Fabrication of polyamide thin film composite membranes using aliphatic tetra-amines and terephthaloyl chloride crosslinker for organic solvent nanofiltration

Abstract

Given the huge significance of organic solvents in several industrial processes, the use of membranes for recovering the solvents has evolved into an industrially viable process. The current work has been focused on studying the effect of minor changes in the chemistry of the reacting monomers on the organic solvent nanofiltration/solvent resistance nanofiltration (OSN/SRNF) performance of the membranes. The two aliphatic amines with varying aliphatic chain lengths between primary and secondary amines were selected for this purpose. Based on the structure of the resultant active layer, the Janus nanofiltration performance of the membrane was evaluated. The two membranes, 4A-TPC@crosslinked PAN and 4A-3P@crosslinked PAN were fabricated by using two different tetra-amines, 4A (N,N′-bis(3-aminopropyl)ethylenediamine) and 4A-3P (N,N′-Bis(2-aminoethyl)-1,3-propanediamine) crosslinked with terephthaloyl chloride (TPC) on a crosslinked polyacryonitrile (PAN) support through interfacial polymerization (IP). The presence of multiple hydrophobic –CH2– groups in the structures of the aliphatic amines 4A and 4A-3P develops hydrophobic sites in the hydrophilic polyamide active layers of the membranes. In addition, 4A has two secondary amino groups separated by ethylene (–CH2–CH2–) groups, whereas in 4A-3P, the two secondary amino groups are separated by propylene (–CH2–CH2–CH2–) leading to variation in the structural features and performance of the two membranes. Both membranes were fully characterized by several membrane characterization techniques and applied for OSN/SRNF using both polar (methanol, ethanol, and isopropanol) and non-polar (n-hexane and toluene) solvents. Different dyes (Congo red, Eriochrome black T, and Methylene blue) were used as model solutes during the filtration experiment. The 4A-3P-TPC@crosslinked PAN showed n-hexane and toluene flux of 109.9 LMH and 95.5 LMH, respectively. The Congo red (CR) showed the highest rejection, reaching 99.1% for the 4A-TPC@Crosslinked PAN membrane and 98.8% for the 4A-3P-TPC@Crosslinked PAN membrane.