Recovery of isobutanol from esterified wastewater by PDMS composite membrane
(2.Nanjing Jiusi High-Tech Co., Ltd., Nanjing, Jiangsu, China 211816)
【Abstract】The esterification reaction of acetic acid and isobutanol produces isobutyl acetate, which generates a large amount of wastewater containing isobutanol. The conventional biochemical treatment is heavy and wastes resources. The effects of isobutanol concentration on the swelling degree and separation performance of polydimethylsiloxane (PDMS) membrane, the operating parameters of the pervaporation process, and the effect of isobutyl acetate on the recovery of isobutanol by PDMS membrane were studied. The results show that with the isobutanol concentration increases from 1% (mass) to 3% (mass), the swelling degree of the PDMS membrane increases first and then stabilizes, the flux of isobutanol increases, and the separation factor is about 15. When the operating temperature increases from 30 °C to 60 °C, the flux increases, the separation factor of isobutanol decreases, and the total apparent activation energy is 33.87 kJ/mol. With the increase in the flow rate, the isobutanol flux is stable while the separation factor increases slightly. The trace amounts of isobutyl acetate can promote the recovery of isobutanol by the membrane. The recovery rate of isobutanol by PDMS membrane is greater than 94.0%, and the concentration of isobutanol in the retentate can be reduced to 0.1% (mass). The research results can provide a basis for PDMS composite membrane to treat low-concentration organic solvent wastewater.
【Keywords】 PDMS composite membrane; esterification wastewater; isobutanol; pervaporation;
(Translated by KANG GD)
 Jayamani I, Cupples A M. Effect of isobutanol on toluene biodegradation in nitrate amended, sulfate amended and methanogenic enrichment microcosms [J]. Biodegradation, 2013, 24 (5): 657–663.
 Schaefer C E, Yang X, Pelz O, et al. Anaerobic biodegradation of iso-butanol and ethanol and their relative effects on BTEX biodegradation in aquifer materials [J]. Chemosphere, 2010, 81 (9): 1111–1117.
 Gai H, Lin K, Feng Y, et al. Conceptual design of an extractive distillation process for the separation of an azeotropic mixture of n-butanol–isobutanol–water [J]. Chinese Journal of Chemical Engineering, 2018, 26 (10): 44–51.
 Xing W H, Gu X H. High-Performance Membrane Materials and Membrane Technology [M]. Beijing: Chemical Industry Press, 2017: 369 (in Chinese).
 Shi B L, Jia L N, Zhang X. Polydimethylsiloxane and Pervaporation Separation Membrane [M]. Beijing: Science Press, 2017: 228 (in Chinese).
 Shao P, Huang R. Polymeric membrane pervaporation [J]. Journal of Membrane Science, 2007, 287 (2): 162–179.
 Liu H, Wang N, Zhao C, et al. Membrane materials in the pervaporation separation of aromatic/aliphatic hydrocarbon mixtures—a review [J]. Chinese Journal of Chemical Engineering, 2018, 26 (1): 1–16.
 Zong C X, Ding X B, Nan J P, et al. Research progress of membrane VOCs gas separation technology [J]. Membrane Science and Technology, 2020, 40 (1): 284–293 (in Chinese).
 Yang W, Zhou H, Zong C, et al. Study on membrane performance in vapor permeation of VOC/N2 mixtures via modified constant volume/variable pressure method [J]. Separation and Purification Technology, 2019, 223 (1): 24–30.
 Castro-Muñoz R, Galiano F, Fíla V, et al. Mixed matrix membranes (MMMs) for ethanol purification through pervaporation: current state of the art [J]. Reviews in Chemical Engineering, 2019, 35 (5): 565–590.
 Hou Y F, Xu Y, Li H P, et al. Research progress of pervaporation membrane modification technology [J]. Membrane Science and Technology, 2018, 38 (1): 136–142 (in Chinese).
 Yong W, Xiang M, Tengfei M, et al. Green recovery of hazardous acetonitrile from high-salt chemical wastewater by pervaporation [J]. Journal of Cleaner Production, 2018, 197 (1): 742–749.
 Han X L, Zhang X M, Ma X X, et al. Modified ZSM-5/polydimethylsiloxane mixed matrix membranes for ethanol/water separation via pervaporation [J]. Polymer Composites, 2016, 37 (4): 1282–1291.
 Mou C X, Zhang S Y, Zou J, et al. Separation of n-butyl acetate in water with PDMS membrane filled with hydrophobic SiO2 [J]. CIESC Journal, 2017, 68 (6): 2407–2414 (in Chinese).
 Wang X, Chen J, Fang M, et al. ZIF-7/PDMS mixed matrix membranes for pervaporation recovery of butanol from aqueous solution [J]. Separation and Purification Technology, 2016, 163 (4): 39–47.
 Xue C, Du G Q, Chen L J, et al. A carbon nanotube filled polydimethylsiloxane hybrid membrane for enhanced butanol recovery [J]. Scientific Reports, 2014, 4 (1): 5925–5932.
 Li S, Chen Z, Yang Y, et al. Improving the pervaporation performance of PDMS membranes for n-butanol by incorporating silane-modified ZIF-8 particles [J]. Separation and Purification Technology, 2019, 215 (4): 163–172.
 Hu M J, Wu Z Y, Sun L, et al. Improving pervaporation performance of PDMS membranes by interpenetrating polymer network for recovery of bio-butanol [J]. Separation and Purification Technology, 2019, 228 (1): 160–178.
 Jee K Y, Lee Y T. Preparation and characterization of siloxane composite membranes for n-butanol concentration from ABE solution by pervaporation [J]. Journal of Membrane Science, 2014, 456 (4): 1–10.
 Chovau S, Gaykawad S, Straathof A J J, et al. Influence of fermentation by-products on the purification of ethanol from water using pervaporation [J]. Bioresource Technology, 2011, 102 (2): 1669–1674.
 Liu G, Gan L, Liu S, et al. PDMS/ceramic composite membrane for pervaporation separation of acetone–butanol–ethanol (ABE) aqueous solutions and its application in intensification of ABE fermentation process [J]. Chemical Engineering and Processing: Process Intensification, 2014, 86 (4): 162–172.
 Grimaldi J, Imbrogno J, Kilduff J, et al. New class of synthetic membranes: organophilic pervaporation brushes for organics recovery [J]. Chemistry of Materials, 2015, 27 (11): 4142–4148.
 Liu Q G, Ma L X, Xiang S G. Chemical and Chemical Physical Property Data Manual: Organic Volume [M]. Beijing: Chemical Industry Press, 2013: 1103 (in Chinese).
 Hansen C M. Hansen Solubility Parameters: A User’s Handbook [M]//Boca Raton: CRC Press Inc., 2007: 546.
 Liu Y Q, Hu T T, Lu L Y, et al. Preparation of PDMS/ZSM-5 membrane and separation of n-butyl acetate and ethyl acetate in water by pervaporation [J]. CIESC Journal, 2020, 71 (2): 843–853 (in Chinese).
 J G Wijmans, R W Baker. The solution–diffusion model: a review [J]. Journal of Membrane Science, 1995, 107 (1): 1–21.
 Pan Y, Hang Y T, Zhao X H,, et al. Optimizing separation performance and interfacial adhesion of PDMS/PVDF composite membranes for butanol recovery from aqueous solution [J]. Journal of Membrane Science, 2019, 579 (4): 210–218.
 Zhang S Y, Zou J, Wei T Y, et al. Preparation of β-cyclodextrin/polyether copolyacetamide filling membrane and pervaporation separation of trace phenol in water [J]. CIESC Journal, 2016, 67 (11): 4662–4670 (in Chinese).
 Li S Y, Srivastava R, Parnas R S. Separation of 1-butanol by pervaporation using a novel tri-layer PDMS composite membrane [J]. Journal of Membrane Science, 2010, 363 (1/2): 287–294.
 Chen Z X, Gu F Y. Chemical Thermodynamics [M]. 3nd ed. Beijing: Chemical Industry Press, 2001: 335 (in Chinese).
 Wang X, Chen J, Fang M, et al. ZIF–7/PDMS mixed matrix membranes for pervaporation recovery of butanol from aqueous solution [J]. Separation and Purification Technology, 2016, 163 (4): 39–47.
 Segarceanu O, Leca M. Improved method to calculate Hansen solubility parameters of a polymer [J]. Progress in Organic Coatings, 1997, 31 (4): 307–310.
 Bonnet L, Rayez J C. Dynamical derivation of eyring equation and the second-order kinetic law [J]. International Journal of Quantum Chemistry, 2010, 110 (13): 2355–2359.
 Fariba S K, Toraj M, Fereshteh N. Fast, facile and scalable fabrication of novel microporous silicalite-1/PDMS mixed matrix membranes for efficient ethanol separation by pervaporation [J]. Separation and Purification Technology, 2019, 229 (10): 55–59.
 Bakhshi A, Mohammadi T, Aroujalian A. Pervaporation separation of binary and ternary mixtures with polydimethylsiloxane membranes [J]. Journal of Applied Polymer Science, 2008, 107 (3): 1777–1782.
 Zhou H L, Su Y, Yi S L, et al. Effects of acetone and ethanol on pervaporation of butanol [J]. CIESC Journal, 2010, 61 (5): 77–83 (in Chinese).
 Zhou H, Lv L, Liu G, et al. PDMS/PVDF composite pervaporation membrane for the separation of dimethyl carbonate from a methanol solution [J]. Journal of Membrane Science, 2014, 471 (11): 47–55.