High-efficiency adsorption of heavy metal ions by Na2S modified biochar: preparation and adsorption mechanism

doi:10.11949/0438-1157.20240098

Abstract

Abstract:

In this study, Na₂S modified biochar (BCS) with efficient adsorption properties for Pb²⁺, Cd²⁺, and Zn²⁺ was prepared by using waste reed as raw material and sodium sulfide (Na₂S) as modifier. The biochar before and after modification was characterized by scanning electron microscopy-EDS (SEM-EDS), infrared spectroscopy (FTIR) and elemental analysis. The results showed that the Na₂S modification was able to introduce various sulfur-containing functional groups into the biochar, enhance the pore volume and increase the specific surface area. The Langmuir model fitting results indicated that the adsorption capacity of BCS for heavy metal ions was enhanced with the increase of the concentration of the modifier Na₂S solution. In the pH range of 2.0—6.0, the adsorption capacity of BCS on heavy metal ions was gradually enhanced with the increase of pH. At pH=6.0, the maximum adsorption amounts of BCS on Pb²⁺, Cd²⁺ and Zn²⁺ were 494.99, 131.14 and 94.89 mg/g, respectively. Based on the results of the kinetic experiments, it can be seen that the adsorption behaviors of BCS on heavy metal ions were in accordance with the pseudo-secondary kinetic model. The adsorption mechanism mainly includes complexation of surface functional groups, ion exchange and electrostatic adsorption. Overall, this study provides an environmentally friendly and feasible solution for the reuse of waste and the efficient removal of heavy metals from wastewater.

Key words: biochar, heavy metals, Na₂S, adsorption, wastewater

摘要：

以废弃芦苇为原料、硫化钠（Na₂S）为改性剂，制备了对Pb²⁺、Cd²⁺、Zn²⁺具有高效吸附性能的Na₂S改性生物炭（BCS）。通过扫描电镜-能谱（SEM-EDS）、红外光谱（FTIR）、元素分析等手段对改性前后的生物炭进行了表征。结果显示，Na₂S改性能够为生物炭引入多种含硫官能团，提升孔体积并增加比表面积。Langmuir模型拟合结果表明，随着改性剂Na₂S溶液浓度的增加，BCS对重金属离子的吸附能力得到提升。在pH为2.0~6.0的范围内，BCS对重金属离子的吸附能力随pH增加逐步增强。在pH=6.0时，BCS对Pb²⁺、Cd²⁺、Zn²⁺的最大吸附量分别为494.99、131.14、94.89 mg/g。根据动力学实验结果可知，BCS对重金属离子的吸附行为符合伪二级动力学模型。吸附机理主要包括表面官能团的络合、离子交换和静电吸附。本研究可为废弃物的再利用以及废水中的重金属的高效去除提供一种环境友好且可行的解决方案。

关键词: 生物炭, 重金属, Na₂S, 吸附, 废水

CLC Number:

X 703

Linfeng MA, Aitong OU, Zhiyuan LI, Yao LI, Runze LIU, Xiaole WU, Jingtao XU. High-efficiency adsorption of heavy metal ions by Na₂S modified biochar: preparation and adsorption mechanism[J]. CIESC Journal, 2024, 75(7): 2594-2603.

马林峰, 欧爱彤, 李志远, 李垚, 刘润泽, 吴晓乐, 徐景涛. Na₂S改性生物炭高效吸附重金属离子：制备及吸附机理[J]. 化工学报, 2024, 75(7): 2594-2603.

Figures/Tables 14

References 40

1	Cheng S P. Heavy metal pollution in China: origin, pattern and control[J]. Environmental Science and Pollution Research, 2003, 10(3): 192-198.
2	Zamora-Ledezma C, Negrete-Bolagay D, Figueroa F, et al. Heavy metal water pollution: a fresh look about hazards, novel and conventional remediation methods[J]. Environmental Technology & Innovation, 2021, 22: 101504.
3	Saleh T A, Mustaqeem M, Khaled M. Water treatment technologies in removing heavy metal ions from wastewater: a review[J]. Environmental Nanotechnology, Monitoring & Management, 2022, 17: 100617.
4	Wang Z, Luo P P, Zha X B, et al. Overview assessment of risk evaluation and treatment technologies for heavy metal pollution of water and soil[J]. Journal of Cleaner Production, 2022, 379: 134043.
5	Wang X Q, Guo Z Z, Hu Z, et al. Recent advances in biochar application for water and wastewater treatment: a review[J]. Peer, 2020, 8: e9164.
6	Kamali M, Appels L, Kwon E E, et al. Biochar in water and wastewater treatment—a sustainability assessment[J]. Chemical Engineering Journal, 2021, 420: 129946.
7	Wang L, Wang Y J, Ma F, et al. Mechanisms and reutilization of modified biochar used for removal of heavy metals from wastewater: a review[J]. Science of the Total Environment, 2019, 668: 1298-1309.
8	Hu X L, Xue Y W, Liu L N, et al. Preparation and characterization of Na₂S-modified biochar for nickel removal[J]. Environmental Science and Pollution Research International, 2018, 25(10): 9887-9895.
9	Enders A, Lehmann J. Comparison of wet-digestion and dry-ashing methods for total elemental analysis of biochar[J]. Communications in Soil Science and Plant Analysis, 2012, 43(7): 1042-1052.
10	Seredych M, Bandosz T J. Removal of dibenzothiophenes from model diesel fuel on sulfur rich activated carbons[J]. Applied Catalysis B: Environmental, 2011, 106(1/2): 133-141.
11	Figueiredo J L, Pereira M F R, Freitas M M A, et al. Modification of the surface chemistry of activated carbons[J]. Carbon, 1999, 37(9): 1379-1389.
12	Qiu B B, Tao X D, Wang H, et al. Biochar as a low-cost adsorbent for aqueous heavy metal removal: a review[J]. Journal of Analytical and Applied Pyrolysis, 2021, 155: 105081.
13	Wang Y, Hu Y T, Zhao X, et al. Comparisons of biochar properties from wood material and crop residues at different temperatures and residence times[J]. Energy & Fuels, 2013, 27(10): 5890-5899.
14	Leng L J, Xiong Q, Yang L H, et al. An overview on engineering the surface area and porosity of biochar[J]. Science of the Total Environment, 2021, 763: 144204.
15	徐昊, 史广宇, 田晓庆, 等. 颗粒状污泥生物炭对锌铜共污染水体的吸附效应分析[J]. 环境科学学报, 2024, 44(3): 95-104.
	Xu H, Shi G Y, Tian X Q, et al. Enhanced adsorption of zinc and copper co-pollution in water using modified granular sludge biochar[J]. Acta Scientiae Circumstantiae, 2024, 44(3): 95-104.
16	Schimmelpfennig S, Glaser B. One step forward toward characterization: some important material properties to distinguish biochars[J]. Journal of Environmental Quality, 2012, 41(4): 1001-1013.
17	Choudhury A, Lansing S. Adsorption of hydrogen sulfide in biogas using a novel iron-impregnated biochar scrubbing system[J]. Journal of Environmental Chemical Engineering, 2021, 9(1): 104837.
18	Lyu H H, Tang J C, Huang Y, et al. Removal of hexavalent chromium from aqueous solutions by a novel biochar supported nanoscale iron sulfide composite[J]. Chemical Engineering Journal, 2017, 322: 516-524.
19	Yu S X, Zhang W, Dong X W, et al. A review on recent advances of biochar from agricultural and forestry wastes: preparation, modification and applications in wastewater treatment[J]. Journal of Environmental Chemical Engineering, 2024, 12(1): 111638.
20	Banik C, Lawrinenko M, Bakshi S, et al. Impact of pyrolysis temperature and feedstock on surface charge and functional group chemistry of biochars[J]. Journal of Environmental Quality, 2018, 47(3): 452-461.
21	da Silva Veiga P A, Cerqueira M H, Gonçalves M G, et al. Upgrading from batch to continuous flow process for the pyrolysis of sugarcane bagasse: structural characterization of the biochars produced[J]. Journal of Environmental Management, 2021, 285: 112145.
22	Huang S Z, Liang Q W, Geng J J, et al. Sulfurized biochar prepared by simplified technic with superior adsorption property towards aqueous Hg(Ⅱ) and adsorption mechanisms[J]. Materials Chemistry and Physics, 2019, 238: 121919.
23	Zhang H C, Wang T, Sui Z F, et al. Enhanced mercury removal by transplanting sulfur-containing functional groups to biochar through plasma[J]. Fuel, 2019, 253: 703-712.
24	Wu C, Shi L Z, Xue S G, et al. Effect of sulfur-iron modified biochar on the available cadmium and bacterial community structure in contaminated soils[J]. Science of the Total Environment, 2019, 647: 1158-1168.
25	Leng L J, Liu R F, Xu S Y, et al. An overview of sulfur-functional groups in biochar from pyrolysis of biomass[J]. Journal of Environmental Chemical Engineering, 2022, 10(2): 107185.
26	Rao C N R, Venkataraghavan R. The C ̿ S stretching frequency and the “—N—C ̿ S bands” in the infrared[J]. Spectrochimica Acta Part A: Molecular Spectroscopy, 1989, 45: 299-305.
27	Shao F L, Xu J T, Chen F Y, et al. Insights into olation reaction-driven coagulation and adsorption: a pathway for exploiting the surface properties of biochar[J]. Science of the Total Environment, 2023, 854: 158595.
28	Dou S, Ke X X, Shao Z D, et al. Fish scale-based biochar with defined pore size and ultrahigh specific surface area for highly efficient adsorption of ciprofloxacin[J]. Chemosphere, 2022, 287: 131962.
29	Dhar A K, Himu H A, Bhattacharjee M, et al. Insights on applications of bentonite clays for the removal of dyes and heavy metals from wastewater: a review[J]. Environmental Science and Pollution Research International, 2023, 30(3): 5440-5474.
30	Vigneshwaran S, Sirajudheen P, Karthikeyan P, et al. Fabrication of sulfur-doped biochar derived from tapioca peel waste with superior adsorption performance for the removal of Malachite green and Rhodamine B dyes[J]. Surfaces and Interfaces, 2021, 23: 100920.
31	张奎, 王雪梅, 李玉环, 等. 硫改性牛粪生物炭对Hg²⁺的高效吸附及其机理[J]. 环境工程, 2022, 40(4): 79-88.
	Zhang K, Wang X M, Li Y H, et al. High efficiency adsorption of Hg²⁺ by sulfur-modified cow manure biochar and its mechanism[J]. Environmental Engineering, 2022, 40(4): 79-88.
32	闵炳坤, 李坤权. 高比表面硫脲改性花生壳炭的制备及对四环素和铜的吸附[J]. 环境科学, 2023, 44(3): 1528-1536.
	Min B K, Li K Q. Preparation of high specific surface thiourea modified peanut shell carbon and adsorption of tetracycline and copper[J]. Environmental Science, 2023, 44(3): 1528-1536.
33	Yin M M, Bai X G, Wu D P, et al. Sulfur-functional group tunning on biochar through sodium thiosulfate modified molten salt process for efficient heavy metal adsorption[J]. Chemical Engineering Journal, 2022, 433: 134441.
34	Cao B, Qu J H, Yuan Y H, et al. Efficient scavenging of aqueous Pb(Ⅱ)/Cd(Ⅱ) by sulfide-iron decorated biochar: performance, mechanisms and reusability exploration[J]. Journal of Environmental Chemical Engineering, 2022, 10(3): 107531.
35	Zhao R, Cao X F, Li T, et al. Co-removal effect and mechanism of Cr(Ⅵ) and Cd(Ⅱ) by biochar-supported sulfide-modified nanoscale zero-valent iron in a binary system[J]. Molecules, 2022, 27(15): 4742.
36	Khokhlov A V, Sych N V, Khokhlova L I. Using modified biochar from bagassa for removal heavy metal[J]. Journal of Chemistry and Technologies, 2022, 30(3): 459-465.
37	Tang Y, Chen Q M, Li W Q, et al. Engineering magnetic N-doped porous carbon with super-high ciprofloxacin adsorption capacity and wide pH adaptability[J]. Journal of Hazardous Materials, 2020, 388: 122059.
38	Wan S L, Qiu L, Tang G, et al. Ultrafast sequestration of cadmium and lead from water by manganese oxide supported on a macro-mesoporous biochar[J]. Chemical Engineering Journal, 2020, 387: 124095.
39	Li H B, Dong X L, da Silva E B, et al. Mechanisms of metal sorption by biochars: biochar characteristics and modifications[J]. Chemosphere, 2017, 178: 466-478.
40	Tang N, Niu C G, Li X T, et al. Efficient removal of Cd²⁺ and Pb²⁺ from aqueous solution with amino- and thiol-functionalized activated carbon: isotherm and kinetics modeling[J]. Science of the Total Environment, 2018, 635: 1331-1344.

生物炭	元素含量/%						原子比			灰分/%
生物炭	C	H	O	N	S	Na	H/C	O/C	（N+O）/C	灰分/%
BC	62.44	3.44	30.15	3.18	—	—	0.06	0.48	0.53	11.82
BCS（0.1）	63.08	2.48	29.15	2.97	0.89	1.43	0.05	0.46	0.51	12.53
BCS（0.3）	64.58	3.58	28.94	2.48	2.47	5.11	0.04	0.45	0.49	13.35
BCS	58.11	3.15	26.52	2.33	3.46	6.44	0.05	0.46	0.50	14.27

生物炭	元素含量/%						原子比			灰分/%
生物炭	C	H	O	N	S	Na	H/C	O/C	（N+O）/C	灰分/%
BC	62.44	3.44	30.15	3.18	—	—	0.06	0.48	0.53	11.82
BCS（0.1）	63.08	2.48	29.15	2.97	0.89	1.43	0.05	0.46	0.51	12.53
BCS（0.3）	64.58	3.58	28.94	2.48	2.47	5.11	0.04	0.45	0.49	13.35
BCS	58.11	3.15	26.52	2.33	3.46	6.44	0.05	0.46	0.50	14.27

生物炭	比表面积/(m²/g)	孔体积/(cm³/g)	平均孔径/nm
BC	46.16	0.049	2.16
BCS（0.1）	49.34	0.066	2.74
BCS（0.3）	52.13	0.089	3.17
BCS	54.45	0.102	3.74

生物炭	比表面积/(m²/g)	孔体积/(cm³/g)	平均孔径/nm
BC	46.16	0.049	2.16
BCS（0.1）	49.34	0.066	2.74
BCS（0.3）	52.13	0.089	3.17
BCS	54.45	0.102	3.74

重金属离子	最大吸附量/(mg/g)
重金属离子	BC	BCS（0.1）	BCS（0.3）	BCS
Pb²⁺	19.69	464.11	477.25	494.99
Cd²⁺	15.63	99.94	121.45	131.14
Zn²⁺	13.98	79.29	81.03	94.89

High-efficiency adsorption of heavy metal ions by Na₂S modified biochar: preparation and adsorption mechanism

Na₂S改性生物炭高效吸附重金属离子：制备及吸附机理

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 14

References 40

Related Articles 15

Recommended Articles

Metrics

Comments

重金属离子	Langmuir			Freundlich
重金属离子	K_L/(L/mg)	Q_m/(mg/g)	R²	K_F	1/n	R²
Pb²⁺	0.05	494.99	0.96	10.19	0.29	0.75
Cd²⁺	0.45	131.14	0.95	4.55	0.33	0.73
Zn²⁺	1.49	94.89	0.93	5.33	0.14	0.72

重金属离子	生物质	改性剂	吸附量/(mg/g)	文献
Hg²⁺	玉米秸秆	S	268.45	[22]
Hg²⁺	牛粪	S	407.8	[31]
Cu²⁺	花生壳	CH₄N₂S、H₃PO₄	21.20	[32]
Cu²⁺	玉米芯	Na₂S₂O₃	165.00	[33]
Pb²⁺	玉米秸秆	CS₂、FeCl₃·6H₂O	124.62	[34]
Pb²⁺	玉米芯	Na₂S₂O₃	421.80	[33]
Pb²⁺	芦苇秸秆	Na₂S	438.86	本研究
Cd²⁺	玉米秸秆	CS₂、FeCl₃·6H₂O	57.71	[34]
Cd²⁺	玉米秸秆	Fe₂(SO₄)₃	32.55	[35]
Cd²⁺	芦苇秸秆	Na₂S	131.14	本研究
Zn²⁺	甘蔗	Na₂S₂O₃	27.00	[36]
Zn²⁺	芦苇秸秆	Na₂S	94.89	本研究
Ni²⁺	玉米芯	Na₂S	15.40	[8]

重金属离子	伪一级动力学模型			伪二级动力学模型			Elvoich动力学模型
重金属离子	Q_e/(mg/g)	k_l	R²	Q_e/(mg/g)	k₂	R²	α	β	R²
Pb²⁺	475.51	0.22	0.96	514.29	0.10	0.98	2.03	0.73	0.88
Cd²⁺	123.91	0.11	0.96	144.74	0.09	0.98	5.87	0.75	0.97
Zn²⁺	89.22	0.17	0.96	99.97	0.26	0.98	4.23	0.89	0.94

[1]	Taohong WANG, Chao WANG, Zheng LI, Ying LIU, Ge TIAN, Ganggang CHANG, Xiaoyu YANG, Zongbi BAO. Immobilize Cu(Ⅰ) into π-complexed MOF adsorbent for selectivity separation of ethane/ethylene [J]. CIESC Journal, 2024, 75(7): 2565-2573.
[2]	Yan WANG, Jiawen ZHOU, Peiliang SUN, Yong CHEN, Yuanhong QI, Chong PENG. Removal of Hg²⁺ from water by magnetic polyaminothiazole adsorbent [J]. CIESC Journal, 2024, 75(6): 2283-2298.
[3]	Zhong JI, Yanling ZHAO, Yumeng CHEN, Linxia GAO, Yipeng WANG, Huan LIU. Adsorption performance and mechanism of ZSM-5 molecular sieves on typical coating VOCs [J]. CIESC Journal, 2024, 75(6): 2332-2343.
[4]	Lei GAO, Wen DAI, Zhonglian YANG, Shuping LI, Gangyin YAN, Qi SUN, Yongze LU, Guangcan ZHU. Effect of Hg on nitrogen removal performance of wastewater treatment system in low-pressure conditions [J]. CIESC Journal, 2024, 75(5): 2036-2046.
[5]	Hansong QIN, Guoliang LI, Hao YAN, Xiang FENG, Yibin LIU, Xiaobo CHEN, Chaohe YANG. Theoretical study on the adsorption and diffusion behavior of methyl oleate catalytic cracking in hierarchical ZSM-5 zeolite [J]. CIESC Journal, 2024, 75(5): 1870-1881.
[6]	Tiantian LYU, Min YUAN, Jiang WANG, Meizhen GAO, Jiahui YANG, Hong XU, Jinxiang DONG, Qi SHI. Preparation of ZTIF based hydrophobic micro-mesoporous carbon and their adsorption and separation performance of 5-hydroxymethylfurfural [J]. CIESC Journal, 2024, 75(4): 1642-1654.
[7]	Kaibo ZHANG, Jiaxin SHEN, Yuxia LI, Peng TAN, Xiaoqin LIU, Linbing SUN. Controllable construction of Cu(Ⅰ) in Y zeolite for adsorptive separation of ethylene/ethane [J]. CIESC Journal, 2024, 75(4): 1607-1615.
[8]	Yuan MENG, Shan NI, Yafeng LIU, Wenjie WANG, Yue ZHAO, Yudan ZHU, Liangrong YANG. Adsorption properties of functionalized porous carbon nitride materials for uranium [J]. CIESC Journal, 2024, 75(4): 1616-1629.
[9]	Yiru WEN, Jia FU, Dahuan LIU. Advances in machine learning-based materials research for MOFs: energy gas adsorption separation [J]. CIESC Journal, 2024, 75(4): 1370-1381.
[10]	Ying LIU, Fang ZHENG, Qiwei YANG, Zhiguo ZHANG, Qilong REN, Zongbi BAO. Recent progress in adsorption and separation of xylene isomers [J]. CIESC Journal, 2024, 75(4): 1081-1095.
[11]	Tianyong ZHANG, Jingyi ZHANG, Shuang JIANG, Bin LI, Dongjun LYU, Dumin CHEN, Xue CHEN. Preparation and utilization of carbon-based adsorbent from organic pollutants in waste salt during acidic blue AS dye production [J]. CIESC Journal, 2024, 75(3): 890-899.
[12]	Zhuoyu LI, Peng JIN, Xiaoyan CHEN, Zeyu ZHAO, Qinghong WANG, Chunmao CHEN, Yali ZHAN. Effect and mechanism on the degradation of aqueous bisphenol A by zero valent iron activated peroxyacetic acid system [J]. CIESC Journal, 2024, 75(3): 987-999.
[13]	Zhicheng DENG, Shifeng XU, Qidong WANG, Jiarui WANG, Simin WANG. Process and energy consumption analysis of high salt and high COD wastewater treatment by submerged combustion [J]. CIESC Journal, 2024, 75(3): 1000-1008.
[14]	Xiangjun MENG, Yingxi HUA, Changjin ZHANG, Chi ZHANG, Linrui YANG, Ruoxi YANG, Jianyi LIU, Chunjian XU. Preparation and purification of 6N electronic-grade deuterium gas [J]. CIESC Journal, 2024, 75(1): 377-390.
[15]	Kexin YAN, Hongtao JIANG, Weiqun GAO, Xiaohui GUO, Weizhen SUN, Ling ZHAO. Recent advances in the removal of trace boron and phosphorus impurities from electronic grade silicon raw materials [J]. CIESC Journal, 2024, 75(1): 83-94.