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

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

化工进展 ›› 2021, Vol. 40 ›› Issue (10): 5804-5811.DOI: 10.16085/j.issn.1000-6613.2021-0147

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

李小斐¹(), 杜改平¹, 段潍超²^,³, 孙慧²^,³, 赵东风¹^,³, 李石¹^,³()

^1.中国石油大学(华东)化学工程学院，山东青岛 266580
^2.青岛欧赛斯环境与安全技术有限责任公司，山东青岛 266555
^3.中国石油大学(华东)安全环保与节能技术中心，山东青岛 266580

收稿日期:2021-01-21 修回日期:2021-03-15 出版日期:2021-10-10 发布日期:2021-10-25
通讯作者: 李石
作者简介:李小斐（1984—），男，博士研究生，从事石化企业“三废”治理技术研究。E-mail：18960161063@163.com。
基金资助:
山东省自然科学基金(ZR2017MEE018);中央高校基本科研基金(17CX05017)

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

LI Xiaofei¹(), DU Gaiping¹, DUAN Weichao²^,³, SUN Hui²^,³, ZHAO Dongfeng¹^,³, LI Shi¹^,³()

^1.College of Chemical Engineering, China University of Petroleum(East China), Qingdao 266580, Shandong, China
^2.Qingdao Oasis Environmental and Safety technology Co. , Ltd. , Qingdao 266555, Shandong, China
^3.Center for Safety, Environmental & Energy Conservation Technology, China University of Petroleum(East China), Qingdao 266580, Shandong, China

Received:2021-01-21 Revised:2021-03-15 Online:2021-10-10 Published:2021-10-25
Contact: LI Shi

摘要/Abstract

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

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

中图分类号:

X705

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.

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.

图/表 13

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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

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

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

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