含钛高炉渣制备复合吸附剂及其铬吸附性能

doi:10.16085/j.issn.1000-6613.2023-0343

摘要/Abstract

摘要：

Cr(Ⅵ)是一种有害污染物，既污染水环境，也会对人体造成伤害。本文以工业固废含钛高炉渣为原料，通过酸浸得到浸出渣基体，经壳聚糖改性，制备一种新型GLZ-jcz/CS复合吸附剂，用来去除废水中的Cr(Ⅵ)。研究了吸附温度、废水pH、吸附剂量、Cr(Ⅵ)初始浓度、吸附时间对Cr(Ⅵ)吸附性能的影响。以Cr(Ⅵ)吸附率为评价指标，确定最优实验条件，并研究了GLZ-jcz/CS复合吸附剂的再生性能。采用扫描电子显微镜、傅里叶红外变换光谱仪、X射线光电子能谱仪、BET比表面积测试仪对GLZ-jcz/CS复合吸附剂进行表征，结合吸附动力学模型和吸附等温线模型分析，确定吸附机理。实验结果表明：当吸附温度为70℃、废水pH=4、吸附剂用量为0.13g、Cr(Ⅵ)初始浓度为50mg/L、吸附时间为2h时，吸附率达到99.8%，吸附容量可以达到67mg/g，GLZ-jcz/CS复合吸附剂经过6次洗脱，吸附率仍可达到96%以上，吸附模型符合拟二级动力学模型和Langmuir吸附等温模型。

关键词: 复合吸附剂, Cr(Ⅵ)吸附率, 动力学模型, 等温线模型, 含钛高炉渣, 壳聚糖改性

Abstract:

Cr(Ⅵ) is a harmful pollutant that not only pollutes the water environment but also causes harm to humans. In this paper, a new composite adsorbent (GLZ-jcz/CS) was prepared for the removal of Cr(Ⅵ) from wastewater, using industrial solid waste containing titanium blast furnace slag as raw material, and the leached slag matrix was obtained by acid leaching and modified by chitosan. The effects of adsorption temperature, pH of wastewater, adsorbent dosage, initial concentration of Cr(Ⅵ) and adsorption time on the adsorption performance of Cr(Ⅵ) were studied. The optimal experimental conditions were determined using the Cr(Ⅵ) adsorption rate as the evaluation index, and the regeneration performance of GLZ-jcz/CS composite adsorbent was investigated. The GLZ-jcz/CS composite adsorbent was characterized by SEM, FTIR, XPS and BET, combined with adsorption kinetic model and adsorption isotherm model analysis to determine the adsorption mechanism. The experimental results showed that the adsorption rate reached 99.8% and the adsorption capacity could reach 67mg/g when the adsorption temperature was 70℃, the pH of wastewater was 4, the amount of adsorbent was 0.13g, the initial concentration of Cr(Ⅵ) was 50mg/L and the adsorption time was 2h. The GLZ-jcz/CS composite adsorbent can still reach over 96% adsorption after six elutions, and the adsorption model was compounded with the proposed secondary kinetic model and the Langmuir adsorption isotherm model.

Key words: composite adsorbents, Cr(Ⅵ) adsorption rate, dynamical models, isotherm models, titanium-containing blast furnace slag, chitosan modification

中图分类号:

董晓涵, 田月, 苏毅. 含钛高炉渣制备复合吸附剂及其铬吸附性能[J]. 化工进展, 2024, 43(3): 1552-1564.

DONG Xiaohan, TIAN Yue, SU Yi. Study on the preparation of composite adsorbent with titanium-containing blast furnace slag and chromium adsorption performance[J]. Chemical Industry and Engineering Progress, 2024, 43(3): 1552-1564.

图/表 22

参考文献 44

1	MEI Peng, LI Meng, ZHANG Qian, et al. Prediction model of drinking water source quality with potential industrial-agricultural pollution based on CNN-GRU-Attention[J]. Journal of Hydrology, 2022, 610: 127934.
2	ZUANE J D. Handbook of drinking water quality: Standards and controls[J]. Choice Reviews Online, 1991, 28(9): 28-5057.
3	DROSTE R L. Theory and practice of water and wastewater treatment[J]. Choice Reviews Online, 1997, 34(8): 34-4491.
4	VINOD Kumar, RIPU Daman Parihar, ANKET Sharma, et al. Global evaluation of heavy metal content in surface water bodies: A meta-analysis using heavy metal pollution indices and multivariate statistical analyses[J]. Chemosphere, 2019, 236: 124364.
5	AYDıN Yaşar Andelib, AKSOY Nuran Deveci. Adsorption of chromium on chitosan: Optimization, kinetics and thermodynamics[J]. Chemical Engineering Journal, 2009, 151(1/2/3): 188-194.
6	MONDAL Supriyo Kumar, SAHA Prabirkumar. Separation of hexavalent chromium from industrial effluent through liquid membrane using environmentally benign solvent: A study of experimental optimization through response surface methodology[J]. Chemical Engineering Research and Design, 2018, 132: 564-583.
7	CHEN Zhongshan, WEI Benben, YANG Shanye, et al. Synthesis of PANI/AlOOH composite for Cr(Ⅵ) adsorption and reduction from aqueous solutions[J]. ChemistrySelect, 2019, 4(8): 2352-2362.
8	OLIVEIRA Helena. Chromium as an environmental pollutant: Insights on induced plant toxicity[J]. Journal of Botany, 2012, 2012: 375843.
9	KARTHIK Rathinam, MEENAKSHI Sankaran. Removal of hexavalent chromium ions using polyaniline/silica gel composite[J]. Journal of Water Process Engineering, 2014, 1: 37-45.
10	RAI M K, GIRI B S, NATH Y, et al. Adsorption of hexavalent chromium from aqueous solution by activated carbon prepared from almond shell: Kinetics, equilibrium and thermodynamics study[J]. Journal of Water Supply: Research and Technology-Aqua, 2018, 67(8): 724-737.
11	JOBBY Renitta, Pamela JHA, YADAV Anoop Kumar, et al. Biosorption and biotransformation of hexavalent chromium[Cr(Ⅵ)]: A comprehensive review[J]. Chemosphere, 2018, 207: 255-266.
12	MOHAMED Laabd, ABDELAZIZ Imgharn, ABDELGHANI Hsini, et al. Efficient detoxification of Cr(Ⅵ)-containing effluents by sequential adsorption and reduction using a novel cysteine-doped PANi@faujasite composite: Experimental study supported by advanced statistical physics prediction[J]. Journal of Hazardous Materials, 2022, 422: 126857.
13	BEUKES J P, DU PREEZ S P, VAN ZYL P G, et al. Review of Cr(Ⅵ) environmental practices in the chromite mining and smelting industry—Relevance to development of the Ring of Fire, Canada[J]. Journal of Cleaner Production, 2017, 165: 874-889.
14	EDITION F. Guidelines for drinking-water quality[M]. World Health Organization, 2011.
15	GOLDER Animes K, CHANDA Ajoy K, SAMANTA Amar N, et al. Removal of Cr(Ⅵ) from aqueous solution: Electrocoagulation vs chemical coagulation[J]. Separation Science and Technology, 2007, 42(10): 2177-2193.
16	LI Yujiang, GAO Baoyu, WU Tao, et al. Hexavalent chromium removal from aqueous solution by adsorption on aluminum magnesium mixed hydroxide[J]. Water Research, 2009, 43(12): 3067-3075.
17	BABU B V, GUPTA S. Adsorption of Cr(Ⅵ) using activated neem leaves: Kinetic studies[J]. Adsorption, 2008, 14(1): 85-92.
18	ZHANG Ailin, LI Xin, XING Jia, et al. Adsorption of potentially toxic elements in water by modified biochar: A review[J]. Journal of Environmental Chemical Engineering, 2020, 8(4): 104196.
19	QIU Jinli, LIU Fuqiang, CHENG Song, et al. Recyclable nanocomposite of flowerlike MoS₂@Hybrid acid-doped PANI immobilized on porous PAN nanofibers for the efficient removal of Cr( Ⅵ )[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(1): 447-456.
20	DENG Fang, LU Xiaoying, LUO Yingbo, et al. Novel visible-light-driven direct Z-scheme CdS/CuInS₂ nanoplates for excellent photocatalytic degradation performance and highly-efficient Cr( Ⅵ ) reduction[J]. Chemical Engineering Journal, 2019, 361: 1451-1461.
21	LI Meirun, SONG Chi, WU Ying, et al. Novel Z-scheme visible-light photocatalyst based on CoFe₂O₄/BiOBr/Graphene composites for organic dye degradation and Cr( Ⅵ ) reduction[J]. Applied Surface Science, 2019, 478: 744-753.
22	JIAO Handong, TIAN Donghua, WANG Shuai, et al. Direct preparation of titanium alloys from Ti-bearing blast furnace slag[J]. Journal of the Electrochemical Society, 2017, 164(7): D511-D516.
23	王海波, 孙青竹, 张雪峰, 等. 磷酸三钠对高钛高炉渣制备微晶泡沫玻璃的影响[J]. 钢铁钒钛, 2021, 42(4): 57-61.
	WANG Haibo, SUN Qingzhu, ZHANG Xuefeng, et al. Effect of Na₃PO₄·12H₂O on foam glass-ceramics prepared from high titanium blast furnace slag[J]. Iron Steel Vanadium Titanium, 2021, 42(4): 57-61.
24	张宇鑫, 丁长坤, 岳程飞, 等. 壳聚糖微球的制备及其对甲基橙和Cr(Ⅵ)的吸附性能研究[J]. 天津化工, 2021, 35(4): 29-32.
	ZHANG Yuxin, DING Changkun, YUE Chengfei, et al. Preparation of chitosan microspheres and study of adsorption performancefor methyl orange and Cr(Ⅵ)[J]. Tianjin Chemical Industry, 2021, 35(4): 29-32.
25	JIANG Chunlu, WANG Rui, CHEN Xing, et al. Preparation of chitosan modified fly ash under acid condition and its adsorption mechanism for Cr(Ⅵ)in water[J]. Journal of Central South University, 2021, 28(6): 1652-1664.
26	钟少锋, 吉婉丽, 刘晓云. 壳聚糖超细纤维的制备及其铬离子吸附性能研究[J]. 化学试剂, 2020, 42(3): 226-231.
	ZHONG Shaofeng, JI Wanli, LIU Xiaoyun. Preparation of chitosan/poly(methacylic acid) superfine fiber mat and application in chromium ion removal[J]. Chemical Reagents, 2020, 42(3): 226-231.
27	周丽莎, 李若男, 卞雨洁, 等. TOCNF与磁性羧甲基壳聚糖纳米粒子复合物的制备及吸附Pb²⁺的特性[J]. 化工进展, 2022, 41(2): 901-910.
	ZHOU Lisha, LI Ruonan, BIAN Yujie, et al. Preparation of TOCNF and magnetic carboxymethyl chitosan nanoparticles composite and adsorption properties of Pb²⁺ [J]. Chemical Industry and Engineering Progress, 2022, 41(2): 901-910.
28	冯辉霞, 杨洋, 李全珍, 等. 硅藻土复合磁性壳聚糖对Cr(Ⅵ)离子吸附性能[J]. 精细化工, 2018, 35(4): 668-675.
	FENG Huixia, YANG Yang, LI Quanzhen, et al. Adsorption of Cr(Ⅵ) ions on diatomite composite magnetic chitosan material[J]. Fine Chemicals, 2018, 35(4): 668-675.
29	张宇, 李倩, 任欢杰. 壳聚糖载铜改性及吸附Cr(Ⅵ)的试验研究[J]. 湿法冶金, 2019, 38(1): 35-38.
	ZHANG Yu, LI Qian, REN Huanjie. Modifying of chitosan by supported Cu and adsorption of Cr(Ⅵ) in solution[J]. Hydrometallurgy of China, 2019, 38(1): 35-38.
30	王先利. 壳聚糖/有机酸复合物的制备及其除铬应用研究[D]. 东营: 中国石油大学(华东), 2017.
	WANG Xianli. Study on preparation of chitosan/organic acid complex and its application in chromium removal[D]. Dongying: China University of Petroleum (Huadong), 2017.
31	WANG Xiangyu, DU Yi, MA Jun. Novel synthesis of carbon spheres supported nanoscale zero-valent iron for removal of metronidazole[J]. Applied Surface Science, 2016, 390: 50-59.
32	HSINI Abdelghani, BENAFQIR Mohamed, NACIRI Yassine, et al. Synthesis of an arginine-functionalized polyaniline@FeOOH composite with high removal performance of hexavalent chromium ions from water: Adsorption behavior, regeneration and process capability studies[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 617: 126274.
33	李强. 壳聚糖/TiO₂复合吸附剂的制备及吸附特性研究[D]. 北京: 北京化工大学, 2007.
	LI Qiang. Preparation and adsorption characteristics of chitosan/TiO₂ composite adsorbent[D]. Beijing: Beijing University of Chemical Technology, 2007.
34	HAN Shiqi, ZHOU Xuelei, XIE Honghao, et al. Chitosan-based composite microspheres for treatment of hexavalent chromium and EBBR from aqueous solution[J]. Chemosphere, 2022, 305: 135486.
35	NESIC Aleksandra R, VELICKOVIC Sava J, ANTONOVIC Dusan G. Characterization of chitosan/montmorillonite membranes as adsorbents for Bezactiv Orange V-3R dye[J]. Journal of Hazardous Materials, 2012, 209/210: 256-263.
36	HALDORAI Yuvaraj, SHIM Jae Jin. Novel chitosan-TiO₂ nanohybrid: Preparation, characterization, antibacterial, and photocatalytic properties[J]. Polymer Composites, 2014, 35(2): 327-333.
37	LI Qiang, SU Haijia, TAN Tianwei. Synthesis of ion-imprinted chitosan-TiO₂ adsorbent and its multi-functional performances[J]. Biochemical Engineering Journal, 2008, 38(2): 212-218.
38	Ting LYU, MA Ronggang, KE Ke, et al. Synthesis of Gallic acid functionalized magnetic hydrogel beads for enhanced synergistic reduction and adsorption of aqueous chromium[J]. Chemical Engineering Journal, 2021, 408: 127327.
39	夏远涛. 黑曲霉菌丝体-壳聚糖复合吸附剂的制备及对Cr(Ⅵ)的吸附机理研究[D]. 南宁: 广西民族大学, 2019.
	XIA Yuantao. Preparation of Aspergillus Niger mycelium-chitosan composite adsorbent and its adsorption mechanism for Cr( Ⅵ )[D]. Nanning: Guangxi University for Nationalities, 2019.
40	CHEN Na, CAO Shiyu, ZHANG Lin, et al. Structural dependent Cr(Ⅵ) adsorption and reduction of biochar: Hydrochar versus pyrochar[J]. Science of the Total Environment, 2021, 783: 147084.
41	HUANG Xiaopeng, HOU Xiaojing, SONG Fahui, et al. Facet-dependent Cr( Ⅵ ) adsorption of hematite nanocrystals[J]. Environmental Science & Technology, 2016, 50(4): 1964-1972.
42	CHEN Lifeng, LIANG Haiwei, LU Yang, et al. Synthesis of an attapulgite Clay@Carbon nanocomposite adsorbent by a hydrothermal carbonization process and their application in the removal of toxic metal ions from water[J]. Langmuir, 2011, 27(14): 8998-9004.
43	BHAUMIK Madhumita, MCCRINDLE Rob I, MAITY Arjun, et al. Polyaniline nanofibers as highly effective re-usable adsorbent for removal of reactive black 5 from aqueous solutions[J]. Journal of Colloid and Interface Science, 2016, 466: 442-451.
44	SAHNOUN Sousna, BOUTAHALA Mokhtar. Adsorption removal of tartrazine by chitosan/polyaniline composite: Kinetics and equilibrium studies[J]. International Journal of Biological Macromolecules, 2018, 114: 1345-1353.

初始条件	参数	参数值
pH=5.5，C_0,Cr(Ⅵ)=50mg/L，m_adsorbent=0.1g，t=4h	T/℃	25，35，45，60，70，80
T=70℃，C_0,Cr(Ⅵ)=50mg/L，m_adsorbent=0.1g，t=4h	pH	1，3，4，5，6，7，8，10
T=70℃，pH=4，C_0,Cr(Ⅵ)=50mg/L，t=4h	m_adsorbent/g	0.03，0.05，0.08，0.1，0.13，0.16
T=70℃，pH=4，m_adsorbent=0.13g，t=4h	C_0,Cr(Ⅵ)/mg·L^-1	50，70，90，100，110
T=70℃，pH=4，m_adsorbent=0.13g，C_0,Cr(Ⅵ)=50mg/L	t/h	0.5，1，1.5，2，2.5，4

初始条件	参数	参数值
pH=5.5，C_0,Cr(Ⅵ)=50mg/L，m_adsorbent=0.1g，t=4h	T/℃	25，35，45，60，70，80
T=70℃，C_0,Cr(Ⅵ)=50mg/L，m_adsorbent=0.1g，t=4h	pH	1，3，4，5，6，7，8，10
T=70℃，pH=4，C_0,Cr(Ⅵ)=50mg/L，t=4h	m_adsorbent/g	0.03，0.05，0.08，0.1，0.13，0.16
T=70℃，pH=4，m_adsorbent=0.13g，t=4h	C_0,Cr(Ⅵ)/mg·L^-1	50，70，90，100，110
T=70℃，pH=4，m_adsorbent=0.13g，C_0,Cr(Ⅵ)=50mg/L	t/h	0.5，1，1.5，2，2.5，4

样品	TiO₂	SiO₂	CaO	MgO	Fe₂O₃	Al₂O₃	MnO	SO₃	Na₂O	K₂O
含钛高炉渣	10.40	25.29	29.14	9.62	11.79	11.21	0.33	0.63	1.35	0.30
浸出渣	19.64	49.75	0.66	0.18	8.42	9.03	0.05	0.38	0.04	0.03

样品	TiO₂	SiO₂	CaO	MgO	Fe₂O₃	Al₂O₃	MnO	SO₃	Na₂O	K₂O
含钛高炉渣	10.40	25.29	29.14	9.62	11.79	11.21	0.33	0.63	1.35	0.30
浸出渣	19.64	49.75	0.66	0.18	8.42	9.03	0.05	0.38	0.04	0.03

Cr(Ⅵ)初始浓度/mg·L^-1	拟合方程	q_e	k₁	R²
40	y=-0.0317x+0.8070	6.41	0.0317	0.9610
70	y=-0.0072x+1.2355	17.2	0.0072	0.9668
90	y=-0.0028x+1.4615	28.9	0.0028	0.9857