Full Paper

Designing Wet Scrubbers for SO2 Absorption into Fairly

Concentrated Sulfuric Acid Solutions Containing Hydrogen
Peroxide
By Diane Thomas*, Sandrine Colle, and Jacques Vanderschuren

Absorption of SO2, diluted with nitrogen up to concentrations of 500 Pa, was performed at 20 C and 1 atm, with water and
sulfuric acid solutions containing hydrogen peroxide in two different contactors: a packed column and a cable scrubber. The
absorption rate was determined for various SO2 partial pressures, as well as different concentrations of sulfuric acid (up to
40 wt %) and of hydrogen peroxide in the scrubbing liquid. It was found that the SO2 absorption rate increases with the hydrogen
peroxide concentration, and decreases as the acidity of the scrubbing liquid increases. Taking into account hydrodynamic and
mass transfer characteristics of the packing for both scrubbers, a practical enhancement factor depending on the liquid phase
H2SO4 and H2O2 contents, was deduced from semi-continuous tests. As a good concordance was observed between results
determined for both contactors, a single correlation is proposed, allowing the computation of this kinetic factor for quite simple
simulation or design of SO2 scrubbers, provided the gas and liquid phase mass transfer coefficients kGa and kLa are known.

1 Introduction concentration of reactants and pH greater than ±0.3 with first

Sulfur oxides exist to a significant extent in flue gases of
power plants burning fossil fuels, and of some chemical or
metallurgical plants. These oxides react in the atmosphere
forming sulfuric acid, which leads to acid rain. Because of the
lowering of the permissible emission limits, there has been a
rise in interest in new treatment processes for absorbing
gaseous SO2, using various reactants. The most effective wet
processes use alkaline solvents such as sodium or calcium
hydroxides, but absorption then produces liquid or solid
effluents, which must be treated correctly or disposed of, if
they are not marketable.
The aim of this study is to investigate a recovery method
where the abatement of sulfur oxides is carried out with
recycled sulfuric acid solutions containing hydrogen peroxide,
in such a benefical way that the reaction,
SO2 + H2O2 ! H2SO4 (1)
provides a valuable or reusable high strength H2SO4 solution.
While absorption of SO2 into water [1±4] and into NaOH
and Na2SO3 solutions [5,6] is quite well detailed in the
literature, little information is available on scrubbing with
hydrogen peroxide [7,8], especially in the presence of
concentrated sulfuric acid. The solubility of SO2 diminishes
as the sulfuric acid concentration increases, as can be inferred
from published data relative to a wide range of temperatures
and various H2SO4 concentrations, both rather low [9±12] and
high [13±16]. Moreover only a few kinetic results concerning
the conversion in the atmosphere by hydrogen peroxide of gas
phase sulfur species into sulfate aerosol particles, can be found
in the literature [17,18]. Rate laws are reported for low
± total height 0.455 m, packed with 10 mm glass Raschig rings.
[*] Dr. D.Thomas (author to whom correspondence should be addressed,
e-mail: diane.thomas@fpms.ac.be), Dr. S. Colle, Prof. J.Vanderschuren,
Chemical Engineering Department, FacultØ Polytechnique de Mons, Rue
de l'Epargne 56, 7000 Mons, Belgium.
order in both sulfur dioxide (HSO3± ion) and H2O2. The
second order rate constant is found to be a complex function of
the H3O+ concentration. It had to be verified if these data can
be applied to the higher acidic conditions of the desulfuriza-
tion process studied in this work.
A few years ago, Thomas and Vanderschuren thoroughly
studied the reduction of nitrogen oxides through an absorption
process using hydrogen peroxide [19±21]. They found that
nitric acid has a catalytic effect on the absorption performances,
and that the NOx absorption process is zero order with respect
to the hydrogen peroxide concentration. Kinetic parameters
relative to the absorption of the different NOx species were
determined at increasing acidities from tests runs performed in
a small packed column, at 20 C for various NOx partial
pressures up to 500 Pa and different NO-NO2 ratios. There-
fore, the aim of the present study is to investigate, with a quite
similar experimental procedure, the SO2 absorption process in
presence of hydrogen peroxide and finally to determine
kinetics characteristics for the SO2-H2O2-H2SO4 system,
which can be applied to simulation or design of SO2 scrubbers.
2 Experimental
The experimental equipment is illustrated in Fig. 1. It
includes a scrubber (A or B), a liquid supply, a gas supply and a
gas sampling part.
2.1 Contactor A
It consists of a small laboratory column of i.d. 0.045 m and
The details of the equipment used are given in a previous study
(relative to the NOx absorption [19]), but the packing height
had to be reduced due to a faster absorption of SO2.

Chem. Eng. Technol. 26 (2003) 4, Ó 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 0930-7516/03/0404-0497
0930-7516/03/0404-0497 $ 17.50+.50/0
$ 17.50+.50/0 497
 Full Paper
Membrane dryers
UV analyser
Water
TI
Data acquisition
C
O
N
T
A
Thermostated
water
C
T
O
R sulfuric acid solutions of initial concentrations in the range of 0
TI
Scrubbing solution
Magnetic analysis
stirrer
SO2 N2 acid-base iodometric
Figure 1. Experimental apparatus with two different contactors.
2.2 Contactor B
The absorption device is a ring-shaped column made of a
vertical glass tube, with a polypropylene rod which supports the
cables standing in the axis. Distributed with a pitch of 8 mm
along the mid cylindrical surface in the annular space, 12 twisted
polypropylene yarns of 1.7 mm diameter are stretched in
parallel, constituting the packing. Outside and inside diameters
of the annulus are equal to 0.045 and 0.02 m respectively and
the useful height of this micro-contactor is 0.54 m.
In both cases, the absorbent is fed to the top distributing
chamber with a peristaltic pump. The liquid feed temperature
is controlled by means of a heat exchanger operated counter-
currently with water supplied from a thermostatic bath. The
liquid temperature is checked by means of thermometers
placed at both ends of the column. The liquid phase analysis is
made by classical titration of H2SO4 with sodium hydroxide,
and an iodometric method for H2O2.
The gas phase is nitrogen humidified in a saturator, in which
SO2 is added to obtain the desired concentration. The gas flow
rates are metered by rotameters. Sampling of gas simulta-
neously at the input and the output of the column, is
performed continuously through membrane dryers followed
by a two-channel U.V. analyser. Data are collected by a
computer with a scan time interval depending on the test's
duration, allowing the calculation of the absorption rate
A = (pSO2in±pSO2out)/pSO2in.
All experiments reported here are carried out at atmo-
spheric pressure and a temperature of 20 ± 0.5 C1).
The superficial gas velocity was maintained at 0.175 m/s
(gas flowrate: 1 m3/h) for contactor A and 0.41 m/s (flowrate
1.88 m3/h) for contactor B. The liquid flow rate was fixed to
6.67 cm3/s for the packed column, and 33.3 cm3/min/cable for
the cable contactor (total flow rate : 6.67 cm3/s), which is the
nominal value for a cable scrubber.
Preliminary tests of SO2 absorption into water and sulfuric
acid solutions of different concentrations, containing hydro-
± requirement of one mole of H2O2 per mole of SO2 absorbed,
1) List of symbols at the end of the paper.
498 Ó 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
gen peroxide were achieved for various SO2 inlet partial
pressures: 40±500 Pa. For sake of comparison, SO2 absorption
Contactor A : tests were also performed with demineralised water and
Packed
column sodium hydroxide solutions 0.5 M [22].
Semi-continuous tests were performed with total recycle of
the scrubbing solution from a liquid vessel containing 1 l,
perfectly mixed, in a counter-current manner, and continu-
ously with respect to the gas phase. In these experiments,
Contactor B :
Cables-bundle up to 40 % by weight, and containing a large initial
scrubber concentration of hydrogen peroxide (about 1±1.15 mol/L)
become progressively more concentrated in H2SO4 and
depleted in H2O2 in the course of time. These tests were
achieved for a given SO2 partial pressure in the gas at the inlet
of the column close to 400 Pa (see Tab. 1 for details). A scan
period of 15 min (contactor A) or 5 min (contactor B), was
chosen here for the data acquisition.
3 Results and Discussion
It was clearly observed and explained in a previous article
[22] that for water, a rise in hydrogen peroxide concentration
involves increasing fractional absorption of SO2, for the whole
range of SO2 partial pressures investigated ; this is also true for
a constant acidity of the absorbent. On the other hand, for a
given H2O2 content in the liquid phase, an increased H2SO4
concentration results in smaller absorption efficiencies.
Relative to pure water (minimum absorption efficiencies
due to a reaction of SO2 with water which is instantaneous and
reversible [1±4]), and sodium hydroxide solutions (maximum
absorption efficiencies due to a proton transfer reaction
known to be irreversible and instantaneous [5,6]), absorption
performances observed in water-H2SO4±H2O2 mixtures are
intermediate between these two extremes.
It was concluded that the enhancement effect on the mass
transfer, due to the chemical reaction of SO2 with H2O2, is
raised thanks to a higher liquid phase H2O2 content, but
remains always lower than for a sodium hydroxide solution,
whichimpliesthatthe rateof reactionwithH2O2 remainsfinite.
The combined influence of H2O2 and H2SO4 concentrations
on the absorption rate was studied in both contactors through
several semi-continuous tests. A large range of operating
conditions is covered (see Tab. 1): from 0±6.4 M and 0±1.15 M
for cH2SO4 and cH2O2 respectively, the runs being continued up
to the quasi-total depletion of H2O2, with a duration of several
hours.
Typical variations with time of the fraction of SO2 removed
and H2O2 and H2SO4 concentrations are given in Fig. 2(a) and
Fig. 2(b), corresponding to tests nr 3 and 10. From the
measurement of initial and intermediate concentrations in
the liquid and the inlet and outlet SO2 partial pressures in the
gas, the H2SO4 production and the H2O2 consumption are
computed according to mass balances, assuming, due to the
stoechiometry of the oxidation reaction (1), the theoretical
producing one mole of H2SO4.
0930-7516/03/0404-0498 $ 17.50+.50/0 Chem. Eng. Technol. 26 (2003) 4
 Full Paper

Table 1. Operating conditions for semi-continuous tests.

Test nr pSO2in cH2SO4 cH2SO4 cH2O2 Duration Comparison between calculated and experimental
(Pa) initial final initial (min) intermediate concentrations
(mol/L) (mol/L) (mol/L)

cH2SO4 calc. cH2SO4 exp. cH2O2 calc. cH2O2 exp.

(mol/L) (mol/L) (mol/L) (mol/L)

Contactor A

1 362 0 0.852 1.15 520

2 396 1.087 2.127 1.15 465

3 368 2.324 3.368 1.15 560

4 372 5.313 6.347 1.135

Contactor B

5 420 0 0.492 0.488 140 / / 0.017 0.017

6 400 0.494 1.443 0.975 305 1.025 1.012 0.433 0.447

1.411 1.418 0.040 0.035

7 380 1.450 2.446 1.015 305 1.953 1.927 0.505 0.490

2.420 2.378 0.031 0.024

8 390 2.402 3.291 1.020 325 2.874 2.872 0.478 0.467

3.241 3.244 0.055 0.059

9 370 3.354 4.288 1.020 380 3.881 3.926 0.451 0.444

4.166 4.161 0.142 0.143

10 460 4.296 5.261 1.020 345 4.805 4.802 0.486 0.473

5.064 5.012 0.214 0.216

11 400 5.253 6.143 1.025 470 5.609 5.632 0.615 0.605

5.959 5.941 0.213 0.217

1,6 4 As shown in Fig. 2(b), relative to test nr 10 achieved in

c H2SO4 scrubber B, the experimental measurements (points) fit the
1,2 3 computed values (lines) quite well, requiring only small
adjustments.
0,8 c H2O2 2 For all the semi-continuous tests achieved with the cables-
A
bundle scrubber, measured absorption rates versus concen-
tration cH2SO4 are reported in Fig. 3, where lines correspond-
0,4 1
ing to constant H2O2 concentrations are drawn, to show

0 0 90
0 100 200 300 400 500 600
t (min) 80
6 70 70
H 2 SO 4 H2O2
5 60 60
concentration (mol/l)

0,8 M
50
A (%)

4
50 0,6 M
A 0,4 M
40
A (%)

40 0,2 M
3
30 30 0,1 M
test
2 6 7 8 9 10
20 20 5 11
1 H 2O 2 10 10
0 0 0
0 100 200 300 400 0 1 2 3 4 5 6 7
t (min)
c H2SO4 (mol/l)
Figure 2. Typical variations of the SO2 fractional absorption and computed
H2O2 and H2SO4, concentrations (lines) for semi-continuous tests (a) nr 3 Figure 3. Simultaneous effects of hydrogen peroxide and sulphuric acid
(packed column) and (b) nr 10 (cable scrubber). concentrations on the SO2 absorption rate (tests nr 5±10).

Chem. Eng. Technol. 26 (2003) 4, Ó 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 0930-7516/03/0404-0499 $ 17.50+.50/0 499
 Full Paper

clearly the combined influences of both reactant and product 3.5

concentrations.
3 11
10
2.5 9
4 Determination of Kinetic Parameters
2
(Enhancement Factors) H2O2

Experimental absorption results were interpreted to deter-
mine a liquid-phase contribution to the overall height of
transfer unit. The gas-side overall height of transfer unit of the
absorber was first computed from the measured absorption
rate:
HOG ˆ
h
(2)
ln…1 A†
with the assumption that the equilibrium partial pressure of
SO2 over the solution was zero. The liquid-phase contribution
HLR was then obtained by subtracting the part due to the gas-
film resistance:
Gm
HLR ˆ HOG (3)
kG a P S
The gas mass-transfer coefficients kGa were determined
by absorbing SO2 into sodium hydroxide solutions of
concentrations 0.5 M and 3.7 M, this latter having a kinematic
viscosity equivalent to that of a 40 wt.-% H2SO4 solution.
Only a small difference was detected between results for the
two concentrations, and an average value was chosen for
nominal L and G:
mol
kG a ˆ 120:3 for contactor A and
s m3 atm
mol
kG a ˆ 47:4 for scrubber B
s m3 atm
The liquid part HLR of the overall gas height of transfer unit
is obviously a lumped parameter including the physical mass
transfer resistance 1/kLa (kLa being characteristic of the mass
transfer of SO2 in solutions containing H2SO4 and H2O2), the
gas-liquid equilibrium coefficient (Henry's coefficient H) and
the enhancement factor E due to the chemical reaction, all
variables that depend on the liquid phase concentrations
cH2SO4 and cH2O2. The variations of HLR versus cH2SO4 and cH2O2
are presented in Fig. 4 for tests achieved with contactor B.
The following equation can be readily established thanks to
the two-film theory:
H Gm
HLR ˆ (4)
E kL a P S
Due to the large discrepancies concerning the variation of
the Henry's constant H with cH2SO4 [9±16] and the fact that the
liquid-phase mass transfer coefficient kLa was not yet
HLR
8
1.5 0,1 M
1 test 6
7 0,2 M
5 0,4 M
0.5 0,6 M
0,8 M
0
0 1 2 3 4 5 6 7
c H2SO4 (mol/l)
Figure 4. Variation of the liquid part of the height of transfer unit HLR versus
H2SO4 and H2O2 concentrations.
investigated for sulfuric acid solutions, a reference to water
was chosen (superscribed ):
H0 Gm
HLR ˆ 0 (5)
Eprat kL a† P S
The Henry's law constant H0 for the physical dissolution of
SO2 into water can be found in the literature [23,24] to be
0.000707 atm.m3/mol at 20 C.
As to the liquid-phase volumetric mass-transfer coefficients
kLa)0, they were measured by absorbing pure CO2 into water
and corrected with the square root of the ratio of the liquid
diffusivities in water of SO2 and CO2:
kLa)0 = 0.019 s±1 for contactor A and
kLa)0 = 0.0101 s±1 for contactor B.
For the experimental temperature of 20 C, values of the
practical enhancement factor Eprat were then obtained for all
the runs 1±11, including effects of cH2SO4 on solubility and
mass-transfer, and combined influence of H2SO4 and H2O2
concentrations on the reaction kinetics:
Eprat. = 10.492 exp(1.09863 cH2O2±0.43772 cH2SO4) (6)
in the range cH2O2 : 0.1±1 mol/L , cH2SO4 : 0.5±6 mol/L.
This practical enhancement factor is obviously not equal to
the actual enhancement factor E.
It has to be mentioned that gas-phase and liquid-phase
resistance are of the same order of magnitude, which allows
enough precision on HLR and Eprat determinations.
Fig. 5 presents the comparison between practical enhance-
ment values experimentally obtained (points ± diamond-
shaped for contactor A and square for contactor B) and
computed thanks to Eq. (6), from low kinetics (Eprat= 3)
observed for high cH2SO4, to fast kinetics (Eprat=15) obtained
with high cH2O2 and low cH2SO4. A satisfactory agreement can
be noted.

500 Ó 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 0930-7516/03/0404-0500 $ 17.50+.50/0 Chem. Eng. Technol. 26 (2003) 4
 Full Paper

6 experimental study will be required to obtain a reliable

Eprat=3 variation of the solubility of SO2 with cH2SO4. The liquid phase
5 mass transfer coefficient must also be measured for the more
c H2SO4 (mol/l)

4 Eprat=5 viscous sulfuric acid solutions. The final aim of the authors is to
investigate the variation with temperature and the H2SO4
3 Eprat=10 molarity (up to 6±7 M), of the second order kinetic constant
2 for the liquid phase reaction (1).
Eprat=15 Received: July 2, 2002 [CET 1646]
1
0
0 0,2 0,4 0,6 0,8 1 1,2 Symbols used
c H2O2 (mol/l) A [±] absorption rate
Figure 5. Comparison between experimental (points; diamond shaped for a [m±1] specific interfacial area
contactor A and square for contactor B) and computed (lines) practical
cA [mol/L] concentration of component A
enhancement factors.
E [±] enhancement factor
G [m3/s] volumetric gas flow rate
Gm [mol/s] molar gas flow rate
h [m] height of the contactor
5 Conclusion HOG [m] overall gas-phase height of transfer
unit
A typical way to remove acid pollutants like SO2 and NOx is HLR [m] liquid part of the height of transfer
wet treatment, which is a complex physical and chemical unit
absorption process. It is now required to avoid liquid wastes H0 [atm m3/mol] Henry's coefficient of SO2 into water
containing sulfate and nitrate salts in relation to dissolved H [atm m3/mol] Henry's coefficient of SO2 into
sulfur and nitrogen oxides. The presence in the liquid phase of sulfuric acid solutions
an oxidising agent such as hydrogen peroxide makes the kG [mol/m2 s atm] gas-phase mass transfer coefficient
treatment of flue gases feasible, with production of fairly kL [m/s] liquid-phase mass transfer coefficient
concentrated acid solutions, which can be recovered or L [m3/s] liquid flow rate on the cable
recycled in the process. pSO2 [Pa] partial pressure of sulfur dioxide
The present investigation of sulfur dioxide absorption into P [atm] total pressure
H2SO4-H2O2 solutions clearly shows that the absorption S [m2] cross-section of the column
performances increase with the H2O2 concentration, and T [K] temperature
decrease with a rise of the H2SO4 liquid content. t [min] time
It is therefore concluded that a comprehensive description ySO2 [±] mole fraction of SO2
of the absorption process will require a complete knowledge
of the dependence of the rate of SO2 oxidation in the liquid
phase, with the three variables pSO2, cH2O2 and cH2SO4, and also Subscripts
with temperature.
In the present paper, only the contribution of the liquid film in inlet of the column
to the overall height of transfer unit, was computed for a large out outlet of the column
range of operating conditions, and correlated with the liquid
phase H2O2 and H2SO4 contents.
A so-called practical enhancement factor of the liquid- References
phase mass transfer was deduced from semi-continuous tests,
achieved with two very different contactors from an hydro- [1] H. Hikita, S. Asai, H. Nose, AIChE J. 1978, 24 (1), 147
[2] W. Van den Broeke, J. B. Lefers, Chem. Eng. Tech. 1984, 56 (10), 792.
dynamic point of view: a packed column and a cable scrubber. [3] D. A. Pearson, L. A. Lundberg, Chem. Eng. Prog. 1951, 47 (5), 257.
Combined with the Henry coefficient for molecular SO2 in [4] C. S. Chang, G. T. Rochelle, AIChE J. 1981, 27 (2), 292.
water, and the proper gas and liquid phase mass transfer [5] H. Hikita, S. Asai, T. Tsuji, AIChE J. 1977, 23 (4), 538.
[6] M. Schultes, Chem. Eng. Tech. 1998, 21 (1), 201.
characteristics kGa and kLa of the contactor, it can be used [7] H. Soldavini, W. Von Wedel, Info Chimie 1991, 334, 181.
quite simply for simulation and design of SO2 scrubbers, which [8] P. V. Deo, Chem Prot Environ. 1988, 34, 275.
[9] T. Hunger, F. Lapicque, A. Storck, J. Chem. Eng. Data 1990, 35, 453.
will be operated with solutions of H2SO4 containing H2O2. [10] V. Govindarao, K. Gopalakrishna, Ind. Eng. Chem. Res. 1993, 32, 2111.
The authors have been developing a more precise model, [11] J. Krissmann, M. A. Siddiqi, K. Lucas, Fluid Phase Equilibria 1997, 141,
based on the theory of absorption with chemical reaction, and 221.
[12] J. Krissmann, M. A. Siddiqi, K. Lucas, Chem. Eng. Tech. 1998, 21 (8),
with the necessary evaluation of Hatta numbers to identify 641.
real kinetic parameters. Furthermore, a thermodynamic [13] F. D. Miles, J. Fenton, J. Chem. Soc. 1920, 117, 59.

Chem. Eng. Technol. 26 (2003) 4, Ó 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 0930-7516/03/0404-0501 $ 17.50+.50/0 501
 Full Paper
[14] J. Milbauer, Bull. Soc. Chim. 1935, 3, 221.
[15] W. Hayduk, H. Asatani, B. Lu, J. Chem. Eng. Data. 1988, 33, 506.
[16] Q. Zhang, H. Wang, I. Dalla Lana, K. Chuang, Ind. Eng. Chem. Res.
1998, 37, 1167.
[17] F. Maas, H. Elias, K. Wannowius, Atmos. Environ. 1999, 33 (27), 4413.
[18] L. R. Martin, D. E. Damschen, Atmos. Environ. 1981, 15 (9), 1615.
[19] D. Thomas, J. Vanderschuren, Chem. Eng. Sci. 1996, 51 (11), 2649.
_______________________
502 Ó 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
[20] D. Thomas, J. Vanderschuren, Ind. Eng. Chem. Res. 1997, 36, 3315.
[21] D. Thomas, J. Vanderschuren, Chem. Eng. Tech. 1998, 21 (12), 975.
[22] D. Thomas, J.Vanderschuren, Proc. of 3rd Eur. Congress on Chem. Eng.
(ECCE3), 2nd Int. Symp. Multif. Reactors 2001, VDI-GVC, Dechema,
EFCE, Nuremberg, Com. PA-17
[23] A. Rabe, J. Harris, J.Chem. Eng. Data 1963, 8 (3), 333.
[24] B. Rumpf, G. Maurer, Fluid Phase Equilibria 1992, 81, 241.
0930-7516/03/0404-0502 $ 17.50+.50/0 Chem. Eng. Technol. 26 (2003) 4