Applied Catalysis A: General 186 (1999) 321342

FischerTropsch-synthesis with nitrogen-rich syngas

Fundamentals and reactor design aspects
A. Jess a, , R. Popp b , K. Hedden b
a

Institut fr Technische Chemie und Makromolekulare Chemie, RWTH Aachen, Worringer Weg 1, D-52074 Aachen, Germany
Engler-Bunte-Institut, Bereich Gas, Erdl und Kohle, Universitt Karlsruhe (TH), Richard-Willsttter-Allee 5, D-76131 Karlsruhe, Germany

Abstract
An option in bringing remote natural gas reserves to the market is its conversion by FischerTropsch (FT)-synthesis into
diesel oil and wax. The use of nitrogen-rich syngas (50 vol.%) could be an alternative to classical processes with nitrogen-free
syngas because the investment costs are probably lower: syngas is produced by partial oxidation with air, which eliminates
the need for an air separation plant, and a process with nitrogen-rich syngas does not utilize a recycle loop and a recycle
compressor.
For the development of such a process, the kinetics of FT-synthesis was studied on an Fe-catalyst, indicating that nitrogen
only dilutes syngas, and therefore, has no influence on the kinetics if the partial pressures of carbon monoxide and hydrogen
are kept constant. Subsequently, the FT-synthesis with nitrogen-rich syngas was investigated in wall-cooled single tube
reactors.
Based on the experimental data, a mathematical model for industrial multitubular FT-reactors was developed. Model
calculations indicate that nitrogen plays an important role in the operation of multitubular reactors by helping to remove the
heat generated by the FT-reaction. This leads to an optimum diameter of the tubes of 70 mm for nitrogen-rich syngas with
respect to a stable and safe operation of the reactor, whereas for nitrogen-free syngas, the diameter is limited to about 45 mm.
The production rate of diesel oil and wax per tube is, in case of nitrogen-rich syngas, about three times higher, which will
decrease the number of tubes and the investment costs of industrial multitubular reactors. Detailed economic studies are still
necessary to validate or disprove whether and under which circumstances the proposed process with nitrogen-rich syngas is
an attractive alternative to classical processes with nitrogen-free syngas, especially in areas with remote natural gas resources.
1999 Elsevier Science B.V. All rights reserved.
Keywords: FischerTropsch (FT)-synthesis; Iron-catalyst; Nitrogen-rich syngas; Fixed bed reactor; Multitubular reactor; Parametric
sensitivity

1. Introduction
About 50% of the proven natural gas reserves are
today distant from any sizeable market [1], e.g. large
Corresponding
author.
Tel.:
+49-241-80-6470;
+49-241-8888177
E-mail address: jess@itc.rwth-aachen (A. Jess)

fax:

reserves in the Middle East (Table 1). The economic

utilization of this natural gas is limited by its costly
transportation. An option in bringing remote natural
gas to the market is its conversion by FischerTropsch
(FT)-synthesis into higher hydrocarbons like diesel
oil and wax. These products are of high value and can
easily be shipped, obviating the need for dedicated
cryogenetic transportation, equipment and tankage.

0926-860X/99/$ see front matter 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 9 9 ) 0 0 1 5 2 - 0

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A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

Table 1
Global natural gas reserves [2]
Country

Natural gas reserves in 1012 m3 (STP)

1985

1996

CIS (former USSR) 42.5

Iran
13.3
Qatar
4.2
United Arab Emirates 0.9
Saudi-Arabia
3.4
USA
5.6
Venezuela
1.7
Algeria
3.0

55.9
21.0
7.1
5.8
5.3
4.7
4.0
3.7

World

98.8

138.1

The FT-synthesis can be summarized by the following reactions:

CO + 2H2 CH2 + H2 O;
0
= 152 kJ/mol
R H298

(1)

CO + 3H2
CH4 + H2 O;
0
R H298
= 206 kJ/mol

CO + H2
CO2 + H2 ;

(2)
0
R H298
= 41 kJ/mol

(3)
The first two equations describe the formation of
higher hydrocarbons and of methane, respectively;
the CH2 group in Eq. (1) indicates a link of a hydrocarbon molecule. Carbon monoxide can also react
with water vapor, which is formed (Eqs. (1) and (2))
or already present in syngas, to carbon dioxide and
hydrogen (Eq. (3)).
Since the mid of the 1950s up to the beginning of
the 90s, the FT-synthesis was operated industrially
only in South Africa and exclusively with syngas generated by coal-gasification [3]. In recent years, a renaissance of the FT-synthesis based on syngas from
natural gas can be stated, which takes into account the
growing importance of natural gas, in particular of resources, which are remote from the market:
Since 1992, liquid fuels are being produced from
natural gas in the Mossel Bay gas conversion project
in South Africa [4,5]. In a first step, syngas is generated by steam reforming as well as by partial oxidation of natural gas with oxygen. The combined syngas streams are converted into liquid fuels (0.9 Mt

per annum) by FT-synthesis on an iron-based catalyst in circulating fluidized-bed reactors.

A second industrial FT-plant for the production of
liquid hydrocarbons (about 0.5 Mt per annum) from
natural gas is in operation in Malaysia since 1993
[4]. The so-called Shell Middle Distillate Synthesis (SMDS)-process, developed by Shell, uses multitubular FT-fixed bed reactors and a co-catalyst
[6]. The main product is wax, which is further converted by hydrocracking into diesel oil.
Exxon announced in 1994 the development of a
so-called second generation process, the Advanced
Gas Conversion (AGC-21) process [1]. Syngas is
generated by the catalytic conversion of natural gas
with oxygen and steam in a fluidized bed reactor,
where partial oxidation and steam reforming take
place simultaneously. Syngas is subsequently converted on a co-catalyst in a FT-slurry reactor. The
main product is wax, which is further cracked to
liquid fuels. The process was tested in a pilot plant.
In 1996, South African Coal, Oil and Gas Corp.
Ltd. (Sasol) and Haldor Topsoe from Denmark announced a cooperation agreement for combined promotion of Sasols slurry phase FT-technology and
Haldor Topsoes technology for the conversion of
natural gas to syngas [7].
In the 90s, Rentech Inc. (USA) was operating a
small FT-unit, which uses an iron catalyst in a
slurry reactor to produce gasoline, diesel oil and
wax (about 15,000 tons per annum) [4]. In 1996,
this plant was sold, dismantled and shipped to its
Indian licensee, Donyi Polo Petrochemicals. It is
now installed in northeastern India and should be
in operation in the near future. The plant will use
about 100,000 m3 (STP) per day of presently flared
gas.
In 1997, Qatar General Petroleum Corp. started
negotiations with Sasol for the construction of an
FT-plant in Qatar with an annular capacity of about
1 Mt middle distillates. In addition, talks are going
on with Exxon about a plant with a capacity of 5 Mt
per annum [8].
Also in 1997, Sasol and the Norwegian company
Statoil announced a cooperation for the construction
of small floating FT-plants in order to utilize oil
associated gas offshore in areas of the North Sea,
where it is uneconomical to build a pipeline for the
gas [8].

A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

Although very little data are available from the literature, the production costs of these capital-intensive
processes are probably above the break-even point.
In contrast to the common philosophy of constructing chemical plants of high efficiency, i.e. of high investment costs in order to keep energy and feedstock
costs down, we are convinced that, for countries in
remote areas with low prices of energy of natural gas the only economical solution for the conversion of natural gas to higher hydrocarbons is a
low-cost technology, even if the conversion efficiency
is lower [9,10]. The concept of the following low-cost
FT-process based on nitrogen-rich syngas (Fig. 1)
was investigated on a semi-technical scale from 1987
to 1997 at the Engler-Bunte-Institute of the University
of Karlsruhe.
After desulphurization, the natural gas is converted into a nitrogen-rich (about 50 vol.% nitrogen)
and soot-free syngas by catalytic partial oxidation
with air at a pressure of about 25 bar. Using air
instead of oxygen eliminates the need for an air
separation plant. The autothermal reactor is (on industrial scale) a refractory-lined vessel utilizing a
nickel-based catalyst. This reactor is compared
to a steam-reformer relatively inexpensive. In addition, no soot-separation is needed [11,12] as for
non-catalytic partial oxidation with pure oxygen,
which is used both in the Mossel Bay project and the
SMDS-process.
Without further compression, the nitrogen-rich
syngas is converted by FT-synthesis in multitubular
fixed bed reactors to higher hydrocarbons. A commercial precipitated iron catalyst (Hoechst-Ruhrchemie,
Germany), similar to the one in the common industrial
fixed bed FT-process, the so-called ARGE-process
(Sasolburg, South Africa, coal-based syngas), was
used in the experiments. In contrast to this process, which uses nitrogen-free syngas, the proposed
low-cost process with nitrogen-rich syngas (about
50%) does not utilize a recycle loop to avoid any
build-up of nitrogen in the system. This configuration
is probably less expensive because a recycle compressor is not needed. In addition, the nitrogen in syngas
plays a significant role by helping to remove the large
amounts of heat generated by the FT-reaction, which
will be discussed in detail in this paper. The products
are separated by cooling down into organic condensates (wax and diesel oil), water and an off-gas, which

323

may be used to generate power, and in countries like

in the Middle East, to desalinate sea water.
The task of the project was to develop and to test this
low-cost process on a semi-technical scale in order to
obtain the basic data for further economic evaluations.
The concept of this process, which was invented by
Hedden in 1987 [9], and experimental data of syngas
generation and of the FT-synthesis on lab-scale as
well as in semi-technical reactors have already been
discussed in detail elsewhere [1018]. Therefore,
only some major results of the final experiments with
the semi-technical plant for the production of liquid
hydrocarbons from natural gas are subsequently
presented.
2. FT-synthesis with nitrogen-rich syngas:
experiments on a semi-technical scale
2.1. Experimental set-up
The experiments were carried out with the
semi-technical unit shown in Fig. 2. Briefly, the apparatus consists of the syngas generation unit (up
to 10 m3 syngas (STP)/h; details in [11,12]), the
FT-unit with three single-tube fixed bed reactors in
series (details in [16]), and the product separation.
In some experiments, e.g. where the steam content
of syngas was varied, syngas was made by mixing
its components. The diameter of the semi-technical
FT-reactors corresponds to a single tube of a typical
industrial multitubular reactor (Fig. 3); the experimental results are, therefore, directly transferable to a
technical scale.
The FT-synthesis is highly exothermic (see Eqs.
(1) and (2)) with an enthalpy of about 20 % of the
one released by the total oxidation of syngas. The
heat removal and control of the reaction temperature
are, therefore, extremely critical steps since the damage of the catalyst at temperatures above 260 C [14]
decreases the conversion rate. In addition, the product distribution shifts with increasing temperature towards the production of more unwanted methane 1 . In
1 The hydrocarbon distribution of the FT-synthesis is governed
by the so-called probability of chain growth, which generally decreases with increasing temperature. So more short-chain hydrocarbons, and therefore, less diesel oil and wax are formed at higher
temperatures. Details of the Fe-catalyst used here are given in
[1315,18].

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A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

Fig. 1. Simplified block diagram of the proposed low-cost process for the conversion of natural gas to higher hydrocarbons based on
nitrogen-rich syngas.

Fig. 2. Simplified flow scheme of the semi-technical unit for the conversion of natural gas to higher hydrocarbons (R: FT-reactor, HS: hot
separator, S: separator, H: heater, C: condenser; for details of desulphurization and syngas generation see [11,12]; for the FT-synthesis
unit, see [16]).

industrial FT-fixed bed reactors, this is avoided by

using multitubular reactors, which are cooled by pressurized boiling water. In the semi-technical reactors,
this was obtained by cooling with oil (Fig. 3).
Syngas passes through the single tube reactors and

is converted at a total pressure of about 24 bar and

temperatures of 220 C up to 260 C. The product gas
is cooled in several steps, whereby the organic condensates (wax, diesel oil, (heavy) gasoline) and water
are separated.

A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

325

Fig. 3. Comparison of a common technical multitubular FT-reactor with the semi-technical single tube reactor used in the experiments.

2.2. Experimental results

The semi-technical FT-plant was successfully
run in several experiments for a period of altogether about 1400 h (8 weeks), thereby using syngas obtained by mixing its components. Finally, the
complete semi-technical plant for the production
of higher hydrocarbons from natural gas (desulphurization of natural gas syngas generation
FT-synthesis product separation, see Fig. 2) was
run for 1 week without any interruption [16,17]. The
CO-conversion in the FT-unit was 55%. A typical
product-distribution is shown in Fig. 4, indicating that,
under the given reaction conditions, diesel oil and wax
are the main organic products of FT-synthesis. The
selectivity to the (unwanted) product carbon dioxide
is about 25 C%, which is typical for iron-catalysts.
The diesel oil with a cetane number >70 has a very
good quality (standard value according to DIN 51601:
45). The diesel oil and wax contain no sulphur or other
impurities and the wax is an excellent feed for hydrocracking to produce middle distillates like diesel
oil and jet fuel. The diesel oil may also be used for
blending to fit present and after all future state regulations. Very little gasoline was obtained, only about
15 C%, of the total organic condensates. The quality

Fig. 4. Typical product-distribution of FT-synthesis obtained with

the semi-technical FT-unit as shown in Fig. 2 (Note that CO2
and CH4 already present in syngas are not counted as products;
temperature (depending on axial and radial position): 225260 C;
for details see [16,17]).

of FT-gasoline with a research octane number of less

than 0 is very poor (standard value according to DIN
51600: >91). Therefore, the (heavy) gasoline fraction
was added to the diesel oil fraction, which improves its
quality by increasing the boiling-point curve to standard values [16]. The off-gas, which contains not only
more than 60 vol.% nitrogen, but also unconverted carbon monoxide and hydrogen, methane and higher hydrocarbons, has a low net calorific value Hu of about
4 MJ/m3 (STP), and can be used to generate power and
to desalinate sea water.

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A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

Fig. 5. Steady state-equations of the model for the FT-reactor.

3. Reactor modeling
3.1. General
The processes in the single tube of a multitubular
FT-reactor can be described by a model based on a
complex set of equations that encounter the heat and
mass transfer as well as the kinetics of the main reactions. The purpose of the model was to determine
the temperature and concentration profiles of the reactor. The validity of the model was proven by comparison of the computed and experimental results, which

were obtained with the semi-technical unit. Based on

the reactor model (and the corresponding computer
program, which are, in the following, synonymously
denoted as the model), the influence of different
parameters (steam and nitrogen content of syngas,
tube diameter, volume rate, cooling temperature) on
the behavior of industrial multitubular FT-reactors
was studied. Subsequently, the major results of reactor modeling will be discussed, especially with respect to the performance of industrial multitubular
FT-reactors if nitrogen-free or nitrogen-rich syngas is
used.

A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

The so-called parameteric sensitivity was also considered to determine the allowable diameter of the
tubes, i.e. a further increase in the diameter would lead
to a situation where the reactor gets very sensitive to
small unavoidable fluctuations of the reaction conditions (e.g. the cooling temperature), and so a temperature runaway is likely. In the following (Section 4.3),
the results of the parametric sensitivity towards the
cooling temperature are presented.
3.2. Detailed description of the reactor model
According to the common classification of fixed
bed reactor models [19], the model used here is a
pseudo-homogeneous two-dimensional model, thereby
neglecting the axial dispersion of mass and heat as
well as the radial concentration gradients. The radial
temperature profile is considered, and the corresponding heat transfer in radial direction within the catalyst
bed is expressed in terms of an effective heat conduction with a constant effective radial heat conductivity
rad,eff . To calculate the heat transfer from the catalyst bed to the reactor wall, an inner wall heat transfer
coefficient W,i has to be introduced to account for
the particular conditions of the heat transfer near the
wall. In addition, the heat conductivity of the wall W
and the outer wall heat transfer coefficient W,o (wall
to cooling medium) have to be considered. The coefficients rad,eff , W,i , and W,o were calculated with
standard correlations taken from the literature (rad,eff
[20], W,i [21,22], and W,o [23]). The basic equations of the model are listed in Figs. 5 and 6. Details
of the model and the computer program are given in
[16].
The total rate of CO-consumption 6rCO,i (in Fig. 6)
in the complex reaction system of FT-synthesis can
be described by three parallel main reaction paths and
their respective reaction rates:
formation of C2+ -hydrocarbons and H2 O (Eq. (1)
and Eq. (7)),
formation of CH4 and H2 O (Eq. (2) and Eq. (8)),
and
formation of CO2 and H2 (Eq. (3) and Eq. (9)).
The kinetic equations and parameters (reaction orders, activation energies etc., see Fig. 6) were determined by classical isothermal methods in lab-scale reactors [1315], and in the case of methanation and
shift reaction by the best fit of the model with the ex-

327

perimental results of the semi-technical reactor [16];

the latter two kinetic equations should, therefore, be
proved by further measurements.
Thereby must be noted that experiments with syngases containing different amounts of nitrogen clearly
indicate that nitrogen only dilutes syngas and has no
influence on the kinetics of the synthesis, if the partial
pressures of carbon monoxide and hydrogen are kept
constant [13,14]. It is also important to note that the
kinetic parameters listed in Fig. 6 (e.g. kFT ) consider
pore diffusion limitations and only refer to the particle diameter of 2.5 mm as used in the semi-technical
(as well as in industrial) FT-reactors: after a short
start-up period with a fresh catalyst, the pores of the
catalyst are completely filled with liquid higher hydrocarbons (wax) [15,18], which leads to a relatively
slow diffusion of carbon monoxide and hydrogen inside the pores, and in turn, to an effective depth of
penetration of the catalyst particles by carbon monoxide of only about 0.3 mm (compared to the particle
diameter of about 2.5 mm) at temperatures of about
250 C. The effectiveness factor, defined as the ratio of
the actual rate of reaction in the particle as a whole,
to the rate, which would be expected, if there were no
concentration gradients inside the particle, is, therefore, only about 0.2 (at 250 C). As expected in the
range of pore diffusion, the apparent activation energies given in Fig. 6 are only half of the true activation
energies of the chemical reactions 2 (details are given
in [1315,18]).
The model equations given in Figs. 5 and 6 are
solved numerically by computer, thereby dividing
the catalyst bed in small annular segments, typically
1 mm 1 mm.
Fig. 7 compares the experimental and computed results for different steam contents of fresh syngas and
for different total pressures. The agreement between
measured and calculated values (axial temperatures in
the center of the reactor tube, CO-conversion) is quite
satisfactory.

2 The values of the kinetic parameters given in Fig. 6 refer only to

the temperature range where the influence of the pore diffusion on
the effective rate of reaction is fully developed, i.e. in the case of
a particle diameter of 2.5 mm, temperatures of more than 170 C.
External diffusion limitations can be neglected up to a temperature
of about 400 C, which is a hypothetic value because the catalyst
already deactivates at temperatures of more than 260 C.

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A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

Fig. 6. Kinetic data of the three main reactions during FT-synthesis on the iron-catalyst (ARGE-Lurgi-Ruhrchemie).

Fig. 7 (upper part) also clearly indicates the strong

inhibition of the FT-reaction (Eq. (1)) by steam,
which was, in two experiments, already present in the
fresh syngas and not just produced within the catalyst
bed. The inhibition is also reflected by the kinetic
equation of this reaction (Eq. (7) in Fig. 6). Along the
catalyst bed, the rate of the FT-reaction is decreased
more and more by the steam which is formed (Eqs.
(1) and (2)), and by the decreasing partial pressure of
hydrogen. After passing a maximum value of about
260 C at a bed length of about 0.5 m, the reactor
cooling dominates the heat released by the chemical
reactions, and the axial temperatures start to decline
(Fig. 7).

4. Modeling of technical FT-reactors

4.1. Aims and assumptions
Based on the experience obtained from the application of the model to the semi-technical reactors, it was
then used to calculate the basic data of industrial multitubular FT-reactors. In these calculations, the process parameters (e.g. the diameter of the single tubes
and the cooling temperature) were varied with respect
to improving CO-conversion and the production rate
of diesel oil and wax per tube. In addition, the parametric sensitivity of the reactor was considered as this
limits the maximum diameter of the single tubes with
respect to a safe operation of the reactor.

A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

Fig. 7. Comparison of computed and experimental results: axial

temperature profiles and CO-conversion of the first semi-technical
FT-reactor for different steam contents of syngas and for different total pressures (symbols: measured values; lines: model calculation).

As already mentioned, the nitrogen content of syngas plays a significant role in the removal of the
reaction heat to the cooling medium. Therefore, in
the following, the reactor behaviour will always be
compared if nitrogen-free or nitrogen-rich syngas
(50 vol.% nitrogen) is converted. The latter represents
syngas, which is produced by catalytic partial oxidation of natural gas with air, as proposed in this paper
for a low-cost process. Nitrogen-free syngas stands
for a typical syngas, which is produced by classical
processes like steam-refoming of natural gas, coal
gasification or partial oxidation of heavy oil. 3 For the
calculations, the following test case was considered:
The tubes of the FT-reactor have a length of 8 m.
The fresh syngas is free from steam and the molar ratios of carbon monoxide, hydrogen, carbon
dioxide and methane are constant (see Fig. 8). The
syngas has a nitrogen content of 50 vol.% or is
nitrogen-free3 .

3 Technical syngases of these processes always contain small

amounts of nitrogen (about 1 vol.%), which is here for simplification neglected.

329

Fig. 8. Axial temperature profiles of a single tube of a multitubular FT-reactor for nitrogen-free and nitrogen-rich syngas; for
comparison, the adiabatic operation in each case is also shown
(Tcool = Tin ; optimal working temperature Topt = 250 C to keep a
safe distance to the deactivation temperature Tdeact of 260 C as
well as to reach the highest possible CO-conversion).

The product gas is not recycled. This configuration

is less expensive 4 because a recycle compressor is
not needed.
Unless otherwise stated, the temperature at the reactor inlet and the cooling temperature are the same.
The pressure (24 bar in case of 50 vol.% nitrogen) is
reduced by half in the case of nitrogen-free syngas
to ensure the same partial pressure of hydrogen and
thus the same rate of reaction 5 and heat production,
at least at the reactor entrance.
Remark: For the given reaction conditions (no recycle of product gas), the reduction of the total pressure is, in case of nitrogen-free syngas, unavoidable
with respect to a temperature runaway. Calculations
with the model clearly indicate that, for the given reaction conditions, the parametric sensitivity is otherwise too high in the case of nitrogen-free syngas
4 In case of N -free syngas, a recycle compressor is normally
2
installed; for the comparison of both cases, this is not considered
here.
5 The FT-reaction is a first-order reaction with respect to hydrogen (see Eq. (7) in Fig. 6); the formation of methane is assumed
to be a first-order reaction with respect to hydrogen (see Eq. (8)
in Fig. 6).

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A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

The rate of CO-conversion by the FT-reaction (Eq.

(1)) strongly depends on the reaction temperature:
in a typical temperature range for FT-synthesis of
200 C up to 250 C, the reaction rate is doubled in
case of the iron catalyst if the temperature is increased by about 30 K. On the other hand, temperatures of more than 260 C should be avoided because
the Fe-catalyst deactivates [14], and the product distribution shifts towards the production of more unwanted methane. With respect to both a high production rate of diesel oil and wax and to a safe distance of 10 K to the deactivation temperature Tdeact
of 260 C, an optimal working temperature Topt of
250 C is assumed here. So the temperature profile
has to be adjusted by the appropriate cooling temperature Tcool , so that Topt is just reached at the
temperature maximum.

4.2. Influence of nitrogen on CO-conversion

Fig. 9. Typical radial profiles of temperature and of reaction rate
in a single tube of a multitubular FT-reactor at the axial position
z (250 C), where the optimal temperature of 250 C is reached
(computed results; conditions see Fig. 8).

(without a gas recycle), and even the smallest tube

diameter taken into consideration of only 41 mm
cannot be realized with respect to a runaway. (The
parametric sensitivity will be discussed in detail in
Section 4.3.)
For a given tube diameter, the (standard) volume
rates of carbon monoxide and hydrogen are kept
constant to ensure the same production rate of
diesel oil and wax (in kg/s) for a given degree of
CO-conversion (see below). Consequently, the total
(standard) volume rate of syngas has to be doubled in the case of nitrogen-rich syngas compared
to nitrogen-free syngas. This results in a constant
residence time (25 s with respect to the empty
tube) in both cases (nitrogen-free and nitrogen-rich
syngas) because the total pressure is, in the case
of nitrogen-rich syngas, twice as big as in case of
nitrogen-free syngas (see above).
For different tube diameters, the appropriate
volume rate of syngas is adjusted to reach a
CO-conversion of about 30%. (This is equivalent
to a total CO-conversion of at least about 60% in
an FT-unit with two reactors arranged in series.)

The axial temperature profiles both for nitrogen-rich

and for nitrogen-free syngas are shown in Fig. 8 for
a constant tube diameter of 70 mm and the optimal
working temperature of 250 C. For comparison, the
temperature profiles in adiabatic operation are also
shown, indicating that a strong cooling and a small
tube diameter are essential for the operation of multitubular FT-reactors.
The Tcool is about 20 C lower in the case of
nitrogen-free syngas compared to a syngas with
50 vol.% nitrogen. So less carbon monoxide is converted in the case of nitrogen-free syngas (27% compared to 35% in the case of nitrogen-rich syngas)
because the mean (with respect to the kinetics) axial
temperature is lower (Fig. 8). In addition, the mean
radial temperature for a given axial temperature in
the center of the tube is also lower, as is shown as an
example in Fig. 9 for the respective axial positions
of the temperature maximum of 250 C. The profiles
of the radial temperature and of the corresponding
rate of CO-conversion by the FT-reaction indicate
that the reaction rate near the wall is still about 70%
of the one in the center of the tube in the case of
nitrogen-rich syngas, but only 40% in the case of
nitrogen-free syngas. (It should be noted here that the
reactor is, in case of nitrogen-free syngas, almost at
runaway for the given single tube diameter of 70 mm.

A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

Fig. 10. Parametric sensitivity of the FT-reactor towards Tcool

for different tube diameters and nitrogen-free syngas (volume rate
of syngas according to e = 25 s; other conditions as in Fig. 8;
dot-dash lines: hypothetical profiles as T > Tdeact = 260 C).

The temperature profile shown in the lower part of

Fig. 8 is, therefore, unrealistic with respect to a safe
operation of the reactor, which will be discussed in
detail in Section 4.3.)
Both radial profiles also make clear that the radial
temperature gradient within the catalyst bed can not
be neglected in modeling wall-cooled reactors with a
strong exothermic reaction, i.e. that a two-dimensional
model, as used here, is essential.

331

For nitrogen-free syngas, a tube diameter of 50 mm

would lead to a very sensitive situation (lower part of
Fig. 10): if Tcool is increased by only 2 K, then the
maximum temperature already exceeds the catalysts
deactivation temperature of 260 C. A further increase
of Tcool by 2 K would definitely lead to a runaway.
In case of nitrogen-rich syngas (upper part of Fig.
11), a much larger tube diameter of 70 mm can be
realized without the danger of a temperature runaway.
Increasing the diameter further to 90 mm would then
also lead to a sensitive behavior of the reactor (lower
part of Fig. 11).
The pronounced influence of the nitrogen content
of the syngas on the sensitivity of the multitubular
FT-reactor is even more evident in the case of a constant tube diameter, as shown in Fig. 12 for a diameter of 70 mm by the plot of the maximum temperature Tmax versus the cooling temperature Tcool , which
can be taken as a measure of the response of the reactor (Tmax ) to a small variation in a reaction parameter
(Tcool ).
At first, Tmax rises at about the same rate as Tcool .
With increasing Tcool , the temperature curve gets a
pronounced curvature because the rate of reaction, and
therefore, the heat produced by the chemical reactions
increase exponentially according to Arrheniuss law,

4.3. Parametric sensitivity of the FT-reactor

Even more important than the increase in COconversion with increasing nitrogen content of syngas
is the much lower parametric sensitivity in the case of
nitrogen-rich syngas compared to nitrogen-free syngas. This is illustrated in Figs. 10 and 11, which show,
for both types of syngas, a typical sensitive (lower
part of each figure) and insensitive situation (upper
part). The full lines represent the temperature profiles,
where the optimal working temperature of 250 C is
just reached, but not exceeded. It is important to note
that each case is attached to a different tube diameter
which can or can not be realized without the danger
of a temperature runaway.

Fig. 11. Parametric sensitivity of the FT-reactor towards Tcool

for different tube diameters and nitrogen-rich syngas (volume rate
of syngas according to e = 25 s; other conditions as in Fig. 8;
dot-dash lines: hypothetical profiles as T > Tdeact = 260 C).

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A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

Fig. 12. Influence of Tcool on the maximum axial temperature

for nitrogen-rich and nitrogen-free syngas and a tube diameter of
70 mm (reaction conditions as in Fig. 8).

whereas the heat removal increases only linearly with

temperature. At a certain Tcool , a pronounced increase
nearly a jump of Tmax occurs.
At this point, more heat is generated by the chemical reaction than is removed by the cooling medium,
and the catalyst heats up suddenly until a new stable operating point is reached, at which the temperature difference (Tmax Tcool ) is again sufficient to remove the generated heat from the catalyst to the cooling medium. This upper operating temperature is very
high (>1000 C), as the adiabatic temperature rise is
about 760 C in the case of syngas with 50 vol.% nitrogen and 1520 C for nitrogen-free syngas. So the upper stable operating points (not shown in Fig. 12) are
only of theoretical interest because the catalyst will
already be deactivated at 260 C.
As already stated before, a temperature of 250 C
can be regarded as the optimal working temperature
with respect both to a high production rate of diesel
oil and wax and to a safe distance (10 K) to the deactivation temperature of 260 C. So the increase in Tmax
with Tcool for Tmax = 250 C can be taken as a good
measure for the sensitivity of the reactor if operated
under optimal conditions.
As shown in Fig. 12 (right-hand side) for a constant
tube diameter of 70 mm, the increase in Tmax with
Tcool (dTmax /dTcool for Tmax = Topt = 250 C) is 4.5 K/K
in the case of nitrogen-rich syngas. This means that
the deactivation temperature of 260 C is not reached
unless the fluctuation of Tcool is higher than 2.2 K
(={260250 C}/4.5 K/K). This seems to be an acceptable value, which can be secured by an appropriate
control of Tcool .

Fig. 13. Determination of the critical working temperature with respect to a temperature runaway for nitrogen-rich and nitrogen-free
syngas and a tube diameter of 70 mm (reaction conditions as in
Fig. 8).

On the contrary, in the case of nitrogen-free syngas, the corresponding increase in Tmax with Tcool is
much higher (50 K/K, see left-hand side of Fig. 12),
and therefore, a fluctuation of Tcool of only 0.2 K
(={260250 C}/50 K/K) would lead to an exceeding
of the deactivation temperature. So the optimal working temperature of 250 C can not be realized with
respect to a stable operation of the reactor, and the
temperature profile shown before in the lower part of
Fig. 8 for nitrogen-free syngas and a tube diameter of
70 mm is unrealistic.
To evaluate the allowable or critical working temperature Tcrit , which should not be exceeded to avoid
a temperature runaway, the following practical criterion was chosen, which leads to a very simple method
for the determination of the critical temperature with
respect to a runaway: Tcrit is equal to the temperature
at which the two tangents to the lower and upper part
of the curve Tmax (Tcool ) intersect. As shown in Fig. 13,
this definition of Tcrit is, here, equivalent to an allowable increase in Tmax with Tcool of 5 K/K, at least for
the given reaction conditions and the kinetic parameters of FT-synthesis with the Fe-catalyst used here. 6
In the case of nitrogen-free syngas and a tube diameter of 70 mm, Tcrit is only 221 C (Tcool = 180 C,
see left-hand side of Fig. 13), which in turn leads to
a low CO-conversion of 20%. In contrast to this, a
safe operation of the reactor would be possible for
nitrogen-rich syngas up to a temperature of 253 C if
6 According to the classical theory of ignition, the critical temperature difference (Tmax Tcool ) is given by the expression
Tmax 2 EA , which is, here, about 45 K. This value is exactly reached
in both critical cases (Fig. 13).

A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

Fig. 14. Influence of the diameter of the single tubes of a

FT-reactor on the critical maximum temperature for nitrogen-rich
and nitrogen-free syngas (volume rate of syngas according to
e = 25 s; other conditions as in Fig. 8).

the catalysts temperature would not be limited by the

assumed optimal working temperature of 250 C with
respect to a save distance of 10 K to the deactivation
temperature of 260 C.
For a given syngas composition and a constant residence time (e.g., here, 25 s), the critical working temperature can only be increased by decreasing the tube
diameter. Further calculations for different tube diameters indicate that, for nitrogen-free syngas, the critical tube diameter dT,crit is about 45 mm compared to
73 mm for nitrogen-rich syngas, if the optimal working temperature of 250 C should be reached (Fig. 14).
4.4. Heat transfer parameters
At first sight, these results are striking because the
reaction conditions are the same in both cases (gas velocity and residence time, respectively, inlet temperature, partial pressures of all reactants and thus the rate
of CO-conversion at least at the reactor entrance). The
key to understand the strong and positive influence of
the nitrogen content of syngas on the reactor behavior is the role of nitrogen in the removal of the heat
of reaction by convection in axial direction as well as
by the radial heat transfer to the cooled wall of the
reactor tubes.
Firstly, the ratio of the heat capacity of syngas to
the heat generated n SG cp / (XCO n CO |1R H |)
increases with increasing nitrogen content. So the
rise in the axial temperature in the front section of the
tubes decreases with increasing nitrogen content. For
example, the adiabatic rise in temperature
1Tad

n CO XCO |1R H |
=
1 yN2
n SG cp

(10)

333

Fig. 15. Influence of the superficial gas velocity (with respect to

standard conditions) uS,n on the effective radial heat conductivity
rad,eff and on the inner wall heat transfer coefficient W,i (remarks: W,i and eff are within the regions discussed here practically independent of the tube diameter and of the gas composition,
i.e. identical for nitrogen-free and nitrogen-rich syngas; both coefficients were calculated with the correlations given in [2023]
for particles (cylinders) with a length of 5 mm and a diameter
of 2.5 mm; for comparison: outer wall heat transfer coefficient
W,o = 365 W/(m2 K).

is only about 7 K for a CO-conversion XCO of 1% compared to 14 K in case of a nitrogen-free syngas. Correspondingly, the fall in temperature in the rear section
of the tubes is reduced in the case of nitrogen-rich syngas. So the axial temperature profile gets more shallow
with increasing nitrogen content, and the mean (with
respect to the kinetics) axial temperature and thus the
CO-conversion for a given limit of the temperature
(here, 250 C) increase.
Secondly this effect is even more important than
the one described above rad,eff increases with increasing nitrogen content of syngas if like in the
present case the standard volume rates of carbon
monoxide and hydrogen are kept constant: rad,eff is
proportional to the superficial gas velocity 7 uS as well
as to the molar density ct and to the molar specific
heat cp of syngas [16,20]:
rad,eff cp ct uS

(11)

Rewriting of Eq. (11) leads to

rad,eff cp ct,n

vn,SG
dT2

(12)

So for a given diameter of the tube dT , rad,eff only

depends on the total standard volume rate of syngas as
7 The static contribution (u = 0) to
S
rad,eff is very small
(0.21 W/(m K) [16]; see Fig. 15) and is neglected in the Eqs. (11)
and (12)).

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A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

Fig. 16. Parametric sensitivity of the FT-reactor towards Tcool

for a nitrogen-free syngas at a relative high feed rate of syngas
of 85 m3 syngas/h (STP) (other reaction conditions as in Fig. 8;
dot-dash line: hypothetical profile as T > Tdeact = 260 C).

the molar specific heat of syngas, as well as, the molar

density with respect to standard conditions can be considered to be independent of the nitrogen content. In
case of the proposed process with nitrogen-rich syngas
(about 50 vol.% nitrogen), the standard volume rate of
syngas and the gas velocity with respect to standard
conditions are doubled compared to nitrogen-free syngas in order to adjust the same standard volume rates
of carbon monoxide and hydrogen. Therefore rad,eff
is also doubled (Fig. 15), which helps to transfer the
reaction heat from the catalyst to the wall and thus
to remove it by the cooling medium. Similar considerations are true for the inner wall heat transfer
co-efficient W,i , which also increases with increasing nitrogen content, although not as pronounced as
rad,eff (Fig. 15).
Consequently, a tube diameter of more than 45 mm
can only be realized in the case of nitrogen-free syngas by a much higher gas velocity and total volume
rate of syngas. As shown in Fig. 16, a diameter of
70 mm is only possible in the case of nitrogen-free
syngas if the total standard volume rate of syngas is
increased from 28.5 to 85 m3 /h ( e decreases 25 to
8.4 s). rad,eff as well as W,i increase, and in addition, the heat generated per length of the reactor decreases because of the shorter residence time, which
decreases the CO-conversion from 36% (see Fig. 10,
dT = 41 mm) down to only 15%.
Similar considerations are true for a smaller tube
diameter but a higher total pressure. For example, the
multitubular FT-reactors, which are in operation in
South Africa, work (with respect to a nitrogen-free
syngas) at a relatively high total pressure of 24 bar and

with a diameter of the singe tubes of 46 mm. In order

to assure a high gas velocity, which is needed for the
safe operation of the reactor, fresh syngas is mixed
with recycle gas in a ratio of 1 : 2. In addition, the
partial pressure of hydrogen is thereby reduced (Fig.
17), which also decreases the danger of a runaway.
Although the tubes are 12 m long, the CO-conversion
is about the same as in case of a nitrogen-rich syngas
and a tube length of 8 m (Fig. 17, see also the upper
part of Fig. 8). The calculated critical working temperature of the ARGE-reactor is exactly equivalent to
the maximum temperature of the process of 250 C
[24] (Fig. 17), and a further increase in the diameter
is impossible without the danger of a runaway.
The calculated data of the ARGE-process underline, that the reactor model is quiet accurate: the calculated CO-conversion is 34% with respect to the total feed gas, and 82% with respect to the fresh feed
gas, which is in good agreement with data reported in
the literature (31% and 73%, respectively), especially
if one considers that the process data were taken from
different literature [2426].

Fig. 17. Data of the technical fixed-bed multitubular ARGE-reactor

as operated in South Africa (data were calculated with the reactor
model; reaction conditions as given in [2426]; the ARGE-reactor
is equipped with 2052 single tubes with an inner diameter of
46 mm).

A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

Fig. 18. Influence of the tube diameter on the production rate of

diesel oil and wax per tube (volume rate of syngas according to
e = 25 s; other conditions as in Fig. 8).

335

with 50 vol.% nitrogen, the tube diameter can be extended to 70 mm (Fig. 18).
As the dilution of syngas with nitrogen very effectively helps to remove the heat generated by the
FT-reaction, the total number of tubes can be significantly reduced, whereas for a given production rate of
diesel oil and wax, the total mass of catalyst is almost
the same.
Nevertheless, up to now, only nitrogen-free syngas
is used in industrial practice (e.g. in the ARGE-process
in South Africa). Therefore, the diameter of the reactor
tubes is smaller (46 mm), and in addition, a recycle
loop of syngas is installed to increase the gas velocity
and to decrease the partial pressure of hydrogen.
If nitrogen-rich syngas is converted, like in the proposed process, the diameter of the tubes can be increased, e.g. in the present case, up to about 70 mm,
which will very effectively increase the production rate
of diesel oil and wax per tube, and therefore, decrease
the investment costs (manufacturing costs of the multitubular FT-reactors).

4.5. Production rate of diesel oil and wax

The strong influence of the tube diameter as well as
of the nitrogen content of syngas on the production rate
of diesel oil and wax per tube m
cond is shown in Fig.
18. Due to the effects described before reduction of
the mean (with respect to the kinetics) axial as well as
of the radial temperatures and thus of CO-conversion
with increasing diameter m
cond is proportional to
dT1.4 (nitrogen-free syngas) and to dT1.7 (nitrogen-rich
syngas), respectively, and not to dT2 , as expected, if
only the alteration of the cross-section of the tubes
would have to be considered 8 . Correspondingly, the
total number of tubes for a given production rate of
diesel oil and wax is inversely proportional to dT1.4 and
to dT1.7 .
If, in addition, the parametric sensitivity is considered, then the production rate of diesel oil and wax
per tube is, in the case of nitrogen-rich syngas, higher
by a factor of about 3 than in the case of nitrogen-free
syngas because the tube diameter is limited in the case
of nitrogen-free syngas to 45 mm, whereas for syngas
8 If the CO-conversion is constant, then m
cond per tube is proportional to the volume rate of syngas, and therefore, for a constant
gas velocity and pressure, proportional to dT2 .

5. Technical FT-process based on nitrogen-rich

syngas
For the calculation of the basic data of a technical
process for the conversion of natural gas to diesel oil
and wax according to the proposed low-cost process
based on nitrogen-rich syngas (Fig. 19), the following
assumptions were made:
The steam content of syngas entering the first multitubular reactor is 5 vol.%, which corresponds to
syngas generated by catalytic partial oxidation of
natural gas with air [11,12,16,17].
Syngas is converted in two FT-reactors arranged
in series. The single tubes of both reactors have a
diameter of 70 mm and a length of 8 m.
The product gas of the first reactor is cooled, e.g. to
30 C, and the water, which inhibits FT-synthesis,
is separated. The feed gas of the second reactor is,
therefore, practically dry.
The gas velocity in the first reactor is limited corresponding to a maximum pressure loss of 2 bar; the
pressure loss of the second reactor is then about the
same.
The temperature should not exceed 250 C (safe distance to the deactivation temperature of 260 C),

336

A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

Fig. 19. Flow sheet of the proposed low-cost process for the conversion of natural gas to diesel oil and wax based on nitrogen-rich syngas.

which is ensured by adjusting the respective Tcool .

For the optimal design of both multitubular
FT-reactors, three questions still have to be treated
with respect to maximize the CO-conversion and the
production rate of diesel oil and wax per tube:
1. What is the optimal total pressure, as up to
now, a pressure of 24 bar was assumed for the
nitrogen-rich syngas?
2. What is the influence of the steam content of syngas on the performance of the first FT-reactor, as
in the cases discussed before, only dry syngas was
considered, and syngas of the proposed low-cost
process, which is produced by catalytic partial oxidation of natural gas with air, has a steam content
of about 5 vol.%?
3. What are the optimal inlet and cooling temperatures? As of now, both temperatures have always
been set equal.
The answers are given in Figs. 20, 21 and 22,
thereby assuming in each case that the optimal working temperature of 250 C is reached:
1. As shown in Fig. 20, the total pressure should be
less than about 26 bar because at higher pressures,
the danger of a runaway occurs. So a pressure of
24 bar, as assumed before for the calculations, is a
good value with respect to a high production rate
as well as to a safe operation of the reactor.

Fig. 20. Influence of the total pressure on the production rate of

diesel oil and wax per tube for nitrogen-rich syngas and a tube
diameter of 70 mm (first multitubular FT-reactor; volume rate of
syngas according to a pressure loss of 2 bar, i.e. 33 m3 /h (STP) at
8 bar and 74 m3 /h (STP) at 40 bar; Tcool = Tin ; Tmax = Topt = 250 C;
syngas without steam as in Fig. 8).

2. Steam inhibits FT-synthesis (see e.g. the upper

part of Fig. 7). Therefore, the critical tube diameter increases slightly with increasing steam content of the fresh syngas (Fig. 21). Nevertheless,
for the design of the FT-reactors of the proposed
process, a tube diameter of 70 mm was still chosen to be far away enough from the regime where
a temperature runaway could occur, and to avoid
an extrapolation from experimentally proved data,
which is too far away from the diameter of the
semi-technical reactors (41 mm). Further experi-

A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

Fig. 21. Influence of the steam content of syngas on the critical

tube diameter with respect to a temperature runaway of the first
multitubular FT-reactor (Tcool = Tin ; Tmax = Topt = 250 C; volume
rate of syngas according to e = 25 s; pt = 24 bar (nitrogen-rich
syngas) and 12 bar (nitrogen-free syngas); molar ratios of syngas
components as in Fig. 8).

Fig. 22. Influence of the inlet temperature of syngas on the performance of the first multitubular reactor of the proposed low-cost
process for the conversion of nitrogen-rich syngas to diesel oil and
wax (dT = 70 mm; Tmax = Topt = 250 C; other reaction conditions
as in Table 2).

ments should, therefore, have to be done to prove

whether it is possible to extend the diameter to
80 mm, which would increase the production of
diesel oil and wax per tube by a factor of 1.3. Fig.
21 also indicates that in the case of a nitrogen-free
syngas, the diameter could only be extended
for a syngas with 5 vol.% steam, and for the
given reaction conditions, from 45 mm to about
50 mm.

337

3. The influence of the inlet temperature of syngas

on CO-conversion is shown in Fig. 22 for the
first multitubular FT-reactor. Tcool was simultaneously changed until, for each inlet temperature,
the optimal working temperature of 250 C was
reached.
For the given reaction conditions (as listed in Table
2), the CO-conversion as well as Tcool only slightly
increase up to an inlet temperature of 230 C. A further increase in the inlet temperature then results in
a pronounced decline of both CO-conversion and
Tcool . 9 So for the first FT-reactor, the optimal inlet
and cooling-temperature, respectively, are 230 and
216 C. A similar calculation was done for the second
reactor.
The optimal design parameters of the two multitubular FT-reactors arranged in series according to
the criteria as stated above are listed in Table 2. The
respective temperature profiles of both reactors are
shown in Fig. 23. The total CO-conversion reached
after passing both reactors arranged in series is 63%.
The corresponding basic data of an industrial plant
(Fig. 19) for the annual production of about 500,000 t
diesel oil and wax are also listed in Table 2, indicating
that 16 multitubular FT-reactors are needed, equivalent to 8 parallel production lines with two reactors in
series. Each reactor is equipped with 4000 tubes with
a length of 8 m and a diameter of 70 mm, and the total number of tubes of the FT-unit is 64,000. For an
evaluation of this result, two cases should be finally
mentioned:
In case of the classical tube diameter of 46 mm,
the total number of tubes would be about two
times higher than in the proposed low-cost process
with a diameter of 70 mm (see Fig. 18, number of
tubes (1/dT )1.7 ). This underlines the significant
influence of the tube diameter on the total number
of tubes and on the manufacturing costs of the
FT-reactors.
In the multitubular FT-reactors of the ARGE-process in South Africa, 16,000 t per annum of valuable
products (mainly diesel oil and wax) are produced
per reactor, which is equipped with 2052 tubes of
12 m length and an inner diameter of 46 mm. For the
9 In addition, the lowest cooling temperature with respect to a
runaway is about 205 C (for the given maximum temperature of
250 C), see footnote 6.

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A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

Table 2
Basic data of an industrial plant of the proposed low-cost process for the conversion of natural gas to diesel oil and wax on the basis of
nitrogen-rich syngas with about 50 vol.% nitrogen (availability of the plant: 8000 h per annum)
Synthesis gas generation
2.53 109 (1.35 106 tC per annum) (Hu = 36 MJ/m3 )
9.3 109
14.6 109

Volume rate of natural gas (m3 per annum) (STP)

Volume rate of air (m3 per annum) (STP)
Volume rate of fresh syngas (composition see Fig. 4),
(m3 per annum) (STP)
Total pressure (bar)
Diameter of syngas reactor (catalyst bed) (m)
Number of syngas reactors (calculated with data from [11,12])

26
3
4

FischerTropsch synthesis

1. Synthesis step

2. Synthesis step

25
216
230
8
70
32,000
8
7.5
36

23
215
180
8
70
32,000
8
7.5
42

248,000c
484,000 (415,000
tC per annum) (XCO,t = 63%)
10.7 109
3.5

236,000c

inlet)a

Total pressure (reactor

(bar)
Cooling temperature ( C)
Temperature at the reactor inlet ( C)
Length of reactor tubes (m)
Diameter of reactor tubes (inner) (mm)
Total number of tubes
Number of FT-reactors (4000 tubes/reactor)
Diameter of reactor (inner)b (m)
CO-conversion (related to CO in the syngas of
each reactor) (%)
Production rate of diesel oil and wax (t per annum)
Total production rate of diesel oil and wax (t per annum)
Volume rate of off-gas (m3 per annum) (STP)
Heating value Hu of off-gasd (MJ/m3 ) (STP)

a The pressure loss is as of now not considered in the model, and is calculated separately. For the calculations, a mean total pressure
(=(Pin + Pout )/2) of 24 bar (reactor 1) and 22 bar (reactor 2) was assumed.
b Calculated with data from [27], thereby assuming an interval between the tubes of 30 mm.
c The selectivity to CO , which is formed by the shift reaction (see Eq. (3) and Eq. (9)), is higher in the first reactor than in the second
2
one because steam is already present in the syngas of the first reactor, whereas the syngas of the second reactor is dry. The production
rate of diesel oil and wax is, therefore, not exactly proportional to the CO-conversion, which is reached in each reactor.
d Typical off-gas composition: 64 vol.% N , 21 vol.% H , 8 vol.% CO, 5.5 vol.% CO , 1.5 vol.% CH , 0.4 vol.% C C
2
2
2
4
2
10 (calculated as
C3 H8 )[16,17].

production rate, which is assumed here (484,000 t of

diesel oil and wax per annum, see Table 2), 62,000
single tubes of 12 m length would be needed compared to 64,000 single tubes of 8 m length in the
proposed process. So about the same production
rate per tube is reached in the proposed process
with nitrogen-rich syngas, but without any syngas
recycle, and without a costly syngas generation by
steam reforming or by partial oxidation with oxygen, which requires an air separation plant.
6. Conclusions and outlook

Fig. 23. Axial temperature profiles of the single tubes of the first
and second multitubular FT-reactor of the proposed low-cost
process with nitrogen-rich syngas for the conversion of natural
gas to higher hydrocarbons (reaction conditions as in Table 2).

The economic utilization of natural gas resources

in remote areas is limited by its costly transportation.
A solution of this problem could be the conversion to

higher hydrocarbons by the following low-cost process: after desulphurization, natural gas is converted
into a nitrogen- rich and soot-free syngas by catalytic

A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

partial oxidation with air. This syngas is then converted by FT-synthesis into diesel oil and wax in two
fixed bed multitubular reactors in series.
This concept was successfully tested in a semi-technical plant. For the experiments, FT-reactors with a
diameter corresponding to a single tube of common
industrial multitubular reactors (41 mm) were used.
A mathematical model for the FT-reactor has been
developed, which is based on a set of equations that
encounter the heat and mass transfer and the reaction
kinetics.
Calculations with this model indicate that under the
specific conditions of the proposed low-cost process
with nitrogen-rich syngas (about 50 vol.% nitrogen)
a diameter of the reactor tubes of 70 mm can be realized without the danger of a temperature runaway
because nitrogen helps very effectively to remove the
large amounts of heat generated by the FT-reaction.
In the case of nitrogen-free syngas, the tube diameter
is limited to about 45 mm to avoid a runaway if no recycle of syngas is installed. Thereby, the production
rate of diesel oil and wax per tube is compared
to nitrogen-rich syngas reduced by a factor of 3,
which underlines the advantage of the low-cost concept based on nitrogen-rich syngas: the increase in the
tube diameter leads to a drastic reduction in the total
number of tubes and thus to a decrease in the investment costs of an industrial FT-plant (manufacturing
costs of the multitubular FT-reactors) for the conversion of natural gas to diesel oil and wax.
Detailed economic studies are still necessary to validate or disprove whether and under which circumstances the proposed process with nitrogen-rich syngas is an attractive alternative to classical processes
with nitrogen-free syngas (like the SMDS-process of
Shell), especially in areas with remote natural gas resources. The effect of off-gas usefulness and value
should also be included. In addition, the compression
costs, which are higher in the case of an air compressor (compared to oxygen) should be considered. Nevertheless, the results presented in this paper indicate
that it is promising to go ahead with further model calculations as well as with experimental investigations
in order to improve the efficiency of the FT-reactors
(output of diesel oil and wax per tube), especially with
regard to the following subjects:
The model calculations, which indicate an allowable tube diameter of 70 mm for nitrogen-rich syn-

339

gas (and a feasible extension to 80 mm, see Fig.

21), should be proven by experiments with single
tube reactors of larger diameters (as up to now,
dT = 41 mm).
The model for the simulation of the FT-reactor
is based on the assumptions of constant porosity,
constant effective radial heat conductivity and plug
flow. The radial heat transfer near the wall is evaluated from a postulated near-wall temperature jump
in combination with W,i , which is then needed to
account for the particular conditions of heat transfer
near the wall (near-wall flow channelling, near-wall
porosity and velocity changes).
According to the literature, e.g. [28,29], the predictions of temperature profiles and hot spots of
wall-cooled fixed bed reactors can be improved by
incorporating velocity and porosity profiles, especially in the region of smaller Reynolds numbers Rep
up to about 400 10 . The radial heat transfer near the
wall (typically within a distance of 2dp ) can then
alternatively to the concept used here be described
by a locally varying rad,eff (r), and so the introduction of W,i can be omitted. It would be of interest to
investigate whether or not a refinement of the present
reactor model is justified.
The mean chain length, and therefore, the hydrocarbon distribution of FT-synthesis changes with temperature. At higher temperatures, the mean chain
length is smaller, and more methane and lighter hydrocarbons and less diesel oil and wax are formed.
Nevertheless, the influence of the reaction temperature on the product distribution (see [1315]) is,
of now, not considered in the model used here. The
results presented in this paper were calculated with
the hydrocarbon distribution, which was obtained in
the semi-technical plant (Fig. 4), and which, therefore, only represents a mean distribution in the temperature range of 225260 C. For an accurate determination of the amounts of different product fractions like diesel oil, wax, lighter hydrocarbons, and
methane, the influence of the temperature on the
probability of chain growth should be introduced
into the model.

10 For comparison: for typical conditions (d = 2.5 mm; mean temp

perature = 240 C, uS = 0.3 m/s), Rep is 365 for syngas with 50 vol.%
nitrogen (p = 24 bar) and 125 for nitrogen-free syngas (p = 12 bar).

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A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

In addition, the model for the reactor simulation

should be extended and improved by including the
dynamic behaviour of the reactor, e.g. to investigate
the start-up or shut-down behaviour of the reactor.
The temperature control of the FT-reactors can be
improved by a defined change of the overall heat
transfer coefficient along the reactor tubes corresponding to the respective heat generated, either by
a defined insulation of the rear section of the tubes
or by a dilution of the catalyst in the front section
(see Fig. 23). Both options will probably lead to a
more well-balanced axial temperature profile, and
thus, to a higher mean (with respect to reaction kinetics) axial temperature, and therefore, to a higher
CO-conversion.
Other catalysts should be tested, e.g. such as those
based on cobalt, which have, according to the literature (e.g. [30,31]), a very low CO2 -selectivity of
less than 1 C% compared to about 25 C% in case of
the Fe-catalyst (Fig. 4).
At the end, economic evaluations based on these
data should be done in order to develop an economical process for the production of diesel oil and wax
from natural gas in areas which are remote from the
market.

k0,FT
k0,M
k0,S
L
mcat
m
cond
n co
n SG

pt
r
rCO,i
rCO,FT
rCO,M
rCO,S
R
Ri
Ro

7. Nomenclature
7.1. Symbols and abbreviations
ci
ct
cp
dP
dT
dT,crit
EA
FT
Hu
kFT
kM
kS

concentration (i: CO, H2 , H2 O) (mol/m3 )

total concentration of syngas (mol/m3 )
specific heat of syngas (J/(mol K))
particle diameter (m)
(inner tube) diameter (m)
critical (inner) tube diameter with respect to
a temperature runaway (for Tmax = Topt ) (m)
activation energy (J/mol)
FischerTropsch
net calorific value (J/m3 )
rate constant of FT-reaction (Eq. (1))
(m3 /(kgcat s))
rate constant of methanation reaction (Eq. (2))
(m3 /(kgcat s))
rate constant of shift reaction (Eq. (3))
(m3 /(kgcat s)

Rep
STP
T
Tcool
Tcrit
Tdeact
Tmax
Topt

uS
v
XCO,R1
XCO,R2

pre-exponential factor of the FT-reaction

(Eq. (1)) (m3 /(kgcat s))
pre-exponential factor of methanation reaction (Eq. (2)) (m3 /(kgcat s))
pre-exponential factor of shift reaction (Eq.
(3)) (m3 /(kgcat s))
length of the FT-reactor (catalyst bed) (m)
mass of catalyst (kg)
production rate of organic condensates (diesel
oil and wax) (kg/s)
molar flux of carbon monoxide (mol/s)
molar flux of syngas (mol/s)
total pressure (Pa)
radial coordinate (reactor axis at r = 0) (m)
reaction rate of CO-conversion by the reaction
i (molCO /(kgcat s))
reaction rate of CO-conversion by the FTreaction (Eq. (1)) (molCO /(kgcat s))
reaction rate of CO-conversion by the methanation reaction (Eq. (2)) (molCO /(kgcat s))
reaction rate of CO-conversion by the shift
reaction (Eq. (3)) (molCO /(kgcat s))
universal gas constant (8.314 J/(mol K))
inner radius (of the tube of the FT reactor)
(m)
outer radius (of the tube of the FT reactor)
(m)
Reynolds number (uS dp /n) (dimensionless)
standard conditions (1.013 bar, 0 C)
reaction temperature ( C, K)
temperature of cooling medium ( C, K)
critical working temperature with respect to a
temperature runaway ( C, K)
deactivation temperature of the Fecatalyst = 260 C
maximum temperature ( C, K)
optimal working temperature (250 C) with respect both to a safe distance to Tdeact and to
the highest possible degree of CO-conversion
( C, K)
superficial gas velocity (m/s)
volume rate (m3 /s)
degree of CO-conversion in the first (technical) FT-reactor (dimensionless)
degree of CO-conversion in the second (technical) FT-reactor (with respect to the CO at
the reactor inlet) (dimensionless)

A. Jess et al. / Applied Catalysis A: General 186 (1999) 321342

XCO,t degree of total CO-conversion (reactor 1 and

2) (dimensionless)
yH2 O molar content of steam (dimensionless)
yN2 molar content of nitrogen (dimensionless)
z
axial coordinate (reactor entrance at z = 0) (m)
7.2. Greek letters
W,i

inner wall heat transfer coefficient

(W/(m2 K))
outer wall heat transfer coefficient
W,o
(W/(m2 K))
enthalpy of reaction (J/mol)
1R H
1R H 298 standard enthalpy of reaction (1.013 bar,
25 C) (J/mol)
1Tad adiabatic temperature rise (K)
heat conductivity of the wall (W/(m K))
W
rad,eff effective radial heat conductivity
(W/(m K))

kinematic viscosity (m2 /s)

catalyst bulk density (kg/m3 )
B
residence time with respect to the empty
e
reactor (s)
7.3. Subscripts (if not already listed above)
in inlet (of reactor)
n standard conditions (1.013 bar, 0 C)

Acknowledgements
Financial support by the Federal Ministry of Research and Technology of Germany is gratefully acknowledged (0326563A). The authors also wish to
thank Ruhrchemie AG (now Celanese Inc., Hoechst
AG) for supplying the catalyst.
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