选矿废水中残留药剂生物降解技术研究进展
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摘要
选矿药剂通常用于调节矿物表面和浮选介质的物理化学性质,扩大有用矿物与脉石矿物间的亲疏水性差异,从而达到更好的分选效果。选矿药剂种类繁多,含有残留药剂的选矿废水直接外排会造成环境污染。生物降解作为一种新型生化处理方法,具有成本低、能耗少、无二次污染等优点,因此研究高效降解选矿废水中残留药剂的方法尤为重要。论述了当前黄药、黑药、羟肟酸类、松醇油等选矿药剂生物降解技术的研究进展,分析了影响降解效果的工艺因素和选矿药剂生物降解研究存在的主要问题,并对今后的研究工作进行展望。影响黄药生物降解效果的因素有黄药初始浓度、pH、温度,振荡速率、降解时间、碳氮比、氮源和金属离子等。外加碳源可促进黄药的降解。CS2、ROCSSH和单硫代碳酸盐是烃基黄药的主要降解产物,并伴有少许双黄药油液滴生成,属于一级酶促降解动力学。黄原酸盐分解的中间产物是过氧化黄原酸盐。不同外加碳源同样会促进黑苯胺药的降解。羟肟酸类捕收剂降解反应是一级反应动力学。影响对松醇油的降解因素有pH值、接种量、温度、摇床转速、松醇油初始浓度、反应时间等。针对选矿药剂生物降解研究存在的主要问题,今后的研究工作应借鉴相近领域的生物技术手段筛选出高效降解菌株,在降解机理上开展更深入研究,在分子水平上改造基因,利用基因工程技术构建新的降解菌株。同时,应加快选矿废水生物降解设备的研制。
Beneficiation agents usually regulate the physical and chemical properties of selected minerals and flodation media,which can expand the hydrophilic-to-hydrophobic differences between valuable minerals and gangue minerals and then achieve the best separation effect.There are many kinds of beneficiation agents and the direct discharge of mineral processing wastewater which contains residual chemicals will cause serious pollution to the environment.As a new biochemical treatment method,biodegradation has many advantages,such as low lost,low energy consumption and no secondary pollution.Therefore,it is of practical significance to study high efficiency biodegradation of residual agents in mineral processing wastewater.In this paper the current biodegradable research progress of mineral processing agents,such as xanthate,aerofloat,hydroxamic acid and pine oil were reviewed.The main factors affecting the degradation and biodegradation problems of beneficiation agents were analyzed and the future research work were also forecasted.The results show that the initial concentration,p H,temperature,shaking rate,time,C/N ratio,nitrogen source and metal ions are the main factors affecting the biodegradation of xanthate.External carbon sources can promote the degradation of xanthate.CS2,ROCSSH and mono-thiocarbonate are the main degradation products of alkyl-xanthate,accompanied by a few oil droplets of double-xanthate,which belongs to the first-order enzymatic degradation kinetics.The intermediate product of xanthate decomposition is xanthate peroxide.The analysis concluded that additional carbon sourses can promote the degradation of aniline aerofloat.Hydroxamic acid collectors are a first-order reaction kinetics.Besides,factors influencing the degradation of pine oil include p H,inoculation amount,temperature,shaking speed,initial concentration,time,etc.In view of the main problems about biodegradation of mineral processing agents,the future work should imitate the biotechnological means of similar fields to screen highly efficient degradation strains.The research on degradation mechanism should be deeply studied and new biodegradable strains should be constructed by genetic engineering at the molecular level.Meanwhile,the development of biodegradation equipment should be accelerated.
Beneficiation agents usually regulate the physical and chemical properties of selected minerals and flodation media,which can expand the hydrophilic-to-hydrophobic differences between valuable minerals and gangue minerals and then achieve the best separation effect.There are many kinds of beneficiation agents and the direct discharge of mineral processing wastewater which contains residual chemicals will cause serious pollution to the environment.As a new biochemical treatment method,biodegradation has many advantages,such as low lost,low energy consumption and no secondary pollution.Therefore,it is of practical significance to study high efficiency biodegradation of residual agents in mineral processing wastewater.In this paper the current biodegradable research progress of mineral processing agents,such as xanthate,aerofloat,hydroxamic acid and pine oil were reviewed.The main factors affecting the degradation and biodegradation problems of beneficiation agents were analyzed and the future research work were also forecasted.The results show that the initial concentration,p H,temperature,shaking rate,time,C/N ratio,nitrogen source and metal ions are the main factors affecting the biodegradation of xanthate.External carbon sources can promote the degradation of xanthate.CS2,ROCSSH and mono-thiocarbonate are the main degradation products of alkyl-xanthate,accompanied by a few oil droplets of double-xanthate,which belongs to the first-order enzymatic degradation kinetics.The intermediate product of xanthate decomposition is xanthate peroxide.The analysis concluded that additional carbon sourses can promote the degradation of aniline aerofloat.Hydroxamic acid collectors are a first-order reaction kinetics.Besides,factors influencing the degradation of pine oil include p H,inoculation amount,temperature,shaking speed,initial concentration,time,etc.In view of the main problems about biodegradation of mineral processing agents,the future work should imitate the biotechnological means of similar fields to screen highly efficient degradation strains.The research on degradation mechanism should be deeply studied and new biodegradable strains should be constructed by genetic engineering at the molecular level.Meanwhile,the development of biodegradation equipment should be accelerated.
引文
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[8]林伟雄,孙水裕,黄绍松,等.生物膜法处理硫化铅锌矿尾矿库外排废水[J].环境工程学报,2014,8(1):67-71.LIN Weixiong,SUN Shuiyu,HUANG Shaosong,et al. Biofilmprocess for treating Pb-Zn sulfide ore tailing wastewater[J]. Chi-nese Journal of Environmental Engineering,2014,8(1):67-71.
[9]鄢恒珍,龚文琪,梅光军,等.共基质代谢条件下丁基黄药的生物降解实验研究[J].环境污染与防治,2010,32(4):1-5.YAN Hengzhen,GONG Wenqi,MEI Guangjun,et al. Studyon co-metabolism biodegradation of butyl xanthate[J]. Environ-mental Pollution&Control,2010,32(4):1-5.
[10]程皝,林海,朱亦珺,等.厌氧好氧一体生物滤池处理选矿废水的研究[J].环境科学与技术,2012,35(7):68-72.CHENG Huang,LIN Hai,ZHU Yijun,et al.Treating ore floatationwastewater by an anaerobic-aerobic biological filter[J]. Environ-mental Science&Technology,2012,35(7):68-72.
[11] CHENG Huang,LIN Hai,HUO Hanxin,et al.Continuous removalof ore floatation reagents by an anaerobic-aerobic biological filter[J].Bioresource Technology,2012,114:255-261.
[12]姜彬慧,黄娅琼,王宇佳,等.采用膜生物反应器处理丁基黄药废水[J].中南大学学报(自然科学版),2013,44(7):3072-3079.JIANG Binhui,HUANG Yaqiong,WANG Yujia,et al. Treatmentof butyl xanthogenate wastewater by membrane bioreactor[J].Journal of Central South University(Science and Technology),2013,44(7):3072-3079.
[13]宋卫锋,林梓河,罗丽丽,等.SBR法处理选矿废水的影响因素研究[J].环境工程学报,2012,6(2):509-514.SONG Weigfeng,LIN Zihe,LUO Lili,et al. Study on influencingfactors of flotation wastewater treatment with SBR method[J].Chinese Journal of Environmental Engineering,2012,6(2):509-514.
[14]张新,周洪波.序批式生物反应器处理选矿黄药废水的研究[J].水处理技术,2011,37(1):108-111,132.ZHANG Xin,ZHOU Hongbo. Treatment of butyl xanthate waster-water by sequencing batch reactor[J].Technology of Water Treat-ment,2011,37(1):108-111,132.
[15]宋卫锋,林梓河,罗丽丽,等.外加碳源对选矿废水浮选药剂生物降解效果的影响[J].化工环保,2011,31(3):218-221.SONG Weifeng,LIN Zihe,LUO Lili,et al.Effects of external car-bon resource on biodegradation of flotation reagents in ore millingwastewater[J]. Environmental Protection of Chemical Industry,2011,31(3):218-221.
[16]宋卫锋,唐铁柱,林梓河,等.生物接触氧化法处理选矿废水的影响因素[J].环境工程学报,2013,7(2):603-607.SONG Weifeng,TANG Tiezhu,LIN Zihe,et al. Some influencingfactors of flotation wastewater treatment with bio-contact oxida-tion method[J]. Chinese Journal of Environmental Engineering,2013,7(2):603-607.
[17]宋卫锋,武纯,林丽婷,等.苯胺黑药降解菌降解条件优化及降解酶特性的研究[J].安徽农业科学,2013,41(35):13486-13488.SONG Weifeng,WU Chun,LIN Liting,et al. Optimization of deg-radation conditions for degrading bacteria of dianilinodithiophos-phoric acid and properties of degrading enzyme[J].Journal of An-hui Agricultural Sciences,2013,41(35):13486-13488.
[18]鄢恒珍,龚文琪,梅光军,等.羟肟酸类捕收剂的生物降解性能及机理研究[J].中国给水排水,2010,26(15):89-91.
[19] YAN Hegnzhen,GONG Wenqi,MEI Guangjun,et al. Study onbiodegradability and mechanism of hydroxamic acid collectors[J].China Water&Wastewater,2010,26(15):89-91.
[19]梅光军,陈晓东,龚文琪,等.羟肟酸类捕收剂的好氧生物降解性评价[J].安全与环境学报,2010,10(3):57-61.MEI Guangjun,CHEN Xiaodong,GONG Wenqi,et al. Evaluationof aerobic biodegradability of hydroxamic acid collentor[J]. Jour-nal of Safety and Environment,2010,10(3):57-61.
[20] ZHOU Wenjun,GONG Wenqi,MEI Guangjun.Effect of co-me-tabolism on biodegradation of hydroxamic acid[C]//Internati-nal conference on Electric Technology and Civil Engineering(ICETCE2011),Lushan:[s.n.],2011:5900-5903.
[21]梁杰慧,孙水裕,杜青平,等.松醇油降解菌的分离鉴定及降解条件优化[J].中国有色金属学报,2012,22(11):3278-3284.LIANG Jiehui,SUN Shuiyu,DU Qingping,et al. Isolation andidentification of pine oil degrading bacteria and optimization ofdegrading conditions[J].The Chinese Journal of Nonferrous Met-als,2012,22(11):3278-3284.
[2]陈绍华,龚文琪,梅光军,等.共基质条件下黄药的生物降特性研究[J].水处理技术,2010,36(9):60-64.CHEN Shaohua,GONG Wenqi,MEI Guangjun,et al.Study on bio-degradability of xanthate under the conditions of co-substrate[J].Technology of Water Treatment,2010,36(9):60-64.
[3]陈绍华,龚文琪,梅光军.烃基黄药类捕收剂的生物降解性评价[J].中南大学学报(自然科学版),2011,42(2):546-553.CHEN Shaohua,GONG Wenqi,MEI Guangjun. Evaluation of bio-degradability of alkyl xanthates flotation collecters[J]. Journal ofCentral South University(Science and Technology),2011,42(2):546-553.
[4] CHEN Shaohua,GONG Wenqi,MEI Guangjun,et al.Primary bio-degradation of sulfide mineral flotation collectors[J].Minerals En-gineering,2011,24(8):953-955.
[5] CHEN Shaohua,GONG Wenqi,MEI Guangjun,et al.Quantitativestructure-biodegradability relationship of sulfide mineral flota-tion collectors[J]. International Journal of Mineral Processing,2011,101:112-115.
[6] ZHONG Xisun,FORSLING W.The degradation kinetics of ethyl-xanthate as a function of p H in aqueous solution[J].Minerals En-gineering,1997,10(4):389-400.
[7]夏丽娟,胡学伟,张雅琳,等.选矿废水中黄药的生化处理[J].环境工程学报,2016,10(1):21-26.XIA Lijuan,HU Xuewei,ZHANG Yalin,et al. Biological treatmentof xanthate in floatation wastewater[J].Chinese Journal of Environ-mental Engineering,2016,10(1):21-26.
[8]林伟雄,孙水裕,黄绍松,等.生物膜法处理硫化铅锌矿尾矿库外排废水[J].环境工程学报,2014,8(1):67-71.LIN Weixiong,SUN Shuiyu,HUANG Shaosong,et al. Biofilmprocess for treating Pb-Zn sulfide ore tailing wastewater[J]. Chi-nese Journal of Environmental Engineering,2014,8(1):67-71.
[9]鄢恒珍,龚文琪,梅光军,等.共基质代谢条件下丁基黄药的生物降解实验研究[J].环境污染与防治,2010,32(4):1-5.YAN Hengzhen,GONG Wenqi,MEI Guangjun,et al. Studyon co-metabolism biodegradation of butyl xanthate[J]. Environ-mental Pollution&Control,2010,32(4):1-5.
[10]程皝,林海,朱亦珺,等.厌氧好氧一体生物滤池处理选矿废水的研究[J].环境科学与技术,2012,35(7):68-72.CHENG Huang,LIN Hai,ZHU Yijun,et al.Treating ore floatationwastewater by an anaerobic-aerobic biological filter[J]. Environ-mental Science&Technology,2012,35(7):68-72.
[11] CHENG Huang,LIN Hai,HUO Hanxin,et al.Continuous removalof ore floatation reagents by an anaerobic-aerobic biological filter[J].Bioresource Technology,2012,114:255-261.
[12]姜彬慧,黄娅琼,王宇佳,等.采用膜生物反应器处理丁基黄药废水[J].中南大学学报(自然科学版),2013,44(7):3072-3079.JIANG Binhui,HUANG Yaqiong,WANG Yujia,et al. Treatmentof butyl xanthogenate wastewater by membrane bioreactor[J].Journal of Central South University(Science and Technology),2013,44(7):3072-3079.
[13]宋卫锋,林梓河,罗丽丽,等.SBR法处理选矿废水的影响因素研究[J].环境工程学报,2012,6(2):509-514.SONG Weigfeng,LIN Zihe,LUO Lili,et al. Study on influencingfactors of flotation wastewater treatment with SBR method[J].Chinese Journal of Environmental Engineering,2012,6(2):509-514.
[14]张新,周洪波.序批式生物反应器处理选矿黄药废水的研究[J].水处理技术,2011,37(1):108-111,132.ZHANG Xin,ZHOU Hongbo. Treatment of butyl xanthate waster-water by sequencing batch reactor[J].Technology of Water Treat-ment,2011,37(1):108-111,132.
[15]宋卫锋,林梓河,罗丽丽,等.外加碳源对选矿废水浮选药剂生物降解效果的影响[J].化工环保,2011,31(3):218-221.SONG Weifeng,LIN Zihe,LUO Lili,et al.Effects of external car-bon resource on biodegradation of flotation reagents in ore millingwastewater[J]. Environmental Protection of Chemical Industry,2011,31(3):218-221.
[16]宋卫锋,唐铁柱,林梓河,等.生物接触氧化法处理选矿废水的影响因素[J].环境工程学报,2013,7(2):603-607.SONG Weifeng,TANG Tiezhu,LIN Zihe,et al. Some influencingfactors of flotation wastewater treatment with bio-contact oxida-tion method[J]. Chinese Journal of Environmental Engineering,2013,7(2):603-607.
[17]宋卫锋,武纯,林丽婷,等.苯胺黑药降解菌降解条件优化及降解酶特性的研究[J].安徽农业科学,2013,41(35):13486-13488.SONG Weifeng,WU Chun,LIN Liting,et al. Optimization of deg-radation conditions for degrading bacteria of dianilinodithiophos-phoric acid and properties of degrading enzyme[J].Journal of An-hui Agricultural Sciences,2013,41(35):13486-13488.
[18]鄢恒珍,龚文琪,梅光军,等.羟肟酸类捕收剂的生物降解性能及机理研究[J].中国给水排水,2010,26(15):89-91.
[19] YAN Hegnzhen,GONG Wenqi,MEI Guangjun,et al. Study onbiodegradability and mechanism of hydroxamic acid collectors[J].China Water&Wastewater,2010,26(15):89-91.
[19]梅光军,陈晓东,龚文琪,等.羟肟酸类捕收剂的好氧生物降解性评价[J].安全与环境学报,2010,10(3):57-61.MEI Guangjun,CHEN Xiaodong,GONG Wenqi,et al. Evaluationof aerobic biodegradability of hydroxamic acid collentor[J]. Jour-nal of Safety and Environment,2010,10(3):57-61.
[20] ZHOU Wenjun,GONG Wenqi,MEI Guangjun.Effect of co-me-tabolism on biodegradation of hydroxamic acid[C]//Internati-nal conference on Electric Technology and Civil Engineering(ICETCE2011),Lushan:[s.n.],2011:5900-5903.
[21]梁杰慧,孙水裕,杜青平,等.松醇油降解菌的分离鉴定及降解条件优化[J].中国有色金属学报,2012,22(11):3278-3284.LIANG Jiehui,SUN Shuiyu,DU Qingping,et al. Isolation andidentification of pine oil degrading bacteria and optimization ofdegrading conditions[J].The Chinese Journal of Nonferrous Met-als,2012,22(11):3278-3284.