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

doi:10.11949/0438-1157.20211693

Abstract

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

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

CLC Number:

TQ 126.3

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.

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.

Figures/Tables 22

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

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

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

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

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

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

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

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

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

Fig. 9 Fitting curve of reaction kinetic model

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

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

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

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

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

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

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

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

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

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

Fig.17 Schematic diagram of ligand exchange

Fig.18 Schematic diagram of electrostatic attraction

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