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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

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 ow 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 The industrially used alcohol dehydrogenation catalysts 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 determines whether the dehydration or the dehydrogenation 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: (J.N. Keuler).

pH) favour the dehydrogenation reaction, while acidic 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 copperbased catalyst, namely, precipitation, urea hydrolysis, electroless plating and impregnation were discussed by Keuler [4]. The percentage copper on the support 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

0926-860X/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 6 - 8 6 0 X ( 0 1 ) 0 0 6 3 9 - 1


J.N. Keuler et al. / Applied Catalysis A: General 218 (2001) 171180

Nomenclature F k K Keq P rA T W feed ow rate (mol/s) reaction rate constant (mol/kg cat kPa h) adsorption coefcient (kPa1 ) equilibrium constant (kPa) pressure (kPa) rate of generation for component A in reaction (mol/kg cat h) temperature (K) catalyst mass (kg)

Subscripts A 2-butanol R MEK S hydrogen copper loading of 2025 wt.% gave an optimum copper surface area of about 40 m2 /g catalyst. Chang and Saleque [6] investigated cyclohexanol conversion 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 conversion on copper/-alumina with 1820 wt.% copper loadings. For alumina-based catalysts, the selectivity towards aldehyde or ketone formation increases with increasing copper loading [7,8]. The reason is that the acidic centres, which reduce dehydrogenation selectivity, become covered and thus neutralised. Jeon and Chung [9] observed a continuous decrease in cyclohexanol conversion with an increase in copper 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-butanol) to yield methyl ethyl ketone (MEK) is an important 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 adsorption 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 (surface 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 ask containing a copper nitrate solution (in distilled water) of a specic concentration. The ask was placed on a magnetic stirrer and the solution stirred for 2 h. Thereafter, the CuMgO particles were ltered, 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 particles were then placed in heated copper nitrate solutions (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 support 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 rst stage, the optimum catalyst was determined and during the second stage the kinetic parameters of the optimised catalyst was determined. The rst 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 (Institut de Recherches sur la Catalyse, Centre National de la Recherche Scientique) 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 syringe. 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 analysed on a HP 5850 gas chromatograph equipped with a FID detector. Two capillary columns, a 30 m HP

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 ow 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 reaction products were analysed with a HP G1800A gas chromatograph, equipped with a mass spectrometer and ame ionisation detector. A 50 m capillary column (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 ow reactor. Lower ow 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 ow 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 gures were tted by a smooth spline. Figures were constructed in the Statistica package.


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 increasing temperature. The total 2-butanol conversion was the highest for pure MgO, because of the large

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 support, the MEK yield increased to an optimum yield at 16.9 wt.% Cu on MgO (Fig. 3). For that catalyst, the total 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 ow 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 ow rate (in mol/s). The selectivity declined with an increase in temperature as more butenes were formed. The longer residence time at the low ow 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 ow rates meant that insufcient time was allowed for the 2-butanol to

Fig. 3. MEK yield for Cu on MgO catalysts as a function of temperature and Cu% on the support.

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.

Fig. 7. MEK yield for Cu on silica catalysts as a function of temperature and Cu% on the support.

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 signicant by-products were a mixture of butenes. Total 2-butanol conversion increased sharply with an increase in temperature,

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 occurred 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 silica) as a function of temperature and 2-butanol feed ow rate. The x- and y-axis in Fig. 9 were swapped to obtain a more visible t to the data. With the standard axis in Fig. 9, the trend in the data could not be observed. As mentioned previously the yield increased with temperature. The optimum yield shifted to higher temperatures when the owrate 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.

Fig. 6. Total 2-butanol conversion for Cu on silica catalysts as a function of temperature and Cu% on the support.


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.

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 selectivity towards MEK production than the SiO2 supported catalyst. At 300 C and below, the selectivities for the optimum catalysts at the different ow rate tests varied 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 ow rate tests were as follows: MgO = 626%; SiO2 = 5693%. Further work was only performed on the SiO2 supported 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

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 ow rates. 3.3. Comparing SiO2 and MgO supported catalysts The MEK selectivities for the optimum MgO supported 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.

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.

Fig. 12. MEK production rate as a function of time for a 14.4 wt.% Cu on silica catalyst.

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 temperature 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 temperatures 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. Stability 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. Further, 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.

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 rst 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 dependent 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 ow 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 resistance, the reaction rate will be independent of the feed


J.N. Keuler et al. / Applied Catalysis A: General 218 (2001) 171180

Fig. 13. The effect of 2-butanol feed ow rate on the MEK production rate.

ow rate and the lines on Fig. 13 will be horizontal. For the 2-butanol dehydrogenation reaction, there was no signicant interphase mass transfer resistance (Fig. 13). The MEK production rate remained fairly constant with an increase in 2-butanol feed ow rate at all temperatures tested. There were some uctuations in the MEK production rates, with a slight downward trend in production rates at the lower temperatures. Rates at different feed ows were averaged at each temperature. Raizada et al. [14] reported similar results on interphase mass transfer resistance for the dehydrogenation of n-butanol over zinc oxide. They concluded that bulk diffusion was not signicant. 3.7. Determining kinetic parameters for 2-butanol dehydrogenation Perona and Thodos [11] determined reaction kinetics 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) 190 220 250 280

tube (60% copper and 40% zinc) as catalyst and carried 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 temperatures the reaction was dual site, hydrogen desorption controlling. As a rst approximation, kinetic data for 2-butanol dehydrogenation from 190 to 280 C and 1 atm was tted 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. rA = k (PA PR PS /Keq ) (1 + KA PA + KR PR + KS PS )2 (1)

with A, R, S = 2-butanol, MEK, hydrogen. More detail on calculating the different coefcients 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) signicant deactivation took place. From initial experiments it could be concluded that some deactivation took place at 280 C, which resulted in lower measured reaction rates and a distortion in the kinetic data. Both KA and KS (the adsorption coefcients for 2-butanol and hydrogen) were negligible compared to the adsorption coefcient of MEK (KR ). When adsorption took place, the reaction rate slowed down. This was because diffusion resistance of the feed molecules to

k (mol/kg cat h kPa) 0.339 0.772 1.713 3.342

KA (kPa1 ) 0.001433 0.001195 0.002987 0.003225

KS (kPa1 ) 0.00129 0.00126 0.00225 0.00109

KR (kPa1 ) 0.11735 0.06075 0.05232 0.06432

A: 2-butanol; S: hydrogen; R: MEK.

J.N. Keuler et al. / Applied Catalysis A: General 218 (2001) 171180


the active sites increased. Negative hydrogen adsorption coefcients 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 unexpected where coking tends to deactivate the catalysts. Sheintuch and Dessau [16] cited many references where hydrogen was co-fed with either an alcohol 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 dehydrogenation was taken from Kolb and Burwell [17] and the units were transformed from atm to kPa. Combining the equilibrium equitation with Arrhenius ts of k and KR yielded the following kinetic expression: 8.290 105 e6903/T (PA PR PS / (3.538 108 e7100/T )) rA = (1 + 8.804 105 e3298/T PR )2

mass transfer resistance. The 2-butanol and hydrogen adsorption coefcients were negligible compared to the MEK adsorption coefcient.

Acknowledgements We want to acknowledge Sasol and the FRD (both in South Africa) for their nancial contributions towards the project. We want to acknowledge the Direction des Relations Internationales of CNRS (France) for nancial support.

[1] G. Ertl, H. Knzinger, J. Weitkamp, Handbook of Heterogeneous Catalysis, Vol. 5, VCH, Weinheim, Germany, 1997, p. 2140. [2] I. Carrizosa, G. Munuera, Study of the interaction of aliphatic alcohols with TiO2 , J. Catal. 49 (1977) 189. [3] M.P. Rosynek, R.J. Koprowski, G.N. DelliSante, The nature of catalytic sites on lanthanum and neodymium oxides for dehydration/dehydrogenation of ethanol, J. Catal. 122 (1990) 80. [4] J.N. Keuler, Optimising catalyst and membrane performance and performing a fundamental analysis on the dehydrogenation of ethanol and 2-butanol in a catalytic membrane reactor, Ph.D. Thesis, University of Stellenbosch, South Africa, 2000. [5] C.H. Sivaraj, P. Kantarao, Characterization of copper/alumina catalysts prepared by depositionprecipitation using urea hydrolysis, Appl. Catal. 45 (1988) 103. [6] H. Chang, M.A. Saleque, Dependence of selectivity on the preparation method of copper/-alumina catalysts in the dehydrogenation of cyclohexanol, Appl. Catal. A: Gen. 103 (1993) 233. [7] H. Chang, M.A. Saleque, Catalytic activities of electroless plated Cu/alumina catalysts for the dehydrogenation of cyclohexanol, J. Mol. Catal. 88 (1994) 223. [8] C. Sivaraj, S.T. Srinivas, V.N. Rao, P.K. Rao, Selectivity dependence on the acidity of copper-alumina catalysts in the dehydrogenation of cyclohexanol, J. Mol. Catal. 60 (1990) L23. [9] G.S. Jeon, J.S. Chung, Preparation and characterization of silica-supported copper catalysts for the dehydrogenation of cyclohexanol to cyclohexanone, Appl. Catal. A: Gen. 115 (1994) 29. [10] R.H. Perry, C.H. Chilton, Chemical Engineers Handbook, 5th Edition, McGraw-Hill, Tokyo, Japan, 1973, Chapter 34. [11] J.J. Perona, G. Thodos, Reaction kinetic studies: Catalytic dehydrogenation of sec-butyl alcohol to methyl ethyl ketone, AIChE J. 3 (1957) 230.


with pressures in kPa and temperatures in K. The equitation 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 increasing 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


J.N. Keuler et al. / Applied Catalysis A: General 218 (2001) 171180 [15] A. Peloso, M. Moresi, C. Mustachi, B. Soracco, Kinetics of the dehydrogenation of ethanol to acetaldehyde on unsupported catalysts, Can. J. Chem. Eng. 57 (1979) 159. [16] M. Sheintuch, R.M. Dessau, Observations, modelling and optimization of yield, selectivity and activity during dehydrogenation of isobutane and propane in a Pd membrane reactor, Chem. Eng. Sci. 51 (1996) 535. [17] H.J. Kolb, R. L Burwell, Equilibrium in the dehydrogenation of secondary propyl and butyl alcohols, J. Am. Chem. Soc. 67 (1945) 1084.

[12] L.H. Thaller, G. Thodos, The dual nature of a catalytic reaction: the dehydrogenation of sec-butyl alcohol to methyl ethyl ketone at elevated pressures, AIChE J. 6 (1960) 369. [13] F.E. Ford, D.D. Perlmutter, The kinetics of the brass-catalysed dehydrogenation of sec-butyl alcohol, Chem. Eng. Sci. 19 (1964) 371. [14] V.K. Raizada, V.S. Tripathi, D. Lal, G.S. Singh, C.D. Dwivedi, Kinetic studies on dehydrogenation of butanol to butyraldehyde using zinc oxide as catalyst, J. Chem. Tech. Biotechnol. 56 (1993) 265.