1 Transport of Small Molecules in Polymers: Overview of Research Activities Benny D. Freeman (Brandon Rowe) Department of Chemical Engineering University of Texas at Austin Office: CPE and CEER 1.308B Tel.: (512) , March 2009

Develop fundamental structure/function rules to guide the preparation of high performance polymers or polymer-based materials for gas and liquid separations as well as barrier packaging applications. Freeman Research Group Focus

21 Ph.D. students: –Gas Separations: Brandon Rowe, Victor Kusuma, Grant Offord, Tom Murphy, James Kyzar, Katrina Czenkusch, David Sanders, Zach Smith –Liquid Separations: Alyson Sagle, Bryan McCloskey, Hao Ju, Yuan-Hsuan Wu, Lauren Greenlee, Liz Van Wagner, Wei Xie, Dan Miller, Joe Cook, Geoff Geise, Michelle Oh –Barrier Materials: Richard Li, Kevin Tung 1 Postdoc: Dr. Claudio Ribeiro Sponsors: –NSF - 5 projects –DOE – 2 projects –Office of Naval Research - 1 project –Sandia - 1 project –Industrial sponsors: Air Liquide, Kuraray, Kraton Polymers, ConocoPhillips, Statkraft, Dow Water Solutions Freeman Research Group Profile

University of Texas: –Don Paul (Chem. Eng.), Roger Bonnecaze (Chem. Eng.). Mukul Sharma (Petroleum Eng.), Des Lawler (Env. Eng.), Andy Ellington (Biochemistry) Prof. Eric Baer, Anne Hiltner, Dave Schiraldi (Case Western Reserve Univ.) Prof. Jim McGrath (Virginia Tech) Prof. Doug Kalika (Univ. of Kentucky) Prof. Todd Emrick (Univ. of MA, Amherst) Dr. Anita Hill (CSIRO, Melbourne, Australia) Prof. Giulio Sarti (Univ. of Bologna, Italy) Prof. Philippe Moulin (Univ. Paul Cézanne, Aix-en-Provence, France) Prof. Young Moo Lee (Hanyang Univ., Seoul, Korea) Prof. Toshio Masuda (Kyoto Univ., Kyoto, Japan) Collaborations

5 Spreading Water Shortage Science 313, , 2006

Over 1 billion people live without access to reliable drinking water. 2.3 billion people (41% of the Earth’s population) live in water stressed areas; expected to increase to 3.5 billion by Annual global costs in excess of $100 billion in medical costs and loss of productivity. Magnitude of the Problem Science 313, , 2006

7 Why Chlorine is Used in Water Treatment Bacteria-laden untreated water kills more than 3.4 million people every year in developing countries. 1 Un-disinfected water causes biofouling of desalination membranes. Chlorine is the most economical disinfectant for deactivation of pathogenic microorganisms in drinking water. Over 98% of all water treatment facilities in the U.S. disinfect water with chlorine and chlorine-based products. But the problem is: Chlorine degrades desalination membranes, reducing salt rejection and membrane lifetime. 1 Houston Chronicle, Jan.8,

8 Membranes A-D: commercial polyamide membranes Chlorine as hypochlorite pH > 8.5 Chlorine as hypochlorous acid pH < 5.5 T. Knoell, Ultrapure Water, April 2006, pp OCl - HOCl Chlorine Attacks Desalination Membranes

9 Chlorinate (0.2-5 ppm) Dechlorinate (Free chlorine < 0.01 ppm) Polyamide desalination membrane Rechlorinate (1-2 ppm) Feed water Product water To protect membranes from chlorine Desalination 64 (1987) 411; Desalination 124 (1999) 251 Current Desalination Process

10 Disulfonated Polysulfone Membranes Exhibit High Chlorine Tolerance 33 h16 h0 h24 h8 h Cross-flow pH = 9.5 Feed = 2000 ppm NaCl Pressure = 400 psig Flow rate = 0.8 GPM Chlorine = 500 ppm Hydrophilic block Hydrophobic block High water permeability High chlorine tolerance Excellent fouling-resistance Good reproducibility H.B. Park, B.D. Freeman, Z.B. Zhang, M. Sankir, and J.E. McGrath, Highly Chlorine- Tolerant Polymers for Desalination, Angew. Chem.-Int. Edit (2008)

11 Potential Desalination Process Using Chlorine-Tolerant Membranes Chlorinate New membrane Feed water Product water  Extend membrane lifetime  Simplify maintenance and operation  Process intensification  Cost savings via elimination of dechlorination required by current membranes

Research in Water Purification Appears to be Gaining Traction in the Scientific Community

New Gas Separation Membrane Materials with Performance Better than Conventional Membranes Science, vol. 318, 12 October 2007, pp

Lin et al., Science, 311, pp (2006). Beating the Permeability-Selectivity Tradeoff for H 2 Purification

CO 2 Selective Materials

Using Nanocomposites to Enhance Membrane Separations

Using Nanolayering to Enhance Gas Barrier Properties

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