磁性生物炭及其老化后对Cd<sup>2+</sup>的吸附性能影响

杨婷; 徐荣; 寇祥明; 张家宏; 马林杰; 张诚信; 朱凌宇; 杨军; 袁秦; 王守红

doi:10.12153/j.issn.1674-991X.20221019

磁性生物炭及其老化后对Cd²⁺的吸附性能影响

doi: 10.12153/j.issn.1674-991X.20221019

杨婷^1,,
徐荣^1, ,,
寇祥明¹,
张家宏^{1, 2},
马林杰¹,
张诚信¹,
朱凌宇¹,
杨军¹,
袁秦^{1, 2},
王守红^1, ,

1.
江苏里下河地区农业科学研究所
2.
江苏省生态农业工程技术研究中心

基金项目: 江苏省“六大人才高峰”培养资金（NY-244）；扬州市重点研发计划项目（YZ2022064）；江苏里下河地区农科所科研专项基金项目〔SJ（21）303〕

详细信息

作者简介:
杨婷（1994—），女，硕士，主要研究方向为农业废弃物资源化利用，yt15295166601@163.com

通讯作者:
徐荣（1988—），男，助理研究员，硕士，主要从事农业废物资源化利用等研究，realmaridreal@126.com

王守红（1970—），男，研究员，硕士，主要从事农业废物资源化利用等研究，yzwish@126.com

中图分类号: X703
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出版历程
- 收稿日期: 2022-10-18

Effect of magnetic biochar and its aging on the adsorption performance of Cd²⁺

YANG Ting^1
,,
XU Rong^{1
, ,},
KOU Xiangming¹,
ZHANG Jiahong^{1, 2},
MA Linjie¹,
ZHANG Chengxin¹,
ZHU Lingyu¹,
YANG Jun¹,
YUAN Qin^{1, 2},
WANG Shouhong^{1
, ,}

1.
Institute of Agricultural Sciences for Lixiahe Region in Jiangsu
2.
Research Center for Eco-Agricultural Engineering and Technology of Jiangsu Province

摘要

摘要:
磁性生物炭（FBC）是一种具有良好吸附性能且可实现磁分离的吸附材料，但制备过程磁性前驱体用量及老化作用是否影响其结构和吸附重金属的能力却鲜有研究。以水稻秸秆和铁盐为原料制备不同铁炭质量比（1∶4、1∶2和1∶1，记作FBC-4、FBC-2、FBC-1）的FBC，比较其表面形态、官能团等理化性质，以及对Cd²⁺的吸附性能的差异；利用自然老化和高温老化2种物理方法研究老化作用对磁性生物炭理化性质和吸附性能的影响。结果表明：与普通生物炭（BC）相比，FBC具有更大的比表面积和孔容，含氧官能团数量增多，并且出现Fe—O的特征峰，FBC-4、FBC-2、FBC-1的饱和磁化强度随着单位生物炭载铁量增加而增大，分别为0.64、2.21和17.69 A·m²/kg；BC和FBC对Cd²⁺吸附等温线和动力学曲线均符合Langmuir方程和准二级动力学方程，拟合出的平衡吸附量和理论最大吸附量关系为FBC-1>FBC-4>FBC-2>BC，即磁改性可以提高对Cd²⁺的平衡吸附量，且FBC-1对Cd²⁺的吸附能力最强；FBC-1经过2个月的自然老化和高温老化后，比表面积分别下降45.8%和36.4%，平均孔径分别增加72.7%和43.2%，饱和磁化强度分别增加至33.53和26.65 A·m²/kg；老化作用会降低磁性生物炭对Cd²⁺的吸附能力，其平衡吸附量由老化前的36.97 mg/g减小至30.97 mg/g（自然老化）和28.22 mg/g（高温老化），理论最大吸附量由63.80 mg/g分别下降至46.68和40.29 mg/g，相比于自然老化，高温老化作用对磁性生物炭Cd²⁺的吸附性能的抑制作用更明显。
- 磁性生物炭 /
- 镉(Cd) /
- 老化 /
- 比表面积 /
- 饱和磁化强度 /
- 吸附性能
Abstract:
Magnetic biochar (FBC) is an adsorption material with good adsorption performance and magnetic separation. However, there are few studies on whether the amount of magnetic precursor in the preparation process and the aging effect affect its structure and the ability to adsorb heavy metals. FBC with different iron-carbon ratios (1∶4, 1∶2 and 1∶1, denoted as FBC-4, FBC-2 and FBC-1) were prepared from rice straw and iron salts, and their surface morphology, functional groups and other physical and chemical properties, as well as the adsorption properties of Cd²⁺ were compared. Two physical aging methods (spontaneous aging and high temperature aging) were used to study the effect of aging on the physicochemical properties and adsorption properties of magnetic biochar. The results showed that compared with ordinary biochar (BC), FBC had a larger specific surface area and pore volume, the number of oxygen-containing functional groups increased, and the characteristic peaks of Fe—O appeared. The saturation magnetization of FBC-4, FBC-2 and FBC-1 increased with the increase of iron content per unit biochar, which were 0.64, 2.21 and 17.69 A·m²/kg, respectively. The adsorption isotherms and kinetic curves of BC and FBC for Cd²⁺ were consistent with the Langmuir equation and the pseudo-second-order kinetic equation. The relationship between the fitted equilibrium adsorption capacity and the theoretical maximum adsorption capacity was FBC-1>FBC-4>FBC-2>BC, that is, magnetic modification could improve the equilibrium adsorption capacity of Cd²⁺, and FBC-1 had a stronger adsorption capacity for Cd²⁺. After two months of spontaneous aging and high temperature aging, the specific surface area of FBC-1 decreased by 45.8% and 36.4%, the average pore size increased by 72.7% and 43.2%, and the saturation magnetization increased to 33.53 and 26.65 A·m²/kg, respectively. Aging could inhibit the adsorption capacity of magnetic biochar for Cd²⁺. The equilibrium adsorption capacity decreased from 36.97 mg/g before aging to 30.97 mg/g (spontaneous aging) and 28.22 mg/g (high temperature aging), and the theoretical maximum adsorption capacity decreased from 63.80 mg/g to 46.68 mg/g and 40.29 mg/g, respectively. Compared with spontaneous aging, high temperature aging had a more obvious inhibitory effect on the adsorption performance of magnetic biochar for Cd²⁺.
- magnetic biochar /
- cadmium (Cd) /
- aging /
- specific surface area /
- saturation magnetization /
- adsorption properties

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图 1 不同生物炭及其老化后的扫描电镜图

Figure 1. SEM of BC and FBC and after their aging treatments

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图 2 不同生物炭及其老化后的孔径分布曲线

Figure 2. Pore size distribution curves of BC and FBC and after their aging treatments

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图 3 不同生物炭及其老化后的红外光谱图

Figure 3. FTIR spectrum of BC and FBC and after their aging treatments

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图 4 磁性生物炭老化前后的磁滞回线

注：BC没有磁学性能，故在磁滞回线中未体现。

Figure 4. Magnetization of FBC before and after aging treatments

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图 5 不同生物炭及其老化后对Cd²⁺吸附动力学拟合曲线

Figure 5. Kinetic fitting curve for Cd²⁺ adsorption by BC and FBC and after their aging treatments

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图 6 不同生物炭及其老化后对Cd²⁺的Langmuir等温吸附曲线拟合

Figure 6. Langmuir isothermal adsorption curve fitting of Cd²⁺ by BC and FBC and after their aging treatments

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表 1 不同生物炭及其老化后的微观结构性质

Table 1. Microstructural properties of BC and FBC and after their aging treatments

性质	生物炭	比表面积 /(m²/g)	外比表面积 /(m²/g)	微孔比表面积 /(m²/g)	总孔容 /(cm³/g)	微孔孔容 /cm³	平均孔径 /nm
老化前	BC	5.73	2.52	3.21	0.02	0.001 3	10.43
	FBC-4	94.89	88.44	6.45	0.31	0.001 7	12.93
	FBC-2	122.13	117.31	4.82	0.38	0.001 0	12.49
	FBC-1	115.05	107.33	7.72	0.30	0.002 4	10.48
老化后	BC_SPON	3.92	2.06	1.86	0.01	0.000 8	11.91
	BC_HT	9.80	3.86	5.83	0.01	0.002 5	4.94
	(FBC-1)_SPON	62.35	57.87	4.48	0.28	0.001 5	18.10
	(FBC-1)_HT	73.17	67.17	6.00	0.27	0.002 0	15.01

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表 2 不同生物炭及其老化后对Cd²⁺吸附动力学拟合参数

Table 2. Kinetic fitting parameters for Cd²⁺ adsorption by BC and FBC and after their aging treatments

性质	生物炭	准一级动力学方程			准二级动力学方程
性质	生物炭	Q_e/ (mg/g)	k₁/h^-1	R²	Q_e/ (mg/g)	k₂/ 〔g/(mg·h)〕	R²
老化前	BC	27.53	1.58	0.63	30.00	0.076	0.91
	FBC-4	31.31	1.65	0.74	33.73	0.077	0.95
	FBC-2	30.07	1.72	0.68	32.42	0.083	0.93
	FBC-1	34.64	1.84	0.70	36.97	0.084	0.94
老化后	BC_SPON	26.15	1.49	0.60	28.67	0.073	0.88
	BC_HT	24.83	1.56	0.62	27.09	0.083	0.90
	(FBC-1)_SPON	28.96	1.83	0.74	30.97	0.097	0.96
	(FBC-1)_HT	26.33	1.82	0.69	28.22	0.105	0.93

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表 3 不同生物炭及其老化后对Cd²⁺的等温吸附拟合参数

Table 3. Isotherm fitting parameters for Cd²⁺ adsorption by BC and FBC and after their aging treatments

生物炭	Langmuir 方程			Freundlich 方程
生物炭	Q_m/ (mg/g)	K_L/ (L/mg)	R²	K_F/ 〔mg^{（1−1/n）}·L^1/n/g〕	1/n	R²
BC	48.80	0.011 6	0.990	3.335	0.417	0.912
FBC-4	61.33	0.009 4	0.998	3.291	0.449	0.919
FBC-2	57.07	0.009 9	0.994	3.28	0.44	0.921
FBC-1	63.80	0.009 3	0.994	3.36	0.452	0.914
BC_SPON	46.54	0.015 3	0.955	4.419	0.369	0.780
BC_HT	38.81	0.017 4	0.964	4.103	0.357	0.822
(FBC-1)_SPON	46.68	0.014 8	0.971	4.233	0.377	0.819
(FBC-1)_HT	40.29	0.017 1	0.970	4.226	0.357	0.818

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