Full Text:   <1277>

Summary:  <1329>

CLC number: O622

On-line Access: 2020-03-17

Received: 2019-09-07

Revision Accepted: 2020-01-09

Crosschecked: 2020-02-19

Cited: 0

Clicked: 2036

Citations:  Bibtex RefMan EndNote GB/T7714


Piriya Pinthong


Bunjerd Jongsomjit


-   Go to

Article info.
Open peer comments

Journal of Zhejiang University SCIENCE A 2020 Vol.21 No.3 P.218-228


Oxidative dehydrogenation of ethanol over Cu/Mg-Al catalyst derived from hydrotalcite: effect of ethanol concentration and reduction conditions

Author(s):  Piriya Pinthong, Piyasan Praserthdam, Bunjerd Jongsomjit

Affiliation(s):  Center of Excellence on Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand

Corresponding email(s):   bunjerd.j@chula.ac.th

Key Words:  Oxidative dehydrogenation, Ethanol, Copper, Mg-Al hydrotalcite, Acetaldehyde, Catalyst

Piriya Pinthong, Piyasan Praserthdam, Bunjerd Jongsomjit. Oxidative dehydrogenation of ethanol over Cu/Mg-Al catalyst derived from hydrotalcite: effect of ethanol concentration and reduction conditions[J]. Journal of Zhejiang University Science A, 2020, 21(3): 218-228.

@article{title="Oxidative dehydrogenation of ethanol over Cu/Mg-Al catalyst derived from hydrotalcite: effect of ethanol concentration and reduction conditions",
author="Piriya Pinthong, Piyasan Praserthdam, Bunjerd Jongsomjit",
journal="Journal of Zhejiang University Science A",
publisher="Zhejiang University Press & Springer",

%0 Journal Article
%T Oxidative dehydrogenation of ethanol over Cu/Mg-Al catalyst derived from hydrotalcite: effect of ethanol concentration and reduction conditions
%A Piriya Pinthong
%A Piyasan Praserthdam
%A Bunjerd Jongsomjit
%J Journal of Zhejiang University SCIENCE A
%V 21
%N 3
%P 218-228
%@ 1673-565X
%D 2020
%I Zhejiang University Press & Springer
%DOI 10.1631/jzus.A1900451

T1 - Oxidative dehydrogenation of ethanol over Cu/Mg-Al catalyst derived from hydrotalcite: effect of ethanol concentration and reduction conditions
A1 - Piriya Pinthong
A1 - Piyasan Praserthdam
A1 - Bunjerd Jongsomjit
J0 - Journal of Zhejiang University Science A
VL - 21
IS - 3
SP - 218
EP - 228
%@ 1673-565X
Y1 - 2020
PB - Zhejiang University Press & Springer
ER -
DOI - 10.1631/jzus.A1900451

The copper-modified Mg-Al catalyst (Cu/Mg-Al) was synthesized using the incipient wetness impregnation of copper onto the mg-Al hydrotalcite derived from co-precipitation method. The effects of copper on the characteristics of catalyst were obtained using several characterization techniques. We found that only copper (I) oxide (CuO) species were obtained on the surface after calcination in air by X-ray Diffraction (XRD). However, the basicity of the base decreases slightly, while the density of the base increases due to the decrease in Brunauer-Emmett-Teller (BET) surface area. We carried out the catalytic activity of the Cu/Mg-Al catalyst in the continuous flow reactor through oxidative dehydrogenation of ethanol. We obtained that the copper enhances the catalytic activity in this reaction, and the ethanol conversion increases with increase in temperature, while the acetaldehyde selectivity decreases because of the decomposition of acetaldehyde to carbon dioxide. The highest acetaldehyde yield of 41.8% was at 350 °C. Moreover, we studied the effects of the ethanol concentration by varying the ethanol feed concentrations (99.9%, 75%, and 50%). The ethanol conversion decreases with a decrease in the ethanol concentration due to the high adsorption of water molecules on the catalyst surface. Thus, the negative effect decreases at higher reaction temperature (350–400 °C). Furthermore, we investigated the effect of the reduction condition of catalyst by varying the reduction temperature (300 and 400 °C). The reduction process affects the catalytic activity. The Cu/Mg-Al was comparatively stable for 10 h upon time-on-stream test. It is used as a promising catalyst in oxidative dehydrogenation of ethanol without any reduction step.

This manuscript targets the selective acetaldehyde production from ethanol via oxidative dehydrogenation. The studied reaction is of the highest interest due to acetaldehyde applications and large amounts of bioethanol obtained. Authors considered the use of heterogeneous catalysis by a Cu-modified hydrotalcite derived Mg-Al mixed oxide. Apart from optimizing the ethanol conversion and acetaldehyde selectivity, they examined the role of water and Cu oxidation state (by comparing between CuO and Cu0 phases) in the performance of the proposed reaction. Furthermore, the work is appropriately structured and rigorous.


创新点:1. 制备Cu改性的Mg-Al催化剂用于乙醇氧化脱氢反应,获得了更高的乙醛收率和选择性; 2. Cu/Mg-Al催化剂制备方法简单,制备价格低廉(无需贵金属),制备条件温和(无需高温高压); 3. Cu/Mg-Al催化剂在使用前无需预还原.
方法:1. 采用共沉淀法和浸渍法制备Cu/Mg-Al催化剂; 2. 通过乙醇氧化脱氢反应对催化剂进行考评,以探究Cu改性、乙醇浓度和催化剂的还原条件对催化活性的影响.
结论:1. 与Mg-Al催化剂相比,经由Cu改性的Mg-Al催化剂的乙醇氧化脱氢活性显著提高; 在350 °C,乙醛最大收率为41.8%. 2. 进料气中水的存在(乙醇浓度下降)会对Cu/Mg-Al的催化性能产生不利影响,使得乙醇转化率和乙醛收率下降; 但在高温区间(350~400 °C),这个不利影响有所减弱. 3. 反应前,催化剂在氢气气氛下的还原步骤对Cu/Mg-Al催化活性的影响不明显.

关键词:氧化脱氢; 乙醇; 铜; Mg-Al水滑石; 乙醛; 催化剂

Darkslateblue:Affiliate; Royal Blue:Author; Turquoise:Article


[1]Ahmed R, Sinnathambi CM, Subbarao D, 2011. Kinetics of de-coking of spent reforming catalyst. Journal of Applied Sciences, 11(7):1225-1230.

[2]Andrushkevich TV, Kaichev VV, Chesalov YA, et al., 2017. Selective oxidation of ethanol over vanadia-based catalysts: the influence of support material and reaction mechanism. Catalysis Today, 279:95-106.

[3]Aramendía MA, Avilés Y, Borau V, et al., 1999. Thermal decomposition of Mg/Al and Mg/Ga layered-double hydroxides: a spectroscopic study. Journal of Materials Chemistry, 9(7):1603-1607.

[4]Blokhina AS, Kurzina IA, Sobolev VI, et al., 2012. Selective oxidation of alcohols over Si3N4-supported silver catalysts. Kinetics and Catalysis, 53(4):477-481.

[5]Campisano ISP, Rodella CB, Sousa ZSB, et al., 2018. Influence of thermal treatment conditions on the characteristics of Cu-based metal oxides derived from hydrotalcite-like compounds and their performance in bio-ethanol dehydrogenation to acetaldehyde. Catalysis Today, 306:111-120.

[6]Chen GW, Li SL, Jiao FJ, et al., 2007. Catalytic dehydration of bioethanol to ethylene over TiO2/γ-Al2O3 catalysts in microchannel reactors. Catalysis Today, 125(1-2):111-119.

[7]Constantino VRL, Pinnavaia TJ, 1995. Basic properties of Mg2+1−xAl3+x layered double hydroxides intercalated by carbonate, hydroxide, chloride, and sulfate anions. Inorganic Chemistry, 34(4):883-892.

[8]Dai WL, Cao Y, Ren LP, et al., 2004. Ag–SiO2–Al2O3 composite as highly active catalyst for the formation of formaldehyde from the partial oxidation of methanol. Journal of Catalysis, 228(1):80-91.

[9]di Cosimo JI, Díez V, Xu M, et al., 1998. Structure and surface and catalytic properties of Mg-Al basic oxides. Journal of Catalysis, 178(2):499-510.

[10]Dias MOS, Modesto M, Ensinas AV, et al., 2011. Improving bioethanol production from sugarcane: evaluation of distillation, thermal integration and cogeneration systems. Energy, 36(6):3691-3703.

[11]Dixit M, Mishra M, Joshi PA, et al., 2013. Physico-chemical and catalytic properties of Mg–Al hydrotalcite and Mg– Al mixed oxide supported copper catalysts. Journal of Industrial and Engineering Chemistry, 19(2):458-468.

[12]Golay S, Doepper R, Renken A, 1999. Reactor performance enhancement under periodic operation for the ethanol dehydration over γ-alumina, a reaction with a stop-effect. Chemical Engineering Science, 54(20):4469-4474.

[13]Gomez MF, Arrua LA, Abello MC, 1997. Kinetic study of partial oxidation of ethanol over VMgO catalyst. Industrial & Engineering Chemistry Research, 36(9):3468-3472.

[14]Gucbilmez Y, Dogu T, Balci S, 2006. Ethylene and acetaldehyde production by selective oxidation of ethanol using mesoporous V-MCM-41 catalysts. Industrial & Engineering Chemistry Research, 45(10):3496-3502.

[15]Hosoglu F, Faye J, Mareseanu K, et al., 2015. High resolution NMR unraveling Cu substitution of Mg in hydrotalcites– ethanol reactivity. Applied Catalysis A: General, 504: 533-541.

[16]Idriss H, Seebauer EG, 2000. Reactions of ethanol over metal oxides. Journal of Molecular Catalysis A: Chemical, 152(1-2):201-212.

[17]Janlamool J, Jongsomjit B, 2017. Catalytic ethanol dehydration to ethylene over nanocrystalline χ- and γ-Al2O3 catalysts. Journal of Oleo Science, 66(9):1029-1039.

[18]Kaneda K, Ueno S, Imanaka T, 1995. Catalysis of transition metal-functionalized hydrotalcites for the Baeyer-Villiger oxidation of ketones in the presence of molecular oxygen and benzaldehyde. Journal of Molecular Catalysis A: Chemical, 102(3):135-138.

[19]Krutpijit C, Jongsomjit B, 2017. Effect of HCl loading and ethanol concentration over HCl-activated clay catalysts for ethanol dehydration to ethylene. Journal of Oleo Science, 66(12):1355-1364.

[20]Kumar S, Gupta R, Kumar G, et al., 2013. Bioethanol production from Gracilaria verrucosa, a red alga, in a biorefinery approach. Bioresource Technology, 135:150-156.

[21]Leofanti G, Padovan M, Tozzola G, et al., 1998. Surface area and pore texture of catalysts. Catalysis Today, 41(1-3):207-219.

[22]Li X, Wang LJ, Xia QB, et al., 2011. Catalytic oxidation of toluene over copper and manganese based catalysts: effect of water vapor. Catalysis Communications, 14(1):15-19.

[23]Liu P, Li T, Chen HP, et al., 2017. Optimization of Au0–Cu+ synergy in Au/MgCuCr2O4 catalysts for aerobic oxidation of ethanol to acetaldehyde. Journal of Catalysis, 347: 45-56.

[24]Mallat T, Baiker A, 2004. Oxidation of alcohols with molecular oxygen on solid catalysts. Chemical Reviews, 104(6):3037-3058.

[25]Nagaraja BM, Padmasri AH, Seetharamulu P, et al., 2007. A highly active Cu-MgO-Cr2O3 catalyst for simultaneous synthesis of furfuryl alcohol and cyclohexanone by a novel coupling route—combination of furfural hydrogenation and cyclohexanol dehydrogenation. Journal of Molecular Catalysis A: Chemical, 278(1-2):29-37.

[26]Nair H, Gatt JE, Miller JT, et al., 2011. Mechanistic insights into the formation of acetaldehyde and diethyl ether from ethanol over supported VOx, MoOx, and WOx catalysts. Journal of Catalysis, 279(1):144-154.

[27]Ob-eye J, Praserthdam P, Jongsomjit B, 2019. Dehydrogenation of ethanol to acetaldehyde over different metals supported on carbon catalysts. Catalysts, 9(1):66.

[28]Papong S, Malakul P, 2010. Life-cycle energy and environmental analysis of bioethanol production from cassava in Thailand. Bioresource Technology, 101(S1):S112-S118.

[29]Pinthong P, Praserthdam P, Jongsomjit B, 2019. Effect of calcination temperature on Mg-Al layered double hydroxides (LDH) as promising catalysts in oxidative dehydrogenation of ethanol to acetaldehyde. Journal of Oleo Science, 68(1):95-102.

[30]Quaranta NE, Soria J, Corberán VC, et al., 1997. Selective oxidation of ethanol to acetaldehyde on V2O5/TiO2/SiO2 catalysts. Journal of Catalysis, 171(1):1-13.

[31]Quesada J, Faba L, Díaz E, et al., 2018. Copper-basic sites synergic effect on the ethanol dehydrogenation and condensation reactions. ChemCatChem, 10(16):3583-3592.

[32]Ramasamy KK, Gray M, Job H, et al., 2016. Role of calcination temperature on the hydrotalcite derived MgO–Al2O3 in converting ethanol to butanol. Topics in Catalysis, 59(1):46-54.

[33]Shan JJ, Janvelyan N, Li H, et al., 2017. Selective non-oxidative dehydrogenation of ethanol to acetaldehyde and hydrogen on highly dilute NiCu alloys. Applied Catalysis B: Environmental, 205:541-550.

[34]Sikander U, Sufian S, Salam MA, 2017. A review of hydrotalcite based catalysts for hydrogen production systems. International Journal of Hydrogen Energy, 42(31):19851-19868.

[35]Tu YJ, Chen YW, 2001. Effects of alkali metal oxide additives on Cu/SiO2 catalyst in the dehydrogenation of ethanol. Industrial & Engineering Chemistry Research, 40(25):5889-5893.

[36]Velu S, Swamy CS, 1996a. Alkylation of phenol with 1-propanol and 2-propanol over catalysts derived from hydrotalcite-like anionic clays. Catalysis Letters, 40(3-4):265-272.

[37]Velu S, Swamy CS, 1996b. Selective C-alkylation of phenol with methanol over catalysts derived from copper-aluminium hydrotalcite-like compounds. Applied Catalysis A: General, 145(1-2):141-153.

[38]Wu L, Zhou T, Cui Q, et al., 2013. The catalytic dehydration of bio-ethanol to ethylene on SAPO-34 catalysts. Petroleum Science and Technology, 31(22):2414-2421.

[39]Yang WS, Kim Y, Liu PKT, et al., 2002. A study by in situ techniques of the thermal evolution of the structure of a Mg-Al-CO3 layered double hydroxide. Chemical Engineering Science, 57(15):2945-2953.

Open peer comments: Debate/Discuss/Question/Opinion


Please provide your name, email address and a comment

Journal of Zhejiang University-SCIENCE, 38 Zheda Road, Hangzhou 310027, China
Tel: +86-571-87952783; E-mail: cjzhang@zju.edu.cn
Copyright © 2000 - 2022 Journal of Zhejiang University-SCIENCE