New nanostructured sorbents for desulfurization of natural gas

Abstract

Desulfurization of natural gas is achieved commercially by absorption with liquid amine solutions. Adsorption technology could potentially replace the solvent extraction process, particularly for the emerging shale gas wells with production rates that are generally lower than that from the large conventional reservoirs, if a superior adsorbent (sorbent) is developed. In this review, we focus our discussion on three types of sorbents: metal-oxide based sorbents, Cu/Ag-based and other commercial sorbents, and amine-grafted silicas. The advantages and disadvantages of each type are analyzed. Possible approaches for future developments to further improve these sorbents are suggested, particularly for the most promising amine-grafted silicas.

Key words： desulfurization; natural gas desulfurization; hydrogen sulfide sorbent; amine-silica sorbent

References

1 Haring H W. Industrial Gas Processing. Weinheim: Wiley-VCH, 2008, 217–238

2 George D L, Bowles E C. Shale gas measurement and associated issues.

3 Posey M L, Tapperson K G, Rochelle G T. A simple model for prediction of acid gas solubilities in alkanolamines. Gas Separation & Purification, 1996, 10(3): 181–186

4 Pani F, Gaunand A, Richon D, Cadours R, Bouallou C. Absorption of H₂S by an aqueous methyldiethanolamine solution at 296 and 343 K. Journal of Chemical & Engineering Data, 1997, 42(5): 865–870

5 Kohl A L, Nielsen R. Gas Purification. Houston: Gulf Publishing Company, 1997, 40–186

6 Kikkinides E S, Sikavitsas V I, Yang R T. Natural gas desulfurization by adsorption: Feasibility and multiplicity of cyclic steady states. Industrial & Engineering Chemistry Research, 1995, 34(1): 255–262

7 Yang R T. Gas Separation by Adsorption Processes. London: Imperial College Press, 1997, 201–36

8 Shah V, Quale M. Dow Chemical Company, private communications, June, 2013

9 Yang R T. Adsorbents: Fundamentals and Applications. New York: Wiley, 2003, 131–156

10 Huang H Y, Yang R T, Chinn D, Munson C L. Amine grafted MCM-48 and silica xerogel as superior sorbents for acidic gas (H₂S and CO₂) removal from natural gas. Industrial & Engineering Chemistry Research, 2003, 42(12): 2427–2433

11 Ma X, Wang X, Song C. Molecular basket sorbents for separation of CO₂ and H₂S from various gas streams. Journal of the American Chemical Society, 2009, 131(16): 5777–5783

12 Belmabkhout Y, Weireld G D, Sayari A. Amine-bearing mesoporous silica for CO₂ and H₂S removal from natural gas and biogas. Langmuir, 2009, 25(23): 13275–13278

13 Xue Q, Liu Y S. Removal of minor concentration of H₂S on MDEA-modified SBA-15 for gas purification. Journal of Industrial and Engineering Chemistry, 2012, 18(1): 169–173

14 Hunger B, Matysik S, Heuchel M, Geidel E, Toufar H. Adsorption of water on zeolites of different types. Journal of Thermal Analysis, 1997, 49(1): 553–565

15 Tanada S, Bok K. Adsorption behavior hydrogen sulfide inside micropores of molecular sieve carbon 5A and molecular sieve zeolite 5A. Bulletin of Environmental Contamination and Toxicology, 1982, 29(5): 624–629

16 Steuten B, Pasel C, Luckas M, Bathen D. Trace level adsorption of toxic sulfur compounds, carbon dioxide, and water from methane. Journal of Chemical & Engineering Data, 2013, 58(9): 2465–2473

17 Bagreev A, Bandosz T J. Role of sodium hydroxide in the process of hydrogen sulfide adsorption/oxidation on caustic-impregnated activated carbons. Industrial & Engineering Chemistry Research, 2002, 41(4): 672–679

18 Bagreev A, Bandosz T J. On the mechanism of hydrogen sulfide removal from moist air on catalytic carbonaceous adsorbents. Industrial & Engineering Chemistry Research, 2005, 44(3): 530–538

19 Chiang H L, Tsai J H, Tsai C L, Hsu Y I C H U N. Adsorption characteristics of alkaline activated carbon exemplified by water vapor, H₂S and CH₃SH gas. Separation Science and Technology, 2000, 35(6): 903–918

20 Bandosz T J. On the adsorption/oxidation of hydrogen sulfide on activated carbons at ambient temperatures. Journal of Colloid and Interface Science, 2002, 246(1): 1–20

21 Hamon L, Serre C, Devic T, Loiseau T, Millange F, Ferey G, Weireld G D. Comparative study of hydrogen sulfide adsorption in the MIL-53(Al, Cr, Fe), MIL-47(V), MIL-100(Cr), and MIL-101(Cr) metal-organic frameworks at room temperature. Journal of the American Chemical Society, 2009, 131(25): 8775–8777

22 Li Y, Yang R T. Gas adsorption and storage in metal-organic framework MOF-177. Langmuir, 2007, 23(26): 12937–12944

23 Wang L, Lachawiec A J Jr, Yang R T. Nanostructured adsorbents for hydrogen storage at ambient temperature: High-pressure measurements and factors influencing hydrogen spillover. RSC Advances, 2013, 3(46): 23935–23952

24 Han S, Huang Y, Watanabe T, Nair S, Walton K S, Sholl D S, Carson M. MOF stability and gas adsorption as a function of exposure to water, humid air, SO₂ and NO₂. Microporous and Mesoporous Materials, 2013, 173: 8691

25 Wang L F, Yang R T. Hydrogen storage on carbon-based adsorbents and storage at ambient temperature by hydrogen spillover. Catalysis Reviews. Science and Engineering, 2010, 52(4): 411461

26 Westmoreland P R, Harrison D P. Evaluation of candidate solids for high-temperature desulfurization of low-Btu gases. Environmental Science & Technology, 1976, 10(7): 659–661

27 Xue M, Chitrakar R, Sakane K, Ooi K. Screening of adsorbents for removal of H₂S at room temperature. Green Chemistry, 2003, 5(5): 529534

28 Ko T, Chu H, Chaung L. The sorption of hydrogen sulfide from hot syngas by metal oxides over supports. Chemosphere, 2005, 58(4): 467474

29 Huang C C, Chen C H, Chu S M. Effect of moisture on H₂S adsorption by copper impregnated activated carbon. Journal of Hazardous Materials, 2006, 136(3): 866873

30 Nguyen-Thanh D, Bandosz T J. Effect of transition-metal cations on the adsorption of H₂S in modified pillared clays. Journal of Physical Chemistry B, 2003, 107(24): 5812–5817

31 Garcia C L, Lercher J A. Adsorption of hydrogen sulfide on ZSM-5 zeolites. Journal of Physical Chemistry, 1992, 96(5): 2230–2235

32 Gasper-Galvin L, Atimtay A T, Gupta R P. Zeolite-supported metal oxide sorbents for hot-gas desulfurization. Industrial & Engineering Chemistry Research, 1998, 37(10): 4157–4166

33 Kyotani T, Kawashima H, Tomita A, Palmer A, Furimsky E. Removal of H₂S from hot gas in the presence of Cu-containing sorbents. Fuel, 1989, 68(1): 74–79

34 Montes D, Tocuyo E, González E, Rodríguez D, Solano R, Atencio R, Ramos M A,Moronta A. Solano, Atencio R, Ramos M A, Moronta A. Reactive H₂S chemisorption on mesoporous silica molecular sieve-supported CuO or ZnO. Microporous and Mesoporous Materials, 2013, 168: 111–120

35 Ayala R E, Marsh D W. Characterization and long-range reactivity of zinc ferrite in high-temperature desulfurization processes. Industrial & Engineering Chemistry Research, 1991, 30(1): 55–60

36 Baird T, Denny P J, Hoyle R, Mcmonagle F, Stirling D, Tweedy J. Modified zinc-oxide absorbents for low-temperature gas desulfurization. Journal of the Chemical Society, Faraday Transactions, 1992, 88(22): 3375–3382

37 Gasper-Galvin L, Atimtay A T, Gupta R P. Zeolite-supported metal oxide sorbents for hot-gas desulfurization. Industrial & Engineering Chemistry Research, 1998, 37(10): 4157–4166

38 Polychronopoulou K, Fierro J L G, Efstathiou A M. Novel Zn-Ti-based mixed metal oxides for low-temperature adsorption of H₂S from industrial gas streams. Applied Catalysis B: Environmental, 2005, 57(2): 125–137

39 Yang H Y, Tatarchuk B. Novel-doped zinc oxide sorbents for low temperature regenerable desulfurization applications. AIChE Journal. American Institute of Chemical Engineers, 2010, 56(11): 2898–2904

40 Israelson G. Results of testing various natural gas desulfurization adsorbents. Journal of Materials Engineering and Performance, 2004, 13(3): 282–286

41 King D L, Birnbaum J C, Singh P. Sulfur removal from pipeline natural gas fuel: Application to fuel cell power generation systems. Pacific Northwest National Laboratory. Fuel Cell Seminar, Palm Springs, CA, November 18–21, 2002

42 Satokawa S, Kobayashi Y, Fujiki H. Adsorptive removal of dimethylsulfide and t-butylmercaptan from pipeline natural gas fuel on Ag zeolites under ambient conditions. Applied Catalysis B: Environmental, 2005, 56(1–2): 51–56

43 Alptekin G O. Sorbents for desulfurization of natural gas, LPG and transportation Fuels. Sixth Annual SECA Workshop, Pacific Grove, CA, 2004-April-21

44 Crespo D, Qi G, Wang Y, Yang F H, Yang R T. Superior sorbent for natural gas desulfurization. Industrial & Engineering Chemistry Research, 2008, 47(4): 1238–1244

45 Lasperas M, Llorett T, Chaves L, Rodriguez I, Cauvel A, Brunel D. Amine functions linked to MCM-41-type silicas as a new class of solid base catalysts for condensation reactions. Studies in Surface Science and Catalysis, 1997, 108: 75–82

46 Angeletti E, Canepa C, Martinetti G, Venturello P. Silica gel functionalized with amino groups as a new catalyst for Knoevenagel condensation under heterogeneous catalysis conditions. Tetrahedron Letters, 1988, 29(18): 2261–2264

47 Burwell R L, Leal O. Modified silica-gels as selective adsorbents for sulfur-dioxide. Journal of the Chemical Society. Chemical Communications, 1974, 9(9): 342–343

48 Leal O, Bolivar C, Ovalles C, Garcia J J, Espidel Y. Reversible adsorption of carbon dioxide on amine surface-bonded silica gel. Inorganica Chimica Acta, 1995, 240(1–2): 183–189

49 Choi S H, Drese J H, Jones C W. Adsorbent materials for CO₂ capture from large anthropogenic point sources. ChemSusChem, 2009, 2(9): 796–854

50 D’Alessandro D M, Smit B, Long J R. Carbon dioxide capture: Prospect for new materials. Angewandte Chemie International Edition, 2010, 49(35): 6058–6082

51 Bollini P, Didas S A, Jones C W. Amine-oxide hybrid materials for acid gas separations. Journal of Materials Chemistry, 2011, 21(39): 15100–15120

52 Samanta A, Zhao A, Shimazu G K H, Sarkar P, Gupta R. Post-combustion CO₂ capture using solid sorbents: A review. Industrial & Engineering Chemistry Research, 2012, 51(4): 1438–1463

53 Beck J S, Vartuli J C, Roth W J, Leonowicz M E, Kresge C T, Schmitt K D, Chu C T W, Olson D H, Sheppard E W, McCullen S B, Higgins J B, Schlenker J L. A new family of mesoporous molecular-sieves prepared with liquid-crystal templates. Journal of the American Chemical Society, 1992, 114(27): 10834–10843

54 Kresge C T, Leonowicz M E, Roth W J, Vartuli J C, Beck J S. Ordered mesoporous molecular-sieves synthesized by a liquid-crystal template mechanism. Nature, 1992, 359(6397): 710–712

55 Sayari A, Yang Y, Kruk M, Jaroniec M. Expanding the pore size of MCM-41 silicas: Use of amines as expanders in direct synthesis and postsynthesis procedures. Journal of Physical Chemistry B, 1999, 103(18): 3651–3658

56 Chen Q, Fan F, Long D, Liu X, Liang X, Qiao W, Ling L. Poly(ethyleneimine)-loaded silica monolith with a hierarchical pore structure for H₂S adsorptive removal. Industrial & Engineering Chemistry Research, 2010, 49(22): 11408–11414

57 Wang L, Yang R T. Increasing selective CO₂ adsorption on amine-grafted SBA-15 by increasing silanol density. Journal of Physical Chemistry C, 2011, 115(43): 21264–21272

58 Zhuravlev L T. Surface characterization of amorphous silica—A review of work from the former USSR. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 1993, 74(1): 71–90

59 Perry J B. Infrared study of OH and NH₂ groups on the surface of a dry silica aero-gel. 1966. Journal of Physical Chemistry, 1966, 70(9): 2937–2945

60 Zhuravlev L T. The surface chemistry of amorphous silica. Zhuravlev model. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2000, 173(1–3): 1–38

61 Zhao D Y, Feng J L, Huo Q S, Melosh N, Fredrickson G H, Chemelka B F, Stucky G D. Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores. Science, 1998, 279(5350): 548–552

62 Cassiers K, Van Der Voort P, Vansant E F. Synthesis of stable and directly usable hexagonal mesoporous silica by efficient amine extraction in acidified water. Chemical Communications, 2000, 24(24): 2489–2490

63 Tian B Z, Liu X Y, Yu C Z, Gao F, Luo Q, Xie S H, Tu B, Zhao D Y. Microwave assisted template removal of siliceous porous materials. Chemical Communications, 2002, 11(11): 1186–1187