Al2O3和SiC微滤膜的疏水改性及其油固分离性能研究

doi:10.11949/0438-1157.20190176

摘要/Abstract

摘要：

以正辛基三乙氧基硅烷和乙醇分别作为改性剂和溶剂，采用接枝聚合法对平均孔径为500 nm的Al₂O₃膜和SiC膜进行疏水改性，考察了改性剂浓度、改性液温度和改性时间对膜表面疏水效果的影响，并对比了疏水改性前后两种陶瓷膜的表面性质及疏水改性后的油固分离性能，进行了反冲实验和稳定性测试。结果表明，两种陶瓷膜材料在改性剂浓度为0.2 mol·L^-1，改性液温度为40℃，改性时间为12 h时，疏水改性效果最好，得到的疏水Al₂O₃膜和SiC膜的水接触角分别为134°±1°和140°±1°，经改性后的SiC膜的疏水效果优于Al₂O₃膜。在油固分离实验中，疏水Al₂O₃膜和SiC膜均对固体炭黑有良好的截留性能，但疏水改性对SiC膜的油品通量提升更为显著，两种膜的稳态通量分别为1134 L·m^-2·h^-1和1408 L·m^-2·h^-1。反冲操作对疏水SiC膜的通量恢复更有利。

关键词: 陶瓷膜, 碳化硅, 油固分离, 疏水改性

Abstract:

The Al₂O₃ film and the SiC film with an average pore diameter of 500 nm were hydrophobically modified by n-octyltriethoxysilane and ethanol as modifiers and solvents, respectively. The concentration and modification of the modifer were investigated by graft polymerization. The wettability and oil-solid separation performance of the modified Al₂O₃ and SiC MF membranes were investigated. The backflushing operation and long-term stability test for the modified membranes were conducted. Under the optimal modification conditions with grafting agent concentration of 0.2 mol·L^-1, grafting temperature of 40℃ and grafting time of 12 h，the water contact angles (WCAs) of the modified Al₂O₃ and SiC membranes were as high as 134°±1°and 140°±1°, respectively. It was found that the hydrophobic SiC membrane showed higher hydrophobicity than that of the Al₂O₃ membrane. For oil-solid separation experiments, both modified membranes exhibited excellent rejection to impurities in oil phase. However, the hydrophobic modification had a more significant effect on the flux of SiC membrane. The fluxes of hydrophobic Al₂O₃ and SiC MF membranes were 1134 L·m^-2·h^-1 and 1408 L·m^-2·h^-1, respectively, with transmembrane pressure of 0.25 MPa. Backflushing operation was beneficial to the flux recovery of ceramic membrane, especially hydrophobic SiC membrane.

Key words: ceramic membrane, SiC, oil-solid separation, hydrophobic modification

中图分类号:

TQ 028.8

李秀秀, 魏逸彬, 谢子萱, 漆虹. Al₂O₃和SiC微滤膜的疏水改性及其油固分离性能研究[J]. 化工学报, 2019, 70(7): 2737-2747.

Xiuxiu LI, Yibin WEI, Zixuan XIE, Hong QI. Hydrophobic modification of Al₂O₃ and SiC microfiltration membranes for oil-solid separation[J]. CIESC Journal, 2019, 70(7): 2737-2747.

图/表 18

表1 陶瓷膜规格参数

Table 1 Specification parameters of ceramic membranes

Membrane

Porosity/%

Outer/inner diameter

/mm

Effective membrane area/cm²

Al₂O₃

图1 陶瓷膜疏水改性示意图

Fig.1 Schematic diagram for hydrophobic modification of ceramic membrane

图2 陶瓷膜错流过滤装置

Fig.2 Schematic diagram of cross-flow filtration apparatus

图3 Al2O3和SiC微滤膜的水接触角随时间的变化

Fig.3 Time dependence of water contact angles for Al2O3 and SiC membranes

图4 Al2O3和SiC微滤膜的纯水通量

Fig.4 Pure water fluxes of Al2O3 and SiC membranes

图5 改性剂浓度对陶瓷膜疏水效果的影响

Fig.5 Effect of grafting agent concentration on water contact angles of Al2O3 and SiC membranes

图6 改性液温度对陶瓷膜疏水效果的影响

Fig.6 Effect of grafting temperature on water contact angles of Al2O3 and SiC membranes

图7 改性时间对陶瓷膜疏水效果的影响

Fig.7 Effect of grafting time on water contact angles of Al2O3 and SiC membranes

表2 接枝聚合法制备疏水陶瓷膜的疏水性对比

Table 2 Comparison of hydrophobicity of hydrophobic ceramic membranes prepared via chemical grafting method

Membranes	Average pore size	WCA	Application	Ref.
Al₂O₃	0.76 μm	133°	NaCl	[10]
TiO₂-Al₂O₃	12.9 nm	116°	NaCl	[24]
Al₂O₃	0.7 μm	130°	NaCl	[25]
γ/α-Al₂O₃	5 nm	134°	H₂/CO₂	[26]
ZrO₂	0.2 μm	134°	W/O	[27]
Al₂O₃	0.5 μm	134°	W/O	this work
SiC	0.5 μm	140°	W/O	this work

表3 改性前后陶瓷膜的质量损失以及—OH官能团含量

Table 3 Mass loss within 110—230℃ and hydroxyl group content of ceramic membranes before and after modification

Membranes	Mass loss(110—230℃)/%	n_(-OH)/(mmol·g^-1)
A-500	0.0197	0.0394
A-500HB	0.0154	0.0308
S-500	0.0757	0.151
S-500HB	0.0128	0.0256

表4 改性前后陶瓷膜的接触角及表面自由能

Table 4 Contact angles and surface free energy of ceramic membranes before and after modification

Ceramic membrane	Contact angle/(°)			Surface free energy/(mN·m^-1)
Ceramic membrane	Water	Ethylene glycol	Diiodo-methane	Dispersive component	Non-dispersive component	Total
A-500	23	24	19	42.3	7.67	50.0
A-500HB	134	55	39	36.6	3.01	39.6
S-500	10	20	8	44.5	7.39	51.9
S-500HB	140	58	42	35.4	2.68	38.1

图8 改性前后陶瓷膜的表面SEM照片和EDS能谱图

Fig.8 SEM images and EDS spectra of ceramic membranes before and after modification

图9 改性前后陶瓷膜的断面SEM图

Fig.9 Cross-section SEM images of ceramic membranes before and after modification

图10 改性前后陶瓷膜的FTIR谱图

Fig.10 FTIR spectra of ceramic membranes before and after modification

图11 改性前后陶瓷膜在不同跨膜压差下的稳态通量

Fig.11 Trans-membrane pressure dependence of steady-state fluxes for ceramic membranes before and after modification

图12 经疏水陶瓷膜分离前后的原料液和渗透液光学照片

Fig.12 Optical photographs for oil-solid mixture (a), filtrates obtained by using membrane A-500HB (b) and filtrates obtained by using membrane S-500HB (c)

图13 反冲操作对疏水陶瓷膜过滤过程的影响

Fig.13 Effect of backflushing on filtration process of hydrophobic ceramic membranes

图14 操作时间对疏水陶瓷膜通量的影响

Fig.14 Effect of operation time on oil flux of hydrophobic ceramic membranes

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Al₂O₃和SiC微滤膜的疏水改性及其油固分离性能研究

Hydrophobic modification of Al₂O₃ and SiC microfiltration membranes for oil-solid separation

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