氧化钙对污泥炭重金属稳定性及其吸附性能的影响

doi:10.19964/j.issn.1006-4990.2022-0453

摘要/Abstract

摘要：

鉴于CaO对生物质的热解产气、焦油重整具有催化作用，并可显著提升生物炭的吸附性能，将CaO与市政污泥以1∶10的质量比混合共热解，制备改性污泥炭（BC-Ca）。研究了CaO对污泥炭特性及重金属（Pb、Zn、Cu、Cr、Mn）形态分布的影响，采用风险评价编码法（RAC）评价污泥炭的生态风险，并采用静态吸附实验考察改性污泥炭对Cr（Ⅵ）的吸附效果。结果表明：BC-Ca中Zn、Pb、Cr、Mn和Cu处于残渣态（F4）的比例较未改性污泥炭（BC）分别增加11.76%、13.03%、26.96%、5.55%和2.11%，且均为RAC低风险；BC-Ca的比表面积较BC增大122.99%，孔隙结构得到改善；BC-Ca对Cr（Ⅵ）的吸附过程符合Langmuir等温吸附模型和拟二级动力学模型，吸附容量随着温度的升高而增大，吸附速率主要由化学吸附机理控制；BC-Ca对Cr（Ⅵ）的最大吸附容量较BC提高51.13%，去除率显著提高。

关键词: 污泥炭, 重金属稳定性, 生态风险, Cr（Ⅵ）吸附

Abstract:

In view of the catalytic effect of CaO on gas production and tar reforming during biomass pyrolysis process，which can significantly improve the adsorption performance of biochar，the modified sludge derived biochar（BC-Ca） was prepared by co-pyrolysis of CaO and sewage sludge at a mass ratio of 1∶10.The effect of CaO on the characteristics of the sludge-derived biochar，as well as the speciation distribution of heavy metals（Pb，Zn，Cu，Cr，Mn） were investigated.The ecological risk of the biochar was assessed based on the risk assessment code（RAC）.The adsorption properties of the modified sludge derived biochar on Cr（Ⅵ） was evaluated by the static adsorption experiments.The results showed that compared with unmodified biochar（BC），the fraction of residual state（F4） of Zn，Pb，Cr，Mn，and Cu in BC-Ca were increased by 11.76%，13.03%，26.96%，5.55%，and 2.11%，respectively，which were all in a low risk condition according to the RAC standard.Compared with BC，the specific surface area of BC-Ca was increased by 122.99%，indicating that the microstructure performance of BC-Ca was improved.The adsorption behavior of BC-Ca for Cr（Ⅵ） was described by the Langmuir model and pseudo-second order dynamic sorption model，indicating that the adsorption capacity of BC-Ca was increased with increasing temperature，and the adsorption rate was mainly controlled by chemical adsorption mechanism.The maximum adsorption capacity of BC-Ca for Cr（Ⅵ） was improved by 51.13% than that of BC，showing outstanding removal effect on Cr（Ⅵ）.

Key words: sludge-derived biochar, heavy metal stability, ecological risk, Cr（Ⅵ） adsorption

中图分类号:

TQ132.32

田玉玲, 程阳, 韩融, 周梅, 王成杰, 葛强茹. 氧化钙对污泥炭重金属稳定性及其吸附性能的影响[J]. 无机盐工业, 2023, 55(6): 124-129.

TIAN Yuling, CHENG Yang, HAN Rong, ZHOU Mei, WANG Chengjie, GE Qiangru. Effect of CaO on heavy metals stability and adsorption properties of sludge-derived biochar[J]. Inorganic Chemicals Industry, 2023, 55(6): 124-129.

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参考文献 21

1	QIAN Lili， WANG Shuzhong， XU Donghai，et al.Treatment of municipal sewage sludge in supercritical water：A review［J］.Water Research，2016，89：118-131.
2	LEDAKOWICZ S， STOLAREK P， MALINOWSKI A，et al.Thermochemical treatment of sewage sludge by integration of drying and pyrolysis/autogasification［J］.Renewable and Sustainable Energy Reviews，2019，104：319-327.
3	CHEN Dezhen， YIN Lijie， WANG Huan，et al.Reprint of：Pyrolysis technologies for municipal solid waste：A review［J］.Waste Management，2015，37：116-136.
4	AGARWAL M， TARDIO J， VENKATA MOHAN S.Pyrolysis of activated sludge：Energy analysis and its technical feasibility［J］.Bioresource Technology，2015，178：70-75.
5	李复生，高慧，耿中峰，等.污泥热化学处理研究进展［J］.安全与环境学报，2015，15（2）：239-245.
	LI Fusheng， GAO Hui， GENG Zhongfeng，et al.Progress in research of thermochemical treatment of sewage sludge［J］.Journal of Safety and Environment，2015，15（2）：239-245.
6	梁宁，莫福金，周街荣，等.污泥生物炭制备及其对磷的吸附性能研究［J］.无机盐工业，2021，53（6）：174-179.
	LIANG Ning， MO Fujin， ZHOU Jierong，et al.Study on preparation of sludge biochar and its adsorption performance for phosphorus［J］.Inorganic Chemicals Industry，2021，53（6）：174-179.
7	DONG Jun， NZIHOU A， CHI Yong，et al.Hydrogen-rich gas production from steam gasification of bio-char in the presence of CaO［J］.Waste and Biomass Valorization，2017，8（8）：2735-2746.
8	CHEN Tan， ZHANG Yaxin， WANG Hongtao，et al.Influence of pyrolysis temperature on characteristics and heavy metal adsorptive performance of biochar derived from municipal sewage sludge［J］.Bioresource Technology，2014，164：47-54.
9	OGINNI O， YAKABOYLU G A， SINGH K，et al.Phosphorus adsorption behaviors of MgO modified biochars derived from waste woody biomass resources［J］.Journal of Environmental Chemical Engineering，2020，8（2）：103723.
10	JIN Junwei， WANG Minyan， CAO Yucheng，et al.Cumulative effects of bamboo sawdust addition on pyrolysis of sewage sludge：Biochar properties and environmental risk from metals［J］.Bioresource Technology，2017，228：218-226.
11	MARTINS B L， CRUZ C C V， LUNA A S，et al.Sorption and desorption of Pb²⁺ ions by dead Sargassum sp.biomass［J］.Biochemical Engineering Journal，2006，27（3）：310-314.
12	RAURET G， LÓPEZ-SÁNCHEZ J F， SAHUQUILLO A，et al.Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference ma-terials［J］.Journal of Environmental Monitoring，1999，1（1）：57-61.
13	LIU Yucheng， LIU Qian， CHEN Mingyan，et al.Evaluation of migration of heavy metals and performance of product during co-pyrolysis process of municipal sewage sludge and walnut shell［J］.Environmental Science and Pollution Research，2017，24（27）：22082-22090.
14	PEZOTI O Jr， CAZETTA A L， GOMES R C，et al.Synthesis of ZnCl₂-activated carbon from macadamia nut endocarp（Macadamia integrifolia） by microwave-assisted pyrolysis：Optimization using RSM and methylene blue adsorption［J］.Journal of Analytical and Applied Pyrolysis，2014，105：166-176.
15	陈坦，周泽宇，孟瑞红，等.改性污泥基生物炭的性质与重金属吸附效果［J］.环境科学，2019，40（4）：1842-1848.
	CHEN Tan， ZHOU Zeyu， MENG Ruihong，et al.Characteristics and heavy metal adsorption performance of sewage sludge-derived biochar from Co-pyrolysis with transition metals［J］.Environmental Science，2019，40（4）：1842-1848.
16	SCOTT S A， DAVIDSON J F， DENNIS J S，et al.The rate of gasification by CO₂ of chars from waste［J］.Proceedings of the Combustion Institute，2005，30（2）：2151-2159.
17	KHADHAR S， SDIRI A， CHEKIRBEN A，et al.Integration of sequential extraction，chemical analysis and statistical tools for the availability risk assessment of heavy metals in sludge amended soils［J］.Environmental Pollution，2020，263：114543.
18	徐楠楠，林大松，徐应明，等.玉米秸秆生物炭对Cd²⁺的吸附特性及影响因素［J］.农业环境科学学报，2014，33（5）：958-964.
	XU Nannan， LIN Dasong， XU Yingming，et al.Adsorption of aquatic Cd²⁺ by biochar obtained from corn stover［J］.Journal of Agro-Environment Science，2014，33（5）：958-964.
19	LI Jie， PAN Lanjia， YU Guangwei，et al.Synthesis of an easily recyclable and safe adsorbent from sludge pyrochar for ciprofloxacin adsorption［J］.Environmental Research，2021，192：110258.
20	KHAN Z H， GAO Minling， QIU Weiwen，et al.Mechanisms for cadmium adsorption by magnetic biochar composites in an aqueous solution［J］.Chemosphere，2020，246：125701.
21	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.

样品	Zn	Pb	Cr	Mn	Cu
BC	16.45%/MR	4.87%/LR	5.33%/LR	16.19%/MR	2.17%/LR
BC-Ca	7.01%/LR	2.90%/LR	8.36%/LR	15.41%MR	1.85%/LR

温度/ ℃	Langmuir方程				Fredundlich方程
温度/ ℃	Q_e/ （mg·g^-1）		K_L/ （L·g^-1）	R²	K_F	n	R²
15	24.59	0.740		0.942	11.873	4.403	0.894
25	24.71	0.855		0.972	12.366	4.546	0.912
35	24.84	1.107		0.974	13.056	4.780	0.932

拟一级反应				拟二级反应
Q_m/（mg·g^-1）	k₁/min^-1	R²		Q_m/（mg·g^-1）	k₂/（mg·min）^-1	R²
16.637	0.140	0.922		17.891	0.010	0.984

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