Cover Image

Hydrodeoxygenation of stearic acid over Co-Mg-Al-O mixed oxide catalysts

Aleksandr Nepomniashchii, Alina Markelova, Liudmila Buluchevskaya, Aleksandr Lavrenov

Abstract


The influence of the Co/Mg molar ratio on the physicochemical and catalytic properties of Co-Mg-Al-O mixed oxides obtained by thermal treatment of layered double hydroxides (LDH) was investigated. Characterization of the mixed oxides by ICP, XRD, and TPR revealed that the catalysts form solid solutions with well-dispersed cobalt particles, where increasing cobalt content weakens the interaction between Co and spinel, promoting the formation of larger Co3O4 crystallites and decreasing the cobalt reduction temperature. With increasing Co/Mg ratio, the conversion of stearic acid and the yield of C15–C18 hydrocarbons increased. The conversion of stearic acid to hydrocarbons proceeds through the formation of intermediate products–1-octadecanol and stearyl stearate–whose proportion increases with higher catalyst calcination temperature, indicating the key role of the hydrogenation metal in the conversion pathway. Complete conversion of stearic acid with heptadecane as the main product is achieved using a catalyst with a Co/Mg molar ratio of 3 at 270 °C and 4 MPa hydrogen pressure. The possibility of oxidative regeneration of this catalyst and its multi-cycle reuse was demonstrated.

Keywords


stearic acid; hydrodeoxygenation; cobalt; layered hydroxides; mixed oxides

Full Text:

PDF

References


Verma D, Rana BS, Kumar R, Sibi MG, Sinha AK. Diesel and aviation kerosene with desired aromatics from hydroprocessing of jatropha oil over hydrogenation catalysts supported on hierarchical mesoporous SAPO-11. Appl Catal A Gen. 2015;490(1):108–116. doi:10.1016/j.apcata.2014.11.007

Alalwan HA, Alminshid AH, Aljaafari HAS. Promising evolution of biofuel generations. Renew Energy Focus. 2019;28:127–139. doi:10.1016/j.ref.2018.12.006

Douvartzides SL, Charisiou ND, Papageridis KN, Goula MA. Green diesel: biomass feedstocks, production technologies, catalytic research, fuel properties and performance in compression ignition internal combustion engines. Energies. 2019;12(5):809. doi:10.3390/en12050809

Mittelbach M. Fuels from oils and fats: recent developments and perspectives. Eur J Lipid Sci Technol. 2015;117(11):1832–1846. doi:10.1002/ejlt.201500125

Antar M, Lyu D, Nazari M, Shah A, Zhou X, Smith DL. Biomass for a sustainable bioeconomy: an overview of world biomass production and utilization. Renew Sustain Energy Rev. 2021;139:110691. doi:10.1016/j.rser.2020.110691

Chen S, Zhou G, Miao C. Green and renewable bio-diesel produce from oil hydrodeoxygenation: Strategies for catalyst development and mechanism. Renew Sustain Energy Rev. 2019;101:568–589. doi:10.1016/j.rser.2018.11.027

Bezergianni S, Dimitriadis A. Comparison between different types of renewable diesel. Renew Sustain Energy Rev. 2013;21:110–116. doi:10.1016/j.rser.2012.12.042

Satyarthi JK, Chiranjeevi T, Gokak DT, Viswanathan PS. An overview of catalytic conversion of vegetable oils/fats into middle distillates. Catalysis Sci Technol. 2013;3(1):70–80. doi:10.1039/C2CY20415K

Barbosa IV, Scapim LA, Cavalcante RM, Young AF. Industrial production of green diesel in Brazil: Process simulation and economic perspectives. Renew Energy. 2023;219:119591. doi:10.1016/j.renene.2023.119591

Othman MF, Adam A, Najafi G, Mamat R. Green fuel as alternative fuel for diesel engine: A review. Renew Sustain Energy Rev. 2017;80:694–709. doi:10.1016/j.rser.2017.05.140

Mailaram S, Maity SK. Techno-economic evaluation of two alternative processes for production of green diesel from karanja oil: A pinch analysis approach. Renew Sustain Energy Rev. 2019;11:025906. doi:10.1063/1.5078567

Ding S, Parlett CMA, Fan X. Recent developments in multifunctional catalysts for fatty acid hydrodeoxygenation as a route towards biofuels. Mol Catal. 2022;523:111492. doi:10.1016/j.mcat.2021.111492

Jeniˇstová K, Hachemi I, Maki-Arvela P, Kumar N, Peurla M, Capek L, Warnå J, Murzin DY. Hydrodeoxygenation of stearic acid and tall oil fatty acids over Nialumina catalysts: Influence of reaction parameters and kinetic modelling. Chem Eng J. 2017;316:401–409. doi:10.1016/j.cej.2017.01.117

Kumar P, Yenumala SR, Maity SK, Shee D. Kinetics of hydrodeoxygenation of stearic acid using supported nickel catalysts: Effects of supports. Appl Catal A Gen. 2014;471:28–38. doi:10.1016/j.apcata.2013.11.021

Taromi AA, Kaliaguine S. Green diesel production via continuous hydrotreatment of triglycerides over mesostructured γ -alumina supported NiMo/CoMo catalysts. Fuel Proces Technol. 2018;171:20–30. doi:10.1016/j.fuproc.2017.10.024

Wang H, Li G, Rogers K, Lin H, Zheng Y, Ng S. Hydrotreating of waste cooking oil over supported CoMoS catalyst – Catalyst deactivation mechanism study. Mol Catal. 2017;443:228–240. doi:10.1016/j.mcat.2017.10.016

Cao Y, Shi Y, Bi Y, Wu K, Hu S, Wu Y, Huang S. Hydrodeoxygenation and hydroisomerization of palmitic acid over bi-functional Co/H-ZSM-22 catalysts. Fuel Proces Technol. 2018;172:29–35. doi:10.1016/j.fuproc.2017.09.020

Zhang H, Lin H, Zheng Y. The role of cobalt and nickel in deoxygenation of vegetable oils. Appl Catal B Environ. 2014;160:415–422. doi:10.1016/j.apcatb.2014.05.043

Srifa A, Faungnawakij K, Itthibenchapong V, Assabumrungrat S. Roles of monometallic catalysts in hydrodeoxygenation of palm oil to green diesel Chem Eng J. 2015;278:249–258. doi:10.1016/j.cej.2014.09.106

Ojeda M, Osterman N, Dražić G, Žilnik LF, Meden A, Kwapinski W, Balu AM, Likozar B, Tušar NN. Conversion of Palmitic Acid Over Bi-functional Ni/ZSM-5 Catalyst: Effect of Stoichiometric Ni/Al Molar Ratio. Top Catal. 2018;61:1757–1768. doi:10.1007/s11244-018-1046-7

Zhou Y, Liu X, Yu P, Hu C. Temperature-tuned selectivity to alkanes or alcohol from ethyl palmitate deoxygenation over zirconia-supported cobalt catalyst. Fuel. 2020;278:118295. doi:10.1016/j.fuel.2020.118295

Arun N, Sharma RV, Dalai AK. Renew Sustain Energy Rev. 2015;48:240-255. doi:10.1016/j.rser.2015.03.074

Li Q, Bie Y, Qiu S, Zhang Q, Sainio J, Wang T, Ma L, Lehtonen J. Hydrogenolysis of methyl heptanoate over Co based catalysts: Mediation of support property on activity and product distribution. Appl Catal B Environ. 2014;147:236–245. doi:10.1016/j.apcatb.2013.08.045

Wang P, Zhang XQ, Zhou B, Meng FP, Wang YH, Wen GW. Recent advance of layered double hydroxides materials: structure, properties, synthesis, modification and applications of wastewater treatment. J Environ Chem Eng. 2023;11:111191. doi:10.1016/j.jece.2023.111191

Romero M, Pizzi A, Toscano G, Bosio B, Arato E. Study of an innovative process for the production of biofuels using non-edible vegetable oils. Chem Eng J. 2014;37:883–888. doi:10.3303/CET1437148

Patil SJ, Vaidya PD. On the production of bio-hydrogenated diesel over hydrotalcite-like supported palladium and ruthenium catalysts. Fuel Proces Technol. 2018;169:142-149. doi:10.1016/j.fuproc.2017.09.026

Abidin S, Lee H, Mijan N, Juan JC, Rahman N, Mastuli MS, Taufiq-Yap YH, Kong PS. Ni, Zn and Fe hydrotalcite-like catalysts for catalytic biomass compound into green biofuel. Pure Appl Chem. 2020;92(4):587-600. doi:10.1515/pac-2019-0820

Nguyen HKD, Nguyen HV, Dao DS, Hoang LL. Preparation and characterization of ordered mesoporous Mg–Al–Co hydrotalcite based catalyst for decarboxylation of jatropha oil. J Porous Mater. 2017;24:731–740. doi:10.1007/s10934-016-0310-0

Goulas KA, Mironenko AV, Jenness GR, Mazal T. Vlachos DG. Fundamentals of C–O bond activation on metal oxide catalysts. Nat Catal. 2019;2:269–276. doi:10.1038/s41929-019-0234-6

Žula M, Grilc M, Likozar B. Hydrocracking, hydrogenation and hydro-deoxygenation of fatty acids, esters and glycerides: mechanisms, kinetics and transport phenomena. Chem Eng J. 2022;444:136564. doi:10.1016/j.cej.2022.136564

Cheah KW, Yusup S, Loy ACM, How BS, Skoulou V, Taylor MJ. Recent advances in the catalytic deoxygenation of plant oils and prototypical fatty acid models compounds: catalysis, process, and kinetics. Mol Catal. 2022;523:111469. doi:10.1016/j.mcat.2021.111469

Frolich K, Kocík J, Mück J, Kolena J, Skuhrovcová L. The role of Zn in the CuZn-Al mixed oxide catalyst and its effect on glycerol hydrogenolysis. Mol Catal. 2022;533:112796. doi:10.1016/j.mcat.2022.112796

Issa S. Production of hydrogen by dry reforming of methane in the presence of mixed oxides Co-Mg-Al-O and the effect of adding Ru on the catalytic properties of these oxides; 2009; Balamand: University of Balamand, Lebadon.

Vaccari A, Gazzano M. Hydrotalcite-type anionic clays as precursors of highsurface-area Ni/Mg/Al mixed oxides. Stud Surf Sci Catal. 1995;91:893–902. doi:10.1016/S0167-2991(06)81832-X

Ribet S, Tichit D, Coq B, Ducourant B, Morato F. Synthesis and activation of CoMg-Al layered double hydroxides. J Solid State Chem. 1999;142:382–392. doi:10.1006/jssc.1998.8053

Kobzar EO, Stepanova LN, Nepomniashchii AA, Vasilevich AV, Gulyaeva TI, Trenikhin MV, Lavrenov AV. CuCoMgAlOx Mixed Oxides as Selective Catalysts for the Hydrogenation of Furan Compounds. Hydrogen. 2023;4:644–657. doi:10.3390/hydrogen4030041

Li N, Xing X, Sun YG, Cheng J, Wan G, Zhang ZS, Hao ZP. Catalytic oxidation of o-chlorophenol over Co2XAl (X = Co, Mg, Ca, Ni) hydrotalcite-derived mixed oxide catalysts. Front Environ Sci Eng. 2020;14:105–161. doi:10.1007/s11783-020-1284-3

Gennequin C, Kouassi S, Tidahy L, Cousin R, Lamonier J-F, Garcon G, Shirali P, Cazier F, Aboukaïs A, Siffert S. Co-Mg-Al oxides issued of hydrotalcite precursors for total oxidation of volatile organic compounds. Identification and toxicological impact of the by-products. C R Chim. 2010;13:494–501. doi:10.1016/j.crci.2010.01.001

Dou LG, Fan T, Zhang H, A novel 3D oxide nanosheet array catalyst derived from hierarchical structured array-like CoMgAl-LDH/graphene nanohybrid for highly effcient NOx capture and catalytic soot combustion. Catal Sci Technol. 2015;5:5153–5167. doi:10.1039/C5CY00846H

Qin LZ, Lu WMZ, Wu Z, Zhou WY. Catalyst performance of the calcined products of CoAl layered double hydroxide in the aerobic oxidation of ethylbenzene. Catal Lett. 2023;153:1818–1825. doi:10.1007/s10562-022-04117-w

Li Q, Meng M, Tsubaki N, Li XG, Li ZQ, Xie YN, Hu TD, Zhang J. Performance of K-promoted hydrotalcite-derived CoMgAlO catalysts used for soot combustion, NOx storage and simultaneous soot-NOx removal. Appl Catal B Environ. 2009;91(1–2):406–415. doi:10.1016/j.apcatb.2009.06.007

Wang HY, Ruckenstein E. Conversion of methane to syngas over Co/Al2O3. Catal Lett. 2001;75:13-18. doi:10.1023/A:1016719703118

Gennequin C, Barakat T, Tidahy HL, Cousin R, Lamonier J-F, Aboukaïs A, Siffert S, Use and observation of the hydrotalcite «memory effect» for VOC oxidation. Catal Today. 2010;157:191–197. doi:10.1016/j.cattod.2010.03.012

Wang Z, Jiang Z, Shangguan W. Simultaneous catalytic removal of NOx and soot particulate over Co-Al mixed oxide catalysts derived from hydrotalcites. Catal Commun. 2007;8:1659–1664. doi:10.1016/j.catcom.2007.01.025

Aoun A, Aouad S, El-Khoury B, El-Nakat H, Abi-Aad E, Aboukaïs A. Catalytic oxidation of carbon black over Ru/MgxCoyAlz catalysts. Phys Procedia. 2011;21:1–5. doi:10.1016/j.phpro.2011.10.001

Kubickova I, Snare M, Eranen K, Maki-Arvela P, Murzin DYu. Hydrocarbons for diesel fuel via decarboxylation of vegetable oils. Catal Today. 2005;106:197–200. doi:10.1016/j.cattod.2005.07.188

Snare M, Kubickova I, Maki-Arvela P, Eranen K, Murzin DYu. Heterogeneous Catalytic Deoxygenation of Stearic Acid for Production of Biodiesel. Ind Eng Chem Res. 2006;45:5708–5715. doi:10.1021/ie060334i

Do PТ, Chiappero M, Lobban LL, Resasco DE. Catalytic Deoxygenation of Methyl-Octanoate and Methyl-Stearate on Pt/Al2O3. Catal Let. 2009;130:9–18. doi:10.1007/s10562-009-9900-7

Kumar P, Maity SK, Shee D. Hydrodeoxygenation of stearic acid to produce green diesel over alumina supported CoMo catalysts: Role of Co/Mo mole ratio. Renew Energy. 2024;237:121700. doi:10.1016/j.renene.2024.121700

Kumar P, Maity SK, Shee D. Role of NiMo alloy and Ni species in the performance of NiMo/Alumina catalysts for hydrodeoxygenation of stearic acid: A kinetic study. JACS Omega. 2019;4:2833–2843. doi:10.1021/acsomega.8b03592

Cheng S, Ding J, Chen Y, Pan G, Feng X, Xu X, Xu J. Enhanced catalytic transfer hydrogenation of biomass-based furfural into furfuryl alcohol over Co3O4-based mixed oxide catalysts from hydrotalcite. App Catal A Gen. 2024;684:119909. doi:10.1016/j.apcata.2024.119909

Zhang A, Ma Q, Wang K, Liu X, Shuler P, Tang Y. Naphthenic acid removal from crude oil through catalytic decarboxylation on magnesium oxide. Appl Catal A Gen. 2006;303:103–109. doi:10.1016/j.apcata.2006.01.038

Morgan T, Santillan-Jimenez E, Harman-Ware AE, Ji Y, Grubb D, Crocker M. Catalytic deoxygenation of triglycerides over supported nickel catalysts. Chem Eng J. 2012;189:346–355. doi:10.1016/j.fuel.2012.08.035

Espitia-Sibaja M, Muñoz M. Effects of the cobalt content of catalysts prepared from hydrotalcites synthesized by ultrasound-assisted coprecipitation on hydrogen production by oxidative steam reforming of ethanol (OSRE). Fuel. 2017;194:7–16. doi:10.1016/j.fuel.2016.12.086




DOI: https://doi.org/10.15826/chimtech.9146

Copyright (c) 2025 Aleksandr Nepomniashchii, Alina Markelova, Liudmila Buluchevskaya, Aleksandr Lavrenov

Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 International License.

Scopus logo WorldCat logo DOAJ logo CAS logo BASE logo eLibrary logo

Chimica Techno Acta, 2014–2025
eISSN 2411-1414
Copyright Notice