Surface-modified polyvinyl alcohol (PVA) membranes for pervaporation dehydration of epichlorohydrin (ECH), isopropanol (IPA), and water ternary feed mixtures Shivshankar Chaudhari a , YongSung Kwon a , MinYoung Shon a, *, SeungEun Nam b , YouIn Park b a Department of Industrial Chemistry, Pukyong National University, San 100, Yongdang-Dong, Nam-Gu, Busan 608-739, South Korea b Center for membranes, Korea Research Institute of Chemical Technology, 141 Gajeong-ro, Yuseong-gu, Daejeon 305-600, South Korea A R T I C L E I N F O Article history: Received 13 June 2019 Received in revised form 29 July 2019 Accepted 1 September 2019 Available online xxx Keywords: Pervaporation Surface modification Poly (vinyl alcohol) (PVA) (PVAm) Epichlorohydrin Poly (vinyl amine) Silicotungstic acid (STA) A B S T R A C T Conventional distillation failed to separate a ternary azeotropic mixture of ECH, IPA and water (50/30/ 20 w/w, %) exist in the epoxy resin manufacturing process. Thus, we prepared a PVA-tetraethyl orthosilicate organic–inorganic hybrid membrane and modified the membrane by layer-by-layer deposition of a PVAm/silicotungstic acid polyelectrolyte for the pervaporation (PV) dehydration of ECH/ IPA/water mixtures. In PV experiments at 30  C, the flux decreased from 0.14 to 0.05 kg m 2 h 1 and separation factor increased from and 2099 to 13,320 with TEOS addition in the PVA membrane was observed. And for the layer by layer deposition on PVA-TEOS (4) membranes flux increased and separation factor decreased from 0.14 to 0.28 kg m 2 h 1 and 2099 to 416 with the number of layer of deposition were observed respectively. On varying the feed water content from 20 to 10 wt. %, the pervaporation flux at 30  C decreased from 0.22 to 0.0066 kg m 2 h 1 and the separation factor increased from 1061 to 9094 was observed. By applying the Arrhenius equation, permeation activation energies of ECH and IPA (97.42 and 111.96 kJ mol-1, respectively) are higher than that of water (40.88 kJ mol 1 ) were reported for the layer by layer membrane. © 2019 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved. Introduction Epichlorohydrin (ECH) is made up of organochlorine moieties and epoxide ring, is an extremely susceptible electrophilic compound primarily employed in the manufacturing of epoxy resins, plastics and glycerol [1,2]. The polymerization of ECH with phenol gives an epoxy resin product. The bisphenol-A (BPA) and isopropyl alcohol (IPA) is served as the solvent and excess of ECH is charge in the reaction batch to adjust the molecular weight of the finished epoxy resin yield. In the final stages of reaction; a chlorine-containing impurities and ECH/IPA/water mixture as byproducts are present along with the finished product epoxy resin. A vacuum distillation can be used to recover the ECH and IPA and again recycled in the form of raw materials. However, during the recycling; the impurity content concentrate gradually in the byproduct mixture. This is because, ECH and IPA exhibit an azeotropic mixture with water at ECH/IPA/water, 50:30:20 (wt. %) composition; in the recovery of IPA and ECH by vacuum distillation that restrict the recovery process to purify an IPA and ECH at desired purity level. In addition not only point of energy consumption and reuse of recycled materials concern, but ECH can also have serious environmental hazards if it released as waste in environment, because ECH is carcinogenic compound [3,4]. Adsorption method can be used to dehydrate the ECH/IPA/water, 50:30:20 (wt. %) azeotropic composition, however the adsorption of water from the mixture demands a high capacity adsorption bed depending on epoxy resin production process, 0.6 ton of ECH/IPA/ water mixture generated per 1 ton of epoxy resin production. Additionally, frequent regeneration of adsorption bed was required to remove the contaminants through series of different step, that may further increase the operation cost of epoxy resin production process [5]. On other hand, PV-distillation is a hybrid process consist of synergy between the feature of pervaporation (PV) and distillation process individually. PV can successfully remove the moisture from recovery mixture and by the distillation, recovery and purification of ECH and IPA can be increase energy efficiency and competitive- ness of product. By this approach the costs associated with the * Corresponding author. E-mail address: myshon@pknu.ac.kr (M. Shon). https://doi.org/10.1016/j.jiec.2019.09.007 1226-086X/© 2019 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved. Journal of Industrial and Engineering Chemistry xxx (2019) xxx–xxx G Model JIEC 4766 No. of Pages 11 Please cite this article in press as: S. Chaudhari, et al., Surface-modified polyvinyl alcohol (PVA) membranes for pervaporation dehydration of epichlorohydrin (ECH), isopropanol (IPA), and water ternary feed mixtures, J. Ind. Eng. Chem. (2019), https://doi.org/10.1016/j.jiec.2019.09.007 Contents lists available at ScienceDirect Journal of Industrial and Engineering Chemistry journal homepa ge: www.elsev ier.com/locate/jie c