生物质炭改性微球去除化工废水中无机磷的性能研究

doi:10.11949/0438-1157.20211693

化工学报 ›› 2022, Vol. 73 ›› Issue (5): 2158-2173.DOI: 10.11949/0438-1157.20211693

生物质炭改性微球去除化工废水中无机磷的性能研究

赵希强¹(),张健¹,孙爽¹,王文龙¹,毛岩鹏¹,孙静¹,刘景龙²,宋占龙¹()

^1.山东大学能源与动力工程学院，燃煤污染物减排国家工程实验室，环境热工技术教育部工程研究中心，山东省能源碳减排技术与资源化利用重点实验室，山东济南 250061
^2.山东电力研究院，山东济南 250001

收稿日期:2021-11-29 修回日期:2022-01-27 出版日期:2022-05-05 发布日期:2022-05-24
通讯作者: 宋占龙
作者简介:赵希强（1981—），男，博士，副教授，zxq@sdu.edu.cn
基金资助:
山东省重点研发项目(2019GSF109091);山东电力研究院科技项目(ZY2020-06)

Study on the performance of biochar modified microspheres to remove inorganic phosphorus from chemical wastewater

Xiqiang ZHAO¹(),Jian ZHANG¹,Shuang SUN¹,Wenlong WANG¹,Yanpeng MAO¹,Jing SUN¹,Jinglong LIU²,Zhanlong SONG¹()

^1.National Engineering Laboratory for Reducing Emissions from Coal Combustion, Engineering Research Center of Environmental Thermal Technology of Ministry of Education, Shandong Key Laboratory of Energy Carbon Reduction and Resource Utilization, School of Energy and Power Engineering, Shandong University, Jinan 250061, Shandong, China
^2.Shandong Electric Power Research Institute, Jinan 250001, Shandong, China

Received:2021-11-29 Revised:2022-01-27 Online:2022-05-05 Published:2022-05-24
Contact: Zhanlong SONG

摘要/Abstract

摘要：

我国化工废水排放量巨大，其中含有的无机磷会导致淡水富营养化。选用来源广泛且环境友好的海藻酸钠为载体，微波一步热解活化法制得的高比表面积甘蔗渣生物炭为添加剂，氯化铁溶液为交联剂，通过溶胶凝胶法和包埋法制备了SA-Fe、SA-C-Fe和SA-C-Fe(C)三种吸附材料，并用其进行了无机磷的去除实验。研究发现三种材料的吸附过程均符合准二级动力学模型，其中SA-Fe和SA-C-Fe的吸附过程符合Langmuir等温模型，其对无机磷的最大吸附量分别为53.79 mg/g和78.75 mg/g；SA-C-Fe(C)对无机磷的吸附过程符合Langmuir-Freundlich等温吸附模型。SA-C-Fe材料吸附无机磷过程存在配体交换、静电吸引和表面沉积三种吸附机制，吸附容量最高；SA-C-Fe(C)微球经过碳化后，羟基官能团数量减少，配体交换作用减弱，且形成了铁氧化物沉积层，吸附容量最低。

关键词: 无机磷, 化工废水, 生物炭, 微波热解, 海藻酸钠

Abstract:

The discharge of chemical wastewater in China is huge, and the inorganic phosphorus contained in wastewater can lead to eutrophication of fresh water. Using sodium alginate from a wide range of sources and environment-friendly as the carrier, the bagasse biochar with high specific surface area prepared by one-step microwave pyrolysis and activated method as the additive, and ferric chloride as the cross-linking agent, three kinds of adsorbents (SA- Fe, SA-C-Fe and SA-C-Fe(C)) were prepared by the sol-gel method and the embedding method, and they were used to perform inorganic phosphorus removal experiments. The results showed that the adsorption process of the three materials conforms to the quasi-second-order kinetic model. The entire adsorption process of SA-Fe gel spheres and SA-C-Fe gel spheres conforms to the Langmuir isotherm model, and the maximum adsorption capacity of SA-Fe spheres and SA-C-Fe spheres to be 53.79 mg/g and 78.75 mg/g, respectively. The removal process of inorganic phosphorus by SA-C-Fe(C) gel spheres conforms to the Langmuir-Freundlich adsorption isotherm model. SA-C-Fe gel spheres have three adsorption mechanisms: ligand exchange, electrostatic attraction and surface deposition, with the highest adsorption capacity. After carbonization of SA-C-Fe(C) microspheres, the number of hydroxyl functional groups was reduced, the ligand exchange was weakened, and iron oxide deposits were formed, with the lowest adsorption capacity.

Key words: inorganic phosphorus, chemical wastewater, biochar, microwave pyrolysis, sodium alginate

中图分类号:

TQ 126.3

赵希强, 张健, 孙爽, 王文龙, 毛岩鹏, 孙静, 刘景龙, 宋占龙. 生物质炭改性微球去除化工废水中无机磷的性能研究[J]. 化工学报, 2022, 73(5): 2158-2173.

Xiqiang ZHAO, Jian ZHANG, Shuang SUN, Wenlong WANG, Yanpeng MAO, Jing SUN, Jinglong LIU, Zhanlong SONG. Study on the performance of biochar modified microspheres to remove inorganic phosphorus from chemical wastewater[J]. CIESC Journal, 2022, 73(5): 2158-2173.

图/表 22

图1 甘蔗渣生物炭的制备实验装置图

Fig.1 Diagram of the experimental device for the preparation of bagasse biochar

图2 海藻酸钠改性微球的制备工艺流程

Fig.2 Process flow chart of preparation of sodium alginate modified microspheres

图3 pH对无机磷去除效率的影响

Fig.3 The effect of pH on the removal efficiency of inorganic phosphorus

图4 SA-Fe、SA-C-Fe和SA-C-Fe(C)微球的Zeta电位

Fig.4 Zeta potential of SA-Fe, SA-C-Fe and SA-C-Fe(C)

图5 吸附剂投加量对无机磷去除效率的影响

Fig.5 The effect of adsorbent dosage on the removal efficiency of inorganic phosphorus

图6 接触时间对无机磷去除效率的影响

Fig.6 The effect of contact time on the removal efficiency of inorganic phosphorus

图7 初始质量浓度对无机磷去除效率的影响

Fig.7 The effect of initial mass concentration on the removal efficiency of inorganic phosphorus

图8 Langmuir、Freundlich和Langmuir-Freundlich等温模型拟合

Fig.8 Langmuir, Freundlich,and Langmuir-Freundlich isothermal model fitting

表1 Langmuir、Freundlich和Langmuir-Freundlich等温模型相关参数

Table1 Related parameters of Langmuir， Freundlich and Langmuir-Freundlich isotherm models

材料	Langmuir等温模型			Freundlich等温模型			Langmuir- Freundlich等温模型
材料	Q_m/(mg/g)	K_L/(10^-2L/mg)	R²	K_F/(L/mg)	1/n	R²	Q_m/(mg/g)	K_b/(10^-2L/mg)	n	R²
SA-Fe	53.79	1.47	0.970	4.85	0.38	0.930	55.85	1.34	0.94	0.965
SA-C-Fe	78.75	1.17	0.955	5.31	0.42	0.945	97.94	0.65	0.78	0.951
SA-C-Fe(C)	44.31	1.40	0.961	3.85	0.39	0.965	63.65	0.50	0.66	0.972

图9 反应动力学模型拟合曲线

Fig. 9 Fitting curve of reaction kinetic model

表2 吸附动力学模型及其参数

Table 2 Adsorption kinetic model and parameters

材料	准一级动力学模型			准二级动力学模型			颗粒内扩散模型
材料	Q_e/(mg/L)	k₁/(10^-2min^-1)	R²	Q_e/(mg/L)	k₂/(10^-3g/(mg·min))	R²	k_p/(mg/(g·min^0.5))	R²
SA-Fe	16.14	0.19	0.989	19.26	0.23	0.991	0.33	0.924
SA-C-Fe	9.07	0.15	0.907	21.91	0.87	0.997	0.190	0.738
SA-C-Fe(C)	6.86	0.19	0.945	15.89	1.27	0.999	0.152	0.693

图10 SA-C-Fe和SA-C-Fe(C)的N2吸附脱附等温线及孔径分布

Fig.10 The N2 adsorption desorption isotherm and pore size distribution of SA-C-Fe and SA-C-Fe(C)

表3 海藻酸钠改性微球（SA-Fe、SA-C-Fe、SA-C-Fe（C））的BET表征结果

Table 3 BET characterization results of sodium alginate modified microspheres （SA-Fe， SA-C-Fe， SA-C-Fe（C））

性质	SA-Fe	SA-C-Fe	SA-C-Fe(C)
比表面积/（m²/g）	85.58	756.25	987.55
平均孔径/nm	7.30	3.48	3.41
总孔容/（cm³/g）	0.16	0.66	0.84

图11 SA-Fe、SA-C-Fe和SA-C-Fe(C)微球的XRD谱图

Fig.11 XRD patterns of SA-Fe, SA-C-Fe and SA-C-Fe(C) microspheres

图12 SA-Fe、SA-C-Fe和SA-C-Fe(C)微球的FTIR谱图

Fig.12 FTIR spectra of SA-Fe, SA-C-Fe and SA-C-Fe(C) microspheres

图13 SA-Fe、SA-C-Fe和SA-C-Fe(C)的扫描电镜图

Fig.13 SEM images of SA-Fe, SA-C-Fe and SA-C-Fe(C)

表4 SA-Fe放大50倍外表面的EDS能谱分析

Table 4 EDS energy spectrum analysis of the outer surface of SA-Fe magnified 50 times

Element	W/%	A/%
C	11.56	28.22
O	14.57	26.70
Cl	20.88	17.26
Fe	52.99	27.82

图14 反应前后复合材料的傅里叶红外光谱图

Fig.14 FTIR spectra of the composite material before and after the reaction

图15 反应前后复合材料的XRD谱图

Fig.15 XRD patterns of the composite material before and after the reaction

图16 SA-Fe、SA-C-Fe、SA-C-Fe(C)材料的XPS表征谱图

Fig.16 XPS characterization spectra of SA-Fe, SA-C-Fe, SA-C-Fe(C) materials

图17 配体交换示意图

Fig.17 Schematic diagram of ligand exchange

图18 静电吸引作用示意图

Fig.18 Schematic diagram of electrostatic attraction

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生物质炭改性微球去除化工废水中无机磷的性能研究

Study on the performance of biochar modified microspheres to remove inorganic phosphorus from chemical wastewater

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