花生壳复合水凝胶的制备及其吸附铅、镉性能

杨志林; 唐成波; 易筱筠; 郝鑫瑞; 王卓

doi:10.12153/j.issn.1674-991X.20230916

花生壳复合水凝胶的制备及其吸附铅、镉性能

doi: 10.12153/j.issn.1674-991X.20230916

杨志林^1,,
唐成波²,
易筱筠^{3, 4, ,},
郝鑫瑞⁵,
王卓⁶

1.
长江三峡水务（宜昌）有限公司
2.
三峡生态环境有限公司
3.
华南理工大学环境与能源学院
4.
华南理工大学环境与能源学院，工业聚集区污染控制与生态修复教育部重点实验室
5.
中国电建集团华东勘测设计研究院有限公司
6.
珠海基石科技有限公司

基金项目: 国家自然科学基金项目（41931288）；广东省重点领域研究开发计划项目（2019B110207001）

详细信息

作者简介:
杨志林（1995—），男，工程师，硕士，主要研究方向为水体重金属污染控制、环境功能材料研发、环境污染修复，zhilinyang@yeah.net

通讯作者:
易筱筠（1970—），女，教授，主要从事重金属污染水土环境生态修复、矿区土壤重金属形态分布的地球化学机制研究，xyyi@scut.edu.cn

中图分类号: X703
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- 文章访问数: 12
- HTML全文浏览量: 5
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- 被引次数: 0
出版历程
- 收稿日期: 2023-12-23
- 录用日期: 2024-07-25
- 修回日期: 2024-07-19
- 网络出版日期: 2024-09-30

Preparation of peanut shell composite hydrogel and its adsorption properties of lead and cadmium

YANG Zhilin^1
,,
TANG Chengbo²,
YI Xiaoyun^{3, 4
, ,},
HAO Xinrui⁵,
WANG Zhuo⁶

1.
Three Gorges Water (Yichang) Co., Ltd.
2.
Three Gorges Ecological Environment Co., Ltd.
3.
School of Environment and Energy, South China University of Technology
4.
Key Laboratory of Pollution Control and Ecosystem Restoration in Industrial Clusters, Ministry of Education, School of Environment and Energy, South China University of Technology
5.
Power-China Huadong Engineering Corporation Limited
6.
Zhuhai Cornerstone Technologies Co., Ltd.

摘要

摘要:
以花生壳（PS）、丙烯酸（AA）为聚合单体，过硫酸钾（APS）为引发剂，N,N-亚甲基双丙烯酰胺（MBA）为交联剂，β-环糊精（β-CD）作为增强材料，通过自由基聚合反应合成花生壳木质纤维素/β-环糊精/丙烯酸复合水凝胶〔PS（H）/β-CD/PAA）〕；研究了PS（H）/β-CD/PAA的表面性质和微观形貌，考察了在不同环境因子条件下PS（H）/β-CD/PAA对Cd²⁺、Pb²⁺的吸附行为和吸附机理。结果表明：PS（H）/β-CD/PAA具有多孔网络结构，加入β-CD后制备的复合水凝胶有更好的机械性能；PS（H）/β-CD/PAA合成成本低，并且可以循环使用；PS（H）/β-CD/PAA对Cd²⁺、Pb²⁺可在60 min内达到吸附平衡，最大吸附容量分别为115.67、181.71 mg/g，在pH为3~8的较宽范围有良好的效果；PS（H）/β-CD/PAA对Cd²⁺、Pb²⁺的吸附过程主要通过离子交换、络合作用或配位作用来进行；此外，PS（H）/β-CD/PAA在处理实际废水时，对Pb²⁺、Cd²⁺、Cu²⁺、Zn²⁺的去除率分别达76.4%、88.6%、72.9%、31.6%。PS（H）/β-CD/PAA处理水体重金属效果良好，能够充分利用资源、节约成本，可作为一种重金属废水处理的潜在新材料。
- 复合水凝胶 /
- 花生壳 /
- β-环糊精 /
- 铅 /
- 镉 /
- 废水处理
Abstract:
Peanut shells lignocellulose/β-cyclodextrin/acrylic acid composite hydrogel (PS(H)/β-CD/PAA) was prepared by free radical polymerization, using peanut shells(PS) and acrylic acid(AA) as polymerization monomers, potassium persulfate(APS) as initiator, N,N-methylenebisacrylamide(MBA) as crosslinking agent, β-cyclodextrin(β-CD) as reinforcing material. The surface properties and size morphology of the composite hydrogel adsorbent were characterized. The adsorption behavior and mechanism of PS(H)/β-CD/PAA on Cd²⁺ and Pb²⁺ under different environmental factors were investigated. As a result, PS(H)/β-CD/PAA had a porous network structure and positive mechanical properties when β-CD was added. PS(H)/β-CD/PAA presented lower synthesis cost and recyclability. The adsorption of PS(H)/β-CD/PAA on Cd²⁺ and Pb²⁺ reached adsorption equilibrium within 60 min and worked effectively in a wide pH range of 3-8. The maximum adsorption capacity of PS(H)/β-CD/PAA composite hydrogel for Cd²⁺ and Pb²⁺ was 115.67 and 181.71 mg/g, respectively. The adsorption process of PS(H)/β-CD/PAA on Cd²⁺ and Pb²⁺ was mainly carried out through ion exchange, complexation or coordination interaction. In addition, when treating actual wastewater, the removal efficiency of PS(H)/β-CD/PAA on Pb, Cd²⁺, Cu²⁺ and Ni²⁺ was 76.4%, 88.6%, 72.9% and 31.6%, respectively. In a word, PS(H)/β-CD/PAA exhibited good effectiveness in treating heavy metals in water, took full advantage of resources and saved costs, and could serve as a potential new material for heavy metal wastewater treatment.
- composite hydrogel /
- peanut shell /
- β-cyclodextrin /
- lead /
- cadmium /
- wastewater treatment

HTML全文

图 1 水凝胶的压缩应力-应变曲线

Figure 1. Compressive stress-strain curves of hydrogel

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图 2 PS、PS（H）/β-CD/PAA的SEM图谱

Figure 2. SEM spectra of peanut shell and PS(H)/β-CD/PAA composite hydrogel

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图 3 β-CD、PS（H）、PS（H）/β-CD/PAA的FT-IR光谱

Figure 3. FT-IR spectra of β-CD, PS(H), PS(H)/β-CD/PAA

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图 4 β-CD、PS（H）、PS（H）/β-CD/PAA的XRD 图谱

Figure 4. XRD patterns of β-CD, PS(H), PS(H)/β-CD/PAA

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图 5 溶液pH对PS（H）/β-CD/PAA去除Cd²⁺、Pb²⁺效果的影响

Figure 5. Effect of solution pH on Cd²⁺ and Pb²⁺ adsorption by PS(H)/β-CD/PAA composite hydrogel

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图 6 Cd²⁺、Pb²⁺初始浓度对Cd²⁺、Pb²⁺去除效果的影响

Figure 6. Initial mass concentration of Cd²⁺ and Pb²⁺ on the effect of removing Cd²⁺ and Pb²⁺

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图 7 PS（H）/β-CD/PAA投加量对Cd²⁺、Pb²⁺去除效果的影响

Figure 7. Effect of PS(H)/β-CD/PAA composite hydrogel dosage on the removal of Cd²⁺ and Pb²⁺

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图 8 PS（H）/β-CD/PAA对Pb²⁺、Cu²⁺、Cd²⁺和Ni²⁺的选择性吸附

Figure 8. Selective adsorption of Pb²⁺, Cu²⁺, Cd²⁺ and Ni²⁺ by PS(H)/β-CD/PAA composite hydrogel

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图 9 PS（H）/β-CD/PAA的吸附动力学曲线

Figure 9. Adsorption kinetic curves of PS(H)/β-CD/PAA

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图 10 PS（H）/β-CD/PAA吸附Cd²⁺、Pb²⁺的颗粒内扩散模型

Figure 10. Intra-particle diffusion model of adsorbed Cd²⁺ and Pb²⁺ by PS(H)/β-CD/PAA

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图 11 Cd²⁺和Pb²⁺在PS（H）/β-CD/ PAA上的吸附等温线拟合结果

Figure 11. Sorption isotherm fitting results of Cd²⁺ and Pb²⁺ on PS(H)/β-CD/PAA hydrogel

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图 12 PS（H）/β-CD/PAA吸附Cd²⁺、Pb²⁺前后的ATR-FTIR光谱图与XPS光谱图

Figure 12. ATR-FTIR spectra and XPS spectra of PS(H)/β-CD/PAA composite hydrogel before and after adsorption of Cd²⁺ and Pb²⁺

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图 13 循环次数对PS（H） /β-CD/ PAA去除Cd²⁺和Pb²⁺效果的影响

Figure 13. Effect of recycling number on the removal efficiency of Pb²⁺ and Cd²⁺ by PS(H)/β-CD/PAA hydrogel

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表 1 PS（H）/β-CD/PAA对Cd²⁺、Pb²⁺的吸附动力学模型拟合参数

Table 1. Fitting parameters of adsorption kinetic model of PS(H)/β-CD/PAA for Cd²⁺ and Pb²⁺

金属离子	Q_e,exp/（mg/g）	准一级反应动力学			准二级反应动力学
金属离子	Q_e,exp/（mg/g）	k₁/（L/min）	Q_e,cal /（mg/g）	R²	k₂/〔g/（mg·min）〕	Q_e,cal/（mg/g）	R²
Pb²⁺	159.90	0.163 7	154.92	0.990 3	0.001 3	164.73	0.997 1
Cd²⁺	98.50	0.070 0	94.46	0.957 3	0.000 9	103.53	0.990 7

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表 2 不同温度下Langmuir和Freundlich等温模型的拟合参数

Table 2. Parameters of Langmuir and Freundlich isotherm models at different temperatures

方程		Cd²⁺溶液温度/K			Pb²⁺溶液温度/K
方程		293	303	313	293	303	313
Langmuir	Q_m	108.45	114.30	115.67	160.42	168.52	181.71
	K_L	13.60	10.84	1.06	1.47	1.52	1.21
	R²	0.972	0.967	0.973	0.982	0.982	0.963
Freundlich	K_F	81.23	84.83	72.01	120.81	124.99	121.55
	n	0.076	0.078	0.117	0.076	0.082	0.119
	R²	0.969	0.962	0.939	0.886	0.864	0.954

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表 3 金属离子吸附的热力学参数值

Table 3. Values of thermodynamic parameters for metal ion sorption

金属离子	溶液温度/K	ΔG^0/（kJ/mol）	ΔS⁰/〔J/（mol·K）〕	ΔH⁰/（kJ/mol）
Cd²⁺	293	−1.78	2.44	12
	303	−1.9
	313	−2.02
Pb²⁺	293	−3.11	2.44	19.0
	303	−3.35
	313	−3.49

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表 4 不同吸附剂的吸附效果及成本比较

Table 4. Comparison of adsorption effect and cost of different adsorbents

吸附剂	Q_e/（mg/g）	成本/（元/t）
纳米二氧化钛^[35]	15.3（Cd²⁺）	66 500
钙蒙脱石^[36]	30.7（Cd²⁺）	120 000
活性炭^[37]	33.6（Cd²⁺）	15 000
交联壳聚糖^[38]	79.2（Pb²⁺）	1 600 000
麸皮^[39]	87.0（Pb²⁺）	3 600
氧化石墨烯^[40]	106.3（Cd²⁺）	1 189 000 000
PS（H）/β-CD/PAA	115.67（Cd²⁺）、181.71（Pb²⁺）	2 905
注：（Cd²⁺）、（Pb²⁺）表示吸附剂对Cd²⁺、Pb²⁺的吸附。

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表 5 不同PS（H）/β-CD/PAA投加量时AMD废水中各离子的去除率

Table 5. Removal rates of different ions in AMD wastewater at different dosages of PS(H)/β-CD/PAA %　

吸附剂投加量/（g/L）	Cd²⁺	Pb²⁺	Cu²⁺	Ni²⁺	Zn²⁺	总Fe	${\mathrm{SO}}_4^{2-} $	Cl^-
1	23.3	69.5	67.2	8.4	11.1	100	1.9	0.6
2	45.8	73.2	76.0	12.1	21.7	100	2.1	2.2
3	60.2	73.7	83.9	15.4	25.2	100	9.6	3.3
4	72.9	76.4	88.6	21.7	31.6	100	4.6	6.6

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