Preparation and toluene adsorption performance of sludge based activated carbon with loading Cu and Mn

doi:10.16085/j.issn.1000-6613.2021-0147

Abstract

Abstract:

Sludge-based activated carbon loaded by copper and manganese (SAC-CuMn) of different ratios were prepared by using the residual activated sludge from petrochemical enterprise as carbon source, 4mol/L ZnCl₂ solution as activator, CuC₂O₄ and_{MnC₂O₄as modifiers via one-step calcined technique of solid phase blending. SAC-CuMn samples were applied to adsorb toluene gas and the adsorptive performances were studied to optimize the proportion of copper and manganese in SAC. When the mass ratio of CuC₂O₄ and_{MnC₂O₄ is 4∶1, the yield, BET surface area, total pore volume, and granularity of SAC-CuMn are 52%, 617.77m2/g, 0.61cm3/g, and 0.5mm, respectively, and the performances of toluene adsorption is optimal. At the same time, the SAC-CuMn samples were characterized by ICP, SEM, TEM, FTIR, XRD, EDS, MAPPING, and XPS and their differences were compared. Furthermore, the mechanisms of toluene adsorption by SAC-CuMn were discussed. The results indicated that Cu and Mn were uniformly loaded in the structure of SAC-CuMn samples by solid-phase blending method. In the process of toluene adsorption, physical adsorption and Cu(Ⅰ) complex adsorption played the roles simultaneously to improve the toluene adsorption ability of SAC efficiently. The adsorption amounts of toluene in the optimal SAC-CuMn sample can reach 459.09mg/g and the breakthrough time of dynamic adsorption exceeds 500min.}}

Key words: sludge-based activated carbon, Cu and Mn loading, adsorption, toluene

摘要：

以石化企业剩余活性污泥为碳源、4mol/L ZnCl₂溶液为活性剂、草酸铜和草酸锰为改性剂，采用固相共混一步煅烧技术制备了不同配比的铜锰负载型污泥基活性炭（SAC-CuMn），并将其用于甲苯气体的吸附研究。考察了不同配比SAC-CuMn样品的吸附性能，探究了铜锰的最优配比方案。当草酸铜和草酸锰质量配比为4∶1时，制备的SAC-CuMn样品产率为52%、比表面积617.77m2/g、总孔容0.61cm3/g、粒度0.5mm，吸附性能最好。同时，利用电感耦合等离子体发射光谱（ICP）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、傅里叶变换红外光谱仪（FTIR）、X射线衍射（XRD）、能谱分析（EDS）、Mapping和X射线光电子能谱分析（XPS）等手段对SAC-CuMn样品进行了表征分析和对比研究，并探究了SAC-CuMn样品吸附甲苯的微观机理。实验结果表明，铜锰均匀地负载在固相共混法制备的SAC-CuMn材料结构中，当吸附甲苯时，物理吸附和Cu(Ⅰ)络合吸附作用同时进行，可以有效提升污泥基活性炭的甲苯吸附性能，最优SAC-CuMn样品对甲苯的吸附量可达459.09mg/g，动态吸附穿透时间超过500min。

关键词: 污泥基活性炭, 铜锰负载, 吸附, 甲苯

CLC Number:

X705

LI Xiaofei, DU Gaiping, DUAN Weichao, SUN Hui, ZHAO Dongfeng, LI Shi. Preparation and toluene adsorption performance of sludge based activated carbon with loading Cu and Mn[J]. Chemical Industry and Engineering Progress, 2021, 40(10): 5804-5811.

李小斐, 杜改平, 段潍超, 孙慧, 赵东风, 李石. 铜锰负载型石化企业剩余活性污泥基活性炭制备及吸附甲苯性能[J]. 化工进展, 2021, 40(10): 5804-5811.

Figures/Tables 13

References 24

1	王海林, 郝润, 方莉, 等. 城市挥发性有机物治理体系构建初探[J]. 环境保护, 2020, 48(9): 37-41.
	WANG Hailin, HAO Run, FANG Li, et al. Primary study on treatment and management of volatile organic compounds in urban areas[J]. Environmental Protection, 2020, 48(9): 37-41.
2	武宁, 杨忠凯, 李玉, 等. 挥发性有机物治理技术研究进展[J]. 现代化工, 2020, 40(2): 17-22.
	WU Ning, YANG Zhongkai, LI Yu, et al. Research progress in VOCs treatment technology[J]. Modern Chemical Industry, 2020, 40(2): 17-22.
3	GUAN Q Q, GAO K X, NING P, et al. Value-added utilization of paper sludge: preparing activated carbon for efficient adsorption of Cr(Ⅵ) and further hydrogenation of furfural[J]. Science of the Total Environment, 2020, 741: 140265.
4	许伟, 刘军利, 孙康. 活性炭吸附法在挥发性有机物治理中的应用研究进展[J]. 化工进展, 2016, 35(4): 1223-1229.
	XU Wei, LIU Junli, SUN Kang. Application progresses in the treatment of volatile organic compounds by adsorption on activated carbon[J]. Chemical Industry and Engineering Progress, 2016, 35(4): 1223-1229.
5	田洁, 刘宝友. VOCs治理技术分析及研究进展[J]. 现代化工, 2020, 40(4): 30-35.
	TIAN Jie, LIU Baoyou. Analysis and advances on governance technologies for VOCs[J]. Modern Chemical Industry, 2020, 40(4): 30-35.
6	孟凡飞, 王海波, 刘志禹, 等. 工业挥发性有机物处理技术分析与展望[J]. 化工环保, 2019, 39(4): 387-395.
	MENG Fanfei, WANG Haibo, LIU Zhiyu, et al. Analysis and prospect on treatment technologies of industrial volatile organic compounds[J]. Environmental Protection of Chemical Industry, 2019, 39(4): 387-395.
7	马超, 薛志钢, 李树文, 等. VOCs排放、污染以及控制对策[J]. 环境工程技术学报, 2012, 2(2): 103-109.
	MA Chao, XUE Zhigang, LI Shuwen, et al. VOCs emission, pollution and control measures[J]. Journal of Environmental Engineering Technology, 2012, 2(2): 103-109.
8	余倩, 邓欣, 李俊, 等. 活性炭吸附技术对VOCs净化处理的研究进展[J]. 材料研究与应用, 2010, 4(4): 368-371.
	YU Qian, DENG Xin, LI Jun, et al. Application of activated carbon adsorption technology in VOCs purification technology[J]. Materials Research and Application, 2010, 4(4): 368-371.
9	赵亚飞, 叶凯, 庄烨, 等. 锰基催化剂协同等离子降解VOCs研究进展[J]. 化工进展, 2020, 39(S2): 175-184.
	ZHAO Yafei, YE Kai, ZHUANG Ye, et al. Progress of manganese catalysts for non-thermal plasma catalysis on VOCs degradation[J]. Chemical Industry and Engineering Progress, 2020, 39(S2): 175-184.
10	李石, 邢亚彬, 孙慧, 等. 污泥基活性炭制备改性及其吸附甲苯性能[J]. 化工进展, 2020, 39(6): 2463-2471.
	LI Shi, XING Yabin, SUN Hui, et al. Preparation and modification of sludge based activated carbon and performance of toluene adsorption[J]. Chemical Industry and Engineering Progress, 2020, 39(6): 2463-2471.
11	陈丽媛, 李大鹏, 朱文娟, 等. 污泥水热炭对亚甲基蓝的吸附特性[J]. 环境科学, 2020, 41(4): 1761-1769.
	CHEN Liyuan, LI Dapeng, ZHU Wenjuan, et al. Adsorption properties of sludge-hydrochar for methylene Blue[J]. Environmental Science, 2020, 41(4): 1761-1769.
12	刘国华, 陈瑾惠, 王园园, 等. 改性污泥基吸附剂深度处理出水有机物的研究[J]. 环境科学学报, 2020, 40(4): 1196-1203.
	LIU Guohua, CHEN Jinhui, WANG Yuanyuan, et al. Study on advanced treatment of organic matter in effluent by modified sludge-based adsorbent[J]. Acta Scientiae Circumstantiae, 2020, 40(4): 1196-1203.
13	于翔, 李如洋, 翟静雯，等. 低VOC含量的PET/PAAS/活性炭复合材料的制备及性能研究[J]. 中国塑料, 2020, 34(6): 80-86.
	YU Xiang, LI Ruyang, ZHAI Jingwen, et al. Preparation and properties of PET/PAAS/activated carbon composites with low VOC content[J]. China Plastics, 2020, 34(6): 80-86.
14	王忠, 陈立贵, 付蕾, 等. 共混法制备HDPE/活性炭纤维复合物及其表征[J]. 化工新型材料, 2008, 36(11): 74-76.
	WANG Zhong, CHEN Ligui, FU Lei, et al. Preparation of HDPE/active carbon fiber composites by blending and their characterization [J]. New Chemical Materials, 2008, 36(11): 74-76.
15	王倩雯, 张丽, 刘东方, 等. 改性活性炭吸附湿法冶金高盐废水中有机物的研究[J]. 工业水处理, 2020, 40(6): 64-67.
	WANG Qianwen, ZHANG Li, LIU Dongfang, et al. Study on adsorption of organic matter in hydrometallurigical high-salt wastewater by modified activated carbon[J]. Industrial Water Treatment, 2020, 40(6): 64-67.
16	刘大壮, 杨碧光, 吴至丽, 等. 浸渍法制造HgCl₂-活性炭催化剂的吸附速度[J]. 石油化工, 1979, 8(11): 746-749.
	LIU Dazhuang, YANG Biguang, WU Zhili, et al. Adsorption rate of HgCl₂-activated carbon catalyst produced by impregnation method[J]. Petrochemical Technology, 1979(11): 746-749.
17	环境保护部. 环境空气苯系物的测定活性炭吸附/二硫化碳解吸-气相色谱法: [S]. 北京: 中国环境科学出版社, 2010.
	Ministry of Environmental Protection of the People’s Republic of China. Ambient air—Determination of benzene and its analogies by activated charcoal adsorption carbon disulfide desorption and gas chromatography: [S]. Beijing: China Environment Science Press, 2010.
18	周泉竹, 徐海波, 杜敏, 等. 碳纳米管的表面改性及在铜基复合材料中的应用[J]. 功能材料, 2019, 50(4): 4201-4206.
	ZHOU Quanzhu, XU Haibo, DU Min, et al. Surface modification of carbon nanotubes and its application in copper matrix composites[J]. Journal of Functional Materials, 2019, 50(4): 4201-4206.
19	STÖCKL Q S, HSIEH Y C, MAIRENA A, et al. Aggregation of C70-fragment buckybowls on surfaces: π-H and π-π bonding in bowl up-side-down ensembles[J]. Journal of the American Chemical Society, 2016, 138(19): 6111-6114.
20	周玉梅, 刘晓勤, 姚虎卿. π络合吸附分离技术的研究进展[J]. 石油化工, 2005, 34(10): 1004-1009.
	ZHOU Yumei, LIU Xiaoqin, YAO Huqing. Review of adsorption separation via π-complexation[J]. Petrochemical Technology, 2005, 34(10): 1004-1009.
21	陈俊霖, 赵基钢, 江洪波, 等. 原位红外研究噻吩在硫化后Co-Mo/γ-Al₂O₃催化剂上吸附行为[J]. 化工进展, 2020, 39(S2): 221-226.
	CHEN Junlin, ZHAO Jigang, JIANG Hongbo, et al.. Adsorption behavior of thiophene on Co-Mo/γ-Al₂O₃ catalyst by in-situ IR[J]. Chemical Industry and Engineering Progress, 2020, 39(S2): 221-226.
22	OH G Y, 刘呈坤. 静电纺嵌锰聚丙烯腈基活性碳纳米纤维及其甲苯吸附性表征[J]. 合成纤维, 2008, 37(10): 49-53.
	OH G Y, LIU Chengkun. Electrospun manganese-intercalated polyacrylonitrile-based activated carbon nanofibers and characterization of toluene adsorption[J]. Synthetic Fiber, 2008, 37(10): 49-53.
23	赵珂, 宁平, 李凯, 等. Mn/Cu-BTC催化剂同时脱硫脱硝实验研究[J]. 化工进展, 2020, 39(5): 1784-1791.
	ZHAO Ke, NING Ping, LI Kai, et al. Experimental study on simultaneous removal of SO₂ and NO by Mn/Cu-BTC catalyst[J]. Chemical Industry and Engineering Progress, 2020, 39(5): 1784-1791.
24	李永峰, 李宇, 余林, 等. 锰掺杂六铝酸镧催化剂上甲苯催化燃烧净化研究[J]. 燃料化学学报, 2012, 40(1): 100-104.
	LI Yongfeng, LI Yu, YU Lin, et al. Catalytic combustion of toluene over manganese-substituted hexaaluminate catalysts[J]. Journal of Fuel Chemistry and Technology, 2012, 40(1): 100-104.

样品名称	SAC炭源/g	CuC₂O₄/g	MnC₂O₄/g	CuC₂O₄/MnC₂O₄
SAC-CuMn-1	10g	1.00	0.00	1∶0
SAC-CuMn-2	10g	0.00	1.00	0∶1
SAC-CuMn-3	10g	0.67	0.33	2∶1
SAC-CuMn-4	10g	0.75	0.25	3∶1
SAC-CuMn-5	10g	0.80	0.20	4∶1
SAC-CuMn-6	10g	0.84	0.16	5∶1

样品名称	SAC炭源/g	CuC₂O₄/g	MnC₂O₄/g	CuC₂O₄/MnC₂O₄
SAC-CuMn-1	10g	1.00	0.00	1∶0
SAC-CuMn-2	10g	0.00	1.00	0∶1
SAC-CuMn-3	10g	0.67	0.33	2∶1
SAC-CuMn-4	10g	0.75	0.25	3∶1
SAC-CuMn-5	10g	0.80	0.20	4∶1
SAC-CuMn-6	10g	0.84	0.16	5∶1

元素名称	含量/mg·kg^-1	元素名称	含量/mg·kg^-1
As	70.2	Mn	15.7
Cd	0.3	Pb	18.9
Fe	2127.6	Zn	12365.2
Hg	0.5	Si	1427.8

元素名称	含量/mg·kg^-1	元素名称	含量/mg·kg^-1
As	70.2	Mn	15.7
Cd	0.3	Pb	18.9
Fe	2127.6	Zn	12365.2
Hg	0.5	Si	1427.8

类别	BET比表面积/m2·g^-1	微孔比表面积/m2·g^-1	总孔容积/cm3·g^-1	微孔容积/cm3·g^-1	平均孔径/nm
SAC-original^［10］	614.43	340.74	0.57	0.15	3.72
SAC-CuMn-1	570.37	326.56	0.49	0.12	3.51
SAC-CuMn-2	650.52	375.29	0.81	0.23	3.33
SAC-CuMn-3	637.88	362.37	0.68	0.19	3.43
SAC-CuMn-4	629.33	351.51	0.63	0.17	3.49
SAC-CuMn-5	617.77	346.22	0.61	0.16	3.58
SAC-CuMn-6	609.29	340.39	0.59	0.14	3.69