CN102432136A - Method for treating wastewater of rubber vulcanization accelerator N-cyclohexyl-2-benzothiazole sulfonamide - Google Patents
Method for treating wastewater of rubber vulcanization accelerator N-cyclohexyl-2-benzothiazole sulfonamide Download PDFInfo
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- CN102432136A CN102432136A CN2011102800972A CN201110280097A CN102432136A CN 102432136 A CN102432136 A CN 102432136A CN 2011102800972 A CN2011102800972 A CN 2011102800972A CN 201110280097 A CN201110280097 A CN 201110280097A CN 102432136 A CN102432136 A CN 102432136A
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Abstract
The invention belongs to a method for treating wastewater of a rubber vulcanization accelerator N-cyclohexyl-2-benzothiazole sulfonamide (CZ). The method comprises: returning 30%-40% of generated wastewater into a CZ synthesis reaction vessel for indiscriminate application, subjecting the rest part to vacuum distillation, recovering cyclohexylamine; precipitating organic components dissolved in cyclohexylamine, filtering the recovered mother liquid, and putting the precipitated organic matter into the synthesis reaction vessel for continuous reaction, and leading the filtrate to multiple-effect evaporation so as to obtain a sodium chloride saturated solution, conducting concentration so as to obtain a supersaturated solution of sodium chloride, and carrying out centrifugation, thus obtaining sodium chloride; returning part of the evaporated water to the device for reuse, and leaving the left part to biochemical treatment. In order to make the raw material M completely reacted during production, excess cyclohexylamine is added, so that a great amount of cyclohexylamine is contained in the wastewater. By adopting a mother liquid indiscriminate application technology, the mother liquid can be recycled, the primary utilization rate of cyclohexylamine can be enhanced, simultaneously the mother liquid treatment cost can be reduced, and the CZ yield can be improved. After mother liquid indiscriminate application, the CZ product has no abnormal change in appearance, and no obvious change in melting point as well as ash content.
Description
Technical field
The invention belongs to thiofide N-cyclohexyl-2-benzothiazole sulfonamide method of wastewater treatment, belong to field of fine chemical.
Background technology
Rubber vulcanizing accelerator CBS (CZ), chemical name is a N cyclohexyl 2 benzothiazole sulfenamide, is one of important kind of sulfenamide vulcanization accelerator, has advantages such as anti-burning property and vulcanization rate be fast concurrently.Be difficult to the high-salt wastewater administered in a large number but produce during it is produced, cause that progress is slow for many years,, still have waste liquid directly to discharge, caused baneful influence for our living environment though auxiliary agent industry waste water is treated at present.According to rubber ingredients wastewater treatment present situation, main at present physico-chemical process, the biochemical treatment process of adopting.Physico-chemical processes is simple, and is easy to operate, but processing cost is high; The biochemical method processing cost is low, but complex process, the harsh difficult operation of condition.The present invention is based on present present situation, propose new operational path, effectively solve auxiliary agent industry high-salt wastewater and handle problems.
Summary of the invention
The object of the invention is to solve the difficult problem that the thiofide high-salt wastewater is handled, and a kind of production technique of cleaning is provided for Rubber Chemicals Industries.
The present invention is the method for wastewater treatment of rubber vulcanization accelerant CZ, the waste liquid 30%-40% that produces is turned back to the CZ synthesis reaction vessel apply mechanically, and remaining part reclaims hexahydroaniline through vacuum distilling; The organic composition that is dissolved in hexahydroaniline is separated out, and the mother liquor after reclaiming is filtered, and the organism of separating out drops into and continues reaction in the synthesis reaction vessel; Filtrating is introduced multiple-effect evaporation; Obtain sodium chloride saturated solution, be concentrated to the supersaturated solution of sodium-chlor, the mode through spinning obtains sodium-chlor; Evaporate the water section return mechanism reuse that, remaining part carries out biochemical treatment.
The present invention is when vacuum distilling, and it is temperature required to be 70～80 ℃, and vacuum tightness is-0.6～-0.8MPa.
Biochemical treatment is to add flocculation sediment behind the acid-alkali accommodation, through second resin absorption, add hypochlorite oxidation again after emission concentration reach COD
CrBe lower than 60mg/L.
Described resin is the nonpolar macroporous adsorption resin that adopts vinylbenzene-divinylbenzene skeleton.
Through the mother liquor distillation, can recycle hexahydroaniline; Through multiple-effect evaporation, can effectively extract sodium-chlor wherein; Through biochemical treatment, can effectively remove pollution factor in the water, reduce its COD
Cr, final row's mouthful emission concentration is COD
CrBe lower than 60mg/L.This handles more satisfactory technology for the rubber ingredients high-salt wastewater, has solved the Rubber Chemicals Industries high-salt wastewater and has handled a difficult problem.
Production process reacts completely for making raw material M, adds excessive hexahydroaniline, so contains a large amount of hexahydroaniline in the waste liquid; Adopt mother liquid recycle technology, mother liquid recycling improves a utilization ratio of hexahydroaniline (10%-30%); Reduce the mother liquor processing costs simultaneously, improve the CZ yield.CZ product behind mother liquid recycle, the no abnormal variation of outward appearance, fusing point, ash content do not have considerable change.
Description of drawings
Fig. 1: process flow diagram of the present invention.
Embodiment
In the production process, with raw material M, hexahydroaniline, Youxiaolin (process water 3.5-4.0m proportionally
3, M1.2t, the about 1kg of skimmer) and the input reaction kettle synthesizes successively, oxidizing reaction, when technology proceeds to synthetic CZ slip, obtains CZ mother liquor (COD after the filtration
CrAbout 1500mg/L) time, mother liquor is the waste water that rubber vulcanization accelerant CZ produces.Through filtering CZ mother liquor and material are separated, mother liquor sedimentation for some time, extract the mother liquor of bottom about 1/3 (30%-40%) out with pump; To send in the CZ synthesis reaction vessel, replace process water to pull an oar, the residue mother liquor is-0.6 in vacuum tightness～-0.8MPa; Temperature is underpressure distillation under 70～80 ℃ of states, reclaims hexahydroaniline, after the distillation mother liquor is filtered; Filtrating is introduced multi-effect evaporating device, concentrates the supersaturated solution that obtains sodium-chlor, and the mode through spinning obtains sodium-chlor.Evaporate the water (COD that
Cr500mg/L) 50% (according to the actual production consumption) return mechanism reuse; Remaining part carries out biochemical treatment; The mode that adopts acid adjustment alkali flocculating settling+resin absorption (nonpolar macroporous adsorption resin of vinylbenzene-divinylbenzene skeleton)+deep oxidation to handle (hypochlorite oxidation) is handled, and concrete technology is divided into three steps:
Acid adjustment alkali filtration process: sewage gets into equalizing tank after grille well is removed foreign material wherein, adds acid successively, adds the alkali adjusting: to pH=3-4, flocculation separated out the material that is insoluble to acid in the sewage more than 4 hours, carried out one-level and filtered through acid adjustment.Again through toning alkali to pH=7-8, flocculated 2-4 hour, the material that is insoluble to alkali in the sewage is separated out, carry out cascade filtration.
Resin absorption technique: filter back sewage entering resin absorption post and carry out adsorption treatment, reduce organic composition in the sewage, the resin after the absorption adopts the blowback of methyl alcohol adverse current to carry out desorption and regeneration; Select the nonpolar macroporous adsorption resin of vinylbenzene-divinylbenzene skeleton, the absorption flow rate control is at 1BV/h～1.5BV/h, and operation scheme is twin columns series adsorption, the reverse desorption of single-column, and desorbing agent selects to organically blend agent methyl alcohol.
Biochemical processing process: the aeration oxidation pond adopts hypochlorite oxidation technology, and organic CODcr in the sewage after the resin absorption is further reduced (COD
CrAbout 60mg/L).Sewage after the absorption carries out biochemical treatment, further removes wherein organism and ammonia nitrogen, removes suspended substance and organism through husky filter, activated charcoal filter again.
Adopt the mode of mother liquid recycle to reduce the CZ wastewater treatment capacity, improved utilization ratio of hexahydroaniline (improving 10%-30%), reduce the mother liquor processing costs simultaneously; Adopt multiple-effect evaporation, extract sodium-chlor wherein, effectively reduce waste water saltiness (reducing by 95%).The final emission concentration COD of CZ waste water
CrBe lower than 60mg/L, meet the requirement of DB12/356-2008 " integrated wastewater discharge standard " secondary standard.
Claims (4)
1. thiofide N-cyclohexyl-2-benzothiazole sulfonamide method of wastewater treatment is characterized in that: the waste liquid 40%-60% that produces is turned back to the CZ synthesis reaction vessel apply mechanically, remaining part is through vacuum distilling, the recovery hexahydroaniline; The organic composition that is dissolved in hexahydroaniline is separated out, and the mother liquor after reclaiming is filtered, and the organism of separating out drops into and continues reaction in the synthesis reaction vessel; Filtrating is introduced multiple-effect evaporation; Obtain sodium chloride saturated solution, be concentrated to the supersaturated solution of sodium-chlor, the mode through spinning obtains sodium-chlor; Evaporate the water section return mechanism reuse that, remaining part carries out biochemical treatment.
2. method according to claim 1 is characterized in that: during vacuum distilling, it is temperature required to be 70～80 ℃, vacuum tightness is-0.6～-0.8MPa.
3. method according to claim 1 is characterized in that: described biochemical treatment is to add flocculation sediment behind the acid-alkali accommodation, through second resin absorption, add hypochlorite oxidation again after emission concentration reach COD
CrBe lower than 60mg/L.
4. method as claimed in claim 3 is characterized in that described resin is the nonpolar macroporous adsorption resin that adopts vinylbenzene-divinylbenzene skeleton.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826696A (en) * | 2012-09-25 | 2012-12-19 | 科迈化工股份有限公司 | Rubber vulcanization accelerator TBBS (N-tert-butyl-2-benzothiazolesulfenamide) wastewater treatment method |
| CN102838238A (en) * | 2012-09-25 | 2012-12-26 | 科迈化工股份有限公司 | Wastewater treatment method for rubber vulcanization accelerator MBT (2-meraptobenzothiazole) |
| CN102838237A (en) * | 2012-09-25 | 2012-12-26 | 科迈化工股份有限公司 | Treatment method of rubber vulcanization accelerator MBTS (2,2'-dithiobis(benzothiazole)) wastewater |
| CN102838239A (en) * | 2012-09-25 | 2012-12-26 | 科迈化工股份有限公司 | DPG wastewater treatment method by using rubber vulcanization accelerator |
| CN103804319A (en) * | 2014-03-06 | 2014-05-21 | 东营万通橡胶助剂有限公司 | Process for recycling accelerator M from residual liquid of rubber accelerator CZ distillation still |
| CN105417822A (en) * | 2015-12-17 | 2016-03-23 | 科迈化工股份有限公司 | Method for treating rubber vulcanization accelerator wastewater by combination of MVR (mechanical vapor recompression) evaporation and chemical treatment |
| CN106495393A (en) * | 2016-10-12 | 2017-03-15 | 湖北绿色家园精细化工股份有限公司 | A kind of method of diluent wastewater treatment with recycling |
| CN106587476A (en) * | 2016-12-21 | 2017-04-26 | 科迈化工股份有限公司 | Method for treatment of mixed wastewater produced during production of rubber accelerator NS\CZ\DZ |
| CN107619145A (en) * | 2017-11-06 | 2018-01-23 | 山东阳谷华泰化工股份有限公司 | A kind of processing method of anti-recovery agent production waste water |
| 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 |
| CN109896714A (en) * | 2019-04-16 | 2019-06-18 | 郑州铂来化研科技有限公司 | The preprocess method of rubber chemicals CBS production waste water |
| CN114516978A (en) * | 2022-03-02 | 2022-05-20 | 山东阳谷华泰化工股份有限公司 | Method for mechanically applying vulcanization accelerator DZ mother liquor for rubber and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5507951A (en) * | 1994-02-23 | 1996-04-16 | Wright Chemical Corporation | Method for treating hexamine waste water |
| CN101407344A (en) * | 2008-11-12 | 2009-04-15 | 山东阳谷华泰化工有限公司 | Process for treating waste water of rubber vulcanization accelerator NS production |
| CN101885494A (en) * | 2010-06-24 | 2010-11-17 | 山东阳谷华泰化工股份有限公司 | Purification technology for producing salt in waste water by thiofide |
-
2011
- 2011-09-20 CN CN2011102800972A patent/CN102432136A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5507951A (en) * | 1994-02-23 | 1996-04-16 | Wright Chemical Corporation | Method for treating hexamine waste water |
| CN101407344A (en) * | 2008-11-12 | 2009-04-15 | 山东阳谷华泰化工有限公司 | Process for treating waste water of rubber vulcanization accelerator NS production |
| CN101885494A (en) * | 2010-06-24 | 2010-11-17 | 山东阳谷华泰化工股份有限公司 | Purification technology for producing salt in waste water by thiofide |
Non-Patent Citations (2)
| Title |
|---|
| 王力友: "橡胶助剂CBS废水处理的试验研究", 《化学工程师》, no. 1, 28 February 2003 (2003-02-28) * |
| 陈一良,张全兴,王海玲等: "树脂吸附-NaClO曝气氧化法处理促进剂M废水的研究", 《环境污染治理技术与设备》, vol. 5, no. 7, 31 July 2004 (2004-07-31) * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838238A (en) * | 2012-09-25 | 2012-12-26 | 科迈化工股份有限公司 | Wastewater treatment method for rubber vulcanization accelerator MBT (2-meraptobenzothiazole) |
| CN102838237A (en) * | 2012-09-25 | 2012-12-26 | 科迈化工股份有限公司 | Treatment method of rubber vulcanization accelerator MBTS (2,2'-dithiobis(benzothiazole)) wastewater |
| CN102838239A (en) * | 2012-09-25 | 2012-12-26 | 科迈化工股份有限公司 | DPG wastewater treatment method by using rubber vulcanization accelerator |
| CN102826696A (en) * | 2012-09-25 | 2012-12-19 | 科迈化工股份有限公司 | Rubber vulcanization accelerator TBBS (N-tert-butyl-2-benzothiazolesulfenamide) wastewater treatment method |
| CN103804319A (en) * | 2014-03-06 | 2014-05-21 | 东营万通橡胶助剂有限公司 | Process for recycling accelerator M from residual liquid of rubber accelerator CZ distillation still |
| CN105417822B (en) * | 2015-12-17 | 2018-03-27 | 科迈化工股份有限公司 | The method for being combined processing thiofide waste water is evaporated and is chemically treated using MVR |
| CN105417822A (en) * | 2015-12-17 | 2016-03-23 | 科迈化工股份有限公司 | Method for treating rubber vulcanization accelerator wastewater by combination of MVR (mechanical vapor recompression) evaporation and chemical treatment |
| CN106495393A (en) * | 2016-10-12 | 2017-03-15 | 湖北绿色家园精细化工股份有限公司 | A kind of method of diluent wastewater treatment with recycling |
| CN106587476A (en) * | 2016-12-21 | 2017-04-26 | 科迈化工股份有限公司 | Method for treatment of mixed wastewater produced during production of rubber accelerator NS\CZ\DZ |
| CN107619145A (en) * | 2017-11-06 | 2018-01-23 | 山东阳谷华泰化工股份有限公司 | A kind of processing method of anti-recovery agent production waste water |
| CN107619145B (en) * | 2017-11-06 | 2020-11-17 | 山东阳谷华泰化工股份有限公司 | Treatment method of anti-vulcanization reversion agent production wastewater |
| 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 |
| CN109896714A (en) * | 2019-04-16 | 2019-06-18 | 郑州铂来化研科技有限公司 | The preprocess method of rubber chemicals CBS production waste water |
| CN109896714B (en) * | 2019-04-16 | 2022-01-04 | 郑州铂来化研科技有限公司 | Pretreatment method of rubber auxiliary CBS production wastewater |
| CN114516978A (en) * | 2022-03-02 | 2022-05-20 | 山东阳谷华泰化工股份有限公司 | Method for mechanically applying vulcanization accelerator DZ mother liquor for rubber and application thereof |
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Application publication date: 20120502 |