United States Patent [19] [11] Patent Number: 4,479,864

Kauai et al. [45] Date of Patent: Oct. 30, I984

[54] ANODE FOR ELECTROLYSIS OF 4,248,906 2/ 1981 Saito et al. ........................ .. 427/128
SEAWATER
FOREIGN PATENT DOCUMENTS
[75] Inventors: Hideo Kauai; Akihiro Shinagawa,
both of Maebashi; Takahiro 771125 1l/l967 Canada .......................... .. 204/290 F
Yamazaki, Shibukawa; Reiichi Itai, 68076 6/1977

146887 ll/l98l
Japan . . . . . . . . . .. 204/290 F

Japan ............................ .. 204/290 R

Maebashi, all of Japan
[73] Assignee: The Japan Carlit C0., Ltd., Tokyo, Primary Examiner~T. Tung
Japan Assistant Examiner-Terryence Chapman
[21] Appl. No.: 518,220 Attorney, Agent, or Firm-Frishauf, Holtz, Goodman &
Woodward
[22] Filed: Jul. 28, 1983
[57] ABSTRACT
[30] Foreign Application Priority Data
An anode for generating available chlorine from seawa
Aug. 4, 1982 [JP] Japan .............................. .. 57-135200 ter by electrolysis which comprises a substrate made of
[51] Int. Cl.3 ........................................ .. C25B 11/06 titanium or an alloy thereof, and a coating on said sub
[52] US. Cl. .......................... .. 204/290 F; 204/290 R; strate which is made up of an active anode material
204/291 layer containing 15-85 wt % of platinum, 5-35 wt % of
[58] Field of Search ............. .. 204/290 R, 290 F, 291; iridium dioxide, and 10~l5 wt % of ruthenium dioxide.
427/125, 126.3, 126.5, 229 The anode has greatly improved anode performance
[56] References Cited such as current efficiency, cell voltage, and durability.
Therefor, its use for a long period of time becomes
U.S. PATENT DOCUMENTS possible in any condition of seawater.
3,711,385 l/l973 Beer ............................... .. 204/290 F
4,233,340 1/1980 Saito et al. ........................ .. 427/125
4 Claims, 2 Drawing Figures

CURENTEEFICENY
CEL TEclvgaRATU
1
> r
V .

l
100 200 300 400 500 600 700
ELECTROLYSIS PERIOD (DAYS)
UM Patant 0a. 30, 1984 Sheet 1 of 2 4,479,864

Fig. I

CURENT (0/0)
E

CEL VTEOFMLPICRAGNUYPo)
8
6 l I

CEL
).J>01
0 l

Am
I00 200 300 400 500 600 700
ELECTROLYSIS PERIOD (DAYS)
i1'*atent Oct. 30, 1984 Sheet 2 of 2 4,479,864

Fig. 2

@L 90
/

w
m
/.

SEAWATER TEMPERATURE (C)

 1
4,479,864
2
damage such as erosion and against an environment of
ANODE lFOR ELECIROLYSIS OF SEAWATER oxygen evolution.
Still another object of this invention is to provide a
FIELD OF THE INVENTION process for producing an anode for seawater electroly
This invention relates to an anode which is suitable sis which has greatly improved durability and charac
for electrolytic generation of hypochlorites from sea teristics.
water. The invention also relates to an anode for seawa Other objects and advantages of the present invention
ter electrolysis which has excellent anode characteris may become apparent to those skilled in the art from the
tics and adequate durability even in cold seawater. The following description and disclosure.
invention also relates to a process for producing such an BRIEF DESCRIPTION OF THE DRAWINGS
anode.
This invention is further described with reference to
DESCRIPTION OF PRIOR ART the accompanying drawings.
In land-based seawater cooling, there may arise fre FIG. 1 represents the relationship between the results
quent troubles due to marine organism growths and of using an anode of this invention and operation period
deposits on pipings. To avoid this, chlorination of sea (days) of seawater electrolysis.
water is successfully carried out by feeding hypochlor FIG. 2 represents the relationship between a given
ites generated by direct electrolysis of seawater. But, in temperature of seawater and current ef?ciency for
such a process, there are many factors which affect available chlorine obtained with an anode of this inven
electrolytic performance and anode life. For example, tion as compared with other conventional anodes.
low chloride ion concentration gives rise to a reduction DESCRIPTION OF THE PREFERRED
of current ef?ciency and promotes generation of oxy EMBODIMENT
gen instead of useful chlorine. This side reaction practi
cally excludes the use of ruthenium oxide anodes for For the purpose of producing an anode that is satis
this purpose, since such ruthenium oxide anodes are factory for use in seawater electrolysis, we have made
known to be particularly susceptible to the environment extensive studies on the anodic characteristics and the
of oxygen evolution. The lowering temperature of sea durability of anode materials, the combination of coat
water in winter also can cause extreme deterioration of
ing materials and the operating conditions for produc
current ef?ciency and durability of anodes. Further ing the anode. As a result, we have found that an anode
more, abrasions due to suspended solids in seawater and
for seawater electrolysis that has greatly improved
anode characteristics in cold seawater and that has ex
the pressure of high speed seawater flows combined can
cause mechanical damages such as erosion.
cellent durability against mechanical damages and an
environment of oxygen evolution can be produced by
In spite of successful uses of a number of metal anodes
forming a coating made of the following preferred con
in brine electrolysis as in the chlor-alkali industry, the 35
tents: platinum, iridium dioxide, and ruthenium dioxide
only anodes which have proved fairly durable in seawa as an anode active material. ,
ter electrolysis have been platinum-coated titanium Therefore, this invention relates to an anode for sea
anodes and a few others. Even these anodes are not water electrolysis which has on a substrate made of
satisfactory for extended uses on account of the follow
titanium or its alloy a coating made of platinum (15-85
ing defects. For example, both an anode coated with a 40 wt %), iridium dioxide (5-35 wt %), and ruthenium
solid solution of ruthenium dioxide and titanium dioxide dioxide (l0~50 wt %) formed by heating a layer of an
(see US. Pat. No. 3,632,498) and an anode coated with organic solution containing the halides of said metals
platinum, ruthenium dioxide, palladium oxide, and tita applied onto said substrate either by brushing or by
nium dioxide (see Japanese Patent No. 1,083,040 immersion or by any other known method of applica
Japanese patent publication No. 55-35473) did not 45 tion. The invention also relates to a process for produc
have adequate durability for electrolysis in cold seawa ing such an anode.
ter. An anode coated with an alloy of platinum and The substrate used in this invention is made of tita
iridium (see British Patent No. 964,913) was not suitable nium or a titanium alloy such as titanium-palladium of
in such electrolysis owing mainly to its susceptibility to commercial grades in the form of sheets, wire, screens,
erosion. Even platinum-coated titanium anodes used 50 bars, or any other shapes desired.
now, presently give relatively high cell voltages and a Within the limits of the composition of the coating
current ef?ciency of less than 80%, thus being unsatis materials of this invention, the advantageous properties
factory, too. In this way, an improvement in the anode of each component of the coating materials can be effec
manifesting excellent anodic characteristics and durabil tively exhibited and can sufficiently make up for weak
ity in low temperatures has been long sought for in the points manifested by the other components. Namely,
?eld of seawater electrolysis for the chlorination of more than 15 wt % of platinum increases oxygen over
cooling systems in land-based industries. voltage and durability as well, while preventing the
SUMMARY OF THE INVENTION deterioration of the current ef?ciency for generating
available chlorine in cold seawater. Likewise, more
An object of this invention is to obtain an anode that 60 than 5 wt % of iridium dioxide prevents deterioration of
is satisfactory for use in seawater electrolysis in all sea the current ef?ciency in cold seawater and improves
sons. durability against oxygen and mechanical stability
Another object of this invention is to obtain an anode against erosion. Furthermore, more than 10 wt % of
that assures a high current efficiency for generating ruthenium dioxide causes both a lowering of chlorine
available chlorine in excess of 80% even in cold seawa 65 overvoltage and an increase in mechanical strength.
ter. Even if an anode for seawater electrolysis is coated
Still another object of this invention is to obtain an with the same materials as speci?ed by this invention
anode that has excellent durability against mechanical but with a composition detached from the preferable
 4,479,864
3 4
ranges of this invention, the electrolytic performances The coating is formed by applying hexachloroplatinic
such as current efficiency, cell voltages, and durability acid, iridium tetrachloride, and ruthenium trichloride
will become insufficient. Namely, platinum contained in dissolved in isopropyl alcohol on to the surface treated
an amount of more than 85 wt % results in a decrease in substrate, drying, and then heat treating. The solution is
the current efficiency and rise in the cell voltage, adjusted so that each component after heat treatment
whereas platinum contained in an amount less than 15 might fall within the preferred range of composition of
wt % causes an excessively lowered oxygen overvolt this invention. An example of solution makeup is as
age, an increase deterioration of the current efficiency follows; First, 6.6 parts by weight of hexachloroplatinic
in cold seawater, and a reduced durability. If the con acid, 1.2 parts by weight of iridium tetrachloride and 1.0
tent of iridium dioxide exceeds 35 wt %, the oxygen O part by weight of ruthenium trichloride are weighed,
overvoltage begins to decline, thus lowering current mixed, and added to 40 parts by weight of isopropyl
ef?ciency. On the other hand, if the content of iridium alcohol to dissolve. In order to accelerate dissolution,
dioxide is less than 5 wt %, then the deterioration of 2-6 parts by weight of hydrochloric acid may be added.
current efficiency, especially in cold seawater, and the Similarly, to prevent excessive oxidation, a reducing
lack of durability against oxygen becomes remarkable. agent such as anise oil or lavender oil can also be effec
Furthermore, ruthenium dioxide contained in an tively used. This solution is applied to the pre-treated
amount of more than 50 wt % results in an excessive substrate by painting or immersing, and then dried.
decrease in current efficiency and durability for elec After drying, the unit is heated in an electric oven at
trolysis in cold seawater, whereas ruthenium dioxide 450~500 C. for 20 to 90 minutes. The cycle of applica
contained in an amount less than 10 wt % lowers both tion, drying, and heating is repeated until a desired
erosion resistance and current ef?ciency. metal loading is obtained. The preferable range of the
The role played by each component of the coating metal loading or the total weight of the platinum group
layer in improving the anode performance has not been metals per unit active area of the anode is between 5 and
fully explained, but as far as we know, the high oxygen 60 g/m2. ,
overvoltage characteristics of metallic platinum com The anode produced in compliance with this inven
bines synergistically with the low chlorine overvoltage tion can be used with particular advantage for generat
characteristics of iridium dioxide and ruthenium dioxide ing available chlorine from seawater by electrolysis.
to increase the difference between the oxygen evolving However, it can equally well be used for electrolysis of
diluted brine at a concentration similar to seawater for a
potential and the chlorine evolving potential, thus in wide area of applications including disinfection of city
creasing the current efficiency. Furthermore, the incre
ment of mechanical strength can most certainly be at water, swimming pools, and sewage.
When used for electrolysis of seawater, the anode of
tributed to the excellent hardness of iridium and ruthe this invention can give a current efficiency in excess of
nium oxides, and the improvement of anode perfor 80 percent even at a low temperature. This, in combina
mance in cold seawater that is achieved appears to have
tion with a low cell voltage, allows an electric power
been derived from the low temperature electrode char consumption reduced by one-third of that required for a
acteristics of platinum and iridium dioxide and from the conventional platinum-coated titanium anode. Also due
durability characteristics of iridium dioxide in oxygen to its resistance against mechanical wear, such as ero
environments. Furthermore, the low cell voltage char sion, and to its electrochemical stability, it was recog
acteristics obtained are probably derived from the high nised that it permit continuous operation for over 1.5
conductivity of each component as well as the low years. Moreover, the process for producing the anode
chlorine overvoltage characteristics of ruthenium diox of this invention has proved economical, since the pro~
ide. ducing procedure is simple and requires less platinum
The anode of this invention is produced by the fol group metals than the electroplating process for making
lowing procedure. A titanium or titanium alloy sub 45 conventional platinum-plated titanium anodes. These
strate is degreased with an organic solvent such as tri advantages obtained in practical production are much
chloroethylene and ethylene chloride, and after being greater than those obtained formerly, and hence the
roughened by a sandblast treatment, is surface washed process of this invention is highly valuable as an indus
with acid. On the surface of this substrate, a coating trial means.
consisting of metallic platinum, iridium dioxide and This invention is now described in greater detail by
ruthenium dioxide within the preferred range of compo reference to the following examples which are given
sition is formed by a heating method. The coating is here for illustrative purposes only and are by no means
made of a platinum halide selected from the group con intended to limit the scope of the invention.
sisting of platinum dichloride, platinum tetrachloride,
hexachloroplatinic acid, and platinum tetraiodide, an 55 EXAMPLE 1
iridium halide selected from the group consisting of A titanium sheet measuring 155 mm><400 mmX 3 mm
iridium monochloride, iridium trichloride, iridium tetra was degreased in a degreasing apparatus containing
chloride, iridium tetrabromide, and hexachloroiridic trichloroethylene. The surface of the titanium sheet was
acid and a ruthenium halide selected from the group roughened by sandblast treatment and then washed by
consisting of ruthenium dichloride and ruthenium tri immersion in a 5% hydrofluoric acid solution, followed
chloride. As the solvent to dissolve these halides, iso by a water wash. A coating solution, the composition of
propyl alcohol, n-butyl alcohol, and amyl alcohol can which is shown below, was prepared by mixing in the
be used. A combination of hexachloroplatinic acid, order listed. The solution was applied to the titanium
iridium tetrachloride, ruthenium trichloride and isopro substrate with a brush and then dried.
pyl alcohol is most preferred on account of the suitable
solubility relationship. The following description as
sumes the use of these halides as the material for coat Composition of coating solution
mg. 1. Hexachloroplatinic acid 6.6 g
 4,479,864
5 6
_Continued as for the anode of Example 1 the results being shown in
Table 1 below:
TABLE 1
Average
power
consump
Seawater Cell Current tion Test
temp. voltage ef?ciency (kWh/kg. period
(C.) (V) (%) C12) (days) Remarks
Anode of 8-28 3.7-5.0 86-95 3.7 696
Example 1 (4.5) (91)
Pt-plated " 4.8-5.6 72-75 5.4 720
Ti anode (5.2) (73)
Titanium Anode " 3.9-7.0 67-94 4.8 200 The
with (4.8) (75) anode
R1102 (40 mol %) life
T102 (60 mol %) tenni
coating nated.
Note:
The ?gures in parentheses are averages.

Composition of coating solution

As shown in Table 1, the anode of Example 1 gave an
2. Iridium tetrachloride 1.2 g
3. Ruthenium trichloride 1.0 g
average current ef?ciency higher than 90% over the
4. Hydrochloric acid 5.0 ml whole duration of electrolysis, the current ef?ciency at
5. Isopropyl alcohol 40 ml low temperature periods being kept higher than 85%.
6. Lavender oil 10 ml
25 COMPARATIVE EXAMPLE 1
The unit was transferred into an electric oven where An anode prepared as in Example 1 was compared
it was heated in air at 500 C. for 1 hour. The cycle of with other types of anode in the electrolysis of seawa
application, drying and heating was repeated seven ter. The relationship obtained between temperature of
times. - seawater and current ef?ciency is shown in FIG. 2.
30
Analysis of the composition of the coating layer wit Curves a, b, c and d represent the anode prepared as
an X-ray diffractometer gave 65 wt % metallic plati in Example 1, a titanium anode coated with ruthenium
num, 20 wt % iridium dioxide'and 15 wt % ruthenium dioxide and titanium dioxide, a platinum-plated titanium
dioxide. Measurements of the thickness of the coating anode and an in'dium dioxide-coated titanium anode,
with an RI ?uorescent X-ray spectrometer (source : 35 respectively. The anode coated with ruthenium dioxide
plutonium 238 ; Measuring time : 40 seconds) gave a (40 mol %) and titanium dioxide (60 mol %) showed
metal loading of 3O'g/m2. lower current efficiencies at lower temperatures and the
temperature at which a drop of current efficiency was
EXAMPLE 2 observed was higher than the others.
An anode prepared as in Example 1 was used for 40 The Platinum-coated titanium anode and the titanium
electrolysis of seawater under the following conditions. anode coated with iridium dioxide showed little de
The results are shown in FIG. 1. crease in current ef?ciency with lowering temperature
but its values were as low as 75% (9.5 C.) and 66%
(8.5 C.), respectively. In contrast, the anode of this
Electrolysis conditions invention showed little decrease in current ef?ciency
Electrolyte seawater during the low temperature operations and still main
Electrolyte temperature 8-28' C. tained a current ef?ciency of more than 80% even at a
Anode current density 10 A/dm2 temperature of 8 C.
Flow rate of electrolyte 20 l/min
COMPARATIVE EXAMPLE 2
No abnormal increase in the cell voltage was ob 50 In order to examine the validity of the preferred
served during the electrolysis which lasted for one year range of composition of the anode coatings of this in
and eleven months. Likewise, no abnormal decrease in vention, various specimens having a composition shown
current ef?ciency took place. in Table 2 were prepared and were subjected to the
For the purpose of comparison, a platinum-plated electrolysis of seawater at anode current density: 20
titanium electrode and a titanium anode coated with 55 A/dmz.
ruthenium dioxide and titanium dioxide were used in The results are shown in Table 2 below.
the electrolysis of seawater under the same conditions
TABLE 2
Composition Flow rate
of coating Sea of sea Cell Current Test
Sample (wt %) water water voltage ef?ciency period
No. Pt IrO; RuOz ("C.) (m/sec) (V) (%) (days) Appearance
1 65 20 15 10-17 0.8 4.8-5.6 86-94 90 No change
2 15 20 65 10-15 " 4.9-7.5 75-90 70 The surface
coat thinned.
3 I5 70 15 10-17 5.0-5.7 74-76 90 No change
4 90 5 5 5.3-6.0 75-76 " A trace of
' erosion was
 4,479,864
7 It;
TABLE 2-continued
Composition Flow rate
of coating Sea of sea Cell Current Test
Sample twt %! water water voltage efficiency period
No. Pt lrOg RuOz (C.) (m/sec) (V) (%) (days) Appearance
detected.

Satisfactory results were obtained with Anode-l of Available chlorine of which the concentration was
which the coating composition was within the preferred 8,000 ppm was continuously obtained from 3% brine.
range. . No abnormal increase in the cell voltage and no
But with Anode-2 through 4 of which the coating change of surface was observed during the electrolysis
composition was outside the preferred range, only very which lasted for one year and it was possible to do
low current efficiencies were obtained. In particular, stable electrolysis.
Anode-2 showed a remarkable decrease in current effi 5
ciency at a low temperature and an increase in the cell EXAMPLE 4
voltage as well. A titanium sheet measuring 155 mm X400 mm X 3 mm
These experiments were conducted at an elevated was degreased in a degreasing apparatus containing
seawater flow rate of 0.8 m/s to accelerate the process trichloroethylene. The surface was roughened by sand
of mechanical deterioration. 20 blast treatment and then washed by immersion in a 5%
At this flow rate, Anode-4 showed traces of erosion hydro?uoric acid solution, followed by a water wash.
after 90 days. . A coating solution the composition of which is shown
EXAMPLE 3 below was prepared by mixing in the order listed.
The solution was applied to the titanium substrate
A titanium-palladium alloy sheet measuring 50 with a brush and then dried.
mm>< 150 mm><3 mm was degreased by ethylene chlo
ride. The surface was roughened by sandblast treat
ment. The sheet was then immersed in a hot oxalic acid Composition of coating solution
solution for 1 hour and washed with water. 1. Hexachloroplatinic acid 4.9 g
A coating solution the composition of which is shown 2. Hexachloroiridic acid 0.9 g
3. Ruthenium trichloride 2.5 g
below was prepared by mixing in the order listed. The 4. Hydrochloric acid 5.0 ml
solution was applied to the titanium-palladium alloy 5. Isopropyl alcohol 40 ml
substrate with a brush and then dried. 6. Lavender oil 10 l

Composition of coating solution 35 The unit was transferred into an electric oven where
1. Platinum tetrachloride 657 mg
it was heated in air at 500 C. for 1 hour. The cycle of
2. Hexachloroiridic acid 408 mg application, drying and heating was repeated seven
3. Ruthenium trichloride 381 mg times.
4. Hydrochloric acid 0.6 mg Analysis of the composition of the coating layer with
5. N-butyl alcohol 8.0 mg an X-ray diffractometer gave: 50 wt % metallic plati
6. Anise oil 1.0 mg
num, 10 wt % iridium dioxide and 40 wt % ruthenium
dioxide.
The unit was transferred into an electric oven where Measurement of the thickness of the coating with an
it was heated in air at 480 C. for 1.5 hours. The cycle RI ?uoresent X-ray spectrometer gave a metal loading
of application, drying and heating was repeated ten 45 of 30 g/m2.
times. This anode was used for electrolysis of seawater
Analysis of the composition of the coating layer with under the same conditions as Example 2.
an X-ray diffractometer gave: 40 wt % metallic plati No abnormal increase in the cell voltage was ob
num, 30 wt % iridium dioxide and 30 wt % ruthenium served during the electrolysis which lasted for one year
dioxide. 50 and six months. Likewise, no abnormal decrease in
Measurement of the thickness of the coating with an current efficiency took place.
RI fluorescent X-ray spectormeter gave a metal loading What is claimed is:
of 50 g/m2. 1. An anode for generating available chlorine from
This anode was used for electrogeneration of hypo seawater by electrolysis which comprises a titanium or
chlorite as a sterilization agent for a swimming pool. 55 titanium alloy substrate having an outer active anode
The results are shown in Table 3. For the purpose of coating on said substrate, said outer coating consisting
comparison, the results using a normal platinum-plated essentially of an active anode layer containing from 15
titanium anode are also shown in Table 3. to 85% by weight of platinum, from 5 to 35% by weight
TABLE 3
effec- current power
cell current cell tive efii- consump
Electro- temp. density voltage C12 ciency tion
lyte ("C) (A/dmz) (V) (ppm) (%) (kWh/ks - C12)
Anode of 3% 30 10 3.5 8,000 84 3.1
Example 3 NaCl
Pt-plated 3% " " 4.8 6,000 54 6.7
Ti anode NaCl
 4,479,864
9 10
of iridium dioxide and from 10 to 50% by Weight of strate consists essentially of titanium and is integral with
ruthenium dioxide _ , _ _ said outer active coating.
2' The anode according to Glam 1 where! Said coat- 4. The anode according to claim 1 wherein said sub
ing is integral with said substrate and has a metal load- _ _ _ , _ _ .
ing of 5_60 g/mz expressed as the total weight of p1ati_ 5 strate consists essentially of titanium and is integral with
num group metals per unit active area of the anode. said outer ?ctiv? Coating
3. The anode according to claim 2 wherein said sub- * * * * *

10

2O

25

3O

35

45

so

55

60

65