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Simulation of hydrogen sulphide absorption in


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Article in Environmental Technology December 2014
DOI: 10.1080/09593330.2014.931470 Source: PubMed

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Environmental Technology
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Simulation of hydrogen sulphide absorption in alkaline


solution using a packed column
abc

Mohamed Azizi

ab

, Pierre-Franois Biard , Annabelle Couvert

ab

& Mohamed Ben Amor

cole Nationale Suprieure de Chimie de Rennes, CNRS, UMR 6226, 11 alle de Beaulieu,
CS 50837, 35708 Rennes Cedex 7, France
b

Universit Europenne de Bretagne, 5 boulevard Lannec, 35000 Rennes, France

Laboratoire de Traitement des Eaux Naturelles, Centre des Recherches et Technologies des
eaux, BP 273 Soliman 8020, Tunisia
Accepted author version posted online: 20 Jun 2014.Published online: 03 Jul 2014.

To cite this article: Mohamed Azizi, Pierre-Franois Biard, Annabelle Couvert & Mohamed Ben Amor (2014): Simulation
of hydrogen sulphide absorption in alkaline solution using a packed column, Environmental Technology, DOI:
10.1080/09593330.2014.931470
To link to this article: http://dx.doi.org/10.1080/09593330.2014.931470

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Environmental Technology, 2014


http://dx.doi.org/10.1080/09593330.2014.931470

Simulation of hydrogen sulphide absorption in alkaline solution using a packed column


Mohamed Azizia,b,c , Pierre-Franois Biarda,b , Annabelle Couverta,b and Mohamed Ben Amorc
a cole

Nationale Suprieure de Chimie de Rennes, CNRS, UMR 6226, 11 alle de Beaulieu, CS 50837, 35708 Rennes Cedex 7, France;
Europenne de Bretagne, 5 boulevard Lannec, 35000 Rennes, France; c Laboratoire de Traitement des Eaux Naturelles,
Centre des Recherches et Technologies des eaux, BP 273 Soliman 8020, Tunisia

b Universit

Downloaded by [University of Rennes 1], [Pierre-Francois BIARD] at 00:50 15 July 2014

(Received 27 February 2014; nal version received 1 June 2014 )


In this work, a simulation tool was developed for hydrogen sulphide (H2 S) removal in an alkaline solution in packed columns
working at countercurrent. Modelling takes into account the mass-transfer enhancement due to the reversible reactions

between H2 S and the alkaline species (CO2


3 , HCO3 and HO ) in the liquid lm. Many parameters can be controlled by the
user such as the gas and liquid inlet H2 S concentrations, the gas and liquid ow rates, the scrubbing liquid pH, the desired
H2 S removal eciency, the temperature, the alkalinity, etc. Since the inuence of the hydrodynamic and mass-transfer
performances in a packed column is well known, the numerical resolutions performed were dedicated to the study of the
inuence of the chemical conditions (through the pH and the alkalinity), the temperature and the liquid-to-gas mass ow rate
ratio (L/G). A packed column of 3 m equipped with a given random packing material working at countercurrent and steady
state has been modelled. The results show that the H2 S removal eciency increases with the L/G, the pH, the alkalinity
and more surprisingly with the temperature. Alkalinity has a very signicant eect on the removal eciency through the
mass-transfer enhancement and buering eect, which limits pH decreasing due to H2 S absorption. This numerical resolution
provides a tool for designers and researchers involved in H2 S treatment to understand deeper the process and optimize their
processes.
Keywords: hydrogen sulphide; mass-transfer; absorption; alkaline solution; packed column

Nomenclature
A
absorption rate (dimensionless)
Acolumn
column section (m2 )
ao
specic gasliquid interfacial area (m2 m3 )
Ca
H2 S concentration at the interface (mol m3 )
CG
H2 S concentration in the gas phase (mol m3 )
CL
H2 S concentration in the liquid phase
(mol m3 )
CT
H2 S + HS concentration in the liquid phase
(mol m3 )
DG
molecular diusion coecient of H2 S in the
gas phase (m2 s1 )
Di
diusion coecient of any compound i
(m2 s1 )
DL
molecular diusion coecient of H2 S in the
liquid phase (m2 s1 )
dp
particle size (m)
E
enhancement factor
G
gas mass ow rate (kg s1 )
Ga
Galilei number (dimensionless)
g
gravitational acceleration constant
(9.81 m s2 )
H
Henrys law constant of H2 S in water
(dimensionless)
Corresponding

author. Email: pierre-francois.biard@ensc-rennes.fr

2014 Taylor & Francis

Hcolumn
KL ao
k
L
L/G
Lw
M
pKa
pKwater
P
Q
Re
E
R
Sc
Sp
T
UFlood
U
We
Zi

total column height (m)


overall volumetric liquid-side
mass-transfer coecient (s1 )
local mass-transfer coecient
(m s1 )
liquid mass ow rate (kg s1 )
gas-to-liquid mass ow rate ratio
(dimensionless)
wetting rate (m2 s1 )
molar mass (kg mol1 )
acid dissociation constant
water dissociation constant
pressure (Pa)
volume ow rate (m3 s1 )
Reynolds number (dimensionless)
removal eciency
gas constant (8.314 J mol1 K1 )
Schmidt number (dimensionless)
packing surface area (m2 m3 )
temperature (K)
ood velocity (m s1 )
supercial velocity (m s1 )
Weber number (dimensionless)
height of stage i (m)

M. Azizi et al.

Downloaded by [University of Rennes 1], [Pierre-Francois BIARD] at 00:50 15 July 2014

Greek letters

, , and

dynamic viscosity (Pa s)


surface tension (N m1 )
density (kg m3 )
void ratio
advancements of the reactions 14,
respectively
Superscripts and subscripts
G
gas phase
in
inlet
i
stage i
L
liquid phase
o
outlet
p
particle (packing material)
*
gasliquid interface

1. Introduction
Hydrogen sulphide (H2 S) is recognized as a very toxic
gas.[13] Yet, there are few data on the sources and amounts
of H2 S emitted in the atmosphere. It is estimated that more
than 100 million tons would be transferred to the atmosphere each year.[1] Its formation often results from the
bacterial breakdown of organic matter in the absence of
oxygen, such as in swamps and sewers. This process is commonly known as anaerobic digestion.[4] These emissions
are either anthropogenic or natural.[1,5,6] H2 S is considered as a broad-spectrum poison, meaning that it can poison
several systems in the body especially the nervous system.
H2 S has a low odour threshold and needs to be treated before
emission in the atmosphere.[7]
Activated carbon adsorption, chemical scrubbing, incineration and bioltration are the main technologies used for
odour treatment [8] and many dierent chemical pollutants
such as volatile organic compounds,[9,10] radioactive elements and heavy metals.[11,12] H2 S can be reduced or
removed using all these industrial processes although bioltration and chemical scrubbing are the most encountered
processes.[1316]
Despite tray columns could be used, packed columns
are the main gasliquid contactors used for H2 S removal
by chemical scrubbing.[17] A packed column consists of a
cylindrical tower containing a packing material (usually in
plastic, steel or ceramic) dedicated to gasliquid (or liquid
liquid) mass transfer. The scrubbing solution is pumped into
the top of the tower, and blowers are used to introduce the
polluted gas at countercurrent through the bottom of the
tower. Hydrodynamics and mass-transfer characteristics of
such packed columns are well documented.[18,19]
The occurrence of a chemical reaction in the liquid lm
in the vicinity of the gasliquid interface can increase the
mass-transfer rate compared with it without reaction.[18,
2022] This eect can be quantied by the enhancement
factor E. The prediction of enhancement factors for various classes of reaction is quite complex and requires the
knowledge of the reaction path and rate. In addition, the

enhancement factor depends on many parameters: nature


(irreversible or reversible), kinetics and stoichiometry of
the reaction, reagents and products diusion coecients
and concentrations.[23] In 2013, Biard and Couvert demonstrated that the enhancement factor reaches large values at
appropriated pH for acid gas transfer in alkaline solution
and that the mass-transfer resistance in the liquid lm can
be reduced.
When H2 S is absorbed in a basic solution, it can react
directly with hydroxyl ion and with water by a proton
transfer reaction:
H2 S + HO  HS + H2 O

H2 S + H2 O  HS + H3 O

(1)
(2)

This enables to improve the mass-transfer driving force


by decreasing the liquid bulk concentration (i.e increasing
the concentration gradient). Moreover, these reactions are
very rapid and can enhance the mass-transfer rate. They
have been considered as instantaneous by several authors
to simplify the enhancement factor determination.[24,25]
However, other authors consider that the reaction should
not be considered as instantaneous compared with the mass
transfer except for a few specic cases.[23]
Salts can be added or naturally present in the scrubbing
liquid, including sodium and potassium carbonate, phosphate, borate, arsenite and phenolate, as well as salts of weak
organic acids. They enable to buer the solution at a pH in
the range of 911 to increase H2 S apparent solubility and
enhance the absorption of H2 S.[23] Alkaline salt absorption
systems can be improved using an oxidant.[2631] The carbonate system is the main buer of the scrubbing solution
and can also react with H2 S in the liquid lm and enhance
its mass-transfer rate through the following reactions [23]:

H2 S + HCO
3  HS + H2 CO3

(3)

H2 S + CO2
3  HS + HCO3

(4)

Up to now, the design of packed column used for H2 S


removal at alkaline pH is largely based on eld experience,
trying to respect a given contact time of approximately 1 s.
In this manner, the physics and chemistry of this operation
are not well understood and not optimized (particularly, the
inuence of the temperature and alkalinity). To describe
the process at given operating conditions, the model used
should take into account the mass-transfer performances of
the packed column, the kinetics of the various acidbase
reactions (to account for the mass transfer enhancement

factor) and the pH and species (H2 S, HS , CO2


3 , HCO3 )
concentrations evolution along the column. A few studies
are focused on acid or basic species absorption simulations
in caustic solutions.[32] Brettschneider et al. [32] developed a pertinent simulation for simultaneous absorption of
NH3 , CO2 and H2 S in solution. However, they considered

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Environmental Technology
the acidbase reactions as irreversible for enhancement factor calculation and the inuence of the dierent operating
conditions was not particularly assessed.
Therefore, the objective of this study is to simulate H2 S
scrubbing in packed tower in water in alkaline conditions
(controlled pH and alkalinity) and at steady state. No chemical oxidants such as sodium hypochlorite are added. The
two main goals are to provide a tool for designers and to
understand deeper the process to be able to optimize it. The
simulations performed were planned to assess the inuence
of the scrubbing liquid pH, the temperature, the gas-toliquid mass ow rates ratio (L/G) and alkalinity (HCO
3
and CO2
3 ). A packed column of 3 m equipped with a given
random packing material has been selected.

2.

Modelling procedure

2.1. Principle
The simulation is written in Visual Basic for Applications
(VBA) programming language. The simulation enables the
determination of the height and of the diameter of the column for a given removal eciency. The program works in
several steps (Figure 1): the rst is to select the physical
and chemical operating conditions (QG , L/G, UG /UFlood ,
CG,in , CT = CL + [HS ], carbonate species concentration,
temperature (T ), pressure (P), the inlet pH (pHin ) and
the desired removal eciency (E)). The second step is
to select a commercial random packing whose characteristics are known (dp , p , Sp , and F). Then, before
running the numerical resolution, the program calculates
the various physico-chemical constants (water and acid dissociation constants, diusion coecients, etc.) and hydrodynamic parameters required for the determination of the
column height and diameter using classical correlations
used for random packed columns (Lw , ao , kG , kL , UL , UG ,
UFlood , etc.). The temperature inuence on the equilibrium constants, gas and liquid diusion coecients of H2 S
and the reactive solutes,[33] densities, H2 S Henrys law
constant,[34] surface tensions and viscosities is taken into
account (see Tables A.1 and A.2 in Appendix). Finally, after
running the numerical resolution, the software displays the
main features of the column design: the height and the diameter of the column, the pressure drop (not considered in this
article) and the outlet concentration of H2 S in the liquid
phase.
The process is considered as isothermal since for a
treated concentration lower than a few g Nm3 , which is
rarely the case for H2 S treatment, the enthalpy of reactions
are not enough to increase signicantly the temperature of
the scrubbing liquid.[23]

since they are constant along the column. It requires to


determine previously the diameter of the column. This
determination is based on the calculation of the ood
velocity (UFlood ) in the selected random packing material
according to the following set of equations [18]:


L 0.5
g
UFlood = Y
F
G

0.25

Y = exp(4X )

L G

if 0.02 X = G L 4,
with

0.286

)
or Y = 0.684 exp (3.61X

L G

10.
if 4 X =
G L

Usually, for a random packing, a gas supercial velocity


(UG ) equals to 70% of the ood velocity (UFlood ) is selected,
but the operator has the opportunity of modifying this percentage. Once UG is xed, the diameter of the column is
simply deduced from the gas ow rate (QG ). Then, from
the desired L/G ratio, the liquid supercial velocity (UL ) is
calculated. One can note that at a given temperature, for a
given liquid and gas phases, the diameter only depends on
the physical properties of the selected packing material.
The determination of the gas and liquid supercial
velocities enables the determination of the gasliquid interfacial area (ao in m2 m3 ) and the two local mass-transfer
coecients (kL and kG in m s1 ) through the well-known
correlations of Onda et al. [35], cited by Roustan [18]:

a = Sp 1 exp 1.45
o

Ga

0.05

P
L

0.75

We

(SP dP )0.35


0.2

DG
1/3
(SP dP )1.7 Re0.7
G ScG
dP


L g 1/3
kL = 0.0051
(SP dP )0.27
L
 o 2/3
a
2/3

ReL Sc0.5
L
SP

kG = 5.23

(6)
(7)

(8)

The Galilei and the Weber dimensionless numbers were


used to describe uid lm ow in the column:
Ga =

2.2. Hydrodynamic parameters


The mass-transfer and hydrodynamic parameters (kL , kG
and ao ) are calculated before the numerical resolution starts

(5)

We =

g dp3 L2
2L
dp L2
L L A2column

(9)
(10)

M. Azizi et al.
The wetting rate (m2 s1 ) has a signicant eect on the
column performance and, therefore, the gasliquid mass
transfer:
L
Lw =
(15)
Sp L Acolumn

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This value must be between 2 105 and 2 104 m2 s1


to ensure a continuous lm of liquid on the surface of
the packing.[18,19] In this software, before the numerical
resolution starts, the user is advised to increase the liquid ow rate (through L/G ratio) if Lw < 2 105 m2 s1 ,
and decrease it if Lw > 2 104 m2 s1 or to change the
packing material used.
2.3. Numerical resolution procedure
After the determination of ao , kL and kG (Section 2.2), the
outlet concentration of H2 S in the gas phase is deduced from
the desired removal eciency (E):
CG,o = CG,in (1 E)

(16)

Then, the mass balance is written assuming that the gas and
liquid ow rates are constant along the column and enables
to determine CT,o the total sulphide concentration in the
liquid phase at the outlet (bottom of the column):
QG (CG,in CG,o ) = QL (CT,o CT,in )

(17)

Following the procedure presented later (Section 2.5), the


outlet pH is nally determined.
The numerical resolution starts after that from the bottom of the column. To achieve it, the column was discretized
into several stages of height Zi (Figure 2). This value should
be low (Zi = 0.01 or 0.05 m; Figure 1) to assume that the
liquid is perfectly mixed within a stage.
In each stage, the overall liquid-phase mass-transfer
coecients (KL ao ) is calculated knowing kL , kG , ao
(Section 2.2) and the enhancement factor:
1
1
1
=
+
KL a o
EkL ao
HkG ao

(18)

The Reynolds and the Schmidt dimensionless numbers in


the liquid phase or in the gas phase are:

The enhancement factor must be calculated in each stage


knowing the pH and the sulphide and carbonate concentrations, which is described in Section 2.4.
Using the mass-transfer rate equation and the mass balance for a perfectly mixed liquid phase and a gas plug-ow,
one can write [36]

UL dp L
L
UG dp G
ReG =
G
L
ScL =
DL L
G
ScG =
DG G

QG (CG,i+1 CG,i ) = KL ao Acolumn Zi


 


CG,i
CG,i+1
CL,i
CL,i
H
H

C
G,i+1
CL,i

H
ln

CG,i+1
CL,i
H
(19)

Figure 1.
software.

Numerical resolution procedure implemented in the

ReL =

(11)
(12)
(13)
(14)

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Environmental Technology

Figure 2.

Discretization of the column.

CT,i is the total sulphide concentration, which is deduced in


each stage from the mass balance:
CT,i =

QG
(CG,i+1 CG,i ) + CT,i1
QL

(20)

The H2 S liquid concentration (CL,i ) in each stage is deduced


from the total sulphide concentration (CT,i ), the H2 S acid
dissociation constant and the pH:
CL,i =

CT,i
1 + 10pHi pKaH2 S

(21)

Equation (19) can be rewritten to calculate the gas concentration at the inlet of the stage i (CG,i+1 ):

CG,i+1

CG,i (exp(A + 1) 1) + A
H CL,i1 (1 exp B)
=
A 1 + exp B

2.4.

Enhancement factor (E) and gasliquid interface


concentration (Ca )
To calculate the enhancement factor due to the various acid
base reactions in the liquid lm at each stage, the liquid
interface concentration must be previously calculated from
the following equation [23]:

Ca,i
=

(22)

A (absorption rate), A (modied absorption rate to account


for sulphide equilibrium) and B are equal to
QL
H QG

Step by step, CG,i+1 is calculated until it reaches the outlet concentration (CG,o ), i.e. the top of the column. The
total column height is the number of stage multiplied by the
height of a stage (Zi ). In each stage, the enhancement factor
is calculated knowing the liquid composition and its pH.

kG (CG,i HCL,i )
+ CL,i
(HkG + Ei kL )

(26)

If we assume that the reversible acidbase reactions are


instantaneous compared with mass transfer, the enhancement factor E can be calculated:

(23)

E = EHO + EH2 O + ECO2


+ EHCO3 3
3

A = A(1 + 10pHi pKaH2 S )

(24)

KL ao Acolumn Zi
A QL

(25)

Details for the calculations of E are given by Biard and


Couvert [23] and are summarized in Appendix (Table A.3).

To initialize the calculation, Ca,1


and E1 in the rst
stage (bottom of the column) are calculated, thanks to the

A=

B=

(27)

M. Azizi et al.
Table 1.

Synthesis of the dierent equations used to determine the pH evolution.

Inlet concentrations
[OH ]in = 10pHin pKwater
[H3

O+ ]

in

[H2 S]in =


CO2
3


in

10pHin
CT , in

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[H2 CO3 ]in =

Equations

(28)

[OH ]o = 10pHo pKwater

(33)

[H3

pKa1 pHin

+ 10
TAC

pKa1 pKa2 2pHin

1 + 10pKa1 pHin + 10pKa2 pHin

(31)
(32)

O+ ]

[H2 S]o =

(30)
TAC

1 + 10

Outlet concentrations

(29)

1 + 10pHin pKa H2 S
=

Equations

CO2
3

10pHo

(34)

CT,o
1 + 10

pHo pKaH

TAC

1 + 10pKa1 pHo + 10pKa1 pKa2 2pHo


TAC
[H2 CO3 ]o =
pKa1 pHo
1 + 10
+ 10pKa2 pHo
o

(35)

2S

(36)
(37)

2
Note: pKa1 and pKa2 are, respectively, the acid dissociation constants of H2 CO3 /HCO
3 and HCO3 /CO3 .

Figure 3.

Numerical resolution procedure for pH determination.

outlet pH (see Section 2.5) and the gas outlet concentration (determined with Equation (16)). This determination
enables to check the mass-transfer driving force Ca CL,o
at the bottom of the column for the desired removal eciency. This dierence depends signicantly on the outlet
pH, which is calculated through the procedure presented
later (Section 2.5) and on the mass balance. If this dierence is negative, it means that a too high removal eciency
has been selected by the user for a given L/G ratio. Therefore, the software warns the user that he needs to decrease
the removal eciency or increase the initial pH or L/G ratio
to improve the absorption capacity of the scrubbing liquid.

the column, especially for low L/G ratio and/or high inlet
H2 S concentration.
We can consider that in the liquid bulk, all the acidic and
basic species are in equilibrium (which is not necessarily the
case in the liquid lm [23]). Equations (28)(37) relative to
these equilibriums are synthesized in Table 1. In each stage
(or in the whole column as well), the transfer of a known
amount of H2 S leads to an equilibrium displacement. The
mass balance linked to this displacement can be written as
CT,o
CT,in
= [H2 S]transfered +
1 + 10pHo pKaH2 S
1 + 10pHin pKaH2 S

2.5. pH modelling
One of the main features of the developed numerical resolution is to simulate the pH prole along the column. Indeed,
due to the acid characteristics of H2 S, the pH is expected
to decrease signicantly between the top and the bottom of

(38)

, , and are, respectively, the advancements of the


reactions 14. From Equation (38), it is possible to determine pHo using the numerical resolution whose procedure
is presented in Figure 3. This procedure is also used and
adapted to determine the pH evolution along the column.

Environmental Technology
Synthesis of the dierent parameters investigated.

Packing characteristics
Commercial name
Particle size
Specic surface area
Packing factor
Bed density of particle

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Material characteristics
Packing material
Surface tension
Liquidgas parameters
Gas ow rate
UG /UFlood
Pressure
Column height
Temperature
Inlet pH (pHin )
Gas inlet concentration (H2 S)
Liquid-to-gas mass ow rate ratio (L/G)
2
[HCO
3 ] + [CO3 ]

100
90

Plastic Pall-Ring
50 103 m
102 m2 m3
82 m2 m3
68 kg m3
PVC
0.04 N m1

H2S removal efficiency (%)

Table 2.

10, 000 m3 h1
0.70
1.013 bar
3m
293.15 K
10
20 mg m3
3
100 mgCO2 L1

3. Results and discussion


The eect of dierent parameters such as the inlet pH
solution, the temperature, the L/G ratio and the carbonate species concentration on the H2 S absorption eciency
has been investigated. A column height of 3 m has been
selected, and the numerical resolution is used to determine the corresponding removal eciency with the selected
operating conditions. Only one parameter was changed
during each simulation compared with the central values
selected, which are synthesized in Table 2. The results
of the numerical resolution has been compared with the
experimental results of Chen et al. [27] and shows a good
agreement even if an exact comparison was not possible
because the alkalinity used in their study was unknown.
3.1. pH inuence
Tests were conducted to determine the inuence of the pH
on the H2 S removal eciency. Naturally and in agreement
with the literature, the removal eciency increases with the
pH.[27,31] The results of these simulations are presented in
Figure 4. It emphasizes that the control of the pH remains
essential for process designers and operators, especially
when the pH is low (9). In this case, the enhancement
factor is limited (E from approximately 20100 depending on the pH and the stage of the column) and the pH
decreases along the column (approximately an outlet pH of
8.7 is reached in these simulations). In this case, H2 S absorption becomes almost negligible in a signicant part of the
column (a low pH limits the H2 S dissociation in HS and
then limits the mass-transfer driving force). It means that a
signicant part of the column is not active for H2 S absorption. To limit this pH decreasing, operators can select larger
values of the L/G ratio (a compromise has nevertheless to
be nd regarding the pressure drop) or can work with an

80
70
60
Eff (L/G=3)

50

Eff (L/G=1)

40

Eff (L/G=5)

30
20
10
9

9,5

10

10,5

11

pH

Figure 4. Inuence of the pH on the H2 S removal eciency for


dierent L/G ratios (conditions of Table 2).

higher alkalinity to buer the pH (section 3.4). At large pH,


the L/G ratio has a lower inuence because the enhancement factor is so large that the mass-transfer resistance is
located mainly in the gas phase and the pH decreasing over
the column is limited (for pHin = 11 and L/G = 3, pHo
equals to 10.93).
3.2. Temperature inuence
The temperature inuence has been evaluated from 5 to
50 C. As shown in Figure 5, for a given pH value (pH
10) if the temperature is increased, the H2 S removal eciency increases for a xed L/G ratio. This result was not
expected since, usually, designers consider that the solubility decreases with the temperature (H = 0.245 at 5 C
and 0.588 at 50 C). It emphasizes that the solubility is not
the most inuent parameter, at least at high pH. Indeed,
in this case, the enhancement factor is quite large and the
mass-transfer resistance is mainly located in the gas phase.
Since the mass-transfer performance increases with the temperature, the removal eciency increases. Indeed, kG drops
from 5.9 102 m s1 at 50 C to 5.1 102 m s1 at 5 C.
Additionally, we note that the buering eect of the solution
is better at high temperature (i.e. the pH decreasing along
the column is reduced). Finally, interesting removal eciencies can be obtained at L/G ratios up to 5 for a limited
pH of 10. This result is quite interesting because working at
pH 10 limits very signicantly the parasite CO2 absorption
and by the way the NaOH consumption of the process.
3.3.

Gas-to-liquid mass ow rate ratio inuence (L/G)

The L/G ratio is an important parameter in contactors


design. Naturally and in agreement with the literature, the
removal eciency increases with the L/G ratio.[27,31]
High L/G ratio improves the absorption rate, this is to say
the absorption capacity of the process, and limits the pH

M. Azizi et al.

95

90

85

80
75

Eff (L/G=1)
Eff (L/G=3)
Eff (L/G=5)

70
65

80

pH=9
pH=10
pH=11

70
60
50
40
30
20

60

10

55

0
0

50
5

15

25
35
Temperature (C)

45

91
86

81
T=5C
T=25C
T=45C

71
66
61

56
51
1

1,5

2,5

100

Figure 7. Inuence of the alkalinity on the H2 S removal eciency for dierent pH (conditions of Table 2).

(at pHin 10, the outlet pH is equal to 8.78 without any carbonate species in solution, whereas it is equal to 9.86 for a
carbonate species concentration of 100 mgCO2 L1 ). At pH
11, the inuence of the alkalinity is not signicant anymore.
In this case, the enhancement factor is so large that all the
resistance is located in the gas phase and the pH decreasing
remains low. Therefore, the mass-transfer eciency is not
inuenced by the chemical conditions anymore.

96

76

20
40
60
80
1
Alkalinity[HCO3] + [CO2
3 ] (mgCO L )
2

Figure 5. Inuence of the temperature on the H2 S removal


eciency for dierent L/G ratios (conditions of Table 2).

H2S removal efficiency (%)

Downloaded by [University of Rennes 1], [Pierre-Francois BIARD] at 00:50 15 July 2014

90

H2S removal efficiency (%)

100

H2S removal efficiency (%)

100

3,5

L/G

Figure 6. Inuence of the L/G ratio on the H2 S removal


eciency for dierent temperature (conditions of Table 2).

decreasing of the scrubbing solution. However, a high L/G


ratio increases the pressure drop and limits the ood velocity. The results show that for a L/G ratio higher than 3,
this parameter inuence stays limited (Figure 6). Therefore, this value that is currently used in chemical scrubbing
is justied.[31]
3.4. Alkalinity inuence
Dierent types of alkaline solutions such as potassium carbonate and/or sodium carbonate solution have been used
for H2 S removal.[37,38] We can note that the presence
2
of such species (HCO
3 and CO3 ) in the process water
enhances the gasliquid mass transfer.[23] This eect is
clearly demonstrated in Figure 7. Another interesting aspect
linked to the use of high alkalinity is the buer power of such
solutions, which limits the pH decreasing along the column

4. Conclusion
A mathematical model has been developed to describe H2 S
absorption into alkaline solutions. The simulation results
show good agreement with the experimental results of Chen
et al.[27] To design the column, several parameters must
be taken into account (temperature, inlet pH, carbonate
species concentration, L/G ratio, etc.). The H2 S removal
eciency increases with the pH, the temperature, the L/G
ratio and total alkalinity of solution. This tool enables to
understand deeper the chemical and physical phenomena
involved during H2 S absorption in alkaline solutions and
provide guidelines for designers. The pH can be limited to
moderate values (10) within the condition that a minimal
L/G ratio of 3 is used. A pH of 10 is suitable to avoid
CO2 absorption and, therefore, caustic reagent overconsumption. A high alkalinity is a very good lever to improve
H2 S removal eciency. Contrary to the expectations, the
temperature has a positive eect to improve the removal
eciency at pH 10.
References
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lhydrogne sulfur: propos de deux cas. Toxicologie.
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hydrogen sulde as an endogenous smooth muscle relaxant in synergy with nitric oxide. Biochem Biophys Res
Commun. 1997;237:527531.

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Environmental Technology
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[4] Le Cloirec P. Introduction aux traitements de lair. Tech
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[5] Ouali S, Chader S, Belhamel M, Benziada M. The exploitation of hydrogen sulde for hydrogen production in geothermal areas. Int J Hydrogen Energy. 2011;36:41034109.
[6] Robinson E, Robbins RC. Gaseous sulfur pollutants from
urban and natural source. J Air Pollut Contr Assoc.
2012;20:233235.
[7] Rognon C, Pourtier L. Mesurer les odeurs. Tech lingnieur.
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[8] Balsamo M, Budinova T, Erto A, Lancia A, Petrova B, Petrov
N, Tsyntsarski B. CO2 adsorption onto synthetic activated
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[10] Park B, Hwang G, Haama S, Lee C, Ahna IS, Lee K. Absorption of a volatile organic compound by a jet loop reactor with
circulation of a surfactant solution: performance evaluation.
J Hazard Mater. 2008;153:735741.
[11] Groudev SN, Bratcova SG, Komnitsas K. Treatment of
water with radioactive elements and heavy metals by
means of laboratory passive system. Mineral Eng. 1999;12:
261270.
[12] Volesky B, Holm ZR. Biosorption of heavy metals. Biotechnol Prog. 1995;11:235250.
[13] Xue M, Chitrakar R, Sakane K, Ooi K. Screening of adsorbents for removal of H2S at room temperature. Green Chem.
2003;5:529534.
[14] Nguyen-Thanh D, Bandosz TJ. Activated carbons with metal
containing bentonite binders as adsorbents of hydrogen
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[15] Czernichowski. Plasmas pour la destruction de lH2 S et des
mercaptans. Oil Gas Sci Technol. 1999;54:337355.
[16] Busca G, Chiara P. Technologies for the abatement of sulphide compounds from gaseous streams: a comparative
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[17] Martin G, Laort P. Odeurs et dsodorisation dans
lenvironnement. Paris: Tec & Doc - Lavoisier; 1991.
[18] Roustan M. Transferts gaz-liquide dans les procds de
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Doc - Lavoisier; 2003.
[19] Perry RH, Green DW. Perrys chemical engineers handbook.
7th ed. New-York: McGraw-Hill; 1997.
[20] Danckwerts PV. Gasliquid reactions. New-York: McGrawHill; 1970.
[21] Coulson JM, Richardson JF. Particle technology and separation processes chemical engineering. Oxford: Pergamon
Press; 1990.
[22] Roizard C, Wild G, Charpentier JC. Absorption avec raction
chimique. Tech lingnieur. 1997; J1079:121.

[23] Biard PF, Couvert A. Overview of mass-transfer enhancement factor determination for acidic and basic compounds
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[24] Danckwerts PV. Gas absorption with instantaneous reaction.
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[25] Astarita G, Savage DW. Gas absorption and desorption with
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[26] Bonnin C. Les sources de nuisances olfactives dans les
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traitement par lavage leau chlore en milieu basique [PhD
Thesis]. Rennes: Universit de Rennes I; 1991.
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Requieme B. Treatment of odorous sulphur compounds by
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[32] Brettschneider O, Thiele R, Faber R, Thielert H, Wozny G.
Experimental investigation and simulation of the chemical
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[36] Vilmain JB, Courousse V, Biard PF, Azizi M, Couvert A.
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[39] Zeebe RE. On the molecular diusion coecients of dis2
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10

M. Azizi et al.

Appendix
Table A.1.

Equations used for the dierent physico-chemical properties determination.

Downloaded by [University of Rennes 1], [Pierre-Francois BIARD] at 00:50 15 July 2014

Parameters

Equations

References

105
29
P
8.314 1000
273.15 + T

G (kg m3 )

G =

G (Pa s)

G = 0.01827

L (Pa s)

L =

L (N m1 )

L = 0.07275 (1 0.002 (T 291))

0.555 524.07 + 120


((1.8 T + 32 + 459.67)/524.07)1.5

0.555 (1.8 T + 32 + 459.64) + 120


1000

101.5668+(230.298/(T +273.15146.797))
1000
Mwater / 105 10(4.6543(1435.264)/(T 64.848))
exp((4.51499 647.096)/T + (5.23538 647.096)/(T (1 T /647.096)0.355 )

+4.42126 (T /647.096)0.41 exp(1 T /(647.096)))


8.314 T


12995.4
1
218.482
33.5471 Ln T
pKa H2 S/HS =
2.3
T



9137.258
pKa Hco /CO2 = log exp
18.11192 LnT 0.02245619 T + 116.7371
3
3
T



7726.01
pKa H2 co3 /HCO = log exp
14.50613 LnT 0.0279842 T + 102.2755
3
T

Hdimen =

H
pKa H2 S/HS
pKa Hco /CO2
3

pKa H2 CO3 /HCO


3

[34]
[32]
[18]
[18]

Note: T , temperature (K); P, pressure (bar); Mwater , molar mass of water (kg mol1 ).

Table A.2.

Equations used for the diusion coecients determination.

Parameters
DG (m2 s1 )

Equations
DG =

1.43 107 (273 15 + T )1.75


P (2 29 32/(29 + 32))0.5 (19.70.33 + (22.9 + 2 2.31)0.33 )2

[18]

7.4 1012 (2.26 Meau 1000)0.5 T


(L 1000 35.860.6 )

[18]

DL (m2 s1 )
DHO (m2 s1 )
DH+ (m2 s1 )
DCO2 (m2 s1 )
3

DHCO (m2 s1 )
3

DH2 CO3 (m2 s1 )

DL =
DHO =

References

(96500)2

2 8.314 T 104

1/(50.1 T /(331 103 L )) + 1/(197.6 T (331 103 L ))

8.314 T 104
(96500)2 349.8 T /(331 103 L )
2.1929

T
DCO2 = 5.4468 109
3
210.2646 1
2.3942

T
DHCO = 7.0158 109
3
204.0282 1
1.997

T
DH2 CO3 = 14.3836 109
217.2056 1

DH + =

Note: T , temperature (K); Mwater , molar mass of water (kg mol1 ).

[18]
[18]
[39]
[39]
[39]

Environmental Technology
Table A.3.

Equations used for the enhancement factors determination.

Enhancement
factor Ex

Equations
DHO CHO ,O

EHO = 1 +

EHO

DL DHO /(DHS 10


EH 2 O = 1 +

ECO2

ECO2 = 1 +

Downloaded by [University of Rennes 1], [Pierre-Francois BIARD] at 00:50 15 July 2014

pKwater pK
a

H2 S/HS

)+DL CH 2 S

(DH+ 10(pHo ) + DHS CHS ,o )2 4(1 CH 2 S /CH2 S,o ) (DH+ 10(pHo ) DHS CHS ,o )
(DH+ 10(pHo ) + DHS CHS ,o )

EH 2 O

11

2DL (CH 2 S CH2 S,o )

DHS

(2DL (CH2 S CH2 S,o ))




2


pK

p
K


D
D
aH S/HS
 HCO3
a
/CO3
HCO3
2

HCO
3
CH 2 S CHS ,o

 D CHCO3 , o + D 2 10
HS
CO
3






pKa
pK a
2
H2 S/HS

HCO
/CO
3
3
+ 4 10
C

H2 S

DHCO
3

DHS

EHCO
3

DHCO
3

DHS

EHCO = 1 + 
3

CHCO ,o
3

DHCO
3

DCO2

2
HCO
3 /CO3

pKa H2 S/HS

3
DCO2
3


CHS ,o


pKa

10

CCO2 +

DHCO

CH 2 S

CHS ,o

DHS


2DL CH 2 S CH2 S,o

2




pKa
D
D
pKaH S/HS
H
CO
H
CO

2
3
2
3
H
CO
/HCO

2
2 3
3

CH2 CO3 ,o +
10
CH2 S CHS ,o
DHS
DHCO
3






pKa
pK a
H2 S/HS

H2 CO3 /HCO
3
+ 4 10
C

H2 S

DH2CO3
DH CO
10
2 3 CH2 CO3 ,o
DHS
DHCO
3

pKa

H2 CO3 /HCO
3

DH2 CO3
DH2 CO3
CHCO +
CHS ,o
3

DHS
DHCO
3

pKa

H2 S/HS

CH 2 S CHS ,o