Recovery of hydrochloric acid using positively-charged nanofiltration membrane with selective acid permeability and acid resistance.

An acid-recovering nanofiltration (NF) membrane with both acid resistance and selective acid permeability was fabricated via a water-based coating process for the recovery of hydrochloric acid. To achieve this, a thermally cross-linked branched-polyethyleneimine (b-PEI) layer was introduced to a loose polyethersulfone NF membrane by dip-coating of b-PEI and an epoxy linker and heat treatment in a sealed oven with a high-humidity atmosphere. The resulting membrane displayed a positive surface charge with a zeta potential, and exhibited a rejection performance order of MgCl2> MgSO4> NaCl > Na2SO4 characteristic of positive-charge-separation membranes. Mg rejection and Cl permeation experiments showed that the selective permeation of hydrochloric acid was achieved with Mg rejection above 95% and Cl permeation above 70%, and this allowed the acid to be recovered by obtaining permeate at the same pH as the feed. Moreover, the NF membrane maintained selective separation performance and flow rate for a month.

Recovery of sulfuric acid aqueous solution from copper-refining sulfuric acid wastewater using nanofiltration membrane process.

We used a nanofiltration (NF) membrane process to produce purified aqueous sulfuric acid from copper-refining sulfuric acid wastewater. Wastewater generated from a copper-refining process was used to explore the membrane performances and acid stabilities of six commercial NF membranes. A combination of permeate flux, sulfate permeation, and metal ion rejection clearly showed that two polyamide membranes and a polyacrylonitrile-based membrane achieved recovery of a purified sulfuric acid solution. Acid-stability and long-term performance tests showed that the polyamide membranes were unsuitable for copper-refining wastewater treatment because of their low acid stabilities. In contrast, the polyacrylonitrile-based composite membrane showed excellent acid stability, and gave greater than 90% metal ion rejection, with the exception of calcium ions, for 430 d. We also evaluated the recovery performance in 1 ton/d pilot-scale process using wastewater from copper-refining process; 90% metal ion rejection was achieved, with the exception of calcium ions, even at 95% recovery rate.