Chemical Engineering and Processing 40 (2001) 33 40

www.elsevier.com/locate/cep

Kinetics of the synthesis of higher aliphatic alcohols from syngas

over a modified methanol synthesis catalyst
Maria Kulawska *, Jerzy Skrzypek
Institute of Chemical Engineering, Polish Academy of Sciences, 44 -100 Gliwice, Ba*tycka
l
5, Poland
Received 2 February 2000; received in revised form 17 April 2000; accepted 17 April 2000

Abstract
Kinetic investigation on the synthesis of a mixture of methanol and higher aliphatic alcohols from the synthesis gas has been
conducted over a Cs-doped CuZn composite catalyst in an experimental gradientless reactor. The kinetic equation was described
in a simple power law form. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Kinetics; Higher aliphatic alcohols; Methanol; Syngas

1. Introduction
The synthesis of a mixture of methanol and higher
aliphatic alcohols is one of the most interesting processes in C1 chemistry. Recently, the works in this area
are focused on the effective production of an octane
booster for clean gasoline. The reaction requires special
composite catalysts working in severe conditions. The
catalysts can be divided into the two main classes:
modified catalysts for methanol synthesis and those
often referred to as modified catalysts of Fischer Tropsch synthesis. In the first class, by analogy to methanol
synthesis high and low temperature catalysts are
distinguished. A promoter containing alkali or alkali
earths species should be used in all cases.
The products include primary and secondary alcohols of both normal and branched carbon chains. The
stoichiometry of higher alcohol synthesis from synthesis
gas is based on the following reactions:
CO+2H2 l CH3OH

(1)

2CO+4H2 l C2H5OH + H2O

(2)

3CO+6H2 l C3H7OH + 2H2O

(3)

Other oxygenates: ketones, aldehydes and esters are

also formed.
* Corresponding author. Tel./fax: +48-32-2310318.

The water-gas shift reaction is always present and

assumed as attaining chemical equilibrium under the
process conditions [1]:
CO+ H2O l CO2 + H2

(4)

Undesired side reactions of hydrocarbon formation

may occur, especially that of methane:
CO+ 3H2 l CH4 + H2O

(5)

From the thermodynamic point of view, lower temperatures and higher pressures are profitable for the
formation of alcohols, because these reactions are
exothermic and proceed with volume contraction. From
the kinetic point of view, higher temperatures, about
600 K, should be employed to yield a sufficient reaction
rate.
The values of the yield can differ distinctly in spite of
the same composition of catalysts. Table 1 provides
some data concerning low-temperature modified
methanol synthesis (copper-based) catalysts.
The reaction mechanisms suggested in the literature
include a slow step for the formation of C2 species from
C1 species [810]. The rate of ethanol formation appears to limit the overall rate of chain growth. According to Nunan [11], ethanol is produced due to the
reaction between the adsorbed formaldehyde and the
formyl group created by hydrogenation of the adsorbed
CO.

0255-2701/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 2 5 5 - 2 7 0 1 ( 0 0 ) 0 0 1 0 7 - 0

Catalyst composition
(mol.%)

Temperature (K)
Pressure (MPa)
GHSV (l/kgcat/h)
*(1/h)
Gas composition
H2/CO (mol ratio)
Methanol yield
(kg/kgcat/h)
Higher alcohol yield
(kg/kgcat/h)

2
3
4

Reference

Number

0.16

0.16

0.45

583
7.6
3260

Cu/Zn=30/70
+0.34 wt.% Cs

Nunan et al.,
1989 [2]

Table 1
Literature data concerning copper-based catalysts

0.08 c(kg/lcat/h)

0.3 c(kg/lcat/h)

0.5

560
6.2
*9000 [1/h]

Cu/Th/Zr/K
= 63/18/9/9

US patent
4 943 551, 1990 [3]

23.8 wt.% of liquid

product
57.3 wt.% of liquid
product

0.45

598
7.6
*860

Cu/Zn=30/70
+0.4 wt.% Cs

Herman, 1991 [4]

0.38*(l/lcat/h)

1.12 *(l/lcat/h)

1.5

Cu/Mn/Zn/Co=4/3/1/0.025
+10wt.% Cr2O3+4 wt.%
K2CO3
673
17
*40 000

Stiles et al., 1991 [5]

0.30

0.18

0.75

598/678
7.5
18 375

Cu/ZnO/Cr2O3 +3mol.%
CsZn/Cr2O3+4 wt.% Cs

Beretta et al., 1996 [6]

(double bed)

0.36

0.57

0.75

598/613
7.5
18 375

= 30/45/25+3mol.% Cs

Cu/ZnO/Cr2O3

Burcham et al., 1998 [7]

(double bed)

34
M. Kulawska, J. Skrzypek / Chemical Engineering and Processing 40 (2001) 3340

M. Kulawska, J. Skrzypek / Chemical Engineering and Processing 40 (2001) 3340

The growth schemes of the alcohol molecules and the

prediction of the product mixture distribution for assigned values of the operating conditions have been
given by some authors [12,13] for modified methanol
catalysts. Few works have been made at modelling the
kinetics of the overall rate of the synthesis. The paper
of Calverley and Smith [1] concerned the alcohol synthesis over the low-temperature modified methanol catalysts. Recently, Burcham et al. [7] presented a kinetic
reaction network to predict product yields over a double bed CsCu/ZnO/Cr2O3 catalyst. The kinetic model
originally developed by Smith et al. [14,15] was based
on the mechanism of alcohol formation over caesiumpromoted copper-based catalysts proposed by Nunan et
al. [2,11]. The earlier report about double bed reactor
working over high-temperature and low-temperature
catalysts has been given by Beretta et al. [6]. Tronconi
et al. [16] and recently Beretta et al. [17] conducted their
kinetic investigations over the high-temperature
modified methanol synthesis catalyst.
Both the experiments of Calverley and Smith [1] and
Tronconi et al. [16] have been conducted at fixed temperature and fixed pressure, so the dependence of reaction rate on these parameters is not known. Our work
is an attempt of modelling the kinetics of the synthesis
of higher alcohols globally applicable over ranges of
operating conditions.

2. Experimental
The catalyst containing mainly CuO and ZnO with
additions of Zr, Fe, Mo, Th and Cs oxides has been
prepared in our laboratory. It is a kind of low-temperature modified methanol synthesis catalyst. Three different methods of catalyst preparation were used; the best
results were obtained with the thermal decomposition
of organic complexes containing metallic components
of catalyst.
The catalyst was calcined in the temperature range
370 650 K, then reduced in a 3% H2/N2 mixture by a
heating rate 5 K/min to the maximum temperature 450
K at fixed gas flow 60 ml/min. Prior to the reaction, the
catalyst was activated (525 650 K, 4 MPa, 1850 per h).
The optimal composition of the catalyst was CuO
(50 60), ZnO (25 30), ZrO2 (7 14), Fe2O3 (14),
MoO3 (715), ThO2 (1 3), Cs2O (0.5 1.5), wt.%. The
yield obtained was 130 170 g/kgcat/h of liquid product
that contained methanol (35 53), wt.%, higher
aliphatic alcohols C2 + (20 35), wt.%, and water. The
catalyst exhibits a remarkable stability during one-year
experiments and high selectivity towards alcohols. Hydrocarbons were practically absent, but traces of methane were detected. So, a risk of uncontrolled heat
production due to the methanation [5] is ruled out over
this catalyst. Higher aliphatic alcohols C2 + contained

35

ethanol (5164), wt.%, n-propyl alcohol (1927), wt.%,

and C4 C7 linear aliphatic alcohols. Branched aliphatic
alcohols C3 C5 constituted 5.58.5 wt.%. Only traces
of other oxygenates were formed.
The surface area of the catalyst was measured by the
BET method using argon. The surface area of the
oxidized catalyst was 20.3 m2/g and increased to 30.4
m2/g after reduction by hydrogen. The mean pore
radius was 16 10 9 m. The Cu metal surface area of
the reduced catalyst was measured using the pulse N2O
decomposition technique. Assuming a Cu atom density
of 1.46 1019 atoms/m2, the Cu surface area was 6.2
m2/g.
Kinetic experiments were carried out in a high-pressure continuous gradientless stirred tank reactor. This
type of reactor allows a direct determination of the
reaction rate. The gaseous feed was supplied from a
battery of gas cylinders through flowmeters and a gas
mixer placed inside an electric oven maintaining a
suitable temperature. The reactor (Robinson Mahoney
300cc) consisted of stainless steel tube 46 mm in a
diameter with a magnetic stirrer. Grains of the catalyst
(0.40.63 mm in a size, about 30 g in a weight) were
placed into a wire basket (40 mm outer and 32 mm
inner diameter, respectively) inside the reactor tube.
Temperature was controlled by a thermocouple. The
effluent stream, after cooling and after pressure was
reduced to 0.1 MPa, was a liquid mixture of methanol,
higher aliphatic alcohols and water. Liquid products
were analysed chromatographically (Varian, Star 340
with FID and TCD detectors) in a DBWAX column
0.53 mm in a diameter and 30 m long. Inlet and outlet
gases were analysed in a Carbosieve II packed column
4 mm in diameter and 2 m long.
The range of experimental parameters used was P=
4.010.0 MPa, T =593623 K, H2/CO= 0.853.16,
GHSV= 7000 per hour to make sure only low conversions would been attained. The reaction was far from
chemical equilibrium and the reverse reactions were
negligible. The process proceeded in the intrinsic kinetic
regime. The kinetic results are collected in Table 2.

3. Results and discussion

The mechanism of alcohol synthesis is catalyst specific and cannot be generalized from one system to
another. We have considered which mechanism of reaction can be taken into account in this case. It seemed
that a reaction between substrates was the rate-controlling step (LangmuirHinshelwood mechanism). The
increase in the reaction rate followed the increase in
pressure of hydrogen. No maximum was observed in
the rate with an increase in the pressure of hydrogen
(see Figs. 1 and 2). Also, there was not a distinct
dependence of the reaction rate on the CO pressure.

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35

Number

593
608
623
593
608
623
593
608
623
593
608
623
593
608
623
593
608
623
593
608
593
608
623
593
608
623
593
608
623
623
593
608
593
608
623

T (K)

10.0
10.0
10.0
7.0
7.0
7.0
4.0
4.0
4.0
10.0
10.0
10.0
7.0
7.0
7.0
4.0
4.0
4.0
10.0
10.0
7.0
7.0
7.0
4.0
4.0
4.0
10.0
10.0
10.0
10.0
7.0
7.0
4.0
4.0
4.0

P (Mpa)

0.709
0.709
0.709
0.709
0.709
0.709
0.709
0.709
0.709
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.512
0.512
0.512
0.512
0.512
0.512
0.512
0.512
0.427
0.427
0.427
0.427
0.427
0.427
0.427
0.427
0.427

XH 2

Table 2
Results of the kinetic experiments

0.224
0.224
0.224
0.224
0.224
0.224
0.224
0.224
0.224
0.32
0.32
0.32
0.32
0.32
0.32
0.32
0.32
0.32
0.392
0.392
0.392
0.392
0.392
0.392
0.392
0.392
0.501
0.501
0.501
0.501
0.501
0.501
0.501
0.501
0.501

XCO

55.3
56.3
53.1
50.7
50.6
47.9
44.8
41.4
36.4
47.3
47.5
46.5
44.8
47.5
46.8
41.2
37.8
38.3
48.1
47.5
46.0
41.6
42.6
39.7
37.4
35.7
45.9
46.6
42.6
43.4
41.5
40.8
34.8
33.6
33.4

MeOH (wt.%)

14.6
14.6
14.6
14.4
15.2
14.6
14.2
13.7
12.5
13.2
14.6
13.4
12.8
15.3
15.4
13.9
13.0
13.6
18.1
18.5
18.3
19.4
18.4
18.0
17.0
16.3
17.6
16.6
16.2
16.4
17.8
18.7
17.7
17.1
16.1

EtOH (wt.%)

6.0
6.0
6.2
5.7
6.4
6.1
5.9
5.7
5.5
5.6
5.3
5.7
5.2
5.5
5.6
5.1
4.7
5.0
7.9
8.8
8.4
9.6
9.6
9.2
9.2
9.2
7.5
6.5
6.9
6.8
9.3
9.3
10.2
10.1
10.2

PrOH (wt.%)

22.8
22.7
23.0
22.0
23.7
22.7
22.1
21.5
20.2
22.3
23.3
23.2
21.6
24.1
24.5
22.2
20.7
21.8
29.6
31.6
30.7
33.9
32.2
31.8
31.9
32.5
31.3
29.8
29.9
30.2
32.7
34.5
34.5
34.3
33.4

HA (wt.%)

1.563
2.531
2.875
1.031
1.563
2.094
0.50
0.375
0.563
1.375
1.719
2.344
0.813
1.47
1.44
0.219
0.25
0.719
0.75
1.31
0.594
0.75
1.16
0.094
0.188
0.344
0.625
1.41
1.56
1.53
0.41
0.688
0.125
0.125
0.188

r .MeOH 103
(mol/gcat/h)

0.284
0.456
0.549
0.208
0.328
0.446
0.109
0.086
0.132
0.268
0.387
0.472
0.165
0.328
0.377
0.054
0.063
0.182
0.195
0.354
0.170
0.241
0.345
0.028
0.059
0.109
0.170
0.351
0.411
0.400
0.128
0.216
0.040
0.049
0.069

10

r .EtOH 103
(mol/gcat/h)

0.089
0.144
0.179
0.063
0.106
0.143
0.035
0.027
0.044
0.087
0.108
0.154
0.051
0.090
0.105
0.015
0.017
0.051
0.065
0.129
0.060
0.092
0.135
0.011
0.025
0.047
0.056
0.105
0.134
0.127
0.051
0.082
0.018
0.022
0.034

11

r .PrOH 103
(mol/gcat/h)

20.4
32.6
39.8
14.6
23.5
31.9
7.8
6.2
9.8
20.8
28.4
37.6
12.8
23.8
27.6
4.0
4.6
13.4
14.7
27.8
13.1
19.4
27.8
2.3
5.1
10.0
14.0
29.0
34.9
33.9
10.8
18.3
3.6
4.5
6.6

12

r .HA103
(g/gcat/h)

36
M. Kulawska, J. Skrzypek / Chemical Engineering and Processing 40 (2001) 3340

M. Kulawska, J. Skrzypek / Chemical Engineering and Processing 40 (2001) 3340

37

Thus, the effect of CO appeared to be negligible. The

classical Langmuir Hinshelwood expression with terms
in the denominator gave no sufficient results by fitting.
We used simple pseudohomogeneous rate equation [18].
The following expression fits the experimental data
quite well by the mean error 9.7% at confidence level of
0.95.

r = k0 exp(E/RT)p nH2

(6)

Fig. 3. Exactness of fit for the rate of ethanol formation. Open

symbols refer to-T= 593 K; solid symbols T= 608 K; slashed symbols T= 623 K. -P=10 MPa, -P=7 MPa, D-P= 4 MPa.

Fig. 1. Effect of hydrogen pressure on the rate of the formation of

ethanol. Stars refer to T= 593 (K); rhombuses T= 608 (K); circles
T = 623 (K).

where n= 2 for methanol synthesis; n =1.5 for higher

alcohol synthesis. The values of activation energy are
72190, 81450, 78100 J/mol for MeOH, EtOH, PrOH,
respectively, at k0 = 59.4, 268, 48.3 mol/gcat/h/MPan,
respectively. The values of activation energy are typical
for catalytic reactions.
Kinetic conclusions can be drawn from Eq. (6) on the
nature of the catalyst used. Since the methanol formation rate can be described by:
rMeOH = k

Fig. 2. Effect of hydrogen pressure on the rate of the formation of

higher alcohols. Stars refer to T= 593 (K); rhombuses T= 608 (K);
circles T = 623 (K).

pCO
p2
1+ KCOpCO H2

(7)

the correlation (Eq. (6)) would be a good approximation for the case of KCO pCO1 and n=2. Eq. (7)
corresponds to the well-known situation when a reaction of chemisorbed CO with gaseous H2 is the ratecontrolling step. It may suggest that the
LangmuirRideal mechanism can exist [19]. Similar
conclusions can be given for the description of the
reaction rate of higher alcohol formation.
The adequacy of the model is shown in Figs. 3 and 4.
In the paper of Calverley and Smith [1], the expression describing the overall rate of higher alcohol formation was based on LangmuirHinshelwood kinetics.
The assumption was made that the formation of carboncarbon bonds occurs between any two formyl
intermediates, produced from carbon monoxide, carbon
dioxide and methanol on different type of active sites:

3
4

Number

8.5
8.5

673
673

ZnO/Cr2O3 1/1 metal

ratio+3 wt.% K2O
K/Zn/Mn/Cr
2.06/1/1.1/1.03 metal
ratio
Elliot, 1988 [21] CuO/ZnO= 30/70
Calverley and
CuO/ZnO/ Cr2O3+4
Smith, 1991 [22] wt.% K2CO3
(30/60/10 metal
ratio)+0.5 wt.%
K2CO3

Boz et al., 1994

[23]

Tronconi et al.,
1987 [16]
Forzatti et al.,
1988 [20]

4.0

10.0

592

K3O/CuO/ZnO/Al2O3 563
0.5/60/30/10 wt.%

6.5
10.0

558
562

Pressure (MPa)

Temperature (K)

Reaction conditions

Catalyst system

Reference

Table 3
Effect of carbon dioxide presence in the gas on a productivity of higher alcohols

3000

20 000

20 000

8000

8000

GHSV (h1)

2/1

1/2

1/2
1/2

2/1

1/1

Feed gas ratio

H2/(CO+CO2)
(mol.%)

1.25
1.25
1.25

2.74

0.02
1.47

40

0.42

C2+ OH yield
without CO2 in the
gas

6.0

0.15 [mol.% in
outlet gas]
8 [g/lcat/h]

4.0
9.0

9.0
2.0
6.0
10.0

0.06 [g/gcat/h]
0.47
[mmol/gcat/h]
2.12
[mmol/gcat/h]
2.4 [mol/l/h]
0.25
0.0

3.0

CO2 conc.
(mol.%)

C2+ OH yield at CO2 presence

38
M. Kulawska, J. Skrzypek / Chemical Engineering and Processing 40 (2001) 3340

rHA =

M. Kulawska, J. Skrzypek / Chemical Engineering and Processing 40 (2001) 3340

pCO(pH2)
+C pMeOH(pH2) 3/2
A+B pMeOH

39

1/2

pCO2(pH2)1/2
D + E pCO2/pco

(8)

where a =1.0010 5, b =0.126, c =6.82 10 4, d=

3.03; A= 7782, B=1853, C =0.331, D = 34.15, E=
18640; MeOHmethanol; HA mixture of higher
alcohols without methanol.
The direct comparison between this study and our
work cannot be conducted. The experiments of Calverley and Smith [1] were conducted at fixed temperature
558 K and fixed total pressure 10 MPa. The third term
in Eq. (8) indicates the enhancing influence of carbon
dioxide. The role of CO2 is one of controversies about
the kinetics of higher alcohol formation. The suppression of the higher alcohol formation is reported in most
cases see Table 3. Stiles et al. [5] have also found a
decrease in the alcohol formation over composite copper systems at 24 mo1% CO2 concentration in the
feed gas; similarly, Skrzypek et al. [24] observed the
same for Cu/Zn/Zr/Fe/Mo/Th systems doped with both
Cs and K, with traces of CO2 in the feed gas. In
contrast to such findings, Elliott [21] observed an enhancing effect of CO2, although for the undoped Cu
Zn catalyst only.
In our earlier investigations concerning the methanol
synthesis over copper zinc catalyst the Langmuir Hinshelwood mechanism has been found. The detailed
characteristic of this copper zinc catalyst was given
[25]. A similar catalyst but modified to higher alcohol
synthesis, prepared by us as described above, has a
different characteristic.

The mechanism of higher alcohol synthesis is different for different catalytic systems, depending on the
metal, the support, the promoter and the reaction conditions. Probably it is not possibly to determine one
universal mechanism of this process. Different intermediates and therefore different products can be formed.
In our work, the good selectivity towards alcohols and
only traces of by-products allow the simple correlation
suitable for reactor modelling.

Appendix A. Nomenclature

p
r
T
x

activation energy (J/mol)

gas hourly space velocity (per hour)
higher aliphatic alcohols
adsorption equilibrum constant (per
MPa)
rate constant (mol/gcat/h/MPan)
pre-exponential factor (mol/gcat/h/
MPan)
partial pressure (MPa)
reaction rate (mol/gcat/h)
temperature (K)
mole fraction

Subscripts
CO
CO2
EtOH
H2
HA
MeOH
PrOH

carbon oxide
carbon dioxide
ethanol
hydrogen
higher aliphatic alcohols
methanol
propanol

E
GHSV
HA
KCO
k
k0

References

Fig. 4. Exactness of fit for the rate of total higher alcohol formation.
Open symbols refer to T =593 K; solid symbols T= 608 K; slashed
symbols-T=623 K. -P= 10 Mpa; -P= 7 Mpa; D-P= 4 MPa.

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