Desalination 240 (2009) 244
250

Separation of HCl from HCl H2SO4 solutions

by membrane distillation


M. Tomaszewska*, A. Mientka
Szczecin University of Technology, Institute of Chemical and Environment Engineering,
ul. Pulaskiego 10, 70-322 Szczecin, Poland
Tel. +48 914494367; Fax +48 914494686; email: maria.tomaszewska@ps.pl
Received 20 September 2007; revised 19 October 2007; accepted 26 October 2007

Abstract
Hydrochloric acid is a volatile compound; thus it can be separated from its solutions by membrane distillation
(MD). The feed solutions consisted of a mixture of hydrochloric and sulphuric acids with various initial concentrations.
It was found that during MD process the sulphuric acid was completely retained in the feed, thus its concentration
was gradually increasing, whereas hydrochloric acid solutions were concentrated at low concentrations. At higher
con-centration of both acids in the feed, HCl was separated from the mixture under the process conditions. For HCl
concentration in the feeding solution equal to 51.72 g/m3 along with an increase in the H2SO4 concentration from 50
to 150 g/m3, the molar HCl flux increased from 2.27 to 20.12 mol/m2d at 333 K and from 31.22 to 80.12 mol/m2d at
343 K.
During the concentration of solution with an initial concentration of 51 g/m3 of HCl and 51 g/m3 H2SO4 at the feed
temperature 333 K the permeate flux decreased from 225 to 158 dm3/m2d. An increase in the initial concentration of
sulphuric acid to a value of 180 g/m3 in the feed decreased the permeate flux from 202 to 135 dm3/m2d.
Keywords: Membrane distillation; HCl separation

1. Introduction The separation mechanism in the MD process

Membrane distillation (MD) is the process in
which a hydrophobic microporous membrane
separates two aqueous solutions at different
temperatures and compositions.
*Corresponding author.
is associated with equilibrium of the feeding
solution
vapour system [1]. The selectivity of
the process depends on the vapour pressure of
components of the feed under the operation
conditions. This means that the component
with higher vapour pressure will diffuse faster

Presented at the Third Membrane Science and Technology Conference of Visegrad Countries (PERMEA), Siofok,
Hungary, 2–6 September 2007.

0011-9164/09/$– See front matter # 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2007.10.093
 M. Tomaszewska, A. Mientka / Desalination 240 (2009) 244
250
through the membrane. The driving force of the
process originates from the difference in a
vapour pressure across the microporous hydro-
phobic membrane caused by the gradient of
temperature and composition of layers adjacent
to the membrane [2,3]. The hydrophobic
membrane plays the role of a physical support
for the liquid/gas interface. Moreover, the
hydrophobicity of the membrane used main-
tains a gaseous phase inside the membrane
pores, which is the necessary condition of
MD [2
9].
MD is a highly selective operation for
non-volatile solutes. The retention coefficient
reaches 100 g/dm3 for salt and the MD permeate
is high purity water. The MD process has
been investigated mostly in aqueous solutions
of sodium chloride with the purpose of
obtaining fresh water from the sea [10
13].
MD has also been applied successfully to waste
water treatment, yielding a permeate that is
less hazardous to the environment and a
retentate concentrated in valuable chemicals.
The concentration of solutions of non-volatile
solutes can be performed close to the super-
saturated state [2
14]. Additionally, MD has
found success in areas where high temperature
application lead to degradation of the process
fluids [4
9].
Until now MD has been investigated mostly
in the aqueous solutions of non-volatile sub-
stances. Our previous works devoted to recovery
of hydrochloric acid from metal pickling solu-
tions show that the presence of salt in the feed
decreases the HCl solubility causing a significant
transfer of the gas through a hydrophobic
membrane during MD [2
9].
The aim of the present work was to study the
concentration of both acids as well as the
influence of sulphuric acid in HCl solutions
on the separation of hydrogen chloride during
the membrane distillation.
245
2. Experimental
The MD installation, described in detail
previously [2] consisted of two thermostated
loops, feed and distillate, connected to a mem-
brane module. The module was equipped with
capillary membranes (Accurel PP S6/2, Mem-
brana GmbH, Germany) with din/dout 1.8/ /
2.6 mm made from polypropylene (PP). The
membranes were characterised by the pore size
with a maximum and nominal diameter of
0.6 mm and 0.2 mm, respectively, and a porosity
of 73 g/dm3. The working area for capillary
module was 0.0112 m2. The studies were per-
formed with mixtures of HCl and H2SO4 used as
a feed. A wide range of concentration was used
in order to investigate the influence of feed
composition on the possibility of the concentra-
tion both acids and the HCl separation. The feed
solutions contained hydrochloric acid with initial
concentrations of 50 or 100 g/dm3 whereas the
initial concentrations of sulphuric acid were
varied over a range of 50
150 g/dm3. The initial
volume of HCl
H2SO4 solutions used as a feed
was 2000 cm3. The experiments were carried out
at the inlet feed temperatures (TFin) of 333 or
343 K. The inlet temperature of the cold receiv-
ing solution (TRSin) was kept at 293 K for all the
experiments. The cold system was initially
supplied by 500 cm3 of distilled water.
The changes of volume of the cold distillate
were measured every hour to calculate the
volume permeate flux. Simultaneously, the
changes of solutes concentrations in the feed
and distillate were analysed. The concentration
of the sulphates was analysed using a weight
method [15]. The concentrations of H ions and
Cl were measured by titration methods.
The HCl flux was calculated from the
material balance of HCl in the distillate per-
formed every hour taking into account the
changes of volume and the acid concentration
in the distillate:
246 M. Tomaszewska, A. Mientka / Desalination 240 (2009) 244
250

ðctþ1 Vtþ1  ct Vt Þ
JHCl ¼
AMt
where ct and ct+1 are the distillate concentrations
at time t and t1, Vt and Vt1 are the volumes
of the distillate at time t and t1, A the
membrane area inside capillaries, M the molar
weight of HCl and t the time between the
consecutive measurements.
3. Result and discussion
The studies of influence of feed composition
on the HCl flux through the hydrophobic mem-
brane in the direct contact membrane distillation
process were performed. The course of MD for
feeding solution containing initially 51 g/dm3 HCl
and 51 g/dm3 H2SO4 and at temperature of 333 K
was presented in Fig. 1(a). During MD of this
solution it was found that the water vapour and
gaseous hydrogen chloride were transported
across the membrane pores, whereas non-volatile
H2SO4 remained in the feed and its retention
degree amounted to 100 g/dm3. The course of
the curves in Fig. 1(a) presenting the changes in
24
the concentrations of HCl (curve 1) and H2SO4
ðmol HCl=m2 dÞ (curve 2) in the feed indicates that initially the
concentration of both components was gradually
increased. At the beginning of the process only
/ the water vapour was transferred across the
/ PP membrane. When the concentration of HCl
and H2SO4 achieved the values of 52.09 and
54.93 g/dm3, respectively, the HCl transfer
through the membrane pores was observed
(Fig. 1(a)). However, the HCl flux was very
small due to a low concentration of both acids in
the feed.
As the concentration of feed components was
further increased, the molar flux of HCl was
increased to a value of 2.27 mol/m2d (Fig. 2,
curve 2). The concentration of HCl in the
distillate was slightly increased to 0.33 g/dm3
during the process.
At the initial concentration of feed of about
111 g/dm3 HCl and 61 g/dm3 H2SO4, the hydro-
chloric acid concentration increased in a similar
way as at the lower initial concentration of the
acid (Fig. 1(b), curves 1 and 3). However, due to
higher hydrochloric acid concentration and
higher partial pressure of HCl over the feed the

(a) (b)
100 20 160 20
PP capillary membrane PP capillary membrane
18

Concentration of HCI in the distillate (g/dm3)

Concentration of HCI in the distillate (g/dm3)

90 TFin–333 K 18 TFin–333 K
Concentration of acids in the feed (g/dm3)

140
Concentration of acids in the feed (g/dm3)

TDin–293 K TDin–293 K
80 16 16
120
70 14 14
100 12
60 12

50 10 80 10

40 8 8
60
30 6 6
40
20 4 4
20 2
10 2

0 0 0 0
0 1 2 3 4 5 0 1 2 3 4 5
Time (h) Time (h)

1–H2SO4–feed 2–HCl–feed 3–HCl–distillate 1–H2SO4–feed 2–HCl–feed 3–HCl–distillate

Fig. 1. Gradual concentration of HCl/H2SO4 model solution by MD at feed temperature 333 K; curves 1, 2 and
3 *data for the feed: (a) CHCl/CH2SO4 /51/51 g/dm3 and (b) CHCl/CH2SO4 /111/61 g/dm3.
 M. Tomaszewska, A. Mientka / Desalination 240 (2009) 244
250 247

160 60
PP capillary membrane concentration of H2SO4 in the feed e.q.
Concentration of HCI in the feed (g/dm3)

140 TFin–333 K
TDin–293 K
50 80 g/dm3 the HCl flux across the membrane
120 was much higher in the case of feed with higher

HCI flux (mol HCI/m2d)

40
100 initial concentration of HCl. This was caused by
80 30 a significantly higher partial pressure of HCl
60
20
over such solution.
40 The gas phase composition was strictly asso-
20
10 ciated with the composition of liquid phase * at
0 0
the same concentration of hydrochloric acid in the
50 60 70 80 90 100
2
Concentration of H2SO4 in the feed (g/dm )
110 feed, the partial pressure of HCl was higher over
the solution with a higher H2SO4 concentration.
3–feed 2–permeate 4–permeate
1–feed At the initial concentration of the feed amounting
Fig. 2. The influence of the feed composition on the HCl 52 g/dm3 HCl and 183 g/dm3 H2SO4, the hydro-
flux at feed temperature 333 K; curves 1 and 2*data for chloric acid appeared in the distillate after the first
the feed: CHCl/CH2SO4 /51/51 g/dm3 and curves 3 and 4* hour of MD (Fig. 3(a), curve 3). The con-
data for the feed: CHCl/CH2SO4 /111/61 g/dm3. centration of HCl in the distillate increased to
1.46 g/dm3 (Fig. 3(a), curve 3) during the process
component appeared in the distillate after the performed at feed temperature equal to 333 K.
first hour of the concentration process (Fig. 1(b), A higher sulphuric acid (150 g/dm3) in the feed
curve 3). During 5 h of MD operation the HCl favours desorption of HCl and the flux of HCl
concentration in the distillate increased to across the membrane during membrane distillation
4.37 g/dm3. The flux of HCl then amounted to increased almost to 10 times in comparison with
55.25 mol/m2d. An analysis of the course of the that at the concentration of 50 g/dm3 and was
curves in Fig. 2 indicates that at the same equal to 20.12 mol/m2d (Fig. 4).

(a) (b)
250 20 300 50
PP capillary membrane PP capillary membrane
Concentration of HCI in the distillate (g/dm3)

Concentration of HCI in the distillate (g/dm3)

18 TFin–343 K
Concentration of acids in the feed (g/dm3)

TFin–333 K
Concentration of acids in the feed (g/dm3)

TDin–293 K 250 TDin–293 K

200 16 40

14
200
150 12 30

10 150

100 8 20
100
6

50 4 10
50
2

0 0 0 0
0 1 2 3 4 5 0 1 2 3 4 5
Time (h) Time (h)

1–H2SO4–feed 2–HCl–feed 3–HCl –distillate 1–H2SO4–feed 2–HCl–feed 3–HCl–distillate

Fig. 3. Gradual concentration of HCl/H2SO4 model solution by MD; curves 1, 2 and 3 *data for the feed: (a) CHCl/
CH2SO4 /52/183 g/dm3 at 333 K and (b) CHCl/CH2SO4 /60/161 g/dm3 at 343 K.
248 M. Tomaszewska, A. Mientka / Desalination 240 (2009) 244
250

100 80
PP capillary membrane hydrochloride acid solution with higher and
Concentration of HCI in the feed (g/dm3)

90 TFin–333, 343K
TDin–293 K
higher concentration in accordance with the gas
80
60 phase/liquid phase equilibrium. An elevation of

HCI flux (mol HCI/m2d)

70
temperature caused a higher partial pressure of
60
volatile components, the water vapour and HCl,
50 40
and favoured a larger mass transfer across a
40

30
membrane.
20
20 The course of curves in Figs. 3(a) and 5(a)
10
clearly indicates that at temperature of 343 K the
0 0
HCl flux through the PP membrane was signifi-
150 170 190 210 230 250 270 290 310 cantly higher. For a solution with the initial
Concentration of H2SO4 in the feed (g/dm3)
composition of 60 g/dm3 H2SO4 and 52 g/dm3
1–feed 3–feed 2–permeate 4–permeate HCl, it increased to 20.12 mol/m2d (Fig. 4).
Higher H2SO4 concentration equal to 161 g/dm3
Fig. 4. The influence of the feed temperature on HCl flux
caused that HCl flux increased to 80.12 mol/m2d
through the PP membrane; feed: CHCl/CH2SO4 /52/
183 g/dm3, curves 1 and 2*data for 333 K and CHCl/ (Fig. 4).
CH2SO4 /60/161 g/dm3, curves 3 and 4*data for 343 K. In the case of the acids mixture with the
initial concentrations equal to 105 g/dm3 HCl
and 50 g/dm3 H2SO4 at 343 K, the hydrochloric
An elevation of feed temperature to 343 K acid concentration during MD increased close to
caused a faster concentration of H2SO4 and HCl 2-fold. The partial pressure of HCl under such
on the feed side (compare Fig. 1(a) and (b) and conditions was so high that the molar flux of
5(a) and (b)). In the MD process the initial HCl was 5 times higher than that for 333 K and
compositions of feed were the same as for achieved a value of 273.91 mol HCl/m2d that
temperature 333 K. The distillate comprised a can be seen in Fig. 6. The concentration of HCl

(a) (b)
200 50 200 50
PP capillary membrane
PP capillary membrane
TFin–343 K
Concentration of HCI in the distillate (g/dm3)
Concentration of acids in the feed (g/dm3)
Concentration of acids in the feed (g/dm3)

TFin–343 K
Concentration of HCI in the distillate (g/dm3)

TDin–293 K
TDin–293 K 40
40
150 150

30 30

100 100

20 20

50 50
10 10

0 0 0 0
1 2 3 4 5 1 2 3 4 5
Time (h) Time (h)

1–H2SO4–feed 2–HCl–feed 3–HCl–distillate 1–H2SO4–feed 2–HCl–feed 3–HCl–distillate

Fig. 5. Gradual concentration of HCl/H2SO4 model solution by MD at 343 K; curves 1, 2 and 3 *data for the feed:
(a) CHCl/CH2SO4 /50/50 g/dm3 and (b) CHCl/CH2SO4 /105/50 g/dm3.
 M. Tomaszewska, A. Mientka / Desalination 240 (2009) 244
250 249

200 450 300

PP capillary membrane PP capillary membrane
TFin–343 K TFin–333 K
Concentration of HCl in the feed (g/dm3)

180 400
TDin–293 K 250 TDin–293 K
160

Permeate flux (dm3/m2d)

350

HCI flux (mol HCI/m2d)

140 200
300
120
250 150
100
200
80 100
150
60
50
100
40
50 0
20 0 50 100 150 200 250
0 0 Concentration of H2SO4 in the feed (g/dm3)
30 40 50 60 70 80 90 100
Concentration of H2SO2 in the feed (g/dm3)
50 g/dm3 HCl and 50 g/dm3 H2SO4
50 g/dm3 HCl and 150 g/dm3 H2SO2
1–feed 3–feed 2–permeate 4–permeate
50 g/dm3 HCl and 100 g/dm3 H2SO2

Fig. 6. The influence of the feed composition on the Fig. 7. The influence of the feed composition on the
HCl flux; at 343 K curves 1 and 2
data for the feed: volume permeate flux through a hydrophobic membrane
CHCl/CH2SO4 /50/50 g/dm3 and curves 3 and 4 *data during MD at feed temperature of 333 K.
for the feed: CHCl/CH2SO4 /105/50 g/dm3.

3
of sulphuric acid was equal to 183 g/dm3.
in the distillate achieved a value of 20.41 g/dm The permeate flux decreased from 202 to
(Fig. 5(b)). 135 dm3/m2d (Fig. 7). These declines of the
The water vapour was transferred through the permeate flux were caused by the decrease of
membrane pores to distillate together with gas- the water vapour pressure being in the equili-
eous HCl during the concentration of acids brium with the feed solution of increasing of
mixture containing both hydrochloric acid and sulphuric acid concentration. The other factor
sulphuric acid. The sulphuric acid was comple- should be taken into account at the moment. The
tely retained on the feed side, thus its concentra-
viscosity of the feed with higher concentration of
tion constantly increased. The influence of the
sulphuric acid increases, and the concentration
feed composition on the permeate flux at feed
and temperature polarisation phenomena in the
temperature equal to 333 K was presented in
layer adjacent to the membrane have a signifi-
Fig. 7. As can be seen, a reduction of the
cant importance. The phenomena decrease the
permeate flux occurred mainly due to an increase
volumetric permeate flux. The results obtained
of sulphuric acid concentration in the feed.
for MD performed at 343 K have a similar
The permeate flux decreased from 225 to
character.
158 dm3/m2d during 5 h of MD operation at the
concentration of solution containing initially
of 50 g HCl/dm3 and 50 g H2SO4/dm3. The 4. Conclusions
higher initial H2SO4 concentration in the feed,
Based on the results of this work, the
about 118 g/dm3 (HCl concentration equal to
following conclusions can be drawn:
50 g/dm3), caused a decline of the permeate flux
from 256 to 112 dm3/m2d. The same trend was 1. The contents of HCl in the permeate
observed when the process was operated with increases with an increase of the hydrochlo-
the mixture acids, where the initial concentration ric acid in the feed.
250 M. Tomaszewska, A. Mientka / Desalination 240 (2009) 244
250
2. The presence of sulphuric acid in the feed
decreases the solubility of HCl, therefore its
flux across significantly increases with
H2SO4 concentrations.
3. The feed temperature strongly influences
a HCl flux across a membrane at MD
conditions.
Acknowledgement
This work was financed by Polish Govern-
ment in the framework of a grant (2005
2008).
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