负载型纳米Pd/Fe对挥发性氯代烃的去除

现代地质 ›› 2008, Vol. 22 ›› Issue (2): 313-320.

负载型纳米Pd/Fe对挥发性氯代烃的去除

尚海涛，李智灵，杨琦，席宏波，郝春博

中国地质大学水资源与环境学院，北京100083

收稿日期:2007-10-03 修回日期:2008-01-29 出版日期:2008-02-20 发布日期:2008-02-20
作者简介:尚海涛，男，讲师，1974年出生，环境科学工程专业，主要从事水处理工程的研究与教学工作。 Email：shanght@cugb.edu.cn
基金资助:
国家自然科学基金项目（40102027，50578151）；北京市自然科学基金项目（8052017）；北京市教委校企合作项目（51900265005）

Removal of Volatile Chlorinated Hydrocarbons in Water by Supported Nanoscale Pd/Fe Particles

SHANG Hai-tao,LI Zhi-ling, YANG Qi, XI Hong-bo, HAO Chun-bo

School of Water Resources and Environment，China University of Geosciences, Beijing100083,China

Received:2007-10-03 Revised:2008-01-29 Online:2008-02-20 Published:2008-02-20

摘要/Abstract

摘要：

氯代烃的污染治理已成为当今世界最热门的研究领域之一。以水体中最常见的氯代烃污染物1，1-二氯乙烯（1，1-DCE）、林丹（γ-HCH）为主要目标污染物，探讨了不同条件下负载型纳米Pd/Fe对氯代烃的去除效果。负载型纳米Pd/Fe采用浸渍→液相还原→还原沉淀的方法制备，透射电镜显示采用该方法制备的负载型金属钯和铁的平均粒径均在纳米级范围内。负载型纳米Pd/Fe具有较高的表面反应活性，当负载型纳米Pd/Fe 用量为40 g/L、反应时间达2 h时，1.1-二氯乙烯和林丹的去除率分别达到85%和100%。脱氯率与Pd/Fe投加量、钯含量、初始pH值、反应温度等因素有关，与溶液的初始浓度关系不大。负载型纳米Pd/Fe对11-DCE和γ-HCH去除均符合一级反应动力学方程，速率常数分别为0-528 3 h^-1及2-012 9 h^-1，反应的半衰期t1/2分别为1.31 h和0.34 h。推断在反应过程中，Fe腐蚀产生的H2为主要还原剂，Pd是良好的加氢催化剂，在金属颗粒表面形成高浓度反应相，使反应短时间内完成。

关键词: 负载型纳米Pd/Fe, 挥发性氯代烃, 反应动力学, 影响因子, 反应机理

Abstract:

Control of chlorinated hydrocarbons pollution has gradually become the top research field in modern world. In order to investigate the removal ability of chlorinated hydrocarbons, the most widely existent pollutants, dichloroethylene（1.1-DCE） and Lidane（γ-HCH）were chosen as the aim pollutants,and the synthetical supported nanoscale Pd/Fe were chosen as the reaction medium. The supported Pd/ Fe bimetallic catalysts were made by the procedures of impregnation, liquid reduction, and reductive precipitation. The grain size of palladium and iron are at the nanoscale by the transmission electron microscope. The Fe/ Pd systems proved to be very effective, and the removal rate of 1.1-DCE and γ-HCH in 2 hours respectively reached about 85% and 100%. The removal of 1.1-DCE and γ-HCH in water by the supported Pd/Fe bimetallic catalysts follows the pseudofrist order kinetics with the halflife t1/2 of 1.31 h and 0.34 h. The amount of Pd/ Fe, Pd/ Fe ratio, pH and reaction temperatures are the most important factors that affect the removal efficiency and there is little relationship with the initial concentration. During the reactions, H₂，coming from eroded Fe，may be the main reducer. Pd is a good hydrogenation catalyst and it formed a high concentration reaction phase in the surface of Pd/Fe-Al₂O₃particles which accelerated the reaction rate.

Key words: supported nanoscale Pd/Fe, volatile chlorinated hydrocarbons, reaction kinetics, influence factor, reaction , mechanism

中图分类号:

X703
Q657

尚海涛，李智灵，杨琦，席宏波，郝春博. 负载型纳米Pd/Fe对挥发性氯代烃的去除[J]. 现代地质, 2008, 22(2): 313-320.

SHANG Hai-tao,LI Zhi-ling, YANG Qi, XI Hong-bo, HAO Chun-bo. Removal of Volatile Chlorinated Hydrocarbons in Water by Supported Nanoscale Pd/Fe Particles[J]. Geoscience, 2008, 22(2): 313-320.

参考文献

\[1\]余锡宾, 王明辉. 超细Pd-B/SiO2非晶态合金加氢反应的催化活性\[J\]. 分子催化, 1999, 13（1）: 3-8.
\[2\]Ottley C J, Davison W, Edmunds W M. Chemical catalysis of nitrate reduction by iron（II）\[J\]. Geochimica et Cosmochimica Acta, 1997, 61（9）: 1819-1821.
\[3\]Dirk S, Ralf K, Andreas D. Competing TCE and cisDCE degradation kinetics by zerovalent ironexperimental results and numerical simulation\[J\]. Journal of Contaminant Hydrology, 2003, 65: 183-202.
\[4\]Jurka B, Albin P,Djordje M,et al. XPS and TPR examinations of γaluminasupported PdCu catalysts\[J\]. Applied Catalysis A, 2001, 206: 113-124.
\[5\]Jia Jifei,Shen Jianyi,Lin Liwu, et al. A study on reduction behaviors of the supported platinum iron catalysts\[J\]. Journal of Molecular Catalysis A, 1999, 138: 177-184.
\[6\]Florence E, Florence G, Jacques B. Catalytic reduction of nitrate in water on a monometallic Pd/CeO2 catalyst\[J\]. Journal of Catalysis, 2002, 206: 363-367.
\[7\]Florence G, Florence E, Jacques B. Palladium and platinumbased catalysts in the catalytic reduction of nitrate in water, effect of copper, silver, or gold addition\[J\]. Journal of Catalysis, 2003, 220: 182-191.
\[8\]Mark D, Engelmann, John G,et al. The complete dechlorination of DDT by magnesium /palladium bimetallic particles\[J\]. Chemosphere, 2001, 43（2）: 195-198.
\[9\]Gillham R W, O’Hannesin S F. Enhanced degradation of halogenated aliphatics by zerovalent iron\[J\]. Ground Water, 1994, 32（6）: 958-967.
\[10\]Boronina T, Klabunde K J, Sergeev G. Destruction of organohalides in water using metal particles: carbon tetrachloride/water reactions with magnesium, tin, and zinc\[J\]. Environmental Science and Techno1ogy, 1995, 29（6）: 1511-1517.
\[11\]Arnold W A, Ball W P, Roberts A L. Polychlorinated ethane reaction with zerovalent zinc: pathways and rate control\[J\]. Journal of Contaminant Hydrology, 1999, 40（2）: 183-200.
\[12\]Muftikian R, Nebesny K, Fernando Q. Xray photoelectron spectra of the palladiumiron bimetallic surface used for the rapid dechlorination of chlorinated organic environmental contaminant\[J\]. Environmental Science and Techno1ogy, 1996, 30（12）: 3593-3596.
\[13\]国家环保局《水和废水监测分析法》编委会.水和废水监测分析法［M］.北京：中国环境科学出版社，1989：1-297.
\[14\]杨琦，席宏波，尚海涛，等.四氯乙烯的生物吸附和厌氧生物降解研究［J］.现代地质，2007，21（1）：170-174.
\[15\]Zhang Weixian, Wang Chuanbao, Lie Hsinglung. Treatment of chlorinated organic contaminants with nanoscale bimetallic particles\[J\].Catalysis Today, 1998, 40(4): 387-395.
\[16\]Shoemaker S H, Greiner J F, Gillham R W. Assessment of barrier containment technologies \[M\]. Baltimore,Maryland: International Containment Technoloy Workshop, 1995:301-353.第22卷第2期

[1]	聂轶苗，马鸿文，杨静，苏玉柱，李如臣，高飞. 矿物聚合材料固化过程中的聚合反应机理研究[J]. 现代地质, 2006, 20(2): 340-346.
[2]	刘贺，马鸿文，聂轶苗，王蕾. 利用钾长石合成雪硅钙石纳米粉体的反应机理研究[J]. 现代地质, 2006, 20(2): 347-353.