污泥基生物炭处理酸性含U(Ⅵ)废水的效能与机理

doi:10.11949/0438-1157.20191505

摘要/Abstract

摘要：

通过城市污泥（SS）慢速热解制备污泥基生物炭（SSB），并研究初始pH、投加量、共存离子、吸附时间和温度等因素对SSB去除U(Ⅵ)的影响，探讨吸附动力学和吸附等温线特征。通过元素分析、扫描电镜（SEM）、傅里叶红外光谱（FTIR）、X射线衍射（XRD）和X射线光电子能谱（XPS）分析U(Ⅵ)吸附去除的机理。结果表明SSB去除U(Ⅵ)的适宜条件为：pH=3、投加量1 g/L、吸附时间240 min；在此条件下，在温度30℃时最大吸附量为34.51 mg/g。吸附动力学符合拟二级动力学模型；Langmuir吸附等温模型能更好描述生物炭对U(Ⅵ)的吸附行为。U(Ⅵ)吸附去除机理主要包括静电作用，与Si—O—Si的n-π相互作用，与羟基（—OH）、羧基（—COOH）的配位络合。通过5次吸附-解吸试验发现，U(Ⅵ)去除率和SSB再生率均在80%以上。本研究表明污泥基生物炭具备处理与修复酸性含U(Ⅵ)废水污染的潜力。

关键词: 吸附, 热解, 修复, 污泥基生物炭, 含U(Ⅵ)废水, 机理

Abstract:

Sewage sludge-derived biochar (SSB) was prepared by slow pyrolysis of sewage sludge (SS), and the effect factors, including initial pH, dosage, coexisting ions, contact time and temperature, on the U(Ⅵ) adsorption by SSB were investigated. The adsorption kinetics and isotherm were also studied. The mechanism of U(Ⅵ) adsorption removal was analyzed by elemental analysis, scanning electron microscopy (SEM), Fourier infrared spectroscopy (FTIR), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The results showed that the suitable conditions for U(Ⅵ) removal were pH of 3, dosage of 1 g/L and adsorption time of 240 min under 30°C. Under these conditions, a maximum adsorption capacity of 34.51 mg/g was obtained. The adsorption kinetics of U(Ⅵ) was accurately described by a pseudo-second-order model. Langmuir adsorption isotherm model can describe the adsorption behavior of U(Ⅵ) well. The adsorption mechanisms mainly include electrostatic interaction, n-π interaction of Si—O—Si, coordination complexation of hydroxyl (—OH) and carboxyl (—COOH) groups. Based on 5 adsorption-desorption cycles, the efficiencies of both U(Ⅵ) removal and SSB regeneration were above 80%. This study indicated that sewage sludge-derived biochar has the potential for acidic U(Ⅵ)-containing wastewater treatment.

Key words: adsorption, pyrolysis, remediation, sewage sludge-derived biochar, U(Ⅵ)-containing wastewater, mechanism

中图分类号:

X 172

莫官海, 谢水波, 曾涛涛, 刘迎九, 蔡萍莉. 污泥基生物炭处理酸性含U(Ⅵ)废水的效能与机理[J]. 化工学报, 2020, 71(5): 2352-2362.

Guanhai MO, Shuibo XIE, Taotao ZENG, Yingjiu LIU, Pingli CAI. The efficiency and mechanism of U(Ⅵ) removal from acidic wastewater by sewage sludge-derived biochar[J]. CIESC Journal, 2020, 71(5): 2352-2362.

图/表 14

表1 污泥及污泥基生物炭的理化性质

Table 1 Physicochemical properties of sewage sludge and sewage sludge-derived biochar

理化性质	SS	SSB
产率/%	/	77.95±1.47
灰分/%	61.03±0.32	70.46±0.28
挥发分/%	37.94±0.55	27.10±0.86
pH	6.09±0.21	7.75±0.14
微孔孔径/nm	1.34	1.00
介孔孔径/nm	27.10	16.60
孔体积/(cm³/g)	0.12	0.36
比表面积/(m²/g）	11.88	59.81
C/%	12.20	10.98
H/%	2.64	1.66
N/%	2.01	1.37
O/%	22.20	15.53
H/C	0.22	0.15
O/C	1.85	1.41

图1 污泥及其生物炭酸性官能团含量

Fig.1 Acidic functional groups contents of sewage sludge and sewage sludge-derived biochar

表2 污泥及其生物炭中重金属含量/(mg/L)

Table 2 Heavy metal concentrations of sewage sludge and sewage sludge-derived biochar/(mg/L)

样品	Ba	Cr	Cd	Cu	Pb	Zn
SS	5.32	0.82	0.08	1.10	0.66	6.82
SSB	7.14	1.08	0.09	1.37	0.81	8.79
《危险废物鉴别标准浸出毒性鉴别》(GB 5085.3—2007)	100	15	1	100	5	100

图2 初始pH对U(Ⅵ)吸附去除的影响（a）以及污泥基生物炭的零电势点（b）

Fig. 2 Effect of initial pH on U(Ⅵ) adsorption removal (a) and pH of point zero charge (pHPZC) of sewage sludge-derived biochar (b)

图3 投加量对污泥基生物炭吸附U(Ⅵ)的影响

Fig.3 Effect of dosage on U(Ⅵ) adsorption by sewage sludge-derived biochar

图4 共存离子对污泥基生物炭吸附U(Ⅵ)的影响

Fig.4 Effect of coexisting ions on U(Ⅵ) adsorption by sewage sludge-derived biochar

图5 SSB对U(Ⅵ)的吸附动力学拟合（a）和颗粒内扩散拟合曲线（b）

Fig.5 Adsorption kinetics fitting of U(Ⅵ) on SSB (a) and intraparticle diffusion curves (b)

表3 SSB对U(Ⅵ)的吸附动力学参数

Table 3 Kinetic parameters of U(Ⅵ) adsorption by SSB

拟一级动力学方程				拟二级动力学方程
q_e/(mg/g)	k₁/min^-1		R²	q_e/(mg/g)	k₂/(g/(mg·min))		R²
6.67	0.115		0.601	6.88	0.039		0.934
颗粒内扩散模型
k_d1/(mg/(g·min^1/2))		C₁	R²	k_d2/(mg/(g·min^1/2))		C₂	R²
0.165		4.951	0.956	0.004		6.726	0.966

图6 温度对SSB吸附U(Ⅵ)的影响（a）及吸附等温线拟合曲线（b）

Fig.6 Effect of temperature on U(Ⅵ) adsorption by SSB (a) and fitting curves of adsorption isotherms (b)

表4 SSB对U(Ⅵ)的吸附等温线拟合参数

Table 4 Isotherms parameters of U(Ⅵ) adsorption by SSB

温度/℃	Langmuir等温线方程			Freundlich等温线方程
温度/℃	q_max/(mg/g)	K_b/ (L/mg)	R₁²	K_f/ (mg¹⁺ⁿ/(Lⁿ·g))	n	R₂²
20	33.22	1.018	0.996	14.58	3.66	0.902
30	34.51	1.144	0.995	15.48	3.68	0.909
40	35.65	1.287	0.996	16.47	3.72	0.906

图7 干污泥（a）及污泥基生物炭吸附U(Ⅵ)前（b）、后（c）的微观形态结构

Fig.7 Micromorphology of sludge sewage (a), sludge sewage-derived biochar before (b) and after (c) U(Ⅵ) adsorption

图8 污泥及污泥基生物炭吸附U(Ⅵ)前、后的FTIR（a）和XRD图（b）

Fig.8 FTIR (a) and XRD (b) of sludge sewage, sewage sludge-derived biochar before and after U(Ⅵ) adsorption

图9 污泥基生物炭吸附U(Ⅵ)前、后的XPS光谱图

Fig.9 XPS spectra of sewage sludge-derived biochar before and after U(Ⅵ) adsorption(a) overall spectra; (b) U 4f; (c) C 1s; (d) O 1s

图10 污泥基生物炭的吸附-解吸试验

Fig.10 Adsorption and desorption experiments of sewage sludge-derived biochar

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