화학공학소재연구정보센터
Journal of the Korean Industrial and Engineering Chemistry, Vol.13, No.3, 199-215, May, 2002
팔라디움 복합막의 제조 및 응용
Fabrication and Application of Palladium-based Alloy Composite Membranes
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초록
팔라디움(Pd)계 막들은 수소에 대한 선택투과도가 매우 높아서 고온의 혼합 기체 중에서 고순도 수소기체의 분리에 효과적으로 이용되고 있으며 탈수소 반응 등과 연계되어 많은 연구가 이루어져왔다. 순수한 팔라디움 금속 막의 경우 수소를 투과하면 수소농도에 따라 α 상 이외에 β 상이 형성되어 격자 평창에 의한 뒤틀림 현상이 발생하여 부스러지기 쉬우며 이를 보완하기 위해 니켈, 구리, 은 등 다른 금속과의 합금이 반드시 요구된다. 또한 높은 수소투과 속도와 기계적 강도를 함께 유지하기 위해 복합막 형태의 팔라디움 막이 제조되며 복합막 제조시 박막의 핀홀을 최소화하고 장기적 안정성을 유지하는 것이 매우 중요한 문제이다. 이러한 팔라디움 막을 막반응기에 활용함으로써 탈수소 반응이나 수증기 개질 반응 등의 반응효율을 크게 높일 수 있다. 본고에서는 팔라디움 막의 구조 및 수소와 다른 기체투과 메카니즘, 여러 팔라디움 복합막 제조 방법 및 이에 따른 특성 그리고 이들의 응용분야에 대해 살펴보고자 한다.
Palladium(Pd) and Palladium alloy membranes, which are well-known nonporous membranes with high perm-selectivity of hydrogen, have been used to separate hydrogen of high purity from various gas mixtures. The study of these membrane systems as hydrogen separation membranes and membrane reactors has been rather extensive for the past several decades. Pd alloys with other metals such as nickel, copper and silver are preferred over pure Pd, since pure Pd is subject to the α→β phase transformation due to the adsorption of hydrogen, which changes the atom spacing in the metal lattice and becomes brittle after repeated cycles of hydrogen sorption and desorption. For high flux of hydrogen permeation together with mechanical stability, Pd membranes have been mostly composite type structure with thin coating layers over a mechanically strong porous supporting layer. Minimization of pin holes and maintenance of long term stability of thin coating layer are very important factors in the preparation of composit membranes. The reaction efficiency of de-hydrogenation and water vapor reforming reaction was improved by the membrane reactors made with these palladium membranes. In this paper the structure of palladium membranes, the transport mechanism of hydrogne and gases, the preparation and characteristics of various composite palladium membranes and their applications will be discused.
  1. Hsieh HP, Inorganic Membranes for Separation and Reaction, Elsevier (1996)
  2. Shu J, Grandjean BPA, van Neste A, Kaliaguine S, J. Chem. Eng., 69, 1036 (1991)
  3. Lee KH, Hwang ST, J. Colloid Interface Sci., 110(2), 544 (1986) 
  4. 황선탁, 멤브레인, 7(1), 1 (1997)
  5. Hurlbert RC, Konecny JO, J. Chem. Phys., 34, 655 (1961) 
  6. Jayaraman V, Lin YS, J. Membr. Sci., 104(3), 251 (1995) 
  7. Jayaraman V, Lin YS, Pakala M, Lin RY, J. Membr. Sci., 99(1), 89 (1995) 
  8. Bryden KJ, Ying JY, Mater. Sci. Eng. A, 204, 140 (1995) 
  9. Nam SE, Lee KH, J. Membr. Sci., 170(1), 91 (2000) 
  10. Bryden KJ, Ying JY, J. Electrochem. Soc., 145(10), 3339 (1998) 
  11. Shackelford JF, Introduction to Materials Science for Engineers, 4th Ed., Prentice Hall Inter. (1996)
  12. Uemiya S, Kude Y, Sugino K, Sato N, Matsuda T, Kikuchi E, Chem. Lett., 10, 1687 (1988) 
  13. Viehbeck A, Kovac CA, Buchwalter SL, Goldberg MJ, Tisdale SL, Redox seedind and Electroless Metallization of Polyimides, in: E. Sacher, J.J. Pireaux and P. Kowalczyk (Eds.), Metallization of Polymers, ACS Symp. Ser. No. 440, American Chemical Society, Washington DC, 394 (1990)
  14. Uemiya S, Matsuda T, Kikuchi E, J. Membr. Sci., 56, 315 (1991) 
  15. Yan SC, Maeda H, Kusakabe K, Morooka S, Ind. Eng. Chem. Res., 33(3), 616 (1994) 
  16. Li AW, Liang WQ, Hughes R, J. Membr. Sci., 149(2), 259 (1998) 
  17. Nam SE, Lee SH, Lee KH, J. Membr. Sci., 153(2), 163 (1999) 
  18. Mardilovich PP, She Y, Ma YH, Rei MH, AIChE J., 44(2), 310 (1998) 
  19. Govind R, Atnoor D, Ind. Eng. Chem. Res., 30, 591 (1991) 
  20. Smirnov VS, Ermilova MM, Gryaznov VM, Orekova NV, Polyakova VP, Roshan NR, Savitsky EM, U.K. Patent, 2,068,938 (1983)
  21. Knapton AG, Plat. Met. Rev., 21, 44 (1977)
  22. Li AW, Xiong GX, Gu JH, Zheng LB, J. Membr. Sci., 110(2), 257 (1996) 
  23. Collins JP, Way JD, Ind. Eng. Chem. Res., 32, 3006 (1993) 
  24. Yeung KL, Varma A, AIChE J., 41(9), 2131 (1995) 
  25. Li A, Liang W, Hughes R, Sep. Purif. Technol., 15(2), 113 (1999) 
  26. Xomeritakis G, Lin YS, J. Membr. Sci., 120(2), 261 (1996) 
  27. Uemiya S, Kajiwara M, Kojima T, AIChE J., 43(11), 2715 (1997) 
  28. Jun CS, Lee KH, J. Membr. Sci., 176(1), 121 (2000) 
  29. Sturzeneger B, Puippe J, Plat. Met. Rev., 20, 117 (1984)
  30. Kikuchi H, Alloy Plated Membranes for Hydrogen Separation and Their Manufacture, Japanese Patent, 88,294,925 (1988)
  31. Itoh N, Haratania K, Shindo Y, Ceramic Membranes for the Separation of Hydrogen from Gas Mixtures, Japanese Patent, 89,04,216 (1989)
  32. Xomeritakis G, Lin YS, J. Membr. Sci., 133(2), 217 (1997) 
  33. Li ZY, Maeda H, Kusakakabe K, Morooka S, Anzai H, Akiyama S, J. Membr. Sci., 78, 247 (1993) 
  34. Jun CS, Lee KH, J. Membr. Sci., 157(1), 107 (1999) 
  35. Armor JN, J. Membr. Sci., 147(2), 217 (1998) 
  36. Nagamoto H, Inoue H, Chem. Eng. Commun., 34, 315 (1985)
  37. Itoh N, Shindo Y, Haraya K, J. Chem. Eng. Jpn., 23(4), 420 (1990) 
  38. Kusakabe K, Yokoyama S, Morooka S, Hayashi JI, Nagata H, Chem. Eng. Sci., 51(11), 3027 (1996) 
  39. Shu J, Grandjean BP, Kaliaguine S, Ciavarella P, Giroirfendler A, Dalmon JA, Can. J. Chem. Eng., 75(4), 712 (1997)
  40. Collins JP, Way JD, J. Membr. Sci., 96(3), 259 (1994) 
  41. Gobina E, Hughes R, J. Membr. Sci., 90(1-2), 11 (1994) 
  42. Gobina E, Hughes R, Appl. Catal. A: Gen., 137(1), 119 (1996) 
  43. Weyten H, Luyten J, Keizer K, Willems L, Leysen R, Catal. Today, 56(1-3), 3 (2000) 
  44. Lucke SL, Herzog F, Glaubitz D, Hydrogen Energy Progress 7, Vol. 2, Oxford, 819 (1988)
  45. Itoh N, Wu TH, J. Membr. Sci., 124(2), 213 (1997) 
  46. Lee DW, Lee KH, J. Korean Ind. Eng. Chem., 12(1), 45 (2001)
  47. Barbieri G, Violante V, Dimaio FP, Criscuoli A, Drioli E, Ind. Eng. Chem. Res., 36(8), 3369 (1997) 
  48. Adris AM, Elnashaie SSEH, Hughes R, J. Chem. Eng., 69(5), 1061 (1991)
  49. Chai M, Machida M, Eguchi K, Arai H, Chem. Lett., 1, 41 (1993) 
  50. Shu J, Grandjean BP, Kaliaguine S, Appl. Catal. A: Gen., 119(2), 305 (1994) 
  51. Barbieri G, Marigliano G, Perri G, Drioli E, Ind. Eng. Chem. Res., 40(9), 2017 (2001) 
  52. Uemiya S, Sato N, Ando H, Kude Y, Matsuda T, Kikuchi E, J. Membr. Sci., 56, 303 (1991) 
  53. Kikuchi E, Uemiya S, Gas Sep. Purif., 5, 261 (1991) 
  54. Kikuchi E, Catal. Today, 56(1-3), 97 (2000) 
  55. Uemiya S, Sato N, Ando H, Kikuchi E, Ind. Eng. Chem. Res., 30, 585 (1991) 
  56. Nam SE, Lee KH, J. Korean Ind. Eng. Chem., 11(1), 113 (2000)
  57. Nam SE, Lee KH, J. Membr. Sci., 192(1-2), 177 (2001) 
  58. Lee KH, Nam SE, Seo BG, Lee DW, Lee KY, Theor. Appl. Chem. Eng., 7, 905 (2001)
  59. Lin YM, Rei MH, Catal. Today, 67(1-3), 77 (2001) 
  60. Lin YM, Rei MH, Sep. Purif. Technol., 25, 87 (2001)