2336 J. Electrochem. Soc.

: E L E C T R O C H E M I C A L SCIENCE AND TECHNOLOGY October 1985

L electrode length (cm) REFERENCES

M molecular weight of electrodeposited metal (g/tool) 1. J. F. D'Amico, M. A. DeAngelo, J. F. Henrickson, J. T.
n cation valence (eq/mol) Kenney, and D . J . Sharp, This Journal, 118, 1695
T metal deposit thickness (cm) (1971).
V substrate speed (cm/s) 2. J. F. D'Amico, M. A. DeAngelo, and L. D. Noble, ibid.,
W electrode width (cm) 123, 478 (1976).
X axial coordinate (cm) 3. C. Tobias and R. Wijsman, ibid., 100, 459 (1953).
X x/L 4. R. Alkire, ibid., 118, 1935 (1971).
Z horizontal coordinate (cm) 5. R. Alkire and A. Tvarusko, ibid., 119, 340 (1972).
K electrolyte conductivity ( t l - ' - c m -1) 6. R. Alkire and R. Varjian, ibid., 124, 388 (1977).
7. R. Alkire and R. Varjian, ibid., 121, 622 (1974).
~-o, ~-d dimensionless parameter peKL/T for the electrodes 8. D. T. Chin, ibid., 122, 643 (1975).
at y = 0 and y = d, respectively
9. R. S. R. Gorla, ibid., 125, 865 (1978).
tLo, t~d dimensionless parameter Kb/L for the electrodes at 10. J. Hajdu and J. Wynschenk, Abstract 211, p. 530, The
y = 0 and y = d, respectively Electrochemical Society E x t e n d e d Abstracts, Mi-
p density of electrodeposited metal (g/cm 3) ami, FL, Oct. 8-13, 1972.
p~ resistivity of electrodeposited metal (tl-cm) 11. D. R. Turner and G. R. Johnson, This Journal, 109,
r dimensionless parameter (Eq. [2]) 798 (1962).

Electrochemical Production of Potassium Carbonate

F. Hine,* M. Yasuda,* Y. Ogata, and T. Kojima
Nagoya Institute of Technology, Nagoya 466~ Japan

Yang Weiyi ,,2

Jinxi Research Institute of Chemical Industry, China

ABSTRACT
Direct production of potassium carbonate by electrolysis of potassium chloride solution with the m e m b r a n e cell was
studied. The current efficiency was high since the hydroxyl ion concentration in the cathode compartment was low, re-
sulting in m i n i m u m back-migration of O H - through the membrane. The reduction of the cell voltage is discussed in
some detail. The anode and cathode materials having low overvoltages were studied, and Nation 423 was used as the
separator. The operation of a separate reactor for carbonating the catholyte liquor is also described briefly.

Although the production capacity and the market of The catholyte liquor flows down from the top of the
caustic and carbonate potash are small in comparison COx absorption tower packed with the Raschig rings to car-
with the soda products, they are still important chemi- bonate caustic solution into carbonate, then bicarbonate
cals. Potassium carbonate is produced only by absorption after separation of hydrogen. A part of the catholyte liq-
of carbon dioxide with caustic potash, and there is no di- uor is bypassed to the second stage of the absorption
rect route from chloride such as the Solvay process for tower, where carbonate is converted into bicarbonate.
making soda ash because of the large solubility of potas- Water is supplied to the catholyte reservoir to adjust the
sium carbonate: 127g/100g H~O compared to 46g/100g H.~O water balance and the solution concentration.
of Na~CO3 at 60~ (1). The reaction sequence is simple. In the electrolytic cell,
Caustic potash is produced by electrolysis of potassium chlorine and hydrogen are liberated at the anode and the
chloride solution. However, the current efficiency of the cathode, respectively
m e m b r a n e cell is said to be low somewhat caused by
2C1- = C12 + 2e [1]
small transport n u m b e r of K + in the m e m b r a n e compared
and
to the case of NaC1 electrolysis (2).
There are several publications on the electrolytic pro- 2H20 + 2e = H~ + 2 O H - [2]
duction of sodium carbonate where the caustic catholyte Since the catholyte contains bicarbonate ions, reaction [3]
is carbonated to keep the O H - concentration low, re- takes place in the bulk of solution
sulting in high current efficiency (3, 4). In fact, it is troub-
lesome since sodium carbonate and bicarbonate deposit O H - + HCO:,- = CO:32- + H~O [3]
in the cathode compartment. The catholyte effluent is further carbonated in the ab-
In the case of potassium salts, on the other hand, this
sorption tower to keep the O H - concentration low, but
process would be desirable because of no unwanted dep- the bicarbonate content in the product should also be
osition (5). This paper deals with a small cell experiment
controlled.
and a pilot test for the direct electrolytic production of
An excess solution absorbs more CO2 to convert into bi-
potassium carbonate from potassium chloride solution
carbonate in the second stage of the tower
with a m e m b r a n e cell followed by absorption of carbon
dioxide with the catholyte effluent. CO:~2- + CO~ + H20 = 2HCO:;- [4]
Flowsheet and Reaction Sequence CI 2 H2
A proposed flowsheet is illustrated in Fig. 1. Concen-
trated and purified KC1 solution is p u m p e d to the anode g:=-2::2
c om p ar t m en t of the m e m b r a n e cell, and its effluent is
sent back to the reservoir through the gas-solution sepa-
rator where chlorine gas is recovered. Polishing of the
feed brine with the chelating resin column is of great im-
portance in eliminating a trace of hardness ions so as to
keep the cell performance high and in extending the
membrane service life (6, 7). The depleted brine is sent to
the brine treatment yard. It is not shown in this figure.
anolyte catholyte ~2CO1 storage
* Electrochemical Society Active Member. reservoir reservoir tank
' Exchange scholar at Nagoya Institute of Technology
(1981-1982). Fig. 1. Flowsheetfor the electrolyticproductionof potosslumcarbonate
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 Vol. 132, No. 10
thermometer ~reflux
condenser
CIz ouUet I II Lcooting
i1
electricheater
-~ anodel \
cathode ~
magnetic
stirrer
membrane
Fig. 2. A small Lucite cell
Experimental Procedure
A small Lucite cell, shown in Fig. 2, was fabricated to
determine the electrode polarization, the IR drop through
the membrane, and the cathode current efficiency in the
batch-wise system. That is, four Luggin-Haber probes
were positioned on the front of the anode and cathode,
and both sides of the membrane. The Luggin probes lo-
cated at the cathode compartment were connected with
respective reference electrodes composed of Hg/HgO/1M
KOH, while the probes in the anode side were referred to
the saturated calomel electrodes (SCE).
The solution gaps in both the anode and cathode com-
partments were large enough for the convenience of ex-
periment.
The DSA-type (RuO2+ TiO~) anode was prepared by a
conventional manner, and another material--named
MO DE- - was also used. The MODE is a platinized Ti
mesh loaded with Ira2 as the electrode catalyst (8). A
nickel sheet was used as the cathode.
The solutions, 0.2 liter each in v o l u m e at the anode and
cathode sides, were agitated by the magnetically driven
stirrer, and the temperature was controlled at 60~ by
electric heater.
The flowsheet of the pilot e x p e r i m e n t was almost the
same as shown in Fig. 1, with some exceptions. A major
difference was the separate operation of the electrolyzer
from the 'gas absorber.
A vertical and rectangular-type electrolytic cell, also
made of Lucite resin, is illustrated in Fig. 3. The Nation
m e m b r a n e of 5 cm wide and 40 cm long was flanged by
two frames, and supported by the anode mesh. The
Copper busbar
Membrane [ was operated for 2.1 Ah.
Cathode
k gin
Copper busbar u "--'][ ....
Fig. 3. A vertical cell
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PRODUCTION OF K2CO3 2337
membrane-to-cathode gap was adjusted by a frame of a
certain thickness. A MODE mesh was employed with this
cell. A plain Ni sheet was mostly used as the cathode, and
water some experiments were conducted with an activated
mesh cathode consisting of a steel coated with the Raney
nickel. An alloy composed of 50% Ni and 50% A1 was
plasma-sprayed on a steel mesh substrate, then aluminum
was leached out with hot concentrated caustic soda for a
k",.xI
~ e c t ric heater
day. The apparent electrode area was about the same as
of the membrane, so that the current density on both elec-
trode and m e m b r a n e was ca. 40 A/din 2 at 80A in total am-
perage. The current density presented in this paper is
referred to the m e m b r a n e surface.
Nation membranes 315, 417, and 423 were employed.
Most experiments were co n d u ct ed with 423. These mem-
branes were treated with boiling water for about an hour
prior to experiment.
The temperature was controlled by the electric heater
immersed in the reservoir. The solution v o l u m e was 8 li-
ters each side. The anolyte flow was kept constant at 3
liter/min, and was large enough to keep the solution com-
position to be unchanged during experiment. On the
other hand, the catholyte flow rate was varied in a wide
range, 0.04-3.0 liter/min. All the catholyte flows through
the gap between the m e m b r a n e and the flat plate cath-
ode. On the other hand, a part of the catholyte and hydro-
gen bubbles evolved may pass through the back-space
when the mesh cathode is provided.
Potassium chloride of 4.2M in concentration was fed to
the anode compartment. The catholyte was composed of
a mixture of KHCO~ and K2CO3. The total molarity was
kept constant at 2.0M, and the concentration ratio of the
constituents was varied in a wide range. Its composition
and concentration are not optimum, but it is just for the
convenience of experiment. In practice, the higher the
catholyte concentration, the higher is the performance of
the cell. Potassium hydroxide was also added to the
catholyte if necessary. These electrolytes were prepared
with reagent-grade chemicals and deionized water. Also,
the anolyte was further treated by passing through the
chelating resin column when the hardness content
reached unacceptable levels.
The catholyte was titrated with HC1 solution and the in-
dicator composed of methyl red and bromocresol green
before and after electrolysis to evaluate the current
efficiency for the cathode products. The solution compo-
sition was determined by p H titration.
A vertical cell was normally operated continuously for
30 Ah at various current densities, while a small batch cell
Results and Discussion
As is shown in Eq. [3] and [4], the reaction of KOH with
KHCO3 is just a neutralization, so that O H - and CO:32- may
exist in alkaline solution. On the other hand, the solution
containing excess COs or HCO3- is composed of KHCO3
plus K2CO3, but no KOH. In consequence, a parameter a
shown by Eq. [5] is used to represent a nature of the
mixed solution or the KOH-K2CO3-KHCQ system instead
of the molar concentration C of the components
Cco~2- + Coil-
= [5]
o CHCO3-- -}- Cc032_
At a = 1, neither O H - nor HCO~- exist in the solution;
that is, the solution contains only K~CO~. If a < 1, the so-
lution contains excess KHCO3, but no KOH. On the other
hand, O H - remains in the solution, but there is no KHCO3
when a > 1. It is useful to compare the electrolyte
of different composition and concentration.
Figure 4 shows an example of the current efficiency
and the terminal voltage of a small cell shown in Fig. 2 as
functions of a. It is clear that the current efficiency de-
creases when a increases, especially in the region larger
than unity of a caused by a significant migration of O H -
from the cathode co m p ar t m en t to the anode side through
the membrane. On the other hand, the cell voltage goes
down with the increase of a because the IR drop between
 2338 J. E l e c t r o c h e m . Soc.: E L E C T R O C H E M I C A L SCIENCE AND TECHNOLOGY O c t o b e r 1985

HCO3- ( M ) OH- (M) HCO 3- ( M ) OH- (M)

2.0 1.0 0 1.0 2.0 2.0 10 0 10
, , , i . . . . i ' ' ' , I
9 ~
~100 - - - - - - i ~ 100 - ~ o ~ e - ~ . . e

"~J 808 ~ , ~
~- 9 0 :u- 90
Q)

80 E 80
, , , I , , , , I , , , , I , , , , I ,

u 70 I l l l l l l l l l l l l l ]

"~ 12
45i"
.~ ~, "'-~ 9 >

8
0
, , ,I
05
.... I ,,
10
, ~ I ,~ , , I , , /
1.5 20
1 3
0
. . . .
05
I . . . .

O(
I , , ,
10 15

Fig. 5. Current efficiency and voltage of the vertical cell as functions

of the solution composition. Anode: MODE. Cathode: plain Ni. Mem-
O~
brane: Nation 423. Cathode-to-membrane gap: 6 mm. Current density:
Fig. 4. Current efficiency and voltage af the small cell as functions af 20 A/dm 2. Temperature: 60~C. Catholyte flow rate: 3 llter/min.
the solution composition. Closed points: solution containing carbonate.
Open points: solution free of carbonate. Anode: DSA. Cathode: plain Ni.
Membrane: Nation 423. Anode-to-membrane gap: 27 mm. Cathode-to- Flow velocity (crn/s)
membrane gap: 27 ram. Current density: 20 A/dm 2. Temperature: 60~C. 0.5 1 5 10
o

the c a t h o d e and t h e m e m b r a n e decreases with the in- Vl00

crease of t h e ionic strength and/or t h e K O H c o n c e n t r a - o f . 1 1 ~ 9 O
r-
tion. The cell voltage in this figure is v e r y large and is
:5 90
s h o w n as r e f e r e n c e b e c a u s e t h e solution gaps in b o t h the
anode and c a t h o d e sides are large. Q;

This figure also s h o w s t h e c u r r e n t efficiency and t h e ~ 80

cell voltage o b t a i n e d with t h e K O H catholyte free of car-
bonate. The c u r r e n t efficiency is a l m o s t e q u a l to that of , I ,,i,I i I i • i i, l i l l , ,,11 , I
U , i~,,,i
the cell o p e r a t e d w i t h m i x e d solutions. It r e p r e s e n t s that i 9
the b a c k - m i g r a t i o n of O H - t h r o u g h the m e m b r a n e is not e
affected significantly by c a r b o n a t e ions. The cell voltage 9 9 ~ ~
was, of course, v e r y h i g h in w e a k solutions w h e r e a s it was
a l m o s t the s a m e as of t h e cell filled w i t h m i x e d solutions
in t h e c o n c e n t r a t i o n r a n g e of O H - m o r e t h a n 1.5M.
u
0
4
,

0.05
[ ,,,I

0.1
i 9
~ q

0.5
I ,,,JJ

1
[ ~ t f

The current efficiency and t h e voltage of the vertical
cell e q u i p p e d with Nation 423 as f u n c t i o n s of t h e
catholyte c o m p o s i t i o n are s h o w n in Fig. 5. The c u r r e n t
density was 20 A/din 2, and t h e solution t e m p e r a t u r e was
k e p t c o n s t a n t at 60~ The catholyte flow was 3 ]iter/min
or ca. 16.7 cmJs in a 6 m m gap b e t w e e n the flat plate cath-
ode and t h e m e m b r a n e . As is s h o w n by the top draft in
this figure, t h e c u r r e n t efficiency of t h e vertical cell was
almost e q u a l to that of the small cell d e s c r i b e d above.
The cell v o l t a g e in this case is relatively low in compari-
son with that of the small cell b e c a u s e t h e m e m b r a n e tou-
ches on the a n o d e m e s h and t h e c a t h o d e gap is small, b u t
is still insufficient. The flow rate was a small factor on
the c u r r e n t efficiency as s h o w n in Fig. 6. O f course, elec-
trolytic h y d r o g e n b u b b l e s associate with forced circula-
tion to agitate the catholyte and to k e e p the solution com-
position u n i f o r m across the vertical cell.
At t h e flow rate l o w e r than 0.1 liter/min or 0.6 cm/s, t h e
O H - c o n c e n t r a t i o n in the c a t h o d e c o m p a r t m e n t increases
and causes t h e c u r r e n t inefficiency.
F i g u r e 7 illustrates that t h e c u r r e n t efficiency is a l m o s t
i n d e p e n d e n t of t h e c u r r e n t d e n s i t y in the range 10-40
AJdm 2 if a does not e x c e e d unity. Also, the current
efficiency did not c h a n g e in the t e m p e r a t u r e range
40~176 The cell voltage is a l m o s t linear w i t h the c u r r e n t
density in the range 10-40 A/din 2 (see b o t t o m of t h e
figure), w h i c h r e p r e s e n t s that the m a j o r factor of the cell
v o l t a g e is t h e o h m i c c o m p o n e n t , e i t h e r m e m b r a n e or
electrolyte, r a t h e r t h a n t h e overvoltage.
F r o m t h e v i e w p o i n t of p r o d u c t quality, p o t a s s i u m car-
b o n a t e is c o n t a m i n a t e d by either caustic potash or bicar-
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5
FLow r o t e (l/rain)
Fig. 6. Current efficiency and voltage of the vertical cell as functions
of the catholyte flow. Operating conditions were the same as in Fig. 5,
except ~ = 0.9-1.0.
b o n a t e d e p e n d i n g on a, and h e n c e a m u s t be controlled
as exactly as possible.
Table I s h o w s the b r e a k d o w n of the t e r m i n a l voltage of
the small cell a n d t h e vertical cell at a g i v e n current den-
sity (20 A / d m ~) and t e m p e r a t u r e (60~ The figures for
the small cell w e r e o b t a i n e d by e x p e r i m e n t with the ex-
c e p t i o n of t h e catholyte IR drop. Its I R drop was calcu-
lated w i t h an a s s u m p t i o n of 6 m m for the electrolysis gap
to c o m p a r e the voltage drop in two cells u n d e r t h e s a m e
conditions. The solution c o n d u c t i v i t y was m e a s u r e d with
a separate cell for this treatment. The anolyte I R drop of
the small cell was d r o p p e d f r o m the list for the s a m e rea-
son. B o t h cells w e r e e q u i p p e d with a m e s h - t y p e M O D E
anode, a plain Ni cathode, and Nation 423. As s h o w n in
Fig. 2, since the solution gaps in b o t h the a n o d e and cath-
ode c o m p a r t m e n t s of t h e small cell are large enough, the
gas v o i d a g e is small, and h e n c e it is c o n c l u d e d that the
e x p e r i m e n t a l results do not contain any b u b b l e effect of
h y d r o g e n and c h l o r i n e in this case.
In the v e r t i c a l cell, on the o t h e r hand, Nation m e m -
b r a n e is s u p p o r t e d by the a n o d e m e s h w h i l e the c a t h o d e
plate is l o c a t e d at 6 m m f r o m t h e m e m b r a n e , a n d t h e
catholyte is c i r c u l a t e d in b e t w e e n at a c o n s t a n t rate (3
liter/min). Therefore, d e t a c h m e n t of chlorine b u b b l e s
f r o m the a n o d e - m e m b r a n e structure is delayed, and t h e
 Vol. 132, No. 10 PRODUCTION OF K2CO3 2339
'''1 ' ' I . . . . I ' ' I .... f

1.5 anode DSA j 0.2

>.,
i i i i 1.4 o__,~_.~.~~ 0.1
i~--i~ -------~--'o-- e MODE
~00 -| 99 O o9 _ 1.3 ,,,1 , , , I .... L , , t .... C 0
O v
> -08 ~
"" 90 v ~ ~ -0.2

"'--.-... - O./-, >o

-1.2 "'~ 0
~ 80
o "-'~'"---.....Z,0~0 N~ -0.6
(.9 I I 1 I - 1.4 cathode ~"~A

6 ,,,I , , filial p , , t .... I -0.8

1 10 100
Current density (A/dm 2)

5 Fig. 8. Polarization curves of various electrodes. Anolyte: 4.2M KCI.

- O J O Catholyte: 2.0M K2CO3. Temperature: 60~

/~ I t I
10 20 30 40
Current density (A/dm 2)
Fig. 7. Current efficiency and voltage of the vertical cell as functions
of the current density. Operating conditions were the same as in Fig. 5,
except for ~ = 0.9-1.0.
c a t h o l y t e i n t h e e l e c t r o l y s i s z o n e is c r o w d e d b y h y d r o g e n
b u b b l e s to s o m e e x t e n t . A s a result, t h e o v e r v o l t a g e s at
t h e a n o d e a n d t h e c a t h o d e , a n d also t h e m e m b r a n e I R
drop, increase considerably depending on the blinding of
these surfaces.
T h e r e v e r s i b l e p o t e n t i a l s for t h e h y d r o g e n a n d c h l o r i n e
e l e c t r o d e p r o c e s s e s u n d e r o p e r a t i n g c o n d i t i o n s of solu-
tion composition and temperature were measured with
t h e s m a l l cell a n d a g r e e d w i t h t h e o r y . T h e s e r e s u l t s w e r e
u s e d to b r e a k d o w n t h e cell v o l t a g e s h o w n i n T a b l e I.
T h e o v e r v o l t a g e s o b t a i n e d w i t h t h e s m a l l cell are also
s h o w n i n Fig. 8. I n t h i s case, t h e I R d r o p b e t w e e n t h e
working electrode and the Luggin probe was calibrated
b y t h e c u r r e n t i n t e r r u p t i o n t e c h n i q u e . H o w e v e r , t h e an-
o d e p o t e n t i a l of t h e v e r t i c a l cell i n T a b l e I c o n t a i n s s o m e
IR drops between the anode and the Luggin probe.
T h e m e m b r a n e I R d r o p in t h e s m a l l cell w a s s o m e 0.6V,
as s h o w n in T a b l e I, a n d d i d n o t c o n t a i n a n y d i s t u r b a n c e
as t h e v e r t i c a l cell w a s affected. H o w e v e r , it is still v e r y
large in c o m p a r i s o n to t h e I R d r o p of s i m i l a r N a t i o n e m -
p l o y e d i n t h e NaCI cell: c a . 0.3V at 80~ w i t h N a t i o n 427
(9) d u e to d i f f e r e n t c o n d u c t i v i t y in b o t h cases.
As is s h o w n i n T a b l e I I A as e x a m p l e w i t h N a t i o n 315,
the resistance of Nation membranes immersed in potas-
s i u m e l e c t r o l y t e is l a r g e r t h a n t h a t i n s o d i u m salt s o l u t i o n
d u e to d i f f e r e n t p e r m e a b i l i t y of K ~ a n d Na% Also, t h e
specific r e s i s t a n c e i n c a r b o n a t e s o l u t i o n is l a r g e com-
p a r e d to h y d r o x i d e s o l u t i o n . T h e s e f a c t o r s reflect di-
r e c t l y t h e I R d r o p t h r o u g h t h e m e m b r a n e in p o t a s s i u m
c a r b o n a t e cell u n d e r d i s c u s s i o n . T a b l e I I B lists t h e n o m i -
n a l r e s i s t a n c e of N a t i o n m e m b r a n e s i n a d i l u t e KC1 solu-
t i o n (0.6N KC1 at 25~ r e p o r t e d b y d u P o n t ) a n d t h e t e s t
r e s u l t s o b t a i n e d i n t h e s m a l l cell u n d e r o p e r a t i n g condi-
tions.
On the other hand, very large IR drop through the
m e m b r a n e p o s i t i o n e d i n t h e v e r t i c a l cell w a s r e c o r d e d as
s h o w n i n T a b l e I. B e c a u s e t h e m e m b r a n e w a s s u p p o r t e d
by the anode mesh, chlorine bubbles liberated from the
a n o d e w e r e d i s t u r b e d to escape, a n d h e n c e t h e m e m b r a n e
s u r f a c e w a s c o v e r e d b y gas b u b b l e s to a g r e a t e x t e n t .
T h i s c a u s e s l a r g e I R d r o p t h r o u g h t h e m e m b r a n e , also
t h e a n o d e o v e r v o l t a g e . It is k n o w n t h a t gas b u b b l e s c a n
d e t a c h f r o m t h e m e m b r a n e if t h e s u r f a c e is h y d r o p h i l i c .
Uneven current distribution in the membrane attached
to t h e m e s h e l e c t r o d e is also a f a c t o r o n h i g h v o l t a g e
drop; t h a t is, t h e effective area for p a s s i n g e l e c t r o l y t i c
c u r r e n t r e d u c e s to s o m e e x t e n t , w h i c h is a c o m m o n p r o b -
l e m for t h e m e m b r a n e cell t e c h n o l o g y . C o n s e q u e n t l y , a n
a d e q u a t e l y d e s i g n e d e l e c t r o d e m u s t b e e m p l o y e d to elim-
inate, or m i n i m i z e at least, t h e s e t r o u b l e s .
T h e c a t h o d e o v e r v o l t a g e is t h e s e c o n d l a r g e s t f a c t o r o f
the terminal voltage after the membrane IR drop when
t h e p l a i n Ni c a t h o d e is u s e d . S e v e r a l c a t h o d e m a t e r i a l s
s h o w i n g l o w h y d r o g e n o v e r v o l t a g e are a v a i l a b l e in t h e
m a r k e t . T h e h y d r o g e n o v e r v o l t a g e of a R a n e y - t y p e po-
r o u s Ni c a t h o d e is v e r y low (see Fig. 8), a n d its Tafel s l o p e
is s o m e w h a t small, c a . 110 m V / d e c a d e , in c o m p a r i s o n
w i t h 142 m V / d e c a d e o f a p l a i n Ni c a t h o d e .
T h e solid line l a b e l e d 423 i n Fig. 9 s h o w s t h e volt-
a m p e r e c u r v e of t h e cell e q u i p p e d w i t h N a t i o n 423 a n d a
p o r o u s N i - c o a t e d m e s h c a t h o d e a t t a c h e d w i t h Nation.
T h e v o l t a g e s a v i n g f r o m t h e cell w i t h a p l a i n Ni c a t h o d e
(see d o t t e d line) is ca. 0.6V at 20 A / d i n 2. T h e e x p e r i m e n t a l
Table II. Resistance of Nation membranes
A. Nation 315 in various solutions at 60~
Resistance
Anolyte Catholyte (~-cm'-')

Table I. Breakdown of the cell voltage at 20 A/dm 2. 4.2M KCI 2M K2CO3 4.0
Membrane: Nation 423. Anode: MODE mesh. Cathode: plain Ni plate. 1M K~CO:~ + 2M KOH 3.2
Cathode-to-membrane gap: 6 mm. Flow rate: 3 liter/min. ~ = 1. 4M KOH 2.7
Temperature: 60~ 5.4M NaC1 2M Na.2CO3 2.7
1M Na~CO3 + 2M NaOH 2.0
4M NaOH 1.6
Small cell Vertical cell
(V) (V)
B. Nation 423, 417, and 315
Anode potential 1.350 1.563
Reversible potential 1.300 1.300 Resistance (D-cm2)
Overvoltage 0.050 0.263 Type of Nation membranes Nominal ~ Measured h
Cathode potential -1.315 -1.321
Reversible potential -0.735 -0.735 423 5-1200/T-12 5.4 3.3
Overvoltage -0.580 -0.586 417 7-1100/T-12 4.1 2.3
Catholyte IR drop 0.348 0.368 315 2-1500/4-1100/T-12 5.5 4.0
Membrane IR drop 0.662 1.130
Membrane potential -0.010 -0.025
a In 0.6N KC1 at 25~ quoted from du Pont's brochure.
(Sum) Terminal voltage 3.665 4.357 b Anolyte: 4.2M KC1. Catholyte: 2.0M K2CO3 at 60~
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 2340 J. Electrochem. Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y
10 l l I I
9 315
7 ond stage of the tower where the solution absorbs more
> CO~ to obtain bicarbonate (reaction [4A]) to prepare the
O1' 6
~ s.O
-- .-" 423
o
;>
5 .e"
a
2 I J I I _
0 10 20 30 40
Current Density ( A / d m 2)
Fig. 9. Voltage vs. current density curves (solid line) of the vertical cell
equipped with MODE and a porous Ni cathode attached with Nation
membrane at 60~ Dotted line shows the results with a plain Ni cathode
located at 6 mm for the membrane (see Fig. 8). Catholyte flow: 3
liter/min. ~ = 0,9-1.0,
results with other membranes are also shown. The cath-
ode current efficiency at 20 A/dm ~ was, of course higher
than 95% in all cases.
The solution temperature is an important factor for cell
operation. The higher the temperature, the lower is the
cell voltage. The cell voltage could be reduced further by
0.2V when the operating temperature is raised from 60~ to
90~ whereas only few experiments were conducted un-
der such conditions since the plastic cell was affected by
chemical attack.
Most experiments described here were conducted with
the catholyte of 2M total concentration and at the current
density of 20 A/dm ~ for the convenience of experiment. Of
course, the higher the concentration, the lower was the
cell voltage. The current efficiency was almost indepen-
dent of the total catholyte concentration. Therefore, the
concentration must be kept as high as possible. Also, we
estimate that an optimum current density may exist at
higher levels than 20 A/din2, so that the investment or the
fixed charge is lowered while further experiment and en-
gineering considerations are required for evaluating the
economy of this process.
Absorption of carbon dioxide with potassium hydrox-
ide solution (reaction [6]) followed by reaction [4] or [7] is
a typical process of gas absorption accompanied with
chemical reaction (10-12), and is very fast, especially at
high temperatures
CO.2 + 2KOH = K~CQ + H~O
and
CO~ + K2CO3 + H20 = 2KHCO,
The catholyte can be carbonated by introducing CO2 gas
into the cathode, compartment, while the cell configura-
tion is complicated somewhat (4). However, use of a sepa-
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October 1985
rate reactor in parallel with the electrolyzer is preferable
for easy operation and reduction of the energy consump-
tion, as is illustrated in Fig. 1.
Excess caustic in the catholyte effluent is neutralized
in the upper column of the absorption tower (see Fig. 1),
and a part of solution is recovered as an intermediate of
the product, which is concentrated or evaporated, de-
pending on the market. Remains flow down to the sec-
catholyte liquor.
In conclusion, electrochemical production of potassium
carbonate with a m e m b r a n e cell was studied. The cath-
ode current efficiency was high at almost 100% in a wide
range of the operating conditions since the O H - concen-
tration in the cathode compartment was low. The IR drop
through the m e m b r a n e was the largest factor of the ter-
minal voltage. Although Nation 423 was employed most
often in this experiment, any m e m b r a n e having lowest re-
sistivity is preferable since the O H - concentration in the
catholyte liquor is sufficiently low, and further reduction
of the cell voltage is thus anticipated. The flowsheet
shown in Fig. 1 is applicable to practice because of easy
50 operation of the whole process of interest.
Acknowledgments
The Nation membranes were supplied by the Experi-
mental Station of E. I. du Pont de Nemours and Com-
pany, Wilmington, Delaware, by arrangements of Mr. S.
Higuchi of du Pont Japan, Tokyo. The Raney-type Ni-
coated cathode was prepared by Showa Company, Nara,
Japan. The authors wish to thank Y. Ishida, A. Kuroyan-
agi, and N. Yamauchi for their laboratory efforts.
Manuscript submitted March 19, 1985; revised manu-
script received ca. J u n e 28, 1985. This was Paper 423 pre-
sented at the Toronto, Ontario, Canada, Meeting of the
Society, May 12-17, 1985.
Nagoya Institute of Technology assisted in meeting the
publication costs of this article.
REFERENCES
1. "Lange's Handbook of Chemistry," 12th ed., J. A.
Dean, Editor, Section 10, McGraw-Hill, New York
(1979).
2. W. Yang, K. Hara, and F. Hine, Soda to Enso, 33, 123
(1982).
3. H. Kaden, P. Vo]land, K. Z i m m e r m a n n , and H.
Hofmann, Chem. Technol., 27, 356 (1975).
4. D. L. DeRespiris and T. J. Gilligan, Abstract 451, p.
1130, The Electrochemical Society Extended Ab-
stracts, Vol. 78 1, Seattle, WA, May 21-26, 1978.
5. W. Yang and F. Hine, Soda to Enso 33, 192 (1982).
6. K. Sekine and C. Motohashi, ibid., 33, 66 (1982).
7. C. Motohashi, ibid., 34, 516 (1983).
8. T. Asaki, Y. Kamegaya, and K. Takayasu, in "Ad-
vances in the Chlor-Alkali and Chlorate Industry,"
M. M. Silver and E. M. Spore, Editors, p. 165, The
Electrochemical Society Softbound Proceedings
Series, Pennington, NJ (1984).
[6] 9. T. Berzins, Abstract 437, p. 1137, The Electrochemical
Society Extended Abstracts, Vol. 77-2, Atlanta, GA,
Oct. 9-14, 1977.
10. "Chemical Engineers' Handbook," 5th ed., R. H.
[7] Perry and C- H. Chilton, Editors, Section 14,
McGraw-Hill, New York (1973).
11. S. Hatta, Kogyo Kagaku Zasshi, 31, 869 (1928); ibid.,
32, 809 (1929).
12. S. Hatta, ibid., 35, 1397 (1932); ibid., 36, 7 (1933).