Development of PBI based membranes for H₂/CO₂ separation

Başdemir, Merve
Recent developments have confirmed that in the future hydrogen demand in industrial applications will arise because of the growing requirements for H2 in chemical manufacturing, petroleum refining, and the newly emerging clean energy concepts. Hydrogen is mainly produced from the steam reforming of natural gas and water gas shift reactions. The major products of these processes are hydrogen and carbon dioxide. The selective removal of CO2 from the product gas is important because it poisons catalysts in the reactor and it is highly corrosive. Membrane separation processes for hydrogen purification may be employed as alternative for conventional methods such as adsorption, cryogenic distillation. Mixed matrix membranes (MMMs) are composed of an insoluble phase dispersed homogeneously in a continuous polymer matrix. They have potential in gas separation applications by combining the advantageous properties of both phases. The objective of this study is to produce neat polybenzimidazole (PBI) membranes and PBI based mixed matrix membranes for separation of H2/CO2. Furthermore, to test the gas permeation performance of the prepared membranes at permeation temperatures of 35oC to 90oC. Commercial PBI supplied from both Celanese and FumaTech were used as polymer matrix. PBI was selected based on its thermal, chemical stabilities and mechanical properties and its performance as a fuel-cell membrane produced by PBI. Micro-sized Zeolite 3A and nano-sized SAPO-34 are zeolites with 0.30 nm and 0.38 nm pore size respectively have attracted considerable interest and employed as fillers in this study. Commercial Zeolite 3A and synthesized SAPO-34 by our group was used throughout the study. Membranes were prepared using N,N-dimethylacetamide as the solvent. Prepared membranes were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The effect of annealing procedure and operating temperature on gas separation performance of resultant neat PBI, PBI/Zeolite 3A and PBI/SAPO-34 membranes were investigated by gas permeation tests. Hydrogen and carbon dioxide gases were used for single gas permeation measurements. Two different annealing strategies were utilized namely in-line annealing and in-oven annealing. In-oven annealing was performed in an oven in nitrogen atmosphere at 120oC, 0.7 atm while in-line annealing was performed in the gas permeation set-up by feeding helium as permeating gas at 90oC and 3 bar. Neat PBI and PBI/ Zeolite 3A membranes were in-oven annealed. The in-oven annealed membranes showed better selectivities with lower permeabilities, but the performance results of these membranes had low repeatability. On the other hand, in-line annealed membranes showed much higher permeabilities and lower selectivities with stable performance. By changing the annealing method hydrogen permeability increased from 5.16 Barrer to almost 7.77 barrer for neat membranes and for PBI/Zeolite 3A mixed matrix membranes increased from 5.55 to to 7.69 Barrer at 35oC. The selectivities were decreased from 6.21 to 2.31 for neat membranes and for PBI/Zeolite 3A from 5.55 to 2.63. Effect of increasing operating temperature was investigated by using in-line annealed membranes. Increasing temperature from 35oC to 90o improved the performance of the both types of membranes and repeatable results were obtained. Besides neat PBI and PBI/Zeolite 3A, PBI/SAPO-34 membranes were prepared only via in-line annealing. The addition of nano-sized filer to the membranes provided homogeneous distribution in polymer matrix for PBI/SAPO-34 membranes. For this type of membrane hydrogen permeability increased from 8.01 to 26.73 Barrer and with no change in H2/CO2 selectivities via rising temperature. Consequently, it is better to study hydrogen and carbon dioxide separation at high temperature. For all types of membranes hydrogen showed higher activation energies. In between all membranes magnitude of activation energies were the highest for PBI/SAPO-34 membrane which is an indication of good interaction between polymer and zeolite interface. In-line annealed membranes gave the best gas permeation results by providing repeatability of measurements. Among all studied membranes in-line annealed PBI/SAPO-34 membrane exhibited the best gas permeation results.


Development of graphene oxide based aerogels
Doğan, Öznur; Bat, Erhan; Department of Chemical Engineering (2017)
Owing to their large surface area, high hydrophobicity and porous structure, graphene oxide based aerogels have been proposed as feasible and economic solutions for the increasing water pollution caused by crude oils, petroleum products and toxic organic solvents. In this study, graphene oxide based aerogels were prepared via two different routes. In the first route, random copolymers of glycidyl methacrylate and styrene were used as crosslinkers in the aerogel. In the second route, 1,3-diaminopropane was u...
Deposition and testing of thin film hydrogen separation membranes
Pişkin, Fatih; Öztürk, Tayfur; Department of Metallurgical and Materials Engineering (2013)
Industrial production of hydrogen from the syngas, generated from steam reformation of natural gas or coal gasification, sets conditions for hydrogen separation membranes in terms of operating conditions. An alternative source for hydrogen is a syngas generated by gasification of municipal solid wastes which are likely to set more stringent conditions for the separation membranes. There is therefore, a growing demand for separation membranes with improved permeability and particularly of low cost. Among var...
Development and characterization of composite proton exchange membranes for fuel cell applications
Akay, Ramiz Gültekin; Baç, Nurcan; Department of Chemical Engineering (2008)
Intensive research on development of alternative low cost, high temperature membranes for proton exchange membrane (PEM) fuel cells is going on because of the well-known limitations of industry standard perfluoro-sulfonic acid (PFSA) membranes. To overcome these limitations such as the decrease in performance at high temperatures (>80 0C) and high cost, non-fluorinated aromatic hydrocarbon based polymers are attractive. The objective of this study is to develop alternative membranes that possess comparable ...
Development of non-noble Co–N–C electrocatalyst for high-temperature proton exchange membrane fuel cells
Eren, Enis Oğuzhan; Özkan, Necati; Devrim, Yılser (Elsevier BV, 2020-11-27)
© 2020 Hydrogen Energy Publications LLCThe development of a non-noble Co–N/MWCNT (MWCNT = multi-walled carbon nanotubes) electrocatalyst is achieved through the high-temperature pyrolysis method and successfully characterized by five-step physico-chemical analysis. By utilizing high-resolution analytical surface characterization methods, the chemical states of elements are determined, and the presence of Co-Nx sites is confirmed. ORR activity of a Co–N/MWCNT is found to be auspicious. The maximum number of ...
Preparation and performance of membrane electrode assemblies with nafion and alternative polymer electrolyte membranes
Şengül, Erce; Eroğlu, İnci; Department of Chemical Engineering (2007)
Hydrogen and oxygen or air polymer electrolyte membrane fuel cell is one of the most promising electrical energy conversion devices for a sustainable future due to its high efficiency and zero emission. Membrane electrode assembly (MEA), in which electrochemical reactions occur, is stated to be the heart of the fuel cell. The aim of this study was to develop methods for preparation of MEA with alternative polymer electrolyte membranes and compare their performances with the conventional Nafion® membrane. Th...
Citation Formats
M. Başdemir, “Development of PBI based membranes for H₂/CO₂ separation,” M.S. - Master of Science, Middle East Technical University, 2013.