葡甲胺功能化rGO/MWCNTs-OH复合气凝胶的制备及对硼的吸附

doi:10.16085/j.issn.1000-6613.2023-0727

摘要/Abstract

摘要：

气凝胶在吸附领域具有很好的应用前景。本文采用水热合成法和冷冻干燥法制备出葡甲胺功能化还原氧化石墨烯/羟基化碳纳米管气凝胶应用于盐湖卤水除硼，研究了吸附剂对水溶液中硼的吸附行为，吸附过程符合拟二级动力学和Freundlich等温吸附模型。当初始硼浓度为1000mg/L、pH为10、吸附时间为9h、温度298K时，最大吸附量为33.64mg/g。响应面法可以预测实验结果并优化反应条件，在最佳条件下硼吸附量为32.91mg/g。吸附机理分析表明，吸附过程主要是吸附剂上的—OH官能团与B的络合作用。吸附剂经过三次吸附-脱附实验，仍对B有较高吸附容量。吸附剂具有良好的抗共存盐干扰性，在真实卤水中吸附性能良好，吸附量为23.87mg/g。该气凝胶对于从盐湖卤水和废水中提硼具有潜在的价值。

关键词: 葡甲胺, 氧化石墨烯, 碳纳米管, 硼, 响应面法

Abstract:

Aerogels have promising applications in the field of adsorption. In this study, methylglucamine-functionalized reduced graphene oxide/hydroxylated carbon nanotube aerogels were prepared by hydrothermal synthesis and freeze-drying method for boron removal from salt lake brines. The adsorption behavior of the adsorbent on boron in aqueous solution was investigated, and the adsorption process was in accordance with the pseudo-second-order kinetic model and Freundlich isothermal adsorption model. The maximum adsorption amount was 33.64mg/g when the initial boron concentration was 1000mg/L, pH was 10, the adsorption time was 9h and the temperature was 298K. The response surface method could predict the experimental results and optimize the reaction conditions, and the boron adsorption amount was 32.91mg/g under the optimal conditions. The adsorption mechanism analysis showed that the adsorption process mainly consisted of the complexation of the —OH functional group on the adsorbent with B. The adsorbent still had a high adsorption capacity for B after three adsorption-desorption experiments. The adsorbent had good resistance to coexisting salt interference and good adsorption performance in real brine with an adsorption capacity of 23.87mg/g. This aerogel was potentially valuable for boron extraction from salt lake brines and wastewater.

Key words: methylglucamine, graphene oxide, carbon nanotubes, boron, response surface methodology

中图分类号:

TQ424

潘彤彤, 崔香梅. 葡甲胺功能化rGO/MWCNTs-OH复合气凝胶的制备及对硼的吸附[J]. 化工进展, 2024, 43(6): 3386-3397.

PAN Tongtong, CUI Xiangmei. Preparation of methylglucamine-functionalized rGO/MWCNTs-OH composite aerogels and its adsorption of boron[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3386-3397.

图/表 20

图1 NGM气凝胶制备流程图

图2 水凝胶

图3 GM和NGM的SEM图像

图4 NGM的N2吸附-脱附等温线及孔径分布

表1 MIP测试数据总结

参数	数值
孔容积/mL·g^-1	8.3203
总孔面积/m²·g^-1	1.346
中值孔径（V）/μm	66.92
中值孔径（A）/μm	10.05
平均孔径/μm	24.73
堆积密度/g·mL^-1	0.1103
表观密度/g·mL^-1	1.3364
孔隙率/%	91.75

图5 气凝胶的应力-应变曲线

图6 气凝胶的水接触角

图7 pH对NGM气凝胶吸附性能的影响（C0=1000mg/L，t=9h，T=298K）

图8 初始硼浓度对NGM吸附性能的影响及吸附等温线(pH=10，t=9h，T=298K)

表2 NGM对硼酸的吸附的Langmuir和Freundlich模型拟合数据（T=298K）

Langmuir等温线模型				Freundlich等温线模型
Q_m/mg·g^-1	K_L/L·mg^-1	R²		K_F	n	R²
52.91	0.0012	0.8422		0.3264	1.5287	0.9819

图9 吸附时间对NGM吸附性能的影响及吸附动力学(pH=10，t=9h，T=298K)

表3 NGM上吸附硼的动力学模型参数（T=298K）

拟一级动力学模型				拟二级动力学模型				颗粒内扩散模型
Q_e(calc)/mg·g^-1	k₁/min^-1	R²		Q_e(calc)/mg·g^-1	k₂	R²		k_d1	R²	k_d2	R²
54.27	0.4038	0.9567		71.94	0.001357	0.9898		14.41	0.9923	11.62	0.9978

图10 共存离子对NGM吸附性能影响

表4 响应面因素和水平

因素	代码	单位	代码水平
因素	代码	单位	-1	0	1
pH	A	—	7.5	8	8.5
初始硼浓度	B	mg·L^-1	900	1000	1100
吸附时间	C	—	9	10	11
温度	D	K	293	298	303
响应值	吸附量	mg·g^-1

表5 NGM气凝胶对硼酸的吸附能力的方差分析

项目	平方和	自由度	均方	F	显著水平	显著性
模型	583.74	14	41.70	340.71	<0.0001	显著
A-pH	0.035	1	0.035	0.28	0.6051
B-C₀	0.045	1	0.045	0.37	0.5566
C-t	2.73	1	2.73	22.31	0.0006
D-T	2.49	1	2.49	20.38	0.0009
AB	1.35	1	1.35	11.04	0.0068
AC	0.0003062	1	0.0003062	0.002502	0.9610
AD	0.12	1	0.12	1.02	0.3353
BC	0.033	1	0.033	0.27	0.6122
BD	0.13	1	0.13	1.04	0.3288
CD	0.0001563	1	0.0001563	0.001277	0.9721
A²	287.66	1	287.66	2350.61	<0.0001
B²	0.78	1	0.78	6.41	0.0279
C²	0.35	1	0.35	2.89	0.1172
D²	1.79	1	1.79	14.65	0.0028
残差	1.35	11	0.12
失拟项	1.30	10	0.13	2.89	0.4305	不显著
绝对误差	0.045	1	0.045
总和	585.09	25
C.V.%=1.45	R²=0.9977		调整R²=0.0.9948		预测R²=0.9840

图11 不同因素之间相互作用的三维曲面图

表6 盐湖卤水的组成成分

盐湖	pH	组分含量/mg·L^-1
盐湖	pH	K⁺	Ca²⁺	Mg²⁺	Li⁺	Cl^-	SO₄^{2 -}	B
No.1	6.75	2539	1081	634.2	116.1	56800	16556	30.19
No.2	7.87	1989	3010	2025	4.137	164065	31720	31.59

表7 盐湖卤水调pH前后组成成分

项目	No.1含量/mg·L^-1								No.2含量/mg·L^-1
项目	pH	K⁺	Ca²⁺	Mg²⁺	Li⁺	B	Cl^-	$S O 4 2 -$	pH	K⁺	Ca²⁺	Mg²⁺	Li⁺	B	Cl^-	SO₄^2-
调pH前	6.75	2539	1081	634.2	116.1	30.19	56800	16556	7.87	1989	3010	2025	4.137	31.59	164065	31720
调pH后	10.01	2315	921.6	294.3	104.3	16.99	55670	15600	10.02	1644	2771	131.1	3.221	4.209	160195	30918

表7 盐湖卤水调pH前后组成成分

项目	No.1含量/mg·L^-1								No.2含量/mg·L^-1
项目	pH	K⁺	Ca²⁺	Mg²⁺	Li⁺	B	Cl^-	$S O 4 2 -$	pH	K⁺	Ca²⁺	Mg²⁺	Li⁺	B	Cl^-	SO₄^2-
调pH前	6.75	2539	1081	634.2	116.1	30.19	56800	16556	7.87	1989	3010	2025	4.137	31.59	164065	31720
调pH后	10.01	2315	921.6	294.3	104.3	16.99	55670	15600	10.02	1644	2771	131.1	3.221	4.209	160195	30918

图12 吸附前后气凝胶的FTIR和XPS谱图

图13 NGM气凝胶的再生性能

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