桦甸油页岩飞灰吸附特性研究
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摘要
工农业废水、城市生活污水及各种采矿废水均含有大量重金属元素,水环境重金属污染不仅造成重大经济损失,还严重危胁着包括人类在内的各种生命体的健康生存。油页岩电站飞灰的主要成分和物理性质决定其具有很强的吸附能力,适合用于处理废水。开展油页岩飞灰吸附重金属元素的研究具有重要意义。
本文以吉林桦甸热电厂循环流化床锅炉油页岩飞灰为研究对象,采用静态吸附法研究了其对模拟废水中Pb2+、Zn2+、Cu2+、Cd2+的吸附特性。对吸附动力学和吸附热力学进行了分析,并用Langmuir和Freundlich吸附等温线对吸附方程进行了拟合,在此基础上,探讨其对四种重金属离子的吸附机理。试验研究了投加量、时间、pH值等因素对吸附特性的影响。动力学研究表明,Pb2+符合吸附动力学准二级反应方程模型,Cd2+符合准二级反应方程模型和Elovich方程模型,Cu2+、Zn2+则都能与吸附动力学一级反应方程、二级反应方程和Elovich方程相吻合。油页岩飞灰吸附过程是吸热反应,对Cu2+、Zn2+、Cd2+的吸附符合Langmuir和Freundlich吸附等温线,而Pb2+不符合这两种吸附等温线模型。对酸化油页岩飞灰吸附特性研究表明,酸化油页岩飞灰对四种离子最大吸附量都有所增加,达吸附动态平衡时间比油页岩飞灰短。Pb2+吸附量随pH值的增加呈先上升后下降规律,当pH﹥6时,Cu2+、Zn2+、Cd2+都达吸附动态平衡。
四种离子的吸附反应是吸热反应,且都能很好地与吸附动力学一级反应方程、二级反应方程和Elovich方程相吻合。酸化油页岩飞灰对四种离子的吸附是一个非自发进行的过程,且Langmuir型和Freundlich型吸附等温线都能较好地描述酸化油页岩飞灰对四种离子的吸附性能,其中Langmuir型吸附等温线的拟合效果更好。
A large quantity of heavy matel ions are contained in industrial and agricultural wastewater, municipal sewage, and mining wastewater, the pollution of heavy matel in water not only cause momentous economical losses, but also can seriously endanger health of lives, which including human beings. The main components and physical properties of oil shale ash in power plants determained them with strong adsorbability, so it is suitable for treating the wastewater. It has important social and economic meaning to test the oil shale fly ash as adsorbent.
This study puts forward a new adsorbent-oil shale fly ash (OSFA) adsorbent and evaluates the potential use of it to remove heavy metal ions from aqueous solutions as a low-cost-adsorbent. The properties of the novel adsorbent were presented and the adsorbent were then used in batch experiments to study the adsorption properties of Pb2+, Zn2+, Cu2+ and Cd2+ in simulated wastewater. On the basis of theoretical analysis of the adsorption kinetics, adsorption thermodynamics, Langmuir and Freundlich adsorption isotherm, the adsorption mechanism of the four heavy metal ions by oil shale fly ash was investigated. The affects of influential factors including oil shale fly ash dosage, contact time, pH, temperature and initial metal concentration were evaluated in the experiments. The Pb2+ accords with Pseudo second order kinetics model, Cd2+ accords with both Pseudo second order kinetics model and Elovich kinetics model, Cu2+, Zn2+ accords with the all of the three kinetics models. The process of adsorption was a endothermic nature. Equilibrium isotherms at different temperatures have been determined and analyzed by Langmuir model andFreundlich model,we could conclude that Freundlich model. We could conclude that Cu2+, Zn2+, Cd2+ was accordesd with both Langmuir model andFreundlich model, and the Pb2+ did not accord with both of them.
Compared with OSFA, adsorption capacity of the acidification OSFA had increased, and the homeostasis times were shorter than the OSFA adsorption times. The adsorption capacity of Pb2+ was increased first and then descreased with the increased pH, and the Cu2+, Zn2+, Cd2+ could reach to the adsorbed homeostasis when pH greater than 6. The reacted of four heavy matel ions were all the endothermic reaction, and could accord with the Pseudo frist order kinetics model, Pseudo second order kinetics model and Elovich kinetics model welly. The process of adsorbed was a non-spontaneous process for all of four ions. The studies of adsorption isotherms showed that both the Langmuir model and Freundlich model could characterizetion the four heavy matel ions welly, but the Langmuir model fits better than the Freundlich model for them.
本文以吉林桦甸热电厂循环流化床锅炉油页岩飞灰为研究对象,采用静态吸附法研究了其对模拟废水中Pb2+、Zn2+、Cu2+、Cd2+的吸附特性。对吸附动力学和吸附热力学进行了分析,并用Langmuir和Freundlich吸附等温线对吸附方程进行了拟合,在此基础上,探讨其对四种重金属离子的吸附机理。试验研究了投加量、时间、pH值等因素对吸附特性的影响。动力学研究表明,Pb2+符合吸附动力学准二级反应方程模型,Cd2+符合准二级反应方程模型和Elovich方程模型,Cu2+、Zn2+则都能与吸附动力学一级反应方程、二级反应方程和Elovich方程相吻合。油页岩飞灰吸附过程是吸热反应,对Cu2+、Zn2+、Cd2+的吸附符合Langmuir和Freundlich吸附等温线,而Pb2+不符合这两种吸附等温线模型。对酸化油页岩飞灰吸附特性研究表明,酸化油页岩飞灰对四种离子最大吸附量都有所增加,达吸附动态平衡时间比油页岩飞灰短。Pb2+吸附量随pH值的增加呈先上升后下降规律,当pH﹥6时,Cu2+、Zn2+、Cd2+都达吸附动态平衡。
四种离子的吸附反应是吸热反应,且都能很好地与吸附动力学一级反应方程、二级反应方程和Elovich方程相吻合。酸化油页岩飞灰对四种离子的吸附是一个非自发进行的过程,且Langmuir型和Freundlich型吸附等温线都能较好地描述酸化油页岩飞灰对四种离子的吸附性能,其中Langmuir型吸附等温线的拟合效果更好。
A large quantity of heavy matel ions are contained in industrial and agricultural wastewater, municipal sewage, and mining wastewater, the pollution of heavy matel in water not only cause momentous economical losses, but also can seriously endanger health of lives, which including human beings. The main components and physical properties of oil shale ash in power plants determained them with strong adsorbability, so it is suitable for treating the wastewater. It has important social and economic meaning to test the oil shale fly ash as adsorbent.
This study puts forward a new adsorbent-oil shale fly ash (OSFA) adsorbent and evaluates the potential use of it to remove heavy metal ions from aqueous solutions as a low-cost-adsorbent. The properties of the novel adsorbent were presented and the adsorbent were then used in batch experiments to study the adsorption properties of Pb2+, Zn2+, Cu2+ and Cd2+ in simulated wastewater. On the basis of theoretical analysis of the adsorption kinetics, adsorption thermodynamics, Langmuir and Freundlich adsorption isotherm, the adsorption mechanism of the four heavy metal ions by oil shale fly ash was investigated. The affects of influential factors including oil shale fly ash dosage, contact time, pH, temperature and initial metal concentration were evaluated in the experiments. The Pb2+ accords with Pseudo second order kinetics model, Cd2+ accords with both Pseudo second order kinetics model and Elovich kinetics model, Cu2+, Zn2+ accords with the all of the three kinetics models. The process of adsorption was a endothermic nature. Equilibrium isotherms at different temperatures have been determined and analyzed by Langmuir model andFreundlich model,we could conclude that Freundlich model. We could conclude that Cu2+, Zn2+, Cd2+ was accordesd with both Langmuir model andFreundlich model, and the Pb2+ did not accord with both of them.
Compared with OSFA, adsorption capacity of the acidification OSFA had increased, and the homeostasis times were shorter than the OSFA adsorption times. The adsorption capacity of Pb2+ was increased first and then descreased with the increased pH, and the Cu2+, Zn2+, Cd2+ could reach to the adsorbed homeostasis when pH greater than 6. The reacted of four heavy matel ions were all the endothermic reaction, and could accord with the Pseudo frist order kinetics model, Pseudo second order kinetics model and Elovich kinetics model welly. The process of adsorbed was a non-spontaneous process for all of four ions. The studies of adsorption isotherms showed that both the Langmuir model and Freundlich model could characterizetion the four heavy matel ions welly, but the Langmuir model fits better than the Freundlich model for them.
引文
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[2]陈洁渝,严春杰,李子冲等.油页岩灰渣的综合利用.矿产保护与利用,2006,12(6):41～45
[3] J. R. Bai,Q. Wang,S. Y. Li.Research on release of trace elements at retorting of huadian oil shale.Oil Shale,2008,25(1):17～26
[4]柏静儒,王擎,陈艳等.油页岩中几种微量元素的赋存形态.环境科学学报,2008,28(10):2156～2160
[5]王福良.油页岩生产优质高岭土研究.有色金属,2000,52(4):149～150
[6]魏明安.油页岩综合利用途径探讨.矿冶,2002,11(2):32～34
[7] R. Hanni.Energy and valuble material by-product from firing Estonian oil shale.Waste Management,1996,13(2):56～59
[8]李胜强,穆建春,金仁和等.油母页岩渣在我国建材行业的研究与应用.建筑科学,2008,24(3):174～177
[9]冯宗玉,薛向欣,李勇.油页岩飞灰陶粒吸附苯酚的实验研究.材料与冶金学报,2007,6(3):230～233
[10]肖其海.油页岩飞灰聚烯烃填充母粒的应用.塑料科技,1995,110(6):21～23,26
[11] R. B. Finkelman.What we do not know about the occurrence and distribution of trace elements in coals.Coal Qual,1989,8(1):3～4
[12]李勇,冯宗玉,薛向欣等.油页岩飞灰酸碱离解法制备白炭黑的工艺比较.硅酸盐通报,2008,27(1):6～11
[13]李勇,薛向欣,冯宗玉.改性油页岩飞灰吸附Cu2+的研究.材料与冶金学报,2007,6(4):302～305,315
[14]王艳秋.造粒赤泥吸附剂对重金属离子的吸附作用研究:[硕士学位论文].北京:中国地质大学,2007.2～4,46～47,37～38
[15]曹煊.碱渣对重金属吸附的研究:[硕士学位论文].青岛:中国海洋大学,2006,10～11
[16]国家环境保护局.中国环境状况公报(2001).2002:13～14
[17]常学秀,文传浩,王焕校.重金属污染与人体健康.云南环境科学,2000,19(1):59～61
[18]徐灵,王成端,姚岚.重金属废水处理技术分析与优选.广州化工,2006,34(6):44～46
[19]梁平..洋底富钴结壳的开采方法.金属矿山,2002,11:20～22
[20]罗春雷.钴结壳开采装置及方法.中南工业大学学报,2002,6(33):618～619
[21]ям.格鲁什科著,钟祥洪译.工业污水中有毒金属及其无机化合物.科学出版社,北京,1979
[22]简曲.中国大洋采矿技术发展述评.采矿技术,2001,2(1):9～11
[23] W. Li,L. B. Zhang,J. H. Peng.Tobacco stems as a low cost adsorbent for the removal of Pb(II) from wastewater.Industrial Crops and Products,2008,28(3):294～302
[24]张建梅.重金属废水处理技术研究进展(综述).西安联合大学学报,2003,2(6):55～59
[25]王正烈.物理化学.高等教育出版社,2001,12～15
[26]王云波,谭万春,王晓昌等.饮用水沸石除氟的实验研究.净水技术,2001,10(1):63～64
[27]史晓燕,肖波,李建芬,杨小艳.锯末在重金属废水处理中的应用.工业水处理,2007,27(4):9～12,24
[28] I. J. Alinnor.Adsorption of heavy metal ions from aqueous solution by fly ash.Fuel,2007,86(5):853～857
[29] C. Heechan,O. Dalyoung,K. Kwanho,et al.A study on removeal characteristics of heavy metals from aqueous solution by fly ash.Journal of Hazardous Materials,2005,127(3):187～195
[30] P. M. Pimentel,G. Gonzàlez,M. F. A. Melo,et al.Removal of lead ions from aqueous solution by retorted shale.Separation Purification Technology,2007,56(3):48～353
[31] S. B. Wang,Q. Ma,Z. H. Zhu,et al.Characteristics of coal fly ash and adsorption application.Fuel,2008,8(15):3469～3473
[32] S. P. Cetin,E. Pehlivan.The use of fly ash as low cost, environmentally friendly alternative to activated carbon for the removal of heavy metals from aqueous solutions.Colloids and Surfaces,2007,298(2):83～87
[33] K. K. Panday,G. Prasad,V. N. Singh,et al.copper(Ⅱ) removal from aqueous solutions by fly ash.wateres,1985,19(7):69～873
[34] E. Pehlivan,S. Cetin,B. H. Yanik.Equilibrium studies for the sorption of zinc and copper from aqueous solutions using sugar beet pulp and fly ash.Journal of Hazardous Material,2006,135(31):193～199
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