十六烷基三甲基溴化铵修饰P型沸石吸附水中直链烷基苯磺酸钠的研究

doi:10.7503/cjcu20150667

摘要/Abstract

摘要：

通过使用碱液对天然斜发沸石(Z)进行处理制得P型沸石(PZ), 再用十六烷基三甲基溴化铵(CTMAB)对Z和PZ进行修饰, 制得有机改性沸石ZC和PZC, 对比考察了ZC和PZC对直链烷基苯磺酸钠(LAS)的吸附性能. 实验结果表明, 制得的PZ硅/铝比为2, 比Z(4.85)降低58.8%; PZ的零净电荷点、比表面积、孔径和孔容均高于Z; 吸附平衡时间为4 h. 当pH=2时, ZC和PZC对LAS吸附量达到最高, 吸附数据符合Langmuir准二级动力学方程和Langmuir等温吸附方程, 饱和吸附量(q_m)分别为12.658和27.100 mg/g, 吸附过程主要为单分子层的化学吸附, PZC的吸附速率常数大于ZC, 具有更好的动力学性能.

关键词: P型沸石, 十六烷基三甲基溴化铵, 直链烷基苯磺酸钠, 吸附

Abstract:

Zeolite P(PZ) was prepared by the natural clinoptilolite(Z) that was treated with lye, and then Z and PZ were modified by cationic surfactant cetrimonium bromide(CTMAB) to prepare ZC and PZC. The adsorption abilities of ZC and PZC to linear alkylbenzene sulfonate(LAS) were studied. The results indicated that the Si/Al ratio of PZ was 2, 58.8% lower than that of Z(4.85); the point of zero net charge(PZNC), specific surface area, pore radius and pore volume of PZ were higher than those of Z; the adsorption equilibrium was reached after 4 h. ZC and PZC had a maximum adsorption capacity for LAS at pH=2. The adsorption process was well fitted with pseudo-second order kinetic equation and Langmuir isothermal adsorption model. The amount of saturated adsorption of ZC and PZC are 12.658 and 27.100 mg/g, respectivey, showing that the adsorption process is described primarily for the monolayer and chemical adsorption, the adsorption of LAS on PZC is better than that on ZC in view of point of capacities and velocities.

Key words: Zeolite P, Cetrimonium bromide(CTMAB), Linear alkylbenzene sulfonate(LAS), Adsorption

中图分类号:

O647.32

TrendMD:

谭文渊, 徐曼, 曾英. 十六烷基三甲基溴化铵修饰P型沸石吸附水中直链烷基苯磺酸钠的研究. 高等学校化学学报, 2016, 37(1): 65.

TAN Wenyuan, XU Man, ZENG Ying. Study on the Adsorption Ability to Linear Alkylbenzene Sulfonate of Zeolite P Modified by Cetrimonium Bromide in Waste Water. Chem. J. Chinese Universities, 2016, 37(1): 65.

图/表 15

Fig.1 EDS of PZ(a) and Z(b)

Fig.2 SEM images of Z(A), ZC(B), PZ(C) and PZC(D)

Fig.3 XRD patterns of PZ(a) and Z(b)^ Z: Zeolite; Q: Quartz.

Fig.4 Mass titration curves of Z(A) and PZ(B)

Table 1 Results of BET analysis

Zeolite	S_BET/(m²·g^-1)	Total pore volume of adsorption(BJH)/(cm³·g^-1)	Most probable pore size(BJH)/nm
Z	12.794	0.0704	1.86
ZC	9.181	0.0700	1.94
PZ	42.053	0.2147	3.78
PZC	30.135	0.1827	1.92

Fig.5 IR spectra of CTMAB(a), ZC(b), PZC(c) and Z(d)

Table 2 Results of C, H, N measurement and CTMAB loading

Zeolite	C	H	N	Loading of CTMAB/(mg·g^-1)
ZC	8.31	1.54	0.45	11.71
PZC	16.2	2.99	0.95	24.73

Fig.6 Effect of pH on LAS adsorption onto ZC(a) and PZC(b)

Fig.7 Effect of temperature on LAS adsorption onto ZC(a) and PZC(b)

Fig.8 Effect of time on LAS adsorption onto ZC(a) and PZC(b)

Fig.9 Kinetic model fitting of Langmuir pseudo-first order(A) and pseudo-second order(B)

Table 3 Kinetic model fitting parameters of Langmuir pseudo-first and pseudo-second order

Equation type	Zeolite	R²	q_e/(mg·g^-1)	K/min^-1	Δq
Langmuir pseudo-first order	PZC	0.902	12.570	0.018	0.263
	ZC	0.950	3.640	0.015	0.199
Pseudo-second order	PZC	0.999	23.800	0.042	0.037
	ZC	0.999	9.390	0.011	0.025

Fig.10 LAS adsorption isotherms of Langmuir equation^The inset shows the varies of the adsorption capacity with the concentration at equilibrium.

Fig.11 Adsorption isotherms of Freundlich equation

Table 4 Fitting results of isothermal Langmuir and Freundlich equation

Zeolite	Langmuir equation			Freundlich equation
Zeolite	q_m	K_L	R²	K_F	n	r
PZC	27.100	1.157	0.989	14.440	5.464	0.950
ZC	12.658	0.177	0.994	4.547	4.254	0.818

参考文献 38

[1]	Hodges G., Roberts D. W., Marshall S. J., Dearden J. C., Chemosphere,2006, 63(9), 1443—1450
[2]	Hampel M., Moreno-Garrido I., González-Mazo E., Blasco J., Ecotoxicol. Environ. Saf., 2009, 72(4), 1303—1308
[3]	Rico-Rico A., Temara A., Hermens J. L., Environ. Pollut., 2009, 157(2), 575—581
[4]	Oliver-Rodríguez B., Zafra-Gómez A., Reis M. S., Duarte B. P. M., Chemosphere,2015, 131, 1—8
[5]	Gong J. S., Wang Y., Zhang D. D., Li H., Zhang X. M., Zhang R. X., Chem. Res. Chinese Universities, 2015, 31(1), 91—97
[6]	Shah A. A., Nawaz A., Kanwal L., Int. Biodeterior. Biodegrad., 2015, 98, 35—42
[7]	Anachkov S. E., Tcholakova S., Dimitrova D. T., Denkov N. D., Colloids Surf., A: Physicochem. Eng. Asp., 2015, 466, 18—27
[8]	García-Luque E., González-Maz E., Forja J. M., Gómez-Parra A., Coastal andShelf Science, 2009, 81(3), 353—358
[9]	Terechova E. L., Zhang G. Q., Chen J., Sosnina N. A., Yang F. L., J. Environ. Chem. Eng., 2014, 2(4), 2111—2119
[10]	Delforno T. P., Moura A. G. L., Okada D. Y., Sakamoto I. K., Varesche M. B. A., Bioresour. Technol., 2015, 192, 37—45
[11]	Hernández-Soriano M. C., Mingorance M. D., Peña A., J. Environ. Monit., 2012, 95, S223—S227
[12]	García M. T., Campos E., Ribosa I., Latorre A., Sánchez-Leal J., Chemosphere,2005, 60(11), 1636—1643
[13]	Dehghani M. H., Najafpoor A. A., Azam K., Desalination,2010, 250, 82—86
[14]	Song Y., Wang X. J., Mai J. S., China Surfactant Detergent & Cosmeitcs,2008, 38(1), 12—15
	(宋扬, 汪晓军, 麦均生. 日用化学工业, 2008, 38(1), 12—15)
[15]	Bi Y.J., Preparation of Zn/Al Hydrotaicite-liked Compound and the Research on Capability of Adsorption Removal of Anionic Surfactants from Aqueous Solution, Shandong University, Jinan, 2007
	(毕研俊. Zn/Al类水滑石制备及其吸附去除水中阴离子表面活性剂性能研究, 济南: 山东大学, 2007)
[16]	Garcia M. T., Compos E., Dalmau M., Chempsphere,2002, 49(3), 279—286
[17]	Wang L., Zhang C., Zhong M. J., Qian P., Chem. J. Chinese Universities, 2015, 36(7), 1358—1366
	(汪靓, 张超, 钟明静, 钱萍. 高等学校化学学报, 2015, 36(7), 1358—1366)
[18]	Hosseinpou M., Charkhi A., Ahmadi S. J., Journal of Supercritical Fluids, 2015, 102, 40—49
[19]	Hou T. Y., Jiang Y. S., Li F. F., Sun S. M., Chem. J. Chinese Universities, 2006, 27(1), 100—103
	(侯天意, 蒋引珊, 李芳菲, 孙申美. 高等学校化学学报, 2006, 27(1), 100—103)
[20]	Zhang L. L., Liu S. Y., Li Z. J., Yao J., Wang G. Y., Chem. J. Chinese Universities, 2014, 35(4), 812—817
	(张丽雷, 刘绍英, 李子健, 姚洁, 王公应. 高等学校化学学报,2014, 35(4), 812—817), 812—817)
[21]	Courtney T. D., Chang C. C., Gorte R. J., Lobo Raul F., Wei F., Microporous Mesoporous Mater., 2015, 210, 69—76
[22]	Liao Z. L., Chen H., Zhu B. R., Li H. Z., Chemosphere,2015, 134, 127—132
[23]	Benaliouche F., Hidous N., Guerza M., Zouad Y., Boucheffa Y., Microporous Mesoporous Mater., 2015, 209, 184—188
[24]	Camino G. A., Aida G. A., Elena S., Antonio A. R., Javier G. M., Rafael L., J. Mol. Catal. A: Chem., 2015, 406, 40—45
[25]	Nikolay K., Clement A., Gerard J. B., Venkata G. P., Sripathi, Emiel J . M., J. Membr. Sci., 2015, 484, 140—145
[26]	Thiago F. C., Heloise O. P., Peter H., Dilson C., Microporous Mesoporous Mater., 2015, 202, 198—207
[27]	Arezou N., Alireza N. E., J. Ind. Eng. Chem., 2015, 2567, 1—7
[28]	Maedeh B., Alireza N. E., Colloids Surf., A: Physicochemical and Engineering Aspects, 2015, 479, 35—45
[29]	Li X. H., Zhu K., Water Purification Technology, 2008, 27(3), 5—8, 24
	(李效红, 朱琨. 净水技术, 2008, 27(3), 5—8, 24)
[30]	Anaraki A. M., Ejhieh A. N., J. Colloid Interface Sci., 2015, 440, 272—281
[31]	Xiao J. Q., Wei Z. Y., SP & BMH Related Engineering,2007, 5, 19—22
	(肖举强, 魏朝燕. 硫磷设计与粉体工程, 2007, 5, 19—22)
[32]	Zhang Z. H., Dou T., Zhang Z. Y., Industrial Catalysis, 2004, 12(10), 49—53
	(张志华, 窦涛, 张瑛. 工业催化, 2004, 12(10), 49—53)
[33]	Silvio R. T., Rubio J., Miner. Eng., 2010, 23, 771—779
[34]	Xu J., Hou W. G., Zhou W. Z., Tai P. D., Acta Chim. Sinica, 2007, 65(13), 1191—1196
	(徐洁, 侯万国, 周维芝, 台培东. 化学学报, 2007, 65(13), 1191—1196)
[35]	Li L. F., Hou W. G., Dai X. N., Liu C. X., Acta Chim. Sinica, 2004, 62(4), 429—432
	(李丽芳, 侯万国, 戴肖南, 刘春霞. 化学学报, 2004, 62(4), 429—432)
[36]	Kazemian H., Modanls H., J. Radioanal. Nucl. Chem., 2003, 258, 551—560
[37]	Xie J., Wang Z., Wu D. Y., Environmental Science, 2012, 33(12), 4361—4367
	(谢杰, 王哲, 吴德意. 环境科学, 2012, 33(12), 4361—4367)
[38]	Wan D. J., Yuan H. J., Qu D., Chinese Journal of Environmental Engineering,2011, 5(12), 2681—2685
	(万东锦, 袁海静, 曲丹. 环境工程学报, 2011, 5(12), 2681—2685)