硼掺杂二氧化硅杂化膜的制备及渗透汽化脱盐性能

doi:10.11949/0438-1157.20201182

摘要/Abstract

摘要：

以1，2-双（三乙氧基硅基）乙烷（BTESE）和硼酸为前体，通过溶胶-凝胶法制备了硼掺杂的二氧化硅（B-BTESE-SiO₂）杂化膜。采用FTIR、XRD、XPS、TEM、SEM等系列表征手段对合成溶胶及膜的结构和形貌进行了分析，结果表明：硼元素成功掺杂进入SiO₂骨架中，形成了水热稳定的B—O—Si键，能明显影响膜表面的微观结构、亲疏水性、膜孔径大小从而提高膜的脱盐性能和稳定性。当溶胶中的H₃BO₃/BTESE比为0.25时所优化制备SiO₂膜的亲水性最强，脱盐过程中活化能最低，传质阻力最小，膜孔径约为0.61 nm，故表现出最佳的脱盐性能。在60℃以3.5%（质量） NaCl溶液为进料液时，该膜的水通量高达16.5 kg·m^-2·h^-1，盐截留率近乎100%，并且表现出优异的长时间稳定性（>168 h）和高浓度盐水溶液[4.2%~15.0%（质量） NaCl]脱盐性能，在海水淡化和高盐废水处理等领域具有潜在的应用前景。

关键词: 二氧化硅, 膜, 脱盐, 水热稳定性, 活化能, 高盐废水

Abstract:

Using 1, 2-bis(triethoxysilyl)ethane (BTESE) and boric acid as precursors, a boron-doped silica (B-BTESE- SiO₂) hybrid membrane was successfully prepared by the sol-gel method. The boron element was confirmed to be successfully doped into silica frameworks during the sol-gel procedure by various characterizations of FTIR, XRD, XPS, TEM and SEM, which would form hydrothermally stable Si—O—B bonds. It could significantly influence membrane surface microstructure, hydrophilicity and pore size of B-BTESE-SiO₂ hybrid membranes, and then improve their desalination performance and stability. The B-BTESE-SiO₂ membranes prepared under the optimized condition of H₃BO₃/BTESE ratio as 0.25 in the sols, exhibited the strongest hydrophilicity, lowest mass transfer resistance (lowest activation energy during desalination process) and applicable pore size of 0.61 nm, thus demonstrating the highest desalination performance. The high water flux up to 16.5 kg·m^-2·h^-1 and NaCl rejection of nearly 100% were achieved for this SiO₂ membrane towards 3.5%(mass) NaCl feed solution at 60℃. Moreover, this membrane showed excellent long-term stability (>168 h) and desalination performance for high-salinity [4.2%—15.0%(mass) NaCl] solutions, which had promising potential applications in seawater desalination and high-salinity wastewater treatment.

Key words: silica, membrane, desalination, hydrothermal stability, activation energy, high-salinity wastewater

中图分类号:

TQ 028.8

张锐, 邵琦, 张华宇, 金泽龙, 张小亮. 硼掺杂二氧化硅杂化膜的制备及渗透汽化脱盐性能[J]. 化工学报, 2021, 72(4): 2317-2327.

ZHANG Rui, SHAO Qi, ZHANG Huayu, JIN Zelong, ZHANG Xiaoliang. Fabrication of boron-doped hybrid silica membranes for pervaporation desalination[J]. CIESC Journal, 2021, 72(4): 2317-2327.

图/表 15

图1 B-BTESE-SiO2溶胶合成示意图

Fig.1 Schematic diagram of the synthesis of B-BTESE-SiO2 sol

图2 B-BTESE-SiO2溶胶的粒径分布

Fig.2 Particle size distribution of B-BTESE-SiO2 sols

图3 B-BTESE-SiO2凝胶粉末的红外光谱

Fig.3 FTIR spectra of B-BTESE-SiO2 gel powders

图4 B-BTESE-0.25 SiO2凝胶粉末的XPS谱图

Fig.4 XPS survey and the deconvolutions of B 1s and Si 2p spectra (inset) for B-BTESE-0.25 SiO2 powders

图5 B-BTESE-SiO2凝胶粉末的XRD谱图

Fig.5 XRD patterns of B-BTESE-SiO2 gel powders

图6 B-BTESE-0.25 SiO2凝胶粉末的TEM图和SAED图（插图）

Fig.6 TEM images and the corresponding SAED pattern (inset) of B-BTESE-0.25 SiO2 gel powders

图7 B-BTESE-SiO2杂化膜的表面和截面SEM图

Fig.7 Surface and cross-sectional SEM images of B-BTESE-SiO2 hybrid membranes

图8 硼掺杂量对SiO2杂化膜的脱盐性能的影响

Fig.8 The desalination performance of B-BTESE-SiO2 hybrid membranes towards pure water and 3.5%(mass) NaCl solutions at 30—75℃

图9 B-BTESE-SiO2杂化膜的水接触角

Fig.9 Water contact angle of B-BTESE-SiO2 hybrid membranes

图10 B-BTESE-SiO2杂化膜的渗透通量[(a),(b)]和渗透率[(c)、(d)]与温度的Arrhenius关系曲线

Fig.10 Arrhenius plots of temperature dependent water permeation flux [(a), (b)] and permeance [(c), (d)] of B-BTESE- SiO2 hybrid membranes towards pure water and 3.5%(mass) NaCl solutions

表1 B-BTESE-SiO2杂化膜渗透汽化脱盐过程的活化能

Table 1 Activation energy of B-BTESE-SiO2 hybrid membranes for PV desalination processes

Membrane	E_j/(kJ·mol^-1)		E_p/(kJ·mol^-1)		(E_j-E_p)/(kJ·mol^-1)
Membrane	pure H₂O	3.5%(质量) NaCl	pure H₂O	3.5%(质量) NaCl	pure H₂O	3.5%(质量) NaCl
BTESE	16.57±2.18	18.23±1.85	-26.64±2.10	-24.99±1.86	43.21	43.22
B-BTESE-0.05	13.80±1.57	17.40±1.74	-29.42±1.58	-25.82±1.77	43.22	43.22
B-BTESE-0.13	12.83±1.61	17.04±1.90	-30.39±1.38	-26.18±1.41	43.22	43.22
B-BTESE-0.25	10.71±1.54	14.27±1.40	-32.50±1.38	-28.95±1.41	43.21	43.22
B-BTESE-0.50	19.44±0.64	19.00±1.10	-23.73±0.35	-24.22±1.39	43.17	43.22
B-BTESE-1.00	19.98±2.80	20.02±1.80	-23.24±2.75	-23.20±1.74	43.22	43.22

图11 B-BTESE-0.25 SiO2粉末的N2吸附-脱附曲线及其孔径分布

Fig.11 N2 adsorption-desorption isotherms (close symbols for adsorption, open symbols for desorption) and pore size distribution (inset) of B-BTESE-0.25 gel powder

图12 B-BTESE-0.25杂化膜在60℃时于不同浓度NaCl溶液中的脱盐性能

Fig.12 The desalination performance of B-BTESE-0.25 hybrid membrane towards NaCl solutions with different concentrations at 60℃

图13 BTESE和B-BTESE-0.25杂化膜的稳定性

Fig.13 Stability of BTESE and B-BTESE-0.25 hybrid membrane towards 3.5%(mass) NaCl solution at 60℃

表2 SiO2膜渗透汽化脱盐性能比较

Table 2 Comparison of PV desalination performance of SiO2 membranes

Membrane	c(NaCl)/%(mass)	T/℃	J/(kg·m^-2·h^-1)	P/(mol·m^-2·s^-1·Pa^-1)	Rej/%	Ref.
PVA/SiO₂	0.2	60	20.6	16×10^-6	99	[30]
BTESEthy-SiO₂	0.2	70	14.2	7×10^-6	99.6	[31]
PVA/SiO₂	3.5	60	12.3	9.7×10^-6	99.9	[32]
ES40-SiO₂	3.5	60	17.8	14.1×10^-6	99	[33]
Co-TEOS-SiO₂	3.5	60	11.3	9.7×10^-6	99.9	[27]
Ni/TEOS-SiO₂	3.5	25	2.5	23.9×10^-6	97	[34]
La₂₅Y₇₅-BTESE-SiO₂	3.5	60	15.6	12.4×10^-6	99.9	[10]
P123/TEOS-SiO₂	3.5	60	8	6.9×10^-6	99.9	[35]
CTAB/SiO₂	4	25	2.6	12.9×10^-6	99.9	[36]
P123/TEOS-TEVS-SiO₂	15	60	9.2	8.7×10^-6	98.6	[37]
B-BTESE-SiO₂	0.3	60	24.5	19×10^-6	100	本工作
B-BTESE-SiO₂	3.5	60	16.5	13.1×10^-6	100	本工作
B-BTESE-SiO₂	15	60	9.6	8.4×10^-6	99.9	本工作

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