生物炭吸附溶液中Pb2+的定性及定量研究

doi:10.11949/0438-1157.20221299

摘要/Abstract

摘要：

由木质纤维素类生物质经过热解制得的生物炭能够高效地吸附污水中的重金属离子，将其作为Pb²⁺吸附剂，具有广阔的应用前景。本文以松木与大豆秸秆为原料，分别在400、600、800℃下制备了生物炭，考察了其理化特性与吸附性能之间的关系，并对各吸附机制的相对贡献进行了定性及定量分析。研究结果表明：大豆秸秆生物炭的吸附性能（最大吸附容量分别为209.35、180.62和226.64 mg∙g^-1）远优于松木生物炭的（4.62、12.02和23.47 mg∙g^-1）。6种生物炭对Pb²⁺的吸附过程都符合Langmuir模型和拟二级动力学模型，以化学吸附为主，受物理微观结构的影响较小。阳离子交换在生物炭吸附Pb²⁺过程中占据重要作用，其中Ca²⁺的交换能力最强。Pb²⁺在生物炭表面的矿物沉淀主要为水白铅矿和碳酸铅。矿物质沉淀（贡献占比21.9%~76.8%）和阳离子交换（18.1%~72.5%）是大豆秸秆炭和松木炭对Pb²⁺的主要吸附机制，其次是π电子相互作用和官能团络合。

关键词: 生物炭, 吸附特性, 污水, Pb²⁺, 吸附机制, 定量分析

Abstract:

Biochar produced by pyrolysis of lignocellulosic biomass can efficiently adsorb heavy metal ions in sewage, and it has broad application prospects as a Pb²⁺ adsorbent. In this paper, pine wood and soybean straw were applied as raw materials to prepare biochar at 400, 600, and 800℃, respectively. The relationship between physicochemical properties and adsorption performance of biochar was investigated, and the relative contributions of adsorption mechanisms were qualitatively and quantitatively analyzed. The results showed that the adsorption performance of soybean straw biochar (the adsorption capacity was 209.35, 180.62 and 226.64 mg·g^-1respectively) was much higher than that of pine wood biochar (4.62, 12.02 and 23.47 mg·g^-1). The adsorption process of Pb²⁺ on the six biochars were all in accordance with the Langmuir model and the pseudo-second-order kinetic model, and was dominated by chemical adsorption, which was less affected by the microstructure. Cation exchange played an important role in the adsorption of Pb²⁺ by biochar, among which Ca²⁺ had the strongest exchange capacity. The precipitation of Pb²⁺ was mainly to form hydrocerussite and lead carbonate. With the increase of pyrolysis temperature, the content of organic functional groups and aromatic rings on the surface of biochar decreased. Mineral precipitation (relative contribution of 21.9%—76.8%) and cation exchange (18.1%—72.5%) were the main Pb²⁺ adsorption mechanisms of soybean straw biochar and pine wood biochar, followed by π-electron interaction and functional group complexation.

Key words: biochar, adsorption characteristics, waste water, Pb²⁺, adsorption mechanisms, quantitative analysis

中图分类号:

X 52

姜家豪, 黄笑乐, 任纪云, 朱正荣, 邓磊, 车得福. 生物炭吸附溶液中Pb²⁺的定性及定量研究[J]. 化工学报, 2023, 74(2): 830-842.

Jiahao JIANG, Xiaole HUANG, Jiyun REN, Zhengrong ZHU, Lei DENG, Defu CHE. Qualitative and quantitative study on Pb²⁺ adsorption by biochar in solution[J]. CIESC Journal, 2023, 74(2): 830-842.

图/表 14

表1 生物炭的表征（总酸性官能团、pH、灰分、比表面积、产量、元素分析（干燥基基准））

Table 1 Characterization of biochar （total acidity， pH， ash， surface area， yield， elemental analysis（dry basis））

生物炭	总酸性官能团含量/ (mmol∙g^-1)	pH	灰分/ %	比表面积/ (m²∙g^-1)	孔容积/ (cm³∙g^-1)	产率/ %	元素分析/%				C/H	C/N
生物炭	总酸性官能团含量/ (mmol∙g^-1)	pH	灰分/ %	比表面积/ (m²∙g^-1)	孔容积/ (cm³∙g^-1)	产率/ %	C	H	N	S	C/H	C/N
SBC400	1.01	9.54	12.80	5.59	0.0098	33.5	67.44	2.648	1.28	0.662	25.46	52.72
SBC600	0.40	10.39	17.04	28.93	0.0184	25.3	70.01	1.557	1.10	0.272	44.97	63.68
SBC800	0.33	10.76	17.88	86.33	0.0498	23.1	70.55	1.064	1.16	0.415	66.28	60.75
PBC400	1.15	7.45	0.34	53.84	0.0357	28.5	80.99	2.762	0.36	0.221	29.33	226.60
PBC600	1.00	8.75	0.40	411.84	0.1807	19.5	88.54	1.277	0.51	0.310	69.31	173.95
PBC800	0.77	10.02	0.47	440.52	0.2003	15.4	89.74	0.597	0.65	0.192	150.32	138.60

图1 不同生物质及热解温度生物炭的Pb2+吸附性能

Fig.1 Pb2+ adsorption capacity of biochar with different biomass and pyrolysis temperatures

图2 不同生物质炭的Pb2+吸附动力学

Fig.2 Adsorption kinetics for Pb2+ on different biochars

表2 不同生物炭吸附Pb2+的拟一级和拟二级吸附动力学拟合参数

Table 2 Kinetic parameters of the pseudo-first-order and pseudo-second-order model for Pb2+ adsorption onto different chars

Char	Q/(mg∙g^-1)	Pseudo-first-order model			Pseudo-second-order model
Char	Q/(mg∙g^-1)	q_e/(mg∙g^-1)	k₁/ h^-1	R²	q_e/(mg∙g^-1)	k₂/（g∙mg^-1∙h^-1)	R²
SBC400	206.22	195.57	0.394	0.976	218.79	0.002	0.994
SBC600	176.30	160.72	2.989	0.696	166.84	0.031	0.879
SBC800	227.24	205.65	2.699	0.583	213.94	0.021	0.861
PBC400	4.50	3.57	2.301	0.728	3.76	0.887	0.839
PBC600	12.26	11.67	1.275	0.891	12.34	0.151	0.939
PBC800	22.60	21.55	0.930	0.876	23.01	0.057	0.933

图3 不同生物炭对Pb2+的吸附等温线

Fig.3 Adsorption isotherms for Pb2+ on different biochars

表3 不同生物炭吸附Pb2+的Langmuir和Freundlich模型拟合参数

Table 3 Adsorption isotherms parameters of Langmuir and Freundlich model for Pb2+ adsorption onto different chars

Char	Q/(mg∙g^-1)	Langmuir model			Freundlich model
Char	Q/(mg∙g^-1)	q_m/(mg∙g^-1)	K_L/(L∙mg^-1)	R²	n	K_F/(mg^1-ⁿ ∙L ⁿ ∙g^-1)	R²
SBC400	206.22	209.35	3.939	0.994	0.124	91.49	0.797
SBC600	176.30	180.62	2.029	0.999	0.122	78.99	0.771
SBC800	227.24	226.64	2.438	0.898	0.117	100.32	0.665
PBC400	4.54	4.62	2.640	0.901	0.052	3.47	0.684
PBC600	12.26	12.02	0.907	0.930	0.107	6.52	0.809
PBC800	22.60	23.47	1.779	0.967	0.104	12.59	0.712

图4 吸附后Na、K、Ca、Mg离子净释放量分布及与Pb2+吸附量对比

Fig.4 Net release distribution of Na, K, Ca, Mg after adsorption and comparison with Pb2+ adsorption

图5 大豆秸秆炭的阳离子交换量与阳离子含量的对比

Fig.5 The cation exchange of soybean straw biochar and the cations content in biochar

图6 PBC800、SBC400和SBC800吸附前后的微观形貌及吸附后Pb元素分布

Fig.6 Micromorphologies of PBC800, SBC400 and SBC800 before and after adsorption and the Pb distribution after adsorption

表4 生物炭表面的EDS扫描结果

Table 4 EDS results of biochar

生物炭	区域编号	EDS扫描的元素分布/% (mass)
生物炭	区域编号	C	O	Mg	Al	Si	K	Ca	Pb
PBC800	1	96.44	2.92				0.29	0.35
PBC800	2	96.21	3.13				0.39	0.27
SBC400	3	76.26	13.66	0.44			5.68	2.01
SBC400	4	77.84	13.07	0.94			6.59	1.23
SBC800	5	62.38	14.80	2.01			14.26	5.03
SBC800	6	64.48	20.30	1.52			5.23	6.55
PBC800+Pb	7	95.32	3.08						0.60
PBC800+Pb	8	97.18	2.82
SBC400+Pb	9	75.90	14.06						10.04
SBC400+Pb	10	76.85	12.87						10.28
SBC800+Pb	11	56.12	14.06	2.99		0.81		1.53	24.49
	12	69.49	16.10	1.82	0.75	1.86	1.22	1.10	7.67
	13	69.95	17.72	2.16				0.73	9.43

图7 生物炭吸附前后XRD衍射谱图α—Pb3(CO3)2(OH)2;β—PbCO3;χ—CaCO3;δ—C2CaO4;ε—KHCO3

Fig.7 XRD patterns of biochar before and after adsorption

图8 生物炭吸附Pb2+前后的红外吸收光谱

Fig.8 FTIR spectra of biochar before and after adsorption of Pb2+

图9 SBC800和PBC800吸附Pb2+前后的XPS分析

Fig.9 XPS analysis before and after adsorption of Pb2+ by SBC800 and PBC800

图10 生物炭各吸附机制对Pb2+总吸附容量的贡献

Fig.10 The contribution of biochar adsorption mechanisms in the total Pb2+ adsorption capacity

参考文献 41

1	王思远, 杨树俊, 张贺, 等. 土壤中铅污染来源及其危害综述[J]. 农业与技术, 2022, 42(9): 78-81.
	Wang S Y, Yang S J, Zhang H, et al. Source and harm of lead pollution in soil[J]. Agriculture and Technology, 2022, 42(9): 78-81.
2	Zhang J Q, Hu X L, Zhang K J, et al. Desorption of calcium-rich crayfish shell biochar for the removal of lead from aqueous solutions[J]. Journal of Colloid and Interface Science, 2019, 554: 417-423.
3	刘国成. 生物炭对水体和土壤环境中重金属铅的固持[D]. 青岛: 中国海洋大学, 2014.
	Liu G C. Immobilization of Pb²⁺ in contaminated waters and soils by biohcars[D]. Qingdao: Ocean University of China, 2014.
4	吕玉桦. 我国儿童血铅水平现状及对策研究[D]. 衡阳: 南华大学, 2014.
	Lyu Y H. A study of current situations and countermeasures on blood lead level of children in China[D]. Hengyang: University of South China, 2014.
5	高凤凤. 低维碳基电控离子选择渗透膜的制备及重金属离子分离[D]. 太原: 太原理工大学, 2017.
	Gao F F. Preparation of low-dimensional carbon-based eletrochemically switched ion permselectivity membrane and separation of heavy metal ion[D]. Taiyuan: Taiyuan University of Technology, 2017.
6	杨立鹏. 中和沉淀-Fenton混凝处理蓄电池生产废水工艺及机理研究[D]. 哈尔滨: 哈尔滨工业大学, 2010.
	Yang L P. Study on the process and mechanism of storage battery wastewater treatment[D]. Harbin: Harbin Institute of Technology, 2010.
7	杨海, 黄新, 林子增, 等. 离子交换法处理重金属废水的研究进展[J]. 应用化工, 2019, 48(7): 1675-1680.
	Yang H, Huang X, Lin Z Z, et al. Research progress in the treatment of heavy metal wastewater by ion exchange[J]. Applied Chemical Industry, 2019, 48(7): 1675-1680.
8	桂珊, 刘贡钢, 姜珩, 等. 新型多胺羧甲基壳聚糖的合成及对Ni(Ⅱ)的吸附特性[J]. 化工学报, 2015, 66(5): 1785-1791.
	Gui S, Liu G G, Jiang H, et al. Synthesis of carboxymethyl polyamines chitosan and its adsorption properties for Ni(Ⅱ)[J]. CIESC Journal, 2015, 66(5): 1785-1791.
9	刘凌沁, 黄亚继, 胡华军, 等. 流化床制备玉米秸秆生物炭的Pb²⁺吸附特性及机理[J]. 东南大学学报(自然科学版), 2022, 52(4): 666-675.
	Liu L Q, Huang Y J, Hu H J, et al. Pb²⁺ adsorption characteristics and mechanism of corn stalk biochar produced by fluidized bed[J]. Journal of Southeast University (Natural Science Edition), 2022, 52(4): 666-675.
10	张连科, 刘心宇, 王维大, 等. 油料作物秸秆生物炭对水体中铅离子的吸附特性与机制[J]. 农业工程学报, 2018, 34(7): 218-226.
	Zhang L K, Liu X Y, Wang W D, et al. Characteristics and mechanism of lead adsorption from aqueous solutions by oil crops straw-derived biochar[J]. Transactions of the Chinese Society of Agricultural Engineering, 2018, 34(7): 218-226.
11	Shen Z T, Zhang Y Y, Jin F, et al. Qualitative and quantitative characterisation of adsorption mechanisms of lead on four biochars[J]. Science of the Total Environment, 2017, 609: 1401-1410.
12	Li H B, Dong X L, Silva E B, et al. Mechanisms of metal sorption by biochars: biochar characteristics and modifications[J]. Chemosphere, 2017, 178: 466-478.
13	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.
14	Zhang T, Zhu X X, Shi L N, et al. Efficient removal of lead from solution by celery-derived biochars rich in alkaline minerals[J]. Bioresource Technology, 2017, 235: 185-192.
15	Ding Y, Liu Y G, Liu S B, et al. Competitive removal of Cd(Ⅱ) and Pb(Ⅱ) by biochars produced from water hyacinths: performance and mechanism[J]. RSC Advances, 2016, 6(7): 5223-5232.
16	Zhou N, Chen H G, Xi J T, et al. Biochars with excellent Pb(Ⅱ) adsorption property produced from fresh and dehydrated banana peels via hydrothermal carbonization[J]. Bioresource Technology, 2017, 232: 204-210.
17	Lu H L, Zhang W H, Yang Y X, et al. Relative distribution of Pb²⁺ sorption mechanisms by sludge-derived biochar[J]. Water Research, 2012, 46(3): 854-862.
18	Liu L Q, Huang Y J, Meng Y H, et al. Investigating the adsorption behavior and quantitative contribution of Pb²⁺ adsorption mechanisms on biochars by different feedstocks from a fluidized bed pyrolysis system[J]. Environmental Research, 2020, 187: 109609.
19	国家统计局.国家数据[DB/OL]. .
	National Bureau of Statistics. National data[DB/OL]. .
20	Wang Z Y, Liu G C, Zheng H, et al. Investigating the mechanisms of biochar's removal of lead from solution[J]. Bioresource Technology, 2015, 177: 308-317.
21	Gao L Y, Deng J H, Huang G F, et al. Relative distribution of Cd²⁺ adsorption mechanisms on biochars derived from rice straw and sewage sludge[J]. Bioresource Technology, 2019, 272: 114-122.
22	Ma X W, Li F H, Ma M J, et al. Regulation of ash fusibility characteristics for high-ash-fusion-temperature coal by bean straw addition[J]. Energy & Fuels, 2018, 32(6): 6678-6688.
23	Huff M D, Kumar S, Lee J W, et al. Comparative analysis of pinewood, peanut shell, and bamboo biomass derived biochars produced via hydrothermal conversion and pyrolysis[J]. Journal of Environmental Management, 2014, 146: 303-308.
24	Li J H, Burra K G, Wang Z W, et al. Effect of alkali and alkaline metals on gas formation behavior and kinetics during pyrolysis of pine wood[J]. Fuel, 2021, 290: 120081.
25	Liu Z G, Zhang F S. Removal of lead from water using biochars prepared from hydrothermal liquefaction of biomass[J]. Journal of Hazardous Materials, 2009, 167(1/2/3): 933-939.
26	欧阳金波, 陈建, 刘峙嵘, 等. 生物质源多孔碳制备及其对废水中药物吸附研究进展[J]. 化工学报, 2020, 71(12): 5420-5429.
	Ouyang J B, Chen J, Liu Z R, et al. Research progress on preparation of biomass-derived porous carbon and its adsorption of pharmaceuticals in wastewater[J]. CIESC Journal, 2020, 71(12): 5420-5429.
27	Hashimoto K, Miura K, Xu J J, et al. Relation between the gasification rate of carbons supporting alkali metal salts and the amount of oxygen trapped by the metal[J]. Fuel, 1986, 65(4): 489-494.
28	Knudsen J N, Jensen P A, Dam-Johansen K. Transformation and release to the gas phase of Cl, K, and S during combustion of annual biomass[J]. Energy & Fuels, 2004, 18(5): 1385-1399.
29	Okuno T, Sonoyama N, Hayashi J I, et al. Primary release of alkali and alkaline earth metallic species during the pyrolysis of pulverized biomass[J]. Energy & Fuels, 2005, 19(5): 2164-2171.
30	Kołodyńska D, Wnętrzak R, Leahy J J, et al. Kinetic and adsorptive characterization of biochar in metal ions removal[J]. Chemical Engineering Journal, 2012, 197: 295-305.
31	Wang X S, Lu Z P, Miao H H, et al. Kinetics of Pb(Ⅱ) adsorption on black carbon derived from wheat residue[J]. Chemical Engineering Journal, 2011, 166(3): 986-993.
32	Chen X C, Chen G C, Chen L G, et al. Adsorption of copper and zinc by biochars produced from pyrolysis of hardwood and corn straw in aqueous solution[J]. Bioresource Technology, 2011, 102(19): 8877-8884.
33	Mohan D, Pittman Jr C U, Bricka M, et al. Sorption of arsenic, cadmium, and lead by chars produced from fast pyrolysis of wood and bark during bio-oil production[J]. Journal of Colloid and Interface Science, 2007, 310(1): 57-73.
34	Wang R Z, Huang D L, Liu Y G, et al. Investigating the adsorption behavior and the relative distribution of Cd²⁺ sorption mechanisms on biochars by different feedstock[J]. Bioresource Technology, 2018, 261: 265-271.
35	王耀强, 赵怡琳, 李玲慧, 等. 海胆状Fe₃O₄@TiO₂磁性纳米介质对Pb²⁺的选择吸附特性[J]. 化工学报, 2018, 69(1): 446-454.
	Wang Y Q, Zhao Y L, Li L H, et al. Selective adsorption of Pb²⁺ by sea urchin magnetic nano-Fe₃O₄@TiO₂ [J]. CIESC Journal, 2018, 69(1): 446-454.
36	Cheng M, Zeng G M, Huang D L, et al. Hydroxyl radicals based advanced oxidation processes (AOPs) for remediation of soils contaminated with organic compounds: a review[J]. Chemical Engineering Journal, 2016, 284: 582-598.
37	Rwiza M J, Oh S Y, Kim K W, et al. Comparative sorption isotherms and removal studies for Pb(Ⅱ) by physical and thermochemical modification of low-cost agro-wastes from Tanzania[J]. Chemosphere, 2018, 195: 135-145.
38	Ding W C, Dong X L, Ime I M, et al. Pyrolytic temperatures impact lead sorption mechanisms by bagasse biochars[J]. Chemosphere, 2014, 105: 68-74.
39	Sun J K, Lian F, Liu Z Q, et al. Biochars derived from various crop straws: characterization and Cd(Ⅱ) removal potential[J]. Ecotoxicology and Environmental Safety, 2014, 106: 226-231.
40	Li Y F, Liu X, Zhang P Z, et al. Qualitative and quantitative correlation of physicochemical characteristics and lead sorption behaviors of crop residue-derived chars[J]. Bioresource Technology, 2018, 270: 545-553.
41	Yorita H, Otomo K, Hiramatsu H, et al. Evidence for the cation-π interaction between Cu²⁺ and tryptophan[J]. Journal of the American Chemical Society, 2008, 130(46): 15266-15267.

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生物炭吸附溶液中Pb²⁺的定性及定量研究

Qualitative and quantitative study on Pb²⁺ adsorption by biochar in solution

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