Effects of synthesis times and Si-Al ratio of SAPO-34 zeolite membrane on ethanol dehydration performance

doi:10.11949/0438-1157.20201790

Abstract

Abstract:

SAPO-34 zeolite membrane has been favored by many scholars because of its unique pore structure and excellent stability. Most of the studies focused on catalysis, adsorption and gas separation, while there are few studies on liquid separation. In this paper, SAPO-34 zeolite membranes were prepared through primary and secondary synthesis on the surface of Al₂O₃ hollow fiber support, respectively. The effects of four different Si-Al ratios on the structure and performance of the SAPO-34 zeolite membranes were investigated. The obtained membranes were used for the pervaporation dehydration of ethanol solution. The effects of operating temperature, ethanol concentration and synthesis times on the separation properties of the obtained membranes were investigated. The results showed that the SAPO-34 zeolite membrane with Si-Al ratio of 0.5 and secondary synthesis had a continuous and dense separation layer, resulting in the best pervaporation performance. The separation factor of ethanol (90%) - water (10%) at 60℃ was 1170, and the flux was 0.9 kg/(m²·h).

Key words: Si-Al ratio, secondary growth method, SAPO-34 zeolite membrane, pervaporation, ethanol dehydration

摘要：

SAPO-34分子筛膜因其独特的孔道结构和优异的稳定性被广大学者所青睐，目前的研究大多集中在催化、吸附和气体分离等方面，而关于其在液体分离中的研究鲜少报道。本文在Al₂O₃中空纤维支撑体表面分别一次和二次合成制备了SAPO-34分子筛膜，考察了四种不同硅铝比对SAPO-34分子筛膜结构形貌和性能的影响，并用于乙醇溶液的渗透汽化脱水，考察了操作温度、原料液中乙醇浓度以及分子筛合成次数对分离效果的影响。研究结果表明，硅铝比为0.5的二次合成的SAPO-34分子筛膜具有连续而致密的分离层和良好的渗透汽化分离性能，60℃下对乙醇（90%）-水（10%）的分离因子可以达到1170，渗透通量为0.9 kg/(m²·h)。

关键词: 硅铝比, 二次生长法, SAPO-34分子筛膜, 渗透汽化, 乙醇脱水

CLC Number:

TQ 028.8

Wanyue DING, Xiaohua MA. Effects of synthesis times and Si-Al ratio of SAPO-34 zeolite membrane on ethanol dehydration performance[J]. CIESC Journal, 2021, 72(8): 4410-4417.

丁婉月, 马晓华. 合成次数及硅铝比调控SAPO-34分子筛膜的乙醇脱水性能[J]. 化工学报, 2021, 72(8): 4410-4417.

Figures/Tables 9

Fig.1 SEM images of SAPO-34 zeolite membrane and Al2O3 hollow fiber support

Fig.2 Surface SEM images of SAPO-34 zeolite membranes with four different Si-Al ratios after synthesis twice

Fig.3 XRD patterns of SAPO-34 zeolite powder, SAPO-34 zeolite membrane and Al2O3 hollow fiber support

Fig.4 Pervaporation properties of SAPO-34 zeolite membranes with the primary synthesis

Fig.5 Pervaporation properties of SAPO-34 zeolite membranes with the secondary synthesis

Fig.6 Effect of temperature on pervaporation performances of SAPO-34 zeolite membrane

Fig.7 Flux of SAPO-34 zeolite membrane in the process of pervaporation varies with temperature

Fig.8 Effect of feed concentration on pervaporation performances of SAPO-34 zeolite membrane

Fig. 9 Pervaporation performance vs. time of SAPO-34 zeolite membrane in ethanol (90%) -water (10%) system

References 26

1	谢博远, 马晓华, 许振良. MOFs与碳纳米管双重改性渗透汽化复合膜及其性能研究[J]. 华东理工大学学报(自然科学版), 2020, 46(5): 608-612.
	Xie B Y, Ma X H, Xu Z L. MOFs and carbon nanotubes double modified pervaporation composite membrane and its properties[J]. Journal of East China University of Science and Technology, 2020, 46(5): 608-612.
2	王洋, 庄黎伟, 马晓华, 等. 中空纤维膜渗透汽化过程中Dean涡强化传质的CFD模拟[J]. 化工学报, 2018, 69(11): 4655-4662.
	Wang Y, Zhuang L W, Ma X H, et al. CFD simulation of Dean vortex enhanced mass transfer in hollow fiber membrane pervaporation[J]. CIESC Journal, 2018, 69(11): 4655-4662.
3	仲华, 谢浩然, 马晓华, 等. UIO-66-NH₂渗透汽化复合膜制备及乙醇脱水[J]. 膜科学与技术, 2019, 39(3): 79-86.
	Zhong H, Xie H R, Ma X H, et al. Preparation of UIO-66-NH₂ pervaporation composite membrane and its application in dehydration of ethanol[J]. Membrane Science and Technology, 2019, 39(3): 79-86.
4	Magalad V T, Gokavi G S, Nadagouda M N, et al. Pervaporation separation of water-ethanol mixtures using organic-inorganic nanocomposite membranes[J]. The Journal of Physical Chemistry C, 2011, 115(30): 14731-14744.
5	韩小龙, 张杏梅, 马晓迅, 等. 碳纳米管填充PDMS膜的渗透汽化性能[J]. 化工学报, 2014, 65(1): 271-278.
	Han X L, Zhang X M, Ma X X, et al. Pervaporation performance of carbon nanotube filled PDMS membranes[J]. CIESC Journal, 2014, 65(1): 271-278.
6	Han Y J, Wang K H, Lai J Y, et al. Hydrophilic chitosan-modified polybenzoimidazole membranes for pervaporation dehydration of isopropanol aqueous solutions[J]. Journal of Membrane Science, 2014, 463: 17-23.
7	Lok B M, Messina C A, Patton R L, et al. Crystalline silicoaluminophosphates: US4440871[P]. 1984-04-03.
8	Han L, Guo L L, Xue S Z, et al. Polyacrylamide-assisted synthesis of hierarchical porous SAPO-34 zeolites with excellent MTO catalytic performance[J]. Microporous and Mesoporous Materials, 2021, 311: 110676.
9	Wang Y, Gao J Q, Dong L, et al. Tuning SAPO-34 with a tailor-designed zwitterionic amino acid for improved MTO performance[J]. Microporous and Mesoporous Materials, 2021, 310: 110590.
10	Yang G J, Han J, Huang Y J, et al. Busting the efficiency of SAPO-34 catalysts for the methanol-to-olefin conversion by post-synthesis methods[J]. Chinese Journal of Chemical Engineering, 2020, 28(8): 2022-2027.
11	Akhgar S, Towfighi J, Hamidzadeh M. MTO performance over seed-assisted SAPO-34 zeolites synthesized by reducing template consumption[J]. Journal of Materials Research and Technology, 2020, 9(6): 12126-12136.
12	Erucar I, Keskin S. Computational assessment of MOF membranes for CH₄/H₂ separations[J]. Journal of Membrane Science, 2016, 514: 313-321.
13	Kosinov N, Gascon J, Kapteijn F, et al. Recent developments in zeolite membranes for gas separation[J]. Journal of Membrane Science, 2016, 499: 65-79.
14	Huang Y, Wang L, Song Z N, et al. Growth of high-quality, thickness-reduced zeolite membranes towards N₂/CH₄ separation using high-aspect-ratio seeds[J]. Angewandte Chemie International Edition, 2015, 54(37): 10843-10847.
15	Jiang J, Islam S, Dong Q B, et al. Deposition of an ultrathin palladium (Pd) coating on SAPO-34 membranes for enhanced H₂/N₂ separation[J]. International Journal of Hydrogen Energy, 2020, 45(58): 33648-33656.
16	Rehman R U, Song Q N, Peng L, et al. A facile coating to intact SAPO-34 membranes for wet CO₂/CH₄ mixture separation[J]. Chemical Engineering Research and Design, 2020, 153: 37-48.
17	Makertihartha I G B N, Kencana K S, Dwiputra T R, et al. Silica supported SAPO-34 membranes for CO₂/N₂ separation[J]. Microporous and Mesoporous Materials, 2020, 298: 110068.
18	宋庆南, 张玉亭, 张春, 等. 二乙胺导向合成中空纤维负载型SAPO-34分子筛膜[J]. 化工学报, 2019, 70(6): 2316-2324.
	Song Q N, Zhang Y T, Zhang C, et al. Diethylamine template-directed synthesis of hollow fiber supported SAPO-34 membranes[J]. CIESC Journal, 2019, 70(6): 2316-2324.
19	郝阿辉, 刘晓红, 刘秀凤, 等. 微波辅助二次生长法合成SAPO-34分子筛膜与关键影响因素[J]. 化工学报, 2017, 68(2): 716-722.
	Hao A H, Liu X H, Liu X F, et al. Synthesis of SAPO-34 membranes and critical influence factors in microwave-assisted secondary growth[J]. CIESC Journal, 2017, 68(2): 716-722.
20	Alam S F, Kim M Z, Kim Y J, et al. A new seeding method, dry rolling applied to synthesize SAPO-34 zeolite membrane for nitrogen/methane separation[J]. Journal of Membrane Science, 2020, 602: 117825.
21	Chen Y, Zhang Y T, Zhang C, et al. Fabrication of high-flux SAPO-34 membrane on α-Al₂O₃ four-channel hollow fibers for CO₂ capture from CH₄[J]. Journal of CO₂ Utilization, 2017, 18: 30-40.
22	Mohammadi T, Asarehpour S, Samei M. Effects of synthesis temperature and support material on CO₂ and CH₄ permeation through SAPO-34 membranes[J]. Separation Science and Technology, 2012, 47(16): 2320-2330.
23	陈阳, 张玉亭, 张春, 等. 中空纤维SAPO-34分子筛膜的制备及渗透汽化性能[J]. 南京工业大学学报(自然科学版), 2018, 40(1): 46-51.
	Chen Y, Zhang Y T, Zhang C, et al. Preparation and pervaporation performance of hollow fiber supported SAPO-34 zeolite membranes[J]. Journal of Nanjing Tech University (Natural Science Edition), 2018, 40(1): 46-51.
24	Baker R W, Wijmans J G, Huang Y. Permeability, permeance and selectivity: a preferred way of reporting pervaporation performance data[J]. Journal of Membrane Science, 2010, 348(1/2): 346-352.
25	吴琦刚, 韶晖, 钟璟, 等. Sn-silicalite-2分子筛膜的制备及其渗透汽化性能研究[J]. 现代化工, 2019, 39(12): 94-99.
	Wu Q G, Shao H, Zhong J, et al. Synthesis of Sn-silicalite-2 molecular sieve membrane and study on its pervaporation performance[J]. Modern Chemical Industry, 2019, 39(12): 94-99.
26	Ahn S H, Yu X W, Manthiram A. “Wiring” Fe-nx-embedded porous carbon framework onto 1D nanotubes for efficient oxygen reduction reaction in alkaline and acidic media[J]. Advanced Materials, 2017, 29(26): 1606534.

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