DESIGN OF INDUSTRIAL REACTIVE

ABSORPTION PROCESSES IN SOUR GAS

TREATMENT USING RIGOROUS MODELLING
AND ACCURATE EXPERIMENTATION
R. Thiele1,
, R. Faber2, J.-U. Repke2, H. Thielert3 and G. Wozny2
1

BASF AG, GCT/D L540, Ludwigshafen, Germany.

Technical University of Berlin, Germany.
3
Uhde GmbH, Dortmund, Germany.
2

Abstract: In this paper a rigorous rate-based model for the selective absorption and desorption
of sour gases in packed towers within a coke oven gas purication process (VACASULFwprocess) is presented. It considers multi-component mass transfer of CO2, H2S, NH3 and
HCN in aqueous potassium hydroxide (KOH) or potash (K2CO3) solutions and the inuence of
chemical reactions on mass transfer using enhancement factors. A modied Pitzer model is
used to estimate activity coefcients in the electrolyte solution for the calculation of the chemical
and the phase equilibria as well as the reaction kinetics (Bronsted-Bjerrum equation). Using data
from the literature this thermodynamically consistent approach was successfully validated for the
phase equilibria and the reaction kinetic calculation. Since no experimental data for the abovementioned chemical system in packed towers is available in the literature, own experiments were
carried out in a pilot plant packed tower. A newly developed experimental method using redundant measurements and a Data Reconciliation procedure improved the accuracy of concentration proles for the gas and the liquid phase. Using eight absorption and eight desorption
experiments, as well as industrial on-site measurements of the entire plant, the model was successfully validated. In addition, the model was used for global optimization using evolutionary
algorithms, revealing an optimization potential of 30% in operating costs.
Keywords: packed towers; reactive absorption; gas purication; sour gas treatment; mass transfer.

INTRODUCTION


Correspondence to:
R. Thiele, BASF AG, GCT/D
L540, 67056, Ludwigshafen,
Germany.
E-mail: robin.thiele@
basf.com

DOI: 10.1205/cherd06091
02638762/07/
$30.00 0.00
Chemical Engineering
Research and Design
Trans IChemE,
Part A, January 2007
# 2007 Institution
of Chemical Engineers

In the industry design of gas purication

plants is still often done using empirical
methods and simple spreadsheet calculations. Thus, nding an efcient design for
the units and optimal operating parameters
for the entire process is not straightforward.
In this joint research project between an
academic and an industrial partner, reactive
absorption and desorption processes are rigorously modelled using thermodynamic and
chemical engineering fundamentals taking
into account the complex reaction system
and its effects on mass and heat transfer
(Thiele et al., 2003a; Thielert, 1997).
Frequently installed processes like the
ammonia-hydrogensulphide scrubbing process and amine-based processes have
already been modelled with great success
(Brettschneider et al., 2004). However,
models for processes with potash like the
VACASULFw process are still not available.
During the start-up of a recently built industrial

VACASULFw plant, the experimental results

showed a surprisingly large increase in efciency for a specic alkaline concentration
range, which was not predicted by the empirical methods in the design stage.
A literature review revealed that in the
past investigations focussed on absorption
of CO2 in highly concentrated solutions.
Benson characterized the CO2 absorption
with high potassium carbonate concentrations
(Benson et al., 1954). This so-called Beneld
Process was for the rst time rigorously
modelled in 1981 (Joshi et al., 1981) and
later extended with the insertion of dissolved
arsenic as promoter for an enhanced CO2
absorption (Kumar and Rao, 1989). In 1990
a model based on kinetic and equilibrium
data was developed to calculate the CO2
absorption and desorption rates in a highly
loaded potassium solution (Pohorecki and
Kuckarski, 1990). A rate-based model for the
Benson Process based on effective interfacial
area to calculate the mass transfer was also
developed by Cents (Cents et al., 2001).

74

Vol 85 (A1) 7487

DESIGN OF INDUSTRIAL REACTIVE ABSORPTION PROCESSES IN SOUR GAS TREATMENT

In contrary to the extensive modelling of the Benson
Process, a model for processes with a low concentrated
potash absorbent for the selective removal of H2S and
HCN like the VACASULFw process (Currey, 1995) is still
not available. Therefore, a rigorous rate-based nonequilibrium model for a more complex electrolyte system
(NH3-CO2-H2S-HCN-H2O-KOHNaOH) with chemical reactions taking into account the inuence of chemical reactions
on mass transfer using enhancement factors was built at
the Technical University of Berlin (Thiele, 2007).

Instantaneous reversible reactions:

2H2 O

For simulating this absorption/desorption process,

commercial simulators based on either equilibrium or nonequilibrium models (without reactions), fail to predict the
selective absorption and desorption of H2S and HCN over
CO2. CO2-absorption is seriously overestimated by an equilibrium model due to the slow dissociation reactions of CO2 in
water and the also kinetically controlled reaction between
NH3 and CO2. A selective absorption of H2S compared to
CO2 during short contact times in packed towers could therefore not be predicted with the abovementioned models.
Therefore, the development of a complex heat and mass
transfer model taking the interactions of the different chemical
species and their reactions into account was conducted using
FORTRAN. An overview for one transfer unit of the model is
shown in Figure 1 and will briey be explained in the next
subchapters. More details on the model can be found in
Thiele (2007).
A comparison of the simulation results of an equilibrium
model and a rigorous rate-based model with the measurements of a pilot plant experiment is shown in Figure 2.

HCO
3

The given reactive system of weak and strong electrolytes

is described by considering the following reactions with the
dissociation constants Kj.

! H3 O OH

! NH
4 OH
K3

! CO2
3

H3 O

(R:2)

K4

! HS H3 O

K5

! S2 H3 O

HS H2 O
K6

(R:1)

K2

H2 O

H2 S H2 O

! H CN

HCN H2 O

(R:3)
(R:4)
(R:5)
(R:6)

K6

! CN H3 O

Kinetically controlled reactions:

CO2 OH
NH3

K7

! HCO
3
K8

HCO
3

(R:7)


! H2 NCOO H2 O

(R:8)

Strong electrolyte:
KOH

K9

! K OH

(R:9)

The also occurring reaction CO2 2H2 O !HCO2

3 H3 O
is very slow compared to (R.7) especially in alkaline solutions. Its contribution to the overall rate of reaction is therefore small and can be neglected (Cents et al., 2001).
To calculate the concentrations of molecular and ionic
species in solution the chemical equilibria are expressed
with their dissociation constants Kj.

Kj

Electrolyte System

K1

NH3 H2 O

HCN

RATE-BASED MODEL

75

nc
Y
i1

ai i,j

nc
Y

mi i,j gi i,j

(1)

i1

where ai is the activity of component i, ni,j is the stoichiometrical coefcient of component i in reaction j and gi is the
activity coefcient taking non-idealities into account.

Figure 1. One segment of the rate-based model including chemical reactions.

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76

THIELE et al.

Figure 2. Comparison experiment-model (rate-based and equilibrium), absorption in 32 g l21KOH, F 1.8 Pa1/2, B 9 m3 m22 h21.

The chemical equilibrium between the different species in

the bulk liquid is solved by the POWEL routine from the MINPACK library. Then the result for the pseudo and molecular
components is passed to the equations of the transfer unit
(Figure 1) to calculate the mass transfer. Knowledge of the
concentrations of the different dissociated species is also
especially important to calculate the enhancement factors.

Phase Equilibrium
The equilibrium at the interface between the molecular
species is calculated using the Henry coefcient for dissolved
diluted gases as the standard-state fugacity.
xi  gi  HeH2 O,i yi  Fi  P

(2)

considered separately regarding balances for mass, components and enthalpy. Mass transfer between both phases
over the interfacial area is evaluated with the lm theory,
which assumes one-dimensional diffusion in the lm and a
completely mixed bulk phase. The cross-interactions of the
General Maxwell Stefan theory can be neglected due to
the low concentrations (Peters, 1997). The convective term
is also neglected.
The mass transfer rate J of component i for segment j is
then calculated by
Ji,j ki,jv  rvj  aj  (yi,jb  yi,jint )
ki,jl  rlj  aj  Ei,j  (xi,jint  xi,jb )

(3)

i:H2 O, CO2 , H2 S, HCN, NH3 :

with the Henry coefcient HeH2O,i of the component i (CO2,

H2S, HCN, NH3) in water and the fugacity coefcient Fi that
considers the non-ideality of the gas phase. The equilibrium
for water is calculated using the vapour pressure instead of
the Henry coefcient.
In this work the correlations and parameters of Edwards
(Edwards et al., 1975, 1978) are used to calculate the activity
coefcients using a modied Pitzer approach and the Henry
coefcients as well as the activity-based dissociation constants Kj from the previous subsection. In addition binary
interaction parameters for the different pairs of potassium
salts are taken from Pitzer and Mayorga (1973), Roy et al.
(1984), Simonson et al. (1987) and Engel et al. (1997).
Hoogendoorn et al. (1988) found the vapour phase fugacity
coefcients to differ not more than 1% (2% for water) from
unity for pressures less than 0.2 MPa. Therefore, they were
set to unity.

Mass and Heat Transfer

For the non-equilibrium model the column is divided into
stages. In each segment the vapour and the liquid phase is

The mass transfer coefcients kvi,j and kli,j for the gas and
liquid lm are calculated from correlations developed by
Billet and Schultes (1999). The interfacial area aj is calculated
from the same contributions. The increase in concentration
gradients at the interfacial area due to chemical reaction
leads to an enhancement of mass transfer which is
accounted for by the enhancement factor Ei,j, calculated
from correlations also applied by Hoogendoorn et al. (1988).
He used enhancement factors for reversible reactions of
rst order and pseudo-rst order derived from the surface
renewal theory by Danckwerts (1970).
Analogous to the mass transfer models, enthalpy
balances are formulated separately for the liquid and the
vapour phase and the interface, thus, considering the heat
transfer over the interface. Liquid and vapour enthalpies
are calculated from Pawlikowski and Newman (1982) and
Cox et al. (1989) and the liquid and vapour side heat transfer
coefcients are obtained from the weighted corresponding
component mass transfer coefcients using the Lewis
equation.

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DESIGN OF INDUSTRIAL REACTIVE ABSORPTION PROCESSES IN SOUR GAS TREATMENT

Reaction Kinetics
The kinetics for the reactions (R.7) and (R.8) are taken
from Pinsent et al. (1956a). The reaction rate constants
k1
OH2 are given for innite dilution.
The reaction rate for (R.7) is then given in the form
r_ R:7 kOH cOH cCO2

(4)

Pohorecki and Moniuk (1988) measured the inuence of

the ionic strength and the type of the ions in solution on
the reaction rate constant kOH2. For the absorption of CO2
in potassium hydroxide solutions he found the following
relationship:
1
2
 ) 0:287I  0:013I
log (kOH =kOH

(5)

Since this equation can not be applied to mixed solvents the

Bronsted Bjerrum equation is used. It describes the reaction
between an ion B having charge z and a neutral molecule A
which reacts to an ion via an intermediate state (Bronsted,
1922; Bjerrum, 1924; Pohorecki and Moniuk, 1988):
A Bz !(AB)z 
! products

(6)

The reaction rate constant, according to the Bronsted

Bjerrum equation, is then for (R.7) equal to
1

kOH kOH

gCO2 gOH
gHCO3

(7)

Since the activity coefcients can also be calculated for complex solutions, the inuence of the non-ideality of the liquid
phase on the rate constant is accounted for by the thermodynamic model which is also used for the calculation of the
chemical equilibrium and the phase equilibrium. Thus a consistent thermodynamic approach is maintained throughout
the model. Haubrock et al. (2005) used a similar equation
as (7), however he only included the activity coefcients for
the reactants. Using this approach he was able to decrease
the inuence of the ionic strength, however a ratio of 2 for
k exp
OH2/kOH2 for intermediate ionic strength still persists.

Numerical Methods and Implementation

The entire program is written in FORTRAN and inteTM
grated into ChemCAD as a User Added Module. This

77

allows to build the entire process of a plant in the owsheet

simulator. Standard Units like Heat Exchangers, Splitter,
Mixers and Pumps are taken from the ChemCAD library.
These units require ash calculations for the given system.
Using the built-in methods (Sour water and ELECNRTL)
using Version 5.2 the system is either not supported or
cannot be reliably calculated regarding computation time and
convergence behaviour. Thus, the above presented chemical
and phase equilibria calculations are used by inserting a
User Added K-Value calculation method (ADDK) implemented
in FORTRAN into ChemCAD. Which leads to a consistent
thermodynamic model throughout the entire ow sheet.

VALIDATION OF THE PHASE EQUILIBRIUM AND

THE CALCULATION OF THE REACTION KINETICS
To validate the presented thermodynamic modelling of
the phase equilibrium and the reaction kinetics data from
the literature is used. Since absorption behaviour in the
VACASULFw process is mainly governed by the interplay of
CO2 and H2S with the alkaline potash solution, these
components are considered in the validation of the partial
pressures. Concentrations of NH3 are considerably low in
the entire process. Off-gas specications for HCN are usually
met before the specications for H2S are met.
For the relevant concentration region for KOH of
0.5 mol l21 K (resp. of 30 g l21 KOH) experimental liquid
vapour-equilibrium data are given in Dryden (1947). In
Figure 3 the data in terms of partial pressure match well
with the simulated results for the phase equilibrium of the
model. Indeed, for higher concentrations of CO2 and H2S
the accuracy is decreasing. Nevertheless, these results
show that regarding the phase equilibrium, as a decisive
factor for column performance prediction, a reliable basis
for a solid simulation of the entire column is provided.
For the validation of the reaction kinetics the measurement results from Pohorecki and Moniuk (1988), which
have been correlated giving equation (5), are used. The
results for CO2 in a KOH solution with different ionic strength
regarding the reaction rate constant of reaction (R.7) is
shown in Figure 4 in comparison to the literature results.
As can be seen, the thermodynamic model using the
Bronsted Bjerrum equation (7) is able to reproduce the
non-ideality in the liquid phase regarding the reaction
kinetics. It can be expected that the model is also able to
calculate the increase in the reaction rate due to the

Figure 3. KOH-CO2-H2S equilibrium data from Dryden compared to simulation results.

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78

THIELE et al.

Figure 4. Reaction rate constants for absorption of CO2 in KOH for

reaction (R.7) and activity coefcients.

existence of different ions in solution for mixed solvents, as

it occurs in the VACASULFw Process.

PILOT PLANT
For the experimental validation of the simulation a pilot
plant at the TU Berlin was used which has been designed
for both absorption and desorption experiments under
atmospheric pressure and vacuum conditions. It consists

of a stainless steel column ( 100 mm) equipped with

three sections of packings each of 856 mm height. The
structured packing used is a SULZER Mellapak 350.Y. The
pilot plant is described in detail in Brettschneider et al.
(2004) for the absorption mode. The entire experimental procedure including measurement errors is described in detail
in Thiele (2007).
The pilot plant is automated by the process control system
TM
Freelance2000 by ABB. Liquid samples can be taken at
three different heights and are analysed under wet conditions
(measurement errors for CO2: 1%, H2S: 2%, NH3: 5%, KOH:
1%). Gas samples can also be drawn at four different positions and are analysed by a gas chromatograph (measurement error: 10%). In addition to the analytical method
presented in Brettschneider et al. (2004) potassium is
analysed by titration with sodiumtetraphenylborate. The
column is equipped with a glass section for optical examinations. A vacuum pump behind the exhaust gas scrubbers
allows pressures down to 70 mbar in desorption mode.
In absorption conguration (Figure 5) the gas stream is
mixed inline from gas bottles. The CO2 concentration is
measured online using an infrared CO2 analyser from
MAIHAK and is kept constant by a controller. In desorption
mode (Figure 6) steam is generated by a reboiler from
desalinated water and a condenser at the top of the
column partially condenses the vapours coming from the
top of the column. Inerts, mostly CO2, are withdrawn from
the condenser to maintain a constant pressure at the top
of the column.

Figure 5. Flowsheet of the pilot plant in absorption mode. Desorption equipment is hidden.
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DESIGN OF INDUSTRIAL REACTIVE ABSORPTION PROCESSES IN SOUR GAS TREATMENT

79

Figure 6. Flowsheet of the pilot plant in desorption mode. Absorption equipment hidden.

DATA RECONCILIATION METHOD

Since all concentrations of both the liquid and the gas
phase are known for the three packing segments component
balances can be made (Figure 7). This allows the reconciliation of the measurement variables involved, which does
not require any process knowledge except that mass is
preserved.
fj,k (x) Lj cj,k  Lj1 cj1,k Vj1 yj1,k  Vj yj,k
k KOH, CO2 , H2 S, NH3 ,
c liquid concentration,
V gas flow,

(8)

L liquid flow,
j envelope 1, 2 and 3,

y gas concentration

Large deviations in the component balances of up to 20%

which cannot be attributed to measurement errors suggest
that the measurements might contain gross errors. It was
further assumed that the measurement values which are
subject to error are not normally distributed. Thus, a utilization of weighted least squares is not recommendable.

Figure 7. Balance envelopes for the data reconciliation method.

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80

THIELE et al.
MODEL VALIDATION USING PILOT
PLANT EXPERIMENTS

Figure 8. Inuence function for different objective functions.

zyurt
Instead a robust estimator, the Fair-function is used (O
and Pike, 2004). The Data Reconciliation problem can then
be formulated as follows:

min J min

nmv
X
i1

c2





j1i j
j1i j
 ln 1
c
c

xi  x^ i
1i
xi [ V, L, c, y
si
s.t. f (x) 0
Lb  x  Ub

(9)

The Fair function introduces simultaneous gross error detection into the data reconciliation (DR) process. This can be
shown by the inuence function (Figure 8). The contributions
from the Fair function for larger standard errors are signicantly lower than for the weighted least squares (WLS)
function.
The resulting optimization problem [equations (8) and (9)]
consists of 31 variables and 12 equality constraints and is
non-linear. It can be solved using an NLP-Solver like the
SQP-Method. The DR problem including the solver method
has been implemented in MATLAB (Faber et al., 2004).
By applying the DR method the quality of the measurement
data is expected to be improved, which will be validated in the
next section.

The validation of the developed model was carried out using

eight desorption experiments and eight absorption experiments for which the DR was carried out. Experiments were
either conducted under vacuum conditions at 150 mbar or at
mean overpressure of about 1100 mbar (abs.), thus, enabling
to validate the model in a wide pressure and therefore also in a
wide temperature range. The concentration ranges of the
components KOH and CO2 were chosen according to the
VACASULFw process. At rst only a H2O-KOH-CO2 solution
was used as an absorbent. In further experiments the
system was extended with H2S and nally with NH3. Thus,
the inuence of individual components on the model accuracy
for both absorption and desorption can also be identied. All
experiments conducted within the project are presented in
detail in (Thiele, 2007). In this paper, three desorption and
three absorption experiments are exemplarily presented.
The entire feed and operating data, which are required to
carry out the simulation and the measured ows and concentrations of the outlet streams are presented in Table 1 (desorption experiments) and Table 2 (absorption experiments).
During the absorption experiments the gas stream entering
the column at the bottom is saturated in the exhaust gas
scrubbers at the temperature called Presat. temp. in
Table 2. Using this temperature the water concentration
which is also important for the absorption process and the
resulting temperatures can be calculated.
The liquid concentration proles and the temperature
proles for the desorption experiments in comparison to
the simulated values achieved by the model are given in
Figures 911. For all experiments a good agreement is
obtained between the experiments and the simulation results
both the concentrations and the temperature measurements.
For the complete system H2O-KOH-CO2-H2S-NH3 and desorption under vacuum which is relevant for the VACASULFwprocess (Figure 10) the simulation results match well with
the experimental data within an average relative error
below 20%. The model is able to reproduce the selective desorption of H2S over CO2. The simulated temperature prole
also ts closely to the experimental values, hence, conrming
enthalpy and heat transfer model.
The results for the absorption experiments are shown in
Figures 12 14. Besides the liquid concentrations and

Table 1. Experimental parameters for the three desorption experiments (D1, D7 and D8 from Thiele, 2007).
Case 1 (D1)
Process data
Vapour
Flow (kg h21)
Temp. (8C)
Liquid
Flow (l h21)
Temp. (8C)
CO2 (g l21)
H2S (g l21)
NH3 (g l21)
KOH (g l21)
Plant data
Top pres. (mbar)
Pres. drop (mbar)
F-factor (Pa0.5)

Case 2 (D7)

Case 3 (D8)

Feed

Outlet

Feed

Outlet

Feed

20
56.87

53.62

15
56.37

53.45

34
103.22

99.98
45.04
27.52

35.73

101.9
54.58
23.55

33.89

99.78
45.14
19.89
2.12
4.93
30.98

99.35
54.59
18.08
0.049
0.096
30.3

99.82
80.2
20.15
2.53
5.11
29.90

148.8
9.7
2.16

152.9
5.9
1.61

Outlet

102.05
103.52
103.0
14.58
0.624
0.0017
28.09
1123.8
3.12
1.47

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DESIGN OF INDUSTRIAL REACTIVE ABSORPTION PROCESSES IN SOUR GAS TREATMENT

81

Table 2. Experimental parameters for three absorption experiments, results of the DR in brackets (A2, A6, A8 from Thiele, 2007).
Case 4 (A2)
Process data
Vapour
Flow (Nm3 h21)
Temp. (8C)
Presat. temp (8C)
CO2 (Vol%)
H2S (Vol%)
NH3 (Vol%)
Liquid
Flow (l h21)
Temp. (8C)
CO2 (g l21)
H2S (g l21)
NH3 (g l21)
KOH (g l21)
Plant data
Top pres. (mbar)
Pres. drop (mbar)
F-factor (Pa0.5)

Feed
47.09 (47.07)
25.38
23.77
2.383 (2.209)

Case 5 (A6)
Outlet

Feed

46.55 (47.33)
25.06
24.35
2.393 (2.335)
0.410 (0.404)

26.92

1.754 (1.749)

Case 6 (A8)
Outlet

Feed

46.88 (48.84)
25.00
19.78
2.012 (2.131)
0.514 (0.561)
0.9 (1.26)

24.88

2.369 (2.323)
0.0100 (0.0035)

69.95 (69.82)
25.02
5.97 (5.97)

70.37 (70.50)
27.87
12.04 (12.04)

69.95 (70.00)
25.02
12.38 (12.38)
0.25 (0.25)

70.83 (70.75)
25.81
12.59 (12.59)
4.32 (4.32)

35.84 (34.42)

33.42 (34.09)

28.48 (28.58)

28.35 (28.28)

1123
6.34
1.80

1094
6.45
1.80

Figure 9. Desorption experiment case 1 (D1).

Figure 10. Desorption experiment case 2 (D7).

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69.94
24.98
17.33
0.87
0.00
31.98

(70.00)
(17.33)
(0.92)
(0.00)
(32.19)

Outlet

25.39

2.173 (2.072)
0.095 (0.088)
0.0050 (0.0025)
70.59
28.93
18.45
6.94
7.27
31.92
1110
6.11
1.80

(70.47)
(18.44)
(5.92)
(6.60)
(31.97)

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THIELE et al.

Figure 11. Desorption experiment case 3 (D8).

Figure 12. Absorption experiment case 4 (A2).

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DESIGN OF INDUSTRIAL REACTIVE ABSORPTION PROCESSES IN SOUR GAS TREATMENT

83

Figure 13. Absorption experiment case 5 (A6).

temperatures the gas concentrations are also measured for

the absorption experiments. Thus, the data reconciliation
can be carried out and the gures show both the original
measurements, as well as the reconciled variables. It can
be seen that the data reconciliation leads especially for the
gas concentration measurements of CO2 to signicant
improvements. The measurement error for the gas chromatograph is approx. 10% which leads to large deviations in
the mass balances [equation (8)], which is corrected by
the DR method. The DR method does not only change the
measurement values throughout the column but also
the feed streams. Thus, the simulations for comparison with
the DR results have also to be conducted using these reconciled feed streams. Due to the complex interactions in the
electrolyte system the change in the feed composition of
one component can also lead to improvements for other
components.
Table 3 shows for all 8 absorption experiments the average
and maximum deviations between the simulation and the
measurements for both the original measurements and the
reconciled measurement data. The DR method leads to signicant improvements for nearly all components: e.g., the
maximum deviation for the gas concentration of CO2 is

reduced from 14.66% to 3.27% and the average deviation

for KOH is reduced to only 0.37%.
It can be concluded, that the newly developed experimentation concept using redundant measurements and the DR
can provide an improved data basis for validating models
or to estimate important model parameters.
The absorption results show that a reliable prediction of
the chemical absorption using the model is possible. Again,
the model is able to predict the selective absorption of
H2S over CO2. Average deviations are below the range of
5 10% (compare Table 3).
Further investigations also focus on the inuence of
surface active components on hydrodynamics in packed
towers which can cause foaming (Thiele et al., 2003b, 2004).

INDUSTRIAL PLANT
In addition to our own pilot plant experiments, validation of
the model was also done using measurement data from an
industrial VACASULF process of Citizens Gas & Coke Utility
in Indianapolis, Indiana. The plant has been described in
Currey (1995). Measurements were taken in 1997 during a
start-up phase by Uhde GmbH. The data was then processed

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THIELE et al.

Figure 14. Absorption experiment case 6 (A8).

using component balances showing that these industrial

measurement data are questionable. The best data set,
which still showed deviations in the different component balances of up to 30%, was chosen to be used for the simulation
using a owsheet simulation with CHEMCAD with the presented rate-based model as tower units. All design parameters from the process (tower diameters, heights and
internal types) were known and put into the simulation. The
process can be seen in Figure 15.

Table 3. Improvements using redundant measurements and the data

reconciliation method for eight absorption experiments.
Rel. deviation liquid (%)
DR
KOH
CO2
H2S
NH3
a

exp

MaxDR Maxexp

0.37 1.24
1.09
3.37 3.08 12.24
4.94 6.85 13.96
6.66 37.66 18.44

8.25
12.16
32.24
54.57

Rel. deviation gas (%)

DR

exp

MaxDR Maxexp

1.28 4.53
3.27
21.41 36.91a 63.92

Small concentration (,20 ppm) neglected.

14.66
168.41

The results show that, considering the obvious gross errors

in the measurements the model is able to predict the industrial process with a good accuracy. The deviations between
the predicted and the measured data can be seen in
Table 4. Larger deviations do occur for small concentrations,
but the associated component streams are considerably
small. Since the simulation results are in good agreement
with the expectations of the process engineers, the model
for the entire process can also be considered as validated.

PROCESS OPTIMIZATION BASED ON

OVERALL COSTS
The validated rate-based model was then used in the
commercial owsheet simulator CHEMCAD to optimise the
entire process. Therefore the owsheet simulator was
connected to an external evolutionary strategy implemented
in Visual Basic and Excel which had been developed
before in Brettschneider (2003) and Thiele et al. (2003c)
and is shown in Figure 16. Ten process parameters (ows,
KOH-conc., temp, stripper pressure) and ve design parameters (absorber and stripper heights, feed side stream

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DESIGN OF INDUSTRIAL REACTIVE ABSORPTION PROCESSES IN SOUR GAS TREATMENT

85

Figure 15. VACASULF process.

heights) where chosen as decision variables for the optimization routine. The objective function was based on annualized costs comprising both investment and operating costs.
Costs functions were derived using condential cost data
from the industrial partner for running plants regarding operating costs and from realised projects regarding investment
costs. Investment cost functions are simple linear or degressive functions. Parameters for the evolutionary algorithm
were 10 individuals per generation, out of which two parents
were selected which gave by linear recombination the new
parent. The new generation was obtained by normal distributed mutation of the parent.
For an operated industrial VACASULFw plant similar to
Figure 15 the entire optimization resulted in a decrease of
the operation costs by 30% as can be seen from Figure 17.
The optimizer decreased the concentration of the potash
Table 4. Validation using data from the industrial process.
Deviations
Simulation $ Process
Rich potash solution

CCO2
CH2S
CHCN

Normal stripped
Potash solution

CCO2
CH2S
CHCN

213%
6%
65% (low conc.)

Highly stripped
Potash solution

CCO2
CH2S
CHCN

219%
219%
113% (low conc.)

COG H2S gas exit

29%
1%
23%

253.8% (low conc.)

solution which leads to a more selective absorption of H2S

in the process due to the lower concentrations of OH- and
thus lower CO2 reaction and absorption rates in the lower
concentrated solution. The ow rate of the normal-stripped
solution is increased which is responsible for the bulk
removal of H2S. In contrary, the ow of the highly-stripped
solution is decreased. The resulting high ratio of stripping
steam to liquid leads to a efcient use of reboiler duty and
a high regeneration efciency for the highly-stripped solution
in the bottom of the stripper. The highly-stripped solution is
then used for ne removal of H2S in the top of the absorber
to met off-gas specications.

RESULTS
For the design and the optimization of the VACASULFwprocess, a selective absorption and desorption-process, a
new model has been presented. The model was successfully
validated by vapour liquid equilibrium data and reaction
kinetics from the literature and by the conducted eight
desorption experiments and eight absorption experiments in
the packed tower. The developed experimental procedure
included redundant measurements and a data reconciliation
method to improve the accuracy of the measurement data
and also automatically detected gross errors. The model
uses a thermodynamically consistent approach for both the
chemical and phase equilibria as well as the reaction kinetics.
For the rst time, it was shown that the Bronsted Bjerrum
equation is able to reproduce the non-ideality in the liquid
phase regarding the reaction kinetics for the formation of
bicarbonate using a modied Pitzer approach.

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86

THIELE et al.

Figure 16. Optimization environment with an evolutionary algorithm.

NOMENCLATURE
ai
aj
E
J
k
K
L
mi
P
V
xi
yi

Figure 17. Optimization using evolutionary strategies.

In addition, the model was used in the commercially

available owsheet simulator CHEMCAD as a User Added
Module to simulate the entire VACASULFw process. The predicted values compare well with the industrial data. It is now
being used in industrial practice for the design of the individual units and the overall process and can also be utilized
online for model predictive control. Thus, the project allowed
for the rst time the simulation of the entire process (VACASULFw) with recycles using rigorous models and its
application in industrial practice.
Furthermore, the industrial process was systematically
optimized regarding annual costs using an evolutionary strategy. This resulted in a decrease of 30% in operating costs still
complying with the restrictions for the gas outlet concentration. For a new process the heights of the absorber and
stripper were signicantly reduced resulting also in a
decrease in investment costs.

activity of component I
effective interfacial area for segment j, m2 m23
enhancement factor
mass transfer rate, mol s21
reaction velocity constant, 1 s21
equilibrium constant
liquid molar ow, mol h21
molality of component I, mol kg21
pressure, Pa
vapour molar ow, mol h21
mole fraction of component i in liquid
mole fraction of component i in vapour

Greek symbols
1
standard error
gi
activity coefcient of component I
stoichiometric coefcient of component i in reaction j
ni,j
r
density, kg m23

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ACKNOWLEDGEMENTS
The support provided by VDKF e.V. and Chemstations Inc. is
gratefully acknowledged, as well as founding by Deutsche
Forschungsgemeinschaft for the partner project DFG LI806/4-3
that partially supported this work. The work presented in this paper
has been conducted during the previous position of Robin Thiele at
the TU Berlin. Statements and opinions presented in this paper are
not done in the name of BASF AG.
The manuscript was received 11 July 2006 and accepted for
publication after revision 24 October 2006.

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