Membrane and Membrane Separation and Processes Group at Instituto Superior Técnico

The MSP research activity ranges from the synthesis of new polymeric membranes to the modelling and application of membrane in separations, membrane reactors and processes. The main reasearch objectives are:

- Optimization of mass transfer and flow structure in membrane medical systems incorporating new hemocompatible membranes (blood oxygenators, immunoisolation) and membrane modules.

- Correlation of spectroscopic (ATR-FTIR, XPS), microscopic (SEM, TEM, AFM) and electrokinetic characterisation with membrane performance.

- Predictive modelling of Membrane Processes with recourse to Computational Fluid Dynamics (CFD) incorporating quantitative parameters pertaining to membrane characteristics, flow structures and mass transfer mechanisms.

- CFD modelling validation through experimental data of Micro Particle Image Velocimetry (Micro PIV) and Holographic Interferometry (equipments acquired in the project REEQ/1764/EQU/2005, 05/06).

- Development and optimization of Ultrafiltration/Nanofiltration and Integrated Hybrid Processes for the production of drinking water free of health hazards.

- Fractionation/Purification of valuable products from processing wastewaters of cork (tannins), pulp and paper (lignosulfonates) and cheese (proteins, oligosaccharides) by Membrane Processes.

- Nanofiltration/Electrodialysis in wine industry: must concentration and rectification, production of wines with low alcohol content.

The research activities of the MSP group focus on three main areas:

1. Preparation, functionalization and characterization of polymeric membranes

The bi-soft segment Polyurea/polyurethane (PU) membranes synthesized in our laboratories by Zhao & Pinho (Polymer, 40(22) (1999), 6089-6097) revealed important selective permeation characteristics and mechanico-optical properties (Macromolecules, 33 (2000), 7675 - 7679; Molecular Crystals and Liquid Crystals, 365 (2001), 447-457). New PU membranes would be developed during 2002-2004 to enhance their bio and hemocompatibility and the selective separation of the gases involved in the respiratory process. This aims applications in the medical field. As for the cellulose ester membranes special emphasis would be given to the tailoring of surface structures and to the understanding of protein/membrane interactions. Characterization would be carried out for the surface morphology through Atomic Force Microscopy, for the structure of pore water through ATR-FTIR and for the surface charge through zeta-potential measurements (equipment requested to FCT). The PhD thesis of Vitor Magueijo and Ana Rita Costa, initiated in July 2002, address this subject. Dr. Diná Afonso would put strong focus on studies of membrane charge characterization.

2. Modeling of Flow and Mass Transfer at Membrane /Fluid Interfaces

Modelling with the use of Computational Fluid Dynamics (CFD) aims the optimization of ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) equipments. This objective is strategically planned in conjunction with experimental techniques of flow visualization (Particle Imaging Velocimetry (PIV)) and of solute concentration distribution measurements (Holographic Inteferometry (HI)) (AIChE Journal, 1998, 44 (8), 1765-1776), for the validation of the developed numerical models. The equipment of PIV and HI were requested to FCT (proposal "Network of laboratories of functional materials for reactions, membrane processes and fuel cells") in the continuation of the joint action with IDMEC (IST).

3. Development of Membrane Hybrid Processes and Membrane Reactors

The integration of UF, NF, RO and pervaporation (PV) and electrodialysis (ED in sequences of unit operations aims at the optimization of processes for:

a) Wastewater treatments with recovery of water and protein from cheese whey (PAMAF project with "Escola Superior Agrária de Beja" and PhD Thesis "Ultrafiltração e Nanofiltração de Soro de Queijo de Serpa" of Antónia Macedo, initiated in September 2001) and from Fish Meal production wastewaters (Colaboration Dr. Diná Afonso / Dr. Rodrigo Bórquez (Concéption U. /Chile - till July 2002));

b) Marble processing wastewaters (Colaboration Drs. Diná Afonso and Ana Maria Alves / Dr. Mousa Mohsen (Hashmite U. (Jordan)));

c) Downstream processing of fermentation broths for the optimization of the isolation of several different antibiotics (Colaboration Dr. Ana Maria Alves /CIPAN);

d) Production of drinking water from surface water (PhD Thesis "Mecanismos de Colmatação Coloidal em Ultrafiltração e Nanofiltração de Matéria Orgânica Natural de Águas de Superfície" of Ana Rita Gonçalves da Costa );

e) Development of membrane reactors for production of oligosacharides from hemicellulose wastes (PhD Thesis "Processo Integrado de Membranas/Hidrólise Enzimática para Produção/Separação de Xilo-Oligossacáridos" of Maria do Rosário Freixo);

f) Clarification and Tartaric Stabilization of Wines.

■ Equipments


Chemical Analysis	HPLC LC Gas Chromatography · Zetasizer · Campus Access to AFM, TEM, ATR-FTIR, etc...

Bench scale equipments	Ultrafiltration Nanofiltration Reverse osmosis Pervaporation Electrodialysis Gas permeation

Pilot plants	Ultrafiltration, Nanofiltration, Reverse osmosis (1 m² membrane area) Pervaporation (2 m² membrane area) Electrodialisis (0.2 m² membrane area)

Flow and mass transfer Analysis in membrane moduldes	Micro Particle Image Velocimetry Holographic Inteferometry

■ Patents

"Processo Integrado para Concentração e Rectificação Simultânea de Mosto de Uva por Nanofiltração e Electrodiálise", PT103595, IST, Inventors: Maria Norberta de Pinho, Vítor Geraldes and Isabel Catarino (inventors). (2007)
"Processo de Fabrico de Membranas Hemocompatíveis Assimétricas Integrais de Poliuretanas", PT103560, IST, Inventor: Maria Norberta de Pinho (inventors). (2006)
Patent - “Integrated nanofiltration process to reduce the alcohol content of alcoholic beverages”, Quinta de Pancas/IST, Maria Norberta de Pinho, Fernando Gonçalves (inventors), International Patent PCT/PT04/000014 (2004)
Portuguese Patent PT102976 “Processo integrado de nanofiltração para redução do teor alcólico de bebidas”, Quinta de Pancas/IST, De Pinho, M. N. , Fernando Gonçalves (inventors)
Internacional PCT WO 2004/113489 A1 "Integrated nanofiltration process to reduce the alcohol content of alcoholic beverages", Quinta de Pancas/IST, De Pinho, M. N. , Fernando Gonçalves (inventors)

■ Publications in International Journals

2007

D.P. Queiroz, M.C. Gonçalves, M.N. de Pinho, “Tailoring of phase segregation structures in bi-soft segment urethane/urea polymer membranes”, Journal of Applied Polymer Science 103 (2007) 315-320
J.L.C. Santos, V. Geraldes, S. Velizarov, J.G. Crespo, "Investigation of flow patterns, mass transfer in membrane module channels filled with flow-aligned spacers using computational fluid,dynamics (CFD)" J. of Membr. Sci., Volume 305, Issues 1-2, 15 November 2007, Pages 103-117
M. Minhalma, V. Magueijo, D.P. Queiroz, M. N. de Pinho, “Optimization of "Serpa" cheese whey nanofiltration for effluent minimization, by-products recovery”, Journal of Environmental Management 82 (2007) 200-206
M.F. Ferreira Marques, P.M. Gordo, Zs. Kajcsos, C. Lopes Gil, A.P. de Lima, D.P. Queiroz, M.N. de Pinho, “Positron Studies of the Temperature-Dependence of Free-Volumes in Polydimethylsiloxane/poly(propylene oxide) urethane/urea membranes”, Radiation Physics, Chemistry 76 (2007) 129-133
V. Geraldes,, M.D. Afonso "Prediction of the concentration polarization in the nanofiltration / reverse osmosis of multi-ionic solutions" J. of Membr. Sci., 300 (2007) 20-27
V. Geraldes, M.N. de Pinho, C.M.S. Fonseca, E. Duarte, "Spiral-wound Module Nanofiltration of Surface River Water" E-Water - Official Publication of the European Water Association (EWA), December 2007

2006

Afonso, M.D., “Surface charge on loose nanofiltration membranes“, Desalination, 191 262-272, 2006
Cavaco Morão, A.I., Brites Alves, A.M., Afonso, M.D., “Concentration of clavulanic acid broths: Influence of the membrane surface charge density on NF operation”, Journal of Membrane Science, 281 (1-2), 417-428, 2006
Cavaco Morão, A.I., Brites Alves, A.M., Costa, M.C., Cardoso, J.P., “Nanofiltration of a clarified fermentation broth”, Chemical Engineering Science, 61 (8),2418-2427, 2006
Cavaco Morão, A.I., Brites Alves, A.M., Costa, M.C., Cardoso, J.P., “Optimization of operation mode for the concentration by NF of clarified fermentation broths”, Desalination, 200, (1-3), 472- 474, 2006
Brites Alves, A.M., Silva, N., “Recovery of water, sulfides from liming wastewaters”, Desalination, (200), (1-3), 748-749, 2006
Geraldes, V., Afonso, M.D., “Generalized mass-transfer correction factor for nanofiltration, reverse osmosis", AIChE Journal, 52, (10), 3353-3362, 2006
Geraldes, V., de Pinho, M.N., “Mass transfer coefficient determination method for high-recovery pressure-driven membrane modules”, Desalination, 195, 69-77, 2006
Santos, J.L.C., Geraldes, V., Velizarov, S., Crespo, J.G., “Modelling of flow, concentration patterns in spiral wound membrane modules with ladder-type spacers”, Desalination, 200, (1-3), 395-396, 2006
Costa, A.R., de Pinho, M.N., “Performance, cost estimation of nanofiltration for surface water treatment in drinking water production”, Desalination, 196, 55-65, 2006
Costa, A.R., de Pinho, M.N., “Comparison of the performance of ultrafiltration, nanofiltration in surface water treatment, Desalination 199, 1-3, 73-75, 2006
Costa, A.R., Elimelech, M., “Mechanisms of colloidal fouling in ultrafiltration of colloidal NOM solutions”, Journal of Membrane Science, 281, (1-2), 716-725, 2006
Minhalma, M., Domínguez, J.R., de Pinho, M.N., “Cork processing wastewaters treatment by an ozonization/ultrafiltration integrated process”, Desalination,191,148-152, 2006
Minhalma, M., Beal, L.L., Catarino, I., Mateus, M., de Pinho, M.N., “Optimization of saccharide fractionation using nanofiltration/ultrafiltration”, Desalination, 199, 337-339, 2006
Magueijo, V., Semião, V., de Pinho, M.N., “Effect of membrane pore size, membrane-solute interactions on lysozyme ultrafiltration”, Materials Science Forum: Adv Materials Forum III, 514-516, 1483-1488, 2006
Magueijo, V., Semião, V., de Pinho, M.N., “Cross diffusion effects in lysozyme/sodium chloride/water ultrafiltration”, Desalination, 199, 445-447, 2006
Magueijo, V., Semião, V., de Pinho, M.N., “Effects of ultrafiltration permeation rates on the hydrodynamics of a minichannel/slit laminar flow”, Chemical Engineering Science ,61, 7139-7150, 2006
Magueijo, V., Semião, V., de Pinho, M.N., “Integrated modelling of lysozyme ultrafiltration”, Journal of Membrane Science, 286, 133-143, 2006
Pinto, I., Queiroz, D. P., Gil M. H., Guiomar, J. A., de Pinho, M. N., “Polyurethane - Polyurea Membranes for Blood Oxygenation”, Materials Science Forum: Advanced Materials Forum III, 514-516, 803, 2006
Queiroz, D. P., Botelho do Rego, A. M., de Pinho, M. N., “Bi-soft segment polyurethane membranes: Surface studies by X-ray photoelectron spectroscopy”, Journal of Membrane Science, 281, 239-244, 2006
Queiroz, D. P., Pinto, I. M., Besteiro, M. C. F., Silva, A. F. M., Gil, M. H., Guiomar, A. J. M., de Pinho N., “Surface, hemocompatibility studies of bi-soft segment polyurethane membranes”, International Journal of Artificial Organs, 29, 591-595, 2006
Sarbu, A., de Pinho, M.N., Freixo, M.D., Goncalves, F., Udrea, I., “New method for the covalent immobilization of a xylanase by radical grafting of acrylamide on cellulose acetate membranes”, Enzyme, Microbial Technology, 39, (1) 125-130, 2006
Gonçalves, F., de Pinho, M. N., “ Optimization of wine clarification by microfiltration / ultrafiltration”, Chemical Technology, 16 – 18, 2006

2005

Narciso, Diogo, Fernandes, Cristina, Dos Santos, Paulo Cameira, De Pinho, M. N., “New method for the estimation of the potassium hydrogen tartrate saturation temperature of port wines”, Am. J. Enol. Vitic., 56:3 255 – 265, 2005
Costa, A. R., De Pinho, M. N., “Coagulation/ flocculation/ ultrafiltration for natural organic matter removal in drinking water production”, Water Science, Technology: Water Supply, vol. 4 (5-6), 215-222, 2005
Costa, A. R., de Pinho, M.N., “Effect of membrane pore size, solution chemistry on ultrafiltration for natural organic matter removal”, Journal of Membrane Science, 255 (1-2) 49-56, 2005
Geraldes, Vitor, Pereira, Nuno Escórcio, De Pinho, M. N., " Simulation, Optimization of Medium-Sized Seawater Reverse Osmosis Processes with Spiral-Wound Modules" Ind. Eng. Chem. Res., 44(6), 1897-1905, 2005
Queiroz, D. P., De Pinho, M. N., “Structural characteristics, gas permeation properties of Polydimethylsiloxane/poly(propylene oxide) urethane/urea bi-soft segment membranes”, Polymer, 46, 2346-2353, 2005
Magueijo, V., Minhalma, M., Queiroz, D., Geraldes, V., Macedo, A.,, De Pinho, M. N. "Reduction of wastewaters, valorisation of by-products from “Serpa” cheese manufacture using nanofiltration ", Water Science & Technology 52 (10-11), 393–399, 2005
Magueijo, V., Semião. V., De Pinho, M. N., “Fluid flow, mass transfer modeling in lysozyme ultrafiltration”,International Journal of Heat, Mass Transfer, Vol.48, 1716-1726, 2005
Gomes, A. C., Goncalves, I. C., de Pinho, M. N., “The role of adsorption on nanofiltration of azo dyes”, Journal of Membrane Science, 255 (1-2): 157-165, 2005
Chen, Y., C. A. C. Sequeira, Allen, Todd, Chen, Changpin, “ Electrocatalytic activities of AB5 type hydrogen storage alloy as anode electrocatalyst of alkaline fuel cell”, J. Alloy Compounds, 404-406, 661-664, 2005
Madeira, L.M., Portela, M.F., “Mechanistic Effects Resulting from the Cesium – Doping of a NiM0O4 Catalyst in n- Butane Oxidative Dehydrogenation”, Applied Catalysis A: General, 281, 179-189, 2005
Zavoianu, R., Dias, A.P.V.S., Pavel, O.D., Angelescu, E., Portela, M.F., “1- Octene Metathesis on Silica Supported Zn – Doped NiM0O4 Catalysts”, Catalysis Communications, 6, 321-327, 2005
Yuan, Jian-Chao, Silva, L.C., Gomes, P.T., Valerga, P.,.Campos, J.M., Ribeiro, M.R., Chien, J. C. W., Marques, M.M. , “Living, block polymerization of a-olefins using a Ni(II)-a-diimine catalyst containing OSiPh2 tBu groups, Polymer 46, 2122-2132, 2005

Last Updated: January, 2008
Comments: vitor.geraldes@ist.utl.pt