Adsorption of CH4 and CO2 on Cu-BDC Metal-Organic Frameworks Synthesized Using Different Solvent Separation Routes

Document Type: Research Paper

Authors

1 Department of Chemical Engineering, South Tehran Branch, Islamic Azad University, Tehran, Iran

2 Gas Refining Technologies Division, Research Institute of Petroleum Industry (RIPI), Tehran, Iran

3 Young Researcher and Elites Club, Science and Research Branch, Islamic Azad University, Tehran, Iran

4 Nanotechnology Research Center, Research Institute of Petroleum Industry (RIPI), Tehran, Iran

Abstract

Energy storage is one of the major challenges during the last decades. Natural gas adsorption on porous materials has notable advantages in comparison with the other approaches. Due to the lack of adsorption information about Cu-BDC (copper terephthalate), it was synthesized by two different solvent separation procedures and identified using X-ray diffraction (XRD), Brunauer-Emmet-Telller (BET) and thermogravimetric analysis (TGA) techniques. Moreover, equilibrium adsorption measurements were performed for CH4 and CO2 gases in the pressure range 0-50 bar at two various temperatures (293 and 323 K), and experimental adsorption data were modeled with adsorption isotherms. Also, the sample synthesized by the new solvent separation procedure had 918 m2/gr surface area and 0.42 cm3/gr pore volume which were respectively 45% and 50% higher than the traditional method. In addition, this sample has shown CO2 and CH4 adsorption capacity (16.72 and 13.23 mmol gr-1) were desirable in comparison with other conventional Metal-Organic Frameworks (MOFs) and its methane adsorption value was close to DOE (Department of Energy) targets. To investigate the application of the synthesized materials, the selectivity of CO2/CH4 was determined by IAST (ideal adsorbed solution theory) according to the sorption test information of the single components. Finally, adsorption enthalpy of the adsorbates on the two samples was computed using the Clausius-Clapeyron equation and the results were in accordance with the isotherms at two various temperatures (293 and 323 K).

Keywords


  1. Senkovska I, Kaskel S (2008) High pressure methane adsorption in the metal-organic frameworks Cu3(btc)2, Zn2(bdc)2dabco, and Cr3F(H2O)2O(bdc)3, Microporous and Mesoporous Materials, 112, 1–3: 108-115. ##
  2. Alcañiz-Monge J, De La Casa-Lillo MA, Cazorla-Amorós D, Linares-Solano A (1997) Methane storage in activated carbon fibres, Carbon, 35, 2: 291-297. ##
  3. Lozano-Castelló D, Alcaniz-Monge J, De la Casa-Lillo MA, Cazorla-Amoros D, Linares-Solano A (2002) Advances in the study of methane storage in porous carbonaceous materials, Journal of Fuel, 81, 14: 1777-1803. ##
  4. Tagliabue M, Rizzo C, Millini R, Blom R, Zanardi S (2011) Methane storage on CPO-27-Ni pellets, Journal of Porous Materials, 18, 3: 289-296. ##
  5. Cracknell RF, Gordon P, Gubbins  KE (1993) Influence of pore geometry on the design of microporous materials for methane storage, The Journal of Physical Chemistry, 97, 2: 494-499. ##
  6. Liang Z, Marshall M, Chaffee AL (2009) Comparison of Cu-BTC and zeolite 13X for adsorbent based CO2 separation, Energy Procedia, 1, 1: 1265-1271. ##
  7. Lee J.Y, Wood C, Bradshaw D, Rosseinsky M, Cooper A (2006) Hydrogen adsorption in microporous hypercrosslinked polymers, Chemical Communications, 25: 2670-2672. ##
  8. Dietzel PDC, Besikiotis V, Blom R (2009) Application of metal-organic frameworks with coordinatively unsaturated metal sites in storage and separation of methane and carbon dioxide, Journal of Materials Chemistry, 19, 39: 7362-7370. ##
  9. Ma S, Sun D, Simmons J, Collier C, Yuan D, Zhou H (2008) Metal-organic framework from an anthracene derivative containing nanoscopic cages exhibiting high methane uptake, Journal of the American Chemical Society, 130, 3: 1012-1016. ##
  10. Burchell T, Rogers M (2000) Low pressure storage of natural gas for vehicular applications, Energy Efficiency and Renewable Energy, SAE International, 109, 4: 2242-2246. ##
  11. Muris M, Pavlovsky N, Bienfait M, Zeppenfeld P (2001) Where are the molecules adsorbed on single-walled nanotubes?, Surface Science, 492, 1–2: 67-74. ##
  12. Dunne JA, Rao M, Sircar S, Gorte RJ, Myers AL (1996) Calorimetric heats of adsorption and adsorption isotherms. 2. O2, N2, Ar, CO2, CH4, C2H6, and SF6 on NaX, H-ZSM-5, and Na-ZSM-5 Zeolites, Langmuir, 12, 24: 5896-5904. ##
  13. MacDonald JAF and Quinn DF (1995) The preparation of active carbons from natural materials for use in gas storage, Journal of Porous Materials, 1, 1: 43-54. ##
  14. Pfeifer P, Burress JW, Wood MB, Lapilli CM, Barker SA, Pobst JS, Cepel RJ, Wexler C, Shah PS, Gordon MJ, Suppes GJ (2008) High-surface-area biocarbons for reversible on-board storage of natural gas and hydrogen, Materials Research Society symposia proceedings, 1041, 2: 63. ##
  15. Acheson RJ, Galwey AK (1967) The thermal decomposition of nickel terephthalate and nickel salts of other carboxylic acids, Journal of the Chemical Society A: Inorganic, Physical, Theoretical, 0: 1174-1178. ##
  16. Sherif FG (1970) Heavy Metal Terephthalates, Industrial and Engineering Chemistry Product Research and Development, 9, 3: 408-412. ##
  17. Cueto S, Gramlich V, Petter W, Rys FS, Rys P (1991) Structure of copper(II) terephthalate trihydrate, Acta Crystallographica Section C, 47, 1: 75-78.
  18. Carson CG, Hardcastle K, Schwartz J, Liu X, Hoffmann C, Gerhardt RA, Tannenbaum R (2009) Synthesis and structure characterization of copper terephthalate metal–organic frameworks, European Journal of Inorganic Chemistry, 16: 2338-2343. ##
  19. Wasuke M, Fumie I, Keiko Y, Hirokazu N, Satoshi T, Michihiko K (1997) Synthesis of new adsorbent copper(II) terephthalate, Chemistry Letters, 26, 12: 1219-1220. ##
  20. Seki K (2001) Design of an adsorbent with an ideal pore structure for methane adsorption using metal complexes, Chemical Communications, 30, 16: 1496-1497. ##
  21. Chowdhury P, Bikkina C, Meister D, Dreisbach F (2009) Comparison of adsorption isotherms on Cu-BTC metal organic frameworks synthesized from different routes, Microporous and Mesoporous Materials, 117, 1–2: 406-413. ##
  22. Mohamed Eddaoudi JK, Nathaniel Rosi, David Vodak, Joseph Wachter, Michael O’Keeffe, and Omar M. Yaghi (2002) Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage, Science, 295: 469. ##
  23. Taheri A, Babakhani E, Towfighi J (2018) Study of synthesis parameters of MIL-53(Al) using experimental design methodology for CO2/CH4 separation. Adsorption Science & Technology, 36, 1-2: 247-269. ##
  24. Taheri A, Babakhani E, Towfighi J (2017) A MIL-101(Cr) and graphene oxide composite for methane-rich stream treatment, Energy and Fuels, 31, 8: 8792-8802. ##
  25. Thommes M, Kaneko K, Neimark A, Olivier J, Rodriguez F, Rouquerol J, Sing K (2015) Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report), Pure and Applied Chemistry, 87, 9-10. ##
  26. Basu S, Cano-Odena A, Vankelecom IFJ (2010) Asymmetric matrimid®/[Cu3(BTC)2] mixed-matrix membranes for gas separations, Journal of Membrane Science, 362, 1: 478-487. ##
  27. Kenji S, Satoshi T, Wasuke M (2001) Characterization of microporous copper(II) dicarboxylates (Fumarate, terephthalate, and trans-1,4-cyclohexanedicarboxylate) by gas adsorption, Chemistry Letters, 30, 2: 122-123. ##
  28. Llewellyn PL, Maurin G (2005) Gas adsorption microcalorimetry and modelling to characterise zeolites and related materials, Comptes Rendus Chimie, 8, 3: 283-302. ##
  29. Chaemchuen S, Zhou K, Yao C, Ke X, Tendeloo GV, Verpoort F (2015) Tuning metal sites of DABCO MOF for gas purification at ambient conditions, Microporous and Mesoporous Materials, 201, 0: 277-285. ##
  30. Anbia M, Sheykhi S (2012) Synthesis of nanoporous copper terephthalate [MIL-53(Cu)] as a novel methane-storage adsorbent, Journal of Natural Gas Chemistry, 21, 6: 680-684. ##
  31. Li J-R, Ma Y, McCarthy M, Sculley J, Yu J, Jeong H, Zhou H (2011) Carbon dioxide capture-related gas adsorption and separation in metal-organic frameworks, Coordination Chemistry Reviews, 255, 15: 1791-1823. ##
  32. Bourrelly S, Llewellyn P, Serre C, Millange F (2005) Different adsorption behaviors of methane and carbon dioxide in the isotypic nanoporous metal terephthalates MIL-53 and MIL-47, Journal of the American Chemical Society, 127, 39: 13519-13521. ##
  33. Millward AR and Yaghi OM (2005), Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room temperature, Journal of the American Chemical Society, 127, 51: 17998-9. ##
  34. Llewellyn PL, Bourrelly S, Serre C, Vimont A (2008) High uptakes of CO2 and CH4 in Mesoporous Metal-Organic Frameworks MIL-100 and MIL-101, Langmuir, 24, 14: 7245-7250. ##
  35. Chowdhury P, Mekala S, Dreisbach F, Gumma S (2012)  Adsorption of CO, CO2 and CH4 on Cu-BTC and MIL-101 metal organic frameworks: Effect of open metal sites and adsorbate polarity, Microporous and Mesoporous Materials, 152, 0: 246-252. ##
  36. Mishra P, Edubilli S, Mandal B, Gumma S (2013) Adsorption of CO2, CO, CH4 and N2 on DABCO based metal organic frameworks, Microporous and Mesoporous Materials, 169, 0: 75-80. ##
  37. Wang H, Getzschmann H, Senkovska I, Kaskel S (2008) Structural transformation and high pressure methane adsorption of Co2(1,4-bdc)2dabco, Microporous and Mesoporous Materials, 116, 1–3: 653-657. ##
  38. Bolis V (2013) Fundamentals in adsorption at the solid-gas interface, Concepts and Thermodynamics, in Calorimetry and Thermal Methods in Catalysis, Springer Berlin Heidelberg: Berlin, Heidelberg, 3-50. ##
  39. Dada AO, Olalekan AP, Olatunya AM, DADA O (2012) Langmuir, freundlich, temkin and dubinin–radushkevich isotherms studies of equilibrium sorption of Zn2+ unto phosphoric acid modified rice husk, IOSR Journal of Applied Chemistry, 3, 1: 38-45. ##
  40. Duong DD (1998) Adsorption analysis: equilibria and kinetics (1st edition), Imperial College Press, 2: 201-202. ##