Thermal modification of concrete fine powder and the adsorption performance of modified products on arsenic in wastewater

doi:10.19965/j.cnki.iwt.2025-0215

Abstract

Abstract:

Mining and metal smelting have produced a large amount of arsenic-containing wastewater, causing serious environmental pollution. Thermally modified concrete fine powder(TWCP) adsorbent was prepared by calcination modification using concrete fine powder(WCP) as raw material. The effects of thermal modification temperature, initial pH of the system and coexisting ions on the performance of TWCP adsorption of arsenic in wastewater were investigated. The arsenic adsorption mechanism of TWCP was analyzed by XRD, FT-IR, SEM and XPS characterization methods and sequential extraction technology. The results showed that TWCP with thermal modification temperature of 250 ℃ showed excellent arsenic adsorption performance, and the theoretical maximum adsorption capacity was 31.92 mg/g. The coexistence of anions such as Cl^- and PO₄ ^3- inhibited the adsorption process. The adsorption process of arsenic by TWCP conformed to the Langmuir isothermal adsorption model, which was dominated by chemical adsorption, and the adsorption process was an exothermic reaction. The mechanism of arsenic adsorption by TWCP included the formation of Ca-As precipitate by arsenic and Ca²⁺ under alkaline conditions, ion exchange between SO₄ ^2- and CO₃ ^2- with arsenic, complexation between AlOOH and FeOOH with arsenic. The results of sequential extraction showed that ion exchange was dominant under acidic conditions, and chemical precipitation was dominant under alkaline conditions.

Key words: concrete fine powder, adsorbent, thermal modification, arsenic wastewater, adsorption mechanism

摘要：

矿山开采和金属冶炼产生了大量的含砷废水，造成了严重的环境污染。以混凝土细粉（WCP）为原料通过锻烧改性制备了热改性混凝土细粉吸附剂（TWCP），考察了热改性温度、体系初始pH和共存离子对TWCP吸附废水中砷性能的影响，通过XRD、FT-IR、SEM和XPS等表征手段和顺序提取技术分析了TWCP对砷的吸附机制。结果表明，在热改性温度250 ℃下制备的TWCP对砷表现出优异的吸附性能，理论最大吸附量为31.92 mg/g，Cl^-和PO₄ ^3-等阴离子共存抑制了吸附反应的进行。TWCP对砷的吸附过程符合Langmuir等温吸附模型，以化学吸附为主，吸附过程为放热反应。TWCP对砷的吸附去除包含3方面机制，分别为碱性条件下砷和Ca²⁺生成Ca-As沉淀，SO₄ ^2-和CO₃ ^2-与砷发生离子交换，AlOOH和FeOOH与砷发生络合作用。顺序提取结果表明，酸性条件下TWCP对砷的吸附机制以离子交换为主，碱性条件下以化学沉淀为主。

关键词: 混凝土细粉, 吸附剂, 热改性, 含砷废水, 吸附机制

CLC Number:

X703
TQ424

Ying FANG, Zhu WEN, Na DU. Thermal modification of concrete fine powder and the adsorption performance of modified products on arsenic in wastewater[J]. Industrial Water Treatment, 2026, 46(2): 91-101.

方莹, 文祝, 杜娜. 混凝土细粉的热改性及改性产物对废水中砷的吸附性能[J]. 工业水处理, 2026, 46(2): 91-101.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2025-0215

https://www.iwt.cn/EN/Y2026/V46/I2/91

Figures/Tables 15

Table 1 The main chemical composition of WCP，RWCP and TWCP

材料	组分质量分数/%
材料	SiO₂	CaO	MgO	Al₂O₃	Fe₂O₃	Na₂O	K₂O	SO₃	其他
WCP	27.67	52.01	2.45	6.32	5.71	0.13	1.50	1.54	2.67
RWCP	29.46	50.17	2.56	6.28	5.65	0.10	1.47	1.48	2.83
TWCP（150）	34.00	44.87	3.23	6.88	4.72	0.17	1.52	2.16	2.45
TWCP（250）	34.01	44.99	3.22	6.87	4.71	0.17	1.51	2.18	2.34
TWCP（450）	34.17	45.01	3.21	6.86	4.71	0.17	1.51	2.20	2.16
TWCP（650）	34.25	45.25	3.24	6.88	4.72	0.18	1.50	2.21	1.77
TWCP（850）	34.69	46.18	3.23	6.87	4.70	0.19	1.52	2.23	0.39

Fig.1 Effect of modification temperature on the arsenic adsorption performance of TWCP （a），the Ca²⁺ concentration in solution after adsorption （b），and the thermogravimetric behavior during the thermal modification process of WCP （c）

Fig.2 Effect of pH on arsenic adsorption performance of TWCP（a） and the forms of arsenic at different pH（b）

Fig.3 Effect of anion coexistence on the adsorption of arsenic by TWCP

Fig.4 The kinetic fitting curve of arsenic adsorption by TWCP

Table 2 Fitting parameters of adsorption kinetics

C ₀/

（mg·L^-1）

q _e，exp/

（mg·g^-1）

k ₁/min^-1

Fig.5 Isothermal adsorption fitting results of Langmuir model and Freundlich model at different temperatures

Table 3 Fitting parameters of isothermal adsorption

温度/℃	Langmuir模型			Freundlich模型
温度/℃	q _m/（mg·g^-1）	K _L	R ²	K _F	n	R ²
25	31.92	0.006 2	0.99	0.03	1.64	0.90
35	25.48	0.007 8	0.96	0.51	1.80	0.82
45	17.41	0.004 7	0.99	1.15	2.45	0.81

Fig.6 XRD patterns of WCP and TWCP before and after arsenic adsorption

Fig.7 SEM of WCP （a） and TWCP before （b） and after （c） arsenic adsorption， and EDS spectrum （d） of TWCP after arsenic adsorption

Fig.8 FT-IR spectra of WCP and TWCP before and after arsenic adsorption

Fig.9 XPS patterns of TWCP before and after adsorption of arsenic

Fig.10 Different forms of arsenic extracted sequentially at different initial pH

Fig.11 TWCP regeneration performance

Table 4 Arsenic adsorption properties of different adsorption materials

吸附材料	理论最大吸附量/（mg·g^-1）	参考文献
埃洛石纳米管负载ZrO₂	27.46	〔30〕
巯基乙酸改性凹凸棒石	30.72	〔31〕
MnO₂改性粉煤灰	9.71	〔32〕
硫酸改性钢渣	0.021 51	〔33〕
竹箨活性炭	3.87	〔34〕
TWCP（250）	31.92	本研究

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