物理超声改性膨润土吸附结晶紫染料的性能研究

doi:10.19965/j.cnki.iwt.2020-1205

摘要/Abstract

摘要：

为避免化学改性膨润土消耗大量化学试剂和二次污染，利用超声波对钙基膨润土进行改性得到超声钙基膨润土吸附材料，并将其用于吸附处理结晶紫模拟的染料废水。考察了超声制备工艺条件对吸附材料吸附性能的影响，并对其吸附机制及吸附热力学进行了研究。结果表明，在超声功率为100 W，超声时间为7 h的条件下制备得到的改性膨润土吸附效果最佳，对250 mg/L的结晶紫去除率达99.64%，吸附量达249.09 mg/g；准二级动力学方程和Langmuir等温吸附方程更适合描述该吸附机制，即对结晶紫的吸附主要是由化学吸附控制的单分子层吸附为主；热力学分析表明该吸附为自发吸热过程，高温对吸附更有利。

关键词: 超声, 膨润土, 结晶紫, 吸附

Abstract:

To avoid the consumption of massive chemical reagents and secondary pollution when preparing chemically modified bentonite, bentonite was modified by ultrasonic wave to obtain ultrasonic calcium bentonite adsorption material, which was used to treat the simulated dye wastewater of crystal violet. The effects of ultrasonic preparation conditions on the adsorption properties of the adsorbents were investigated, and the adsorption mechanism and thermodynamics were studied. The results showed that the modified bentonite with ultrasonic power 100 W and ultrasonic time 7 h had better adsorption effect, and the removal rate and adsorption capacity reached 99.64% and 249.09 mg/g respectively when the concentration of crystal violet was 250 mg/L; the pseudo-second order kinetic equation and langmuir isotherm adsorption equation were more suitable to describe the adsorption behavior mechanism and the crystal violet molecule is adsorbed on a single layer by chemical action; thermodynamic analysis showed that the adsorption was spontaneous endothermic process, high temperature was more beneficial to adsorption.

Key words: ultrasound, bentonite, crystal violet, adsorption

中图分类号:

X703.1

陈勇,程宁,杨育兵,卢凯玲,罗应. 物理超声改性膨润土吸附结晶紫染料的性能研究[J]. 工业水处理, 2021, 41(9): 98-103.

Yong Chen,Ning Cheng,Yubing Yang,Kailing Lu,Ying Luo. Adsorption of crystal violet dye by physical ultrasonic modified bentonite[J]. Industrial Water Treatment, 2021, 41(9): 98-103.

https://www.iwt.cn/CN/Y2021/V41/I9/98

图/表 10

图1 超声时间对US-Ca-Bent吸附性能的影响

Fig.1 Effect of ultrasonic time on the adsorption of crystal violet by bentonite

表1 膨润土超声改性前后的层间距变化

Table 1 Changes of bentonite interlayer spacing by ultrasound

项目	Ca-Bent(原土)	US-Ca-Bent
时间/h	-	1	3	5	7	9
层间距(d₀₀₁)/nm	1.38	1.43	1.45	1.48	1.52	1.50

图2 超声功率对US-Ca-Bent吸附性能的影响

Fig.2 The effect of ultrasonic power on the adsorption performance of US-Ca-Bent

图3 不同CV浓度溶液的等温吸附曲线

Fig.3 Adsorption isotherms of solutions with different CV concentrations

图4 吸附动力学

Fig.4 Adsorption kinetics

表2 动力学拟合参数

Table 2 Kinetic fitting parameters

ρ₀/(mg·L^-1)	Q_实/(mg·g^-1)	准一级动力学模型			准二级动力学模型
ρ₀/(mg·L^-1)	Q_实/(mg·g^-1)	Q_e/(mg·g^-1)	k₁/min^-1	R²	Q_e(mg·/g^-1)	k₂(g·mg^-1·/min^-1)	R²
200	199.53	0.84	0.07	0.801	199.20	0.11	0.999 9
250	248.10	8.77	0.12	0.920	248.76	0.09	0.999 9
300	298.65	44.61	0.13	0.785	300.30	0.05	0.999 8

图5 吸附等温线

Fig.5 Adsorption isotherm

表3 吸附等温线拟合参数

Table 3 Fitting parameters of adsorption isotherm

温度/℃	Langmuir方程			Freundlich方程
温度/℃	Q_m/(mg·g^-1)	k_L/(L·mg^-1)	R²	k_F/(mg·g^-1)	1/n	R²
30	353.36	1.07	0.999 5	224.00	0.13	0.950
45	353.36	3.78	0.999 7	257.55	0.11	0.690
60	364.96	3.49	0.999 4	290.95	0.05	0.138

图6 US-Ca-Bent吸附CV的lnk_c-T^-1曲线

Fig.6 Ink_c-T^-1 curve of US-Ca-Bent adsorbing CV

表4 US-Ca-Bent吸附CV的热力学参数

Table 4 Thermodynamic parameters of ultrasonic bentonite adsorbing crystal violet

T/K	ΔG/(kJ·mol^-1)	ΔS/(J·mol^-1·K^-1)	ΔH/(kJ·mol^-1)
293.15	-10.67	156.28	35.3
303.15	-11.86
313.15	-13.58
323.15	-16.24
333.15	-16.74

参考文献 30

1	Robinson T , Mcmullan G , Marchant R , et al. Remediation of dyes in textile effluent: A critical review on current treatment technologies with a proposed alternative[J]. Bioresource Technology, 2001, 77 (3): 247- 255. doi: 10.1016/S0960-8524(00)00080-8
2	Qadaene , Allen S J , Walker G M . Adsorption of methylene blue onto activated carbon produced from steam activated bituminous coal: A study of equilibrium adsorption isotherm[J]. Chemical Engineering Journal, 2006, 124 (1/2/3): 103- 110. URL
3	Sun Huaiyan , Jin Xinyu , Long Nengbing , et al. Improved biodegradation of synthetic azo dye by horseradish peroxidase cross-linked on nano-composite support[J]. International Journal of Biological Macromolecules, 2017, 95 (2): 1049- 1055.
4	Gonzalez-bahamon L F , Hoyos D F , Benitez N , et al. New Fe-immobilized natural bentonite plate used as photo-Fenton catalyst for organic pollutant degradation[J]. Chemosphere, 2011, 82 (8): 1185- 1189. doi: 10.1016/j.chemosphere.2010.11.071
5	Lin Jiahong , Fan Ling , Miao Runli , et al. Enhancing catalytic performance of laccase via immobilization on chitosan/CeO₂ microspheres[J]. International Journal of Biological Macromolecules, 2015, 78 (7): 1- 8. URL
6	Bhattacharya D , Ghoshal D , Mondal D , et al. Visible light driven degradation of brilliant green dye using titanium based ternary metal oxide photocatalyst[J]. Results in Physics, 2019, 12 (2): 1850- 1858. URL
7	Li Zhaohui , Potter N , Rasmussen J , et al. Removal of rhodamine 6G with different types of clay minerals[J]. Chemosphere, 2018, 202 (7): 127- 135. URL
8	Marrakchi F , Khanday W A , Asif M , et al. Cross-linked chitosan/sepiolite composite for the adsorption of methylene blue and reactive orange 16[J]. International Journal of Biological Macromolecules, 2016, 93 (12): 1231- 1239. URL
9	Georgiou D , Melidis P , Aivasidis A . Use of a microbial sensor: Inhibition effect of azo-reactive dyes on activated sludge[J]. Bioprocess & Biosystems Engineering, 2002, 25 (2): 79- 83. URL
10	Robinson T , Mcmullan G , Marchant R , et al. Remediation of dyes in textile effluent: A critical review on current treatment technologies with a proposed alternative[J]. Bioresource Technology, 2001, 77 (3): 247- 255. doi: 10.1016/S0960-8524(00)00080-8
11	Yagub M T , Sen T K , Afroze S , et al. Dye and its removal from aqueous solution by adsorption: A review[J]. Advances in Colloid and Interface Science, 2014, 209, 172- 184. doi: 10.1016/j.cis.2014.04.002
12	Li Chaodao , Lu Jianjiang , Li Shanman , et al. Synthesis of magnetic microspheres with sodium alginate and activated carbon for removal of nethylene blue[J]. Materials, 2017, 10 (1): 84. doi: 10.3390/ma10010084
13	Wang Jie , Gao Manglai , Shen Tao , et al. Insights into the efficient adsorption of rhodamine B on tunable organo-vermiculites[J]. Journal of Hazardous Materials, 2019, 366 (3): 501- 511. URL
14	Munir M , Ahmad M , Saeed M , et al. Sustainable production of bioenergy from novel non-edible seed oil(prunus cerasoides) using bimetallic impregnated montmorillonite clay catalyst[J]. Renewable and Sustainable Energy Reviews, 2019, 109, 321- 332. doi: 10.1016/j.rser.2019.04.029
15	Aradwaj G B B , Parida K , Nyamori V O . Transforming inorganic layered montmorillonite into inorganic-organic hybrid materials for various applications: A brief overview[J]. Inorganic Chemistry Frontiers, 2016, 3 (9): 1100- 1111. doi: 10.1039/C6QI00179C
16	Long Hang , Wu Pingxiao , Zhu Nengwu . Evaluation of Cs⁺ removal from aqueous solution by adsorption on ethylamine-modified montmorillonite[J]. Chemical Engineering Journal, 2013, 225 (6): 237- 244. URL
17	Su Jin , Huang Huaiguo , Jin Xiaoying , et al. Synthesis, characterization and kinetic of a surfactant-modified bentonite used to remove As(Ⅲ) and As(Ⅴ) from aqueous solution[J]. Journal of Hazardous Materials, 2011, 185 (1): 63- 70. doi: 10.1016/j.jhazmat.2010.08.122
18	Yu Xubiao , Wei Chaohai , Ke Lin , et al. Development of organovermiculite-based adsorbent for removing anionic dye from aqueous solution[J]. Journal of Hazardous Materials, 2010, 180 (1/2/3): 499- 507. URL
19	Zhu Runliang , Chen Wangxiang , Liu Yun , et al. Application of linear free energy relationships to characterizing the sorptive characteristics of organic contaminants on organoclays from water[J]. Journal of Hazardous Materials, 2012, 233/234 (9): 228- 234. URL
20	胡智强. 改性膨润土对废水中孔雀石绿和亚甲基蓝的吸附性能研究[D]. 呼和浩特: 内蒙古大学, 2016.
21	张寒冰, 张天顺, 唐艳葵. 碱性钙基膨润土对亚甲基蓝和刚果红的吸附去除[J]. 精细化工, 2013, (6): 61- 65. URL
22	李煜珊, 欧阳志云. 铝柱撑膨润土吸附处理水中磷酸根和结晶紫[J]. 矿物学报, 2015, 35 (2): 117- 121. URL
23	王志明, 吕宪俊, 渠美云. 膨润土提纯工艺研究[J]. 现代矿业, 2013, 29 (3): 26- 29. doi: 10.3969/j.issn.1674-6082.2013.03.008
24	刘怡, 唐燕, 郑骏鸣, 等. 物理改性膨润土吸附苯胺的比较研究[J]. 华南农业大学学报, 2007, 28 (2): 116- 118. doi: 10.3969/j.issn.1001-411X.2007.02.030
25	姜文彬, 俞志明, 曹西华, 等. 超声改性对不同粘土去除藻华生物效率的影响[J]. 海洋与湖沼, 2018, 49 (3): 560- 567. URL
26	王萍辉. 超声空化影响因素[J]. 河北理工学院学报, 2003, 25 (4): 158- 165. URL
27	王希越, 明明, 连丽丽, 等. 磁性氧化石墨烯纳米粒子的制备及其对大红染料的去除[J]. 应用化工, 2019, 48 (10): 2324- 2327. doi: 10.3969/j.issn.1671-3206.2019.10.013
28	Liu Kai , Zhang Siyu , Hu Xiyue , et al. Understanding the adsorption of pfoa on mil-101(Cr)-based anionic-exchange metal-organic frameworks: Comparing DFT calculations with aqueous sorption experiments[J]. Environmental Science & Technology, 2015, 49 (14): 8657- 8665. URL
29	Mahmoodi , Mohammad N . Equilibrium, kinetics, and thermodynamics of dye removal using alginate in binary systems[J]. Journal of Chemical & Engineering Data, 2011, 56 (6): 2802- 2811. URL
30	Hsu T C , Yu C C , Yeh C M . Adsorption of Cu²⁺ from water using raw and modified coal fly ashes[J]. Fuel, 2008, 87 (7): 1355- 1359. doi: 10.1016/j.fuel.2007.05.055

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