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  • Concentration polarization quantification and minimization in cork process wastewater ultrafiltration by an ozone pretreatment
    Publication . Minhalma, Miguel; De Pinho, Maria Norberta; Dominguez, Joaquin R.
    Concentration polarization and membrane fouling have been identified as the main problems during the ultrafiltration treatment of cork processing wastewaters. These problems drastically reduce the permeate fluxes and, therefore, their potential applications. In this work, a soft ozonation pretreatment was applied to minimize these undesirable effects. A new systematic study was carried out for membranes with different molecular weight cut-offs and at different operating conditions to monitor and quantify the concentration polarization caused by the wastewater's remaining ozonated compounds. Film theory was used to correlate the mass transfer coefficient, k, and the intrinsic rejection coefficient, f ', with the resistance introduced by concentration polarization. The ultrafiltration treatment was carried out under varying hydrodynamic operating conditions (circulating flow rates of 100-200 L/h) and transmembrane pressures (1-3 bar) for a set of four cellulose acetate membranes covering a wide range of molecular weight cut-offs (5000-100,000 Da) and hydraulic permeabilities (25-110 kg/h/m(2)/bar). The ozone pretreatment (at wastewater pH) reduced the phenolic content selectively (direct oxidation) by more than 50%, reducing membrane fouling and concentration polarization and increasing permeate fluxes (by 22-45%) and mass transfer coefficients (up to six times).
  • Molecular order and dynamics of water in hybrid cellulose acetate-silica asymmetric membranes
    Publication . Beira, Maria Jardim; Condesso, Miguel; Pereira Da Silva, Miguel; Cosme, Pedro; Almeida, Pedro L.; Corvo, Marta C.; Sebastião, Pedro J.; Figueirinhas, João; De Pinho, Maria Norberta
    In this work 2H NMR spectroscopy and 1H NMR relaxometry and diffusometry were used to characterise water order and dynamics in cellulose acetate/silica asymmetric membranes. Two hydrated membranes were characterised allowing the identification of extra ordering of the water molecules and the presence in each membrane of up to two spectral components with different degrees of order and different T1 values. The mechanism behind this order increase was ascribed to the rapid exchange of the water molecules between the pore walls and its interior. T1 relaxometry dispersions allowed for the identification of the relevant mechanisms of pore-confined water motion, with rotations mediated by translational displacements (RMTD) as the dominant mechanism in the low frequency region. Using the RMTD low cut off frequency along with the in situ directly measured diffusion constant it was possible do determine characteristic lengths of correlated water motion in both membranes studied, which fall in ranges compatible with typical pore dimensions in similar membranes.
  • Recovery of phenolic compounds from red grape pomace extract through nanofiltration membranes
    Publication . Arboleda Mejia, Jaime A.; Ricci, Arianna; Figueiredo, Ana Sofia; Versari, Andrea; Cassano, Alfredo; Parpinello, Giuseppina P.; De Pinho, Maria Norberta
    The winemaking process generates a large amount of residues such as vine shots, stalks, grape pomace, and wine lees, which were only recently considered for exploitation of their valuable compounds. The purpose of this work was to investigate the performance of nanofiltration for the recovery of phenolic compounds, with bioactive capacity like antioxidant, from red grape pomace extract. Four membranes were compared in this study-three cellulose acetate (CA series: lab-prepared by phase inversion) and one commercial (NF90). All membranes were characterized for their hydraulic permeability and rejection coefficients to reference solutes like saccharose, glucose, raffinose, polyethylene glycol, sodium chloride, and sodium sulfate. Permeation flowrates and rejection coefficients towards total phenolics content, antioxidant activity, proanthocyanidins, glucose and fructose were measured in the nanofiltration of grape pomace extract using selected operating conditions. Among the investigated membranes, the CA400-22 exhibited the highest permeate flux (50.58 L/m(2) h at 20 bar and 25 degrees C), low fouling index (of about 23%), the lowest rejection coefficients towards the reference solutes and the best performance in terms of separation between sugars and phenolic compounds. Indeed, the observed rejections for glucose and fructose were 19% and 12%, respectively. On the other hand, total phenolics content and proanthocyanidins were rejected for 73% and 92%, respectively.
  • The role of silver nanoparticles on mixed matrix Ag/Cellulose acetate asymmetric membranes
    Publication . Sonawane, Shirish H.; Terrien, Antonine; Figueiredo, Ana Sofia; Gonçalves, Maria Clara; De Pinho, Maria Norberta
    Mixed matrix asymmetric membranes were prepared by the addition of silver nanoparticles to cellulose acetate/acetone/formamide casting solutions with ratios acetone/formamide varying from 1.44 to 2.77 to prepare ultrafiltration/nanofiltration membranes covering a wide range of hydraulic permeabilities. Binding of the silver nanoparticles to the polymer matrix is revealed through comparison of the FTIR spectra of the cellulose acetate and the Ag/cellulose acetate membranes. In the later, there is a decrease of the ratio between the bands intensities at 2,000–2,500 cm 21. Membrane surface charge of the mixed matrix membranes varies with the pore size and pH,and when compared with cellulose acetate membranes there is a decrease of the negative surface charge densities. The silver nanoparticles in all mixed matrix membranes results in an enhancement of the hydraulic permeabilities, ranging from 10.8 kg m 22 h 21 bar 21 to 67.1 kg m 22 h 21 bar21. POLYM. COMPOS., 38:32–39, 2017. VC 2015 Society of Plastics Engineers.
  • Synthesis and bactericide activity of nanofiltration composite membranes - Cellulose acetate/silver nanoparticles and cellulose acetate/silver ion exchanged zeolites
    Publication . Beisl, Stefan; Monteiro, Silvia; Santos, Ricardo; Figueiredo, Ana Sofia; SANCHEZ-LOREDO, MARIA GUADALUPE; Lemos, Maria Amélia; Lemos, Francisco; Minhalma, Miguel; De Pinho, Maria Norberta
    The present work addresses the synthesis of nanofiltration composite membranes with bactericide properties. The cellulose acetate based membranes with polyvinylpyrrolidone coated silver nano particles, silver ion-exchanged beta-zeolite and beta-zeolite are casted by the phase inversion technique and subjected to an annealing post-treatment. They are characterized in terms of the nanofiltration permeation performance and antibacterial properties. The incorporation of silver nanoparticles produces a threefold increase in the membrane hydraulic permeability when compared to the silver-free membranes and the incorporation of silver ion loaded zeolite resulted in a 56.3% increase in hydraulic permeability. In contrast to the influence of silver presence, either in nanometric or in the ionic form, the presence of zeolite does not significantly influence the hydraulic permeability. The rejection coefficients to salts range from 83% to 93% for the silver ion-exchanged zeolite membrane and from 84% to 97% for the polyvinylpyrrolidone coated silver nanoparticles membrane. They are higher for sulfate salts than for chloride salts. The antibacterial properties of the membranes were evaluated against Escherichia coli. The results have shown that the silver ion-exchanged beta-zeolite membrane was effective in inactivating Escherichia coli after just 210 min of contact time. No bacterial activity was detected following 24 h of contact time with the membrane containing polyvinylpyrrolidone coated silver nanoparticles. A reduction of more than 6-log, in the number of Escherichia coli, was achieved for both membranes. The different patterns of bactericide activity are associated to the silver speciation in metallic or ionic form. The high flux nanofiltration composite membranes with bactericidal properties represent a strong asset in water treatment biofouling control.