Topics in Catalysis Vol. 22, Nos.

3–4, April 2003 (# 2003) 191

Deactivation of copper metal catalysts for methanol decomposition,

methanol steam reforming and methanol synthesis
Martyn V. Twigga and Michael S. Spencerb,

a
Johnson Matthey, Orchard Road, Royston, Herts, SG8 5HE, UK
b
Chemistry Department, Cardiff University, Cardiff, Wales, CF10 3TB, UK

Laboratory and industrial results are reviewed to elucidate the general features of the deactivation of supported copper metal
catalysts in various reactions involving methanol as reactant or product. Most catalyst types are based on Cu/ZnO formulations
that contain stabilisers and promoters such as alumina, alkaline earth oxides and other oxides. These additional materials have
several roles, including the inhibition of sintering and absorption of catalyst poisons. All copper catalysts are susceptible to thermal
sintering via a surface migration process, and this is markedly accelerated by the presence of even traces of chloride. Care must be
taken, therefore, to eliminate halides from copper catalysts during manufacture, and from reactants during use. Operating
temperatures must be restricted, usually to below 300 8C.
In methanol synthesis involving modern promoted Cu=ZnO=Al2 O3 catalysts neither poisoning nor coking is normally a
significant source of deactivation; thermal sintering is the main cause of deactivation. In contrast, catalyst poisoning and coking
have been observed in methanol decomposition and methanol steam reforming reactions.
KEY WORDS: copper catalyst; deactivation; zinc oxide; methanol synthesis; methanol steam reforming; methanol decomposition;
sintering; poisoning; sulfur; chloride

1. Introduction the formation of hydrocarbons is thermodynamically

favored, most notably to methane. Zinc oxide/chromia
The three processes of methanol decomposition,
catalysts were used in the early methanol plants with
methanol steam reforming and methanol synthesis
synthesis gas produced from coal. These catalysts were
have many similarities, not least that copper catalysts
barely selective enough for practical operation. Forcing
are effective in all three reactions. There is, however, an
conditions that encouraged hydrocarbon formation
important distinction between methanol synthesis pro-
were necessary because zinc oxide/chromia catalysts
cesses on the one hand and methanol decomposition
did not have high activity, but they had the advantage
(whether direct or by steam reforming) processes on the
that they could operate with relatively high poison levels
other. Methanol synthesis is a well-established process
(mainly sulfur compounds) present in coal-derived
with a catalyst (essentially Cu=ZuO=Al2 O3 ) which has
synthesis gas.
been improved, but not radically changed, in the past 40
In the early 1960s synthesis gas became widely
years [1]. In contrast processes that use the decomposi-
available from the steam reforming of hydrocarbons.
tion of methanol as a source of hydrogen (e.g. for fuel
Compared to the older coal-based synthesis gas this was
cells) are relatively still at the development stage.
effectively poison free, and it allowed the use of highly
Catalyst deactivation occurs in all three processes. In
active copper-based catalysts that could operate at much
methanol synthesis the causes of deactivation are
lower temperatures with extremely high selectivity to
understood, as are strategies to minimise their effects
methanol. The development of copper-based methanol
in industrial plants. Deactivation of copper catalysts is
catalysts followed the introduction of copper-based low-
also significant in methanol decomposition reactions, as
temperature shift catalysts in hydrogen and ammonia
can be seen in other papers in this volume, but it is less
plants. Subsequently, with the efficient large-scale
well understood. Rates and modes of deactivation
production of pure methanol firmly established, metha-
depend on reaction conditions and catalyst formula-
nol itself was seen as a potential feedstock, and as a
tions, and consequently catalyst lives can vary widely [2–
result the number of plants further increased as
4]. In this paper we examine fundamental aspects and
additional outlets for methanol were identified. For
practical consequences of copper catalyst deactivation in
many years methanol has been used as a source of
these processes.
hydrogen, via steam reforming, for use in the electronics
Conversion of synthesis gas (mixtures of H2 and
industry. As might be expected copper catalysts are
CO=CO2 ) to methanol requires kinetic selectivity, since
effective in this application. Here it is necessary to have
extremely pure hydrogen that is obtained by diffusion

To whom correspondence should be addressed. through supported palladium membranes. Currently
E-mail: spencerms@cardiff.ac.uk various methanol steam reforming and methanol

1022-5528/03/0400–0191/0 # 2003 Plenum Publishing Corporation

192 M.V. Twigg, M.S. Spencer/Deactivation of copper metal catalysts
decomposition processes are being considered for
providing on-board hydrogen for non-polluting electric
vehicles powered by fuel cells. Again copper catalysts
are effective in these reactions. The selectivity of copper
catalysts is as important in these processes as in
methanol synthesis itself, because similar thermody-
namic considerations involving hydrocarbon formation
apply.
In the light of the importance of copper catalysts in
methanol synthesis, its steam reforming and its decom-
position reactions, it is surprising there is not a wealth of
information available on the deactivation of catalysts in
these reactions. In contrast the literature on the
deactivation of, for example, platinum and nickel
catalysts is much more extensive than that on the
deactivation of copper catalysts. A substantial source of
information, used in this review, for catalyst deactiva-
tion in industrial methanol synthesis is contained in
Chapter 9 of the Catalyst Handbook [1]. A study of the
deactivation of copper metal catalysts for hydrogena-
tion reactions, including the water-gas shift reaction and
methanol synthesis but not methanol decomposition or
steam reforming, recently appeared [2].
All forms of deactivation are considered in this
review, where we examine both common features and
process-specific features. Typical operating lives of
copper catalysts in large plants vary from a month or
so to several years, depending on the process concerned
and the actual plant configuration [3].
2. Deactivation modes
Compared with nickel or platinum catalysts, copper
catalysts usually are less aggressive in hydrogenation
and dehydrogenation reactions, and this is the origin of
their desirable selectivities, but they are often more
sensitive towards a variety of deactivation processes. In
this section the main thermal sintering, poisoning and
other deactivation processes are reviewed before con-
sidering the actual deactivation of copper catalysts in
the various reactions including methanol.
2.1. Thermal sintering
Various basic aspects of the sintering of copper metal
catalysts used in hydrogenation reactions are detailed in
an earlier review [2]. For metals, the predominant
sintering mechanism in the bulk is vacancy diffusion
which suggests a relationship with cohesive energy.
Hughes [4] gave the following increasing order of
stability for metals: Ag < Cu < Au < Pd < Fe < Ni
< Co < Pt < Rh < Ru < Ir < Os < Re: It is therefore
not surprising that copper-based catalysts are more
susceptible to thermal sintering than other commonly
used metallic catalysts, such as the nickel, iron,
palladium and platinum catalysts used in many hydro-
gen and dehydrogenation reactions. This is also shown
by the low Hüttig temperature of copper [5], which
reflects a relatively low melting point (1063 8C), com-
pared with, for example, that of iron (1535 8C) and
nickel (1455 8C). Therefore, copper-based catalysts have
to be operated at relatively low temperatures, usually no
higher than 300 8C. The general hydrogenation activity
of copper catalysts was appreciated at an early stage [6],
and a comparison of the performance of various
formulations showed copper chromite was easily
reduced to give a hydrogenation catalyst with good
low-temperature activity, and better resistance to
poisons than the unsupported metal [7].
All modern copper catalysts contain one or, more
usually, several oxides to minimise thermal sintering.
Typical formulations contain Cr2 O3 ; and/or Al2 O3 ; in
addition to CuO and ZnO in unreduced commercial
catalysts. The thermal stability of these catalysts is
significantly higher than the early catalysts as a result of
decades of catalyst development. Thermal sintering can
be limited in well-formulated catalysts manufactured
under tightly defined optimal conditions, provided they
are operated under well-controlled conditions. Thermal
stability depends strongly on the manufacturing proce-
dures used, not only on composition [8]. These
considerations are especially relevant for processes
such as methanol steam reforming and methanol
decomposition which have so far been only partially
developed. Also relevant here are the numerous
observations (see, for example, other papers in this
issue [9]) that optimum catalysts for methanol synthesis
are not necessarily optimum for other reactions invol-
ving methanol.
2.2. Sulfur poisoning
Operating catalysts at low temperature thermodyna-
mically favors adsorption of poisons, giving high surface
coverage. As a result, copper catalysts are extremely
sensitive to site-blocking poisons, and they are particu-
larly sensitive to even very low levels of poison such as
reduced sulfur or phosphorus species. Under normal
operating conditions sulfur is a powerful poison for
copper, as indicated by the change in enthalpy in
equation (1); the formation of bulk copper sulfide is
much favored, and the corresponding equilibrium
constant is about 1  105 : The formation of adsorbed
sulfur on copper surfaces is even more thermodynami-
cally favorable. Early work [10,11] on the adsorption
isotherms for hydrogen sulfide adsorption on copper
demonstrated that a significantly lower H2 S=H2 ratio is
required for chemisorptions of sulfur than for bulk
sulfidation.
If present in the reactant feed, sulfur from H2 S or
other sulfur compounds accumulates on copper cata-
lysts, and it is therefore important to eliminate sources