煤化工含酚废水高效萃取研究
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摘要
针对煤化工含酚废水常用的MIBK、DIPE萃取剂对多元酚的萃取效率低等问题,开发出一种新型的酚类物质萃取剂-环己酮,对比了环己酮与MIBK、DIPE萃取效果,探讨了萃取相比、萃取温度、pH等主要影响因素,并进行了萃取剂回收试验。结果表明:环己酮对对苯二酚、间苯三酚的萃取效果分别高达91.65%、83.52%,远高于MIBK的74.05%、49.77%和DIPE的27.95%和7.84%;在温度40℃、相比1∶3、pH在8及以下的最优条件下,环己酮对苯酚、间甲酚、对苯二酚和间苯三酚4种典型的酚的萃取率分别为98.30%、96.83%、96.31%、91.67%;在最优条件下,对按不同配比的初始浓度分别为750 mg/L、1 000 mg/L的混合配水进行环己酮萃取,单元酚和多元酚去除率分别高达97.81%、94.74%、96.96%、94.31%;在温度为155℃,常压下对混合废水萃取液进行蒸馏回收试验,环己酮的回收率可达95.5%以上。新型高效脱酚萃取剂环己酮的开发可以有效降低水中酚的浓度,减轻后续生化处理负担,为该类煤化工废水的处理与综合利用、行业的可持续发展提供技术参考。
Due to the problems of low extraction efficiency of polyphenols by MIBK and DIPE extractants commonly used in coal chemical phenol-containing wastewater,a new phenolic substance extractant-cyclohexanone was developed.The extraction effects of cyclohexanone and MIBK,DIPE were compared.The main influencing factors such as extraction ratio,extraction temperature,and p H were discussed,and the extractant recovery experiment was carried out.The results showed that the extraction effects of cyclohexanone on hydroquinone and phloroglucin were as high as 91.65% and 83.52% respectively,which were much higher than 74.05%,49.77% of MIBK and 27.95%,7.84% of DIPE.Under the optimal conditions such as temperature of 40 ℃,extraction ratio of 1 ∶ 3,and p H value of 8,the extraction rate of cyclohexanone for four types typical phenol such as phenol,m-cresol,hydroquinone and phloroglucin were 98.30%,96.83%,96.31%,and 91.67% respectively.Under the optimal conditions,the cyclohexanone extraction was carried out on mixed waters with different initial concentrations of 750 mg/L and 1 000 mg/L,and the removal rates of unit phenol and polyphenol were as high as respectively 97.81%,94.74%,96.96%,94.31%; The distillation of the mixed wastewater extract was carried out at a temperature of 155 ℃ and constant pressure,the results showed the recovery rate of cyclohexanone was over 95.5%.The development of the new high-efficiency dephenolization extractant cyclohexanone could effectively reduce the concentration of phenol in water and reduce the burden of subsequent biochemical treatment,providing a technical reference for the treatment and comprehensive utilization of such wastewater and the sustainable development of coal chemical industry.
Due to the problems of low extraction efficiency of polyphenols by MIBK and DIPE extractants commonly used in coal chemical phenol-containing wastewater,a new phenolic substance extractant-cyclohexanone was developed.The extraction effects of cyclohexanone and MIBK,DIPE were compared.The main influencing factors such as extraction ratio,extraction temperature,and p H were discussed,and the extractant recovery experiment was carried out.The results showed that the extraction effects of cyclohexanone on hydroquinone and phloroglucin were as high as 91.65% and 83.52% respectively,which were much higher than 74.05%,49.77% of MIBK and 27.95%,7.84% of DIPE.Under the optimal conditions such as temperature of 40 ℃,extraction ratio of 1 ∶ 3,and p H value of 8,the extraction rate of cyclohexanone for four types typical phenol such as phenol,m-cresol,hydroquinone and phloroglucin were 98.30%,96.83%,96.31%,and 91.67% respectively.Under the optimal conditions,the cyclohexanone extraction was carried out on mixed waters with different initial concentrations of 750 mg/L and 1 000 mg/L,and the removal rates of unit phenol and polyphenol were as high as respectively 97.81%,94.74%,96.96%,94.31%; The distillation of the mixed wastewater extract was carried out at a temperature of 155 ℃ and constant pressure,the results showed the recovery rate of cyclohexanone was over 95.5%.The development of the new high-efficiency dephenolization extractant cyclohexanone could effectively reduce the concentration of phenol in water and reduce the burden of subsequent biochemical treatment,providing a technical reference for the treatment and comprehensive utilization of such wastewater and the sustainable development of coal chemical industry.
引文
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[2]何绪文,张晓航,李福勤,等.煤矿矿井水资源化综合利用体系与技术创新[J].煤炭科学技术,2018,46(9):4-11.HE Xuwen,ZHANG Xiaohang,LI Fuqin,et al.Comprehensive utilization system and technical innovation of coal mine water resources[J].Coal Science and Technology,2018,46(9):4-11.
[3]刘艳丽,刘戈.煤化工行业高水耗问题分析与探讨[J].煤炭科学技术,2016,44(4):189-195.LIU Yanli,LIU Ge.Analysis and discussion on high water consumption problem of coal chemical industry.Coal Science and Technology,2016,44(4):189-195.
[4]陈赟,王卓.煤气化污水酚氨回收技术进展、流程优化及应用[J].煤化工,2013,41(4):44-48.CHEN Yun,WANG Zhuo.Application research status of the chemical process of ammonia/phenol recovery from coal-gasification wastewater[J].Coal Chemical Industry,2013,41(4):44-48.
[5]石广梅.煤气化废水的水质分析特性[J].哈尔滨建筑工程学院学报,1993(2):69-76.SHI Guangmei.The analytical characteristics of the coal gasification waste water[J].Journal of Harbin University of Civil Engineering and Architecture,1993(2):69-76.
[6]LI H Q,HAN H J,DU M A,et al.Removal of phenols,thiocyanate and ammonium from coal gasification wastewater using moving bed biofilm reactor.[J].Bioresour Technol,2011,102(7):4667-4673.
[7]周伟,陈赟,李秀喜,等.煤气化废水处理中双侧线汽提塔的应用[J].化学工程,2013,41(3):63-66.ZHOU Wei,CHEN Yun,LI Xiuxi,et al.Application of double side-draw stripper process in coal-gasification wastewater treatment[J].Chemical Engineering(China),2013,41(3):63-66.
[8]何小荣.高浓度含酚废水处理方法研究[J].石油化工应用,2009(2):28-29.HE Xiaorong.High concentration of phenol waste water treatment method[J].Petrochemical Industry Application,2009,28(2):28-29.
[9]BONDY Frederick,GRADINARU Apostol,HILDRETH James Mason.Phenolic wastewater treatment with ethers for removal and recovery of phenolics,6071409[P].2000-07-06.
[10]王卓,王慧敏,刘东,等.煤化工高浓含酚废水萃取脱酚实验研究[J].化学工程,2016(2):7-11.WANG Zhuo,WANG Huimin,LIU Dong,et al.Experimental study on removal of phenols from coal chemical wastewater.Chemical Engineering(China),2016(2):7-11.
[11]CHEN Yun,WANG Zhuo,LI Libo.Liquid-liquid equilibria for ternary systems:methyl butyl ketone+phenol+water and methyl butyl ketone+hydroquinone+water at 298.15 K and 323.15 K[J].Journal of Chemical&Engineering Data,2014,59(9):2750-2755.
[12]杜松,金文标,王吉坤,等.非均相催化臭氧氧化处理煤化工高含盐废水[J].煤炭科学技术,2018,46(9):49-53.DU Song,JIN Wenbiao,WANG Jikun,et al.Study on heterogeneous catalytic ozonation process for treatment of highsalt wastewater from coal chemical industry[J].Coal Science and Technology,2018,46(9):49-53.
[13]王吉坤,董卫果,杜松,等.气化废水络合萃取脱酚影响因素的研究[J].煤炭加工与综合利用,2015(8):39-43.WANG Jikun,DONG Weiguo,DU Song,et al.Study on the factors affecting the dephenolization of gasification wastewater by complex extraction[J].Coal Processing&Comprehensive Utilization,2015(8):39-43.
[14]单欣昌,戴猷元,秦炜,等.有机物络合萃取技术(修订版)[M].北京:化学工业出版社,2007.
[15]盖恒军,江燕斌,钱宇,等.煤气化废水处理过程瓶颈及改进措施分析[J].化学工程,2007(8):57-60.GAI Hengjun,JIANG Yanbin,QIAN Yu,et al.Analysis and debottlenecking retrofits for the coal-gasification watewater treatment process[J].Chemical Engineering(China),2007(8):57-60.
[16]钱宇,周志远,陈赟,等.煤气化废水酚氨分离回收系统的流程改造和工业实施[J].化工学报,2010(7):1821-1828.QIAN Yu,ZHOU Zhiyuan,CHEN Yun,et al.Process retrofit and industrial implementation of phenol and ammonia recovery from coal-gasification wastewater[J].CIESC Journal,2010(7):1821-1828.
[17]LIAO Mingsen,ZHAO Yuehong,NING Pengge,et al.Optimal design of solvent blend and its application in coking wastewater treatment process[J].Industrial&Engineering Chemistry Research,2014,53(39):15071-15079.
[18]薛斌,李月华,郭英伟,等.Ti/SnO2-Sb2O5/PbO2阳极电催化降解含环己酮废水的研究[J].沈阳工业大学学报,2007(4):477-480.XUE Bin,LI Yuehua,GUO Yingwei,et al.Electro-catalytic degradation of cyclohexanone-containing wastewater using Ti/SnO2-Sb2O5/PbO2as anode[J].Journal of Shenyang University of Technology,2007(4):477-480.
[19]陈庆俊.鲁奇炉气化废水处理工艺突破方向探讨[J].化学工业,2012(12):9-13.CHEN Qingjun.Exploration of breakthroughs in Lurgi gasification wastewater treatment process[J].Chemical Industry,2012(12):9-13.
[20]江燕斌,钱宇,李秀喜,等.高浓含酚炼油碱渣碳化液萃取脱酚的研究2:连续逆流萃取实验[J].炼油技术与工程,2001,31(5):45-49.JIANG Yanbin,QIAN Yu,LI Xiuxi,et al.Extraction dephenol for caustic phenolic sludge ing refinery-2:Continuous Counterflow Extraction Test[J].Petroleum Refinery Engineering,2001,31(5):45-49.
[21]鲁辉.萃取精馏在甲醇精馏中的应用[J].化工设计通讯,2018(8):10.LU Hui.Application of extractive distillation in methanol distillation[J].Coal Chemical Methanol,2018(8):10.
[22]杨猛,严文强.炼油厂焦化装置脱钙废水回收工艺研究[J].现代化工,2018(6):195-197.YANG Meng,YAN Wenqiang.Research on recovery process for decalcification wastewater in coking unit of refinery[J].Modern Chemical Industry,2018(6):195-197.
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