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

doi:10.11949/0438-1157.20221299

Abstract

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

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

CLC Number:

X 52

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.

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.

Figures/Tables 14

References 41

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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

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

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

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

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

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

生物炭吸附溶液中Pb²⁺的定性及定量研究

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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

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