A new carbon molecular sieve for propylene/ propane separations

Abstract A new carbon molecular sieve (CMS) with a propylene/propane separation factor of approximately 27 was synthesized by a facile pyrolysis process from a gel-type strong acid cation exchange resin. The micropore shrinkage process during pyrolysis was investigated using a new high throughput adsorption technique with 48 parallel cells. This significantly reduced the characterization time. The ratio of propylene/propane adsorption rate in the CMS adsorbent changes from 1 to more than 150 when the final pyrolysis temperature changes from 550 to 1000 °C. The best performing CMS pyrolyzed at 850 °C was further characterized using a gravimetric adsorption method. The propylene and propane diffusivities are 1.0 × 10 −9 and 1.1 × 10 −11  cm 2  s −1 at 100 kPa and 90 °C. The high propylene/propane diffusivity ratio of 90 is similar to that in zeolite 4A, while the propylene diffusivity was more than 30 times higher than that in zeolite 4A. An effluent of 90 mol% propylene was obtained from a feed of 25 mol% propylene during adsorption/desorption tests using the CMS adsorbent pyrolyzed at 850 °C in a fixed-bed configuration. The new CMS adsorbent is a promising candidate for industrial scale propylene/propane separations.

[1]  D. Ruthven Molecular Sieve Separations , 2011 .

[2]  R. T. Yang,et al.  New sorbents for olefin/paraffin separations by adsorption via π ‐complexation , 1995 .

[3]  H. C. Foley,et al.  Ultrasonic deposition of high-selectivity nanoporous carbon membranes , 1999, Science.

[4]  W. Koros,et al.  Carbon molecular sieve dense film membranes derived from Matrimid® for ethylene/ethane separation , 2012 .

[5]  W. Koros,et al.  Carbon molecular sieve membranes derived from Matrimid® polyimide for nitrogen/methane separation , 2014 .

[6]  A. Mohamed,et al.  Preparation of carbon molecular sieve from lignocellulosic biomass: A review , 2010 .

[7]  D. Ruthven,et al.  A new experimental technique for measurement of intracrystalline diffusivity , 1988 .

[8]  D. L. Gallup,et al.  Use of Ambersorb® carbonaceous adsorbent for removal of BTEX compounds from oil‐field produced water , 1996 .

[9]  Rong Wang,et al.  Separation of CO2/CH4 through carbon molecular sieve membranes derived from P84 polyimide , 2004 .

[10]  M. Dubois,et al.  Pyrolysis and incineration of cationic and anionic ion-exchange resins — Identification of volatile degradation compounds , 1995 .

[11]  Carlos A. Grande,et al.  Crystal Size Effect in Vacuum Pressure-Swing Adsorption for Propane/Propylene Separation , 2004 .

[12]  J. Palmentier,et al.  The determination of six taste and odour compounds in water using Ambersorb 572 and high resolution mass spectrometry. , 2001, The Analyst.

[13]  Pablo A. Denis,et al.  When noncovalent interactions are stronger than covalent bonds: Bilayer graphene doped with second row atoms, aluminum, silicon, phosphorus and sulfur , 2011 .

[14]  A. B. Fuertes,et al.  Supported carbon molecular sieve membranes based on a phenolic resin , 1999 .

[15]  R. Eldridge,et al.  Olefin/Paraffin Separations by Reactive Absorption: A Review , 1998 .

[16]  R. Mahajan,et al.  Pushing the limits on possibilities for large scale gas separation: which strategies? , 2000 .

[17]  A. Ismail,et al.  Fabrication of carbon membranes for gas separation--a review , 2004 .

[18]  P. Tarazona,et al.  Phase equilibria of fluid interfaces and confined fluids , 1987 .

[19]  J. W. Neely Characterization of polymer carbons derived from porous sulfonated polystyrene , 1981 .

[20]  Tiziano Faravelli,et al.  Thermal degradation of polystyrene , 2001 .

[21]  Wang Zhizhong,et al.  Asymmetric molecular sieve carbon membranes , 1996 .

[22]  G. Gavalas,et al.  Preparation of supported carbon membranes from furfuryl alcohol by vapor deposition polymerization , 2000 .

[23]  Y. Harada,et al.  Control of micropore formation in the carbonized ion exchange resin by utilizing pillar effect , 1999 .

[24]  D. Ruthven,et al.  Diffusion in nanoporous materials , 2012 .

[25]  R. Eldridge,et al.  Olefin/paraffin separation technology: a review , 1993 .

[26]  D. Ruthven,et al.  Adsorptive separation of light olefins from paraffins , 2007 .

[27]  W. Ho,et al.  Facilitated transport of olefins in Ag+-containing polymer membranes , 1994 .

[28]  Y. Lee,et al.  Preparation and characterization of carbon molecular sieve membranes derived from BTDA-ODA polyimide and their gas separation properties , 2005 .

[29]  Ryan P. Lively,et al.  Unexpected Molecular Sieving Properties of Zeolitic Imidazolate Framework-8. , 2012, The journal of physical chemistry letters.

[30]  R. T. Yang,et al.  Olefin/paraffin separations by adsorption: π‐Complexation vs. kinetic separation , 1998 .

[31]  A. Da̧browski Adsorption--from theory to practice. , 2001, Advances in colloid and interface science.

[32]  W. Koros,et al.  Matrimid derived carbon molecular sieve hollow fiber membranes for ethylene/ethane separation , 2011 .