Pd/CNTs对4-氯苯酚的液相催化加氢去氯

doi:10.16085/j.issn.1000-6613.2017.06.029

化工进展 ›› 2017, Vol. 36 ›› Issue (06): 2171-2176.DOI: 10.16085/j.issn.1000-6613.2017.06.029

Pd/CNTs对4-氯苯酚的液相催化加氢去氯

兰丽娟^1,2, 刘莺³, 杜芳林¹

1 青岛科技大学材料科学与工程学院, 山东青岛 266042;
2 烟台大学环境与材料工程学院, 山东烟台 264005;
3 鲁东大学资源与环境工程学院, 山东烟台 264025

收稿日期:2016-10-12 修回日期:2017-01-23 出版日期:2017-06-05 发布日期:2017-06-05
通讯作者: 刘莺,杜芳林
作者简介:兰丽娟(1974—),女,博士研究生。
基金资助:
山东省高等学校优势学科人才团队培育计划“蓝黄两区滨海资源与环境”项目及国家自然科学基金项目（21377162，51272115）。

Liquid-phase catalytic hydrodechlorination of 4-chlorophenol over Pd/CNTs

LAN Lijuan^1,2, LIU Ying³, DU Fanglin¹

1 College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, Shandong, China;
2 School of Environment and Materials Engineering, Yantai University, Yantai 264005, Shandong, China;
3 School of Resources and Environmental Engineering, Ludong University, Yantai 264025, Shandong, China

Received:2016-10-12 Revised:2017-01-23 Online:2017-06-05 Published:2017-06-05

摘要/Abstract

摘要： 以浓硝酸酸化后的多壁碳纳米管（CNTs）为原料，PdCl₂为前体，甲醛为还原剂，采用化学浸渍法制备了5% Pd/CNTs催化剂。通过ICP、XRD、BET、TEM对其进行表征，证实5%的钯纳米粒子成功负载在CNTs管外壁上，钯纳米粒子的平均粒径为4.30nm。在合成Pd/CNTs催化剂的基础上，研究了温和条件下其对4-氯苯酚（4-CP）的液相催化加氢去氯（HDC）规律。考察了体系反应温度、催化剂用量、NaOH用量、反应底物浓度对4-CP降解速率的影响，建立了动力学模型。得到了最佳反应条件：反应温度40℃，催化剂用量20mg，Cl^-、OH^-摩尔比1∶1.1；Pd/CNTs对4-CP加氢去氯反应为零级反应，反应活化能为E_a=40.12kJ/mol，指前因子A=1.66×10⁷mol/（L·min）。

关键词: 钯/多壁碳纳米管, 催化剂, 4-氯苯酚, 加氢去氯, 反应动力学

Abstract: 5% Pd/CNTs was synthesized by chemical impregnation method using multi-walled carbon nanotubes(CNTs)which was acidified by concentrated nitric acid as starting materials,PdCl₂ as precursor and formaldehyde as reducing agent. The catalyst was characterized by means of ICP、XRD、BET and TEM. The results showed that 5% Palladium nanoparticles were successfully loaded on the outer wall of the CNTs tubes and the mean diameter of the Pd nanoparticles was 4.30nm. The performance of the Pd/CNTs catalysts in the liquid-phase catalytic hydrodechlorination(HDC)of 4-chlorphenol(4-CP)under mild conditions was also investigated. Effects of reaction temperature,catalyst and NaOH dosage,substrate concentration,as well as the reaction kinetics were studied. The optimized operating parameters were obtained as reaction temperature 40℃,catalyst dosage 20mg,and Cl^-:OH^- =1:1.1(molar ratio). The reaction kinetics could be described by a zero-order kinetics model. The activation energy E_a and pre-exponential factor A were estimated as 40.12kJ/mol,and 1.66×10⁷mol/(L·min),respectively.

Key words: Pd/CNTs, catalyst, 4-chlorphenol(4-CP), hydrodechlorination(HDC), reaction kinetic

中图分类号:

TQ426.94

兰丽娟, 刘莺, 杜芳林. Pd/CNTs对4-氯苯酚的液相催化加氢去氯[J]. 化工进展, 2017, 36(06): 2171-2176.

LAN Lijuan, LIU Ying, DU Fanglin. Liquid-phase catalytic hydrodechlorination of 4-chlorophenol over Pd/CNTs[J]. Chemical Industry and Engineering Progress, 2017, 36(06): 2171-2176.

参考文献

[1] OLANIRAN A O,IGBINOSA E O. Chlorophenols and other related derivatives of environmental concern:properties,distribution and microbial degradation processes[J]. Chemosphere,2011,83(10):1297-1306.
[2] GIMENO O,CARBAJO M,BELTRAN F J,et al. Phenol and substituted phenols AOPs remediation[J]. Journal of Hazardous Materials,2005,119(1/2/3):99-108.
[3] United States Environmental Protection Agency. Emergency planning and community right-to-know section 313:list of toxic chemicals within the chlorophenols category[R]. Washington D C:Office of Pollution Prevention and Toxics,1999:5-6.
[4] 张智平,倪余文,杨志军,等. 垃圾焚烧过程二英生成的研究进展[J]. 化工进展,2004,23(11):1161-1167. ZHANG Z P,NI Y W,YANG Z J,et al. Advances of PCDD/F's formation during the waste incineration[J]. Chemical Industry and Engineering Progress,2004,23(11):1161-1167.
[5] JIANG Y,REN N Q,CAI X,et al. Biodegradation of phenol and 4-chlorophenol by the mutant strain CTM₂[J]. Chinese Journal of Chemical Engineering,2008,16(5):796-800.
[6] 宋爽,林莉莉,何志桥,等. Pd-Ni双金属复合物修饰泡沫镍电极对水中4-氯酚的电化学脱氯[J]. 化工学报,2009,60(6):1554-1559. SONG S,LIN L L,HE Z Q,et al. Electrochemical dechlorination of 4-chlorophenol in aqueous solution using a palladium-nickel bimetallic composite catalyst supported on nickel foam[J]. Journal of Chemical Industry and Engineering(China),2009,60(6):1554-1559.
[7] 徐小妹,潘顺龙,李健生,等. 多孔载体负载型 Fenton催化剂降解酚类污染物的研究进展[J]. 化工进展,2014,33(6):1465-1474. XU X M,PAN S L,LI J S,et al. Reserch progress of phenols degradation with Fenton catalyst supported on porous materials[J]. Chemical Industry and Engineering Progress,2014,33(6):1465-1474.
[8] THOMAS S,ALATRACHE A,PONS M-N,et al. Degradation of the herbicide isoproturon by a photocatalytic process[J]. Comptes Rendus Chimie,2014,17(7/8):824-831.
[9] XIA C H,LIU Y,XU J,et al. Catalytic hydrodechlorination reactivity of monochlorophenols in aqueous solutions over palladium/carbon catalyst[J]. Catalysis Communications,2009,10(5):456-458.
[10] MA X X,ZHOU S W,YANG C Y,et al. The influence of triethylamine on the hydrodechlorination reactivity of chlorophenols over Raney Ni catalyst[J]. Catalysis Communications,2010,12(4):282-285.
[11] ÁLVAREZ-MONTEROl M A,GOMEZ-SAINERO L M,MAYORAL A,et al. Hydrodechlorination of chloromethanes with a highly stable Pt on activated carbon catalyst[J]. Journal of Catalysis,2011,279(2):389-396.
[12] MA X X,LIU Y,LI X Q,et al. Water:the most effective solvent for liquid-phase hydrodechlorination of chlorophenols over Raney Ni catalyst[J]. Applied Catalysis B:Environmental,2015,165:351-359.
[13] XIA C H,MA X X,LIU S J,et al. Studies on remediation of DDT-contaminated soil and dechlorination of DDT[J]. Procedia Environmental Sciences,2012,16:289-292.
[14] XIA C H,LIU Y,ZHOU S W,et al. The Pd-catalyzed hydrodechlorination of chlorophenols in aqueous solutions under mild conditions:a promising approach to practical use in wastewater[J]. Journal of Hazardous Materials,2009,16(1/2/3):1029-1033.
[15] 金燕仙,施梅勤,刘委明,等. Pt/WC-CNTs催化剂的制备及其对氧还原的电催化性能[J]. 化工学报,2014,65(10):4015-4024. JIN Y X,SHI M Q,LIU W M,et al. Pt/WC-CNTs electrocatalyst for oxygen reduction reaction[J]. Journal of Chemical Industry and Engineering(China),2014,65(10):4015-4024.
[16] TAKASHI O,SHINJI I,MASASHI I. Synthesis and activity of the Pt catalyst supported on CNTs[J]. Catalysis Communications,2007,8(4):701-706.
[17] LI F,MA R,CAO B,et al. Effect of loading method on selective hydrogenation of chloronitrobenzenes over amorphous Ni-B/CNTs catalysts[J]. Catalysis Communications,2016,80(5):1-4.
[18] 刘博,刘云芳,迟伟东,等. 不同碱和酸处理对碳纳米管结构和形貌的影响[J]. 炭素技术,2008,27:1-6. LIU B,LIU Y F,CHI W D,et al.Effect of alkali and acid treatment on structures and morphologies of carbon nanotubes[J]. Carbon Techniques,2008,27:1-6.
[19] SINGH P,KULKARNI M V,GILHALE S P,et al. Enhancing the hydrogen storage capacity of Pd-functionalized multi-walled carbon nanotubes[J]. Applied Surface Science,2012,258(8):3405-3409.
[20] 张洪坤. 碳纳米管及锡-碳纳米管复合材料的电化学储锂性能研究[D]. 北京:北京化工大学,2013. ZHANG H K. Lithium storage properties of carbon nanotubes and tin-based carbon nanotube[D]. Beijing:Beijing University of Chemical Technology,2013.
[21] MA X X,LIU Y,LIU S J,et al. Water-promoted catalytic hydridechlorination of transformer oil-contained PCBs in liquid system under mild conditions[J]. Applied Catalysis B:Environmental,2014,144:580-587.
[22] NAVON R,ELDAD S,MACKENZIE K,et al. Protection of palladium catalysts for hydrodechlorination of chlorinated organic compounds in wastewaters[J]. Applied Catalysis B:Environmental,2012,119/120:241-247.
[23] YUAN G,KEANE M K. Liquid phase catalytic hydrodechlorination of 2,4-dichlorophenol over carbon supported palladium:an evaluation of transport limitations[J]. Chemical Engineering Science,2003,58(2):257-267.

Pd/CNTs对4-氯苯酚的液相催化加氢去氯

Liquid-phase catalytic hydrodechlorination of 4-chlorophenol over Pd/CNTs

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