Applied Energy 74 (2003) 8593

www.elsevier.com/locate/apenergy

Fuel from the synthesis gasthe role of process

engineering
Marek Stelmachowski*, Lech Nowicki
Department of Environmental Engineering Systems, Faculty of Process and Environmental Engineering,
Technical University of Lodz, Wolczanska 213, Lodz, 90-154 Poland

Abstract
The paper presents the conclusions obtained in the investigations of methanol synthesis,
FischerTropsch synthesis, and higher alcohols synthesis from syngas as a raw material in
slurry reactors. The overview of the role of process engineering was made on the basis of the
experience in optimizing process conditions, modeling reactors and working out new tech-
nologies. Experimental data, obtained with a laboratory-stirred autoclave and theoretical
considerations were used to develop the kinetic models that can describe the product forma-
tion and the model of the simultaneous phase and chemical equilibrium for the methanol and
FischerTropsch syntheses in the slurry reactors. These models were employed in modeling of
the bubble-column slurry reactor (BCSR). Based on these considerations, a computer simu-
lation of the low-pressure methanol synthesis for the pilot-scale, BCSR, was devised. The
results of the calculations and the conclusions could be employed in the process for designing
an industrial plant.
# 2002 Published by Elsevier Science Ltd.
Keywords: Fuel; Synthesis gas

1. Introduction

Crude oil is the basic resource for manufacturing gasoline. However, liquid fuels
produced from coal, natural gas or biomass may be alternatives in the future. Con-
version of coal, natural gas and biomass to the fuels may be implemented in dierent
ways. The most important manner is conversion to synthesis gas. The syngas, a
mixture of hydrogen and carbon monoxide with carbon dioxide and nitrogen as
additives, is a very good intermediate product for further syntheses. Depending on
reaction conditions and the catalyst used, dierent chemicals may be produced on a

* Corresponding author. Fax: +48-42-636-8133.

E-mail address: marekste@wipos.p.lodz.pl (M. Stelmachowski).

0306-2619/02/$ - see front matter # 2002 Published by Elsevier Science Ltd.

PII: S0306-2619(02)00134-4
86 M. Stelmachowski, L. Nowicki / Applied Energy 74 (2003) 8593

large industrial scale (see Fig. 1). Copper and zinc are the key components of the
methanol synthesis catalysts. Alkali promotion of this catalyst changes the product
composition to a mixture of higher alcohols. Promoted iron catalysts are used in
commercial reactors for the conversion of the syngas to hydrocarbon mixtures (for
example, synthetic gasoline) via the FischerTropsch synthesis. These processes may
be carried out in gas-phase or slurry reactors. Methanol, one of the most industrially
important chemicals, may be directly used as a clean fuel or as an additive to the
gasoline. It may be converted to MTBE (an additive to the gasoline too) or to
gasoline by Mobils methanol-to-gasoline (MTG) process using a shape-selective
(ZSM-5) catalyst. The role of process engineering in the development of technolo-
gies based on the syngas syntheses is very important; for example: to work out new
technologies and new models of reactors, to optimize process conditions, to design
and test new catalysts for high activity and selectivity, and to optimize the catalyst
composition, to optimize the activation process of the catalyst. This role will be
illustrated by a set of examples of experimental investigations and theoretical con-
siderations for the FischerTropsch synthesis, higher alcohols synthesis and metha-
nol synthesis in the slurry reactors.

2. FischerTropsch synthesis

The theoretical basis of the FischerTropsch (FT) synthesis was worked out in
Germany between 1923 and 1934. In 1936, the rst industrial-scale facility was built
in Germany. After the Second World War, gasoline was produced via FT synthesis
only in South Africa (SASOL). In the 1970s, FT synthesis became interesting again
as a result of the crisis in the Middle East.
The FT synthesis is described by the set of equations [1,2]:

Fig. 1. Chemicals produced from the synthesis gas used as fuels, as additives to fuels or intermediate
products for further synthesis.
 M. Stelmachowski, L. Nowicki / Applied Energy 74 (2003) 8593 87

 m
nCO n H2 Cn Hm nH2 O
2
CO H2 O CO2 H2 1

where n is the average length of the hydrocarbon chain and m is the number of
hydrogen atoms per carbon. All reactions are exothermic and the product is a mix-
ture of dierent hydrocarbons in that paran and olens are the main parts. The
distribution of products is described by so called SchulzFlory equation [1]:
yn
n1
2
where yn is the mole fraction of the product n.

Fig. 2. The inuence of the parameter
on the composition of the FT synthesis product.

Fig. 3. Eects of the reduction and reductant type on the synthesis gas conversion.
88 M. Stelmachowski, L. Nowicki / Applied Energy 74 (2003) 8593

Temperature, pressure, the composition of the synthesis gas and the composition
of the catalyst aect on the value of the parameter
. Depending on
, dierent
mixtures of hydrocarbons may be obtained (Fig. 2). The catalyst activation aects
the reaction rate, synthesis gas conversion and deactivation of the catalyst [3]. The
role of process engineering is demonstrated by the example of the experimental
investigations that allowed the best way of activation of the catalyst used in the FT
synthesis to be obtained. The inuence of the dierent ways of activation of the
catalyst is shown in Fig. 3.

3. Higher alcohols synthesis

In the past 25 years, there has been considerable interest in developing a catalyst
for the higher alcohols synthesis (HAS) from CO/H2 mixtures for use as additives to
gasoline to increase the octane number. Methanol and higher alcohols can be
simultaneously produced from synthesis gas via many dierent catalysts. In the
study, the catalyst Cu/Zn/Zr/Fe/Mo/Th/Cs was tested over a wide range of operat-
ing conditions. The experimental data were used to develop a new product dis-
tribution model.
Similar experimental sets were used in the FT-synthesis, HAS and methanol synth-
esis. A detailed description of the reactor and analytical systems used in all studies has
been given elsewhere [2,4,5]. A detailed description of experimental conditions, of the
model and all assumptions of the HAS study can be found in Ref. [2]. The experi-
mental results show that the formation of alcohols and hydrocarbons followed the
SchultzFlorry distribution (see Fig. 4). Three types of reaction are considered for
higher alcohol synthesis: formation of n-alcohols, formation of n-parans, and the
watergas shift. In general, the stoichiometry of these reactions can be written as:
nCO 2nH2 Cn H2n1 OH n  1H2 O; n 1 . . . 6
nCO 2n 1H2 Cn H2n2 OH nH2 O; n 1 . . . 8
CO H2 O CO2 H2 3

A detailed reaction network for linear alcohols from syngas, based on the CO
insertation mechanism, is shown in Fig. 5. As can be seen from Fig. 4, the model
successfully predicts the product formation rates within the range of experimental
conditions used in this study.

4. Methanol synthesis

The rst task that should be usually undertaken for the synthesis performed in the
slurry reactor is developing a mathematical model of the simultaneous phase and
chemical equilibrium. The problem is very important especially the selection of a
solvent in which the catalyst is suspended. Based on theoretical considerations and
our own experimental data, a completely predictive model was built for the systems,
 M. Stelmachowski, L. Nowicki / Applied Energy 74 (2003) 8593 89

Fig. 4. Eect of temperature on product distribution in HAS (7 MPa, 0.045 mol kg1h1, H2/CO=2.2).
Symbols are measured rates of formation. Lines represent model predictions.

Fig. 5. The network of elementary steps in alcohol and hydrocarbon syntheses from syngas.

which consist of organic and inorganic gases and vapours (substrates and products)
as solute and a mixture of high-boiling hydrocarbons as the solvent. The model may
be used for the calculations of the simultaneous phase and chemical equilibrium not
only for the methanol synthesis but for FT synthesis in the slurry reactor. The
90 M. Stelmachowski, L. Nowicki / Applied Energy 74 (2003) 8593

results presented in Fig. 6 show good agreement between the experimental and cal-
culated values of Henrys constants for the dierent systems [6].
The next step was connected with investigations (at a laboratory-scale) of the
reaction rate, conversion of the synthesis gas, the activity of the catalyst and the
formation of the kinetic model [4,5]. The example of the results presented in Fig. 7
shows the inuences of temperature, pressure and composition of the syngas on the
productivity of methanol and the conversion of carbon monoxide.
Based on the reaction-rate data of methanol synthesis on the catalyst suspended in
the solvent, the kinetic parameters in the rate equations were employed in modeling
of the bubble column slurry reactor (BCSR). Three models (for the ow patterns)
describing the performance of the bubble column slurry reactor for low-pressure
methanol synthesis were considered, compared and applied to the simulation of the
process.
Only the following chemical reactions were considered in the models:

CO 2H2 CH3 OH
CO2 3H2 CH3 OH H2 O 4

The model of the process involved the equations for calculating the properties of
both phases, gas-liquid equilibrium and mass transfer coecients. In addition, other
assumptions were made. Based on the assumptions, the balance equations were
formulated and solved. The solution yielded distributions of reactants velocity,
concentration, conversion and methanol productivity along the reactor. An example

Fig. 6. Comparison of calculated and experimental values of Henrys constants versus temperature for
the dierent binary systems.
 M. Stelmachowski, L. Nowicki / Applied Energy 74 (2003) 8593 91

Fig. 7. The inuence of the pressure and temperature on the productivity of the methanol (H2/CO=2,3).

of the results is given in Fig. 8. More detailed information may be found in [7]. It
was concluded that:

 the highest concentration of methanol in the gas phase was for the third
model and the lowest one for the rst model,
 the maximum methanol productivity and concentration occurred for the
second model,
 the resistance of the mass transfer in the liquid phase was negligible.

Next, a computer simulation of the low-pressure methanol synthesis in the bubble-

column slurry reactor was performed. Only one model (completely mixed gas phase
and completely mixed liquid phase) of the ow pattern considered earlier was
employed in the process calculations, which were performed for the semi-technical
reactor. The methanol productivity, production rate, carbon-monoxide conversion
and methanol concentration in the outlet gas were optimized versus temperature,
total pressure, inlet linear gas velocity, inlet gas concentration and catalyst concen-
tration. An example of the results of the calculation is presented in Fig. 9. Optimal,
from the technological point-of-view, process conditions such as optimal pressure,
temperature, inlet linear velocity of syngas and H2/CO ratio in the inlet gas were
found. Results of the calculations and conclusions could be interesting and valid not
92 M. Stelmachowski, L. Nowicki / Applied Energy 74 (2003) 8593

Fig. 8. Conversion of carbon monoxide and methanol productivity along the BCSR height: (1) com-
pletely mixed gas phase and completely mixed liquid phase, (2) plug ow in the gas phase and completely
mixed liquid phase, (3) plug ow in the gas phase and unmixed liquid phase, (4) completely mixed gas
phase and completely mixed liquid phase but without the resistance of the mass transfer in the liquid
phase. P=75 bar, T=523 K, y1=0.04, y4=0, y5=0, y6=0.06, u0G=0.464 Nm3/s, wkat=0.2.

Fig. 9. Production rate of methanol RZA and carbon monoxide conversion versus inlet gas composition
(ckat=152 kg/m3, u0G =0,064 m/s).
 M. Stelmachowski, L. Nowicki / Applied Energy 74 (2003) 8593 93

only for the laboratory and semi-technical reactors, but could be applied in the
design process for industrial plants [8].

5. Conclusions

There are many possible technologies for producing synthetic fuel from dierent
resources. It was proved that the process engineering may play the main role in
inventing and implementing new technologies for producing synthetic fuels. Experi-
mental investigations and theoretical considerations based on the rules of process
engineering lead to optimal solutions for industrial facilities. The global optimal
solutions may be found on the basis of engineering and economic calculations.
Examples demonstrated in this paper show that new technologies for the Fisher
Tropsch synthesis and/or methanol synthesis and for example the slurry reactors
may be a good alternative for producing fuel in the future.

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