Removal of Cr(Ⅵ) from tannery biochemical tail water by chitosan modified hydrothermal carbon

doi:10.19965/j.cnki.iwt.2023-1150

Abstract

Abstract:

The hydrothermal carbon precursor(WBC) was prepared by hydrothermal carbon method and modified with chitosan to obtain the modified hydrothermal carbon(CWBC). The materials were characterized by SEM, FT-IR, and nano-particle size surface potential analyzer, and the adsorption characteristics and adsorption mechanism of CWBC for Cr(Ⅵ) in wastewater were investigated. The results showed that CWBC had a rough surface and compact three-dimensional network structure, and there were functional groups such as C—N/N—H, C—H and C—O on the surface. Most of the pores in CWBC was mesoporous, while a small part was macroporous. It was a typical mixed structure, which enhanced its adsorption performance for Cr(Ⅵ). When the dosage of CWBC was 1.0 g/L, the solution pH was 3, the initial mass concentration of Cr(Ⅵ) was 10 mg/L, and the reaction temperature was 35 ℃, the adsorption capacity of Cr(Ⅵ) in simulated wastewater by CWBC was higher than 9.9 mg/g, and the removal rate of Cr(Ⅵ) was up to 99%. In addition, the removal rate of Cr(Ⅵ) in the biochemical tail water of actual tannery could also reach 73.33%. The regeneration results showed that the removal rate of Cr(Ⅵ) still reached more than 75% after 8 adsorption-desorption cycles, indicating that the composite material had good recycling performance. The adsorption process of Cr(Ⅵ) by CWBC conformed to the quasi-first-order kinetics and Langmuir model, which was a monolayer adsorption, and dominated by physical adsorption. The thermodynamic analysis results showed that the adsorption of Cr(Ⅵ) by CWBC was an active endothermic reaction.

Key words: residual sludge, hydrothermal carbon, chitosan, adsorption, tannery biochemical tail water, Cr(Ⅵ)

摘要：

利用水热炭法制备了水热炭前驱体（WBC），并用壳聚糖对其改性得到改性水热炭（CWBC），利用SEM、FT-IR、纳米粒度表面电位分析仪等对材料进行表征，之后探究了CWBC对废水中Cr（Ⅵ）的吸附特性及吸附机理。结果表明，CWBC具有粗糙表面及紧密的三维网状结构，且表面存在C—N/N—H、C—H和C—O等官能团，CWBC中大部分为介孔，还有一小部分为大孔，是典型的混合结构，强化了其对Cr（Ⅵ）的吸附性能。当CWBC投加量为1.0 g/L，溶液pH为3，Cr（Ⅵ）初始质量浓度为10 mg/L，反应温度为35 ℃时，CWBC对模拟废水中Cr（Ⅵ）的吸附量大于9.9 mg/g，对Cr（Ⅵ）的去除率达99%以上。此外，CWBC对实际制革生化尾水中Cr（Ⅵ）的去除率也可达到73.33%。再生实验结果表明，经8次吸附-脱附循环后，CWBC对Cr（Ⅵ）的去除率仍然达到75%以上，说明该复合材料循环利用性能良好。CWBC吸附Cr（Ⅵ）的过程更符合准一级反应动力学和Langmuir模型，为单分子层吸附，且物理吸附占主导。热力学分析结果表明，CWBC对Cr（Ⅵ）的吸附过程是主动进行的吸热反应。

关键词: 剩余污泥, 水热炭, 壳聚糖, 吸附, 制革生化尾水, Cr（Ⅵ）

CLC Number:

X703.1
TQ424

Sen WANG, Ying WANG, Yuanru ZHANG, Chen LI, Zhikui DONG, Wenhui CHEN, Fule SUN, Renjie JI. Removal of Cr(Ⅵ) from tannery biochemical tail water by chitosan modified hydrothermal carbon[J]. Industrial Water Treatment, 2024, 44(10): 123-132.

王森, 王盈, 张苑茹, 李晨, 董志魁, 陈文慧, 孙福乐, 吉人杰. 壳聚糖改性水热炭对制革生化尾水中Cr（Ⅵ）的去除研究[J]. 工业水处理, 2024, 44(10): 123-132.

/ / Recommend / Download Citations

URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2023-1150

https://www.iwt.cn/EN/Y2024/V44/I10/123

Figures/Tables 15

Fig.1 SEM of residual sludge（a），corn stover（b）， and WBC（c）

Fig.2 Morphology of CWBC（a），and changes in solution before（b） and after（c）adsorption of Cr （Ⅵ）

Fig.3 SEM of CWBC before（a）and after（b）adsorption of Cr （Ⅵ），and the energy spectrum（c）after adsorption of Cr（Ⅵ）

Fig.4 FT-IR of WBC，and CWBC before and after adsorption of Cr （Ⅵ）

Fig.5 Zeta potential of CWBC at different pH

Fig.6 BET analysis of CWBC

Fig.7 The influence of different factors on the adsorption of Cr （Ⅵ） by CWBC

Fig.8 Fitting curves of quasi-first and quasi-second order kinetic models （a-c） and intraparticle diffusion models （d） for Cr（Ⅵ） adsorption by CWBC at different Cr （Ⅵ） mass concentrations

Table 1 Dynamics fitting parameters

Cr（Ⅵ）/（mg·L ^- ¹）	准一级反应动力学模型			准二级反应动力学模型			颗粒内扩散模型
Cr（Ⅵ）/（mg·L ^- ¹）	Q _e / （mg·g ^- ¹）	k ₁/min^-1	R ²	Q _e / （mg·g ^- ¹）	k ₂/ （g·mg^-1 ·min ^- ¹）	R ²	k _p/ （mg·g^-1 ·min^-0.5）	C/（mg·g ^- ¹）	R ²
6	5.896 3	0.011 8	0.998 5	7.226 7	0.001 8	0.999 2	0.244 1	1.552 1	0.918 6
10	9.848 0	0.015 6	0.995 3	11.334 4	0.001 8	0.998 6	0.329 4	4.174	0.876 0
14	12.336 1	0.011 8	0.994 2	15.099 0	0.006 6	0.999 6	0.510 8	3.248 8	0.959 5

Fig.9 Isothermal adsorption fitting results of CWBC adsorption of Cr （Ⅵ） at 25 ℃（a），35 ℃（b）and 45 ℃（c）

Table 2 Isothermal adsorption fitting parameters

温度/℃	Langmuir			Freundlich
温度/℃	K _L / （L∙mg^-1）	Q _max / （mg·g^-1）	R ²	K _F	1/n	R ²
25	0.268 7	62.538 7	0.998 4	17.462 2	0.378 4	0.947 1
35	0.351 6	67.282 7	0.983 3	21.621 1	0.356 0	0.971 1
45	0.703 8	77.296 1	0.983 4	33.620 6	0.288 5	0.932 0

Fig.10 Linear fitting curve of lnK _D and 1/T

Table 3 Thermodynamic parameters

T/K	ΔG/（kJ·mol^-1）	ΔH/（kJ·mol^-1）	ΔS/（kJ·mol^-1·K^-1）
298	-22.71	81.59	0.35
308	-26.21
318	-29.71
328	-33.21

Fig.11 Adsorption-desorption experiment of CWBC

Table 4 Experimental results of validation of real wastewater

项目

COD/

（mg∙L^-1）

References 28

1	林春岭，钟来元，钟晓岚，等. 甘蔗渣生物炭吸附-还原Cr（Ⅵ）的反应研究［J］. 农业环境科学学报，2023，42（10）：2335-2345.
	LIN Chunling， ZHONG Laiyuan， ZHONG Xiaolan，et al. Adsorption-reduction reaction between bagasse-prepared biochar and Cr（Ⅵ）［J］. Journal of Agro-Environment Science，2023，42（10）：2335-2345.
2	AHMED D， ABID H. Lagenaria siceraria peel biomass as a potential biosorbent for the removal of toxic metals from industrial wastewaters［J］. International Journal of Environmental Studies，2018，75（5）：763-773.
3	WANG Bing， ZENG Yao， XIONG Mingyang，et al. Adsorption performance and mechanism of mesoporous carbon-doped Al₂O₃ adsorbent derived from NH₂-MIL-53（Al） for removing Cr（Ⅵ） and methyl orange from aqueous solution［J］. Journal of Environmental Chemical Engineering，2023，11（3）：110081. doi:10.1016/j.jece.2023.110081
4	罗相萍，游少鸿，刘崇敏，等. LDHs及其复合材料处理重金属废水的研究进展［J］. 工业水处理，2022，42（2）：51-59.
	LUO Xiangping， YOU Shaohong， LIU Chongmin，et al. Research progress on treatment of heavy metal wastewater by layered double hydroxides and their composites［J］. Industrial Water Treatment，2022，42（2）：51-59.
5	黄显浪，李小明，杨麒. CTAB改性斜发沸石对剩余污泥的调理作用［J］. 环境工程学报，2016，10（6）：3193-3199.
	HUANG Xianlang， LI Xiaoming， YANG Qi. Conditioning effect of CTAB modified clinoptilolite on waste activated sludge［J］. Chinese Journal of Environmental Engineering，2016，10（6）：3193-3199.
6	王森，袁娇娇，易佩，等. 水热炭化技术及其在废水处理中的应用研究进展［J］. 工业水处理，2022，42（3）：1-8.
	WANG Sen， YUAN Jiaojiao， YI Pei，et al. Hydrothermal carbonization technology and its application research progress in wastewater treatment［J］. Industrial Water Treatment，2022，42（3）：1-8.
7	何佳康，王保明，吴冰玉，等. 凹凸棒土吸附Pb（Ⅱ）的研究进展［J］. 工业水处理，2020，40（8）：11-16.
	HE Jiakang， WANG Baoming， WU Bingyu，et al. Research progress of Pb（Ⅱ） adsorption by attapulgite［J］. Industrial Water Treatment，2020，40（8）：11-16.
8	谢光辉，方艳茹，李嵩博，等. 废弃生物质的定义、分类及资源量研究述评［J］. 中国农业大学学报，2019，24（8）：1-9.
	XIE Guanghui， FANG Yanru， LI Songbo，et al. Review of the definition，classification，and resource assessment of biowaste［J］. Journal of China Agricultural University，2019，24（8）：1-9.
9	MCKENDRY P. Energy production from biomass（Part 1）：Overview of biomass［J］. Bioresource Technology，2002，83（1）：37-46. doi:10.1016/s0960-8524(01)00118-3
10	ZHANG Lei， ZENG Yuexian， CHENG Zhengjun. Removal of heavy metal ions using chitosan and modified chitosan：A review［J］. Journal of Molecular Liquids，2016，214：175-191. doi:10.1016/j.molliq.2015.12.013
11	曹仕文，张鸿，孟驰涵，等. 海藻酸钙-二氧化硅杂化材料的制备及对Cu（Ⅱ）吸附性能［J］. 高分子材料科学与工程，2020，36（2）：169-175.
	CAO Shiwen， ZHANG Hong， MENG Chihan，et al. Preparation of calcium alginate-SiO₂ hybrid materials and adsorption properties for Cu（Ⅱ）［J］. Polymer Materials Science & Engineering，2020，36（2）：169-175.
12	孙永鹏，王刚，何扬洋，等. 巯基改性小麦秸秆对镉吸附与解吸的性能及机制［J］. 中国环境科学，2023，43（5）：2264-2276. doi:10.3969/j.issn.1000-6923.2023.05.017
	SUN Yongpeng， WANG Gang， HE Yangyang，et al. Performance and mechanism of adsorption and desorption for cadmium in aqueous solution with mercaptopropionyl wheat straw［J］. China Environmental Science，2023，43（5）：2264-2276. doi:10.3969/j.issn.1000-6923.2023.05.017
13	贺晓晗，郝鑫瑞，邓郁蓉，等. 生物炭固定耐镉菌群对Cd²⁺的吸附及作用机制［J］. 环境科学学报，2023，43（2）：136-146.
	HE Xiaohan， HAO Xinrui， DENG Yurong，et al. Adsorption of Cd²⁺ by biochar immobilized cadmium-tolerant bacterial flora and the mechanism of action［J］. Acta Scientiae Circumstantiae，2023，43（2）：136-146.
14	周亦圆，孟方，刘振鸿，等. 废弃桉树皮水热碳化制备生物质基水热焦［J］. 材料导报，2015，29（S1）：344-347.
	ZHOU Yiyuan， MENG Fang， LIU Zhenhong，et al. Preparation of hydrochars based on waste Eucalyptus bark by hydrothermal carbonization［J］. Materials Reports，2015，29（S1）：344-347.
15	乔娜. 玉米芯和松子壳的水热碳化及其产物吸附性能研究［D］. 大连：大连理工大学，2015.
	QIAO Na. Hydrothermal carbonization of corncob and pinenut shell and the adsorption performance of its product［D］. Dalian：Dalian University of Technology，2015.
16	TAN Xiaofei， LIU Yunguo， ZENG Guangming，et al. Application of biochar for the removal of pollutants from aqueous solutions［J］. Chemosphere，2015，125：70-85. doi:10.1016/j.chemosphere.2014.12.058
17	VIMALA R，DAS N. Mechanism of Cd（Ⅱ） adsorption by macrofungus pleurotus platypus［J］. Journal of Environmental Sciences（China），2011，23（2）：288-293.
18	倪茂森. MnCeO _x /P84除尘脱硝双功能滤料不同形貌催化界面的构筑及其构效关系［D］. 南京：南京信息工程大学，2023.
	NI Maosen. Construction and structure-activity relationship of catalytic interface with different morphology of MnCeO _x /P84 dual-function filter media［D］. Nanjing：Nanjing University of Information Science & Technology，2023.
19	陈奕名. 丙烯酸/浒苔多糖复合水凝胶的制备及其对染料的吸附性能研究［D］. 青岛：青岛科技大学，2023.
	CHEN Yiming. Preparation of acrylic acid/enteromorpha polysaccharide composite hydrogels and its adsorption properties for dye［D］. Qingdao：Qingdao University of Science & Technology，2023.
20	ZHAO Guixia， LI Jiaxing， REN Xuemei，et al. Few-layered graphene oxide nanosheets as superior sorbents for heavy metal ion pollution management［J］. Environmental Science & Technology，2011，45（24）：10454-10462. doi:10.1021/es203439v
21	刘群. 空心莲子草活性炭对抗生素、染料吸附性能的研究［D］. 济南：山东师范大学，2017.
	LIU Qun. Study on adsorption performance of Alternanthera philoxeroides activated carbon for antibiotics and dyes［D］. Ji’nan：Shandong Normal University，2017.
22	李荣华，张院民，张增强，等. 农业废弃物核桃壳粉对Cr（Ⅵ）的吸附特征研究［J］. 农业环境科学学报，2009，28（8）：1693-1700.
	LI Ronghua， ZHANG Yuanmin， ZHANG Zengqiang，et al. The characteristics of Cr（Ⅵ）adsorbed by walnuts shell powder［J］. Journal of Agro-Environment Science，2009，28（8）：1693-1700.
23	MA Huiling， ZHANG Youwei， HU Qihui，et al. Chemical reduction and removal of Cr（Ⅵ） from acidic aqueous solution by ethylenediamine-reduced graphene oxide［J］. Journal of Materials Chemistry，2012，22（13）：5914-5916. doi:10.1039/c2jm00145d
24	JAIN M， GARG V K， KADIRVELU K. Adsorption of hexavalent chromium from aqueous medium onto carbonaceous adsorbents prepared from waste biomass［J］. Journal of Environmental Management，2010，91（4）：949-957. doi:10.1016/j.jenvman.2009.12.002
25	朱筱曦. 希瓦氏菌-生物质炭-水铁矿凝胶对Cr（Ⅵ）和有机污染物的去除效果［D］. 武汉：华中农业大学，2023.
	ZHU Xiaoxi. Removal of Cr（Ⅵ）and organic pollutant by Shewanella-biochar-ferrihydrite-capsule［D］. Wuhan：Huazhong Agricultural University，2023.
26	YANG Guangxi， JIANG Hong. Amino modification of biochar for enhanced adsorption of copper ions from synthetic wastewater［J］. Water Research，2014，48：396-405. doi:10.1016/j.watres.2013.09.050
27	LIAO W， ZHANG Xiong， KE S，et al. Effect of different biomass species and pyrolysis temperatures on heavy metal adsorption，stability and economy of biochar［J］. Industrial Crops and Products，2022，186：115238.
28	蒋达，许倩倩，吴雪兰，等. 氨基功能化壳聚糖微球对Cr（Ⅵ）的吸附性能及其机理［J］. 高分子材料科学与工程，2024，40（1）：45-56.
	JIANG Da， XU Qianqian， WU Xuelan，et al. Adsorption performance and mechanism of Cr（Ⅵ）by amino-functionalized chitosan microspheres［J］. Polymer Materials Science & Engineering，2024，40（1）：45-56.

[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]	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.
[15]	Pan LIU. Adsorption and regeneration performances of the modified zeolite for high-concentration ammonium in real coal chemical wastewater [J]. Industrial Water Treatment, 2024, 44(7): 141-149.

Please choose a citation manager

Content to export