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Investigation of CO2-philic Oligomers for Carbon Dioxide/HydrogenMembrane Separations

Barillas, Mary Katharine (2011) Investigation of CO2-philic Oligomers for Carbon Dioxide/HydrogenMembrane Separations. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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The objective of this work was to design polymeric membranes that have very high CO2 permeability and high mixed gas selectivity toward CO2 rather than hydrogen. Therefore the membranes were based on "CO2-philic" polymers that exhibit thermodynamically favorable Lewis acid:Lewis base and hydrogen bonding interactions with CO2. CO2-philic polymers that are solid at ambient temperature include polyfluoroacrylate (PFA); polyvinyl acetate (PVAc); and amorphous polylactic acid (PLA). Literature CO2 permeability values for PVAc and PLA are disappointingly low. The cast PFA membranes from this study had low permeabilities (45 barrers at 25 oC) and very low CO2/H2 selectivity of 1.4. CO2-philic polymers that are liquid at ambient conditions include polyethylene glycol (PEG), polypropylene glycol (PPG), polybutylene glycol with a linear -((CH2)4O)- repeat unit (i.e. polytetramethylene ether glycol (PTMEG)), polybutylene glycol (PBG) with a branched repeat unit, perfluoropolyether (PFPE), poly(dimethyl siloxane) (PDMS), and polyacetoxy oxetane (PAO). A small compound, glycerol triacetate (GTA) was also considered because it is similar in chemical structure to a trimer of PVAc. These liquids were tested as supported liquid membranes (SLM) and also (with the exception of PAO and GTA) as rubbery, crosslinked materials. Mixed gas permeability was measured using equimolar mixtures of CO2 and H2 feed streams at one atmosphere total pressure in steady-state flux experiments over the 298 - 423 K temperature range. The most promising SLMs were those composed of a PEG, PTMEG, GTA, and PDMS. For example, at 37 oC the PEG-, PTMEG-, GTA- and PDMS-based SLMs exhibited CO2/H2 selectivity values of ~ 11, 9, 9, and 3.5, respectively, and CO2 permeability values of ~800, 900, 1900, and 2000 barrers, respectively. Crosslinked versions of the PEG, PTMEG and PDMS membranes at 37 oC exhibited selectivity values of ~ 5, 6 and 3.5, respectively, and CO2 permeability values of ~50, 300, and 3000 barrers, respectively.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Barillas, Mary Katharinemkb27@pitt.eduMKB27
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairEnick, Robertrme@pitt.eduRME
Committee MemberLuebke,
Committee MemberVelankar, Sachinvelankar@pitt.eduVELANKAR
Committee MemberFederspiel, Williamfederspielwj@upmc.eduWFEDERSP
Date: 27 June 2011
Date Type: Completion
Defense Date: 4 April 2011
Approval Date: 27 June 2011
Submission Date: 21 March 2011
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Institution: University of Pittsburgh
Schools and Programs: Swanson School of Engineering > Chemical Engineering
Degree: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: Carbon dioxide capture; Gas separation membranes; hydrogen; polyethers; liquid membrane; polymer membrane
Other ID:, etd-03212011-212637
Date Deposited: 10 Nov 2011 19:32
Last Modified: 19 Dec 2016 14:35


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