ISSN 0040-5795, Theoretical Foundations of Chemical Engineering, 2009, Vol. 43, No. 6, pp. 944954. Pleiades Publishing, Ltd.

., 2009.
Original Russian Text T.N. Gartman, F.S. Sovetin, D.K. Novikova, 2009, published in Teoreticheskie Osnovy Khimicheskoi Tekhnologii, 2009, Vol. 43, No. 6, pp. 702712.

Experience in the Application of the CHEMCAD Program

to the Modeling of Reactor Processes
T. N. Gartman*, F. S. Sovetin, and D. K. Novikova
Mendeleev University of Chemical Technology of Russia , Moscow, Russia
* e-mail: gartman@muctr.ru
Received June 02, 2009

AbstractA computer simulation strategy that is focused on the application of modeling programs for the simulation of multistage chemical technology processes with a large number of equipment units, including reactor
ones, is suggested for chemical transformation processes in reactors. The submitted strategy allows for the modeling of homogeneous and heterogeneous processes in reactors of any complexity on the basis of experimental
data processing. The simulation of reactor processes has been performed with the use of the CHEMCAD program for the multistage syntheses of methanol and synthetic liquid fuel from natural gas at the following stages:
synthesis gas production by steam-oxygen conversion, syntheses of hydrocarbons by the FischerTropsch reaction and methanol, and the hydrocracking of heavy hydrocarbons.
DOI: 10.1134/S0040579509060128

INTRODUCTION
At present, chemical engineers are showing great interest in the development of computer models for reactor processes and their application for the simulation and optimization of industrial process flow sheets when designing
resource-saving technologies [1]. The modern approach to
the creation of resource-saving technologies assumes the
application of software to simulate complete multistage
industrial flow sheets, in particular, reactor processes.
The construction of models for the processes in chemical reactors with the application of modeling programs for
the purpose of their inclusion in models of complete industrial flow sheets imposes certain requirements on the procedure of their development [2].
This is connected both with the features of specifying
the parameter values for the standard calculation modules
of the modeling program and with the fact that the latter are
designed not to calculate separate equipment units, but to
simulate complete industrial flow sheets. According to the
fundamental principles of the system analysis, the calculations for reactor units must be carried out together with
those for the processes in other apparatuses of an industrial
flow sheet [3].
The traditional mathematical modeling technique for
reactor processes is based on the application of detailed
kinetic models. Works [46] are devoted to the solution of
problems like this.
However, for many processes kinetic data may be
absent or their kinetics may be studied insufficiently. Moreover, numerical nonconvergence may be observed both for

a single reactor process and for an entire flow sheet while

simulating multistage chemical technology processes with
recirculation. Therefore, it is advisable to abandon the
application of similar kinetic models for reactor processes
when modeling reactor units in chemical technology flow
sheets with a large number of main and subsidiary equipment units.
We suggest applying to the modeling of reactor processes not detailed kinetic models, but approximate ones,
in which key reagent conversions are specified for each
reaction. When this approach is used, the necessary computational accuracy for the material and heat balances and
the numerical stability for the calculation of multistage
flow sheets are provided, and this allows one to solve with
a high degree of reliability the problems of computer modeling, optimization, and synthesis for resource-saving
chemical processes.
For the computation of material and heat balances for
reactor processes, CHEMCAD standard calculation modules are used [7]: modules of reactors operating with key
reagent conversions for all proceeding reactions, and a heat
load transfer module that allows for the calculation of the
supply or removal of heat streams, including those to/from
the other equipment units in a flow sheet.
According to this, the strategy of the calculation of reactor processes with the application of modeling programs in
the construction of computer models for complete flow
sheets of industrial chemical processes consists of the following:
(1) stoichiometric data are specified for each reaction;

944

EXPERIENCE IN THE APPLICATION OF THE CHEMCAD PROGRAM

(2) key component conversions, which can be determined from experimental data [811], are specified for
each reaction; and
(3) the reactor process is calculated with the determination of the flow rate, composition, temperature,
and other characteristics of an outlet stream, as well as
the required flow rate for a heating (or cooling) agent,
if it is necessary to supply/remove heat [12]. This is the
way of solving the direct problem of computer modeling for reactor processes.
To solve the inverse problem of computer modeling
and the determination of kinetic constants for chemical
reactions, in a modeling program (for instance, in
CHEMCAD) it is suggested to define the parameters
for Eq. (1) given below from experimental data, outlet
parameters of a batch stirred tank reactor, or from that
for homophase (in a liquid or vapor phase) or heterophase reactions (in the presence of a solid phase or
catalyst) [12, 13]:
s

ri =

ij A j e

E j / RT

j=1
nj

nj

k=1

a
c kjkj

E / RT b
kj e kj c kjkj
1 +

k=1

(1)
, j = 1, 2, , s ,

i = 1, 2, , m ,
where ri is the reaction rate for the ith component, k is
the reagent index, j is the reaction stage index, Nij is the
stoichiometric coefficient for the ith component at the
jth reaction stage (it is negative for reagents and positive for products), Aj is the frequency factor for the jth
reaction stage, Ej is the activation energy for the jth
reaction stage, R is the universal gas constant, T is the
absolute reaction temperature, k is the reagent concentration (or its partial pressure for a gas-phase reaction),
akj is the reaction exponent for reagent k at the jth reaction stage, m is the number of components, nj is the
number of reagents, s is the number of stages, kj is the
adsorption frequency factor for component k, Ekj is the
energy adsorption factor for component k at the jth
reaction stage, bkj is the adsorption exponent for reagent
k at the jth reaction stage, and j is the adsorption exponent for the jth reaction stages.
The following, the parameters of Eq. (1) are calculated here: activation energy Ej for the reaction, adsorption energy factor Ekj for the components, reaction frequency factor Aj, adsorption frequency factor kj for the
components, reaction akj and adsorption bkj exponents
for the reagents, j = 1, 2, , s, and k = 1, 2, , nj.

945

The calculation of the above-listed parameters is

realized by the minimization of the generalized criterion in the form [14]
m

Gr =

(c
c

calc
ji

exp 2

c ji ) + ( V i
V

calc

exp 2

Vi )

i=1 j=1

+ (Ti
T

calc

exp 2

exp 2

T i ) + R ( Q Ri Q Ri )

+ ( Qi
Q

calc

exp 2

Qi )

calc

(2)

where c, V, T, R , , and Q are the weighting coefficients of the criterion items; N is the number of experimental points; cji is the concentration of the jth component (j = 1, 2, , m); Vi is the volume of the reaction
mass; Ti is the temperature of the reaction mass; QR is
the rate of heat evolution in the reactor; and Q is the
heat accumulated due to the chemical reaction (i = 1, 2,
, N).
If the experimental data that are included in Eq. (2)
are absent, an item with unavailable experimental values is excluded from the criterion, which is then determined using a limited number of items.
Test and estimation calculations can be carried out
for a reactor process with the use of the mentioned
kinetic constants and idealized hydrodynamic models,
which are specified for moving phase streams, and as a
result of this key component conversions can be determined for all chemical reactions.
However, as was mentioned, such an approach is not
always justified, especially in the case of limited stoichiometric data and unavailable reliable kinetic data.
To calculate reactor processes in apparatuses, taking
into account their constructions and the real hydrodynamics of phase streams, it is suggested to use reagent
conversions for main reactions proceeding in a reactor.
In the general case, conversions of the considered process may be known or found. If the assumption is made
that the chemical equilibrium is attained in a reactor,
conversions can be determined using the equilibrium
composition data for reaction mixtures or can be calculated by equations of the temperature dependencies for
the equilibrium constant [15, 16]. If equilibrium is not
attained, the conversions thus found should be multiplied by correction coefficients, which are appropriate
for the given reactor type, and specified values of the
outlet parameters (temperature, pressure, inlet flow
rates, catalyst type, etc.). For those reactors in which a
chemical equilibrium is attained, the values of correction coefficients are equal to unity for all reactions.
Correction coefficient values or products of conversions and correction coefficients (further, it is reasonable to refer to them as conversions) are defined from
experimental data obtained on pilot, semi-industrial,
and/or industrial plants for reactor outlet streams.

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GARTMAN et al.

Table 1. Conversion values specified for the reagents of reactions (3)(5) in the prereforming reactor modeling
Reagent

Reaction

CH4
C2H6, C3H8, n-C4H10, n-C5H12, n-C6H14, 1-C6H12
CO

(3)
(4)
(5)

0.05
1
0.05

It is necessary to emphasize that in the absence of

experimental data on the functioning of an industrial
plant at a specified productivity, it is possible to use
data obtained on a pilot or semi-industrial plant after
scaling [17].
To take into account supplied (removed) heat
streams of reactor processes, a flow sheet unit comprised of different combinations of heat-exchanger
modules and special modules for the transfer (removal)
of heat streams from one equipment (stream) unit to
another one is realized in CHEMCAD [18, 19] during
the calculation of heat balances.
The strategy that is recommended for the modeling
of reactor units in the calculation of complete flow
sheets for chemical industrial processes with the use of
CHEMCAD is illustrated by the example of the calculation for reactor units of four well-known reactor processes [20]: synthesis gas (mixtures of hydrogen and
carbon monoxide) production, syntheses of hydrocarbons by the FischerTropsch reaction and methanol,
and hydrocracking of heavy hydrocarbon fractions.
MODELING OF REACTOR PROCESSES
FOR THE PRODUCTION OF SYNTHESIS GAS
FROM NATURAL GAS IN SYNTHETIC LIQUID
FUEL AND METHANOL SYNTHESES
In the industrial production of synthetic liquid fuel
and methanol synthesis, gas is a necessary raw material, which can be obtained from natural gas in the
steam-oxygen conversion unit. The synthesis gas production technological unit includes three reactor units
(Fig. 1) [9, 20]: prereforming (module 1); primary
steam reforming (modules 2, 3, and 7); and secondary
steam reforming, so-called autothermal reforming
(modules 4, 5, and 8).
The prereforming process is conducted in a tubular
catalytic reactor in adiabatic conditions. The vaporgas
mixture (natural gas saturated by water steam) is converted into a mixture of carbon oxides, hydrogen, and
methane according to the following reactions of steam
reforming (temperature of 400455C, pressure of 44
45 bar):
for methane,
CH4 + H2O = CO + 3H2,
and for other hydrocarbons,

(3)

CxHy + xH2O

xCO + (x + y/2)H2.

(4)

Simultaneously, the CO conversion reaction (socalled water-shift reaction) proceeds:

CO + H2O = H2 + CO2.

(5)

All higher (in comparison with methane) hydrocarbons are completely and irreversibly converted according to reaction (4), and reactions (3) and (5) are close to
equilibrium. The basic function of a prereforming
apparatus is to reform all higher (in comparison to
methane) hydrocarbons simultaneously with methane
reforming.
To simulate the prereforming process, it is suggested to use the standard CHEMCAD module (Fig. 1,
module 1), in which it is required to specify the following parameters [20]: stoichiometric data and key
reagent conversions for reactions (3)(5). At that, the
assumption has been made by us that in the stream fed
to the prereforming stage (inlet stream of the prereforming reactor), the concentration of hydrocarbons
with the number of carbon atoms >6 is insignificant;
therefore, it can be neglected.
The mentioned reagent conversion values that are
suggested for the modeling of prereforming process for
reactions (3)(5) and determined from experimental
data are included in Table 1.
The model suggested for the prereforming process
is realized in the simulation of the complete synthesis
gas production flow sheet, which is comprised of
sweetening, saturation, and separator units in addition
to the reactor one. Therefore, the parameters for the
inlet prereforming reactor stream are determined after
the sweetening and saturation processes have been calculated, i.e., they are calculated data.
Calculated data on the properties of inlet and outlet
prereforming reactor streams are listed in Table 2. The
comparison of calculated and experimental outlet
stream parameters is carried out in the same table.
The primary steam reforming process is conducted
in a primary steam reforming furnace (Fig. 1, modules
2, 3, and 7), representing a tubular catalytic reactor, in
which endothermic reactions (3) and (5) proceed at a
temperature of 700750 and pressure of 40 bar [20].
The heat that is necessary to realize endothermic reactions is supplied by fuel gas combustion in the intertubular space at a temperature of 800900 and pressure
of 31 bar.
The primary steam reforming process modeling is
realized by means of two reactor modules: module 2
simulates the process in furnace tubes (reactionary
stream); at that, the assumption has been made by us
that equilibrium is attained in the given reactor, and
module 3 simulates the fuel gas combustion process in
the intertubular space.
For the module of reactor 2, the following parameters are given: stoichiometric data for reactions (3)(5),

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947

Natural gas
sweetened and
saturated with steam

Adiabatic prereforming
reactor

1
Flue gas for
heating the cascade of heat exchangers

6
Combustion chamber of
the primary steam
reforming furnace
Fuel gas

3
9

Air

2
Steam
Oxygen

10

Primary steam
reforming furnace
(technological unit)

11

Secondary steam
reforming reactor

Reforming gas to
cooling

8
5

Fig. 1. Synthesis gas production unit in the steam oxygen conversion flow sheet:
(1)(5) are the equilibrium reactor modules, (6) is the heat exchanger module, (7) and (8) are the heat load transfer modules, and
(9)(11) are the mixer modules.

CH4 and CO conversions, and thermal conditions (the

heat load is specified).

of module 3 by its absolute value, but has an opposite

sign).

For the module of reactor 3, the following parameters are specified: stoichiometric data for all combustion reactions of hydrocarbons and oxygen-containing
organic compounds contained in fuel gas; conversions
are equal to unity for all combustible components; and
thermal conditions are isothermal, the temperature is
810. The calculated heat load is equal to 88 961 MJ/h
for the module of reactor 3 at the fuel gas flow rate of
23 000 m3/h (in standard conditions).

The model suggested for the primary steam reforming process is realized in the simulation of a complete
synthesis gas production flow sheet. Therefore, the inlet
stream parameters are determined after the calculation
of the heat exchanger (Fig. 1, module 6) has been performed, and the fuel gas flow rate is also a calculated
value.

The mentioned reagent conversion values that are

suggested for the modeling of primary steam reforming
process for reactions (3)(5) and determined from the
data on the component concentrations in an equilibrium
gas mixture [8] are listed in Table 3. The supplied heat
load value is presented in the same table.
The process of fuel gas combustion heat transfer to
the reactionary stream is simulated by the special heat
load transfer module 7, which transmits the calculated
heat load of module 3 to module 2, taking into account
its sign (the heat load of module 2 coincides with that

Calculated data on the properties of the inlet and

outlet streams of the primary steam reforming furnace
are presented in Table 4. The comparison of calculated
outlet stream properties with their experimental values
is carried out in the same table.
In the secondary steam reforming reactor (Fig. 1,
modules 4, 5, and 8), fettled by a refractory material
and supplied with a mixing burner and reforming catalyst, at a temperature of 930 and pressure of 39 bar
the partial oxidation (combustion) chemical reaction
proceeds according to the equation

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING

CO + 2H2O.

CH4 + 1.5O2
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GARTMAN et al.

Table 2. Calculated data on the properties of the inlet and

outlet streams for the adiabatic prereforming reactor and the
comparison of calculated and experimental outlet stream
properties
Inlet stream
(calculated
data)

Outlet stream
(calculated
data)

Outlet stream
(experimental
data)

t, C

530

441

451

p, bar

45

44

44.6

126169.38

133420.81

130574

H2

0.762078

8.135451

6.8

CO

0.031653

2.77105

0.02

CO2

0.11252

0.107901

1.77

N2

0.419799

0.396983

0.41

H2O

63.656503

57.452667

58.37

CH4

34.649292

31.127796

32.62

C2H6

0.158039

C3H8

0.072941

n-C4H10

0.060784

n-C5H12

0.016898

n-C6H14

0.021274

1-C6H12

0.021761

Stream
property

W, m3/h
, vol %

Table 4. Calculated data on the properties of the inlet and

outlet streams for the primary steam reforming furnace and
the comparison of calculated and experimental outlet stream
properties
Inlet stream
(calculated
data)

Outlet stream
(calculated
data)

Outlet stream
(experimental
data)

t, C

690

731

725

p, bar

44

43

43

133420.81

132236.23

134995

Stream
property

W, m3/h
, vol %
H2

8.135451

34.928083

32.34

CO

2.77105

4.391119

4.36

CO2

0.107901

5.806703

5.39

N2

0.396983

0.241794

0.36

H2O

57.452667

37.075058

37.13

CH4

31.127796

17.45812

20.4

Simultaneously, the reactions of methane steam

reforming (3) and CO conversion (5) proceed in the
reactor. At that, in the same reactor the heat of exothermal reaction (6) is used in endothermic reactions (3)
and (5). The reactionary space is divided into four parts:
mixing, combustion, and thermal and catalytic zones.
The process gas of the reactor outlet corresponds to the
equilibrium gas relative to the reactions of methane
steam reforming (3) and CO conversion (5) [8].

The given reactor is modeled by two reactor modules 4 and 5, where the first module corresponds to the
reactor section in which the methane combustion process occurs, and the second one represents the reactor
section in which the steam reforming process proceeds.

Table 3. Conversion values specified for the reagents of reactions (3) and (5) in the modeling of a primary steam reforming furnace and the heat load required to provide the
necessary process temperature

Table 5. Conversion values specified for the reagents of reactions (3), (5), and (6) in the modeling of a secondary steam
reforming reactor and the calculated heat duties for modules
4 and 5

Reagent

Reaction

qmr, MJ/h

CH4

(3)

0.19

88961

CO

(5)

0.54

For module 4, the following parameters are specified: stoichiometric data for reaction (6); key reagent
(oxygen) conversion; and the thermal conditions are
isothermal, the temperature is 700.

Module

Reagent

Reaction

qmr, MJ/h
219620

O2

(6)

CH4

(3)

0.8

CO

(5)

0.24

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EXPERIENCE IN THE APPLICATION OF THE CHEMCAD PROGRAM

Table 6. Calculated data on the properties of inlet and outlet
streams for the secondary steam reforming reactor and the
comparison of calculated and experimental outlet stream
properties
Stream
property
t, C
p, bar
W, m3/h
, vol %
O2
H2
CO
CO2
N2
H2O
CH4

Inlet stream
(calculated
data)

Outlet stream
(calculated
data)

Outlet stream
(experimental
data)

700
40
152951.59

930
39
206968

940
38
207855

44.245875
13.273767
5.794424
0.73908
33.087498
2.854094

47.31
14.53
5.63
0.74
30.94
0.86

10.05
31.19
3.92
5.18
0.26
33.71
15.59

For module 5, the following parameters are specified: stoichiometric data for reactions (3) and (5), key
reagent conversions, and the thermal conditions are
defined by the heat load. The mentioned reagent conversion values suggested for the modeling of a secondary steam reforming process for reactions (3), (5), and
(6) are given in Table 5. The heat load values for the
above-listed modules are presented in the same table.
The heat transfer process is modeled by the special
module for the transfer of heat load 8 from module 4 to
module 5; at that, its sing is also taken into account (see
Table 5).
The model suggested for the secondary steam
reforming process is realized in the simulation of the
flow sheet of complete synthesis gas production. Therefore, the outlet stream parameters are calculated values
that are found after the calculations of the mixer have
been performed (Fig. 1, module 11).
Calculated data on the properties of the inlet and
outlet streams of the secondary steam reforming reactor
are given in Table 6. The comparison of the outlet
stream properties with their experimental values is performed in the same table.

Table 7. Conversion values specified for the reagents of reactions (5) and (7) in the modeling of a methanol synthesis
reactor and the calculated heat duties for modules 1 and 2
Module Reagent Reaction

CO2 + 3H2 = CH3OH + H2O.

qmr, MJ/h

qr, MJ/h
145151.2

CO2

(7)

0.2

87438.2

CO

(5)

0.73

57713

Simultaneously, the CO conversion reaction (5) and

side reactions proceed [8, 9].
The given reactor represents a tubular catalytic
apparatus (Fig. 2, modules 14), into the intertubular
space of which water is fed to provide isothermal conditions for the process.
The methanol synthesis reactor is modeled with the
help of two reactor modules 1 and 2; at that, the
assumption is made by us that side reactions are
neglected in the modeling.
For reactor modules 5 and 6, the following parameters are specified: stoichiometric data for reactions (7)
and (5); key reagent conversions; and the thermal conditions are isothermal, the temperature is 242. The
mentioned reagent conversion values that are suggested
for the modeling of the methanol synthesis process for
reactions (5) and (7) are listed in Table 7. The calculated heat load values are presented in the same table
for the above-listed modules.
The cooling water stream in the intertubular space is
modeled by heat exchanger module 4, and the inlet heat
Synthesis gas

Water

1
3
Methanol
synthesis
reactor
4

(7)

MODELING OF THE PROCESSES

IN THE METHANOL SYNTHESIS
REACTOR UNIT
Synthesis gas is converted into methanol in the
methanol synthesis reactor. The assumption is made
that in the given reactor, chemical transformations proceed at a temperature of 242 and pressure of 78.7 bar
according to the equation [21]

949

Gas mixture for

cooling and separating

Steam

Fig. 2. Methanol synthesis unit: (1) and (2) are the equilibrium reactor modules; (3) is the heat load transfer module;
(4) is the heat exchanger module.

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GARTMAN et al.

load is specified for the given module; the heat transfer

process is modeled by special module 3, which transmits the summary heat load from modules 1 and 2 to
heat exchanger module 4, taking into account its sign.
The cooling water flow rate is 65000 kg/h.
The suggested methanol synthesis process model is
realized in the simulation of the complete methanol
production flow sheet, whence it follows that the
parameters of the inlet streamsthe initial raw synthesis gas stream (basic one) and the water stream (subsidiary one)are calculated values that are found after the
calculations have been performed for the heater of synthesis gas going to the methanol synthesis reactor, and
also for the steam drum of the configuration (not shown
in the figure).
Calculation data on the properties for the inlet and
outlet streams of the methanol synthesis reactor are
included in Table 8. The comparison of calculated and
experimental outlet stream properties is carried out in
the same table.
MODELING OF THE PROCESSES
IN THE REACTOR UNIT FOR THE SYNTHESIS
OF HYDROCARBONS
BY THE FISCHERTROPSCH REACTION
In the reactors for the synthesis of hydrocarbons by
the FischerTropsch reaction, basic chemical processes
proceed in the catalysts. The assumption is made that
the reactions proceed at a pressure of 31 bar and a temperature of 210260C according to the following equation [20]:
xCO + ( 2x + 1 )H 2

( )-C x H 2 x + 2 + xH 2 O,

where 1 x 25.

(8)

At that, the CO conversion reaction and a great number of side reactions proceed concurrently [8, 9]. The
synthesis of hydrocarbons by the FischerTropsch
reaction is carried out in catalytic tubular reactors. As
the FischerTropsch reaction is strongly exothermal, to
provide optimal conditions for the process, water is fed
into the intertubular space of the reactor, where it turns
into steam.
The unit for the synthesis of hydrocarbons by the
FischerTropsch reaction consists of three cascades
connected in a series (Fig. 3): the first cascade consists
of modules 13, 3234, 10, 14, 17, 18, and 2325; the
second one includes modules 46, 3537, 11, 15, 19,
20, and 2628; and the third one comprises modules 7
9, 3840, 12, 13, 16, 21, 22, and 2931.
Synthesis gas is fed into the first cascade. Every cascade includes a reactor, where the synthesis of hydrocarbons proceeds; a three-phase separator intended to separate water; and also a phase separator, where liquid hydrocarbons are separated from the gaseous mixture. It should
be noted that in the three-stage synthesis of hydrocarbons
(three cascades), the yield of liquid hydrocarbons is higher
than in the one-stage synthesis [9].

Table 8. Calculated data on the properties of the inlet and outlet streams for a methanol synthesis reactor and the comparison of calculated and experimental outlet stream properties
Stream
property

Inlet stream
(calculated
data)

Outlet stream
(calculated
data)

Outlet stream
(experimental
data)

t, C

210

242

243

p, bar

79

78.7

78.8

570464

485818

485995

W, m3/h
, vol %
H2

67.81

60.250533

62.38

CO

7.89

2.502676

3.28

CO2

8.43

7.95397

8.1

N2

7.13

8.373605

7.17

H2O

0.04

1.998411

CH4

8.27

9.714512

9.21

Table 9. Specified CO conversion values and heat duties for the

reactors and their appropriate modules
Reactor
of cascade I

of cascade II

of cascade III

Reactor
module

mr

qmr, MJ/h

0.21

56031

0.17

41055

0.38

7606

0.27

45403

0.33

45593

0.0002

0.86

252

0.96

7159

0.92

84554

qr, MJ/h

0.37 104692

0.51

92256

0.99

91965

1260

The models of equilibrium reactors 19 serve for the

modeling of reactionary streams for every reactor (streams
in tubes). The single reactor for the synthesis of hydrocarbons is simulated by means of three reactor modules; at
that, we assume that the side reactions can be neglected in
the modeling.
For reactor modules 19 (Fig. 3), the following parameters are specified: stoichiometric data for each reaction
(8); key reagent conversions; and the thermal conditions are isothermal, the temperature is 255.
The above-mentioned reagent conversion values
that are suggested for the simulation of the process for
the synthesis of hydrocarbons by the FischerTropsch
reaction are given in Table 9 for reactions (8) in every
module. In the same table, the correspondence of every

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951

Steam

41

Steam Collector

32
23

36

38

7
29
26

33

24

5
8

35

30

39

27
3

31

26

34

37

9
40
28

Synthesis gas

Air
cooler

17

18

Separator
for the removal of
liquid
hydrocarbons

18

Hydrogen containing
gases to short-cycle
adsorption

21

10
11
14

12

20

Separator for
water removal

22

Propane and butane

to the collector
43

42
15
16

13

Mixture of liquid
hydrocarbons to
distillation

44
45

46

Water

Condensate

Fig. 3. Unit for the synthesis of hydrocarbons by the FischerTropsch reaction: (1)(9) are the equilibrium reactor modules,
(10)(13) are the phase separator modules, (14)(16) are the three-phase separator modules, (17)(31) are the heat exchanger modules, (32)(40) are the heat load transfer modules; (41)(44) are the mixer modules, and (45) and (46) are the stream splitter modules.

physical reactor to its appropriate module is shown, and

the calculated heat load values are given for the abovelisted modules and reactors.
Cooling water streams in the intertubular space of
each reactor are modeled by heat exchanger modules
2331 (Fig. 3): modules 2325 correspond to the inter-

tubular space for the reactor of cascade I, the cooling

water flow rate is 40 320 kg/h; modules 2628 represent that for the reactor of cascade II, the cooling water
flow rate is 40 269.6 kg/h; and modules 2931 model
the intertubular space for the reactor of cascade III, the
cooling water flow rate is 45 410.39 kg/h.

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GARTMAN et al.

Table 10. Calculated data on the properties of inlet and outlet

streams for the reactor unit of the synthesis of hydrocarbons by
the FischerTropsch reaction and the comparison of calculated and experimental summary outlet stream properties
Summary
Inlet stream
Outlet stream
outlet stream
Stream property (calculated
(experimen(calculated
data)
tal data)
data)
G, kg/h
, wt %
H2, CO, CO2, N2,
H2O
CH4 and C2H6
C3H8 and n-C4H10
C11C13 (kerosene)
C14C20 (diesel fuel)
C21C25 (black oil
and other oils)

104613

69424.09

66335

96.92

55.663726

55.42

2.77

4.991756
4.137915
6.98965

3.08
4.44
7.25

8.695355

9.76

2.125691

2.58

Table 11. Reagent conversion values specified in the hydrocracking reactor modeling for reactions (9)
Reagent

n-C20H42

0.99

n-C21H44

0.99

n-C22H46

0.99

n-C23H48

0.99

n-C24H50

0.98

n-C25H52

0.98

The heat transfer process (reaction heat removal into

the intertubular space in each reactor) is modeled with
the help of special modules, which transmit calculated
heat loads from reactor modules to heat exchanger
ones. Modules 3234 transmit the calculated heat loads
from equilibrium reactor modules 13 to heat
exchanger modules 2325, taking into account their
signs. The modeling of the calculated heat load transfer
by modules 3540 from equilibrium reactor modules
49 to heat exchanger modules 2631 is performed
similarly. The inlet heat load for each heat exchanger
module is equal to the calculated one of the appropriate
reactor module (as outlined above) by its absolute
value, but has an opposite sign.
The model suggested for the reactor unit of hydrocarbon synthesis by the FischerTropsch reaction is
realized in the simulation of the complete flow sheet for
the production of synthetic liquid fuel fractions; therefore, the parameters of the inlet streamsthe initial raw
synthesis gas stream (basic) and cooling water streams
(subsidiary)are calculated values and are found after
the calculations have been performed for the heater of
synthesis gas (Fig. 3, module 17), which is fed into the
hydrocarbon synthesis reactor, and also for the deaerator, which is not shown in the figure.
Calculated data on the properties of the inlet and
outlet streams for the methanol synthesis reactor are
given in Table 10. The comparison of calculated and
experimental properties is performed in the same table
for the summary outlet stream.
SIMULATION OF A HEAVY HYDROCARBON
HYDROCRACKING PROCESS IN SYNTHETIC
LIQUID FUEL PRODUCTION
During the process of hydrocracking in the presence
of a catalyst, heavy hydrocarbons are split into lighter
ones under the action of hydrogen.

Table 12. Calculated data on the properties of inlet and outlet

streams for the hydrocracking reactor and the comparison of calculated and experimental outlet stream properties
Stream
property

Outlet
Inlet stream
Outlet stream
stream
(calculated
(experimental
(calculated
data)
data)
data)

t, C
337
p, bar
31.5
G, kg/h
1947.41
, wt %
8.17
H2 and C1C4 (gases)
C5C10 (gasoline)
0.92
C11C13 (kerosene)
1.9
C14C20 (diesel fuel)
19.81
C21C25 (residue)
64.19

It is assumed that the main reaction equation has the

following form [8]:
n-C x H 2 x + 2 + H 2

n ( iso )-C y H 2 y + 2

+ ( iso )-C z H 2z + 2 ,

where 21 x 25.

(9)

380
31
1947.403

380
31

The process is conducted in a tubular hydrocracking

reactor at a temperature of 380C and pressure of 31 bar.
The assumption has also been made by us that the concentration of hydrocarbons having a branched structure (iso
structure) is low, it can therefore be neglected.

13.04455
17.017
6.356951
51.33431
6.795569

10
15

67
8

The given reactor is modeled by a reactor module; at

that, the following data are specified: stoichiometric
parameters for reactions (9); key reagent conversions; and
the thermal conditions are isothermal, the temperature is
380. For reactions (9), the mentioned reagent conversion
values that which are suggested for the modeling of hydrocracking process are given in Table 11.

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EXPERIENCE IN THE APPLICATION OF THE CHEMCAD PROGRAM

The model suggested for the hydrocracking process is

realized in the simulation of hydrocracking and distillation
units; the inlet stream parameters are calculated values.
Calculated data on the properties of inlet and outlet
streams of the hydrocracking reactor are presented in
Table 12. The comparison of calculated and experimental
properties for the outlet stream is performed in the same
table.
CONCLUSIONS
In the present work, a method has been suggested
for the calculation of reactor units with the use of modeling programs in the modeling of multistage chemical
technology processes with a great number of main and
subsidiary equipment units. The suggested strategy has
the following features: the main chemical reactions that
influence the process in the reactor are chosen; material
and heat calculations for the process in each reactor are
conducted by means of the appropriate combination of
the modeling of the programs standard modules, which
is based on peculiar features for the process in physical
apparatuses; and stoichiometric data are specified for
the main reactions and reagent conversions are determined from the experimental data on the basis of
knowledge about the reactor process for each standard
module. The developed technique has been confirmed
by the calculations by means of the CHEMCAD modeling program for four industrial reactor units in the
multistage productions of methanol and synthetic liquid fuel from natural gas.
NOTATION
frequency (preexponential) factor for the
Arrhenius equation;
areaction exponent for a reagent;
badsorption exponent for a reagent;
creagent concentration, kmol/l;
Crcriterion of experimental and calculated data
inconsistency;
Ejactivation energy, kJ/kmol;
Ekjenergy adsorption factor, kJ/kmol;
Gmass flow rate, kg/h;
mnumber of components;
Nnumber of experimental measurements;
Nijstoichiometric coefficient;
njnumber of reagents;
ppressure, bar;
Qheat accumulated at the expense of a chemical
reaction, kJ;
QRrate of heat evolution (absorption) in a reactor,
kJ/s;
qcalculated heat load, MJ/h;

953

rioverall reaction rate (local rate) for the ith component, kmol/(m3 s);
Tabsolute temperature, K;
ttemperature, ;
snumber of reaction stages;
Vvolume of reaction mass, m3;
Wvolumetric flow rate in standard conditions,
m3/h;
Q

c, V, T, R , Qweighting coefficients;
adsorption exponent;
reagent conversion;
adsorption frequency factor;
component content, vol % or wt %.
SUBSCRIPTS AND SUPERSCRIPTS
i, j, kindices of component, stage, reagent, or
measurement;
mrreactor module;
Rreaction;
rreactor;
x, yindices of carbon and hydrogen atoms;
calccalculated value;
expexperimental value.
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