UNIVERSIDAD COMPLUTENSE DE MADRID FACULTAD DE CIENCIAS FÍSICAS Departamento de Física Aplicada I (Termología) TESIS DOCTORAL Membrane technologies for brine treatment and membrane reuse Tecnologías de membranas para el tratamiento de salmueras y reutilización de membranas / MEMORIA PARA OPTAR AL GRADO DE DOCTOR PRESENTADA POR Julio Antonio Sanmartino Rodríguez Directores Mohamed Khayet Souhaimi María del Carmen García Payo Madrid, 2018 © Julio Antonio Sanmartino Rodríguez, 2017 UNIVERSIDAD COMPLUTENSE DE MADRID Facultad de Ciencias Físicas Departamento de Física Aplicada I (Termología) TESIS DOCTORAL Membrane technologies for brine treatment and membrane reuse Tecnologías de membranas para el tratamiento de salmueras y reutilización de membranas Memoria para optar al grado de Doctor en Física Julio Antonio Sanmartino Rodríguez Directores Mohamed Khayet Souhaimi María del Carmen García Payo UNIVERSIDAD COMPLUTENSE DE MADRID DEPARTMENT OF APPLIED PHYSICS I FACULTY OF PHYSICS Membrane technologies for brine treatment and membrane reuse JULIO ANTONIO SANMARTINO RODRIGUEZ Doctoral Thesis 2017 Supervisors MOHAMED KHAYET SOUHAIMI MARÍA DEL CARMEN GARCÍA PAYO Department of Applied Physics I Faculty of Physics University Complutense of Madrid-UCM Avda. Complutense s/n, 28040 Madrid (Spain) To all those who have made it possible: family, directors, friends List of publications, patents, conferences, congress contributions and contracts with companies Publications derived from the PhD Thesis 1. Desalination and concentration of saline aqueous solutions up to supersaturation by air gap membrane distillation and crystallization fouling Authors: J.A. Sanmartino, M. Khayet, M.C. García-Payo, H. El Bakouri, A. Riaza Journal: Desalination Volume: 393 Pages: 39-51 Date: 2016 2. Modeling and optimization of a solar forward osmosis pilot plant by response surface methodology Authors: M. Khayet, J.A. Sanmartino, M. Essalhi, M.C. García-Payo, N. Hilal Journal: Solar Energy Volume: 137 Pages: 290-302 Date: 2016 Publications in process 3. Treatment of reverse osmosis brines: chemical pretreatments and direct contact membrane distillation Authors: J.A. Sanmartino, M. Khayet, M.C. García-Payo, H. El Bakouri, A. Riaza Journal: Desalination State: To be submitted 4. Reuse of discarded membrane distillation membranes in wastewater treatment by microfiltration Authors: J. A. Sanmartino, M. Khayet, M. C. García-Payo Journal: Journal of Membrane Science State: Under revision VII Chapters in books 5. Desalination by membrane distillation Authors: J. A. Sanmartino, M. Khayet, M. C. García-Payo Book title: Emerging membrane technology for sustainable water treatment Editors: Nicholas P. Hankins and Rajindar Singh Editorial: Elsevier Chapter: 4 ISBN: 978-0-444-63312-5 Date: 2016 Other publications 6. Fouling in Membrane Distillation, Osmotic Distillation and Osmotic Membrane Distillation Authors: Mourad Laqbaqbi, Julio Antonio Sanmartino, Mohamed Khayet, Carmen García-Payo and Mehdi Chaouch Journal: Applied Science Volume: 7 Pages: 334-373 Date: 2017 Patents 1. Conjunto de membranas de fibra hueca y sus aplicaciones Authors: Mohamed Khayet, Carmen García-Payo, Julio Antonio Sanmartino, Juan Pablo Pocostales, Rocío Rodríguez, Abel Riaza and Francisco Javier Bernaola Nº patent: P201630188 International request number: PCT/ES2017/070039 State: pending acceptance Date: 2017 Conferences and congress contributions 1. Desalación de disoluciones salinas de altas concentraciones por destilación en membranas con cámara de aire Authors: J.A. Sanmartino, M. Khayet, M.C. García-Payo, H. El Bakouri, A. Riaza Congress: XXXIV Reunión Bienal de la Real Sociedad Española de Física Place: Valencia (Spain) Type of contribution: oral Date: 15-19 Julio 2013 VIII 2. Destilación en membrana con cámara de aire de disoluciones salinas saturadas Authors: J.A. Sanmartino, M. Khayet, M.C. García-Payo Congress: XXXV Reunión Bienal de la Real Sociedad Española de Física Place: Gijón (Spain) Type of contribution: oral Date: 13-17 Julio 2015 3. Concentration of hypersaline solutions up to supersaturation by different membrane distillation configurations Authors: Julio Sanmartino, Alia Baroudi, Mohamed Khayet, Carmen García-Payo Congress: 12th International Meeting on Thermodiffusion (IMT-12) Place: Madrid (Spain) Type of contribution: poster Date: 30 Mayo-3 Junio 2016 Contracts with companies 1. Project title: Application of hybrid membrane systems for the treatment of brines from desalination plants (MEMsa) Participants: University Complutense of Madrid and Abengoa Water SLU Duration: October 2011 to December 2012 2. Project title: Design, construction and operation of a hollow fiber membrane distillation pilot plant (HOFI-MED-PLANT) Participants: University Complutense of Madrid and Abengoa Water SLU Duration: January 2013 to December 2016 3. Project title: Design and construction of hollow fiber membrane distillation modules (HOFI-Modules) Participants: University Complutense of Madrid and Abengoa Water SLU Duration: October 2014 to March 2015 IX Index of contents Abstract ............................................................................................................... XV Resumen ........................................................................................................... XVII Chapter 1. Introduction 1.1.Motivation and objectives ..................................................................................... 1 1.2. Microfiltration (MF) process and fouling phenomenon ...................................... 3 1.2.1. Transmembrane pressure (TMP) .................................................................. 3 1.2.2. MF Membrane requirements ........................................................................ 4 1.2.3. Fouling phenomenon .................................................................................... 5 1.3. Forward osmosis (FO) process: applications and challenges .............................. 6 1.3.1. FO applications ............................................................................................ 7 1.3.2. FO challenges ............................................................................................... 7 1.3.2.1. Concentration polarization ................................................................... 8 1.3.2.2. Membrane fouling ................................................................................ 8 1.3.2.3. Reverse solute diffusion ....................................................................... 9 1.3.2.4. FO membrane engineering ................................................................... 9 1.3.2.5. Investigation in draw solutions ........................................................... 10 1.4. References .......................................................................................................... 10 Chapter 2. Desalination by membrane distillation 2.1.Introduction ......................................................................................................... 17 2.2.Membrane distillation ......................................................................................... 19 2.2.1. Historical background ................................................................................ 19 2.2.2. MD configurations ..................................................................................... 20 2.2.3. Features and applications ........................................................................... 22 2.2.4. Mechanisms of transport in MD ................................................................ 23 2.2.5. MD membranes .......................................................................................... 26 2.2.6. Commercial modules ................................................................................. 26 2.3.Properties of saline aqueous solutions ................................................................ 27 2.3.1. Composition of seawater and brines .......................................................... 27 2.3.2. Thermodynamic properties of different saline aqueous solutions ............. 30 2.4.MD desalination .................................................................................................. 33 2.4.1. Most commonly used configurations and desalination performance .......... 33 2.4.2. MD desalination of brines and high saline aqueous solutions .................... 34 XI Index of contents (continuation) 2.4.3. Effects of MD process conditions on MD desalination performance ......... 35 2.4.3.1. Feed temperature ................................................................................ 35 2.4.3.2. Feed concentration .............................................................................. 37 2.4.3.3. Flow rate .............................................................................................. 38 2.4.3.4. Other MD operating parameters .......................................................... 39 2.4.3.5. Operating time ..................................................................................... 40 2.4.4.Influence of membrane characteristics on MD desalination performance ...................................................................................................................... 41 2.4.5. MD Hybrid systems and solar energy .......................................................... 42 2.5. Energy consumption and costs of MD desalination .......................................... 45 2.6. Conclusions and future perspectives in MD .....................................................