生物炭负载锌铝层状双氢氧化物吸附磷酸盐和Cr（Ⅵ）的研究

doi:10.19965/j.cnki.iwt.2024-0512

摘要/Abstract

摘要：

通过液相共沉淀法制备了芦苇秸秆生物炭负载锌铝层状双氢氧化物（ZnAl-LDHs）复合材料（ZnAl-LDHs@BC），考察了复合材料中ZnAl-LDHs质量分数、溶液pH、共存阴离子对水中磷酸盐〔Cr（Ⅵ）〕的吸附性能，并对吸附过程进行了吸附动力学和吸附等温模型模拟分析，最后考察了复合材料对磷酸盐和Cr（Ⅵ）二元废水中磷酸盐、Cr（Ⅵ）的吸附效果。结果表明，ZnAl-LDHs和生物炭之间存在协同效应，76.7% ZnAl-LDHs@BC对磷酸盐〔Cr（Ⅵ）〕表现出优异的去除效果。ZnAl-LDHs@BC复合材料吸附去除磷酸盐、Cr（Ⅵ）的最佳pH分别为4、6。共存阴离子对ZnAl-LDHs@BC吸附磷酸盐效果的影响大小为Cl^-<SO₄ ^2-<CO₃ ^2-，对吸附Cr（Ⅵ）效果的影响大小为Cl^-<HPO₄ ^2-<SO₄ ^2-<CO₃ ^2-。Langmuir模型拟合得到的最大磷酸盐和Cr（Ⅵ）吸附量分别为191.8 mg/g和109.7 mg/g，其吸附机制均为单分子层化学吸附。ZnAl-LDHs@BC复合材料处理磷酸盐-Cr（Ⅵ）二元体系研究表明，Cr（Ⅵ）的存在对复合材料吸附磷酸盐具有增效作用。

关键词: LDHs@BC, 芦苇秸秆, 协同效应

Abstract:

Reed straw biochar-loaded zinc-aluminum layered dihydroxide (ZnAl-LDHs) composites (ZnAl-LDHs@BC) were prepared by liquid-phase co-precipitation. The effects of ZnAl-LDHs mass fraction in the composite, solution pH and coexisting anions on the adsorption performance of phosphate/Cr(Ⅵ) in aqueous solutions were investigated. The adsorption process was simulated and analyzed by adsorption kinetics and adsorption isothermal model. Furthermore, the adsorption efficiency of the composite material for phosphate and Cr(Ⅵ) in binary wastewater of phosphate and Cr(Ⅵ) was investigated. The results showed there was synergistic effect between ZnAl-LDHs and biochar, 76.7% ZnAl-LDHs@BC showed excellent performance for phosphate/Cr(Ⅵ) removal. The maximum adsorption efficiencies for phosphate and Cr(Ⅵ) were achieved at pH=4 and pH=6, respectively. The effect of coexisting anions on ZnAl-LDHs@BC adsorption of phosphate followed the order: Cl^-<SO₄ ^2-<CO₃ ^2-, while for Cr(Ⅵ), the order was Cl^-<HPO₄ ^2-<SO₄ ^2-<CO₃ ^2-. The Langmuir model fitted the adsorption data well, yielding maximum adsorption capacities of 191.8 mg/g for phosphate and 109.7 mg/g for Cr(Ⅵ), indicating monolayer chemisorption as the dominant mechanism. The treatment of the binary system of phosphate and Cr(Ⅵ) with composite materials showed that the presence of Cr(Ⅵ) had an enhancing effect on the adsorption of phosphate by the composite materials.

Key words: LDHs@BC, reed straw, synergistic effect

中图分类号:

X703

俞水, 詹旭, 郭倬瑞, 吴婧雯, 汪雨婷, 孟子琦, 孙连军, 黄俊波. 生物炭负载锌铝层状双氢氧化物吸附磷酸盐和Cr（Ⅵ）的研究[J]. 工业水处理, 2025, 45(7): 130-139.

Shui YU, Xu ZHAN, Zhuorui GUO, Jingwen WU, Yuting WANG, Ziqi MENG, Lianjun SUN, Junbo HUANG. Adsorption of phosphate and Cr(Ⅵ) by biochar-loaded Zn-Al layered double hydroxide[J]. Industrial Water Treatment, 2025, 45(7): 130-139.

https://www.iwt.cn/CN/Y2025/V45/I7/130

图/表 12

图1 ZnAl-LDHs@BC的合成示意

Fig.1 Schematic of the synthesis of ZnAl-LDHs@BC

图2 ZnAl-LDHs和ZnAl-LDHs@BC的SEM和EDS （a）ZnAl-LDHs的SEM；（b）76.7% ZnAl-LDHs@BC的SEM；（c）52.4% ZnAl-LDHs@BC的SEM；（d）39.8% ZnAl-LDHs@BC的SEM；（e）ZnAl-LDHs的EDS；（f）76.7% ZnAl-LDHs@BC的EDS。

Fig.2 SEM and EDS of ZnAl-LDHs and ZnAl-LDHs@BC

图3 BC和76.7% ZnAl-LDHs@BC的XRD谱图

Fig.3 XRD spectra of BC and 76.7% ZnAl-LDHs@BC

图4 LDHs归一化前（a）和归一化后（b）ZnAl-LDHs@BC和BC对磷酸盐和Cr（Ⅵ）的吸附效果

Fig.4 The adsorption effects of ZnAl-LDHs@BC and BC on phosphates and Cr（VI） before normalization （a） and after normalization （b）

图5 初始pH对复合材料吸附磷酸盐和Cr（Ⅵ）效果的影响

Fig.5 Effect of initial pH on the adsorption of phosphate and Cr（Ⅵ） by composite materials

图6 共存离子对复合材料吸附磷酸盐和Cr（Ⅵ）效果的影响

Fig.6 Effect of coexisting ions on the adsorption of phosphate and Cr（Ⅵ） by composite materials

图7 复合材料对磷酸盐和Cr（Ⅵ）的吸附动力学拟合曲线

Fig.7 The fitting curves of adsorption kinetics of phosphate and Cr（Ⅵ） by composite materials

表1 吸附动力学模型拟合参数

Table 1 Fitting parameters of adsorption kinetics model

污染物	伪一级吸附动力学			伪二级吸附动力学
污染物	q _e/（mg·g^-1）	k ₁	R ²	q _e/（mg·g^-1）	k ₂	R ²
磷酸盐	65.88	0.038	0.969	69.90	8.081	0.998
Cr（Ⅵ）	33.14	0.170	0.856	33.78	0.009	0.997

图8 复合材料对磷酸盐（a）和Cr（Ⅵ）（b）的吸附等温线

Fig.8 Adsorption isotherms of phosphate （a） and Cr（Ⅵ）（b）on composites

表2 Langmuir和Freundlich等温模型拟合参数

Table 2 Fitting parameters of Langmuir and Freundlich isothermal model

污染物	T/K	Langmuir			Freundlich
污染物	T/K	Q/（mg·g^-1）	K _L	R ²	K _F	n	R ²
磷酸盐	293	165.5	0.005 8	0.999	5.568	0.515	0.983
	303	174.1	0.006 3	0.999	6.617	0.499	0.981
	313	191.8	0.005 9	0.999	6.606	0.512	0.982
Cr（Ⅵ）	293	79.7	0.014 7	0.999	8.964	0.400	0.954
	303	98.4	0.011 5	0.999	8.076	0.383	0.964
	313	109.7	0.009 7	0.999	7.729	0.414	0.969

表3 ZnAl-LDHs@BC与其他吸附剂的吸附性能对比

Table 3 Comparison of adsorption performance of ZnAl-LDHs@BC with other adsorbents

吸附剂	污染物	温度/K	pH	等温线	动力学	Q/（mg·g^-1）	参考文献
氧化铁负载棉花秸秆生物炭	磷酸盐	298	自然	Langmuir		1.2	〔35〕
Fe-Cu二元氧化物	磷酸盐	298	5.0	Langmuir	伪二级动力学	39.8	〔36〕
纤维素基微球（CSPGs-Ech）	磷酸盐	313	自然	Langmuir	伪二级动力学	106.1	〔37〕
4∶1 Mg/Al-LDHs-BC	磷酸盐	296	3.0	Langmuir	伪二级动力学	81.8	〔21〕
76.7% ZnAl-LDHs@BC	磷酸盐	313	4.0	Langmuir	伪二级动力学	191.8	本研究
CoFe-硝酸盐-LDHs	Cr（Ⅵ）	298	7.5	Langmuir	伪二级动力学	27.6	〔38〕
FeH（34%）@kaol-US	Cr（Ⅵ）	298	3.0	Langmuir	伪二级动力学	20.4	〔39〕
NMA-LDHs	Cr（Ⅵ）	313	自然	Langmuir	伪二级动力学	52.4	〔40〕
MgAl-NO₃ ^- LDH	Cr（Ⅵ）	313	6.0	Langmuir	伪二级动力学	75.8	〔41〕
76.7% ZnAl-LDHs@BC	Cr（Ⅵ）	313	6.0	Langmuir	伪二级动力学	109.7	本研究

图9 复合材料对磷酸盐-Cr（Ⅵ）二元体系中磷酸盐、Cr（Ⅵ）的吸附性能及共存污染物的影响

Fig.9 Effects of composite materials on the adsorption properties of phosphate and Cr（Ⅵ） and effects of co-existing pollutants in phosphate-Cr（Ⅵ） binary system

参考文献 44

[1]	KATZ S A， SALEM H. The toxicology of chromium with respect to its chemical speciation：A review［J］. Journal of Applied Toxicology，1993，13（3）：217-224. doi:10.1002/jat.2550130314
[2]	DUPONT L， GUILLON E. Removal of hexavalent chromium with a lignocellulosic substrate extracted from wheat bran［J］. Environmental Science & Technology，2003，37（18）：4235-4241. doi:10.1021/es0342345
[3]	王玉婷，赵泽华，王逸，等. 我国典型印染行业废水处理污泥污染特征研究［J］. 生态与农村环境学报，2020，36（12）：1598-1604.
	WANG Yuting， ZHAO Zehua， WANG Yi，et al. Study on the pollution characteristics of typical textile dyeing sludge（TDS） in China［J］. Journal of Ecology and Rural Environment，2020，36（12）：1598-1604.
[4]	JIANG Yanhong， LI Anyu， DENG Hua，et al. Phosphate adsorption from wastewater using ZnAl-LDO-loaded modified banana straw biochar［J］. Environmental Science and Pollution Research International，2019，26（18）：18343-18353. doi:10.1007/s11356-019-05183-1
[5]	LANGER M， VÄÄNÄNEN J， BOULESTREAU M，et al. Advanced phosphorus removal via coagulation，flocculation and microsieve filtration in tertiary treatment［J］. Water Science and Technology，2017，75（12）：2875-2882. doi:10.2166/wst.2017.166
[6]	PAP S， ZHANG Huiyi， BOGDAN A，et al. Pilot-scale phosphate recovery from wastewater to create a fertiliser product：An integrated assessment of adsorbent performance and quality［J］. Water Research，2023，228：119369. doi:10.1016/j.watres.2022.119369
[7]	KAUŠPĖDIENĖ D， KAZLAUSKIENĖ E， GEFENIENĖ A，et al. Comparison of the efficiency of activated carbon and neutral polymeric adsorbent in removal of chromium complex dye from aqueous solutions［J］. Journal of Hazardous Materials，2010，179（1/2/3）：933-939. doi:10.1016/j.jhazmat.2010.03.095
[8]	HERNÁNDEZ-MONTOYA V， PÉREZ-CRUZ M A， MENDOZA-CASTILLO D I，et al. Competitive adsorption of dyes and heavy metals on zeolitic structures［J］. Journal of Environmental Management，2013，116：213-221. doi:10.1016/j.jenvman.2012.12.010
[9]	KYZAS G Z， SIAFAKA P I， PAVLIDOU E G，et al. Synthesis and adsorption application of succinyl-grafted chitosan for the simultaneous removal of zinc and cationic dye from binary hazardous mixtures［J］. Chemical Engineering Journal，2015，259：438-448. doi:10.1016/j.cej.2014.08.019
[10]	JIANG Tingshun， LIU Wangping， MAO Yulin，et al. Adsorption behavior of copper ions from aqueous solution onto graphene oxide-CdS composite［J］. Chemical Engineering Journal，2015，259：603-610. doi:10.1016/j.cej.2014.08.022
[11]	ZHAO Jian， WANG Zhenyu， WHITE J C，et al. Graphene in the aquatic environment：Adsorption，dispersion，toxicity and transformation［J］. Environmental Science & Technology，2014，48（17）：9995-10009. doi:10.1021/es5022679
[12]	王小平，龚诚，赖玲燕，等. 去除水体中PPCPs的4种改性新型吸附材料研究进展［J］. 工业水处理，2022，42（9）：23-37.
	WANG Xiaoping， GONG Cheng， LAI Lingyan，et al. Research progress of four new modified adsorbents for removal of PPCPs in water［J］. Industrial Water Treatment，2022，42（9）：23-37.
[13]	GOH K H， LIM T T， DONG Zhili. Application of layered double hydroxides for removal of oxyanions：A review［J］. Water Research，2008，42（6/7）：1343-1368. doi:10.1016/j.watres.2007.10.043
[14]	WANG Shengsen， GAO Bin， LI Yuncong. Enhanced arsenic removal by biochar modified with nickel（Ni） and manganese（Mn） oxyhydroxides［J］. Journal of Industrial and Engineering Chemistry，2016，37：361-365. doi:10.1016/j.jiec.2016.03.048
[15]	LING Lili， LIU Wujun， ZHANG Shun，et al. Achieving high-efficiency and ultrafast removal of Pb（Ⅱ） by one-pot incorporation of a N-doped carbon hydrogel into FeMg layered double hydroxides［J］. Journal of Materials Chemistry A，2016，4（26）：10336-10344. doi:10.1039/c6ta02737g
[16]	CHENG Xiaojuan， DENG Jiaqin， LI Xiaodong，et al. Layered double hydroxides loaded sludge biochar composite for adsorptive removal of benzotriazole and Pb（Ⅱ） from aqueous solution［J］. Chemosphere，2022，287：131966. doi:10.1016/j.chemosphere.2021.131966
[17]	CORONADO E， MARTÍ-GASTALDO C， NAVARRO-MORATALLA E，et al. Intercalation of［M（ox）₃］^3-（M=Cr，Rh） complexes into Ni^ⅡFe^Ⅲ- LDH［J］. Applied Clay Science，2010，48（1/2）：228-234. doi:10.1016/j.clay.2009.11.054
[18]	MOHANTY P， NANDA S， PANT K K，et al. Evaluation of the physiochemical development of biochars obtained from pyrolysis of wheat straw，timothy grass and pinewood：Effects of heating rate［J］. Journal of Analytical and Applied Pyrolysis，2013，104：485-493. doi:10.1016/j.jaap.2013.05.022
[19]	SHAABAN A， SE S M， MITAN N M M，et al. Characterization of biochar derived from rubber wood sawdust through slow pyrolysis on surface porosities and functional groups［J］. Procedia Engineering，2013，68：365-371. doi:10.1016/j.proeng.2013.12.193
[20]	KIM P， JOHNSON A， EDMUNDS C W，et al. Surface functionality and carbon structures in lignocellulosic-derived biochars produced by fast pyrolysis［J］. Energy & Fuels，2011，25（10）：4693-4703. doi:10.1021/ef200915s
[21]	LI Ronghua， WANG J J， ZHOU Baoyue，et al. Enhancing phosphate adsorption by Mg/Al layered double hydroxide functionalized biochar with different Mg/Al ratios［J］. Science of the Total Environment，2016，559：121-129. doi:10.1016/j.scitotenv.2016.03.151
[22]	LEI Chunsheng， PI Meng， KUANG Panyong，et al. Organic dye removal from aqueous solutions by hierarchical calcined Ni-Fe layered double hydroxide：Isotherm，kinetic and mechanism studies［J］. Journal of Colloid and Interface Science，2017，496：158-166. doi:10.1016/j.jcis.2017.02.025
[23]	LEHMANN J， RILLIG M C， THIES J，et al. Biochar effects on soil biota：A review［J］. Soil Biology and Biochemistry，2011，43（9）：1812-1836. doi:10.1016/j.soilbio.2011.04.022
[24]	WAN S， WANG Shengsen， LI Yuncong，et al. Functionalizing biochar with Mg-Al and Mg-Fe layered double hydroxides for removal of phosphate from aqueous solutions［J］. Journal of Industrial and Engineering Chemistry，2017，47：246-253. doi:10.1016/j.jiec.2016.11.039
[25]	任树鹏，齐宇彤，石瑶，等. 层状双氢氧化物负载生物炭对磷酸盐的吸附性能研究进展［J］. 环境化学，2023，42（2）：575-584.
	REN Shupeng， QI Yutong， SHI Yao，et al. The adsorption performance of layered double hydroxides functionalized biochar on phosphate：Research advances［J］. Environmental Chemistry，2023，42（2）：575-584.
[26]	DE SOUZA DOS SANTOS G E， DOS SANTOS LINS P V， DE MAGALHÃES OLIVEIRA L M T，et al. Layered double hydroxides/biochar composites as adsorbents for water remediation applications：Recent trends and perspectives［J］. Journal of Cleaner Production，2021，284：124755. doi:10.1016/j.jclepro.2020.124755
[27]	LI Wei， PIERRE-LOUIS A M， KWON K D，et al. Molecular level investigations of phosphate sorption on corundum（α-Al₂O₃） by ³¹P solid state NMR，ATR-FTIR and quantum chemical calculation［J］. Geochimica et Cosmochimica Acta，2013，107：252-266. doi:10.1016/j.gca.2013.01.007
[28]	ASHEKUZZAMAN S M， JIANG Jiaqian. Strategic phosphate removal/recovery by a re-usable Mg-Fe-Cl layered double hydroxide［J］. Process Safety and Environmental Protection，2017，107：454-462. doi:10.1016/j.psep.2017.03.009
[29]	KUMAR N， REDDY L， PARASHAR V，et al. Controlled synthesis of microsheets of ZnAl layered double hydroxides hexagonal nanoplates for efficient removal of Cr（Ⅵ） ions and anionic dye from water［J］. Journal of Environmental Chemical Engineering，2017，5（2）：1718-1731. doi:10.1016/j.jece.2017.03.014
[30]	DAS J， PATRA B S， BALIARSINGH N，et al. Adsorption of phosphate by layered double hydroxides in aqueous solutions［J］. Applied Clay Science，2006，32（3/4）：252-260. doi:10.1016/j.clay.2006.02.005
[31]	LU Jianbo， LIU Huijuan， ZHAO Xu，et al. Phosphate removal from water using freshly formed Fe-Mn binary oxide：Adsorption behaviors and mechanisms［J］. Colloids and Surfaces A：Physicochemical and Engineering Aspects，2014，455：11-18. doi:10.1016/j.colsurfa.2014.04.034
[32]	张楠. 天然纤维素和水滑石的改性及其对重金属和磷酸根的吸咐研究［D］. 合肥：中国科学技术大学，2016.
	ZHANG Nan. Modification of natural cellulose and hydrotalcite and their adsorption of heavy metals and phosphate［D］. Hefei：University of Science and Technology of China，2016.
[33]	XIANG Li， NIU Chenggang， TANG Ning，et al. Polypyrrole coated molybdenum disulfide composites as adsorbent for enhanced removal of Cr（Ⅵ） in aqueous solutions by adsorption combined with reduction［J］. Chemical Engineering Journal，2021，408：127281. doi:10.1016/j.cej.2020.127281
[34]	LI Qimeng， JI Ming， LI Xiang，et al. Efficient co-removal of copper and tetracycline from aqueous solution by using permanent magnetic cation exchange resin［J］. Bioresource Technology，2019，293：122068. doi:10.1016/j.biortech.2019.122068
[35]	CHEN Baoliang， CHEN Zaiming， Shaofang LÜ. A novel magnetic biochar efficiently sorbs organic pollutants and phosphate［J］. Bioresource Technology，2011，102（2）：716-723. doi:10.1016/j.biortech.2010.08.067
[36]	LI Guoliang， GAO Song， ZHANG Gaosheng，et al. Enhanced adsorption of phosphate from aqueous solution by nanostructured iron（Ⅲ）- copper（Ⅱ） binary oxides［J］. Chemical Engineering Journal，2014，235：124-131. doi:10.1016/j.cej.2013.09.021
[37]	WU Jiale， ZHONG Yun， HAO Chen，et al. Emulsion synthesis of cellulose/lanthanum alginate/La（Ⅲ） composite microspheres for efficient and selective adsorption of phosphate［J］. Chemical Engineering Journal，2024，488：150949. doi:10.1016/j.cej.2024.150949
[38]	LING Faling， FANG Liang， LU Yi，et al. A novel CoFe layered double hydroxides adsorbent：High adsorption amount for methyl orange dye and fast removal of Cr（Ⅵ）［J］. Microporous and Mesoporous Materials，2016，234：230-238. doi:10.1016/j.micromeso.2016.07.015
[39]	BOUNAB N， DUCLAUX L， REINERT L，et al. Ferrihydrite coating on kaolinite assisted by ultrasound for improving Cr（Ⅵ） adsorption in aqueous solutions［J］. Applied Clay Science，2024，250：107287. doi:10.1016/j.clay.2024.107287
[40]	LEI Chunsheng， ZHU Xiaofeng， ZHU Bicheng，et al. Superb adsorption capacity of hierarchical calcined Ni/Mg/Al layered double hydroxides for Congo red and Cr（Ⅵ） ions［J］. Journal of Hazardous Materials，2017，321：801-811. doi:10.1016/j.jhazmat.2016.09.070
[41]	KHITOUS M， SALEM Z， HALLICHE D. Effect of interlayer anions on chromium removal using Mg-Al layered double hydroxides：Kinetic，equilibrium and thermodynamic studies［J］. Chinese Journal of Chemical Engineering，2016，24（4）：433-445. doi:10.1016/j.cjche.2015.11.018
[42]	LI Jie， FAN Qiaohui， WU Yijin，et al. Magnetic polydopamine decorated with Mg-Al LDH nanoflakes as a novel bio-based adsorbent for simultaneous removal of potentially toxic metals and anionic dyes［J］. Journal of Materials Chemistry A，2016，4（5）：1737-1746. doi:10.1039/c5ta09132b
[43]	DENG Jiuhua， ZHANG Xiurong， ZENG Guangming，et al. Simultaneous removal of Cd（Ⅱ） and ionic dyes from aqueous solution using magnetic graphene oxide nanocomposite as an adsorbent［J］. Chemical Engineering Journal，2013，226：189-200. doi:10.1016/j.cej.2013.04.045
[44]	CHEN Shixia， HUANG Yifeng， HAN Xinxin，et al. Simultaneous and efficient removal of Cr（Ⅵ） and methyl orange on LDHs decorated porous carbons［J］. Chemical Engineering Journal，2018，352：306-315. doi:10.1016/j.cej.2018.07.012

选择文件类型/文献管理软件名称

选择包含的内容