生物源碳酸钙对污水中Pb(II)和甲基橙吸附行为的研究

doi:10.15541/jim20190349

无机材料学报 ›› 2020, Vol. 35 ›› Issue (3): 315-323.DOI: 10.15541/jim20190349 CSTR: 32189.14.10.15541/jim20190349

所属专题： 2020年环境材料论文精选(三)有机小分子去除；【虚拟专辑】污染物吸附水处理(2020~2021)

生物源碳酸钙对污水中Pb(II)和甲基橙吸附行为的研究

杜旭东¹,唐城元¹,杨小丽²,程建波¹,贾玉珂¹,杨树斌¹()

^1. 烟台大学化学化工学院, 烟台 264005
^2. 华北水利水电大学环境与市政工程学院, 郑州 450045

收稿日期:2019-07-15 修回日期:2019-09-12 出版日期:2020-03-20 网络出版日期:2019-10-23
作者简介:杜旭东(1995-), 男, 硕士研究生. E-mail: 2062296740@qq.com
基金资助:
国家自然科学基金(51708215);山东省自然科学基金-青年基金(ZR201807060384);烟台大学博士启动基金(HY18B04)

High-efficiency Biogenic Calcium Carbonate for Adsorption of Pb(II) and Methyl Orange from Wastewater

DU Xudong¹,TANG Chengyuan¹,YANG Xiaoli²,CHENG Jianbo¹,JIA Yuke¹,YANG Shubin¹()

^1. School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, China
^2. School of Environmental and Municipal Engineering, North China University of Water Resources and Electric Power, Zhengzhou 450045, China

Received:2019-07-15 Revised:2019-09-12 Published:2020-03-20 Online:2019-10-23
About author:DU Xudong (1995-), male, Master candidate. E-mail: 2062296740@qq.com
Supported by:
National Natural Science Foundation of China(51708215);Shandong Provincial Natural Science Foundation(ZR201807060384);PhD Research Startup Foundation of Yantai University(HY18B04)

摘要/Abstract

摘要：

实验采用廉价的牡蛎壳制备绿色、高效的生物源碳酸钙(bio-CaCO₃)吸附材料, 用于去除污水中的Pb(II)和甲基橙(MO)。通过扫描电子显微镜(SEM), 热重分析(TGA), X射线荧光光谱分析(XRF)等表征方法对材料形貌、组成、结构等进行了分析。采用宏观吸附行为和微观表征研究bio-CaCO₃对水体中Pb(II)和MO的吸附过程并阐明机理。研究发现, bio-CaCO₃对MO的去除效率约为45% (m_sorbent/V_solvent=0.2 g/L, [MO]_initial=60 mg/L), SEM分析结果表明bio-CaCO₃吸附MO后, 表面形貌发生了明显的变化。bio-CaCO₃对Pb(II)的饱和吸附量高达1775 mg/g (pH=5.0, T=298 K), 优于传统的皂土、活性炭等吸附材料。bio-CaCO₃吸附Pb(II)的主要吸附机理是CaCO₃+Pb(II)→PbCO₃, 该过程的ΔH ^θ=-7.64 kJ/mol, ΔS ^θ=-17.92 J/(mol·K), ΔG ^θ=-2.30 kJ/mol(pH=5.0, T=298 K), 吸附Pb(II)后产生大量形貌更加规则的四棱柱结构。研究表明实验制备的bio-CaCO₃对Pb(II)和MO均具有良好的吸附性能, 是一种环境友好型高效吸附剂。

关键词: 生物源碳酸钙, Pb(II), 甲基橙, 吸附

Abstract:

A low-cost oyster shell was carried to prepare biogenic calcium carbonate (bio-CaCO₃) to remediate Pb(II) and methyl orange (MO) from contaminated water. The morphology, composition and structure of the material were analyzed mainly by scanning electron microscope (SEM), thermogravimetric analysis (TGA), X-ray fluorescence (XRF). The adsorption of Pb(II) and MO by bio-CaCO₃ was studied by combining batch experiments and microstructure characterization. Batch sorption experiments showed that 45% MO was removed by bio-CaCO₃ (m_sorbent/V_solvent=0.2 g/L, [MO]_initial=60 mg/L). An obviously morphology change took place after MO adsorbed onto bio-CaCO₃. The maximum sorption capacity of bio-CaCO₃ for Pb(II) is 1775 mg/g (pH=5.0, T=298 K), which is higher than that of the traditional nanomaterials such as bentonite and activated carbon. The Pb(II) removal mechanism is expected to be CaCO₃+ Pb(II)→PbCO₃, where the ΔH ^θ, ΔS ^θ and ΔG ^θ of Pb(II) sorption by bio-CaCO₃ (pH=5.0, T=298K) are -7.64 kJ/mol, -17.92 J/(mol·K) and -2.30 kJ/mol, respectively. More regular products with quadrangular structure are formed after Pb(II) adsorption. The results highlight that the bio-CaCO₃ has a high Pb(II) and MO sorption efficiency, demonstrating that it is a promising adsorbent material in environmental pollution management.

Key words: biogenic calcium carbonate, Pb(II), methyl orange, sorption

中图分类号:

TQ174

杜旭东, 唐城元, 杨小丽, 程建波, 贾玉珂, 杨树斌. 生物源碳酸钙对污水中Pb(II)和甲基橙吸附行为的研究[J]. 无机材料学报, 2020, 35(3): 315-323.

DU Xudong, TANG Chengyuan, YANG Xiaoli, CHENG Jianbo, JIA Yuke, YANG Shubin. High-efficiency Biogenic Calcium Carbonate for Adsorption of Pb(II) and Methyl Orange from Wastewater[J]. Journal of Inorganic Materials, 2020, 35(3): 315-323.

图/表 17

表1 牡蛎壳的XRF分析结果

Table 1 XRF results of oyster shell

Element	Na	Mg	Al	Si	P	S	Cl	K	Ca	Fe	Cu	Sr
Mass fraction/wt%	1.10	0.28	0.04	0.11	0.09	0.21	0.29	0.02	97.43	0.07	0.03	0.33
Oxide	Na₂O	MgO	Al₂O₃	SiO₂	P₂O₅	SO₃	Cl	K₂O	CaO	Fe₂O₃	CuO	SrO
Mass fraction/wt%	1.25	0.39	0.07	0.19	0.17	0.43	0.24	0.02	96.92	0.06	0.02	0.24

图1 牡蛎壳的热重曲线图(A)和牡蛎壳煅烧前后的XRD图谱(B)

Fig. 1 TGA curve of oyster shell (A) and XRD patterns of oyster shell before and after calcination (B)

表2 牡蛎壳煅烧前后的物理特性

Table 2 Physical property of oyster and calcined oyster

Adsorbents	BET area/ (m²·g^-1)	Pore size/nm	Zeta potential/mV	Size/ nm
Oyster shell	4.32	6.53	-31.0	836
Calcined oyster shell	4.93	6.22	-19.1	4156

图2 吸附时间对Pb(II)(A)和MO(B)在bio-CaCO3上吸附的影响

Fig. 2 Effect of adsorption time on the sorption of Pb(II) (A) and MO (B) by bio-CaCO3 T=25 ℃, [Pb(II)]initial =753×10-6, m/V=0.2 g/L, and [NaClO4]=0.01 mol/L, pH=5.0

图3 Bio-CaCO3吸附Pb(II)的假一级(A)、假二级(B)和颗粒扩散模型(C)的动力学拟合曲线

Fig. 3 Pseudo-first-order (A), pseudo-second-order (B), and Intraparticle diffusion model (C) fitting for Pb(II) sorption by bio-CaCO3 T=25 ℃, [Pb(II)]initial=753×10-6, msorbent/Vsolvent=0.2 g/L, and [NaClO4]= 0.01 mol/L

表3 Bio-CaCO3吸附Pb(II)的动力学参数

Table 3 Kinetic parameters of Pb(II) sorption by bio-CaCO3

Pseudo-first-order model			Pseudo-second-order model
R²	κ₁/min^-1	q_e/(mg∙g^-1)	R²	κ₂/min^-1	q_e/(mg∙g^-1)
0.477	0.00225	600.94	0.998	2.61×10^-5	2092.05

表4 Bio-CaCO3吸附Pb(II)的颗粒扩散模型参数

Table 4 Intraparticle diffusion model constants and correlation coefficient for Pb(II) sorption by bio-CaCO3

K_d1/(mg∙g^-1∙min^-1/2)	K_d2/(mg∙g^-1∙min^-1/2)	K_d3/(mg∙g^-1∙min^-1/2)	C₁	C₂	C₃	R₁²	R₂²	R₃²
470.71	77.0	8.55	-220.39	1034.38	1747.0	1.0	0.95	0.78

图4 pH (A)和离子强度(B)对bio-CaCO3吸附Pb(II)的影响

Fig. 4 Effects of pH (A) and ionic strength (B) on Pb(II) sorption by bio-CaCO3 T=25 ℃, [Pb(II)]initial=10×10-6, pH=5.0, m/V=0.2 g/L

图5 Bio-CaCO3对Pb(II)的吸附等温线

Fig. 5 Adsorption isothermals of Pb(II) on bio-CaCO3 pH=5.0, m/V = 0.2 g/L and [NaClO4] = 0.01 mol/L

表5 Bio-CaCO3吸附Pb(II)的Langmuir和Freundlich模型参数

Table 5 Parameters of Pb(II) sorption by bio-CaCO3 for Langmuir and Freundlich constants models

T/℃	Langmuir			Freundlich
T/℃	Q_m/ (mg∙g^-1)	K_L/ (L∙mg^-1)	R²	K_F/ (mg∙g^-1)	n	R²
25	1775.33	0.041	0.992	415.3	4.1	0.898
35	1415.94	0.059	0.998	441.1	5.1	0.876
50	1237.35	0.063	0.986	421.8	5.6	0.885

图6 Bio-CaCO3吸附不同浓度Pb(II)的分配系数与温度的变化曲线

Fig. 6 Plots of distribution coefficient against temperature for Pb(II) adsorption with different concentrations by bio-CaCO3 pH=5.0, m/V = 0.2 g/L and [NaClO4]= 0.01 mol/L

图7 Bio-CaCO3吸附Pb(II)后的XRD图谱(A)和白铅矿PbCO3结构图(B)

Fig. 7 XRD patterns of bio-CaCO3 after Pb(II) sorption (A) and structure image of cerussite (B)

图8 Bio-CaCO3吸附Pb(II)前(A)和吸附后(B, C)的SEM照片

Fig. 8 SEM images of bio-CaCO3 before (A) and after Pb(II) sorption (B, C)

表6 Bio-CaCO3吸附Pb(II)的热力学参数

Table 6 Thermodynamic parameters for the adsorption of Pb(II) on bio-CaCO3

[Pb(II)]_initial/ (mol∙L^-1)	ΔH^θ/ (kJ∙mol^-1)	ΔS^θ/ (J∙mol^-1∙K^-1)	ΔG^θ/(kJ∙mol^-1)
[Pb(II)]_initial/ (mol∙L^-1)	ΔH^θ/ (kJ∙mol^-1)	ΔS^θ/ (J∙mol^-1∙K^-1)	298 K	308 K	323 K
9.09×10^-4	-8.24	-14.92	-3.79	-3.64	-3.42
1.36×10^-3	-7.85	-16.35	-2.98	-2.81	-2.57
1.82×10^-3	-8.29	-19.33	-2.53	-2.33	-2.04
2.27×10^-3	-8.09	-20.06	-2.11	-1.91	-1.61
2.73×10^-3	-7.42	-18.98	-1.76	-1.57	-1.29
3.18×10^-3	-7.71	-20.77	-1.52	-1.31	-1.00
3.41×10^-3	-5.87	-15.04	-1.39	-1.23	-1.01
Average	-7.64	-17.92	-2.30	-2.11	-1.85

表7 Bio-CaCO3对Pb(II)吸附能力与其他吸附剂的比较

Table 7 Comparison of Pb(II) adsorption capacity of Bio-CaCO3 with other adsorbents

Adsorbents	C_{s max}/(mg·g^-1)	pH	T/K	Ref.
Activated carbon	21.80	6.0	303	[30]
GMZ bentonite	23.83	5.2	293	[31]
S_3.9%-g-C₃N₄	52.63	4.5	328	[32]
GO	937.65	4.4	298	[33]
r-GO	92.99	4.4	298	[33]
Tianjin oyster shell without calcination	1591	5.0	298	[14]
Guangzhou calcined oyster shell	1067	~7	298	[13]
Rushan calcined oyster shell	1775	5.0	298	This work

图9 Bio-CaCO3与活性炭对MO的去除效率

Fig. 9 MO removal percentage of bio-CaCO3 and activated carbon

图10 Bio-CaCO3吸附MO前(A)和吸附后(B)的SEM照片

Fig. 10 SEM images of bio-CaCO3 before (A) and after (B) MO sorption

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生物源碳酸钙对污水中Pb(II)和甲基橙吸附行为的研究

High-efficiency Biogenic Calcium Carbonate for Adsorption of Pb(II) and Methyl Orange from Wastewater

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