Article
Journal of
Nanoscience and Nanotechnology
Vol. 16, 10887–10891, 2016
Copyright © 2016 American Scientific Publishers
All rights reserved
Printed in the United States of America
Preparation of Nanostructured CuO/ZnO/Al2O3
Catalysts for the Synthesis of Methanol from Syngas
Jaeyong Jang1, Gil-Pyo Kim2, Tae Sun Chang3, Beom-Sik Kim3, Sang Eun Shim1,
Seok Hoon Park4ꢀ∗, and Sung-Hyeon Baeck1ꢀ∗
1Department of Chemistry and Chemical Engineering, Center for Design and Applications of Molecular Catalysts,
Inha University, Incheon 402-751, Korea
2Institute of Chemical Processes, School of Chemical and Biological Engineering, College of Engineering,
Seoul National University, Seoul 151-742, Korea
3Greenhouse Gas Resources Research Group, Research Center for Environmental Resources,
Korea Research Institute of Chemical Technology, Daejeon 305-600, Korea
4Department of Environmental Engineering, Anyang University, Anyang, 430-714, Korea
In this work, the effect of surfactants on the catalytic properties of CuO/ZnO/Al2O3 (CZA) was
studied for methanol synthesis via the hydrogenation of carbon monoxide. CZA catalysts were
prepared by a co-precipitation method with various surfactants (tetrapropylammonium hydroxide
(TPAOH) or cetyltrimethylammonium bromide (CTAB)) and evaluated for the synthesis of methanol
from syngas. CZA catalysts were characterized using X-ray diffraction (XRD), scanning electron
Delivered by Ingenta to: Purdue University Libraries
microscopy (SEM), transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET)
IP: 79.110.19.37 On: Mon, 07 Nov 2016 09:26:22
Copyright: American Scientific Publishers
analysis. The results showed that the surfactants have significant influences on the morphology,
crystalline structure, and surface area. Their catalytic activities for methanol synthesis from syngas
(CO:H2 = 1:2) were evaluated in a fixedbed reactor at 518 K and 45 bar. The as-synthesized
CZA with CTAB exhibited higher reactivity in terms of the conversion and methanol space time
yield (STY).
Keywords: CZA, Methanol Synthesis, Surfactant, Syngas.
1. INTRODUCTION
its low cost and high selectivity to methanol.9 Reduced
copper enables both CO and CO2 to be activated on
sites during the methanol synthesis reaction.10 Alterna-
tively, ZnO minimizes the sintering of Cu during the
calcination process,11 thereby introducing highly active
sites that are exposed to reactants. In addition, it serves
as an active site for the dissociation of H2,12 which
permits the hydrogenation of CO over Cu surfaces. More-
over, numerous efforts have been made to explore vari-
ous CuO/ZnO-based ternary catalysts.13 Presently, various
catalysts such as Cr,14 Mo,15 Au,16 Ga,17 and Al,18
have been incorporated into CuO/ZnO-based catalysts in
attempts to improve the catalytic activity. Among these,
CuO/ZnO/Al2O3 (CZA) has exhibited excellent catalytic
activity and stability for methanol synthesis. This is the
case because Al2O3 can stabilize the uniformly dispersed
CuO/ZnO structure, prevent the sintering of Cu parti-
cles, and increase the thermal stability.19ꢁ20 Saito et al.17
explored CZA composites as a catalyst for methanol
Methanol is an important raw material for the production
of important chemicals such as DME (dimethyl ether),
DMC (dimethyl carbonate), olefin, formaldehyde, acetic
acid, and a wide variety of other products.1–4 In addition,
it can be used as a hydrogen storage material and a trans-
portation fuel, which may help reduce the dependence on
fossil fuels in the near future.5–7 Therefore, syngas-based
methanol synthesis plays an important role in chemical and
energy industries. Therefore, catalysts with large surface
area, high activity, and good thermostability are needed for
the development of economical processes.
Typically, methanol is synthesized from syngas that con-
tains mostly CO and H2 along with a small amount of
CO2ꢀ8 To achieve enhanced catalytic activity, CuO/ZnO
is considered to be an attractive catalyst because of
∗Authors to whom correspondence should be addressed.
J. Nanosci. Nanotechnol. 2016, Vol. 16, No. 10
1533-4880/2016/16/10887/005
doi:10.1166/jnn.2016.13258 10887