Abstract
Chromia/alumina (Cr2O3/γ-Al2O3) catalysts with addition of chelating agents (citric acid or oxalic acid) were prepared by the incipient impregnation method. The resulting catalysts with different citric acid (CA) or oxalic acid (OA) contents were applied to the dehydrogenation of isobutane to isobutene. The influence of chelating agents on the catalysts was investigated by means of BET, SEM, H2-TPR, NH3-TPD, and TG-DTG. The results showed that the Cr2O3/γ-Al2O3 catalysts with addition of CA or OA exerted slightly increase on specific surface area. The addition of the chelating agents as expected, determined a general decrease in the surface acidity. The catalysts with CA or OA have a better anti-coking ability by inhibiting the side reaction of cracking and carbon formation. The addition of CA or OA for preparing these catalysts resulted in a beneficial effect on the reducibility of the Cr species to diminish the reduction temperature. The appropriate content of chelating agents could improve dispersion of metal species in the γ-Al2O3 support. The catalytic activity showed an important enhancement when the metal species was impregnated in the presence of CA or OA.
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Deng J, Zhang L, Liu C et al (2011) Single-crystalline mesoporous CaO supported Cr–V binary oxides: highly active catalysts for the oxidative dehydrogenation of isobutane. Catal Today 164:347–352. https://doi.org/10.1016/j.cattod.2010.10.023
Duan Y, Zhou Y, Zhang Y et al (2011) Effect of sodium addition to PtSn/AlSBA-15 on the catalytic properties in propane dehydrogenation. Catal Lett 141:120–127. https://doi.org/10.1007/s10562-010-0445-6
Fridman VZ, Xing R (2017) Investigating the CrOx/Al2O3 dehydrogenation catalyst model: II. Relative activity of the chromium species on the catalyst surface. Appl Catal A 530:154–165. https://doi.org/10.1016/j.apcata.2016.11.024
Fridman VZ, Xing R, Severance M (2016) Investigating the COx/Al2O3 dehydrogenation catalyst model: I. identification and stability evaluation of the Cr species on the fresh and equilibrated catalysts. Appl Catal A 523:39–53. https://doi.org/10.1016/j.apcata.2016.05.008
Kang KH, Kim TH, Choi WC et al (2015) Dehydrogenation of propane to propylene over CrOy–CeO2–K2O/γ-Al2O3, catalysts: effect of cerium content. Catal Commun 72:68–72. https://doi.org/10.1016/j.catcom.2015.09.009
Klimova T, Lizama L, Amezcua JC et al (2004) New NiMo catalysts supported on Al-containing SBA-16 for 4,6-DMDBT hydrodesulfurization: effect of the alumination method. Catal Today 98:141–150. https://doi.org/10.1016/j.cattod.2004.07.028
Klimova TE, Valencia D, Mendoza-Nieto JA et al (2013) Behavior of NiMo/SBA-15 catalysts prepared with citric acid in simultaneous hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene. J Catal 304:29–46. https://doi.org/10.1016/j.jcat.2013.03.027
Knaeble W, Carr RT, Iglesia E (2014) Mechanistic interpretation of the effects of acid strength on alkane isomerization turnover rates and selectivity. J Catal 319:283–296. https://doi.org/10.1016/j.jcat.2014.09.005
Lei Z, Jiguang D, Hongxing D, Chak TA (2009) Binary Cr–Mo oxide catalysts supported on MgO-coated polyhedral three-dimensional mesoporous SBA-16 for the oxidative dehydrogenation of isobutane. Appl Catal A 354:72–81. https://doi.org/10.1016/j.apcata.2008.11.009
Leilei X, Zhonglai W, Huanling S, Lingjun C (2013) Catalytic dehydrogenation of isobutane over ordered mesoporous Cr2O3–Al2O3 composite oxides. Catal Commun 35:76–81. https://doi.org/10.1016/j.catcom.2013.02.011
Lelias MA, Kooyman PJ, Mariey L (2008) Effect of NTA addition on the formation, structure and activity of the active phase of cobalt–molybdenum sulfide hydrotreating catalysts. Catal Today 130:109–116. https://doi.org/10.1016/j.jcat.2009.07.006
Li Y, Liu D, Liu C (2010) Hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) performance of an ex situ presulfided MoNiP/Al2O3 catalyst: model compounds study and pilot test for fluidized catalytic cracking (FCC) diesel oil. Energy Fuels 24:820–829. https://doi.org/10.1021/ef901084f
Qing L, Zhijun S, Xinggui Z, Yian Z, Jinghong Z, De C (2011) Coke formation on Pt–Sn/Al2O3 catalyst in propane dehydrogenation: coke characterization and kinetic study. Top Catal 54:888–896. https://doi.org/10.1007/s11244-011-9708-8
Rombi E, Cutrufello MG, Solinas V, De Rossi S, Ferraris G, Pistone A (2003) Effects of potassium addition on the acidity and reducibility of chromia/alumina dehydrogenation catalysts. Appl Catal A 251:255–266. https://doi.org/10.1016/S0926-860X(03)00308-9
Sahebdelfar S, Bijani PM, Saeedizad M (2011) Modeling of adiabatic moving bed reactor for dehydrogenation of isobutane to isobutene. Appl Catal A Gen 395:107–113. https://doi.org/10.1016/j.apcata.2011.01.027
Sattler JHB, Ruiz-Martinez J, Santillan-Jimenze E, Weckhuysen BM (2014) Catalytic dehydrogenation of light alkanes on metals and metal oxides. Chem Rev 114:10613–10653. https://doi.org/10.1021/cr5002436
Schlatter JC, Oyama ST, Iii JEM et al (1988) Catalytic behavior of selected transition metal carbides, nitrides, and borides in the hydrodenitrogenation of quinoline. Ind Eng Chem Res 27:1648–1653. https://doi.org/10.1021/ie00081a014
Shee D, Sayari A (2010) Light alkane dehydrogenation over mesoporous Cr2O3/Al2O3 catalysts. Appl Catal A 389:155–164. https://doi.org/10.1016/j.apcata.2010.09.013
Shijian Z, Yuming Z, Junjun S, Yiwei Z, Xiaoli S, Zewu Z (2015) Synthesis of Ce-doped mesoporous γ-alumina with enhanced catalytic performance for propane dehydrogention. J Mater Sci 50:3984–3993. https://doi.org/10.1007/s10853-015-8954-8
Sim S, Gong S, Bae J, Park YK, Kim J, Choi WC et al (2017) Chromium oxide supported on Zr modified alumina for stable and selective propane dehydrogenation in oxygen free moving bed process. Mol Catal 436:164–173. https://doi.org/10.1016/j.mcat.2017.04.022
Soler-Illia GJDAA, Sanchez C, Lebeau B et al (2003) Chemical strategies of design textured materials: from microporous and mesoporous oxides to nanonetworks and hierarchical structures. Chem Rev 34:4093–4138. https://doi.org/10.1002/chin.200303279
Sun P, Siddiqi G, Chi M, Bell AT (2010) Synthesis and characterization of a new catalyst Pt/Mg(Ga)(Al)O for alkane dehydrogenation. J Catal 389:155–164. https://doi.org/10.1016/j.jcat.2010.06.017
Węgrzyniak A, Jarczewski S, Węgrzynowicz A, Michorczyk B, Kuśtrowski P, Michorczyk P (2017) Catalytic behavior of chromium oxide supported on nanocasting-prepared mesoporous alumina in dehydrogenation of propane. Nanomaterials 7:249. https://doi.org/10.3390/nano7090249
Zhang S, Wang X, Yang H, Liang X (2011) Effects of CA and EDTA on catalytic performance of Co-Mo-P/TiO2-γ-Al2O3 selective hydrodesulfurization catalysts. Acta Petrol Sin 27:316–321. https://doi.org/10.3969/j.issn.1001-8719.2011.02.027
Zhao H, Song H, Xu L, Chou L (2013) Isobutane dehydrogenation over the mesoporous Cr2O3/Al2O3 catalysts synthesized from a metal-organic framework MIL-101. Appl Catal A 456:188–196. https://doi.org/10.1016/j.apcata.2013.02.018
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The authors gratefully acknowledge the research grants provided by the National Natural Science Foundation of China (21276130, 21506107), NSF of Shandong Province (ZR2014BP009).
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Wang, G., Sun, X., Niu, X. et al. Effect of chelating agents on catalytic performance of Cr/γ-Al2O3 dehydrogenation catalysts. Chem. Pap. 72, 921–928 (2018). https://doi.org/10.1007/s11696-017-0335-0
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DOI: https://doi.org/10.1007/s11696-017-0335-0