ISSN 2070 0504, Catalysis in Industry, 2009, Vol. 1, No. 4, pp. 300– 305. © Pleiades Publishing, Ltd., 2009.

Original Russian Text © Z.V. Komova, A.V. Zaitsev, A.I. Kreindel’, F.V. Kalinchenko, 2009, published in Kataliz v Promyshlennosti.

CATALYSIS IN CHEMICAL
AND PETROCHEMICAL INDUSTRY

Methanol Formation in the Water Gas Shift Reaction

over Copper Containing Catalysts
Z. V. Komovaa, A. V. Zaitseva, A. I. Kreindel’a , and F. V. Kalinchenkob
a
Süd Chemie Alvigo Catalysts, Moscow, Russia
b Süd Chemie Alvigo Catalysts Ukraine, Severodonetsk, Ukraine

Abstract— In ammonia and hydrogen production, methanol formation takes place mainly at the low tem
perature (second) WGS stage, where the gas composition, catalysts, and operating conditions are similar to
those in methanol synthesis. The methanol formation reaction consumes hydrogen, an expensive gas, and
causes a number of technological and environmental problems. This raises the problem of reducing the meth
anol formation rate. To do this, it is necessary to analyze the kinetics, thermodynamics, and technological
features of methanol formation at the low temperature shift stage. Here, we report the equilibrium methanol
concentrations calculated for CO conversion under near industrial conditions. Systematizing the relevant
experimental data available from the literature, we demonstrate how methanol formation depends on WGS
conditions. The methanol formation rate can be reduced by lowering the CO concentration in the feed gas
and employing low methanol catalysts. Another favorable factor for methanol reduction is the aging of the
catalyst during its operation.
DOI: 10.1134/ S2070050409040060

INTRODUCTION Residual methanol in the process condensate sets

The water gas shift (WGS) reaction, limits on its use.
CO + H 2 O H 2 + CO 2 – ΔH 1 (1) For the above environmental and economic rea
sons, the admissible methanol formation levels for
does not change the volume of the reaction system. hydrogen and ammonia plants are lowered every year.
Since it is exothermic, lowering the process tempera Therefore, the methanol formation problem is
ture shifts the equilibrium towards the reaction prod becoming increasingly more challenging, so it is nec
ucts, raising the CO conversion. essary to carry out a scientific analysis of relevant
In present day plants producing NH 3 and H 2 from experimental data and the physicochemical aspects of
hydrocarbons, CO is converted at 2.5– 3.0 MPa in two methanol formation in the WGS reaction.
stages at different temperatures and with different cat Here, we consider the thermodynamic, kinetic,
alysts. The second, lower temperature stage (finishing and technological aspects of methanol formation in
CO conversion from 2.0– 3.0 to 0.1– 0.3%) generally the WGS reaction over copper containing catalysts
uses Cu– Zn– Al catalysts and is carried out at 190– and systematize experimental data available in this
250°C. Similar catalysts are employed in low temper field.
ature (240– 300°C) methanol synthesis from carbon
oxides and hydrogen at 5– 10 MPa. Because these pro
cesses use similar catalysts and are conducted under THERMODYNAMIC FOUNDATIONS
similar conditions, methanol synthesis occurs as a side OF METHANOL SYNTHESIS FROM CARBON
reaction at the second WGS stage. The methanol con OXIDES AND HYDROGEN
centration in the WGS products can be up to 0.2%.
In the WGS reaction, the formation of methanol is Methanol synthesis from carbon oxides and hydro
gen can be represented as the following reversible exo
quite undesirable because it leads to extra consump thermic reactions:
tion of hydrogen, an expensive gas, and to the pollu
tion of the atmosphere with methanol containing CO + 2H 2 CH 3 OH – ΔH 2 , (2)
gases and amines with a sharp and unpleasant odor.
The amines result from the interaction between meth CO 2 + 3H 2 CH 3 OH + H 2 O – ΔH 3 . (3)
anol and ammonia present in the reacting gas. Both reactions are accompanied by a decrease in
The methanol and amines that remain in the con the volume of the reaction system. By lowering the
verted gas exert an adverse effect on subsequent pro temperature or raising the pressure, it is possible to
cesses, such as CO2 removal, causing the corrosion of shift the thermodynamic equilibrium towards metha
the apparatus. nol formation.

300
 METHANOL FORMATION IN THE WATER GAS SHIFT REACTION 301

Table 1. Gibbs free energies (ΔG) and heats (ΔH) of the function of temperature is presented in Table 3 and
reactions involved in methanol formation* Fig. 1.
Reaction ΔG, kJ ΔH, kJ It is clear from Table 1 that reaction (2) is the most
exothermic and that the Gibbs free energy of
(1) CO + H 2O H 2 + CO2 – 28.62 – 41.20 reaction (3) is positive, indicating that this reaction is
(2) CO + 2H 2 CH 3OH – 24.58 – 90.64 unlikely. Nevertheless, there have been reports on
(3) CO2 + 3H 2 CH 3OH + H 2O + 3.99 – 49.40 methanol synthesis via reaction (3) [3, 4]. Methanol
synthesis by CO2 hydrogenation was also reported by
* The computational procedure is described in [1]. The ΔG and Kagan et al. [5, 6]. Rozovskii et al. [7, 8] described the
ΔH values were taken from [2].
mechanism and kinetics of methanol synthesis from
CO2 and H 2 via reaction (3) in combination with the
Table 2. Equilibrium constants of reactions (1)– (3) as a func WGS process (reaction (1)). This is a so called induc
tion of temperature tion phenomenon (chemical induction) [9], whose
essence is that reaction (1) yields intermediates which
Keq data for reactions (1)– (3) have an effect on reaction (2). According to Rozovskii
T, reaction (1), et al. [7, 8], these intermediates result most likely from
reaction (2), reaction (3), the interaction of active sites on the catalyst surface
°C according according according
to [1] to [1]/ [11] to [1] with reaction components, such as ZCO2 and Z1H 2O
(where Z and Z 1 are adsorption sites on the catalyst
180 6.57 × 102 3.88 × 10– 2/ 7.58 × 10– 2 3.13 × 10– 4 surface). The sum of reactions (1) and (3) is reaction
190 4.65 × 102 2.61 × 10– 2/ 4.33 × 10– 2 2.08 × 10– 4 (2)— methanol synthesis from CO and H 2. It was
noted that the equilibrium in the reaction system is
200 3.29 × 102 1.75 × 10– 2/ 2.53 × 10– 2 1.39 × 10– 4
independent of the methanol formation mechanism
210 2.34 × 102 1.18 × 10– 2/ 1.51 × 10– 2 9.22 × 10– 5 [10].
220 1.65 × 102 0.79 × 10– 2/ – 6.13 × 10– 5 The equilibrium constants, which characterize the
230 1.17 × 102 0.53 × 10– 2/ 0.57 × 10– 2 4.25 × 10– 5 conversion of the initial components of the reaction
240 0.83 × 102 0.36 × 10– 2/ – 3.25 × 10– 5 system, were calculated for reactions (1)– (3) using the
250 0.57 × 102 0.24 × 10– 2/ 0.23 × 10– 2 2.48 × 10– 5 procedure described in [1] and for reaction (2) addi
tionally using the Temkin– Cherednichenko equation
[11], which is believed to be best substantiated theoret
ically (Table 2).
The equilibrium in the reaction system, which limits
the maximum methanol content in the product, will be The equilibrium constants calculated by Pospe
considered for the second WGS stage conditions with khov [11] from experimental data of different authors
the main reaction (1) taken into account. The basic ther for T = 250°C are similar to those calculated in this
study.
modynamic characteristics of reactions (1)– (3),
namely, the Gibbs free energy (ΔG) and heat (ΔH), are The calculation of the equilibrium methanol con
listed in Table 1. The temperature dependent equilib centration in the reaction system is based on the meth
anol synthesis reaction (2) and on the Temkin–
rium constant (Keq) data are presented in Table 2. The Cherednichenko equilibrium constant equation for
equilibrium methanol concentration Ceq (C H 3 OH ) as a this reaction [11].

Table 3. Ceq(CH 3 OH) and outlet temperature (Tout) data for the converted water– gas mixture at 28 MPa as a function of
the inlet temperature (Tin) at various steam/ gas ratios and CO contents of the feed gas

Steam/ gas = 0.46

Tin, °C COin = 2.08 vol % COin = 3.03 vol %

Ceq(CH 3 OH), vol % Tout, °C Ceq(CH 3 OH) , vol % Tout, °C Ceq(CH 3 OH), vol % Tout, °C

190 0.2227 205.4 0.1945 211.7 0.1289 208.5

200 0.1686 214.8 0.1479 221.2 0.0972 218.3
210 0.1290 224.4 0.1136 230.3 0.0738 228.1
220 0.0992 233.4 0.0987 240.2 0.0565 237.9
230 0.0652 243.7 0.0647 249.8 0.0409 247.7
240 0.0475 255.3 0.0470 259.3 0.0269 257.2

CATALYSIS IN INDUSTRY Vol. 1 No. 4 2009