Applied Catalysis A: General 218 (2001) 171180

The dehydrogenation of 2-butanol over copper-based catalysts:

optimising catalyst composition and determining
kinetic parameters
J.N. Keuler a, , L. Lorenzen a , S. Miachon b
a Department of Chemical Engineering, University of Stellenbosch, P.O. Box X1, Matieland 7602, South Africa
b IRC-CNRS, 2 Avenue A. Einstein, Villeurbanne 69626, France

Received 8 January 2001; received in revised form 4 March 2001; accepted 25 April 2001

Abstract
This work examines the dehydrogenation of 2-butanol over copper-based catalyst. The effects of support type (MgO and
SiO2 ) and copper loading on methyl ethyl ketone (MEK) yield were studied. The effects of reaction temperature, 2-butanol
feed flow rate and catalyst particle size were also investigated. The highest MEK yields were obtained with a 15 wt.% copper
on silica catalyst. The optimum catalyst was used to measure the kinetic parameters of the 2-butanol dehydrogenation reaction
at temperatures from 190 to 280 C. At higher temperatures catalyst deactivation took place. 2001 Elsevier Science B.V.
All rights reserved.
Keywords: 2-Butanol dehydrogenation; Catalyst optimisation; Kinetic parameters

1. Introduction pH) favour the dehydrogenation reaction, while acidic

The industrially used alcohol dehydrogenation cata-
lysts are copper and/or zinc-based [1]. Some oxidative
dehydrogenation processes employ silver as a catalyst
[1]. Copper-based catalysts can either be unsupported
or supported. Most are of the supported type, where
the support provides a large surface area for the copper
to be deposited on. Unsupported copper catalysts have
a much smaller surface area. Catalyst supports can be
basic, acidic or both. The acidity of the support deter-
mines whether the dehydration or the dehydrogena-
tion reaction will be favoured. Basic supports (high
Corresponding author. Present address: Sasol Technology,
Andries Brink Building-B level, 1 Klasie Havenga Road,
Sasolburg 1947, South Africa.
E-mail address: johan.keuler@sasol.com (J.N. Keuler).
supports (low pH) favour the dehydration reactions.
Different catalyst supports were listed in [2,3]. Silica
(basic) and alumina (acidic) have very high surface
areas compared to the other oxides (typically in the
hundreds of m2 /g area). High copper surface areas can
be obtained by depositing copper on these supports.
The activity of the catalyst is usually proportional to
the surface area of the active sites and thus a large
copper surface area will yield a more active catalyst.
The four basic techniques for preparing copper-
based catalyst, namely, precipitation, urea hydrolysis,
electroless plating and impregnation were discussed
by Keuler [4]. The percentage copper on the sup-
port has an effect on both reaction conversion and
selectivity. Sivaraj and Kantarao [5] prepared copper
supported on -alumina catalysts by a precipitation
technique. For the 240 m2 /g -alumina support, a

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172 J.N. Keuler et al. / Applied Catalysis A: General 218 (2001) 171180
Nomenclature
F feed flow rate (mol/s)
k reaction rate constant (mol/kg cat kPa h)
K adsorption coefficient (kPa1 )
Keq equilibrium constant (kPa)
P pressure (kPa)
rA rate of generation for component A
in reaction (mol/kg cat h)
T temperature (K)
W catalyst mass (kg)
Subscripts
A 2-butanol
R MEK
S hydrogen
copper loading of 2025 wt.% gave an optimum cop-
per surface area of about 40 m2 /g catalyst. Chang
and Saleque [6] investigated cyclohexanol conver-
sion using copper/-alumina catalysts. Maximum
conversions were obtained with copper loadings of
about 1217 wt.% (prepared by electroless plating),
1217 wt.% (prepared by precipitation) and about
10 wt.% (prepared by impregnation). Chang and
Saleque [7] obtained a maximum cyclohexanol con-
version on copper/-alumina with 1820 wt.% copper
loadings. For alumina-based catalysts, the selectiv-
ity towards aldehyde or ketone formation increases
with increasing copper loading [7,8]. The reason is
that the acidic centres, which reduce dehydrogena-
tion selectivity, become covered and thus neutralised.
Jeon and Chung [9] observed a continuous decrease
in cyclohexanol conversion with an increase in cop-
per loading on copper/silica catalysts. The selectivity
remained constant (very high) over a wide range of
copper values.
The dehydrogenation of sec-butyl alcohol (2-buta-
nol) to yield methyl ethyl ketone (MEK) is an im-
portant industrial process. The MEK is a widely
used industrial solvent. Perry and Chilton [10]
listed six possible rate equations for solid-catalysed
dehydrogenation reactions. Perona and Thodos [11]
determined the kinetics of 2-butanol dehydrogenation
between 340 and 400 C and 1 atm, using a brass
catalyst (65 wt.% Cu, 35 wt.% Zn). Using a similar
catalyst, Thaller and Thodos [12] studied the reaction
between 290 and 370 C at pressures up to 15 atm.
Ford and Perlmutter [13] observed a change in
reaction mechanism with temperature. Below about
320 C and above about 425 C, the single site surface
reaction was rate limiting. In the temperature range in
between, especially from 350 to 400 C, the adsorp-
tion of the alcohol was the controlling mechanism.
In the present study, a porous support impregnated
with copper was used and the kinetic parameters for
2-butanol dehydrogenation were determined at 1 atm
between 190 and 280 C. This paper forms part of
a larger project, where 2-butanol dehydrogenation
was modelled in a catalytic membrane reactor [4]. To
construct an accurate membrane reactor model, pure
kinetic data was required.
2. Experimental
Engelhard supplied the silica catalyst support
(product code = C500-234). The purity was 99.5%
silica and the BET surface area about 440 m2 /g. The
as received pellets were crushed and then sieved to
obtain different particle size fractions. A commercial
magnesium oxide (MgO) powder from Merck (sur-
face area = 27.4 m2 /g) was mixed with a binder and
pressed into extrusions. The extrusions were heated
to 1200 C to agglomerate the powder particles. The
extrusions were then crushed and sieved into only a
300850 m fraction. The BET surface area of the
particles was 16.7 m2 /g. The BET surface area and
chemisorption experiments were performed with a
Micrometrics ASAP 2010.
Copper was deposited onto the silica support via
impregnation. The low porosity of the MgO support
made impregnation unsuitable hence adsorption was
used for depositing copper. The MgO support was
introduced into a flask containing a copper nitrate
solution (in distilled water) of a specific concentra-
tion. The flask was placed on a magnetic stirrer and
the solution stirred for 2 h. Thereafter, the CuMgO
particles were filtered, washed and dried at 90 C. The
catalyst was calcinated at 500 C and then reduced in
hydrogen, in situ, at 350 C for 2 h.
The silica support was dried at 200 C for at least
23 h and then stored in a desiccator. The dried par-
ticles were then placed in heated copper nitrate solu-
tions (in distilled water) of different concentrations.
 J.N. Keuler et al. / Applied Catalysis A: General 218 (2001) 171180
Fig. 1. Set-up used for testing the kinetics of the catalyst at the CNRS, France.
The copper solution was kept warm on a hotplate
while the support was added. The support-solution
mixture was stirred throughout while adding the sup-
port particles. The hotplate was kept at about 80 C
to evaporate the remaining solution. The paste was
stirred every few minutes. When all the water had
evaporated, the catalyst was dried in an oven at 120 C
for at least 4 h. The catalyst was then calcinated at
500 C and reduced in situ in hydrogen at 350 C for
2 h. The copper concentrations on the catalysts were
measured using atomic adsorption analysis.
Catalyst testing was performed in two stages.
During the first stage, the optimum catalyst was
determined and during the second stage the kinetic
parameters of the optimised catalyst was determined.
The first set of experimental tests was performed
at the laboratories of the University of Stellenbosch
(Stellenbosch, South Africa). The kinetic testing was
conducted at the laboratories of the IRC-CNRS (Insti-
tut de Recherches sur la Catalyse, Centre National de
la Recherche Scientifique) in Villeurbanne, France.
Fig. 1 is the set-up used at the CNRS. A gas sample
was extracted at the sample point with a heated sy-
ringe. The syringe was kept inside a stainless steel tube
and the temperature of the syringe was controlled at
about 110 C. Carbon-containing products were anal-
ysed on a HP 5850 gas chromatograph equipped with
a FID detector. Two capillary columns, a 30 m HP
173
Innowax column and a 30 m HP Plot/Al2 O3 column,
were used in series. Hydrogen analysis was done on a
similar GC with a TCD detector. A Porapak Q column
and a molecular sieve column were operated in series.
The set-up at Stellenbosch University differed in the
following way: Hastings flow controllers (HFC 202C)
were used in stead of Brooks, the inner diameter of
the quartz tube was 8 mm (10 mm outer diameter) and
a Braun perfusion pump was used. The 2-butanol re-
action products were analysed with a HP G1800A gas
chromatograph, equipped with a mass spectrometer
and flame ionisation detector. A 50 m capillary col-
umn (50QGI.5/BPI PONA from SGE) was used.
3. Results and discussion of results
For catalyst optimisation experiments, the reactor
was operated as a plug flow reactor. Lower flow rates
were used to optimise the 2-butanol conversion. When
the kinetic parameters of the reaction was measured,
the reactor was operated in the differential mode. High
feed flow rates and small catalyst masses (typically
<0.2 g) were used to limit the reaction conversion to
<10%. The data presented in all three-dimensional
figures were fitted by a smooth spline. Figures were
constructed in the Statistica package.
174 J.N. Keuler et al. / Applied Catalysis A: General 218 (2001) 171180
Fig. 2. Total 2-butanol conversion for Cu on MgO catalysts as a
function of temperature and Cu% on the support.
3.1. 2-Butanol dehydrogenation over
MgO supported catalysts
When 2-butanol reacted over Cu/MgO catalysts,
the products were a mixture of butenes and MEK.
There was <1% additional by-products. Figs. 2 and 3
indicate total 2-butanol conversion and MEK yields as
a function of temperature and copper loading on the
catalyst. In both cases, the values increased with in-
creasing temperature. The total 2-butanol conversion
was the highest for pure MgO, because of the large
Fig. 3. MEK yield for Cu on MgO catalysts as a function of
temperature and Cu% on the support.
increase in butene yield in the absence of copper on the
support. The addition of copper to the MgO support
suppressed butene formation at all temperatures. The
reaction of 2-butanol to butene mainly took place on
the MgO. The 2-butanol to MEK reaction took place
on both the MgO and copper. With no Cu on MgO,
similar amounts of butenes and MEK were formed at
all temperatures. When copper was added to the sup-
port, the MEK yield increased to an optimum yield at
16.9 wt.% Cu on MgO (Fig. 3). For that catalyst, the to-
tal BET surface area (9.3 m2 /g) was about one-third of
the value of the pure MgO support (27.3 m2 /g). Further
copper addition to the support resulted in a decline in
MEK yield. Copper surface areas were not measured
due to the low BET values. Copper had much higher
catalytic activity for MEK production than MgO did.
Figs. 4 and 5 show the effect of flow rate on MEK
yield and selectivity for the best performing MgO
supported catalyst (16.9 wt.% Cu on MgO). The
W/F-ratio is the catalyst mass (in kg) divided by the
2-butanol feed flow rate (in mol/s). The selectivity
declined with an increase in temperature as more
butenes were formed. The longer residence time at
the low flow rates (high W/F values) improved the
MEK yield (Fig. 4), but resulted in a sharp decline
in selectivity (Fig. 5). The total 2-butanol conversion
dropped from 65 to 35% when W/F decreased from
206 to 51 kg s/mol. The higher flow rates meant that
insufficient time was allowed for the 2-butanol to
Fig. 4. MEK yield for a 16.9 wt.% Cu on MgO catalyst as a
function of temperature and W/F-ratio.
 J.N. Keuler et al. / Applied Catalysis A: General 218 (2001) 171180
Fig. 5. MEK selectivity for a 16.9 wt.% Cu on MgO catalyst as a
function of temperature and W/F-ratio.
fully react. This is clear in Fig. 4 where the MEK
yield dropped as W/F decreased.
3.2. 2-Butanol dehydrogenation over
silica supported catalysts
Fig. 6 shows total 2-butanol conversion as a function
of temperature and copper loading. The main product
was MEK (Fig. 7) and the only significant by-products
were a mixture of butenes. Total 2-butanol conversion
increased sharply with an increase in temperature,
Fig. 6. Total 2-butanol conversion for Cu on silica catalysts as a
function of temperature and Cu% on the support.
175
Fig. 7. MEK yield for Cu on silica catalysts as a function of
temperature and Cu% on the support.
but started levelling off at about 360 C. For MEK
production, there was an optimum temperature. This
temperature was between 300 and 360 C for average
W/F values. The optimum temperature did not vary
with copper loading. The maximum MEK yield was
very dependent on the copper content on the support.
At low copper loadings the MEK yield was lower due
to butene formation. As the copper loading increased,
butene formation decreased. Butene formation also
increased with temperature. Butene formation mainly
took place on the silica, while MEK formation took
place on the copper. The optimum MEK yield oc-
curred at 15 wt.% copper on silica. Other research
groups [57] also found an optimum Cu% on their
catalysts, which resulted in maximum yields for the
alcohol dehydrogenation reactions that they studied.
Figs. 8 and 9 show the MEK yield and selectivity
for the best performing catalyst (15 wt.% Cu on sil-
ica) as a function of temperature and 2-butanol feed
flow rate. The x- and y-axis in Fig. 9 were swapped
to obtain a more visible fit to the data. With the stan-
dard axis in Fig. 9, the trend in the data could not
be observed. As mentioned previously the yield in-
creased with temperature. The optimum yield shifted
to higher temperatures when the flowrate increased
(W/F decreased). For example,
W/F = 206 kg s/mol: 9391% yield at 270300 C,
W/F = 103 kg s/mol: 9392% yield at 300330 C,
W/F = 51 kg s/mol: 8987% yield at 330360 C.
176 J.N. Keuler et al. / Applied Catalysis A: General 218 (2001) 171180
Fig. 8. MEK yield for a 15 wt.% Cu on silica catalyst as a function
of temperature and W/F-ratio.
The selectivity towards MEK production (Fig. 9)
decreased with an increase in temperature and
decreased very marginally with an increase in W/F.
Longer residence times (lower feed rates) increased
butene formation. At 390 C, the selectivity varied
between 83 and 86% for the different feed flow rates.
3.3. Comparing SiO2 and MgO supported catalysts
The MEK selectivities for the optimum MgO sup-
ported catalyst were better than those for the optimum
Fig. 9. MEK selectivity for a 15 wt.% Cu on silica catalyst as a
function of temperature and W/F-ratio.
SiO2 supported catalyst. Pure MgO is >50% selective
towards MEK production, while pure SiO2 is almost
100% selective towards butene formation. If a similar
fraction of support sites are not covered by copper, the
MgO supported catalyst should have a higher selectiv-
ity towards MEK production than the SiO2 supported
catalyst. At 300 C and below, the selectivities for the
optimum catalysts at the different flow rate tests var-
ied as follows: MgO 100%; SiO2 > 93%.
The MEK yields were, however, much higher for the
SiO2 supported catalysts, due to their higher support
area as mentioned previously. At 300 C and below, the
yields at the different flow rate tests were as follows:
MgO = 626%; SiO2 = 5693%.
Further work was only performed on the SiO2 sup-
ported catalysts due to the higher yields obtained at
lower temperatures.
3.4. Effect of SiO2 support particle size on MEK yield
Figs. 10 and 11 show the effects of support particle
size on total 2-butanol conversion and on MEK yield
for copper on silica catalysts. At 270 C and above,
catalyst particles up to 1180 m gave similar values
for total 2-butanol conversion. The high conversions
indicate very little mass transfer resistance with an
increase in particle size. Particles of 3000 m gave
lower 2-butanol conversion due to channelling of the
alcohol feed gas [4].
The MEK yields (Fig. 11) were the highest for the
300850 m fraction. Smaller particles (150300 m)
and particles ranging from 8501180 m gave higher
Fig. 10. Effect of catalyst particle size on total 2-butanol
conversion.
 J.N. Keuler et al. / Applied Catalysis A: General 218 (2001) 171180
Fig. 11. Effect of catalyst particle size on MEK yield percentage.
butene yields, which decreased the MEK yield.
The BET surface area of the catalysts were similar
(300 m2 /g) and the copper surface areas determined
by H2 chemisorption were as follows:
150300 m: 3.8 m2 /g Cu,
300850 m: 3.8 m2 /g Cu,
8501180 m: 5.0 m2 /g Cu.
3.5. Catalyst deactivation testing
Keuler [4] studied the effects of reduction tem-
perature on catalyst stability and concluded that the
copper on silica catalyst should be reduced at 260 C
in hydrogen for 1 h. That optimised reduction process
was used and not the process mentioned previously
(2 h in hydrogen at 350 C). Higher reduction tem-
peratures resulted in a lower initial catalyst activity
due to a decrease in copper surface area by partial
sintering. A 14.4 wt.% copper on silica catalyst was
employed for the dehydrogenation of 2-butanol. Sta-
bility was tested at 250 and 310 C (see Fig. 12). Two
different runs were performed at 310 C. Selectivity
towards MEK production was very high (>99%) at
both temperatures. At 250 C, the catalyst was very
stable over a 24 h period, but deactivation took place
when the temperature was increased to 310 C. Fur-
ther, deactivation testing was not conducted.
Keuler [4] performed an intensive investigation
into the deactivation mechanisms of the same catalyst
for ethanol dehydrogenation. Total organic carbon
analysis (TOC) was employed to detect coking at
reaction temperatures ranging from 240 to 400 C.
177
Fig. 12. MEK production rate as a function of time for a 14.4 wt.%
Cu on silica catalyst.
The X-Ray diffraction analysis, transmission electron
microscopy and copper surface area measurements
were used to determine the degree of sintering of the
catalyst at reaction temperatures ranging from 240 to
400 C. Deactivation occurred due to both sintering
and coking for ethanol dehydrogenation above 280 C.
Results of re-oxidation experiments indicated that
most of the sintering occurred within the first 24 h
of use. Addition of different amounts of chromium
and/or cobalt to copper [4] did not improve the high
temperature stability of the catalyst and furthermore,
it reduced the selectivity towards the desired product.
The same sintering effects that were present for the
ethanol catalyst should also be valid for this reaction,
as the same catalyst was used.
3.6. Determining reaction rate mass
transfer resistance
To obtain accurate kinetic data, the reaction must
be operated in the region free from interphase mass
transfer resistance. Mass transfer resistance is depen-
dent on the particle Reynolds number, which in turn
is a function of the linear gas velocity past the catalyst
particles. The linear gas velocity can be increased to
eliminate mass transfer resistance by increasing the
feed flow rate and/or decreasing the inside diameter of
the quartz tube housing the catalyst. A quartz U-tube
with small inside diameter (4 mm) was used for all
experiments. Catalyst particles for kinetic testing
varied from 350 to 500 m.
In the absence of interphase mass transfer resis-
tance, the reaction rate will be independent of the feed
178 J.N. Keuler et al. / Applied Catalysis A: General 218 (2001) 171180
Fig. 13. The effect of 2-butanol feed flow rate on the MEK
production rate.
flow rate and the lines on Fig. 13 will be horizontal.
For the 2-butanol dehydrogenation reaction, there
was no significant interphase mass transfer resistance
(Fig. 13). The MEK production rate remained fairly
constant with an increase in 2-butanol feed flow rate at
all temperatures tested. There were some fluctuations
in the MEK production rates, with a slight downward
trend in production rates at the lower temperatures.
Rates at different feed flows were averaged at each
temperature. Raizada et al. [14] reported similar re-
sults on interphase mass transfer resistance for the
dehydrogenation of n-butanol over zinc oxide. They
concluded that bulk diffusion was not significant.
3.7. Determining kinetic parameters for
2-butanol dehydrogenation
Perona and Thodos [11] determined reaction ki-
netics for the dehydrogenation of 2-butanol between
343 and 399 C over solid brass spheres (65% copper
and 35% zinc). Under those conditions, they found
the desorption of hydrogen from a single site to be
rate limiting. Ford and Perlmutter [13] used a brass
Table 1
Reaction rate parameters for 2-butanol dehydrogenationa
T ( C) k (mol/kg cat h kPa)
190 0.339
220 0.772
250 1.713
280 3.342
a A: 2-butanol; S: hydrogen; R: MEK.
tube (60% copper and 40% zinc) as catalyst and car-
ried out the dehydrogenation reaction at temperatures
between 316 and 427 C. From 350 to 400 alcohol
adsorption was rate limiting, while at both higher and
lower temperatures the single site surface reaction
was rate limiting. Thaller and Thodos [12] performed
experiments with smaller brass catalyst particles
(5060 mesh; 65% copper and 35% zinc) with a larger
surface area. Below 300 C the reaction was dual site,
surface reaction controlling, while at higher tempera-
tures the reaction was dual site, hydrogen desorption
controlling. As a first approximation, kinetic data for
2-butanol dehydrogenation from 190 to 280 C and
1 atm was fitted to the reaction mechanism described
by Eq. (1). Reaction rate data in this study indicated
a strong inverse quadratic relationship between the
observed reaction rate and the MEK partial pressure.
k  (PA PR PS /Keq )
rA = (1)
(1 + KA PA + KR PR + KS PS )2
with A, R, S = 2-butanol, MEK, hydrogen.
More detail on calculating the different coefficients
were supplied in Keuler [4]. Table 1 lists the different
calculated reaction rate parameters. The trends in the
k and KR values were in line with Peloso et al. [15],
except at 280 C where KR showed an increase instead
of a decrease.
Very little catalyst deactivation took place at 250 C
and below (see Fig. 12), but at 310 C (Fig. 12) signifi-
cant deactivation took place. From initial experiments
it could be concluded that some deactivation took
place at 280 C, which resulted in lower measured re-
action rates and a distortion in the kinetic data. Both
KA and KS (the adsorption coefficients for 2-butanol
and hydrogen) were negligible compared to the ad-
sorption coefficient of MEK (KR ). When adsorption
took place, the reaction rate slowed down. This was
because diffusion resistance of the feed molecules to
KA (kPa1 ) KS (kPa1 ) KR (kPa1 )
0.001433 0.00129 0.11735
0.001195 0.00126 0.06075
0.002987 0.00225 0.05232
0.003225 0.00109 0.06432
 J.N. Keuler et al. / Applied Catalysis A: General 218 (2001) 171180
the active sites increased. Negative hydrogen adsorp-
tion coefficients indicated an increase in reaction rates.
The reasons for the increase in reaction rate with
hydrogen in the feed have been documented for
other dehydrogenation reactions and is not unex-
pected where coking tends to deactivate the catalysts.
Sheintuch and Dessau [16] cited many references
where hydrogen was co-fed with either an alco-
hol or an alkane and where hydrogen improved the
dehydrogenation activity. Hydrogen in the feed stream
reduces coking [16] and it reduces the partial pressure
of the alkane or the alcohol, which is favourable for
higher conversions [1].
The equilibrium constant for 2-butanol dehydro-
genation was taken from Kolb and Burwell [17] and
the units were transformed from atm to kPa. Combin-
ing the equilibrium equitation with Arrhenius fits of
k and KR yielded the following kinetic expression:
8.290 105 e6903/T (PA PR PS /
(3.538 108 e7100/T ))
rA = (2)
(1 + 8.804 105 e3298/T PR )2
with pressures in kPa and temperatures in K. The eq-
uitation is valid for temperatures from 190 to 250 C
(463523 K).
4. Conclusions
The reaction of 2-butanol over MgO and SiO2 ,
impregnated with copper, yielded MEK and butenes.
MEK was the main product (except for catalysts
without copper), with a mixture of butenes as the
by-product. MgO supported catalysts gave low MEK
yields due to their low BET surface area. For silica
supported catalysts, there was an optimum copper
concentration on the support (15 wt.%), which gave
the highest MEK yields. Silica support particles in
the range of 300850 m gave the highest MEK
yields. Smaller or larger particles produced increas-
ing amounts of butenes. For a 15 wt.% Cu on silica
catalyst, the selectivity towards MEK production was
close to 100% at 240 C, but declined to between 83
and 86% at 390 C.
The catalyst was stable at 250 C over a 24 h
period, but deactivated at 310 C. For the 2-butanol
dehydrogenation reaction, there was little interphase
179
mass transfer resistance. The 2-butanol and hydrogen
adsorption coefficients were negligible compared to
the MEK adsorption coefficient.
Acknowledgements
We want to acknowledge Sasol and the FRD (both in
South Africa) for their financial contributions towards
the project. We want to acknowledge the Direction
des Relations Internationales of CNRS (France) for
financial support.
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