磁性MCM-41分离回收RT培司废水中四甲基氢氧化铵的研究

doi:10.15541/jim20150591

无机材料学报 ›› 2016, Vol. 31 ›› Issue (7): 694-698.DOI: 10.15541/jim20150591

磁性MCM-41分离回收RT培司废水中四甲基氢氧化铵的研究

李裕, 米琴, 薛泽慧

(中北大学化工与环境学院, 太原 030051)

收稿日期:2015-11-30 修回日期:2015-12-29 出版日期:2016-07-20 网络出版日期:2016-06-22
基金资助:
山西省科技重大专项资助(20111101013)

Magnetic MCM-41 for TMAOH Recovery from RT Base Wastewater

LI Yu, MI Qin, XUE Ze-Hui

(School of Chemical Engineering and Environment, North University of China, Taiyuan 030051, China)

Received:2015-11-30 Revised:2015-12-29 Published:2016-07-20 Online:2016-06-22
Supported by:
The Major Program of Science and Technology of Shanxi Province (20111101013)

摘要/Abstract

摘要：

硝基苯法合成RT培司(4-氨基二苯胺)的废水色度高、组分复杂、催化剂四甲基氢氧化铵(TMAOH)难以分离回收。提出采用磁性MCM-41对RT培司废水中有机副产物进行选择性吸附分离。制备的磁性MCM-41样品采用X射线衍射仪(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、N₂吸附-脱附和振动样品磁场计(VSM) 等手段进行表征。结果表明, 磁性MCM-41颗粒的粒径范围为200~300 nm, BET比表面积约为655.2 m²/g, 孔径分布为0.5~4 nm, 内核铁酸镍的存在使磁性MCM-41具有超顺磁性。吸附研究表明磁性MCM-41对RT培司废水中吩嗪、偶氮苯和苯胺等有机物具有良好吸附作用, 经5次吸附磁分离后, RT培司废水中四甲基氢氧化铵能够达到回用要求, 吸附后的磁性MCM-41在外加磁场下极易分离。

关键词: RT培司废水, 磁性MCM-41, 四甲基氢氧化铵, 吸附分离

Abstract:

RT base wastewater has high colority, complex components and troubles to recover the TMAOH catalyst in the process of RT base production by nitrobenzene method. Selectively adsorption and separation of by-product from RT base wastewater with magnetic MCM-41 adsorbent was proposed to recover the TMAOH. The magnetic MCM-41 samples prepared were characterized by transmission electron microscopy (TEM), scanning electron microscope (SEM), X-ray diffraction (XRD), N₂ adsorption-desorption vibrating sample magnetometer (VSM). The results showed that the samples had an obvious core-shell structure with an average size of about 200~300 nm in diameter. The N₂ adsorption-desorption results showed that the magnetic MCM-41 exhibited micro-mesoporous structure with specific area of 655 m²/g and pore size distribution of 0.5-4 nm. The as-prepared magnetic MCM-41 displayed typical super paramagnetic property due to the inside component of NiFe₂O₄. The adsorption experiments showed that magnetic MCM-41 selectively adsorbed phenazine, azobenzene and aniline from RT base wastewater. TMAOH aqueous solution could be reused after 5 times adsorptive separation. The synthesized magnetic MCM-41 exhibits high adsorption efficiency and potential applications for the recover for TMAOH catalyst from RT base wastewater with the help of magnetic separation.

Key words: RT base wastewater, magnetic MCM-41, TMAOH, adsorption and separation

中图分类号:

O644

李裕, 米琴, 薛泽慧. 磁性MCM-41分离回收RT培司废水中四甲基氢氧化铵的研究[J]. 无机材料学报, 2016, 31(7): 694-698.

LI Yu, MI Qin, XUE Ze-Hui. Magnetic MCM-41 for TMAOH Recovery from RT Base Wastewater[J]. Journal of Inorganic Materials, 2016, 31(7): 694-698.

图/表 8

图1 磁性MCM-41的TEM(a)和SEM(b)照片

Fig. 1 TEM (a) and SEM (b) images of the magnetic MCM-41 particles

图2 磁性MCM-41的XRD图谱

Fig. 2 XRD patterns of the magnetic MCM-41 particles samples

图3 磁性MCM-41的N2吸附-脱附等温线

Fig. 3 N2 adsorption-desorption isotherms of the magnetic MCM-41 samples

表1 磁性MCM-41的比表面积及孔径分布

Table 1 Specific surface area and pore size distribution of the magnetic MCM-41

Samples	Surface area/ (m²•g^-1)	Microporous average pore size/nm	Pore volume of micropores/ (cm³•g^-1)	Mesoporous average pore size/nm	Total pore volume of pores/(cm³•g^-1)
MCM-41	988.0	0.87	0.42	2.78	1.12
Magnetic MCM-41	655.2	0.56	0.32	2.77	0.56

图4 NiFe2O4和磁性MCM-41样品的磁滞回线

Fig. 4 Magnetization of NiFe2O4 and magnetic MCM-41 samples

图5 磁性MCM-41吸附分离RT培司废水的循环使用效果

Fig. 5 Reused adsorption separation from RT base wastewater of the magnetic MCM-41 samples

表2 磁性MCM-41对RT培司废水等温吸附拟合参数

Table 2 Isotherm parameters for organics adsorption onto magnetic MCM-41

Isotherm equation	Parameters	Phenazine	Azobenzene	Aniline
Langmuir q_e=bq⁰c_e/ (1+bc_e)	q⁰/(mg·g^-1)	403	480	387
	b/(L·g^-1)	2.49	25.30	6.74
	R²	0.99	0.98	0.99
Freundlich q_e=K_Fc_e^1/ⁿ	K/(L·g^-1)	7.17	10.10	7.30
	n	1.70	3.70	1.35
	R²	0.97	0.86	0.94

图6 磁性MCM-41吸附分离RT培司废水中四甲基氢氧化铵机理示意图

Fig. 6 TMAOH separation mechanism from RT base wastewater by using magnetic MCM-41

参考文献 12

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磁性MCM-41分离回收RT培司废水中四甲基氢氧化铵的研究

Magnetic MCM-41 for TMAOH Recovery from RT Base Wastewater

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