Study on the performance of mesoporous sludge biochar for the removal of Rhodamine B

doi:10.19965/j.cnki.iwt.2023-1133

Abstract

Abstract:

In this study, modified sludge biochar(ASBC) was prepared by impregnation-pyrolysis method with municipal sludge as raw material and ZnCl₂ as activator. ASBC/Peroxymonosulfate(PMS) system was constructed and used to degrade Rhodamine B(RhB). The effects of ASBC dosage, PMS concentration, reaction pH, and co-existing inorganic anions on the degradation of RhB in ASBC/PMS system were investigated. BET results showed that the specific surface area of activated biochar increased from 8.19 m²/g to 175.04 m²/g, pore volume increased from 0.017 cm³/g to 0.189 cm³/g, and activated sludge biochar had more active sites. When the dosage of ASBC was 0.2 g/L and the concentration of PMS was 0.8 mmol/L, the removal rate of RhB was as high as 99.7% after 5 min reaction, and the reaction could work in a wide pH range(3-11). H₂PO₄ ^- and NO₃ ^- had no significant effect on the degradation of ASBC/PMS system, HCO₃ ^- had inhibitory effect and Cl^- had promotional effect. RhB degradation by ASBC/PMS system was a non-radical pathway with ¹O₂as the main active substance.

Key words: modification of ZnCl₂, sludge biochar, peroxymonosulfate, rhodamine B, non-radical

摘要：

以市政污泥为原料，ZnCl₂为活化剂，通过浸渍-热解法制备改性污泥生物炭（ASBC），通过构建ASBC/过一硫酸氢钾（PMS）体系并用于降解罗丹明B（RhB），探究ASBC投加量、PMS浓度、反应pH和共存无机阴离子等反应条件对ASBC/PMS体系降解RhB的影响。BET结果表明，经过活化后的生物炭的比表面积从8.19 m²/g提高至175.04 m²/g，孔容从0.017 cm³/g提高至0.189 cm³/g，活化后的污泥生物炭具备更多的反应活性位点；当ASBC投加量为0.2 g/L、PMS浓度为0.8 mmol/L，反应5 min后对RhB的去除率高达99.7%，反应可在较宽的pH范围（3~11）内发挥作用；H₂PO₄ ^-和NO₃ ^-对ASBC/PMS体系降解效果无显著影响，HCO₃ ^-具有抑制作用，Cl^-具有促进作用；ASBC/PMS体系降解RhB是非自由基路径，主要活性物质是¹O₂。

关键词: ZnCl₂改性, 污泥生物炭, 过一硫酸盐, 罗丹明B, 非自由基

CLC Number:

X703.1

Yuting XIONG, Caigui LUO, Xuekun TANG, Xianping LUO. Study on the performance of mesoporous sludge biochar for the removal of Rhodamine B[J]. Industrial Water Treatment, 2024, 44(12): 94-103.

熊瑜婷, 罗才贵, 唐学昆, 罗仙平. 介孔污泥生物炭去除罗丹明B的性能研究[J]. 工业水处理, 2024, 44(12): 94-103.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2023-1133

https://www.iwt.cn/EN/Y2024/V44/I12/94

Figures/Tables 13

Fig.1 SEM images of SBC and ASBC-1

Fig.2 N₂ adsorption/desorption curves（a） of sludge biochar and pore size distribution （b）

Table 1 Data of sludge biochar pore structure

样品	比表面积/（m²·g^-1）	微孔面积/ （m²·g^-1）	总孔容/ （cm³·g^-1）	平均孔径/nm
SBC	8.19	2.46	0.017	8.52
ASBC-0.2	131.69	87.01	0.105	3.18
ASBC-1	175.04	29.84	0.189	4.31
ASBC-2.5	131.32	18.67	0.133	4.04

Fig.3 XRD（a） and FTIR（b） of four kinds of biochar

Fig.4 XPS spectra of ASBC before and after the reaction

Table 2 Elements content in SBC and ASBC before and after reaction

样品	原子数分数/%
样品	C	O	N	Si	Zn
SBC	46.22	38.97	2.88	11.85	0.09
ASBC反应前	56.3	27.94	5.88	8.64	1.23
ASBC反应后	56.28	28.7	7.71	6.63	0.68

Fig.5 Kinetics of degradation of Rhodamine B（a） and corresponding pseudo-first-order reaction kinetics（b） in different systems

Fig.6 Effect of ASBC dosage on RhB degradation in ASBC/PMS system（a） and corresponding pseudo-first-order reaction

Fig.7 Effect of PMS dosage on RhB degradation in ASBC/PMS system（a） and corresponding pseudo-first-order reaction kinetics in different systems（b）

Fig.8 Effect of initial pH on RhB degradation in ASBC/PMS system（a） and corresponding pseudo-first-order reaction kinetics in different systems（b）

Fig.9 Effect of inorganic anions on RhB degradation in ASBC/PMS system（a） and corresponding pseudo-first-order reaction kinetics in different systems（b）

Fig.10 ESR spectra of ASBC/PMS system

Fig.11 Degradation of RhB in different quencher systems

References 38

1	秦彬，谷晋川，殷萍，等. 染料废水处理技术研究进展［J］. 化工环保，2021，41（1）：9-18． doi:10.3969/j.issn.1006-1878.2021.01.002
	QIN Bin， GU Jinchuan， YIN Ping，et al. Research progresses on dye wastewater treatment technology［J］. Environmental Protection of Chemical Industry，2021，41（1）：9-18． doi:10.3969/j.issn.1006-1878.2021.01.002
2	DONG Weiyang， LEE C W， LU Xinchun，et al. Synchronous role of coupled adsorption and photocatalytic oxidation on ordered mesoporous anatase TiO₂-SiO₂ nanocomposites generating excellent degradation activity of RhB dye［J］. Applied Catalysis B：Environmental，2010，95（3/4）：197-207． doi:10.1016/j.apcatb.2009.12.025
3	LOPS C， ANCONA A， DI CESARE K，et al. Sonophotocatalytic degradation mechanisms of Rhodamine B dye via radicals generation by micro- and nano-particles of ZnO［J］. Applied Catalysis B：Environmental，2019，243：629-640． doi:10.1016/j.apcatb.2018.10.078
4	YE Hanchen， CHEN Dongyun， LI Najun，et al. Azine-linked covalent organic framework-modified GO membrane for high-efficiency separation of aqueous dyes and salts in wastewater［J］. Journal of Membrane Science，2022，655：120546． doi:10.1016/j.memsci.2022.120546
5	MU Yongkang， DU Huixin， HE Wenyan，et al. Functionalized mesoporous magnetic biochar for methylene blue removal：Performance assessment and mechanism exploration［J］. Diamond and Related Materials，2022，121：108795． doi:10.1016/j.diamond.2021.108795
6	TU Yuming， SHAO Gaoyan， ZHANG Wenjing，et al. The degradation of printing and dyeing wastewater by manganese-based catalysts［J］. Science of the Total Environment，2022，828：154390． doi:10.1016/j.scitotenv.2022.154390
7	LEE J， VON GUNTEN U， KIM J H. Persulfate-based advanced oxidation：Critical assessment of opportunities and roadblocks［J］. Environmental Science & Technology，2020，54（6）：3064-3081． doi:10.1021/acs.est.9b07082
8	ZHAO Chenhui， SHAO Binbin， YAN Ming，et al. Activation of peroxymonosulfate by biochar-based catalysts and applications in the degradation of organic contaminants：A review［J］. Chemical Engineering Journal，2021，416：128829． doi:10.1016/j.cej.2021.128829
9	SHAD A， CHEN Jing， QU Ruijuan，et al. Degradation of sulfadimethoxine in phosphate buffer solution by UV alone，UV/PMS and UV/H₂O₂：Kinetics，degradation products，and reaction pathways［J］. Chemical Engineering Journal，2020，398：125357． doi:10.1016/j.cej.2020.125357
10	ZHENG Xiaoxian， NIU Xiaojun， ZHANG Dongqing，et al. Metal-based catalysts for persulfate and peroxymonosulfate activation in heterogeneous ways：A review［J］. Chemical Engineering Journal，2022，429：132323． doi:10.1016/j.cej.2021.132323
11	GUO Dongli， YOU Shijie， LI Fang，et al. Engineering carbon nanocatalysts towards efficient degradation of emerging organic contaminants via persulfate activation：A review［J］. Chinese Chemical Letters，2022，33（1）：1-10． doi:10.1016/j.cclet.2021.06.027
12	肖鹏飞，安璐，吴德东. 炭材料在过硫酸盐高级氧化技术中的应用进展［J］. 新型炭材料，2020，35（6）：667-683． doi:10.1016/s1872-5805(20)60521-2
	XIAO Pengfei， AN Lu， WU Dedong. The use of carbon materials in persulfate-based advanced oxidation processes：A review［J］. New Carbon Materials，2020，35（6）：667-683． doi:10.1016/s1872-5805(20)60521-2
13	关朝婷. 碳纳米管/过硫酸盐体系氧化机制与卤代副产物生成控制［D］. 哈尔滨：哈尔滨工业大学，2020．
	GUAN Chaoting. Oxidation mechanism of carbon nanotubes/persulfate system and control of halogenated by-products formation［D］. Harbin：Harbin Institute of Technology，2020．
14	郑晚. 氮掺杂石墨烯激活过硫酸盐降解水中有机污染物的性能及作用机理［D］. 杭州：浙江大学，2019．
	ZHENG Wan. Performance and mechanism of nitrogen doped graphene activated persulfate for degradation of organic pollutants in water［D］. Hangzhou：Zhejiang University，2019．
15	YE Yuanyao， NGO H H， GUO Wenshan，et al. A critical review on utilization of sewage sludge as environmental functional materials［J］. Bioresource Technology，2022，363：127984． doi:10.1016/j.biortech.2022.127984
16	赵迎新，麻泽浩，杨知凡，等. 污泥生物炭催化高级氧化过程进展［J］. 化工进展，2021，40（7）：3984-3994．
	ZHAO Yingxin， MA Zehao， YANG Zhifan，et al. Progress of advanced oxidation process catalyzed by sludge biochar［J］. Chemical Industry and Engineering Progress，2021，40（7）：3984-3994．
17	LI Meng， LI Dongya， GUAN Zeyu，et al. Carboxy-functionalized sludge-derived biochar for efficiently activating peroxymonosulfate to degrade bisphenol A［J］. Separation and Purification Technology，2022，297：121525． doi:10.1016/j.seppur.2022.121525
18	LIOU T H. Development of mesoporous structure and high adsorption capacity of biomass-based activated carbon by phosphoric acid and zinc chloride activation［J］. Chemical Engineering Journal，2010，158（2）：129-142． doi:10.1016/j.cej.2009.12.016
19	徐增华. 生物质水热炭基多孔炭的制备及其电化学性能研究［D］. 杭州：浙江大学，2021．
	XU Zenghua. Preparation and electrochemical properties of porous carbon based on biomass hydrothermal carbon［D］. Hangzhou：Zhejiang University，2021．
20	DING Kaili， ZHOU Xinyun， HADIATULLAH H，et al. Removal performance and mechanisms of toxic hexavalent chromium 〔Cr（Ⅵ）〕 with ZnCl₂ enhanced acidic vinegar residue biochar［J］. Journal of Hazardous Materials，2021，420：126551． doi:10.1016/j.jhazmat.2021.126551
21	YAN Lilong， LIU Yue， ZHANG Yudan，et al. ZnCl₂ modified biochar derived from aerobic granular sludge for developed microporosity and enhanced adsorption to tetracycline［J］. Bioresource Technology，2020，297：122381． doi:10.1016/j.biortech.2019.122381
22	DI Jing， JAMAKANGA R， CHEN Qiang，et al. Degradation of Rhodamine B by activation of peroxymonosulfate using Co₃O₄-rice husk ash composites［J］. Science of the Total Environment，2021，784：147258． doi:10.1016/j.scitotenv.2021.147258
23	HU Zhonghua， SRINIVASAN M P. Mesoporous high-surface-area activated carbon［J］. Microporous and Mesoporous Materials，2001，43（3）：267-275． doi:10.1016/s1387-1811(00)00355-3
24	XIAO Wei， GARBA Z N， SUN Shichang，et al. Preparation and evaluation of an effective activated carbon from white sugar for the adsorption of rhodamine B dye［J］. Journal of Cleaner Production，2020，253：119989． doi:10.1016/j.jclepro.2020.119989
25	RUAN Xiuxiu， SUN Yuqing， DU Weimeng，et al. Formation，characteristics，and applications of environmentally persistent free radicals in biochars：A review［J］. Bioresource Technology，2019，281：457-468． doi:10.1016/j.biortech.2019.02.105
26	WU Danping， CHEN Quan， WU Min，et al. Heterogeneous compositions of oxygen-containing functional groups on biochars and their different roles in rhodamine B degradation［J］. Chemosphere，2022，292：133518． doi:10.1016/j.chemosphere.2022.133518
27	郑大洋，邹佳丽，徐皓，等. 污泥生物炭活化过一硫酸盐降解环丙沙星［J］. 环境科学，2023，44（12）：6801-6810．
	ZHENG Dayang， ZOU Jiali， XU Hao，et al. Degradation of ciprofloxacin by activating peroxymonosulfate with sludge biochar［J］. Environmental Science，2023，44（12）：6801-6810．
28	MIAN M M， LIU Guijian， FU Biao，et al. Facile synthesis of sludge-derived MnO _x -N-biochar as an efficient catalyst for peroxymonosulfate activation［J］. Applied Catalysis B：Environmental，2019，255：117765． doi:10.1016/j.apcatb.2019.117765
29	WANG Yuxian， AO Zhimin， SUN Hongqi，et al. Activation of peroxymonosulfate by carbonaceous oxygen groups：Experimental and density functional theory calculations［J］. Applied Catalysis B：Environmental，2016，198：295-302． doi:10.1016/j.apcatb.2016.05.075
30	王宇航，邓德明. 氮掺杂生物炭活化过硫酸盐去除罗丹明B［J］. 武汉大学学报（理学版），2022，68（2）：137-145．
	WANG Yuhang， DENG Deming. Removal of rhodamine B by persulfate activated with N-doped biochar［J］. Journal of Wuhan University （Natural Science Edition），2022，68（2）：137-145．
31	OH W D， LIM T T. Design and application of heterogeneous catalysts as peroxydisulfate activator for organics removal：An overview［J］. Chemical Engineering Journal，2019，358：110-133． doi:10.1016/j.cej.2018.09.203
32	ZENG Tao， LI Shuqi， HUA Jianan，et al. Synergistically enhancing Fenton-like degradation of organics by in situ transformation from Fe₃O₄ microspheres to mesoporous Fe，N-dual doped carbon［J］. Science of the Total Environment，2018，645：550-559． doi:10.1016/j.scitotenv.2018.07.162
33	SUN Ping， LIU Hui， FENG Mingbao，et al. Nitrogen-sulfur Co-doped industrial graphene as an efficient peroxymonosulfate activator：Singlet oxygen-dominated catalytic degradation of organic contaminants［J］. Applied Catalysis B：Environmental，2019，251：335-345． doi:10.1016/j.apcatb.2019.03.085
34	WANG Lingli， LAN Xu， PENG Wenya，et al. Uncertainty and misinterpretation over identification，quantification and transformation of reactive species generated in catalytic oxidation processes：A review［J］. Journal of Hazardous Materials，2021，408：124436． doi:10.1016/j.jhazmat.2020.124436
35	ZHANG Guicheng， YANG Xueying， WU Zhangxiong，et al. Fe-Mn bimetallic oxide-enabled facile cleaning of microfiltration ceramic membranes for effluent organic matter fouling mitigation via activation of oxone［J］. ACS ES & T Water，2022，2（7）：1234-1246． doi:10.1021/acsestwater.2c00076
36	ZHANG Wei， YAN Liangguo， WANG Qiaodi，et al. Ball milling boosted the activation of peroxymonosulfate by biochar for tetracycline removal［J］. Journal of Environmental Chemical Engineering，2021，9（6）：106870． doi:10.1016/j.jece.2021.106870
37	ZHU Hui， GUO An， WANG Siming，et al. Efficient tetracycline degradation via peroxymonosulfate activation by magnetic Co/N Co-doped biochar：Emphasizing the important role of biochar graphitization［J］. Chemical Engineering Journal，2022，450：138428． doi:10.1016/j.cej.2022.138428
38	ZHANG Qiuya， SONG Jiabao， ZHANG Yanan，et al. Preparation of MnCeO _x -modified tea waste biochar as peroxodisulfate activator for tetracycline degradation［J］. Journal of Water Process Engineering，2022，50：103209． doi:10.1016/j.jwpe.2022.103209

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