MBT 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 MBT 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 MBT 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 MBT 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 MBT 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 vulcanization accelerant MBT 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%.
2. a kind of rubber vulcanization accelerant MBT method of wastewater treatment of claim 1: 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%.
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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563217A (en) * | 2019-08-13 | 2019-12-13 | 广东上智环保科技有限公司 | Sewage treatment process and equipment |
| CN112479462A (en) * | 2020-12-09 | 2021-03-12 | 山东宸奎环保科技有限公司 | Zero-discharge treatment system and process for industrial wastewater containing MBT (moving bed reactor) |
| 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 |
Citations (4)
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| KR20020076063A (en) * | 2001-03-27 | 2002-10-09 | 금호산업 주식회사 | Dispersion-Improved Silica-filled SBR compounds for Tire |
| JP2007231177A (en) * | 2006-03-01 | 2007-09-13 | Toyo Tire & Rubber Co Ltd | Rubber composition for tire tread |
| CN101734817A (en) * | 2009-12-31 | 2010-06-16 | 江苏苏净集团有限公司 | Method for treating organic chemical waste water |
| CN102432136A (en) * | 2011-09-20 | 2012-05-02 | 科迈化工股份有限公司 | Method for treating wastewater of rubber vulcanization accelerator N-cyclohexyl-2-benzothiazole sulfonamide |
-
2012
- 2012-09-25 CN CN2012103633581A patent/CN102838238A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020076063A (en) * | 2001-03-27 | 2002-10-09 | 금호산업 주식회사 | Dispersion-Improved Silica-filled SBR compounds for Tire |
| JP2007231177A (en) * | 2006-03-01 | 2007-09-13 | Toyo Tire & Rubber Co Ltd | Rubber composition for tire tread |
| CN101734817A (en) * | 2009-12-31 | 2010-06-16 | 江苏苏净集团有限公司 | Method for treating organic chemical waste water |
| CN102432136A (en) * | 2011-09-20 | 2012-05-02 | 科迈化工股份有限公司 | Method for treating wastewater of rubber vulcanization accelerator N-cyclohexyl-2-benzothiazole sulfonamide |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563217A (en) * | 2019-08-13 | 2019-12-13 | 广东上智环保科技有限公司 | Sewage treatment process and equipment |
| CN112479462A (en) * | 2020-12-09 | 2021-03-12 | 山东宸奎环保科技有限公司 | Zero-discharge treatment system and process for industrial wastewater containing MBT (moving bed reactor) |
| 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 |
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Application publication date: 20121226 |