Application of Hybrid Membrane Processes Coupling Separation and Biological or Chemical Reaction in Advanced Wastewater Treatment.

The rapid urbanization and water shortage impose an urgent need in improving sustainable water management without compromising the socioeconomic development all around the world. In this context, reclaimed wastewater has been recognized as a sustainable water management strategy since it represents an alternative water resource for non-potable or (indirect) potable use. The conventional wastewater remediation approaches for the removal of different emerging contaminants (pharmaceuticals, dyes, metal ions, etc.) are unable to remove/destroy them completely. Hybrid membrane processes (HMPs) are a powerful solution for removing emerging pollutants from wastewater. On this aspect, the present paper focused on HMPs obtained by the synergic coupling of biological and/or chemical reaction driven processes with membrane processes, giving a critical overview and particular emphasis on some case studies reported in the pertinent literature. By using these processes, a satisfactory quality of treated water can be achieved, permitting its sustainable reuse in the hydrologic cycle while minimizing environmental and economic impact.

Application of NF Polymeric Membranes for Removal of Multicomponent Heat-Stable Salts (HSS) Ions from Methyl Diethanolamine (MDEA) Solutions.

This study presents an efficient and scalable process for removing the heat-stable salts (HSS) ions from amine solution while recovering methyl diethanolamine (MDEA) solution for its reuse in gas sweetening plants. The presence of HSS in the amine solution causes the loss of solvent capacity, foaming, fouling, and corrosion in gas sweetening units so their removal is crucial for a more well-performing process. Furthermore, the recovery of the amine solution can make the sweetening step a more sustainable process. In this study, for the first time, the removal of a multicomponent mixture of HSS from MDEA solution was investigated via a nanofiltration process using flat-sheet NF-3 membranes. The impact of operating parameters on salts and amine rejection, and flux, including the operating pressure, HSS ions concentration, and MDEA concentration in the feed solution was investigated. Results based on the nanofiltration of an amine stream with the same composition (45 wt.% MDEA solution) as that circulating in a local gas refinery (Ilam Gas refinery), demonstrated a removal efficiency of HSS ions in the range from 75 to 80% and a MDEA rejection of 0% indicating the possibility of reusing this stream in the new step of gas sweetening.

Treatment of Flue Gas Desulfurization Wastewater by an Integrated Membrane-Based Process for Approaching Zero Liquid Discharge.

An integrated membrane process for the treatment of wastewaters from a flue gas desulfurization (FGD) plant was implemented on a laboratory scale to reduce their salt content and to produce a water stream to be recycled in the power industry. The process is based on a preliminary pretreatment of FGD wastewaters, which includes chemical softening and ultrafiltration (UF) to remove Ca2+ and Mg2+ ions as well as organic compounds. The pretreated wastewaters were submitted to a reverse osmosis (RO) step to separate salts from water. The RO retentate was finally submitted to a membrane distillation (MD) step to extract more water, thus increasing the total water recovery factor while producing a high-purity permeate stream. The performance of RO and MD membranes was evaluated by calculating salts rejection, permeate flux, fouling index, and water recovery. The investigated integrated system allowed a total recovery factor of about 94% to be reached, with a consequent reduction of the volume of FGD wastewater to be disposed, and an MD permeate stream with an electrical conductivity of 80 µS/cm, able to be reused in the power plant, with a saving in fresh water demand.

Photothermal Membrane Distillation for Seawater Desalination.

Thermoplasmonic effects notably improve the efficiency of vacuum membrane distillation, an economically sustainable tool for high-quality seawater desalination. Poly(vinylidene fluoride) (PVDF) membranes filled with spherical silver nanoparticles are used, whose size is tuned for the aim. With the addition of plasmonic nanoparticles in the membrane, the transmembrane flux increases by 11 times, and, moreover, the temperature at the membrane interface is higher than bulk temperature.

Preparation of Pd-Loaded Hierarchical FAU Membranes and Testing in Acetophenone Hydrogenation.

Pd-loaded hierarchical FAU (Pd-FAU) membranes, containing an intrinsic secondary non-zeolitic (meso)porosity, were prepared and tested in the catalytic transfer hydrogenation of acetophenone (AP) to produce phenylethanol (PE), an industrially relevant product. The best operating conditions were preliminarily identified by testing different solvents and organic hydrogen donors in a batch hydrogenation process where micron-sized FAU seeds were employed as catalyst support. Water as solvent and formic acid as hydrogen source resulted to be the best choice in terms of conversion for the catalytic hydrogenation of AP, providing the basis for the design of a green and sustainable process. The best experimental conditions were selected and applied to the Pd-loaded FAU membrane finding enhanced catalytic performance such as a five-fold higher productivity than with the unsupported Pd-FAU crystals (11.0 vs. 2.2 mgproduct gcat(-1)·h(-1)). The catalytic performance of the membrane on the alumina support was also tested in a tangential flow system obtaining a productivity higher than that of the batch system (22.0 vs. 11.0 mgproduct gcat(-1)·h(-1)).

Selective separation of copper(II) and nickel(II) from aqueous media using the complexation-ultrafiltration process.

The polyethylenimine (PEI) as complexing agent was used to study the complexation-ultrafiltration (CP-UF) process in the selective removal of Cu(II) from Ni(II) contained in aqueous media. Preliminary tests showed that optimal chemical conditions for Cu(II) and Ni(II) complexation by the PEI polymer were pH>6.0 and 8.0, respectively, and polymer/metal weight ratio of 3.0 and 6.0, respectively. The effect of some important operating parameters on process selectivity was studied by performing UF tests at different parameters: pH, polymer/metal weight ratio, transmembrane pressure (TMP), and membrane cut-off in a batch experimental set-up. It was observed that process selectivity was achieved by choosing the pH value for obtaining a preferential copper complexation (pH 6.0), and the polymer/metal ratio needed to bound only the copper ion (3.0). The selective separation by UF tests was performed by using both a laboratory aqueous solution and a real aqueous effluent (water from Emoli torrent, Rende (CS)). The Iris 30 membrane at TMP of 200 kPa (2 bar) for both aqueous media gave the best results. A complete nickel recovery was reached, and copper recovery was the highest for this membrane (94% and 92%). Besides at this pressure, a lower water amount was needed to obtain total nickel recovery by diafiltration. A little higher membrane fouling was obtained by using the river effluent due to the presence of dissolved organic and inorganic matter.

Metal ions removal from wastewater or washing water from contaminated soil by ultrafiltration-complexation.

In the present paper a process for removal of ions from wastewater or from washing water of contaminated soil by using the weakly basic water-soluble polymer polyethylenimine (PEI) as chelating agent and the Cu(2+) ion as model in combination with an ultrafiltration process was investigated. The complexing agent was preliminarily tested to establish the best operative conditions of the process. Next, ultrafiltration tests by using five different membranes were realised to check membrane performance like flux and rejection. Finally, the possibility for recovering and recycling the polymer was tested in order to obtain an economically sustainable process. Obtained results showed that complexation conditions depends on pH: indeed, at a pH>6 PEI-Cu(2+) complexes are formed, while at pH<3 the decomplexation reaction takes place. Saturation condition is 0.333 mg Cu(2+)/mg PEI, meaning a ratio PEI/Cu(2+)=3(w/w). UF tests showed good results using the PAN 40 kDa membrane reaching an average copper concentration in the permeate of 2 mg/l and a flux of 135.4 and 156.5l/h.m(2) at 2 and 4 bar, respectively. Metal rejection, permeate flow rate, and possibility to regenerating and recycling the polymer makes the polymer-assisted ultrafiltration process (PAUF) very interesting for metal ion removal from waters.

Sandwich liquid membrane in the separation and concentration of Cu++.

Some tests of mass transport on a sandwich liquid membrane (SwLM) for separation and concentration of Cu++ ion are reported and the results compared with the traditional supported liquid membrane (SLM) system both in terms of stability and flux. Moreover a chemical-physical model was developed evidencing the differences in the mass transport between the two systems studied. The obtained results showed an higher Cu++ flux in the SwLM (110.4 vs. 52.4 mmol/h.m2 referred to the effective pore surface) while lifetime was lower (6 vs. 15 h). The model evidenced a lower overall resistance to Cu++ ions transport through the SwLM than the SLM because the transport in the free solution did not suffer of the pores presence. Use of permanent hydrophilic membranes can improve the SwLM lifetime in view of industrial applications.