Abstract
CaO-supported non-precious CuO and metallic Cu catalysts were prepared by subsequent impregnation, calcination, and H2 reduction procedures. The synthesis of lactic acid via the dehydrogenation of glycerol catalyzed by the resultant CuO/CaO and Cu/CaO catalysts was investigated at a higher initial glycerol concentration up to 2 mol L‒1 in a Ca(OH)2 aqueous solution. The CaO-supported metallic Cu catalysts showed higher catalytic activity than the CaO-supported CuO catalysts. When the glycerol dehydrogenation was catalyzed by the Cu(16)/CaO catalyst with the Ca(OH)2/glycerol molar ratio and catalyst/glycerol weight ratio of 0.8:1 and 5:100 at 230 °C for 4‒6 h, the lactic acid selectivity could reach 97.1% at the glycerol conversion of above 98%. The reaction kinetics simulation with the use of an empirical power type model showed that the reaction activation energies on the Cu(16)/CaO and CuO(16)/CaO catalysts were 22.2 and 102.8 kJ mol−1, respectively. The metallic Cu active component much more effectively catalyzes the glycerol dehydrogenation reaction than the CuO active component.
Similar content being viewed by others
References
Fan R, Ebrahimi M, Czermak P (2017) Anaerobic membrane bioreactor for continuous lactic acid fermentation. Membranes 7(2):26. https://doi.org/10.3390/membranes7020026
Othman M, Ariff AB, Rios-Solis L, Halim M (2017) Extractive fermentation of lactic acid in lactic acid bacteria cultivation: A review. Front Microbiol 8:2285. https://doi.org/10.3389/fmicb.2017.02285
De Oliveira RA, Alexandri M, Komesu A, Venus J, Vaz Rossell CE, Filho RM (2019) Current advances in separation and purification of second-generation lactic acid. Sep Purif Rev 49(2):159–175. https://doi.org/10.1080/15422119.2019.1590412
Knothe G, Razon LF (2017) Biodiesel fuels. Prog Energy Combust Sci 58:36–59. https://doi.org/10.1016/j.pecs.2016.08.001
Ardi MS, Aroua MK, Hashim NA (2015) Progress, prospect and challenges in glycerol purification process: a review. Renew Sust Energ Rev 42:1164–1173. https://doi.org/10.1016/j.rser.2014.10.091
OECD, FAO (2022) OECD-FAO agricultural outlook 2022–2031. OECD Publishing, Paris. https://doi.org/10.1787/f1b0b29c-en
Kishida H, Jin F, Zhou Z, Moriya T, Enomoto H (2005) Conversion of glycerin into lactic acid by alkaline hydrothermal reaction. Chem Lett 34(11):1560–1561. https://doi.org/10.1246/cl.2005.1560
Ramírez-López CA, Ochoa-Gómez JR, Fernández-Santos M, Gómez-Jiménez- Aberasturi O, Alonso-Vicario A, Torrecilla-Soria J (2010) Synthesis of lactic acid by alkaline hydrothermal conversion of glycerol at high glycerol concentration. Ind Eng Chem Res 49(14):6270–6278. https://doi.org/10.1021/ie1001586
Chen L, Ren S, Ye XP (2014) Lactic acid production from glycerol using CaO as solid base catalyst. Fuel Process Technol 120:40–47. https://doi.org/10.1016/j.fuproc.2013.11.019
Arcanjo MRA, Silva IJ, Rodríguez-Castellón E, Infantes-Molina A, Vieira RS (2017) Conversion of glycerol into lactic acid using Pd or Pt supported on carbon as catalyst. Catal Today 279(2):317–326. https://doi.org/10.1016/j.cattod.2016.02.015
Shen L, Yu Z, Zhang D, Yin H, Wang C, Wang A (2019) Glycerol valorization to lactic acid catalyzed by hydroxyapatite-supported palladium particles. J Chem Technol Biotechnol 94(1):204–215. https://doi.org/10.1002/jctb.5765
Bruno AM, Chagas CA, Souza MMVM, Manfro RL (2018) Lactic acid production from glycerol in alkaline medium using Pt-based catalysts in continuous flow reaction system. Renew Energ 118:160–171. https://doi.org/10.1016/j.renene.2017.11.014
Zhang C, Wang T, Liu X, Ding Y (2016) Selective oxidation of glycerol to lactic acid over activated carbon supported Pt catalyst in alkaline solution. Chin J Catal 37(4):502–509. https://doi.org/10.1016/S1872-2067(15)61055-5
Sever B, Yildiz M (2020) Conversion of glycerol to lactic acid over Au/bentonite catalysts in alkaline solution. Reac Kinet Mech Cat 130(2):863–874. https://doi.org/10.1007/s11144-020-01805-9
Celik D, Yildiz M (2020) Activation conditions of bentonite supports over gold-based catalysts for production of lactic acid from glycerol. Reac Kinet Mech Cat 129(2):693–705. https://doi.org/10.1007/s11144-020-01766-z
Palacio R, López D, Hernández D (2019) Bimetallic AuCu nanoparticles supported on CeO2 as selective catalysts for glycerol conversion to lactic acid in aqueous basic medium. J Nanopart Res 21:148. https://doi.org/10.1007/s11051-019-4594-2
Dodekatos G, Schünemann S, Tüysüz H (2018) Recent advances in thermo-, photo-, and electrocatalytic glycerol oxidation. ACS Catal 8(7):6301–6333. https://doi.org/10.1021/acscatal.8b01317
Evans CD, Douthwaite M, Carter JH, Pattisson S, Kondrat SA, Bethell D, Knight DW, Taylor SH, Hutchings GJ (2020) Enhancing the understanding of the glycerol to lactic acid reaction mechanism over AuPt/TiO2 under alkaline conditions. J Chem Phys 152(13):134705. https://doi.org/10.1063/1.5128595
Shen L, Zhou X, Wang A, Yin H, Yin HB, Cui W (2017) Hydrothermal conversion of high-concentrated glycerol to lactic acid catalyzed by bimetallic CuAux (x = 0.01–0.04) nanoparticles and their reaction kinetics. RSC Adv 7(49):30725–30739. https://doi.org/10.1039/c7ra04415a
Mimura N, Muramatsu N, Hiyoshi N, Sato O, Yamaguchi A (2021) Continuous production of glyceric acid and lactic acid by catalytic oxidation of glycerol over an Au–Pt/Al2O3 bimetallic catalyst using a liquid-phase flow reactor. Catal Today 375(1):191–196. https://doi.org/10.1016/j.cattod.2020.03.029
Sharninghausen LS, Campos J, Manas MG, Crabtree RH (2014) Efficient selective and atom economic catalytic conversion of glycerol to lactic acid. Nat Commun 5:5084. https://doi.org/10.1038/ncomms6084
Yin H, Yin HB, Wang A, Shen L, Liu Y, Zheng Y (2017) Catalytic conversion of glycerol to lactic acid over metallic copper nanoparticles and reaction kinetics. J Nanosci Nanotechnol 17(2):1255–1266. https://doi.org/10.1166/jnn.2017.12573
Shen L, Yin H, Yin HB, Liu S, Wang A (2017) Conversion of glycerol to lactic acid catalyzed by different-sized Cu2O nanoparticles in NaOH aqueous solution. J Nanosci Nanotechnol 17(1):780–787. https://doi.org/10.1166/jnn.2017.12395
Moreira ABF, Bruno AM, Souza MMVM, Manfro RL (2016) Continuous production of lactic acid from glycerol in alkaline medium using supported copper catalysts. Fuel Process Technol 144:170–180. https://doi.org/10.1016/j.fuproc.2015.12.025
Bruno AM, Simões TDR, Souza MMVM, Manfro RL (2020) Cu catalysts supported on CaO/MgO for glycerol conversion to lactic acid in alkaline medium employing a continuous flow reaction system. RSC Adv 10(52):31123–31138. https://doi.org/10.1039/d0ra06547a
Aramendía MA, Borau V, Jiménez C, Marinas A, Marinas JM, Ruiz JR, Urbano FJ (2004) Magnesium-containing mixed oxides as basic catalysts: base characterization by carbon dioxide TPD–MS and test reactions. J Mol Catal A-Chem 218(1):81–90. https://doi.org/10.1016/j.molcata.2004.04.006
Acknowledgements
Our present work was financially supported by the fund from the Liaoning Science and Technology Department, China (2021JH1/10400063).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Wang, A., Xu, Q. & Yin, H. Synthesis of lactic acid starting from glycerol catalyzed by CaO-supported CuO and metallic Cu catalysts in Ca(OH)2 aqueous solution. Reac Kinet Mech Cat 135, 3205–3221 (2022). https://doi.org/10.1007/s11144-022-02328-1
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11144-022-02328-1