石墨化生物质炭对磺胺甲唑的吸附性能

doi:10.16085/j.issn.1000-6613.2023-0201

摘要/Abstract

摘要：

以废弃生物质核桃壳为原料，KOH为改性剂，制备了石墨化生物质炭WSC600K-B，并通过SEM、TEM、BET、XRD、拉曼光谱等对材料进行了表征，考察了其吸附磺胺甲唑（SMX）的性能和机理。研究结果表明，经KOH活化后，WSC600K-B表面呈现排列整齐的石墨晶格条纹，对应I_D/I_G为1.037，石墨化程度较高；孔隙结构大大提高，呈蜂窝煤状，孔隙均匀分布，比表面积增大为733.64m²/g。室温下，pH=5时，0.25g/L WSC600K-B对50mg/L SMX的去除率可达94.28%，吸附容量为203.64mg/g。WSC600K-B对SMX的吸附过程受pH和共存离子影响，pH越高去除率越低，共存离子会抑制吸附过程。吸附过程符合二级动力学模型以及Freundlich等温模型，为多分子层化学吸附，反应存在孔径填充、π-π堆积、氢键作用、疏水作用和静电作用，吸附行为是自发进行的放热反应。

关键词: 石墨化, 核桃壳, 生物质炭, 磺胺甲唑, 吸附

Abstract:

The graphitized biochar WSC600K-B was prepared using waste walnut shell as raw material and KOH as modifier. The material was characterized by SEM, TEM, BET, XRD and Raman spectrum. The adsorption performance and mechanism of sulfamethoxazole (SMX) by WSC600K-B were investigated. The results showed that after activated by KOH, the surface of WSC600K-B presented orderly graphite lattice articles, the corresponding I_D/I_G was 1.037,and the degree of graphitization was high. The pore structure of WSC600K-B with honeycomb briquette shape was greatly improved, the pore was uniformly distributed, and the specific surface area increased to 733.64m²/g. At room temperature and pH=5, the removal rate of 50mg/L SMX by 0.25g/L WSC600K-B could reach 94.28%, and the adsorption capacity was 203.64mg/g. The adsorption process was significantly affected by pH and coexisting ions. The higher the pH value, the lower the adsorption efficiency. Coexisting ions inhibited the adsorption process. The adsorption process was in accordance with the second-order kinetic model and the Freundlich isothermal model, which was a multi-molecular layer chemical adsorption. Pore filling, π-π stacking, hydrogen bonding, hydrophobic interaction, and electrostatic interaction occurred during the reaction and the adsorption behavior was a spontaneous exothermic reaction.

Key words: graphitization, walnut shell, biochar, sulfamethoxazole, adsorption

中图分类号:

TU99

马丽然, 张彦平, 李芬, 李一兵, 马行迪. 石墨化生物质炭对磺胺甲唑的吸附性能[J]. 化工进展, 2023, 42(12): 6631-6640.

MA Liran, ZHANG Yanping, LI Fen, LI Yibing, MA Xingdi. Adsorption performance of sulfamethoxazole by graphitized biochar[J]. Chemical Industry and Engineering Progress, 2023, 42(12): 6631-6640.

图/表 14

参考文献 35

1	李佳琳, 巨龙, 崔梦, 等. 磺胺类抗生素的污染现状与去除技术研究进展[J]. 安徽农业科学, 2021, 49(21): 27-32.
	LI Jialin, JU Long, CUI Meng, et al. Status of sulfonamides pollution and research progress of removal technology[J]. Journal of Anhui Agricultural Sciences, 2021, 49(21): 27-32.
2	XU Jian, XU Yan, WANG Hongmei, et al. Occurrence of antibiotics and antibiotic resistance genes in a sewage treatment plant and its effluent-receiving river[J]. Chemosphere, 2015, 119: 1379-1385.
3	张润源. 磁性石墨化生物炭的制备及其对水中磺胺甲𫫇唑的吸附研究[D]. 广州: 华南理工大学, 2020.
	ZHANG Runyuan. Preparation of magnetic graphited biochar and its adsorption study of sulfamethoxazole in water[D]. Guangzhou: South China University of Technology, 2020.
4	姜蕾, 金磊, 胡涛. 粉末活性炭去除原水中典型抗生素的试验[J]. 净水技术, 2022, 41(12): 127-130, 152.
	JIANG Lei, JIN Lei, HU Tao. Experiment of typical antibiotics removal in raw water by powdered activated carbon[J]. Water Purification Technology, 2022, 41(12): 127-130, 152.
5	CRISAFULLY R, MILHOME M A L, CAVALCANTE R M, et al. Removal of some polycyclic aromatic hydrocarbons from petrochemical wastewater using low-cost adsorbents of natural origin[J]. Bioresource Technology, 2008, 99(10): 4515-4519.
6	LEILI M, FAZLZADEH M, BHATNAGAR A. Green synthesis of nano-zero-valent iron from Nettle and Thyme leaf extracts and their application for the removal of cephalexin antibiotic from aqueous solutions[J]. Environmental Technology, 2018, 39(9): 1158-1172.
7	陈建, 欧阳金波, 赖伟鑫, 等. 功能化玉米芯生物炭对水中磺胺甲𫫇唑的去除[J]. 东华理工大学学报(自然科学版), 2022, 45(1): 87-95.
	CHEN Jian, OUYANG Jinbo, LAI Weixin, et al. Removal of sulfamethoxazole from water by functionalized corncob biochar[J]. Journal of East China University of Technology (Natural Science), 2022, 45(1): 87-95.
8	WANG Yinghui, SRINIVASAKANNAN C, WANG Huihao, et al. Preparation of novel biochar containing graphene from waste bamboo with high methylene blue adsorption capacity[J]. Diamond and Related Materials, 2022, 125: 109034.
9	SHANG Shanshan, TAO Zeyu, YANG Chao, et al. Facile synthesis of CuBTC and its graphene oxide composites as efficient adsorbents for CO₂ capture[J]. Chemical Engineering Journal, 2020, 393: 124666.
10	徐文媛, 秦晓丹, 况熙. TiO₂/RGO和Fe₃O₄/RGO催化处理模拟废水的研究[J]. 华东交通大学学报, 2019, 36(5): 109-114.
	XU Wenyuan, QIN Xiaodan, KUANG Xi. Study on catalytic treatment of simulated wastewater by TiO₂/RGO and Fe₃O₄/RGO[J]. Journal of East China Jiaotong University, 2019, 36(5): 109-114.
11	郑志锋, 邹局春, 花勃, 等. 核桃壳化学组分的研究[J]. 西南林学院学报, 2006, 26(2): 33-36.
	ZHENG Zhifeng, ZOU Juchun, HUA Bo, et al. Study on the constituents of walnut shell[J]. Journal of Southwest Forestry College, 2006, 26(2): 33-36.
12	方振华, 张常虎, 杨玲, 等. 氢氧化钾高温活化处理核桃壳制备活性炭研究[J]. 化学工程师, 2017, 31(10): 8-9.
	FANG Zhenhua, ZHANG Changhu, YANG Ling, et al. Research and preparation of activated carbon from walnut shell by high temperature activation with KOH[J]. Chemical Engineer, 2017, 31(10): 8-9.
13	张硕, 余宏军, 蒋卫杰. 发酵玉米芯或甘蔗渣基质的黄瓜育苗效果[J]. 农业工程学报, 2015, 31(11): 236-242.
	ZHANG Shuo, YU Hongjun, JIANG Weijie. Seedling effects of corncob and bagasse composting substrates in cucumber[J]. Transactions of the Chinese Society of Agricultural Engineering, 2015, 31(11): 236-242.
14	HUSSAINOVA I, IVANOV R, STAMATIN S N, et al. A few-layered graphene on alumina nanofibers for electrochemical energy conversion[J]. Carbon, 2015, 88: 157-164.
15	王涵, 余海溶, 梁婷, 等. GO/Fe₃O₄纳米复合物用于亚甲基蓝的高效吸附研究[J]. 化工新型材料, 2021, 49(6): 265-270.
	WANG Han, YU Hairong, LIANG Ting, et al. Study on the GO/Fe₃O₄ nanocomposite for highly efficient adsorption of methylene blue[J]. New Chemical Materials, 2021, 49(6): 265-270.
16	WANG Jiacheng, KASKEL S. KOH activation of carbon-based materials for energy storage[J]. Journal of Materials Chemistry, 2012, 22(45): 23710-23725.
17	贾小芃. 马尾藻基碳材料定向合成及其电化学特性研究[D]. 徐州: 中国矿业大学, 2021.
	JIA Xiaopeng. Preparation of sargassum-based activated carbon materials and research on the electrochemical performance[D]. Xuzhou: China University of Mining and Technology, 2021.
18	刘妮. 类石墨烯磁性生物炭对水体中雌二醇的吸附性能及机理研究[D]. 长沙: 湖南大学, 2020.
	LIU Ni. Research on the adsorption performance and mechanism of 17β‍-estradiol onto graphene-like magnetic biochar in aqueous solution[D]. Changsha: Hunan University, 2020.
19	WANG Lei, MU Guang, TIAN Chungui, et al. Porous graphitic carbon nanosheets derived from cornstalk biomass for advanced supercapacitors[J]. ChemSusChem, 2013, 6(5): 880-889.
20	DONG Xinwei, HE Lingzhi, HU Hui, et al. Removal of 17β-estradiol by using highly adsorptive magnetic biochar nanoparticles from aqueous solution[J]. Chemical Engineering Journal, 2018, 352: 371-379.
21	鲁秀国, 张耀, 盘贤豪, 等. 酸洗废液制备纳米铁酸锌及光催化实验研究[J]. 华东交通大学学报, 2019, 36(3): 99-103.
	LU Xiuguo, ZHANG Yao, PAN Xianhao, et al. Study on preparation of nano zinc ferrite from hydrochloric acid pickling wastewater and the photocatalytic experiment[J]. Journal of East China Jiaotong University, 2019, 36(3): 99-103.
22	GONG Youning, LI Delong, LUO Chengzhi, et al. Highly porous graphitic biomass carbon as advanced electrode materials for supercapacitors[J]. Green Chemistry, 2017, 19(17): 4132-4140.
23	FERRARI A C, BASKO D M. Raman spectroscopy as a versatile tool for studying the properties of graphene[J]. Nature Nanotechnology, 2013, 8(4): 235-246.
24	沈博. 磁性石墨化生物炭活化过硫酸盐催化降解磺胺甲𫫇唑的去除性能及机理研究[D]. 长沙: 湖南大学, 2020.
	SHEN Bo. Catalytic degradation of sulfamethoxazole by persulfate activated with magnetic graphitized biochar and its mechanism[D]. Changsha: Hunan University, 2020.
25	AHMED M B, ZHOU J L, Huu Hao NGO, et al. Competitive sorption affinity of sulfonamides and chloramphenicol antibiotics toward functionalized biochar for water and wastewater treatment[J]. Bioresource Technology, 2017, 238: 306-312.
26	XIE Mengxing, CHEN Wei, XU Zhaoyi, et al. Adsorption of sulfonamides to demineralized pine wood biochars prepared under different thermochemical conditions[J]. Environmental Pollution, 2014, 186: 187-194.
27	范明霞, 赵春玲. pH值、离子强度和共存离子对活性炭吸附Cr(Ⅵ)的影响[J]. 化学工程师, 2017, 31(10): 25-27.
	FAN Mingxia, ZHAO Chunling. Effect of pH, ion strength and coexistence ion for Cr(Ⅵ) adsorption on activated carbon[J]. Chemical Engineer, 2017, 31(10): 25-27.
28	LAI Bo, ZHOU Yuexi, QIN Hongke, et al. Pretreatment of wastewater from acrylonitrile-butadiene-styrene (ABS) resin manufacturing by microelectrolysis[J]. Chemical Engineering Journal, 2012, 179: 1-7.
29	张艳杰, 董伟羊, 王欢, 等. 玉米芯对磺胺甲𫫇唑和甲氧苄啶的吸附效果及机制[J]. 环境工程技术学报, 2023, 13(3): 1108-1117.
	ZHANG Yanjie, DONG Weiyang, WANG Huan, et al. Adsorption effect and mechanism of sulfamethoxazole and trimethoprim on corncob[J]. Journal of Environmental Engineering Technology, 2023, 13(3): 1108-1117.
30	俞伟, 赵思钰, 王宇航, 等. 苜蓿生物炭对磺胺甲𫫇唑的吸附机理研究[J]. 西北大学学报(自然科学版), 2022, 52(1): 115-127.
	YU Wei, ZHAO Siyu, WANG Yuhang, et al. Mechanism of adsorption of sulfamethoxazole by alfalfa biochar at different pyrolysis temperatures[J]. Journal of Northwest University (Natural Science Edition), 2022, 52(1): 115-127.
31	ANNADURAI G, JUANG Ruey-Shin, LEE Duu-Jong. Use of cellulose-based wastes for adsorption of dyes from aqueous solutions[J]. Journal of Hazardous Materials, 2002, 92(3): 263-274.
32	MEAD J A. A comparison of the Langmuir, Freundlich and Temkin equations to describe phosphate adsorption properties of soils[J]. Soil Research, 1981, 19(3): 333.
33	CHIOU C T, PETERS L J, FREED V H. A physical concept of soil-water equilibria for nonionic organic compounds[J]. Science, 1979, 206(4420): 831-832.
34	Junke OU, ZHANG Yongzhi, CHEN Li, et al. Nitrogen-rich porous carbon derived from biomass as a high performance anode material for lithium ion batteries[J]. Journal of Materials Chemistry A, 2015, 3(12): 6534-6541.
35	徐龙凤, 魏群山, 吕强, 等. 水体模拟颗粒物对四环素的吸附特性及基本规律[J]. 环境科学, 2018, 39(4): 1668-1676.
	XU Longfeng, WEI Qunshan, Qiang LYU, et al. Adsorption of tetracycline on simulated suspended particles in water[J]. Environmental Science, 2018, 39(4): 1668-1676.

样品	S_BET/m²·g^-1	孔径/nm	V/cm³·g^-1
WSC600K	6.00	63.30	0.0032
WSC600K-B	733.64	3.44	0.2158

样品	S_BET/m²·g^-1	孔径/nm	V/cm³·g^-1
WSC600K	6.00	63.30	0.0032
WSC600K-B	733.64	3.44	0.2158

准一级动力学模型			准二级动力学模型			Elovich模型
q_e	k₁	R²	q_e	k₂	R²	a	b	R²
172.530	0.281	0.893	190.190	0.002	0.999	84.319	48.270	0.907

准一级动力学模型			准二级动力学模型			Elovich模型
q_e	k₁	R²	q_e	k₂	R²	a	b	R²
172.530	0.281	0.893	190.190	0.002	0.999	84.319	48.270	0.907

吸附剂	q_e/mg·g^-1	数据来源
玉米芯	0.13	张艳杰等^[29]
苜蓿生物炭	47.88	俞伟等^[30]
功能化玉米芯生物炭	162.08	陈建等^[7]
WSC600K-B	203.64	本文