Application of PVA membrane filled with hydrophilic ZSM-5 molecular sieve on separation of water from ethyl acetate

doi:10.11949/0438-1157.20200577

Abstract

Abstract:

To remove trace water from ethyl acetate with low energy consumption and high efficiency, PVA/ZSM-5 mixed matrix membranes (MMMs) were prepared by adding the hydrophilic ZSM-5 zeolite material into polyvinyl alcohol (PVA) polymer. The morphology, physicochemical properties of MMMs were characterized by SEM, FTIR, XRD, TGA and contact angle. The swelling behavior of the membrane materials in various solutions and the influence of filler content, feed temperature and feed concentration on the performance of pervaporation separation of ethyl acetate and water mixture were investigated by single factor experiments. The results showed that ZSM-5 particles were evenly dispersed into PVA polymer. In addition to the inherent hydrophilicity of ZSM-5, there is also a hydrogen bond interaction between ZSM-5 and PVA, but there is no chemical interaction between them. With the increase of feed concentration, the permeate flux increased, while the separation factor decreased. With the increase of feed temperature, the permeate flux and separation factor increased. With the increase of ZSM-5 filling content, the permeate flux and separation factor increased first and then decreased. When filling content of ZSM-5 was 6%(mass), the permeation flux and separation factor reached the maximum value of 1231 g/(m²·h) and 6072, respectively, which was 2.9 times higher than the pure PVA membrane separation index (PSI). The newly designed PVA/ZSM-5 mixed matrix membranes (MMMs) can be used at the industrial level for the dehydration of ethyl acetate and other similar compounds.

Key words: polyvinyl alcohol, ZSM-5, mixed matrix membrane, pervaporation, dehydration

摘要：

为了实现低能耗且高效分离乙酸乙酯中的低含量水分，选用亲水型纳米ZSM-5沸石分子筛材料作为改性剂，填充到聚乙烯醇(PVA)聚合物中制备PVA/ZSM-5混合基质膜(MMMs)。采用SEM、FTIR、XRD、TGA和接触角测量仪等对膜材料的形态、物化性质进行表征分析，并考察膜材料在不同溶液中的溶胀行为以及通过单因素实验探究填料含量、进料温度、进料浓度对渗透汽化分离乙酸乙酯和水混合物的性能的影响。结果表明，ZSM-5与PVA结合紧密且分散均匀，除了ZSM-5固有的亲水性外，ZSM-5还与PVA分子之间存在氢键相互作用，但两者之间并没有发生化学作用。随着进料浓度的增加，渗透通量增大，而分离因子呈减小趋势；随着进料温度升高，渗透通量和分离因子均增大；随着ZSM-5填充量的增加，渗透通量和分离因子均先增大后减小。当ZSM-5填充量为6%(质量)时，渗透通量和分离因子达到最大值，分别为1231 g/(m²·h)和6072，相比纯PVA膜分离指数(PSI)提高了2.9倍。新设计的PVA/ZSM-5混合基质膜(MMMs)可在工业水平上用于乙酸乙酯及其他类似化合物的脱水。

关键词: 聚乙烯醇, ZSM-5, 混合基质膜, 渗透蒸发, 脱水

CLC Number:

TQ 028.8

Wei WANG, Xueying JIANG, Yue LI, Liping SU, Yun ZOU, Zhangfa TONG. Application of PVA membrane filled with hydrophilic ZSM-5 molecular sieve on separation of water from ethyl acetate[J]. CIESC Journal, 2020, 71(8): 3807-3818.

王维, 姜雪迎, 李悦, 苏丽萍, 邹昀, 童张法. 亲水型ZSM-5分子筛填充PVA膜及分离乙酸乙酯/水的应用[J]. 化工学报, 2020, 71(8): 3807-3818.

Figures/Tables 17

Fig.1 SEM images of surface of PVA with different ZSM-5 loadings

Fig.2 Cross-section SEM images of PVA with different ZSM-5 loadings

Fig.3 EDS analysis((a)—(c)) and C,O,Al,Si element mapping ((d)—(g)) of MMMs

Fig.4 FTIR spectra of ZSM-5 and filled PVA membranes with various ZSM-5 loading

Fig.5 XRD patterns of ZSM-5 and filled PVA membranes with various ZSM-5 loading

Fig.6 Water contact angles of filled PVA membrane with various ZSM-5 loading

Fig.7 TGA curves of ZSM-5 and filled PVA membrane with various ZSM-5 loading

Fig.8 DTG curves of ZSM-5 and filled PVA membrane with various ZSM-5 loading

Fig.9 Swelling degree of PVA/ZSM-5 filled membrane in 4%(mass) water-ethyl acetate feed at different temperatures

Fig.10 Water uptake and EAc uptake of PVA / ZSM-5 filled membrane

Table 1 Solubility parameters of PVA, EAc and water

Material	δ_d/(J/cm³)^1/2	δ_p/(J/cm³)^1/2	δ_h/(J/cm³)^1/2	δ/(J/cm³)^1/2
PVA	22.31	19.92	28.23	41.13
EAc	18.05	5.89	9.17	21.08
water	12.27	7.38	34.15	36.29

Fig.11 Comparison of solubility parameters between MMMs and feed components

Fig.12 Effect of ZSM-5 loading in membrane on pervaporation performance of 4%(mass) water-ethyl acetate feed

Fig.13 Effect of feed concentration on pervaporation performance

Fig.14 Effect of feed temperature on pervaporation performance for 4%(mass) water-ethyl acetate feed

Fig.15 Arrhenius curves of temperature and permeation flux

Table 2 Pervaporation performance of PVA/ZSM-5 MMMs compared with membranes reported in dehydration of water-EAc mixture

Membrane	Feed temperature/℃	Feed water concentration/%(mass)	Total flux/(g/(m²·h))	Separation factor	Ref.
PVA(crosslinked by TAC)	50	2.5	54	4000	[8]
PFSA-TEOS/PAN	40	2	186	496	[14]
PU	30	8	147	42	[36]
PVA/ceramic	60	2.6	192	1265	[13]
NaA zeolite	50	2	315	16300	[37]
PVA/PAN	40	2	34.5	7270	[38]
MXene/CS	50	2	1400	4898	[39]
PBI/PEI	60	2	820	2478	[1]
CS	40	2	336	6270	[40]
UiO-66@graphene oxide	50	2	3233	6951	[31]
PVA/ZSM-5(6)	30	4	1231	6072	this work

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