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Catalytic oxidative dehydrogenation of 1-butene to 1,3-butadiene with CO2 over Fe2O3/γ-Al2O3 catalysts: the effect of acid or alkali modification

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Abstract

Fe2O3/γ-Al2O3 catalysts were modified by acid and alkali (H2SO4, LiOH, NaOH and KOH) and were investigated for 1,3-butadiene (BD) synthesis through the oxidative dehydrogenation of 1-butene with CO2. Nitrogen sorption and XRD results revealed that physical and original crystalline structure of Fe2O3/γ-Al2O3 catalysts remained intact after the modification. The acidity and alkalinity of the catalysts were determined quantitatively and qualitatively by NH3-TPD and CO2-TPD, respectively. The sequence of catalyst activity for these five catalysts was: Li–Fe2O3/γ-Al2O3 > S–Fe2O3/γ-Al2O3 > Fe2O3/γ-Al2O3 > K–Fe2O3/γ-Al2O3 > Na–Fe2O3/γ-Al2O3. The catalytic activity (BD rate) of Fe2O3/γ-Al2O3 catalysts was improved ~41% after the modification of LiOH. Results indicated that too little amount of acid sites as well as the strong basic sites over catalyst surface were not facilitate to the formation of BD. TG characterization results illustrated that the coke resistant ability of the catalysts was enhanced with the catalyst alkalinity.

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References

  1. White WC (2007) Butadiene production process overview. Chem Biol Interact 166:10–14

    Article  CAS  Google Scholar 

  2. Makshina EV, Dusselier M, Janssens W, Degreve J, Jacobs PA, Sels BF (2014) Review of old chemistry and new catalytic advances in the on-purpose synthesis of butadiene. Chem Soc Rev 43:7917–7953

    Article  CAS  Google Scholar 

  3. Yan WJ, Kouk QY, Luo JZ, Liu Y, Borgna A (2014) Catalytic oxidative dehydrogenation of 1-butene to 1,3-butadiene using CO2. Catal Commun 46:208–212

    Article  CAS  Google Scholar 

  4. Yan WJ, Luo JZ, Kouk QY, Zheng JE, Zhong ZY, Liu Y, Borgna A (2015) Improving oxidative dehydrogenation of 1-butene to 1,3-butadiene on Al2O3 by Fe2O3 using CO2 as soft oxidant. Appl Catal A 508:61–67

    Article  CAS  Google Scholar 

  5. Yan W, Kouk QY, Tan SX, Luo J, Liu Y (2016) Effects of Pt0-PtOx particle size on 1-butene oxidative dehydrogenation to 1,3-butadiene using CO2 as soft oxidant. J CO2 Util 15:154–159

    Article  CAS  Google Scholar 

  6. Zhang X, Zhong J, Wang J, Zhang L, Gao J, Liu A (2009) Catalytic performance and characterization of Ni-doped HZSM-5 catalysts for selective trimerization of n-butene. Fuel Process Technol 90:863–870

    Article  CAS  Google Scholar 

  7. Wang SB, Zhu ZH (2004) Catalytic conversion of alkanes to olefins by carbon dioxide oxidative dehydrogenation—a review. Energy Fuels 18:1126–1139

    Article  CAS  Google Scholar 

  8. Wang D, Xu M, Shi C, Lunsford JH (1993) Effect of carbon dioxide on the selectivities obtained during the partial oxidation of methane and ethane over Li+/MgO catalysts. Catal Lett 18:323–328

    Article  CAS  Google Scholar 

  9. Krylov OV, Mamedov AK, Mirzabekova SR (1995) The regularities in the interaction of alkanes with CO2 on oxide catalysts. Catal Today 24:371–375

    Article  CAS  Google Scholar 

  10. Krylov OV, Mamedov AK, Mirzabekova SR (1995) Oxidation of hydrocarbons and alcohols by carbon dioxide on oxide catalysts. Ind Eng Chem Res 34:474–482

    Article  CAS  Google Scholar 

  11. Zhaorigetu B, Kieffer R, Hindermann JP (1996) Oxidative dehydrogenation of propane on rare earth vanadates influence of the presence of CO2 in the feed. Stud Surf Sci Catal 101:1049–1058

    Article  CAS  Google Scholar 

  12. Takahara I, Saito M (1996) Promoting effects of carbon dioxide on dehydrogenation of propane over a SiO2-supported Cr2O3 catalyst. Chem Lett 11:973–974

    Article  Google Scholar 

  13. Takahara I, Chang WC, Mimura N, Saito M (1998) Promoting effects of CO2 on dehydrogenation of propane over a SiO2-supported Cr2O3 catalyst. Catal Today 45:55–59

    Article  CAS  Google Scholar 

  14. Ogonowski J, Skrzynska E (2006) Activity of vanadium magnesium oxide supported catalysts in the dehydrogenation of isobutane. Catal Lett 111:79–85

    Article  CAS  Google Scholar 

  15. Chen M, Wu JL, Liu YM, Cao Y, Guo L, He HY, Fan KN (2011) Study in support effect of In2O3/MOx (M = Al, Si, Zr) catalysts for dehydrogenation of propane in the presence of CO2. Appl Catal A 407:20–28

    Article  CAS  Google Scholar 

  16. Ge X, Zou H, Wang J, Shen JY (2005) Modification of Cr/SiO2 for the dehydrogenation of propane to propylene in carbon dioxide. React Kinet Catal Lett 85:253–260

    Article  CAS  Google Scholar 

  17. Ajayi BP, Jermy BR, Abussaud BA, Al-Khattaf S (2013) Oxidative dehydrogenation of n-butane over bimetallic mesoporous and microporous zeolites with CO2 as mild oxidant. J Porous Mat 20:1257–1270

    Article  CAS  Google Scholar 

  18. Ding JF, Qin ZF, Chen SW, Li XK, Wang GF, Wang JG (2010) Coupling dehydrogenation of isobutane to isobutene in the presence of carbon dioxide over NiO/Al2O3 catalyst. J Fuel Chem Technol 38:458–461

    Article  CAS  Google Scholar 

  19. Lee H, Jung JC, Kim H, Chung YM, Kim TJ, Lee SJ, Oh SH, Kim YS, Song IK (2008) Effect of divalent metal component (Me(II)) on the catalytic performance of Me(II)Fe(2)O(4) catalysts in the oxidative dehydrogenation of n-butene to 1,3-butadiene. Catal Lett 124:364–368

    Article  CAS  Google Scholar 

  20. Akah AC, Nkeng G, Garforth AA (2007) The role of Al and strong acidity in the selective catalytic oxidation of NH3 over Fe-ZSM-5. Appl Catal B 74:34–39

    Article  CAS  Google Scholar 

  21. Chen WH, Ko HH, Sakthivel A, Huang SJ, Liu SH, Lo AY, Tsai TC, Liu SB (2006) A solid-state NMR, FT-IR and TPD study on acid properties of sulfated and metal-promoted zirconia: influence of promoter and sulfation treatment. Catal Today 116:111–120

    Article  CAS  Google Scholar 

  22. Long LL, Lang WZ, Yan X, Xia K, Guo YJ (2016) Yttrium-modified alumina as support for trimetallic PtSnIn catalysts with improved catalytic performance in propane dehydrogenation. Fuel Process Technol 146:48–55

    Article  CAS  Google Scholar 

  23. Mollavali M, Yaripour F, Mohammadi-Jam S, Atashi H (2009) Relationship between surface acidity and activity of solid-acid catalysts in vapour phase dehydration of methanol. Fuel Process Technol 90:1093–1098

    Article  CAS  Google Scholar 

  24. Lin X, Zhang Y, Yin L, Chen C, Zhan Y, Li D (2014) Characterization and catalytic performance of copper-based WGS catalysts derived from copper ferrite. Int J Hydrogen Energy 39:6424–6432

    Article  CAS  Google Scholar 

  25. Li C, Tan PJ, Li XD, Du YL, Gao ZH, Huang W (2015) Effect of the addition of Ce and Zr on the structure and performances of Ni–Mo/CeZr–MgAl(O) catalysts for CH4–CO2 reforming. Fuel Process Technol 140:39–45

    Article  CAS  Google Scholar 

  26. Naeem MA, Al-Fatesh AS, Abasaeed AE, Fakeeha AH (2014) Activities of Ni-based nano catalysts for CO2–CH4 reforming prepared by polyol process. Fuel Process Technol 122:141–152

    Article  CAS  Google Scholar 

  27. Srivastava R, Srinivas D, Ratnasamy P (2006) Sites for CO2 activation over amine-functionalized mesoporous Ti(Al)-SBA-15 catalysts. Microporous Mesoporous Mater 90:314–326

    Article  CAS  Google Scholar 

  28. Yu J, Wang R, Ren S, Sun X, Chen C, Ge Q, Fang W, Zhang J, Xu H, Su DS (2012) The unique role of CaO in stabilizing the Pt/Al2O3 catalyst for the dehydrogenation of cyclohexane. ChemCatChem 4:1376–1381

    Article  CAS  Google Scholar 

  29. Shamsi A, Baltrus JP, Spivey JJ (2005) Characterization of coke deposited on Pt/alumina catalyst during reforming of liquid hydrocarbons. Appl Catal A 293:145–152

    Article  CAS  Google Scholar 

  30. Larsson M, Hultén M, Blekkan EA, Andersson B (1996) The effect of reaction conditions and time on stream on the coke formed during propane dehydrogenation. J Catal 164:44–53

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (NSFC) (Grant No. 21606172, 21306139), the PetroChina Innovation Foundation (2016D-5007-0502), the Project from Tianjin University of Science & Technology (2014CXLG15) and the National Training Program of Innovation and Entrepreneurship for Undergraduates (201610057135).

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Authors and Affiliations

  1. College of Chemical Engineering and Materials Science, Tianjin University of Science and Technology, Tianjin, 300457, China

    Yue Gao, Bolong Wang, Bing Yan, Jian Li, Fakhre Alam, Zaozao Xiao & Tao Jiang

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  1. Yue Gao
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  2. Bolong Wang
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  3. Bing Yan
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  4. Jian Li
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Correspondence to Bing Yan.

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Gao, Y., Wang, B., Yan, B. et al. Catalytic oxidative dehydrogenation of 1-butene to 1,3-butadiene with CO2 over Fe2O3/γ-Al2O3 catalysts: the effect of acid or alkali modification. Reac Kinet Mech Cat 122, 451–462 (2017). https://doi.org/10.1007/s11144-017-1205-z

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