화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Korean Chemical Engineering Research, Vol.56, No.4, 600-606, August, 2018
DOI10.9713/kcer.2018.56.4.600  Export Citation
다양한 입자크기와 산성도를 지닌 MTT 제올라이트의 합성 및 촉매특성 연구
Synthesis and Catalytic Performance of MTT Zeolites with Different Particle Size and Acidity
박성준, 장회구, 조성준†
  • 전남대학교 화학공학부, 61186 광주광역시 북구 용봉로 77
Sung Jun Park, Hoi-Gu Jang, and Sung June Cho†
  • Department of Chemical Engineering, Chonnam National University, 77, Yongboug-ro, Buk-gu, Gwangju, 61186, Korea
E-mail:
초록
다양한 Si/Al 몰비를 지닌 MTT 제올라이트를 합성하여 methanol-to-olefin(MTO) 반응에서 촉매의 산성도가 미치는 영향을 조사하였다. Si/Al 몰비를 조절하기 위해 N,N,N',N'-테트라메틸-1,3-디아미노프로판을 구조유도물질(SDA)로 사용하였으며, 알루민산나트륨의 함량을 달리하여 20SiO2 : 30SDA : x (=0.25~1.25)NaAlO2: 2NaOH: 624H2O 조성으로 모액을 제조한 후 433 K에서 4일 동안 수열 합성하였다. 알루민산나트륨의 함량이 감소함에 따라 MTT 제올라이트의 입자 크기가 증가하였으며 또한 산점의 양도 감소하였다. 제조한 MTT 제올라이트의 촉매 활성을 평가하기 위해 673 K에서 공간속도(WHSV)가 1.2 h-1인 조건으로 MTO 반응을 수행한 결과, Si/Al 몰비가 24인 H-MTT (1.00Al) 촉매가 900분까지 90% 이상의 전환율을 유지함을 확인하였다.
The influence of acidity in MTT zeolite of different Si/Al molar ratio’s on the catalyst activity in methanolto- olefin (MTO) reaction has been investigated. The Si/Al ratio was controlled with the Al content in the gel when N,N, N',N'-tetramethyl-1,3-diaminopropane was used as a structure directing agent (SDA). The gel composition was controlled to 20SiO2 : 30SDA : x (=0.25~1.25)NaAlO2 : 2NaOH : 624H2O, which was subject to the hydrothermal synthesis at 433 K for 4 days. As the composition of sodium aluminate decreased, the particle size of MTT zeolite increased, and also the amount of acid sites decreased. To investigate the catalytic performance, MTO reaction was carried out at 673 K with 1.2 h-1 WHSV. It was found that the H-MTT (1.00Al) catalyst with a Si/Al molar ratio of 24 maintained the methanol conversion over 90% for 900 min.
Keywords:MTT zeolite;Particle size;Acidity;MTO reaction
  1. Smith JV, Zeolites, 4, 309 (1984)
  2. Weitkamp J, Solid State Ion., 131(1-2), 175 (2000)
  3. Vermeiren W, Gilson JP, Top. Catal., 52, 1131 (2009)
  4. Ward JW, J. Catal., 9, 225 (1967)
  5. Tanabe K, Holderich WF, Appl. Catal. A: Gen., 181(2), 399 (1999)
  6. Stocker M, Microporous Mesoporous Mater., 29, 3 (1999)
  7. Wilson S, Barger P, Microporous Mesoporous Mater., 29, 117 (1999)
  8. Teketel S, Skistad W, Benard S, Olsbye U, Lillerud KP, Beato P, Svelle S, ACS Catal., 2, 26 (2012)
  9. Teketel S, Lundegaard LF, Skistad W, Chavan SM, Olsbye U, Lillerud KP, Beato P, Svelle S, J. Catal., 327, 22 (2015)
  10. Losch P, Pinar AB, Willinger MG, Soukup K, Chavan S, Vincent B, Pale P, Louis B, J. Catal., 345, 11 (2017)
  11. Nishiyama N, Kawaguchi M, Hirota Y, Van Vu D, Egashira Y, Ueyama K, Appl. Catal. A: Gen., 362(1-2), 193 (2009)
  12. Wei FF, Cui ZM, Meng XJ, Cao CY, Xiao FS, Song WG, ACS Catal., 4, 529 (2014)
  13. Plank CJ, Rosinski EJ, Rubin MK, “Crystalline Zeolite ZSM-23 and Synthesis Thereof,” US Pat., 4076842(1978).
  14. Wang BC, Tian ZJ, Li P, Wang L, Xu YP, Qu W, He YL, Ma HJ, Xu ZS, Lin LW, Microporous Mesoporous Mater., 134, 203 (2010)
  15. Valyocsik EW, “Synthesis of ZSM-23 Zeolite,” US Pat., 4490342 (1984).
  16. Valyocsik EW, “Synthesis of ZSM-23 Zeolite and the Product Produced,” US Pat., 4619820(1986).
  17. Wang B, Gao Q, Gao JD, Ji D, Wang XL, Suo JS, Appl. Catal. A: Gen., 274(1-2), 167 (2004)
  18. Huybrechts W, Vanbutsele G, Houthoofd KJ, Bertinchamps F, Narasimhan CLS, Gaigneaux EM, Thybaut JW, Marin GB, Denayer JFM, Baron GV, Jacobs PAA, Martens JA, Catal. Lett., 100(3-4), 235 (2005)
  19. Rouleau L, Kolenda F, Benazzi E, US Pat. 6692723(2004).
  20. Wu Q, Wang X, Meng X, Yang C, Liu Y, Jin YY, Yang Q, Xiao FS, Microporous Mesoporous Mater., 186, 106 (2014)
  21. Liu Y, Wang ZD, Ling Y, Li XB, Liu YM, Wu P, Chin. J. Catal., 30(6), 525 (2009)
  22. Lee HJ, Kim SH, Kim JH, Park SJ, Cho SJ, Microporous Mesoporous Mater., 195, 205 (2014)
  23. Molino A, Lukaszuk KA, Rojo-Gama D, Lillerud KP, Olsbye J, Bordiga S, Svelle S, Beato P, Chem. Commun., 53, 6816 (2017)
  24. Sedighi M, Ghasemi M, Jahangiri A, Korean J. Chem. Eng., 34(4), 997 (2017)
  25. Rashidi H, Shariati A, Khosravi-Nikou MR, Hamoule T, Korean J. Chem. Eng., 33(8), 2319 (2016)
  26. Park SJ, Jang HG, Lee KY, Cho SJ, Microporous Mesoporous Mater., 256, 155 (2018)
  27. Kim SJ, Jang HG, Seo G, Korean Chem. Eng. Res., 51(2), 181 (2013)
  28. Muller S, Liu Y, Vishnuvarthan M, Sun XY, van Veen AC, Haller GL, Sanchez-Sanchez M, Lercher JA, J. Catal., 325, 48 (2015)
  29. Marler B, Deroche C, Gies H, J. Appl. Crystallogr., 26, 636 (1993)
  30. Sing KSW, Everett DH, Haul R, Moscou L, Pierotti RA, Rouquerol J, Siemieniewska T, Pure Appl. Chem., 57, 603 (1985)