Reaction Kinetics, Mechanisms and Catalysis

, Volume 126, Issue 1, pp 219–235 | Cite as

Comparison of the properties and catalytic activity of commercially and laboratory prepared Mg/Al mixed oxides in aldol condensation of cyclohexanone with furfural

  • David KadlecEmail author
  • Zdeněk Tišler
  • Romana Velvarská
  • Lenka Pelíšková
  • Uliana Akhmetzyanova


In recent years, for deeper understanding of the behavior of various heterogeneous catalysts, aldol condensation of acetone and furfural has been researched in detail. In this article, the carbonyl reactants are represented by cyclohexanone and furfural as the platform chemicals for synthesis the fundamental building blocks for future biorefineries. Our main goal was to explore the structural and acid–base properties and to compare them with catalytic characteristics of Mg/Al mixed oxides in aldol condensation of cyclohexanone with furfural. The aforesaid basic heterogeneous catalysts were obtained by the calcination of commercially and laboratory prepared hydrotalcites with different molar ratios (1:1–5:1). Their physicochemical properties were determined based on several analytical methods: XRD, ICP-OES, SEM, N2 physisorption, TGA, TGA-MS, DRIFT, TPD-CO2 and TPD-NH3. Through XRD, it was found that as-synthesized laboratory hydrotalcites had the pure crystalline hydrotalcite structure while commercial ones contained also the brucite and MgO phases. By using TPD-CO2 and TPD-NH3, the measured values, especially the total amount of basic sites, provided the best correlation with the catalytic activity of investigated catalysts. Comparable conversions of furfural (ca. 87%) were achieved on laboratory and commercial mixed oxides with the Mg/Al molar ratio 1:1 and 3:1, respectively. They had no obvious difference in selectivity to FCH (about 20%) whereas the commercial samples showed higher selectivity to F2CH (26% at max conversion) than the laboratory ones (17%).


Mg/Al hydrotalcite Layered double hydroxides Mg/Al mixed oxides Aldol condensation Cyclohexanone Furfural 



The publication is a result of the project Reg. No. TH01011223. This project has been funded with support from state funds through the Technology Agency of the Czech Republic. The project has been integrated into the National Sustainability Programme I of the Ministry of Education, Youth and Sports of the Czech Republic (MEYS) through the project Development of the UniCRE Centre (LO1606). The result was achieved using the infrastructure included in the project Efficient Use of Energy Resources Using Catalytic Processes (LM2015039) which has been financially supported by MEYS within the targeted support of large infrastructures.

Supplementary material

11144_2018_1497_MOESM1_ESM.docx (971 kb)
Supplementary material 1 (DOCX 970 kb)


  1. 1.
    Hora L, Kelbichová V, Kikhtyanin O, Bortnovskiy O, Kubička D (2014) Aldol condensation of furfural and acetone over Mg-Al layered double hydroxides and mixed oxides. Catal Today 223:138–147CrossRefGoogle Scholar
  2. 2.
    Lauwaert J, De Canck E, Esquivel D, van der Voort P, Thybaut JW, Marin GB (2015) Effect of amine structure and base strength on acid-base cooperative aldol condensation. Catal Today 246:35–45CrossRefGoogle Scholar
  3. 3.
    Silva CCCM, Ribeiro NFP, Souza MMVM, Aranda DAG (2010) Biodiesel production from soybean oil and methanol using hydrotalcites as catalyst. Fuel Process Technol 91:205–210CrossRefGoogle Scholar
  4. 4.
    Endalew AK, Kiros Y, Zanzi R (2011) Inorganic heterogeneous catalysts for biodiesel production from vegetable oils. Biomass Bioenergy 35:3787–3809CrossRefGoogle Scholar
  5. 5.
    Semwal S, Arora AK, Badoni RP, Tuli DK (2011) Biodiesel production using heterogeneous catalysts. Bioresour Technol 102:2151–2161CrossRefGoogle Scholar
  6. 6.
    Khan AI, O’Hare D (2002) Intercalation chemistry of layered double hydroxides: recent developments and applications. J Mater Chem 12:3191–3198CrossRefGoogle Scholar
  7. 7.
    Takehira K (2017) Recent development of layered double hydroxide-derived catalysts—rehydration, reconstitution and supporting, aiming at commercial application. Appl Clay Sci 136:112–141CrossRefGoogle Scholar
  8. 8.
    Kikhtyanin O, Lesnik E, Kubička D (2016) The occurrence of Cannizzaro reaction over Mg-Al hydrotalcites. Appl Catal A 525:215–225CrossRefGoogle Scholar
  9. 9.
    Vrbková E, Tišler Z, Vyskočilová E, Kadlec D, Červený L (2018) Aldol condensation of benzaldehyde and heptanal: a comparative study of laboratory and industrially prepared Mg-Al mixed oxides. J Chem Technol Biotechnol 93:166–173CrossRefGoogle Scholar
  10. 10.
    Kuśtrowski P, Sulkowska D, Chmielarz L, Rafalska-Łasocha A, Dudek B, Dziembaj R (2005) Influence of thermal treatment conditions on the activity of hydrotalcite-derived Mg-Al oxides in the aldol condensation of acetone. Microporous Mesoporous Mater 78:11–22CrossRefGoogle Scholar
  11. 11.
    Hora L, Kikhtyanin O, Čapek L, Bortnovskiy O, Kubička D (2015) Comparative study of physic-chemical properties of laboratory and industrially prepared layered double hydroxides and their behaviour in aldol condensation of furfural and acetone. Catal Today 241:221–230CrossRefGoogle Scholar
  12. 12.
    Cavani F, Trifiró F, Vaccari A (1991) Hydrotalcite-type anionic clays: preparation, properties and applications. Catal Today 11:173–301CrossRefGoogle Scholar
  13. 13.
    Kikhtyanin O, Čapek L, Smoláková L, Tišler Z, Kadlec D, Lhotka M, Diblíková P, Kubička D (2017) Influence of Mg-Al mixed oxide compositions on their properties and performance in aldol condensation. Ind Eng Chem Res 56:13411–13422CrossRefGoogle Scholar
  14. 14.
    Pérez CN, Monteiro JLF, Nieto JML, Henriques CA (2009) Influence of basic properties of Mg, Al-mixed oxides on their catalytic activity in Knoevenagel condensation between benzaldehyde and phenylsulfonylacetonitrile. Quim Nova 32:2341–2346CrossRefGoogle Scholar
  15. 15.
    Prescott HA, Li ZJ, Kemnitz E, Trunschke A, Deutsch J, Lieske H, Auroux A (2005) Application of calcined Mg-Al hydrotalcites for Michael additions: an investigation of catalytic activity and acid-base properties. J Catal 234:119–130CrossRefGoogle Scholar
  16. 16.
    Nowicki J, Lach J, Organek M, Sabura E (2016) Transesterification of rapeseed oil to biodiesel over Zr-dopped MgAl hydrotalcites. Appl Catal A 524:17–24CrossRefGoogle Scholar
  17. 17.
    Climent MJ, Corma A, Guil-Lopez R, Iborra S, Primo J (1999) Solid catalysts for the production of fine chemicals: the use of ALPON and hydrotalcite base catalysts for the synthesis of arylsulfones. Catal Lett 59:33–38CrossRefGoogle Scholar
  18. 18.
    Ono Y (2003) Solid base catalysts for the synthesis of fine chemicals. J Catal 216:406–415CrossRefGoogle Scholar
  19. 19.
    Velu S, Swamy CS (1994) Alkylation of phenol with methanol over magnesium-aluminium calcined hydrotalcites. Appl Catal A 119:241–252CrossRefGoogle Scholar
  20. 20.
    Kikhtyanin O, Hora L, Kubička D (2015) Unprecedented selectivities in aldol condensation over Mg-Al hydrotalcite in fixed bed reactor setup. Catal Commun 58:89–92CrossRefGoogle Scholar
  21. 21.
    Wang DY, Costa FR, Vyalikh A, Leuteritz A, Scheler U, Jehnichen D, Wagenknecht U, Häussler L, Heinrich G (2009) One-step synthesis of organic LDH and its comparison with regeneration and anion exchange method. Chem Mater 21:4490–4497CrossRefGoogle Scholar
  22. 22.
    Lee JY, Gwak GH, Kim HM, Kim T, Lee GJ, Oh JM (2016) Synthesis of hydrotalcite type layered double hydroxide with various Mg/Al ratio and surface charge under controlled reaction condition. Appl Clay Sci 134:44–49CrossRefGoogle Scholar
  23. 23.
    Cantrell DG, Gillie LJ, Lee AF, Wilson K (2005) Structure-reactivity correlations in MgAl hydrotalcite catalysts for biodiesel synthesis. Appl Catal A 287:183–190CrossRefGoogle Scholar
  24. 24.
    Yun SK, Pinnavaia TJ (1995) Water content and particle texture of synthetic hydrotalcite-like layered double hydroxides. Chem Mater 7:348–354CrossRefGoogle Scholar
  25. 25.
    Hájek M, Kutálek P, Smoláková L, Troppová I, Čapek L, Kubička D, Kocík J, Thanh DN (2015) Transesterification of rapeseed oil by Mg-Al mixed oxides with various Mg/Al molar ratio. Chem Eng J 263:160–167CrossRefGoogle Scholar
  26. 26.
    Abelló S, Medina F, Tichit D, Pérez-Ramírez J, Groen JC, Sueiras JE, Salagre P, Cesteros Y (2005) Aldol condensation over reconstructed Mg-Al hydrotalcites: structure-activity relationships related to the rehydration method. Chem Eur J 11:728–739CrossRefGoogle Scholar
  27. 27.
    Prinetto F, Ghiotti G, Graffin P, Tichit D (2000) Synthesis and characterization of sol-gel Mg/Al and Ni/Al layered double hydroxides and comparison with co-precipitated samples. Microporous Mesoporous Mater 39:229–247CrossRefGoogle Scholar
  28. 28.
    Morato A, Alonso C, Medina F, Cesteros Y, Salagre P, Sueiras JE, Tichit D, Coq B (2001) Palladium hydrotalcites as precursors for the catalytic hydroconversion of CCl2F2 (CFC-12) and CHClF2 (HCFC-22). Appl Catal B 32:167–179CrossRefGoogle Scholar
  29. 29.
    Ece OI, Nakagawa ZE, Schroeder PA (2003) Alteration of volcanic rocks and genesis of kaolin deposits in the Şile region, Northern Istanbul, Turkey. I: clay mineralogy. Clays Clay Miner 51:675–688CrossRefGoogle Scholar
  30. 30.
    Vuković JP, Srića V, Novak P (2015) Fast determination of diesel fuel oxidation stability by 1H NMR spectroscopy. Acta Chim Slov 62:233–236Google Scholar
  31. 31.
    Smoláková L, Frolich K, Kocík J, Kikhtyanin O, Čapek L (2017) Surface properties of hydrotalcite-based Zn(Mg)Al oxides and their catalytic activity in aldol condensation of furfural with acetone. Ind Eng Chem Res 56:4638–4648CrossRefGoogle Scholar
  32. 32.
    Lavalley JC (1996) Infrared spectrometric studies of the surface basicity of metal oxides and zeolites using adsorbed probe molecules. Catal Today 27:377–401CrossRefGoogle Scholar
  33. 33.
    Diko M, Ekosse G, Ogola J (2016) Fourier transform infrared spectroscopy and thermal analyses of kaolinitic clays from South Africa and Cameroon. Acta Geodyn Geomater 13:149–158Google Scholar
  34. 34.
    Kloprogge JT, Hickey L, Frost RL (2004) FT-Raman and FT-IR spectroscopic study of synthetic Mg/Zn/Al-hydrotalcites. J Raman Spectrosc 35:967–974CrossRefGoogle Scholar
  35. 35.
    Di Cosimo JI, Díez VK, Xu M, Iglesia E, Apesteguía CR (1998) Structure and surface and catalytic properties of Mg-Al basic oxides. J Catal 178:499–510CrossRefGoogle Scholar
  36. 36.
    Kikhtyanin O, Kadlec D, Velvarská R, Kubička D (2018) Using Mg-Al mixed oxide and reconstructed hydrotalcite as basic catalysts for aldol condensation of furfural and cyclohexanone. ChemCatChem 10:1464–1475CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2018

Authors and Affiliations

  • David Kadlec
    • 1
    Email author
  • Zdeněk Tišler
    • 1
  • Romana Velvarská
    • 1
  • Lenka Pelíšková
    • 1
  • Uliana Akhmetzyanova
    • 1
  1. 1.UniCRE (Unipetrol Centre for Research and Education, Inc.)LitvínovCzech Republic

Personalised recommendations