The efficiency and mechanism of U(Ⅵ) removal from acidic wastewater by sewage sludge-derived biochar

doi:10.11949/0438-1157.20191505

Abstract

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

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

CLC Number:

X 172

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.

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.

Figures/Tables 14

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

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

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

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)

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

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

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

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

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

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

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

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

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

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

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