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Electrodialysis With Bipolar Membranes: Principles, Optimization, and Applications
Electrodialysis With Bipolar Membranes: Principles, Optimization, and Applications
Abstract—This paper is an overview of the bipolar membrane technology. The process of electrodialysis with
bipolar membrane (EDBM) along with the different EDBM process configurations are presented. Some ways
of optimization of both the bipolar membranes and the EDBM technology are envisaged. Most of the applica-
tions relate to the production or recovery of organic acids while the first plant has been commissioned by 1986
at Washington Steel (USA) for the recovery of HF/HNO3 from waste pickling liquors. In the last few years,
there has been increasing interest in using bipolar electrodialysis stacks in chemical and agro industrial pro-
cesses to directly acidify or basify process streams without the addition of chemicals. This attractive feature of
this technology has contributed to the implementation of several plants in fermentation process for the produc-
tion of organic and amino acids.
INTRODUCTION region. According to the authors, the main force for the
enhanced water dissociation is a reversible protonation
The conventional method for generating ç+ and and deprotonation of the functional groups of the ion-
éç– ions from water utilizes electrolysis. Electrolysis exchange membranes, especially of the tertiary amino
also generates é2 and ç2, and the overvoltage for this groups B of the anion-exchange layer according to (2)
generation consumes about half the electrical energy of and (3). The thickness of the transition region where the
the process. Nowadays, special ion-exchange mem- water dissociation takes place is less than 10 nm [2]
branes are available for splitting water directly into ç+
and éH– ions without generating gases. Membrane 2H2O H3O+ + OH–, (1)
water splitting technology is a general purpose unit
operation for converting water soluble salts to their cor- B + H2O BH+ + OH–, (2)
responding acids and bases. The process uses bipolar
membranes (BPM) in conjunction with conventional BH+ + H2O B + H3O+. (3)
cation- and/or anion-exchange membranes (CEM and
AEM, respectively). The separation and rearrangement Note that BPM can be used not only for the dissoci-
of ions is effected by a direct current driving force. The ation of water but also for the splitting of other self-dis-
BPM electrodialysis (EDBM) is therefore an alterna- sociating liquids like methanol.
tive method to electrolysis for the generation of ç+ and The application of BPM reduces the energy costs
éç– ions which can be used to generate acid and base associated with electrode polarization in the more con-
from salts without the production of oxygen and hydro- ventional electrolytic approach. The theoretical poten-
gen gases. tial to achieve the water splitting capability is 0.83 V at
25°ë. The actual potential drop across a BPM is quite
close to this being in the range of 0.9–1.1 V for current
PRINCIPLES densities between 500 and 1500 A/m2, which is the
The principle of water splitting by a BPM is illus- region of practical interest. The value of the membrane
trated in Fig. 1. The diffusion of water from both sides potential drops equate to theoretical energy consump-
of the BPM allows its dissociation under the electrical tion on the order of 600–700 kW h/ton of Noah. Of
field to generate protons and hydroxyl ions which fur- course, the actual energy consumptions are signifi-
ther migrate from the junction layer through the cation- cantly higher because of the ohmic resistances in the
and anion-exchange layers of BPM. As described in other cell stack components in practical operating units.
[1], the water dissociation in BPM (1) is accelerated up One classical application of BPM is the production
to 50 million times compared to the rate of water disso- of an acid (HX) and a base (MOH) from a salt (MX)
ciation in aqueous solutions. This acceleration is influ- through the reaction
enced by the strong electric field across the transition MX + H2O HX + MOH. (4)
*This article was submitted by the author in English. The basic configuration is illustrated by Fig. 2.
Transition region
H+ OH –
– +
Cathode Anode
H2O H2O
X– å–
H+ OH –
å+ X–
H+ +
– OH –
Anode
Cathode X–
å+
Fig. 2. Conversion of a salt into its respective acid and base by electrodialysis with bipolar membranes.
Salt
(a) solution
(MX)
– + – + – +
H2 O H2O
+ –
– + – M X + – +
Cathode Anode
– + – + – +
– H+ OH – H+ +
– + – + – +
OH –
– + – + – +
Bipolar Bipolar
membrane membrane
Diluate
Base (åéç) Acid (çï)
(b) (c)
H2O Me +X – Me +X – H2O
BIP CEM BIP BIP AEM BIP
– + – – + – + + – +
– + – – + – + + – +
– + – Me + – + – + X– + – +
– + – – + – + + – +
– + – – + – + + X– – +
–
... – + Me + – – + ...
+ – ... – + + – + ... +
– + – – + – + OH +
– – +
– + OH – – H+ – + – + + H+ – +
H + – + – – + OH – H + – + + – + OH –
ëÓθ/ÍËÒÎÓÚ‡
Salt/Acid ëÓθ/ÍËÒÎÓÚ‡
Salt/Base
Me +OH – HX + Me +X – MeOH + Me +X – H +X –
(d) (e)
H2O Me +X – HX + Me +X – MeOH + Me +X – Me +X – H2O
BIP CEM CEM BIP BIP AEM AEM BIP
– + – – Me + – + – + + Me + + – +
– + – – – + – + X– + + – +
– + – Me + – X– – + – + + + – +
– + – – – + – + Me + + X +– – +
– – + – X– – – + + – – + + + – + +
...
– + Me + – – – + ...
... – + + + X– – + ...
– + – – H+ – + – + OH – + Me + + – +
– + + H +
OH –– – – + – + + – +
OH –
H+ – + – HX – X– – + OH – H + – + Me + + OH – + – +
Me +OH – H +X–
ç+ ions permeate through the cation-exchange side of (H2SO4) from MX (Na2SO4) at a significantly lower
the BPM and form HX with the sulfate ions provided by cost than by other methods.
the MX solution from the adjacent cell. The éç– ions There are applications where high purity of both
permeate the anion-exchange side of the BPM and form acid and base is not possible to obtain or even may gen-
MOH with the sodium ions permeating into the cell erate problems during the process, e.g. when producing
from the MX solution through adjacent CEM. The final organic acids or bases from the corresponding salts that
result is the production of MOH (NaOH) and HX reveal low dissociation tendency and therefore low con-
BIP
K AK A
– +– +
å+ OH – H+ X– 1
– +– +
– X– +– +
– å+ 2
+– +
– +– +
+ –
MX – MOH +– HX + MX
Anode Cathode
– +– +
OH – Base Acid H+ 3
– +– +
– +– +
MOH HX
– +– + 4
ductivity in the protonated form. In such cases, a two- brane performances (both bipolar and homopolar), the
compartment cell is recommended as depicted in second are related to the stack technology.
Fig. 3b (for acidification) or in Fig. 3c (for the genera- The performances of a water splitter are controlled
tion of the corresponding base). Moreover, when a by the permselectivities of the ion-exchange mem-
higher ratio of acid and base with respect to the product branes (homopolar and bipolar) and by diffusive trans-
salt content is required, a configuration with two port. Figure 4 illustrates various processes which con-
homopolar membranes of the same type can be applied. tribute to the overall current efficiency. Zone 1 concerns
The outlet of the middle loop is recycled again into the the specific process which generates acid and base from
acidic loop next to the BPM for a more efficient salt and water. Competing with this are the undesirable
exchange between protons and cations (Fig. 3d), or processes which reduce the current efficiency. Zone 2
between éç– ions and anions (Fig. 3e). represents the loss of permselectivity of each homopo-
lar layers of the BPM which affects the purity of the
acid and base obtained. Zone 3 represents the loss of
LIMITING PHENOMENA OF EDBM permselectivity of the associated homopolar mem-
However, and as for all the processes, EDBM pre- branes which affects the efficiency of the EDBM pro-
sents limits [4]. The first are closely related to the mem- cess. Zone 4 concerns the diffusional losses due to the
concentration gradients which significantly occur for
i, A/m2 poorly ionized small molecules (e.g. HF, NH3, SO2,
etc.). Apart from these limits, which are mainly due to
the loss of permselectivity or/and diffusion, consider-
3000 ation must also be paid to water transport through mem-
iop Uop branes which generally limits the concentration level of
the acid and base produced. The analysis of factors lim-
1000
iting the use of BPM is presented in [5]. Among this
~ ~ first set of limits, the main concerns the permselectivity
~ ~ JOH– of the associated homopolar membranes and specially
JOH+ that of the AEM towards protons. Despite this point
20
having been thoroughly investigated [6–11], typical
standard-grade AEMs show proton transport numbers
10 i lim between 0.30 and 0.70, this value increasing with the
poly-acidity (HCl < H2SO4 < H3PO4). Therefore, due to
JM + + |JX– | the specific mechanism of the proton transport in aque-
0 ous media, the current efficiency increases with the
Udiss 1 Um, V temperature [12].
Fig. 5. Current–voltage curve of BPM in a salt environment: There are also other factors which affect the effi-
iop is the operating current density, and ilim is the limiting- ciency of a water splitter. For instance, the installation
current density due to the salt leakage though BPM. of feedback control systems is difficult due to nonlinear
the operating conditions in laboratory-scale EDBM can Single-pass continuous flow. Typically, maximum
be reproduced on a commercial scale. salt removal for any hydraulic stage is 55–60% with
standard design values of 40–50%. To increase the
amount of salt removed in an EDBM, two types of stag-
EDBM PROCESS CONFIGURATIONS ings are used: (i) hydraulic staging (adding more stacks
Taking into account all the previous parameters, in series, as depicted in Fig. 6), or (ii) electrical staging
there are three common process configurations which (adding electrode pairs to the membrane stack). The
are widely in use: advantages are a continuous production, a low expendi-
ture of buffer tanks, tubing, and control instrumentation
Batch-mode configuration. Running in batch and a low energy consumption. The disadvantage is a
means that a given volume of salt solution is driven in later adjustment of unit to altered process conditions
close cycle through the membrane stack until the which is difficult.
desired product concentration is obtained. The advan-
tage is a process which is easily adjusted to individual
demands with respect to product concentration and APPLICATIONS OF EDBM TECHNOLOGY
flow. The disadvantage is a high expenditure for buffer
tanks, tubing, and process control. This mode concerns A large number of applications have been identified.
medium and large scale applications. These are classified under broad categories of pollution
Feed & bleed mode. Similar to the batch-mode, in control/resource recovery and chemical processing in
this configuration a concentration or depletion of the Table 1 [4].
process stream is carried out but in a continuous man- The oldest industrial application of EDBM in pollu-
ner. The main part of the process solution is recycled tion control/resource recovery is the recovery of HF
and only a small part of this stream is bled off. The and HNO3 from a stream containing KF and KNO3 gen-
advantage is a continuous production and steady-state erated from a pickling bath in a steel plant. This first
operation. The advantage and the scale of applications commercial use of BPM began operations in 1987 at
are that of the batch-mode configuration. Washington Steel in Pennsylvania. Figure 7a illustrates
(a) Diluate
Electrodialysis
Depleted stack
salt solution
Concentrate
HF/HNO3
äéç
Bipolar
electrodialysis stack
Steel
Salts
M(OH)n
(b)
2 å NaOH for
Conventional
pH control
electrodialysis
2 å sodium lactate
H2O
Fig. 7. (a) Process for recycling HF/HNO3 steel pickling solution using EDBM (from [16]) and (b) scheme of production of lactic
acid from fermentation broth using both conventional ED and EDBM (from [16]).
the process. Spent pickling acid is neutralized with tion requires addition of a base to maintain this elevated
KOH to precipitate the heavy metals which are then pH. So, the product of the fermentation is a dilute salt
removed by filtration. The remaining neutral solution of of the organic acid. For example, in the case of the lac-
KF + KNO3 is then treated in a three-compartment tic acid production, the conventional process requires a
EDBM cell in which the salts are split to form KOH lot of different ion-exchange steps, resulting in a high
which is directed to the neutralization tank and the volume of waste water and organic solvents that have to
mixed acids (HF + HNO3) which are directed to the be recovered. On top of that, possible losses of product
pickling operation. The dilute salt solution from the salt and a potential contamination of the product have to be
compartment of the EDBM process is then reconcen- taken into account. The recovery of lactic acid from fer-
trated by conventional electrodialysis and returned to mentation broth can also be performed by use of two
the bipolar stack, the diluate is used to rinse the filter electrodialysis steps. In the first, the dilute sodium lac-
cake. tate solution is concentrated by a conventional two-
The main application of EDBM in chemical pro- compartment ED. This step also purifies the product
cessing is the recovery of organic acids which can be because only the ionized components of the broth are
recovered from fermentations. The performance of fer- redirected to the fermentation reactor. In the second
mentations is better when the pH is slightly higher than step, the concentrated sodium lactate is split in a two-
the pKa of the organic acid to be produced. This condi- compartment bipolar ED with a CEM (configuration of
Fig. 3a) to generate lactic acid and NaOH. The acid ACKNOWLEDGMENTS
stream, still containing Na+ ions is then purified by a The author wishes to thank the European Commu-
cation-exchange resin, while caustic soda is recycled to nity (Thematic Network on Bipolar Membrane Tech-
the fermenter for pH control. For economical reasons in nology, contract BRRT-CT97-5038), all the partners of
the bipolar ED step, the conversion rate of sodium lac- the Thematic Network contributing to the Handbook on
tate is kept at 95%, but almost 100% could be easily Bipolar Membrane Technology, (Kemperman, A.J.B.,
achieved. A simplified scheme of this process is Ed.); the Centre National de la Recherche Scientifique,
reported in Fig. 7b. France (program PECO/CEI no. 8768); and the Eurodia
Company.
Analyzing the development of the EDBM technol-
ogy, it is clear now that BPM will be involved in
organic-acid production, organic-acid recovery, or REFERENCES
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