Gas permeance properties of asymmetric carbon hollow fiber membranes at high feed pressures
Graphical abstract
Introduction
The permeation of gases and liquids through microporous membranes has been studied for many decades. A landmark year was 1962 when Loeb and Sourirajan published a paper where high-permeable asymmetric cellulose acetate membranes were developed and studied for sea water demineralization based on the osmotic phenomenon (Loeb and Sourirajan, 1962). The first commercial scale separation process had been presented in the 1960s, achieving the desalination of brackish water by reverse osmosis via utilization of cellulose acetate membranes that selectively retained the salt and allowed pure water to permeate (Sourirajan, 1970). Since the late 60's many types of polymeric and inorganic membranes have been reported as candidate materials for liquid and gas separation applications (Baker, 2004). Gas separation technology is an “outstanding” worldwide challenge for both industry and academic society which can also offer a significant reduction of the environmental impact and the cost in several industrial processes. However, several difficulties are usually encountered, especially in cases where molecules with similar sizes (kinetic diameters) should be separated. The study of gas separation has a long history from the age of Thomas Graham who gave the first description of the solution-diffusion model and his work on porous membranes led to Graham's law of diffusion (Graham, 1866).
During the last few years many types of membranes such as metal (Deveau et al., 2013), polymeric (Lee et al., 2011), ceramic and zeolitic (Smart et al., 2010, Varoon et al., 2011) and mixed matrix membranes (Mahajan and Koros, 2000, Mahajan and Koros, 2002, Song et al., 2008, Favvas et al., 2014a, Favvas et al., 2014b) have been studied and used in gas separation applications. Polymeric membranes have been also studied for high-pressure permeability experiments, but with limited applicability (dependent on the membrane materials) due to swelling phenomena. As swelling phenomenon is described the process of dissolution of a polymer in a defined solvent, liquid or any fluid which provides good solvent properties. At first, the solvent molecules, for example the CO2, slowly diffuse into the polymer to produce a swollen gel. If the polymer–polymer intermolecular forces are high, thanks to crystallinity, crosslinking, or strong hydrogen bonding, this is all what happens. But, if these forces are overcome by the introduction of strong polymer–solvent interactions, a second stage, the relaxation even the dissolution of the polymer, can take place (Wessling et al., 1991, Izák et al., 2007). This phenomenon is also reported as membrane plasticization and is well-known to natural gas industrial membrane systems (Wind et al., 2002, Visser et al., 2005). The gas is typically treated at relatively high pressures of 30–60 bar. Note that at these high pressures of natural gas operations, membrane materials absorb 30–50 cm3(STP) of CO2/(cm3 polymer) (Baker and Lokhandwala, 2008).
The reported studied materials are many, including polyimide, polyamide–imide, polyethersulfone/polyimide, polysulfone etc in which swelling is usually observed in streams of high carbon dioxide content (Wind et al., 2003a, Wind et al., 2003b, Wind et al., 2004, Kapantaidakis et al., 2003, Kosuri and Koros, 2008, Scholes et al., 2010). On the other hand, inorganic membranes have become a promising material for gas separation technology with many potential applications such as the purification of hydrogen rich streams, the separation of olefin/paraffin mixtures, the recovery of CO2 from natural gas, the enrichment of syngas as well as the water treatment and the production of oxygen enriched air (Saufi and Ismail, 2004, Ismail and David, 2001, Koros and Mahajan, 2000, Favvas et al., 2007, Favvas et al., 2011). Nanoporous carbon membranes constitute another promising type of inorganic membranes for gas separation applications thanks to their good separation properties (Favvas and Mitropoulos, 2008, Swaidan et al., 2013, Yoshimune and Haraya, 2013, Favvas et al., 2015). These membranes can be produced by carbonization, under inert atmosphere or vacuum. Lately, numerous synthetic precursors have been used to form carbon membranes, such as polyimide and its derivatives, polyacrylonitrile (PAN), phenolic resin, polyfurfuryl alcohol (PFA), polyvinylidene chloride–acrylate terpolymer (PVDC–AC), phenol formaldehyde, polyetherimide (PEI) and polyvinylpyrrolidone (PVP), cellulose, sulfonated poly(phenylene oxide) (SPPO) phenolic resols, numerous co-polymers and others (Song et al., 2008, Pandey and Chauhan, 2001, Salleh and Ismail, 2013, Yoshimune and Haraya, 2013, Li et al., 2014). To this point of view, Salleh at al., 2011, published a review paper entitled “Precursor Selection and Process Conditions in the Preparation of Carbon Membrane for Gas Separation: A Review” where they presented condensed information regarding the sufficient materials and processes for the preparation of carbon gas separation membranes (Salleh at al., 2011). Certainly, Karvan et al. reported an interesting work regarding the carbon molecular sieve hollow fiber membrane manufacturing in a pilot-scale system (Karvan et al., 2013). Note that the one of the major reasons that the carbon hollow fiber gas separation membranes are not commercially available yet is the difficulty to be produced in a pilot-scale dimension. At this direction, from materials to application, another recent work was focused where cellulose acetate (CA) was chosen as carbon gas separation hollow fiber membrane precursor, while HYSYS simulation was also conducted to evaluate the process feasibility of CO2 capture by HFCMs in a post combustion process (He and Hägg, 2013).
In the present work, two types of CHFs were examined for their permeance properties at high pressures. This work is a continuation of our recent studies where the permeation properties of carbon dioxide at pressures up to 55 bar had been investigated for the same type of membranes (Favvas, 2014). Particularly gas permeances of high purity N2, CO2, CH4 and C2H6 gases were measured at pressures up to ∼60 bar at 307 K. A maximum of the CO2 and C2H6 permeance vs pressure was observed, especially in the case of CHFs with wide micropores. The described methodology in this work is proved to be a very valuable tool for elucidating the gas diffusion mechanism in asymmetric CHFs and for defining the optimum operating window for an efficient gas separation process.
Section snippets
Membrane preparation
BTDA-TDI/MDI, (P84), co-polyimide hollow fibers were developed by the dry/wet phase inversion process via the spinodal decomposition mechanism (Favvas and Mitropoulos, 2008) in a spinning set up described previously (Chatzidaki et al., 2007, Favvas et al., 2008). The carbon membranes were prepared through controlled pyrolysis of the polymeric co-polyimide precursor. In particular, membrane M1 was pyrolyzed at a heating rate of 5 K/min up to 1323 K with 150 mL/min of Ar sweeping the inner side
Membranes’ structural and morphological characterization
The thermal stability of membrane precursors had been determined by TGA. The corresponding thermographs are shown in Fig. 2. Generally, there are two/three temperature regions of appreciable weight loss. The first weight loss below 373 K is attributed to the evaporation of ethanol (non-solvent) and any residual NMP solvent (boiling point: 477.3 K).
The second weight loss, at about 478 K, is attributed to the rearrangement of the polymeric chains packing. The third degradation stage, starting
Conclusions
The experimental approach and the results derived from the high-pressure permeance study (at pressures up to ∼60 bar) of four pure gases, CO2, C2H6, N2 and CH4 through two asymmetric carbon hollow fiber membranes are described and discussed. Their different permeance behavior is relevant to membranes' pore size distribution. Specifically, an increase in flux is apparent for all cases while a reduction at higher pressures is obtained in cases of CO2 and C2H6. This phenomenon was more intense in
Acknowledgments
The present work is a result in the framework of NSRF. The NANOSKAΪ Project (Archimedes Framework) of the Eastern Macedonia and Thrace Institute of Technology is co–financed by Greece and the European Union in the frame of operational program “Education and lifelong learning investing in knowledge society”, Ministry of Education and Religious Affairs, Culture and Sports, NSRF 2007–2013.
References (74)
- et al.
Effect of pyrolysis temperature and operating temperature on the performance of nanoporous carbon membranes
J. Membr. Sci.
(2008) - et al.
New polyimide–polyaniline hollow fibers: synthesis, characterization and behavior in gas separation
Eur. Pol. J.
(2007) - et al.
The “falling cards model” for the structure of microporous carbons
Carbon
(1997) - et al.
Beyond Sieverts' law: a comprehensive microkinetic model of hydrogen permeation in dense metal membranes
J. Membr. Sci.
(2013) Carbon dioxide permeation study through carbon hollow fiber membranes at pressures up to 55 bar
Separ. Purif. Technol.
(2014)- et al.
Helium and hydrogen selective carbon hollow fiber membranes: the effect of pyrolysis isothermal time
Separ. Purif. Technol.
(2015) - et al.
Preparation, characterization and gas permeation properties of carbon hollow fiber membranes based on Matrimid® 5218 precursor
J. Mater. Proc. Tech.
(2007) - et al.
High purity multi-walled carbon nanotubes: preparation, characterization and performance as filler materials in co-polyimide hollow fiber membranes
Separ. Purif. Technol.
(2014) - et al.
A Methodology for the morphological and physicochemical characterisation of asymmetric carbon hollow fiber membranes
J. Membr. Sci.
(2011) - et al.
Mixed matrix hollow fiber membranes with enhanced gas permeation properties
Separ. Purif. Technol.
(2014)
Hollow fiber carbon membranes: from material to application
Chem. Engin. J.
A review on the latest development of carbon membranes for gas separation
J. Membr. Sci.
Swelling of polymeric membranes in room temperature ionic liquids
J. Membr. Sci.
High pressure gas permeability of microporous carbon membrane
Microp. Mater
Pushing the limits on possibilities for large scale gas separation: which strategies?
J. Membr. Sci.
Defect-free asymmetric hollow fiber membranes from Torlon®, a polyamide–imide polymer, for high-pressure CO2 separations
J. Membr. Sci.
A review of reverse osmosis membrane materials for desalination–Development to date and future potential
J. Membr. Sci.
Membranes for gas separation
Prog. Polym. Sci.
Pure- and mixed-gas permeation properties of polydimethylsiloxane for hydrocarbon/methane and hydrocarbon/hydrogen separation
J. Membr. Sci.
Fabrication of carbon membranes for gas separation–a review
Carbon
Plasticization of ultra-thin polysulfone membranes by carbon dioxide
J. Membr. Sci.
High pressure gas separation performance of mixed-matrix polymer membranes containing mesoporous Fe(BTC)
J. Membr. Sci.
Preparation and gas separation properties of poly(furfuryl alcohol)-based C/CMS composite membranes
Separ. Purif. Techn
The structure of adsorbed CO2 in carbon nanopores; A neutron diffraction study
Coll. Surf. A Physicochem. Eng. Asp.
Effects of carbonisation atmosphere on the structural characteristics and transport properties of carbon membranes prepared from Kapton® polyimide
J. Membr. Sci.
High pressure pure- and mixed-gas separation of CO2/CH4 by thermally-rearranged and carbon molecular sieve membranes derived from a polyimide of intrinsic microporosity
J. Membr. Sci.
On the subtle balance between competative sorption and plasticization effects in asymmetric hollow fiber gas separation membranes
J. Membr. Sci.
Plasticization of gas separation membranes
Gas Separ. Purif
Natural gas permeation in polyimide membranes
J. Membr. Sci.
CO2/CH4 mixed gas separation using carbon hollow fiber membranes
Energy Procedia
Effect of bore liquid temperature and dope concentration on mechanical properties and permeation performance of polyacrylonitrile hollow fibers
Sep. Purif. Technol.
Effect of draw ratio and coagulant composition on polyacrylonitrile hollow fiber membranes
Sep. Purif. Technol.
Structure and morphology of microporous carbon membrane materials derived from poly(phthalazinone ether sulfone ketone)
Micropor. Mesopor. Mater.
Intra and intermolecular structure in the condensed phases of ethylene, ethane and carbon dioxide by neutron diffraction
Mol. Phys.
Flow of adsorbable gases and vapours in a microporous medium
Ii. Bin. Mix. Proc. Roy. Soc. A
Membrane Technology and Applications
Natural gas processing with membranes: an overview
Ind. Eng. Chem. Res.
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