有机改性凹凸棒石吸附4-氯苯酚的研究
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摘要
本文用十六烷基三甲基溴化铵(CTAB)改性凹凸棒石,制备了不同负载量的有机改性凹凸棒石,对比研究了不同负载量的有机改性凹凸棒石对4-氯苯酚吸附能力;通过三种方式研究有机改性凹凸棒石对4-氯苯酚溶液的吸附;通过吸附热力学和动力学实验探讨了有机改性凹凸棒石对4-氯苯酚溶液吸附机理。结果表明:
三种不同方式的吸附研究中,第三种方式的吸附效果最好;有机改性凹凸棒石对4-氯苯酚溶液的吸附平衡数据能够较好得符合Freundlich吸附等温方程。对4-氯苯酚的吸附焓变为-11.55kJ/mol,是一个放热过程。对4-氯苯酚吸附自由能为负值,是常温常压下可以自发的过程,是物理和化学吸附并存的过程,并且是熵增过程。有机改性凹凸棒石对4-氯苯酚溶液的吸附能够较好地符合准二级动力学方程;表观活化能为19.24kJ/mol,表明此吸附并不是单一的以化学吸附为速率控制步骤,同时也存在一个以液膜扩散为速率控制步骤,是由液膜扩散和化学吸附共同控制的过程。发现有机改性凹凸棒石对4-氯苯酚溶液的吸附性能与表面活性剂载量呈正相关,有机改性凹凸棒石的吸附性能随着表面活性剂负载的增加而呈现出先增加后减小的变化趋势。
The cetyltrimethyl ammonium bromide (CTAB) is used to prepare organic modified palygorskites at different capacities. The contrast of adsorptive capacity of them to 4-chlorophenols has been studied. In three ways, the adsorption experiments by organic modified palygorskite to 4-chlorophenols are carried out. And the adsorption mechanism is studied through the experiments of adsorption thermodynamics and dynamics. The results are presented as follows:
In the adsorption study, result of the third way has proved to be better. The adsorption results by organic modified palygorskite to 4-chlorophenol can fit well to the Freundlich adsorption equation through isothermal adsorption data. The adsorption enthalpy is 11.55kJ/mol, so the reation is proved to be an exothermic process. While the adsorption free energy is negative, the adsorption is a spontaneous process under the normal atmospheric pressure and at room temperature. Furthermore, through the thermodynamics and dynamics experiments, the process has been proved to be a coexist reaction, which contains both physical and the chemical adsorptions. It can also be found that the entropy increases in the process. The second order dynamic equation is applied to adsorption of 4- chlorophenol by organic modified palygorskite as well, and then the experimental data are proved to fit well into the form. The apparent adsorption active energy is 19.24kJ/mol. This relatively low apparent adsorption activation energy suggests that the adsorption of organic modified palygorskite may be involved in not only chemical but also physicial adsportion process, which is likely attributed to its combined control of chemical adsorption and film diffusion. Finally it is discovered that the adsorption capacity is related to the loaded capacity of used surfactant. The adsorption capacity increases at first, then reduces when the loaded capacity of surfactant increases.
三种不同方式的吸附研究中,第三种方式的吸附效果最好;有机改性凹凸棒石对4-氯苯酚溶液的吸附平衡数据能够较好得符合Freundlich吸附等温方程。对4-氯苯酚的吸附焓变为-11.55kJ/mol,是一个放热过程。对4-氯苯酚吸附自由能为负值,是常温常压下可以自发的过程,是物理和化学吸附并存的过程,并且是熵增过程。有机改性凹凸棒石对4-氯苯酚溶液的吸附能够较好地符合准二级动力学方程;表观活化能为19.24kJ/mol,表明此吸附并不是单一的以化学吸附为速率控制步骤,同时也存在一个以液膜扩散为速率控制步骤,是由液膜扩散和化学吸附共同控制的过程。发现有机改性凹凸棒石对4-氯苯酚溶液的吸附性能与表面活性剂载量呈正相关,有机改性凹凸棒石的吸附性能随着表面活性剂负载的增加而呈现出先增加后减小的变化趋势。
The cetyltrimethyl ammonium bromide (CTAB) is used to prepare organic modified palygorskites at different capacities. The contrast of adsorptive capacity of them to 4-chlorophenols has been studied. In three ways, the adsorption experiments by organic modified palygorskite to 4-chlorophenols are carried out. And the adsorption mechanism is studied through the experiments of adsorption thermodynamics and dynamics. The results are presented as follows:
In the adsorption study, result of the third way has proved to be better. The adsorption results by organic modified palygorskite to 4-chlorophenol can fit well to the Freundlich adsorption equation through isothermal adsorption data. The adsorption enthalpy is 11.55kJ/mol, so the reation is proved to be an exothermic process. While the adsorption free energy is negative, the adsorption is a spontaneous process under the normal atmospheric pressure and at room temperature. Furthermore, through the thermodynamics and dynamics experiments, the process has been proved to be a coexist reaction, which contains both physical and the chemical adsorptions. It can also be found that the entropy increases in the process. The second order dynamic equation is applied to adsorption of 4- chlorophenol by organic modified palygorskite as well, and then the experimental data are proved to fit well into the form. The apparent adsorption active energy is 19.24kJ/mol. This relatively low apparent adsorption activation energy suggests that the adsorption of organic modified palygorskite may be involved in not only chemical but also physicial adsportion process, which is likely attributed to its combined control of chemical adsorption and film diffusion. Finally it is discovered that the adsorption capacity is related to the loaded capacity of used surfactant. The adsorption capacity increases at first, then reduces when the loaded capacity of surfactant increases.
引文
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[2]易发成,李虎杰,田煦,等.坡缕石的酸活化及其吸附性能研究[J].矿产综合利用,1995,(6):41-44.
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[4] Gonzale F, Pesquera C, Benito I. Mechanism of acid activation magnesic palygorskite [J]. Clays and Clay Minerals, 1989, 37(3):258-262.
[5]王连军,黄中华,孙秀云,等.改性凹凸棒土处理染化废水研究[J].南京理工大学学报,1998,22(3):240-243.
[6]裘祖楠,翁性尚,李勇,等.活化凹凸棒石对阳离子染料的脱色作用及其应用研究[J].中国环境科学,1997,17(4):373-376.
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[8]赵萍,姚莹.凹凸棒石改性方法及其应用现状[J].化工生产与技术,2006,13(5):47-55.
[9] Barterlt-Hunt S L, Burns S E, Smith J A. Nonionic organic solute sorption onto two organobentionites as a function of organic-carbon content. J Colloid Interface Sci, 2003, 266: 251-258.
[10] Zhu L, Chen B, Tao S, et al. Interactions of organic contaminants with mineral-adsoebed surfactant. Environ Sci Technol, 2003, 37:4001-4006.
[11]包军杰,余贵芬,蒋新,等,改性凹凸棒石对模拟含酚废水处理机制的研究[J].环境化学,2006,11(25):37-40.
[12]黄健花,王兴国,金清哲,等.超声波处理凹凸棒土的有机改性研究[J].中国油脂,2002, 30(2):28-30.
[13]黄健花,王兴国,金清哲,等,超声波处理凹凸棒土的苯酚吸附性能研究[J].环境污染治理技术与设备,2005,6(9):25-28.
[14]黄健花,王兴国,金清哲,等,超声波改性OTMAC-凹凸棒土的吸附苯酚[J].水处理技术,2005,31(9):61-64.
[15]王瑛,谢刚.有机改性凹凸棒石吸附微污染水中苯酚的实验研究[J].兰州理工大学学报.2006,18(1):111-113.
[16]宋勇,戴友芝.超声波及其联用技术处理有机污染物的研究进展[J].工业安全与环保,2005,31(7):1- 3.
[17]史雅娟,吕永龙,任鸿昌,等.持久性有机污染物研究的国际发展动态[J] .世界科技研究与发展,2003 , 25(2) :73 - 78.
[18]刘建国,唐孝炎,胡建信.持久性生物累积性有毒污染物与国际相关控制策略和行动[J] .环境保护,2003 ,(4) :52 - 56.
[19]孙成均.二恶英类化合物的环境污染、毒性及分析方法[J] .现代预防医学,2000 ,27(1):63 - 66.
[20]王火华,林清.持久性有机污染物[J] .化工技术与开发,2008 ,4 (37) 4: 29-34.
[21]魏瑞霞,陈连龙,陈金龙.三种不同树脂对硫辛酸吸附行为的研究[J].环境化学,2004,23(4): 387-392.
[22] Ajamal M, Rao Ak, Ahmad R, et al. Adsorption studies on citrus reticula fruit peel of orange: removal and recovery of Ni (II) from electroplating wastewater [J]. Journal of Hazardous Materials, 2000, 79(1-2):117-131.
[23] Gürses A, Karaca S, Dogar C, et al. Determination of adsorptive properties of clay/water system: methylene blue sorption [J]. Journal of Colloid and Interface Science, 2004,269 (2):310-314.
[24] HO YS, McKay G. The sorption of lead (II) ions on peat [J]. Water Research,1998,33(2): 578-584.
[25] Lagergern S.About the theory of so-called adsorption of soluble substances [J].Kungliga Svenska Vetenskapsakademiens. Handlingar. Band,1989, 24 (4): 1-39.
[26] Ho YS. Adsorption of heavy metals from waste streams by peat [D]. UK Birmingham: University of Birmingham, 1995.
[27]李济吾,朱利中,蔡伟建.微波作用下表面活性剂在膨润土上的吸附行为特征[J].环境科学,2007,28(11):2642-2645.
[28] Chiou MS, Ho PY, Li HY. Adsorption of anionic dyes in acid solutions using chemically cross-linked chitosan beads [J]. Dyes and Pigments, 2004,60(1): 69-84.
[29] McKay G, HO YS. Pseudo-second order model for sorption process [J]. Process Biochemistry, 1999,34(5):451-465.
[30] Ho YS, Mckay G. Sorption of dye from aqueous solution by peat [J]. Chemical Engineering Journal, 1998, 70(2):115-124 .
[31] Chang CY, Tsai WT, Ing CH, et al. Adsorption of polyethylene glycol(PEG) from aqueous solution onto hydrophobic zeolite [J]. Journal of Colloid and Interface Science, 2003, 260(2):273-279.
[32]陈天虎.水悬浮体系中凹凸棒石与Cu2+作用机理[J].高校地质学报, 2004,10 (3): 385-392.
[33]陈天虎,张国生,范文元.凹凸棒石粘土处理印染废水的研究[J].环境污染与防治,1995,17(1): 24-26.
[34]陈天虎.改性凹凸棒石粘土吸附性能对比实验研究[J].工业水处理, 2000,20(4): 27-29.
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