ZSM-5沸石分子筛膜的制备及脱盐性能研究

doi:10.11949/0438-1157.20210527

摘要/Abstract

摘要：

淡水资源日益短缺，发展膜法海水淡化技术是满足世界淡水供应需求的重要途径，但是寻找合适的膜材料依然是人类面临的挑战。ZSM-5沸石分子筛膜（简称沸石膜）具有规则的孔道结构、合适的孔径尺寸（0.51~0.56 nm）以及可调变的硅铝比，在有机物脱水分离应用中展示了优异的选择性及良好的渗透性和稳定性。基于其孔径尺寸介于水分子和盐离子之间，其在海水淡化脱盐领域也具有应用潜力。在大孔α-Al₂O₃载体上采用二次生长法制备了ZSM-5沸石膜，考察了晶化时间与合成液的硅铝比对ZSM-5沸石膜成膜和渗透蒸发脱盐性能的影响，并采用XRD、SEM、EDS与水接触角表征了合成膜的相结构与结晶度、骨架组成表面特性等膜的结构性质。结果表明：通过二次水热法采用合成液摩尔配比为n（Al₂O₃）∶n（SiO₂）∶n（Na₂O）∶n（NaF）∶n（H₂O）=0.05∶1∶0.21∶1.01∶55的合成液在175℃下晶化48 h为最佳的合成条件，制备了Si/Al比为10、接触角为17.5°的亲水纯相致密ZSM-5沸石膜，并在75℃下对3.5%（质量）的NaCl水溶液进行了渗透蒸发测试，水的通量和盐离子截留率达到8.35 kg·m^-2·h^-1和99.99%，且性能在60 h的时间依存性测试后依然稳定，表现出了很高的海水淡化工业应用潜力。

关键词: ZSM-5沸石分子筛膜, 海水淡化, 渗透蒸发, 二次生长法, 膜

Abstract:

Freshwater resources are increasingly scarce, and membrane desalination technologies continue to develop to meet the world's freshwater supply needs. However, development of high performance membranes for this technology is still under way. ZSM-5 zeolite membrane has been widely used in dehydration of organics due to the uniformed pore structure, suitable pore size (0.51—0.56 nm) and adjustable Si/Al ratio. Considering its pore size is between the size of water molecules and most of the salts, it exhibits excellent selectivity and good permeability and stability in the application of organic matter dehydration and separation. In this work, ZSM-5 zeolite membrane was synthesized on the macroporous α-Al₂O₃ support using secondary growth method. The effects of crystallization time and Si/Al ratio of synthetic solution on membrane formation and desalination performance of ZSM-5 zeolite membrane were investigated. XRD, SEM, EDS and water contact angle characterizations were used to examine the phase structure and crystallinity, framework structure composition of the membranes. The results showed that, high performance ZSM-5 zeolite membrane with Si/Al ratio of 10 and contact angle of 17.5° was obtained with recipe of n(Al₂O₃)∶n(SiO₂)∶n(Na₂O)∶n(NaF)∶n(H₂O) = 0.05∶ 1∶0.21∶1.01∶55 at 175℃ for 48 h. The synthesized membrane was used for seawater desalination by pervaporation, and a high water flux of 8.35 kg·m^-2·h^-1 with ion rejection of 99.99% was obtained for the desalination of 3.5%(mass) NaCl aqueous solution at 75℃, indicating the ZSM-5 zeolite membrane possesses great potential for seawater desalination.

Key words: ZSM-5 zeolite membrane, desalination, pervaporation, secondary growth method, membrane

中图分类号:

TQ 028.8

李子祎,潘恩泽,王佳轩,鲁金明,杨建华. ZSM-5沸石分子筛膜的制备及脱盐性能研究[J]. 化工学报, 2021, 72(10): 5247-5256.

Ziyi LI,Enze PAN,Jiaxuan WANG,Jinming LU,Jianhua YANG. Preparation of ZSM-5 zeolite membrane and its application in desalination[J]. CIESC Journal, 2021, 72(10): 5247-5256.

图/表 15

图1 低硅铝比ZSM-5沸石膜制备过程示意图

Fig.1 Schematic diagram of ZSM-5 zeolite membrane preparation process

图2 ZSM-5沸石膜晶种层的SEM图和XRD谱图

Fig.2 SEM images and XRD patterns of the crystal seed layer of ZSM-5 zeolite membrane

图3 不同硅铝比合成液制备ZSM-5沸石膜的SEM图。Si/Al =7.5[(a)、(b)]、10 [(c)、(d)]、12.5[(e)、(f)]

Fig.3 SEM images of ZSM-5 zeolite membranes prepared by different Si-Al ratios of synthetic liquid. Si/Al =7.5[(a),(b)], 10 [(c),(d)], 12.5[(e),(f)]

图4 不同硅铝比合成液制备ZSM-5沸石膜的XRD谱图

Fig.4 XRD patterns of ZSM-5 zeolite membranes prepared by different Si-Al ratio of synthetic liquid

表1 不同条件下制备的ZSM-5沸石膜的渗透汽化乙酸脱水性能

Table 1 Pervaporation properties of ZSM-5 zeolite membrane prepared under different conditions

编号	硅铝比	渗透蒸发性能(50%(质量)乙酸水溶液)
编号	硅铝比	分离因子α	渗透通量/ (kg·m^-2·h^-1)
M1	7.5	224	0.78
M2	10	＞10000	2.00
M3	12.5	＞10000	0.64

图5 不同晶化时间制备ZSM-5沸石膜的SEM图:24 h [(a)、(b)]、36 h [(c)、(d)]、48 h[(e)、(f)]、72 h[(g)、(h)]

Fig.5 SEM images of ZSM-5 zeolite membranes prepared with different crystallization time: 24 h [(a),(b)],36 h [(c),(d)],48 h[(e),(f)],72 h[(g),(h)]

表2 不同晶化时间制备的ZSM-5沸石膜的渗透蒸发脱盐性能

Table 2 Pervaporation properties for desalination of ZSM-5 zeolite membrane prepared under different conditions

编号	合成条件				渗透蒸发脱盐性能
编号	晶种	晶化温度/℃	硅铝比	晶化时间/h	截留率/%	渗透通量/(kg·m^-2·h^-1)
M2	ZSM-5	175	10	48	99.99	8.35
M4	ZSM-5	175	10	24	99.98	5.84
M5	ZSM-5	175	10	36	99.97	6.63
M6	ZSM-5	175	10	72	99.92	7.15

图6 不同晶化时间制备ZSM-5沸石膜的XRD谱图

Fig.6 XRD patterns of ZSM-5 zeolite membrane prepared with different crystallization times

图7 ZSM-5沸石膜M2用于不同浓度NaCl水溶液的渗透汽化脱盐测试

Fig.7 Pervaporation desalination test of ZSM-5 zeolite membrane M2 in different concentration NaCl aqueous solution

图8 ZSM-5沸石膜M2在不同温度下对3.5%(质量) NaCl水溶液的渗透汽化脱盐测试

Fig.8 Pervaporation desalination test of ZSM-5 zeolite membrane M2 in 3.5%（mass） NaCl aqueous solution at different temperatures

图9 ZSM-5沸石膜M2用于3.5%(质量) NaCl水溶液渗透汽化脱盐的Arrhenius方程拟合图

Fig. 9 Arrhenius equation fitting diagram of ZSM-5 zeolite membrane for pervaporation desalination of 3.5%(mass) NaCl salt solution

图10 ZSM-5沸石膜M2对于75℃3.5%(质量) NaCl水溶液渗透汽化脱盐的时间依存性测试

Fig.10 Time dependence of ZSM-5 zeolite membrane M2 for pervaporation desalination of NaCl aqueous solution at 75°C

表3 模拟海水中的盐离子浓度

Table 3 Ion concentrations of simulated seawater

盐	浓度/(g·L^-1)
NaCl	24.53
Na₂SO₄	4.09
KCl	0.695
KBr	0.101
SrCl₂	0.025
MgCl₂	5.2
CaCl₂	1.16
NaHCO₃	0.201
H₃BO₃	0.027
NaF	0.03

图11 ZSM-5沸石膜M7对于75℃模拟海水渗透汽化脱盐测试

Fig. 11 Pervaporation desalination test of ZSM-5 membrane M7 in simulated seawater at 75℃

表4 不同种类无机分子筛膜的脱盐性能对比

Table 4 Comparison of desalination performance of different kinds of inorganic membranes

无机分子筛膜	膜厚度/μm	操作条件		渗透通量/ (kg·m^-2·h^-1)	离子截留率/%	文献
无机分子筛膜	膜厚度/μm	料液	温度/℃	渗透通量/ (kg·m^-2·h^-1)	离子截留率/%	文献
FAU	2.3	3.5%(质量)模拟海水	90	5.64	＞99.8	[29]
ZSM-5	3.5	3.5%(质量)NaCl溶液	75	5.5	90.0	[25]
Sil.-1	6	3.5%(质量)NaCl溶液	75	5	96	[25]
NaA	2	3.5%(质量)NaCl溶液	75	9.58	＞99.9	[30]
SOD	1	海水	177	3.5	99.99	[31]
NaA	4	海水	69	1.9	＞99.9	[27]
ZSM-5沸石膜 M2	3.5	3.5%(质量)NaCl溶液	75	8.35	＞99.9	本文
ZSM-5沸石膜 M7	3.5	模拟海水	75	6.92	＞99.9	本文

参考文献 31

1	Garcı́a-Rodrı́guez L. Renewable energy applications in desalination: state of the art[J]. Solar Energy, 2003, 75(5): 381-393.
2	Charcosset C. A review of membrane processes and renewable energies for desalination[J]. Desalination, 2009, 245(1/2/3): 214-231.
3	Feng X S, Huang R Y M. Liquid separation by membrane pervaporation: a review[J]. Industrial & Engineering Chemistry Research, 1997, 36(4): 1048-1066.
4	Chapman P D, Oliveira T, Livingston A G, et al. Membranes for the dehydration of solvents by pervaporation[J]. Journal of Membrane Science, 2008, 318(1/2): 5-37.
5	Shao P, Huang R Y M. Polymeric membrane pervaporation[J]. Journal of Membrane Science, 2007, 287(2): 162-179.
6	McLeary E E, Jansen J C, Kapteijn F. Zeolite based films, membranes and membrane reactors: progress and prospects[J]. Microporous and Mesoporous Materials, 2006, 90(1/2/3): 198-220.
7	Yu M, Noble R D, Falconer J L. Zeolite membranes: microstructure characterization and permeation mechanisms[J]. Accounts of Chemical Research, 2011, 44(11): 1196-1206.
8	Ladewig B P, Tan Y H, Lin C X C, et al. Preparation, characterization and performance of templated silica membranes in non-osmotic desalination[J]. Materials, 2011, 4(5): 845-856.
9	Liang B, Zhan W, Qi G G, et al. High performance graphene oxide/polyacrylonitrile composite pervaporation membranes for desalination applications[J]. Journal of Materials Chemistry A, 2015, 3(9): 5140-5147.
10	Yuan W H, Lin Y S, Yang W S. Molecular sieving MFI-type zeolite membranes for pervaporation separation of xylene isomers[J]. Journal of the American Chemical Society, 2004, 126(15): 4776-4777.
11	Wang Z B, Ge Q Q, Shao J, et al. High performance zeolite LTA pervaporation membranes on ceramic hollow fibers by dipcoating-wiping seed deposition[J]. Journal of the American Chemical Society, 2009, 131(20): 6910-6911.
12	Yamanaka N, Itakura M, Kiyozumi Y, et al. Acid stability evaluation of CHA-type zeolites synthesized by interzeolite conversion of FAU-type zeolite and their membrane application for dehydration of acetic acid aqueous solution[J]. Microporous and Mesoporous Materials, 2012, 158: 141-147.
13	Li X S, Kita H, Zhu H, et al. Synthesis of long-term acid-stable zeolite membranes and their potential application to esterification reactions[J]. Journal of Membrane Science, 2009, 339(1/2): 224-232.
14	Li J J, Li L Q. Organotemplate-free synthesis of ZSM-5 membrane for pervaporation dehydration of isopropanol[J]. Membrane Water Treatment, 2018, 10(5): 353-360.
15	Gao X, Zou X, Zhang F, et al. Eco-friendly fabrication of hydrophilic ZSM-5 membranes for alcohol upgrading[J]. Chemical Communications, 2013, 49(78): 8839-8841.
16	Zhu M H, Kumakiri I, Tanaka K, et al. Dehydration of acetic acid and esterification product by acid-stable ZSM-5 membrane[J]. Microporous and Mesoporous Materials, 2013, 181: 47-53.
17	Lai Z, Griselda B, Isabel D, et al. Microstructural optimization of a zeolite membrane for organic vapor separation[J]. Science, 2013, 300(5618): 456-460
18	Yang J, Li L, Li W, et al. Tuning aluminum spatial distribution in ZSM-5 membranes: a new strategy to fabricate high performance and stable zeolite membranes for dehydration of acetic acid[J]. Chemical Communications, 2014, 50(93): 14654-14657.
19	Li L Q, Yang J H, Li J J, et al. Synthesis of high performance mordenite membranes from fluoride-containing dilute solution under microwave-assisted heating[J]. Journal of Membrane Science, 2016, 512: 83-92.
20	Li L Q, Yang J H, Li J J, et al. High performance ZSM-5 membranes on coarse macroporous α-Al₂O₃ supports for dehydration of alcohols[J]. AIChE Journal, 2016, 62(8): 2813-2824.
21	Raza W, Wang J X, Yang J H, et al. Progress in pervaporation membranes for dehydration of acetic acid[J]. Separation and Purification Technology, 2021, 262: 118338.
22	刘秀凤, 徐凯, 张宝泉. ZSM-5和Fe-ZSM-5分子筛膜的合成与表面改性[J]. 化工学报, 2014, 65: 304-309.
	Liu X F, Xu K, Zhang B Q. Synthesis and surface modification of ZSM-5 and Fe-ZSM-5 zeolite membranes[J]. CIESC Journal, 2014, 65: 304-309.
23	Wu Y H, Tan H F, Li T M, et al. Pervaporation of aqueous solution of acetaldehyde through ZSM-5 filled PDMS composite membrane[J]. Chinese Journal of Chemical Engineering, 2012, 20(4): 625-632.
24	Duke M C, O'brien-Abraham J, Milne N, et al. Seawater desalination performance of MFI type membranes made by secondary growth[J]. Separation and Purification Technology, 2009, 68(3): 343-350.
25	Drobek M, Yacou C, Motuzas J, et al. Long term pervaporation desalination of tubular MFI zeolite membranes[J]. Journal of Membrane Science, 2012, 415/416: 816-823.
26	Cheng C H, Juttu G, Mitchell S F, et al. Synthesis, characterization, and growth rates of germanium silicalite-1 grown from clear solutions[J]. The Journal of Physical Chemistry B, 2006, 110(43): 21430-21437.
27	Cho C H, Oh K Y, Kim S K, et al. Pervaporative seawater desalination using NaA zeolite membrane: mechanisms of high water flux and high salt rejection[J]. Journal of Membrane Science, 2011, 371(1/2): 226-238.
28	Volkov A G, Paula S, Deamer D W. Two mechanisms of permeation of small neutral molecules and hydrated ions across phospholipid bilayers[J]. Bioelectrochemistry and Bioenergetics, 1997, 42(2): 153-160.
29	Zhou C, Zhou J J, Huang A S. Seeding-free synthesis of zeolite FAU membrane for seawater desalination by pervaporation[J]. Microporous and Mesoporous Materials, 2016, 234: 377-383.
30	Wang L, Yang J H, Wang J Q, et al. Microwave synthesis of NaA zeolite membranes on coarse macroporous α-Al₂O₃ tubes for desalination[J]. Microporous and Mesoporous Materials, 2020, 306: 110360.
31	Khajavi S, Jansen J C, Kapteijn F. Production of ultra pure water by desalination of seawater using a hydroxy sodalite membrane[J]. Journal of Membrane Science, 2010, 356(1/2): 52-57.

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