Influence of zero valent iron and copper modified biochar on Cr(Ⅵ) adsorption

doi:10.16085/j.issn.1000-6613.2019-2026

Abstract

Abstract:

In view of the easy-agglomeration of nanoscale zerovalent iron (nZVI), chicken bone biochar (BC) supported nZVI(Fe-BC) and copper-modified biochar(BC) supported nZVI (Fe-Cu-BC) to remove chromium(). The adsorption properties of Cr() by Fe-Cu-BC, Fe-BC and BC were compared. The physicochemical properties of materials were characterized by SEM, EDS, XRD, N₂ adsorption isotherm and FTIR. Batch adsorption experiments were conducted to investigate the effects of pH and contact time on the Cr() adsorption. The adsorption characteristics were analyzed by adsorption kinetics and isotherms. Results showed that the removal of Cr() was better at pH=2; the process was better described by the Langmuir isotherm model; and the adsorption process was consistent with the pseudo-second-order model. The Fe-BC materials could be recovered by magnetic separation technique after adsorbing water pollutants. Fe-Cu-BC shortened the adsorption equilibrium time for Cr().The theoretical maximum adsorption on Cr() showed following order: Fe-BC>Fe-Cu-BC>BC.The Cr() adsorption amount by Fe-BC was 153.60mg/g, which showed great improvement compared with the previously reported 85mg/g by zerovalent iron. It indicated that biochar as a carrier successfully addressed the easy-agglomeration shortcomings of zerovalent iron and expanded the practical application.

Key words: nanoscale zero valent iron (nZVI), biochar(BC), copper, adsorption, chromium (Ⅵ)

摘要：

针对纳米零价铁（nanoscale zero valent iron，nZVI）易团聚的特性，本文用鸡骨生物炭（BC）作载体，制备出生物炭-零价铁（Fe-BC）去除Cr(Ⅵ)，并与铜改性的生物炭-零价铁（Fe-Cu-BC）和BC对Cr(Ⅵ)的吸附性能进行了对比。通过扫描电镜（SEM）和能谱仪（EDS）、X射线衍射（XRD）、N₂吸脱附等温线和傅里叶红外光谱（FTIR）对材料表面形貌及结构性质进行分析，同时考察了溶液pH、接触时间等条件对吸附剂吸附容量的影响，通过吸附动力学和吸附等温线分析了吸附特性。结果表明，在pH=2的条件下去除Cr(Ⅵ)效果较好；吸附平衡遵从Langmuir吸附等温式；吸附动力学符合准二级动力学方程。Fe-BC材料吸附水体污染物后可用磁分离技术加以回收。Fe-Cu-BC缩短了对Cr(Ⅵ)的吸附平衡时间。制备出的吸附剂对Cr(Ⅵ)的理论最大吸附量顺序为 Fe-BC>Fe-Cu-BC>BC；同时， Fe-BC吸附量为153.60mg/g，对比于先前报道的nZVI对Cr(Ⅵ)的吸附容量85mg/g左右，有了很大的提升，说明BC作载体成功解决了nZVI易团聚的缺点，拓展了实际应用。

关键词: 纳米零价铁, 生物炭, 铜, 吸附, 六价铬

CLC Number:

X523

Chundi ZHOU, Ting YANG, Xize MIN, Caiyun HAN. Influence of zero valent iron and copper modified biochar on Cr(Ⅵ) adsorption[J]. Chemical Industry and Engineering Progress, 2020, 39(10): 4275-4282.

周春地, 阳婷, 闵熙泽, 韩彩芸. 零价铁、铜改性生物炭及其对Cr(Ⅵ)吸附性能的影响[J]. 化工进展, 2020, 39(10): 4275-4282.

References

1	CHRYSOCHOOU M, JOHNSTON C P, DAHAL G. A comparative evaluation of hexavalent chromium treatment in contaminated soil by calcium polysulfide and green-tea nanoscale zero-valent iron[J]. Journal of Hazardous Materials, 2012, 201(1): 33-42.
2	HU J, CHEN G, LO I M. Removal and recovery of Cr() from wastewater by maghemite nanoparticles[J]. Water Research, 2005, 39(18): 4528-4536.
3	GREER N P, METAL B. National socialist black metal[J]. Patho Publishing, 2011, 22: 3-8.
4	MANDAL S, MAYADEVI S. Cellulose supported layered double hydroxides for the adsorption of fluoride from aqueous solution[J]. Chemosphere, 2008, 72(6): 995-998.
5	DAS D P, DAS J, PARIDA K. Physicochemical characterization and adsorption behavior of calcined Zn/Al hydrotalcite-like compound (HTlc) towards removal of fluoride from aqueous solution[J]. Journal of Colloid & Interface Science, 2003, 261(2): 213-220.
6	MIN Y. Fluoride removal in a fixed bed packed with granular calcite[J]. Water Research, 1999, 33(16): 3395-3402.
7	AMOR Z, BARIOUS B, MAMERI N, et al. Fluoride removal from brackish water by electrodialysis[J]. Desalination, 2001,133(3): 215-223.
8	CHEN L S, YUAN T J, NI R, et al. Multivariate optimization of ciprofloxacin removal by polyvinylpyrrolidone stabilized nZVI/Cu bimetallic particles[J]. Chemical Engineering Journal, 2019,365:183-194.
9	LI X Q, CAO J, ZHANG W X. Stoichiometry of Cr(Ⅵ) immobilization using nanoscale zerovalent iron (nZVI):?a study with high-resolution X-ray photoelectron spectroscopy (HR-XPS)[J]. Industrial & Engineering Chemistry Research, 2008, 47(7): 2131-2139.
10	CAO J, ZHANG W X. Stabilization of chromium ore processing residue (COPR) with nanoscale iron particles[J]. Journal of Hazardous Materials, 2006, 132(2): 213-219.
11	LI X Q, ZHANG W X. Iron nanoparticles:?the core-shell structure and unique properties for Ni() sequestration[J]. Langmuir the ACS Journal of Surfaces & Colloids, 2006, 22(10): 4638-4642.
12	ZHANG S H, WU M F, TANG T T, et al. Mechanism investigation of anoxic Cr(Ⅵ) removal by nano zero-valent iron based on XPS analysis in time scale[J]. Chemical Engineering Journal, 2018, 335: 945-953.
13	吴云海, 李斌, 冯仕训, 等.活性炭对废水中Cr(Ⅵ)、As(Ⅲ)的吸附[J]. 化工环保, 2010, 30(2): 28-32.
13	WU Y H, LI B, FENG S X, et al. Activated carbon adsorption of Cr(Ⅵ) and As() in wastewater[J]. Environmental Protection of Chemical Industry, 2010, 30(2): 28-32.
14	PONDER S M, DARAD J G, MALLOUK T E. Remediation of Cr(Ⅵ) and Pb() aqueous solutions using supported, nanoscale zero-valent iron[J]. Environmental Science & Technology, 2000, 34(12):2564-2569.
15	CHEN H, LUO H, LAN Y, et al. Removal of tetracycline from aqueous solutions using polyvinylpyrrolidone (PVP-K30) modified nanoscale zero valent iron[J]. Journal of Hazardous Materials, 2011, 192(1): 44-53.
16	CHEN Z, WEI D, LI Q, et al. Macroscopic and microscopic investigation of Cr(Ⅵ) immobilization by nano scaled zero-valent iron supported zeolite MCM-41 via batch, visual, XPS and EXAFS techniques[J]. Journal of Cleaner Production, 2018, 181: 745-752.
17	XU C, YANG W, LIU W, et al. Performance and mechanism of Cr(Ⅵ) removal by zero-valent iron loaded onto expanded graphite[J]. Journal of Environmental Sciences, 2018, 5: 14-22.
18	甘超.改性生物炭的表征特性及其对Cr(Ⅵ)的吸附性能研究[D].长沙：湖南大学, 2016.
18	GAN C. Study on the characterization of modified biochar and its adsorption performance for Cr(Ⅵ)[D]. Changsha: Hunan University, 2016.
19	王旭峰. 改性玉米芯生物炭对废水中铜和氨氮的吸附[J]. 工业水处理, 2017, 37(1)： 37-40, 41.
19	WANG X F. Adsorption characters of Cu²⁺and NH4+-N in wastewater by modified corncob biochar[J]. Industrial Water Treatment, 2017, 37(1): 37-40, 41.
20	JIN H, CAPAREDA S, CHANG Z, et al. Biochar pyrolytically produced from municipal solid wastes for aqueous As(V) removal: Adsorption property and its improvement with KOH activation[J]. Bioresource Technology, 2014, 169: 622-629.
21	HOSSEINI S M, ATAIE-ASHTIANI B, KHOLIHI M. Nitrate reduction by nano-Fe/Cu particles in packed column[J]. Desalination, 2011, 276(1/2/3): 214-221.
22	SOARES O S G P, PEREIRA M F R. Nitrate reduction with hydrogen in the presence of physical mixtures with mono and bimetallic catalysts and ions in solution[J]. Applied Catalysis B： Environmental, 2011,102(3): 424-432.
23	ZHANG Z, CISSOKO N, WO J, et al. Factors influencing the dechlorination of 2,4-dichlorophenol by Ni-Fe nanoparticles in the presence of humic acid[J]. Journal of Hazardous Materials, 2009,165(1): 78-86.
24	XI Y H, ZOU J T, LUO Y G, et al. Performance and mechanism of arsenic removal in waste acid by combination of CuSO₄ and zero-valent iron[J]. Chemical Engineering Journal, 2019, 375.
25	国家环境保护局规划标准处. 水质　六价铬的测定　二苯碳酰二肼分光光度法: GB 7467—1987[S]. 北京: 中国标准出版社, 1987.
25	Planning and Standards Division, State Environmental Protection Administration.The reaction of Diphenylcarbonydraide with Cr⁶⁺in water: GB 7467—1987[S]. Beijing: Standards Press of China, 1987.
26	LV D, ZHOU J S, CAO Z, et al. Mechanism and influence factors of chromium(Ⅵ) removal by sulfide modified nanoscale zerovalent iron[J]. Chemosphere, 2019, 224: 306-315.
27	SHI L, DU J, CHEN Z, et al. Functional kaolinite supported Fe/Ni nanoparticles for simultaneous catalytic remediation of mixed contaminants (lead and nitrate) from wastewater[J]. Journal of Colloid & Interface Science, 2014, 428: 302-307.
28	BHOWMICK S, CHAKRABORTY S, MONDAL P, et al. Montmorillonite-supported nanoscale zero-valent iron for removal of arsenic from aqueous solution: kinetics and mechanism[J]. Chemical Engineering Journal, 2014, 243: 14-23.
29	WENG X, SUN Q, LIN S, et al. Enhancement of catalytic degradation of amoxicillin in aqueous solution using clay supported bimetallic Fe/Ni nanoparticles[J]. Chemosphere, 2014, 103(5): 80-85.
30	FANG Z, QIU X, CHEN J, et al. Debromination of polybrominated diphenyl ethers by Ni/Fe bimetallic nanoparticles: influencing factors, kinetics, and mechanism[J]. Journal of Hazardous Materials, 2011, 185(2): 958-969.
31	郑庆福, 王志民, 陈保国, 等.制备生物炭的结构特征及炭化机理的XRD光谱分析[J].光谱学与光谱分析, 2016, 36(10): 3355-3359.
31	ZHENG Q F, WANG Z M, CHEN B G, et al. Analysis of XRD spectral structure and carbonization of the biochar preparation[J]. Spectroscopy and Spectral Analysis, 2016, 36(10): 3355-3359.
32	TANG H X, WERNER S. The coagulating behaviors of Fe(III) polymeric species—Ⅰ. Preformed polymers by base addition[J]. Water Research, 1987, 21(1): 115-121.
33	MUKHOPADHYAY K, GHOSH A, DAS S K, et al. Synthesis and characterisation of cerium()-incorporated hydrous iron(Ⅲ) oxide as an adsorbent for fluoride removal from water[J]. RSC Advances, 2017, 7(42): 26037-26051.
34	赵颖, 王仁国, 陈沿利, 等.枯草芽孢杆菌对Cu²⁺的吸附及菌体表面基团分析[J].环境污染与防治, 2011, 33(11): 72-77.
34	ZHAO Y, WANG R G, CHEN Y L, et al. Study on adsorption of Cu²⁺by bacillus subtilis and quantitative determination of cell surface groups[J]. Environmental Pollution & Control, 2011, 33(11): 72-77.
35	LIU W F, ZHANG J, ZHANG C L, et al. Preparation and evaluation of activated carbon-based iron-containing adsorbents for enhanced Cr() removal: mechanism study[J]. Chemical Engineering Journal, 2012, 189/190: 295-302.
36	FANG Z Q, QIU X Q, HUANG R X, et al. Removal of chromium in electroplating wastewater by nanoscale zero-valent metal with synergistic effect of reduction and immobilization[J]. Desalination, 2011, 280(1): 224-231.
37	LIU T, ZHAO L, SUN D, et al. Entrapment of nanoscale zero-valent iron in chitosan beads for hexavalent chromium removal from wastewater[J]. Journal of Hazardous Materials, 2010, 184(1): 724-730.
38	秦泽敏, 董黎明, 刘平, 等.零价纳米铁吸附去除水中六价铬的研究[J].中国环境科学, 2014, 34(12): 52.
38	QIN Z M, DONG L M, LIU P, et al. Removal Cr⁶⁺ from water using nanoscale zero-valent iron[J]. China Environmental Science, 2014, 34(12): 52.

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