生物炭对Cu(Ⅱ)、Pb(Ⅱ)、Ni(Ⅱ)和Cd(Ⅱ)的单一及竞争吸附研究

doi:10.13209/j.0479-8023.2017.130

摘要/Abstract

摘要：

分别以玉米秸秆、牛粪为原料, 在500ºC氮气保护的无氧气氛下热解生成玉米秸秆生物炭(BC)和牛粪生物炭(DMBC), 分别探讨两种生物炭对水溶液中4种二价重金属离子(Cu²⁺, Pb²⁺, Ni²⁺和Cd²⁺)的单一吸附效果, 并进行4种重金属在生物炭上的竞争吸附实验, 探讨金属离子间在生物炭上的相互作用关系。结果显示, 两种生物质原料具有不同的元素组成, BC具有较大的比表面积, DMBC的平均孔径更大。在单一吸附过程中, BC对金属的吸附动力学过程具有相似性, 而DMBC对不同金属的吸附速率差异较大。4种重金属离子在生物炭上的等温吸附过程可以用Langmuir方程较好地拟合, 吸附容量的顺序为: Pb²⁺>Cu²⁺>Cd²⁺>Ni²⁺。通过金属之间的竞争吸附实验, 发现在生物炭上Pb²⁺的竞争吸附能力最强, Cu²⁺次之, 而Ni²⁺和Cd²⁺竞争吸附能力较弱, 其吸附过程容易受到其他二价金属离子的抑制。

关键词: 生物炭, 单一吸附, 竞争吸附, 二价金属离子

Abstract:

Two kinds of materials including corn stalks and diary manure were used to produce the biochars (BC and DMBC) by pyrolysing at temperature of 500ºC under the protection of nitrogen atmosphere. The single and competitive adsorption characteristics of Cu²⁺, Pb²⁺, Ni²⁺ and Cd²⁺ ions onto these biochars were investigated to reveal the interaction among the metal ions on the biochar. Experimental results show that the biochars have different elemental composition. BC has a larger specific surface area, and DMBC has a bigger average pore diameter. For the single metal adsorption, the kinetics on BC are similar, but obvious differences of adsorption rates were observed on DMBC. Langmuir isotherm model well fits the sorption data of the four metal ions, and the order of sorption capacity is Pb²⁺>Cu²⁺>Cd²⁺>Ni²⁺. Through the competitive adsorption experiments it is found that the competitive sorption capacity of Pb²⁺ is the strongest, and Cu²⁺ follows, while the sorption of Ni²⁺ and Cd²⁺ are weaker and easy to be suppressed by other divalent metal ions.

Key words: biochar, single adsorption, competitive adsorption, divalent metal ion

王棋, 王斌伟, 谈广才, 许楠. 生物炭对Cu(Ⅱ)、Pb(Ⅱ)、Ni(Ⅱ)和Cd(Ⅱ)的单一及竞争吸附研究[J]. 北京大学学报自然科学版, 2017, 53(6): 1122-1131.

Qi WANG, Binwei WANG, Guangcai TAN, Nan XU. Single and Competitive Adsorption of Cu(Ⅱ), Pb(Ⅱ), Ni(Ⅱ) and Cd(Ⅱ) onto Biochar[J]. Acta Scientiarum Naturalium Universitatis Pekinensis, 2017, 53(6): 1122-1131.

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链接本文: https://xbna.pku.edu.cn/CN/10.13209/j.0479-8023.2017.130

https://xbna.pku.edu.cn/CN/Y2017/V53/I6/1122

图/表 11

表1 BC和DMBC的主要元素组成

Table 1 Elemental compositions of BC and DMBC

生物炭	w/%
生物炭	C	O	Na	Mg	Al	Si	P	S	Cl	K	Ca	Fe
BC	61.08	21.67	0.36	1.09	1.65	7.12	0.2	0.13	0.53	2.78	2.75	0.65
DMBC	71.66	16.73	0.16	1.53	0.41	3.03	0.77	0.11	—	2.51	2.84	0.27

图1 玉米秸秆生物炭(BC)和牛粪生物炭(DMBC)的表面形态

Fig. 1 SEM images of corn stalks biochar (BC) and diary manure biochar (DMBC)

表2 生物炭BC和DMBC的BET相关参数

Table 2 Biochar BC and DMBC parameters of BET

生物炭	BET面积/(m²· g^-1)	微孔面积/(m²· g^-1)	孔体积/(cm³· g^-1)	微孔体积/(cm³· g^-1)	平均孔径/nm
BC	42.85	21.72	0.03366	0.01067	3.1422
DMBC	22.568	11.11	0.02035	0.00493	36.066

图2 Cu2+, Pb2+, Ni2+和Cd2+在BC上吸附量随时间变化曲线(金属离子初始浓度为20 mg/L)

Fig. 2 Adsorption of Cu2+, Pb2+, Ni2+ and Cd2+ ions versus time on BC (initial metal ion concentration was 20 mg/L)

图3 Cu2+, Pb2+, Ni2+和Cd2+在DMBC上吸附量随时间变化曲线(金属离子初始浓度为20 mg/L)

Fig. 3 Adsorption of Cu2+, Pb2+, Ni2+ and Cd2+ ions versus time on DMBC (initial metal ion concentration was 20 mg/L)

表3 Cu2+, Pb2+, Ni2+和Cd2+在BC和DMBC上的准一级动力学、准二级动力学和Elovich方程拟合参数

Table 3 Pseudo-first, pseudo-second and Elovich rate constants for sorption process of Cu2+, Pb2+, Ni2+ and Cd2+ by BC and DMBC

金属离子	吸附剂	准一级动力学常数			准二级动力学常数			Elovich动力学常数
金属离子	吸附剂	Q_eq/ (mg · g^-1)	k₁/min^-1	R²	Q_eq/ (mg · g^-1)	k₂/ (g · mg^-1· min^-1)	R²	β / (g · mg^-1)	α / (mg · g^-1· min^-1)	R²
Cu²⁺	BC	18.21	0.081	0.839	18.51	0.116	0.966	0.393	17.72	0.952
Cu²⁺	DMBC	19.45	0.005	0.963	19.52	0.007	0.964	0.183	0.221	0.962
Pb²⁺	BC	18.06	0.243	0.426	18.82	0.388	0.678	0.757	89.24	0.939
Pb²⁺	DMBC	19.98	0.353	0.999	19.88	0.005	0.841	1.806	0.192	0.383
Cd²⁺	BC	18.23	0.081	0.839	18.87	0.113	0.966	0.391	17.72	0.952
Cd²⁺	DMBC	4.741	0.010	0.724	4.821	0.015	0.801	1.061	0.251	0.924
Ni²⁺	BC	10.95	0.119	0.994	11.01	0.188	0.946	0.922	129.1	0.581
Ni²⁺	DMBC	4.689	0.017	0.978	4.711	0.023	0.969	0.831	0.192	0.921

图4 4种金属离子在生物炭上的吸附量随平衡浓度的变化曲线

Fig. 4 Adsorption amount versus the equilibrium concentration of four kinds of metal ions on biochars

表4 4种金属离子在BC和DMBC上的等温吸附模型参数

Table 4 Fitting parameters for adsorption isotherms of four kinds of metal ions on BC and DMBC

金属离子	吸附剂	Langmuir			Freundlich
金属离子	吸附剂	R²	b /(L · mg^-1)	Q_m/(mg · g^-1)	R²	k /(mg · g^-1(mg/L)^-1/ⁿ)	n /(g · L^-1)
Cu²⁺	BC	0.992	0.597	25.07	0.956	12.48	3.389
Cu²⁺	DMBC	0.994	0.582	31.72	0.933	9.121	3.367
Pb²⁺	BC	0.989	0.161	78.08	0.985	22.46	0.857
Pb²⁺	DMBC	0.986	0.211	160.3	0.971	16.43	0.934
Ni²⁺	BC	0.977	0.792	18.02	0.996	9.092	4.608
Ni²⁺	DMBC	0.954	3.803	19.64	0.989	11.14	6.944
Cd²⁺	BC	0.994	0.802	22.85	0.951	11.64	3.636
Cd²⁺	DMBC	0.981	0.715	28.52	0.911	8.729	3.546

图5 4种金属离子在BC上的竞争吸附关系

Fig. 5 Competitive adsorption of four kinds of metal ions on BC

图6 4种金属离子在DMBC上的竞争吸附关系

Fig. 6 Competitive adsorption relations about four kinds of metal ions by DMBC

图7 生物炭样品的FT-IR谱图

Fig. 7 FT-IR spectra of biochar

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