Adsorption of dyes in water by multiwall carbon nanotubes/chitosan composite

doi:10.19965/j.cnki.iwt.2021-0689

Abstract

Abstract:

With the rapid development of printing and dyeing industry in China， a large amount of printing and dyeing wastewater is produced. The printing and dyeing wastewater is characterized by high chroma， high concentration of difficultly degradable organic compounds and high fluctuation of water quality， which poses a risk to environment and human health. Multiwall carbon nanotubes/chitosan composite（MWCNTs/CS） were prepared by alkali deposition cross-linking method to adsorb xylenol orange and alizarin red simulated wastewater， and the effects of different preparation conditions on the adsorption performance were investigated. The results showed that the best adsorption performance of composite was achieved when mass ratio of MWCNTs to CS was 1∶4， the dosage of glutaraldehyde was 2.5 mL， the cross-linking temperature was 50 ℃ and the cross-linking time was 5 h. The maximum adsorption capacity of MWCNTs/CS was up to 291.44 mg/g for alizarin red and 263.59 mg/g for xylenol orange. The adsorption of MWCNTs/Cs on the two dyes was in accordance with the pseudo secondary kinetic model， which was dominated by chemisorption as a spontaneous exothermic process. The Freundlich adsorption isotherm was good fit for the adsorption process with constant n>1， indicating that the adsorption process is preferential.

Key words: carbon nanotube, chitosan, adsorption, dye

摘要：

随着我国印染工业的快速发展，大量印染废水随之产生。印染废水具有色度高、难降解有机物浓度高、水质波动大等特点，对环境和人类健康造成危害。采用碱液沉积交联法制备多壁碳纳米管/壳聚糖复合材料（MWCNTs/CS），对二甲酚橙和茜素红染料模拟废水进行吸附处理，考察不同制备条件对吸附性能的影响。结果表明：多壁碳纳米管与壳聚糖质量比为1∶4、交联剂戊二醛投加量为2.5 mL、交联温度为50 ℃、交联时间为5 h时，制得的复合材料吸附效果最好。MWCNTs/CS对茜素红的最大吸附量可达291.44 mg/g，对二甲酚橙的最大吸附量可达263.59 mg/g。2种染料的吸附过程符合拟二级动力学模型，以化学吸附为主，为自发放热过程。Freundlich吸附等温线能较好地拟合该吸附过程，n大于1，表明吸附过程为优惠吸附。

关键词: 碳纳米管, 壳聚糖, 吸附, 染料

CLC Number:

X703
TQ424

Jun JIN, Conglu ZHANG. Adsorption of dyes in water by multiwall carbon nanotubes/chitosan composite[J]. Industrial Water Treatment, 2022, 42(4): 100-105.

靳君, 张聪璐. 多壁碳纳米管/壳聚糖复合材料对水中染料的吸附[J]. 工业水处理, 2022, 42(4): 100-105.

/ / Recommend / Download Citations

URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2021-0689

https://www.iwt.cn/EN/Y2022/V42/I4/100

Figures/Tables 11

Fig. 1 SEM images of MWCNTs/CS composite

Fig. 2 FTIR spectra of CS， MWCNTs and MWCNTs/CS

Fig. 3 Separation performance of MWCNTs（a） and MWCNTs/CS（b）

Table 1 Effect of preparation conditions on adsorption performance

m（MWCNTs）∶m（CS）	1∶1	1∶2	1∶3	1∶4	2∶1	3∶1
AR去除率/%	75.91	78.65	93.70	95.71	49.60	50.20
XO去除率/%	66.92	67.16	79.25	85.78	50.42	43.22
GA投加量/mL	1.0	1.5	2.0	2.5	3.0
AR去除率/%	87.21	94.25	96.87	98.60	98.24
XO去除率/%	65.42	74.41	80.65	85.14	84.83
温度/℃	30	40	50	60
AR去除率/%	81.41	85.60	98.93	92.91
XO去除率/%	82.52	87.28	98.80	91.46
交联时间/h	3	4	5	6
AR去除率/%	72.82	89.90	99.60	86.81
XO去除率/%	84.55	93.72	99.70	83.53

Table 2 Effect of pH on adsorption performance of MWCNTs/CS

pH	4	5	6	7	8	9
AR去除率/%	91.62	93.95	99.10	86.32	67.20	37.50
XO去除率/%	91.51	95.80	99.70	90.65	35.64	5.32

Fig. 4 Adsorption of MWCNTs/CS on AR（a） and XO（b） at different initial mass concentrations

Table 3 Fitting parameters of pseudo first order and pseudo second order kinetics

项目	$C 0$ /（mg·L^-1）	$Q e'$ /（mg·g^-1）	拟一级动力学			拟二级动力学
项目	$C 0$ /（mg·L^-1）	$Q e'$ /（mg·g^-1）	$K 1$ / $10 - 3$ min^-1	$Q e$ /（mg·g^-1）	$R 2$	$K 2$ /（ $10 - 5$ g·mg^-1·min^-1）	$Q e$ /（mg·g^-1）	$R 2$
AR	20	48.94	41.454	48.854	0.977	85.982	49.02	0.992 0
	40	98.31	39.151	97.97	0.981	53.173	98.03	0.997 7
	60	147.69	32.242	142.39	0.986	32.453	147.05	0.998 0
	80	195.19	16.121	193.37	0.995	11.324	196.07	0.990 6
	100	243.94	16.121	213.01	0.997	11.651	270.27	0.996 3
	120	291.44	18.424	276.37	0.971	11.273	303.03	0.996 7
XO	20	42.14	43.757	21.086	0.946	454.413	44.248	0.999 3
	40	90.01	29.939	43.752	0.955	192.475	92.593	0.999 0
	60	139.10	18.424	81.283	0.993	64.474	142.85	0.995 0
	80	183.03	36.848	116.14	0.995	47.774	192.31	0.998 1
	100	223.01	18.424	129.42	0.988	38.382	232.56	0.997 4
	120	263.59	25.333	150.66	0.978	45.182	270.27	0.999 6

Table 3 Fitting parameters of pseudo first order and pseudo second order kinetics

项目	$C 0$ /（mg·L^-1）	$Q e'$ /（mg·g^-1）	拟一级动力学			拟二级动力学
项目	$C 0$ /（mg·L^-1）	$Q e'$ /（mg·g^-1）	$K 1$ / $10 - 3$ min^-1	$Q e$ /（mg·g^-1）	$R 2$	$K 2$ /（ $10 - 5$ g·mg^-1·min^-1）	$Q e$ /（mg·g^-1）	$R 2$
AR	20	48.94	41.454	48.854	0.977	85.982	49.02	0.992 0
	40	98.31	39.151	97.97	0.981	53.173	98.03	0.997 7
	60	147.69	32.242	142.39	0.986	32.453	147.05	0.998 0
	80	195.19	16.121	193.37	0.995	11.324	196.07	0.990 6
	100	243.94	16.121	213.01	0.997	11.651	270.27	0.996 3
	120	291.44	18.424	276.37	0.971	11.273	303.03	0.996 7
XO	20	42.14	43.757	21.086	0.946	454.413	44.248	0.999 3
	40	90.01	29.939	43.752	0.955	192.475	92.593	0.999 0
	60	139.10	18.424	81.283	0.993	64.474	142.85	0.995 0
	80	183.03	36.848	116.14	0.995	47.774	192.31	0.998 1
	100	223.01	18.424	129.42	0.988	38.382	232.56	0.997 4
	120	263.59	25.333	150.66	0.978	45.182	270.27	0.999 6

Fig. 5 Curves of Q _e versus C _e relationship at adsorption equilibrium

Table 4 Fitting data of different adsorption isotherms

项目		AR	XO
Langmuir	Q_m /（mg·g^-1）	500.0	519.5
	K _L/（L·mg^-1）	0.666 7	0.166 7
	R ²	0.993 9	0.986 8
Freundlich	K/〔mg·g^-1·（L·mg^-1）^1/n〕	134.586	68.549
	n	1.887	1.715
	R ²	0.944 7	0.951 9
Temkin	A _T/（mg·L^-1）	8.384 5	2.451 3
	B _T/（L·g^-1）	258.9	70.57
	R ²	0.991 3	0.950 9

Fig. 6 Relationship between ln（Q _e/C _e） and 1/T for MWCNTs/CS adsorption of dyes

Table 5 Thermodynamic parameters at different temperatures

项目	T/K	ΔG/（kJ·mol^-1）	ΔH/（kJ·mol^-1）	ΔS/（kJ·mol^-1）
AR	298	-13.34	-22.19	-0.029 7
	308	-13.05
	318	-12.75
XO	298	-10.85	-55.84	-0.151
	308	-9.34
	318	-7.83

References 10

1	陈华泉，周雪松，司景航. 茶渣活性炭的制备及其对亚甲基蓝的吸附性能研究［J］. 应用化工，2020，49（6）：1425-1429.
	CHEN Huaquan， ZHOU Xuesong， SI Jinghang. Preparation of tea residue based activated carbon and its adsorption properties for methylene blue［J］. Applied Chemical Industry， 2020， 49（6）： 1425-1429.
2	ANAS M， HAN D S， MAHMOUD K， et al. Photocatalytic degradation of organic dye using titanium dioxide modified with metal and non⁃metal deposition［J］. Materials Science in Semiconductor Processing， 2016， 41： 209-218. doi:10.1016/j.mssp.2015.08.041
3	王可，李虹雨，任华堂，等. 多壁碳纳米管吸附水中典型苯酚类物质［J］. 工业水处理， 2018， 38（11）： 40-44. doi:10.11894/1005-829x.2018.38(11).040
	WANG Ke， LI Hongyu， REN Huatang， et al. Adsorption of MWCNTs for typical phenolic compounds in water［J］. Industrial Water Treatment， 2018， 38（11）： 40-44. doi:10.11894/1005-829x.2018.38(11).040
4	易滢佳，王钰，史俊，等. 碳纳米管及其复合材料在水中有机污染物去除中的应用［J］. 净水技术，2021，40（3）：23-32.
	YI Yingjia， WANG Yu， SHI Jun， et al. Application of carbon nanotubes and composite materials in organic pollutants removal in water［J］. Water Purification Technology， 2021， 40（3）： 23-32.
5	方梦园，赵天慧，赵晓丽，等. 碳纳米管对腐殖酸的吸附及其环境意义［J］. 环境化学，2020，39（10）：2897-2906. doi:10.7524/j.issn.0254-6108.2019111002
	FANG Mengyuan， ZHAO Tianhui， ZHAO Xiaoli， et al. Effect of humic acid on adsorption and sedimentation of carboxylic multi⁃walled carbon nanotubes with different diameters［J］. Environmental Chemistry， 2020， 39（10）： 2897-2906. doi:10.7524/j.issn.0254-6108.2019111002
6	WANG Shi， ZHAI Yanyun， GAO Qiang， et al. Highly efficient removal of acid red 18 from aqueous solution by magnetically retrievable chitosan/carbon nanotube： Batch study， isotherms， kinetics， and thermodynamics［J］. Journal of Chemical & Engineering Data， 2014， 59（1）： 39-51. doi:10.1021/je400700c
7	张亦南，丁佳锋，张小芳，等. 镧负载沸石壳聚糖复合吸附剂高效除磷性能研究［J］. 环境科学学报，2021，41（2）：557-565. doi:10.13671/j.hjkxxb.2020.0407
	ZHANG Yinan， DING Jiafeng， ZHANG Xiaofang， et al. Adsorption properties of high efficient lanthanum⁃loaded zeolite⁃chitosan composite absorbent for phosphorus removal［J］. Acta Scientiae Circumstantiae， 2021， 41（2）： 557-565. doi:10.13671/j.hjkxxb.2020.0407
8	PÉREZ⁃MARÍN A B， ZAPATA V M， ORTUÑO J F， et al. Removal of cadmium from aqueous solutions by adsorption onto orange waste［J］. Journal of Hazardous Materials， 2007， 139（1）： 122-131. doi:10.1016/j.jhazmat.2006.06.008
9	苏龙，张海波，程红艳，等. 木耳菌糠生物炭对阳离子染料的吸附性能研究［J］. 中国环境科学，2021，41（2）：693-703. doi:10.3969/j.issn.1000-6923.2021.02.023
	SU Long， ZHANG Haibo， CHENG Hongyan， et al. Study on adsorption properties of biochar derived from spent Auricularia auricula substrate for cationic dyes［J］. China Environmental Science， 2021， 41（2）： 693-703. doi:10.3969/j.issn.1000-6923.2021.02.023
10	李艳春，张鹏会，张强，等. 4种生物炭对阳离子染料吸附性能［J］. 环境科学与技术，2020，43（7）：101-110. doi:10.1016/j.seppur.2019.116360
	LI Yanchun， ZHANG Penghui， ZHANG Qiang， et al. Adsorption of cationic dye in aqueous solution by four biochars［J］. Environmental Science & Technology， 2020， 43（7）： 101-110. doi:10.1016/j.seppur.2019.116360

[1]	Hengjun TANG, Biao QIU, Weiping SIMA, Jian TANG. Study on the removal of Cr(Ⅵ) by acid-modified distillers’ grains biochar [J]. Industrial Water Treatment, 2025, 45(3): 144-151.
[2]	Wei JIANG, Xiaodie CAI, Xinyu WEN, Sili CHEN, Jinsong WANG, Zhengke ZHANG. Preparation of mesoporous silica/sodium alginate composites and its removal performance of radioactive Sr²⁺ [J]. Industrial Water Treatment, 2025, 45(3): 90-98.
[3]	Qingyuan WANG, Yanping ZHANG, Yibing LI, Fen LI. Adsorption of methylene blue by biochar prepared using straw mixed with agricultural film [J]. Industrial Water Treatment, 2025, 45(3): 110-120.
[4]	Yasong CHEN, Shiyu MIAO, Chi ZHANG, Mingran LI, Jiaqi WANG, Yanyu ZHANG, Wei JIANG. Research progress on the preparation and the adsorption mechanisms of phosphorus removal adsorbents [J]. Industrial Water Treatment, 2025, 45(2): 1-9.
[5]	Wenhao WANG, Yexing CHENG, Yuyin WANG, Tingting HOU, Xiaofeng WU, Yucai LI. Effect of different types of activated carbon on the adsorption- reduction of Cr(Ⅵ) by mZVI/activated carbon [J]. Industrial Water Treatment, 2025, 45(2): 150-158.
[6]	Qing LIU, Jianbin HUANG, Weifan LI, Guodong ZHAO, Jingjing YANG. Performance of U(Ⅵ) enrichment by tannic acid sodium and alginate composite microspheres [J]. Industrial Water Treatment, 2025, 45(1): 58-65.
[7]	Weiye ZHANG, Jing SHEN, Zihe PAN, Yipeng SONG, Huaigang CHENG, Huirong ZHANG. Analysis of heel formation and influencing factors during the thermal regeneration process of saturated activated carbon [J]. Industrial Water Treatment, 2025, 45(1): 17-25.
[8]	Cuihong ZHANG, Jing WANG, Jie WANG, Wenjiao YUAN. Preparation of quaternary ammonium-modified silica and its adsorption of vanadium(V) [J]. Industrial Water Treatment, 2025, 45(1): 104-114.
[9]	Zhihua DENG, Rui LIU, Biqing LI. Preparation of different biochars and their adsorption performance for heavy metals and antibiotics [J]. Industrial Water Treatment, 2025, 45(1): 94-103.
[10]	Zirui GUO, Hongyan LI, Feng ZHANG, Jiali CUI, Qun YANG, Yun LI. Performance and mechanism of catalytic degradation of benzotriazole in water by Fe₂O₃-CuO/rCG [J]. Industrial Water Treatment, 2024, 44(9): 118-126.
[11]	Qin DENG, Yijian ZHONG, Jincheng LI, Huihui SHI, Chunman WEI, Jiajia QIN. Preparation and regeneration ability test of a new type of phosphorus removal filler [J]. Industrial Water Treatment, 2024, 44(8): 140-148.
[12]	Ya HU, Xiaolei SUN, Jingyu LU, Xiuyun SUN. Preparation of Tymycin waste salt activated carbon and its adsorption performance for EDTA-Pb(Ⅱ) [J]. Industrial Water Treatment, 2024, 44(8): 133-139.
[13]	Haoyu ZHANG, Yikang ZHOU, Yan WANG, Le PAN, Yunfei WANG, Dezhang ZHU, Yan WU. Preparation and adsorption study of waste tea-based porous carbon for methyl orange dyes [J]. Industrial Water Treatment, 2024, 44(8): 171-177.
[14]	Gang XUE. Textile printing and dyeing wastewater treatment with low greenhouse gases emission [J]. Industrial Water Treatment, 2024, 44(7): 1-8.
[15]	Huan XI, Geng YANG. Filtration and adsorption of low concentration phosphate by dolomite-biochar composite membrane [J]. Industrial Water Treatment, 2024, 44(7): 132-140.

Please choose a citation manager

Content to export