U.S. patent number 3,926,770 [Application Number 05/421,706] was granted by the patent office on 1975-12-16 for electrolytic cell having silicon bipolar electrodes.
This patent grant is currently assigned to PPG Industries, Inc.. Invention is credited to Howard H. Hoekje.
United States Patent |
3,926,770 |
Hoekje |
December 16, 1975 |
Electrolytic cell having silicon bipolar electrodes
Abstract
Disclosed is a bipolar electrolyzer having a plurality of
bipolar electrodes. The bipolar electrodes are electroconductive
silicon metallic electrodes having an anodic surface on one side
and a cathodic surface on the opposite side.
Inventors: |
Hoekje; Howard H. (Akron,
OH) |
Assignee: |
PPG Industries, Inc.
(Pittsburgh, PA)
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Family
ID: |
27500685 |
Appl.
No.: |
05/421,706 |
Filed: |
December 4, 1973 |
Related U.S. Patent Documents
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Application
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Filing Date |
Patent Number |
Issue Date |
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260790 |
Jun 8, 1972 |
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336288 |
Feb 27, 1973 |
3852175 |
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356972 |
May 3, 1973 |
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336288 |
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356972 |
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260790 |
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356972 |
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336288 |
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Current U.S.
Class: |
204/256; 204/255;
204/291; 205/511; 204/254; 204/268; 204/293; 204/290.12;
204/290.14; 204/290.01 |
Current CPC
Class: |
C25B
11/069 (20210101); C25B 9/75 (20210101); C25B
11/036 (20210101) |
Current International
Class: |
C25B
9/20 (20060101); C25B 11/00 (20060101); C25B
9/18 (20060101); C25B 11/04 (20060101); C25B
011/04 () |
Field of
Search: |
;204/254,255,256,268,29R,291 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Mack; John H.
Assistant Examiner: Solomon; W. I.
Attorney, Agent or Firm: Goldman; Richard M.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This is a continuation-in-part of my commonly assigned, copending
U.S. application Ser. No. 260,790 filed June 8, 1972, now abandoned
of my commonly assigned, copending U.S. application Ser. No.
336,288, filed Feb. 27, 1973, now U.S. Pat. No. 3,852,175, which is
in turn a continuation-in-part of said U.S. application Ser. No.
260,790 and of my commonly assigned, copending U.S. application
Ser. No. 356,972 filed May 3, 1973, now abandoned, which is in turn
a continuation-in-part of said U.S. application Ser. No. 260,790
and Ser. No. 336,288.
Claims
I claim:
1. A bipolar electrolyzer having a plurality of bipolar electrodes
mechanically and electrically in series, with an anodic surface of
one bipolar electrode facing a cathodic surface of the next
adjacent bipolar electrode and forming an electrolytic cell
therebetween, at least one of said bipolar electrodes comprising an
electroconductive metallic silicon member containing at least 45
weight percent silicon and sufficient dopant to provide said member
with an electroconductivity greater than 100
(ohm-centimeters).sup.-.sup.1 and having an anodic surface on one
side of said member and a cathodic surface on the opposite side
thereof.
2. The electrolyzer of claim 1 wherein said dopant is chosen from
the group consisting of boron, aluminum, gallium, phosphorous,
arsenic, antimony, and bismuth.
3. The electrolyzer of claim 1 wherein said metallic bipolar
electrode contains from about 0.01 to about 5 weight percent of the
dopant.
4. The electrolyzer of claim 1 wherein said metallic bipolar
electrode contains from about 45 to about 99 weight percent
silicon.
5. The electrolyzer of claim 1 wherein the anodic surface of the
bipolar metallic electrode comprises a coating of an
electrocatalytic material on the bipolar electrode.
6. The electrolyzer of claim 5 wherein said electrocatalytic
material is characterized by a chlorine overvoltage of less than
0.25 volt when measured in chlorinated brine at a current density
of 125 Amperes per square foot.
7. The electrolyzer of claim 1 wherein the cathodic surface of the
bipolar metallic electrode comprises a coating of a material having
a hydrogen overvoltage less than 0.35 volt at 125 Amperes per
square foot.
8. The electrolyzer of claim 1 wherein the cathodic surface of the
bipolar metallic electrode comprises a coating of a metal chosen
from the group consisting of iron, cobalt, nickel, and
manganese.
9. The bipolar electrolyzer of claim 1 wherein said metallic
bipolar electrode comprises means for spacing said metallic bipolar
electrode from the adjacent bipolar electrode while providing an
electrolyte tight seal therebetween.
10. The bipolar electrolyzer of claim 9 wherein said spacing means
comprise a peripheral wall.
11. The bipolar electrolyzer of claim 10 wherein said means for
providing an electrolyte tight seal comprises gasket means between
the peripheral walls of adjacent bipolar electrodes.
12. The bipolar electrolyzer of claim 1 wherein said metallic
bipolar electrode includes gas header means.
13. The bipolar electrolyzer of claim 12 wherein said gas header
means is mounted on top of the metallic bipolar electrode, extends
beyond the anodic and cathodic surfaces thereof, and comprises
means for the recovery of cathodic gases and means for the recovery
of anodic gases.
14. The bipolar electrolyzer of claim 1 wherein said metallic
bipolar electrode includes liquid header means.
15. The bipolar electrolyzer of claim 14 wherein said liquid header
means is mounted on the bottom of the metallic bipolar electrode
and extends beyond the anodic and cathodic surfaces thereof, and
comprises means for feeding brine and means for recovering cell
liquor.
16. The bipolar electrolyzer of claim 1 wherein said metallic
bipolar electrode comprises:
a. peripheral wall spacing means on the vertical sides thereof to
space said bipolar electrode from adjacent bipolar electrodes and
provide electrolyte volumes therebetween;
b. gas header means on the top of and extending beyond the anodic
and cathodic surfaces of the metallic bipolar electrode; and
c. liquid header means on the bottom of and extending anodic and
cathodic surfaces of the metallic bipolar electrode.
17. The bipolar electrolyzer of claim 16 wherein the leading edges
of said peripheral walls, gas header means, and liquid header means
are substantially in a single plane.
18. The bipolar electrolyzer of claim 16 wherein compressive means
extend from an end cell of said bipolar electrolyzer, through the
metallic bipolar electrodes thereof, to an opposite end cell
thereof.
19. The bipolar electrolyzer of claim 16 wherein said header means
are metallurgically joined to said metallic bipolar electrode.
20. The bipolar electrolyzer of claim 16 wherein said header means
are mechanically joined to said metallic bipolar electrode.
21. The bipolar electrolyzer of claim 20 wherein said header means
are joined to said metallic bipolar electrode by compressive means
extending from said gas header means to said liquid header
means.
22. The bipolar electrolyzer of claim 1 wherein the
electroconductive silicon bipolar electrode comprises a single
silicon member.
23. The bipolar electrolyzer of claim 1 wherein the
electroconductive silicon bipolar electrode comprises a plurality
of individual silicon members having electrolyte tight seals
between adjacent individual silicon members.
24. The bipolar electrolyzer of claim 23 wherein said individual
silicon members are compressively held together to form an
electrolyte tight metallic bipolar electrode.
25. The bipolar electrolyzer of claim 23 wherein said individual
silicon members are metallurgically joined together to form an
electrolyte tight metallic bipolar electrode.
26. The bipolar electrolyzer of claim 1 wherein permeable barrier
means are interposed between said metallic bipolar electrode and an
adjacent bipolar electrode.
27. The bipolar electrolyzer of claim 26 wherein said permeable
means comprise electrolyte permeable diaphragm means.
28. The bipolar electrolyzer of claim 26 wherein said barrier means
comprise ion permeable membrane means.
29. A bipolar electrolyzer having a plurality of individual
electrolytic cells mechanically and electrically in series, at
least one of said cells comprising:
a first silicon cell unit having an anodic surface thereon;
a second silicon cell unit spaced from said first cell unit and
having a cathodic surface thereon facing the anodic surface of the
first silicon cell unit;
said first cell unit and second cell unit defining an electrolyte
chamber therebetween; and
each of said silicon cell units comprising at least 45 weight
percent silicon and sufficient dopant to provide an electrical
conductivity of at least 100 (ohm-centimeters).sup.-.sup.1.
30. The electrolyzer of claim 29 wherein said dopant is chosen from
the group consisting of boron, aluminum, gallium, phosphorous,
arsenic, antimony, and bismuth.
31. The electrolyzer of claim 29 wherein said silicon cell units
contain from about 0.01 to about 5 weight percent of the
dopant.
32. The electrolyzer of claim 29 wherein the surface of said first
silicon cell unit comprises a coating of an electrocatalytic
material on the silicon.
33. The electrolyzer of claim 32 wherein said electrocatalytic
material is characterized by a chlorine overvoltage of less than
0.25 volt when measured in chlorinated brine at a current density
of 125 Amperes per square foot.
34. The electrolyzer of claim 29 wherein the surface of said second
silicon cell unit comprises a coating of a material having a
hydrogen overvoltage less than 0.35 volt at 125 Amperes per square
foot.
35. The electrolyzer of claim 29 wherein the surface of said second
silicon cell unit comprises a coating of material chosen from the
group consisting of iron, cobalt, nickel, and manganese.
36. The bipolar electrolyzer of claim 29 comprising spacing means
and sealing means for maintaining an electrolyte tight seal between
said first cell unit and said second cell unit while maintaining
the anodic surface of the first cell unit spaced from cathodic
surface of the second cell unit, thereby defining an electrolyte
volume therebetween.
37. The electrolyzer of claim 36 wherein said spacing means
comprise a peripheral wall on at least one of said cell units.
38. The electrolyzer of claim 37 wherein said spacing means
comprises a peripheral wall on the edges of at least one of said
cell units.
39. The electrolyzer of claim 38 wherein said sealing means
comprises gasket means between said first cell unit and said second
cell unit.
40. The electrolyzer of claim 29 wherein said first cell unit
includes gas header means.
41. The electrolyzer of claim 40 wherein said gas header means is
mounted on top of said first cell unit, extends beyond the anodic
surface thereof, and comprises means for the recovery of chlorine
from said cell.
42. The electrolyzer of claim 29 wherein said first cell unit
includes liquid header means.
43. The electrolyzer of claim 42 wherein said liquid header means
is mounted on the bottom of said first cell unit, extends beyond
the anodic surface thereof, and includes means for feeding brine to
said cell.
44. The electrolyzer of claim 29 wherein said second cell unit
includes gas header means.
45. The electrolyzer of claim 44 wherein said gas header means is
mounted on top of said second cell unit, extends beyond the
cathodic surface thereof, and comprises means for the recovery of
hydrogen from said cell.
46. The electrolyzer of claim 29 wherein said second cell unit
includes liquid header means.
47. The electrolyzer of claim 46 wherein said liquid header means
is mounted on the bottom of said second cell unit, extends beyond
the cathodic surface thereof, and comprises means for the recovery
of cell liquor from said cell.
48. The electrolyzer of claim 29 wherein:
a. said first cell unit comprises:
1. peripheral wall spacing means on the vertical sides thereof;
2. gas header means on top of and extending beyond the anodic
surface of said first cell unit;
3. liquid header means on the bottom of and extending beyond the
anodic surface of said first cell unit; and
4. the leading edges of said peripheral walls, gas header means,
and liquid header means are substantially in a first single
plane;
b. said second cell unit comprises:
1. peripheral wall spacing means on the vertical sides thereof;
2. gas header means on top of and extending beyond the cathodic
surface of said second cell unit;
3. liquid header means on the bottom of and extending beyond the
cathodic surface of said second cell unit; and
4. the leading edges of said peripheral walls, gas header means,
and liquid header means are substantially in a second single plane;
and
c. gasket means are interposed between said first cell unit and
said second cell unit.
49. The electrolyzer of claim 48 wherein compressive means extend
from an end cell unit through the individual cell units to an
opposite end cell.
50. The electrolyzer of claim 48 wherein said header means are
metallurgically joined to said cell units.
51. The electrolyzer of claim 48 wherein said header means are
mechanically joined to said cell units.
52. The electrolyzer of claim 51 wherein said header means are
joined to said cell units by compressive means extending from said
gas header means to said liquid header means.
53. The bipolar electrolyzer of claim 29 wherein each
electroconductive silicon cell unit comprises a single silicon
member.
54. The bipolar electrolyzer of claim 29 wherein each
electroconductive silicon cell unit comprises a plurality of
individual silicon members having electrolyte tight seals between
adjacent individual silicon members.
55. The bipolar electrolyzer of claim 54 wherein said individual
silicon members are compressively held together to form an
electrolyte tight metallic bipolar electrode.
56. The bipolar electrolyzer of claim 54 wherein said individual
silicon members are metallurgically joined together to form an
electrolyte tight metallic bipolar electrode.
Description
BACKGROUND OF THE INVENTION
Brines, e.g., sodium chloride, potassium chloride, and the like,
may be electrolyzed to yield the halogen, e.g., chlorine, at the
anode and the alkali metal hydroxide, e.g., caustic soda, or
potash, at the cathode. The anode reaction is reported in the
literature to be:
2Cl.sup.- .fwdarw. Cl.sub.2 + 2e.sup.-
The cathode reaction is reported in the literature to be:
2H.sup.+ + 2e.sup.- .fwdarw. H.sub.2
In halogen producing cells, with a barrier interposed between the
anode and the cathode, e.g., an electrolyte permeable diaphragm or
a permionic membrane, alkali metal ion and hydroxyl ion are present
in the catholyte chamber. In such cells, the anolyte is acid,
having a pH of from about 3.0 to about 5.0 while the catholyte is
basic having a pH in excess of about 12, e.g., and frequently as
high as 14.
In the production of alkali metal chlorate, as distinguished from
the production of chlorine and alkali metal hydroxide, the anode
product and the cathode product are not separated by a permeable
barrier. The anode and cathode products are permitted to contact
each other whereby the following reactions are reported in the
literature to take place:
1. 3Cl.sub.2 + 60H.sup.- .fwdarw. 3ClO.sup.- + 3Cl.sup.- + 3H.sub.2
O
2. 2clO.sup.- + 2H.sup.+ .fwdarw. 2HClO
3. 2hclO + ClO.sup.- .fwdarw. ClO.sub.3.sup.- + 2Cl.sup.- +
2H.sup.+
This provides an overall reaction of:
3Cl.sub.2 + 60H.sup.- .fwdarw. ClO.sub.3.sup.- + 5Cl.sup.- +
3H.sub.2 O
In the production of alkali metal chlorate, the electrolyte is
acidic, neutral, or slightly basic, that is, it has a pH of from
about 3.5 to about 7.0 or 8.0 and preferably from about 4.5 to
about 6.8. An acidic electrolyte drives reaction (2) 2ClO.sup.- +
2H+ .fwdarw. 2HClO, i.e., an acidic electrolyte favors the
formation of HClO.
In the electrolytic cells of the prior art, electrolysis was
carried out with graphite anodes and steel cathodes. However,
graphite anodes were characterized by deterioration according to
the following anodic reactions:
2ClO.sup.- .fwdarw. Cl.sub.2 + O.sub.2
C + o.sub.2 .fwdarw. co.sub.2
furthermore, graphite anodes, in addition to deteriorating under
cell conditions, were characterized by a high chlorine overvoltage,
e.g., in excess of about 0.25 volt at an anode current density of
125 Amperes per square foot in chlorinated brine.
The graphite anodes of the prior art have been gradually replaced
by metal anodes. Such metal anodes typically have a valve metal
base with an electroconductive coating thereon. Valve metals are
those metals which form an oxide film when subjected to anodic
conditions in aqueous acidic media. Typically, the valve metals
used in fabricating anodes according to the prior art are titanium,
tantalum, tungsten, zirconium, hafnium, niobium, and the like. Most
commonly, titanium was used in fabricating anodes according to the
prior art. The coating on the valve metal base was typically a
platinum group metal, e.g., ruthenium, rhodium, palladium, osmium,
iridium, or platinum, or an oxide of a platinum group metal, such
as ruthenium oxide, or an oxygen-containing compound of a platinum
group metal. Generally, the platinum group metal or oxide thereof
was present with an oxide of a film-forming metal, such as titanium
dioxide, thereby providing a surface on the valve metal, e.g.,
ruthenium dioxide and titanium dioxide. Additionally, materials
such as magnetite, Fe.sub.3 O.sub.4, and lead dioxide have been
used with satisfactory results. However, electrolytic cells having
precious metal coated valve metal basis are characterized by a high
cost per unit of electrode area.
SUMMARY OF THE INVENTION
It has now surprisingly been found that a particularly outstanding
bipolar electrode useful for the electrolysis of brines is a
silicon metal bipolar electrode containing small amounts of a
dopant, having a suitable anodic coating on the anodic surface
thereof, and having a suitable cathodic coating or film on the
cathodic surface thereof.
DESCRIPTION OF THE INVENTION
The electrolytic cell contemplated herein may be more fully
understood by reference of the Figures:
FIG. 1 is an isometric, partial schematic view of the bipolar
electrolyzer of this invention.
FIG. 2 is an exploded view of an individual cell of the bipolar
electrolyzer of this invention.
FIG. 3 is a front elevation of an individual bipolar electrode of
the electrolytic cell of this invention.
FIG. 4 is a cutaway side elevation of a bipolar electrode useful in
the electrolytic cell of this invention.
The bipolar electrolytic cell of this invention may either be a
chlorine cell, characterized by a permeable barrier between the
anode and cathode of an individual cell thereof, or it may be a
chlorate cell, characterized by the absence of such a permeable
barrier, and the presence of the anode and cathode of a cell within
the same electrolyte chamber.
A bipolar cell of this invention is an electrolytic cell having a
plurality of individual cells in bipolap mechanical and electrical
configuration, each individual cell being separated from the prior
adjacent cell and the subsequent adjacent cell of the electrolyzer
by common structural members. The common structural member is
variously known as a "cell unit", a "backplate", or a "bipolar
electrode". It is to be understood that these terms are equivalent
and may be used interchangeably. In a bipolar electrolytic cell,
the backplate or bipolar electrode includes the cathode of one cell
and the anode of the next adjacent cell, and is electroconductive
so as to provide for a low IR voltage drop between the cathode of
one cell and the anode of the next adjacent cell. Preferably, in a
diaphragm cell, the bipolar electrode is electrolyte impermeable,
so as to prevent the migration of ions from one cell to the
adjacent cell.
The electrolytic cell shown in FIGS. 1 through 4 includes a
plurality of bipolar electrodes 30 between a pair of end electrodes
32, 32. Each individual bipolar electrode 30 has a cathodic surface
34 and an anodic surface 38.
The individual bipolar electrodes 30 are maintained in a spaced
relationship to each other so that the anodic surface 38 of one
bipolar electrode 30 and the cathodic surface 34 of the next
adjacent bipolar electrode 30 in the electrolyzer define an
electrolyte volume of an individual electrolytic cell therebetween.
In this way, an individual electrolytic cell is defined by the
anodic surface 38 of one bipolar electrolyzer 30 and the cathodic
surface 34 of the next adjacent bipolar electrode 30 in the
electrolyzer 1.
An individual bipolar electrode 30 includes a gas header means 71.
The gas header means 71 extends beyond the cathodic surface 34 and
the anodic surface 38 of the bipolar electrode 30. The gas header
means 71 includes a chlorine outlet 73 for recovering chlorine from
the anolyte chamber in contact with the anodic surface 38 of the
bipolar electrode 30, and for feeding the chlorine to the chlorine
recovery system 77.
The gas header 71 also includes a hydrogen outlet 75 for recovering
hydrogen from the catholyte chamber in contact with the cathodic
surface 34 of the bipolar electrode 30. The hydrogen outlet 75 is
in communication with the hydrogen recovery system 79.
The individual bipolar electrode 30 also includes a liquid header
means on the bottom thereof. The liquid header means 81 extends
beyond the cathodic surface 34 and the anodic surface 38 of the
bipolar electrode 30. A brine feed means 83, communicating with a
brine line, extends through the header 81 to the anodic side 38 of
the bipolar electrode 30 while an alkali-metal hydroxide recovery
means 85 extends from the cathodic side 34 of the bipolar electrode
30 to the cell liquor recovery system.
The gas header 71 and liquid header 81 may be metallurgically
joined to the bipolar electrode 30. This may be accomplished by a
copper weld, a nickel weld, or a lead weld, as will be described
more fully hereinafter.
Alternatively, the gas header means 71 and the liquid header means
81 may be mechanically joined to the bipolar electrode 30. For
example, compressive means 91 may compress the gas header means 71
and liquid header means 81 onto the bipolar electrode 30. A pair of
compressive means 91 extend from the gas header means 71 alongside
the bipolar electrode 30 to the liquid header means 81. In a
preferred exemplification of the compressive means 91, a threaded
rod 93 passes through an aperture 100 in the gas header means 71,
from the gas header means 71, alongside the bipolar electrode 30,
to the liquid header means 81, and passes through an aperture 100
in the liquid header means 81. The upper end of the threaded rod 93
may include an eye-bolt 95. The lower end typically includes a nut
97 and washer 99.
The individual bipolar electrodes 91 typically contain peripheral
walls or side walls 61 along the vertical surfaces thereof. These
side walls and the extensions of the gas header means 71 and liquid
header means 81 define a single plane. A gasket means 101 may be
interposed between adjacent bipolar electrodes 30 so as to provide
an electrolyte tight seal between the first or anodic bipolar
electrode or bipolar unit 30 of an individual cell and the second
bipolar unit or cathodic bipolar electrode 30 of the individual
cell. In this way, a substantially electrolyte tight chamber is
provided.
The bipolar electrode 30 may be cast as a single silicon member.
Alternatively, the bipolar silicon electrode 30 may be cast as a
plurality of individual silicon castings 51, 52, 53, 54, 55, 56,
57, and 58. When the silicon bipolar electrode 30 is cast as a
plurality of individual silicon castings 51 through 58, the content
of transition metal silicide is not critical as some thermal
expansion upon solidification may be tolerated. However, if the
silicon bipolar electrode 30 is cast as a single casting,
continuous casting techniques, heat treating techniques, or
measured amounts of transition metal silicides must be provided, in
order to prevent or relieve thermal stresses.
When the silicon bipolar electrode 30 is cast as individual silicon
castings 51 through 58, the individual castings may be suitably
joined together, for example, at tongue and groove joints by
compressive means 91 as shown in the figures. Alternatively,
various metallurgical techniques may be used, such as providing an
adherent surface, e.g., nickel or copper, on the surface of the
silicon castings 51 through 58 to be joined. Thereafter, a molten
flux of aluminum, nickel, copper, lead, tin, or lead-tin alloy may
be provided between the nickel or copper coated surfaces, i.e.,
within the tongue and groove, to effect a metallurgical bond.
In a chlorine cell configuration, a barrier 111 is provided between
the anode 38 and cathode 34 of an individual cell. The permeable
barrier may be an electrolyte permeable barrier, i.e., a diaphragm,
such as is described in Sconce, Chlorine: Its Manufacture,
Properties and Uses (A.C.S. Monograph 154), Reinhold Publishing
Co., New York (1962), at pages 81 to 126, especially pages 105 to
108. Such an electrolyte permeable barrier permits the passage of
alkali metal halide, or halide ion, through the barrier so as to
provide a catholyte product containing in excess of 7 weight
percent alkali metal chloride, and frequently as high as 10 or 12
or even 15 percent alkali metal chloride.
Alternatively, the barrier (111) may be a permionic membrane. A
permionic membrane, such as described in U.S. Pat. No. 2,967,807 to
S. G. Osborne et al for "Electrolytic Decomposition of Sodium
Chloride," and in U.S. Pat. No. 3,438,897 to M. S. Kircher et al
for "Protection of PermSelective Diaphragm During Electrolysis," is
electrolyte impermeable but permeable to cations. Typically, a
permionic membrane permits the recovery of a catholyte liquor
substantially free of alkali metal halide, i.e., a catholyte liquor
containing less than one percent alkali metal halide, and
frequently one-tenth of a percent or even less of alkali metal
halide. Such catholyte liquor frequently contains 10, 20, or even
50 percent alkali metal hydroxide.
In one exemplification of the electrolytic cell of this invention
where the cathode 34 is a surface of the backplate 30, and the
barrier 111 is unsupported, the barrier 111 may be provided with
reinforcement means. Typical reinforcement means include catholyte
liquor resistant mesh, such as steel mesh or fluorocarbon thread
mesh. When the barrier 111 is a diaphragm, the diaphragm may be an
asbestos paper diaphragm, e.g., electrolytic asbestos paper.
The individual bipolar electrodes 30 are maintained in a spaced
relationship, with electrolyte tight seals therebetween, by
suitable compressive means. Typical means for maintaining the
bipolar electrolyzer in an operating condition are compressive
means 141 including a threaded rod 143 having nuts 145 and washers
147 at the opposite ends thereof, thereby applying a compressive
force upon all the individual bipolar electrodes 30 of the
electrolyzer. Preferably the rod 143 is insulated so as to avoid
short circuiting the cell. The rod 143 may pass through apertures
149 in the individual bipolar electrodes 30. Alternatively, the rod
143 may pass alongside the individual bipolar electrodes 30. The
electrolyzer is supported on the support 131.
In the electrolytic cell of this invention, power is supplied to an
anodic end cell 32 of the electrolyzer from an electric power
supply by electrical conduction means 121 and recovered from a
cathodic half cell 32 through electrical conduction means 121 at
the opposite end of the electrolyzer 1.
In the electrolytic cell contemplated herein, the electrodes are
electroconductive members fabricated of silicon. The silicon used
in fabricating the bipolar electrodes should be electroconductive
and preferably at least as electroconductive as graphite, e.g.,
silicon having a bulk electrical conductivity in excess of 100
(ohm-centimeters).sup.-.sup.1 or even 1000
(ohm-centimeters).sup.-.sup.1 or more.
Substantially pure silicon, e.g., silicon having a purity in excess
of 99.99 atomic percent, is at most a poor conductor or even a
semiconductor or non-conductor. The silicon useful in providing the
bipolar electrodes contemplated herein, typically has an
electroconductivity in excess of 100
(ohm-centimeters).sup.-.sup.1.
The silicon useful in providing the bipolar electrodes contemplated
herein has chemical resistance to the electrolyte and to products
of the electrolytic process. This chemical resistance is typically
provided by the formation of a film or a layer of a silicon oxide,
e.g., SiO.sub.2, or suboxides thereof, on the areas of the silicon
exposed to the electrolyte.
Additionally, silicon electrodes contemplated herein for use in
bipolar electrodes should have physical strength in order to be
resistant to impact and abrasion. Physical strength may be provided
by the presence of small amounts of alloying agents.
The electrical conductivity may be provided either by the presence
of a dopant, i.e., an electron donor or an electron acceptor.
Suitable electron donors are phosphorous, arsenic, antimony, and
bismuth. Suitable electron acceptors are boron, aluminum, gallium,
and the like. For electrochemical applications, i.e., for use as
electrodes in electroconductive media, electron acceptors appear to
impart chemical resistance to the silicon.
The dopant used in providing improved electrical conductivity,
which dopant may either be an electron acceptor or an electron
donor, should be present in an amount greater than 0.01 weight
percent of the silicon, and preferably in an excess of about 0.1
percent of the silicon. Generally, the dopant should be less than
about 3 weight percent of the silicon, and almost always less than
about 5 weight percent of the silicon. The presence of small
amounts of the dopant increases the electrical conductivity from
about 10 (ohm-centimeters).sup.-.sup.1 or less which is
characteristic of semi-conductor and rectifier grades of silicon to
in excess of 100 (ohm-centimeters) and preferably to in excess of
1000 or even 10,000 (ohm-centimeters) or even higher which is
comparable to graphite and conventional metallic conductors.
Particularly good results are obtained when the dopant is an
electron acceptor, preferably boron, and the concentration of boron
is from about 0.1 weight percent of the silicon to about 1.5 or
even 2 weight percent of the silicon.
Increased physical strength and castability may be provided by
alloying agents such as aluminum, gallium, manganese, iron, cobalt,
nickel, chromium, or molybdenum. These alloying agents, when
present, may be present in total concentration, i.e., as a silicide
and as the metal, in excess of one-half percent by weight,
preferably in excess of about 8 percent by weight, frequently as
high as 30 percent by weight or even more, but generally not
greatly in excess of about 40 percent by weight. These alloying
agents serve to increase the malleability and ductility of the
elemental silicon. Elemental silicon as the term is used herein is
silicon having a formal valence of 0.
In addition to elemental silicon, the various silicides may be
present within and on the surface of the bipolar electrode useful
in the bipolar electrolyzer of this invention. While the term
silicide is used herein, it is to be understood that such term also
encompasses metallic solid solutions of silicon and the metal
referred to as being present as a silicide, metallic solid
solutions of silicon and the silicide, and metallic solutions of
the silicides. Additionally, it is to be understood that when
silicides and alloying agents are referred to, they may be present
in a complex metallurgical system of substantially pure silicon
phases, substantially pure silicide phases, and phases which are a
metallic solid solution of various silicides and metallic solid
solutions of silicon and various silicides. The silicides serve to
provide additional electroconductivity to the silicon bipolar
electrodes of this invention. Such silicides include the
electroconductive silicides of various metals such as lithium
silicide, boron silicide, sodium silicide, magnesium silicide,
phosphorous silicide, hafnium silicide, calcium silicide, titanium
silicide, vanadium silicide, chromium silicide, iron silicide,
cobalt silicide, copper silicide, arsenic silicide, rubidium
silicide, strontium silicide, zirconium silicide, niobium silicide,
molybdenum silicide, ruthenium silicide, rhodium silicide,
palladium silicide, tellurium silicide, cesium silicide, barium
silicide, silicides of the rarer metals, tantalum silicide,
tungsten silicide, rhenium silicide osmium silicide, iridium
silicide, and platinum silicide.
The silicides themselves, while providing increased
electroconductivity to the elemental silicon base members have
fairly poor mechanical properties and, when present as a dominant
phase, may serve to decrease the ductility of the silicon base
member. For this reason, they will generally not be the major
fraction of the material present within the electrode nor will they
be present as the metallurgically dominant phase. Generally,
silicides when present, should be less than about 50 percent of the
total weight of the electrode. Most frequently, the silicide will
be less than 20 weight percent of the total electrode and
frequently less than about 5 weight percent of the total
electrode.
When silicides are present in the electrodes of this invention,
they will most commonly be the silicides of the dopants and
additives, such as arsenic, boron, copper, iron, cobalt, nickel,
manganese, and phosphorous; the silicides of the valve metals such
as titanium, tantalum, tungsten, zirconium, hafnium, vanadium,
niobium; and the silicides of the platinum group metals, ruthenium,
rhodium, palladium, osmium, iridium, and platinum.
Particularly desired silicides which may be present within the
bipolar electrode of this invention and on the surfaces thereof,
especially on the anodic surface of the bipolar herein contemplated
are the highly electroconductive silicides such as the silicides of
the platinum group metals, e.g., Pt.sub.3 Si, Pd.sub.3 Si, Ir.sub.3
Si.sub.2, Rh.sub.3 Si.sub.2, and Ru.sub.3 Si.sub.2 ; the silicides
of the valve metals, e.g., TiSi.sub.2, ZrSi.sub.2, VSi.sub.2,
NbSi.sub.2, TaSi.sub.2, and WSi.sub.2 ; and the silicides of the
heavy metals, e.g., Cr.sub.3 Si, Cr.sub.5 Si.sub.3, CrSi,
CrSi.sub.2, CoSi.sub.2, and MoSi.sub.2.
A particularly outstanding silicon alloy which may be used to
provide the electroconductive bipolar electrode of this invention
is the silicon alloy containing sufficient dopant to provide an
electrical conductivity in excess of 100 (ohm-centimeters), and
sufficient total transition group metal, either as a metal or as an
alloy with silicon, or as a silicide, to provide a volumetric
coefficient of expansion upon solidification of less than about 10
percent and preferably as low as 1.0 percent or less, balance
silicon. Alloys of this type, which are described in commonly
assigned copending U.S. application Ser. No. 391,118 filed Aug. 27,
1973 now Pat. No. 3,854,940 for "Electroconductive Corrosion
Resistant High Silicon Alloys" are characterized by the substantial
absence of thermal stresses upon solidification and have a
coefficient expansion upon solidification of plus 5 percent or
less. The alloys described therein generally contain sufficient
silicon so that a silicon-rich metallurgical phase is maintained as
a metallographically predominant phase within the alloy with about
two-thirds and preferably three-quarters or more of the silicon
being present in the silicon-rich phase. Generally, the alloys
therein described contain from about 4 to about 14 weight percent
iron or from about 9 to about 12 weight percent total cobalt, or
from 1 to about 7 weight percent total nickel, or from about 1 to
about 7 weight percent chromium, or from about 1 to about 6 weight
percent manganese, or from about 1 to about 18 weight percent
scandium, yttrium, or a lanthanide, or from about 11/2 to about 7
weight percent titanium, zirconium, or hafnium, or from about 1 to
about 16 atomic percent vanadium, columbium, or tantalum, or about
1 atomic percent tungsten or from 1 to about 20 atomic percent
copper, silver, or gold. Additionally, the alloy contains from
about 0.2 to about 2 weight percent boron. The particular alloys
described therein are generally present as a three-phase system
containing a transition metal or transition metal silicide-rich
phase, a dopant or dopant silicide-rich phase, and a silicon
rich-phase. The silicon-rich phase is the metallurgically
predominant phase and is substantially discontinuous, broken into
numerous individual regions of silicon-rich phase. Transition
metal-rich phase forms rivulets around the boundaries of the
regions of the silicon-rich phase, and preferably the rivulets are
substantially continuous around all the regions of silicon-rich
phase. Dopant-rich phases are present as nodules at the boundaries
between the phases and within the individual phases.
The preferred silicon alloys useful in providing bipolar electrodes
contain from 0.01 to about 5 percent of a dopant, as defined above,
from no alloying elements, to about 50 percent alloying elements,
including silicides, and generally from about 5 to about 30 percent
alloying elements, including silicides, as defined above, and the
balance predominantly silicon, e.g., from about 45 to about 99
percent, and preferably from about 67 to about 94 percent total
silicon.
A suitable electroconductive material should be provided on the
anodic surface 38 of the bipolar electrode 30. The
electroconductive material may cover from about one-quarter of one
percent of the anodic surface of the bipolar electrode 30 up to
about 98 or 99 percent of the anodic surface of the bipolar
electrode 30 or even all of the exposed surface of the bipolar
electrode 30, with oxides or silicon forming on those areas of the
silicon exposed to the anodic reaction.
The preferred electroconductive materials are those
electroconductive materials that are known in the art as suitable
materials for the evolution of chlorine, and are characterized by a
low chlorine overvoltage, e.g., less than 0.125 volt at a current
density of 200 Amperes per square foot. The preferred materials are
further characterized by their chemical stability and resistance to
attack by chlorine.
The material on the anodic surface 38 of the silicon bipolar
electrode 30 may be either an electrocatalyst, or an
electroconductive material, or an electroconductive material having
electrocatalytic properties. As used herein, an electrocatalyst or
material with electrocatalytic properties is a material which may
participate in the process of the absorption of the halide ion on
the electrode or in the electron transfer from the halide ion to
the electrode to form neutral halogen atoms, or in the combination
of neutral halogen atoms to form neutral halogen molecules, or in
the desorption of the neutral halogen molecules into the
electrolyte. Electrocatalytic properties, as the term is used
herein, are evidenced by either decreased halogen overvoltage or
decreased dependence of overvoltage on current density, or
both.
The preferred materials used for the electroconductive coating of
the anodic surface 38 of the bipolar electrode 30 are those
materials which are electroconductive, chemically inert or
resistant to anodic attack. They are known and used in the art for
the evolution of chlorine. Many of these materials have a low
chlorine overvoltage, e.g., less than 0.25 volt at a current
density of 200 Amperes per square foot.
A suitable method of determining chlorine overvoltage is as
follows;
A two-compartment cell constructed of polytetrafluoroethylene with
a diaphragm composed of asbestos paper is used in the measurement
of chlorine overpotentials. A stream of water-saturated Cl.sub.2
gas is dispersed into a vessel containing saturated NaCl, and the
resulting Cl.sub.2 saturated brine is continuously pumped into the
anode chamber of the cell. In normal operation, the temperature of
the electrolyte ranges from 30.degree. to 35.degree.C, most
commonly 32.degree.C, at a pH of 4.0. A platinized titanium cathode
is used.
In operation, an anode is mounted to a titanium holder by means of
titanium bar clamps. Two electrical leads are attached to the
anode; one of these carries the applied current between anode and
cathode at the voltage required to cause continuous generation of
chlorine. The second is connected to one input of a high impedance
voltmeter. A Luggin tip made of glass is brought up to the anode
surface. This communicates via a salt bridge filled with anolyte
with a saturated calomel half cell. Usually employed is a Beckman
miniature fiber junction calomel such as catalog no. 39270, but any
equivalent one would be satisfactory. The lead from the calomel
cell is attached to the second input of the voltmeter and the
potential read.
Calculation of the overvoltage, .eta., is as follows:
The International Union of Pure and Applied Chemistry sign
convention is used, and the Nernst equation taken in the following
form: ##EQU1##
Concentrations are used for the terms in brackets instead of the
more correct activities.
E.sub.o = the standard state reversible potential = +1.35 volts
n = number of electrons equivalent.sup.-.sup.1 = 1
R, gas constant = 8.314 joule deg.sup.-.sup.1 mole.sup.-.sup.1
F, the Faraday = 96,500 couloumbs equivalent.sup.-.sup.1
Cl.sub.2 concentration = 1 atm
Cl.sup.- concentration = 5.4 equivalent liter.sup.-.sup.1
(equivalent to 305 grams NaCl per liter)
T = 305.degree.K
For the reaction
Cl.sup.- .fwdarw. 1/2 Cl.sub.2 + e.sup.-,
E = 1.35 + 0.060 log 1/5.4 = 1.30
This is the reversible potential for the system at the operating
conditions. The overvoltage on the normal hydrogen scale is,
therefore, .eta. = V - [E - 0.24] where V is the measured voltage,
E is the reversible potential, 1.30, 0.24 is the potential of the
saturated calomel half cell.
Suitable materials useful in coating the anodic portion of the
bipolar electrode herein contemplated include the platinum group
metals, e.g., platinum, ruthenium, rhodium, palladium, osmium, and
iridium. The platinum group metals may be present in the form of
mixtures or alloys such as platinum and palladium. An especially
satisfactory platinum and palladium combination contains up to
about 15 weight percent platinum and the balance palladium. Another
particularly satisfactory coating is platinum and iridium. An
especially satisfactory platinum-iridium combination is one
containing from about 10 to about 35 weight percent iridium. Other
suitable combinations include ruthenium and osmium, ruthenium and
iridium, ruthenium and platinum, rhodium and osmium, rhodium and
iridium, rhodium and platinum, palladium and osmium, and palladium
and iridium.
Alternatively, the material present on the surface of the anodic
member of the electrode pair may be present in the form of an oxide
of a precious metal such as ruthenium oxide, rhodium oxide,
palladium oxide, osmium oxide, iridium oxide, and platinum oxide.
The oxides may also be a mixture of the platinum group metal oxides
such as platinum oxide with palladium oxide, rhodium oxide with
platinum oxide, ruthenium oxide with platinum oxide, rhodium oxide
with iridium oxide, rhodium oxide with osmium oxide, rhodium oxide
with platinum oxide, ruthenium oxide with platinum oxide, ruthenium
oxide with iridium oxide and ruthenium oxide with osmium oxide.
There may also be present in the electroconductive surfaces of the
anode member of the electrode pair herein contemplated
nonconductive oxides and oxides of low conductivity. Such
materials, while of low conductivity may be catalytic in the sense
of providing surface area or available d shell electrons for
further catalysis of the electrode products. Such materials, while
having low bulk electroconductivities themselves, may nevertheless
have open or porous structures thereby permitting the flow of
electrolyte and electrical current therethrough. For example,
aluminum oxide, silicon oxide, titanium oxide, zirconium oxide,
niobium oxide, hafnium oxide, tantalum oxide, or tungsten oxide may
be present on and in the electroconductive surface in combination
with the high conductivity, low chlorine overvoltage material.
Additionally, other nonconductive materials, and materials of low
conductivity may be present with a more highly conductive material
present on the surface coating of the anode portion of the silicon
electrode. Additionally, there may also be present on the surface
of the anodic member of the electrode herein contemplated the
electroconductive low overvoltage silicides of the platinum group
metals. These silicides, e.g., platinum silicide, palladium
silicide, iridium silicide, rhodium silicide and ruthenium
silicide, especially Pt.sub.3 Si, Pd.sub.3 Si, Ir.sub.3 Si.sub.2,
Rh.sub.3 Si.sub.2, and Ru.sub.3 Si.sub.2 provide an
electrolyte-resistant low overvoltage coating.
The surface of the anodic portion of the electrode herein
contemplated may also include a combination of the oxides and
silicides of the platinum group metals, e.g., ruthenium silicide
with ruthenium dioxide or palladium silicide with palladium
oxide.
The cathodic member of the electrode herein contemplated may be
bulk elemental silicon. Elemental silicon has a hydrogen
overvoltage of 0.5 volt at 200 Amperes per square foot.
Alternatively, the cathodic member of the electrode pair herein
contemplated may include substantial amounts of alloying agents,
e.g., ferro-silicon, magnesium silicide, manganese silicide, cobalt
silicide, molybdenum silicide, and the like. Thus, the cathodic
member of the electrode pair herein contemplated may contain
elemental silicon as well as substantial amounts, e.g., 75 percent
or more by weight of electrolyte-resistant, electroconductive
silicides. The cathode portion of the electrode may additionally,
unlike the anodic member, be porous to the flow of electrolyte and
gases, thereby permitting the introduction of oxygen or an
oxygen-bearing gas.
Additionally, the cathodic surface may also be coated as described
hereinbefore for the anodic surface. Any of the materials described
above may be used, including the platinum group metals, the oxides
and oxygen-containing compounds of the platinum group metals, the
platinum group metal-rich silicides of the platinum group metals,
and various other cathodically active, metal oxides resistant to
basic media as spinels and bronze oxides.
Alternatively, the cathodic surface may be provided by material
resistant to evolved hydrogen and to hydroxyl ion, OH.sup.-, and
having a low hydrogen overvoltage, e.g., less than about 0.35 volt
at a current density of about 125 Amperes per square foot. Such
materials include iron, cobalt, nickel, manganese, and the like.
The surface may be present as a thin sheet, film, or layer, or even
as a porous film on the silicon.
Such surfaces serve to lower the voltage of the cathode against a
standard calomel electrode, e.g., to about 1.25 to 1.30 volts at
100 Amperes per square foot for a ruthenium oxide coated silicon
cathode, as well as to protect the cathode against attack by the
basic electrolyte. Only a small amount of coating is necessary to
protect the silicon, e.g., less than one-tenth of one percent of
the surface area need be coated to obtain a high degree of
protection.
Although this invention has been described with particular
reference to electrolytic cells for the electrolysis of aqueous
alkali metal solutions to produce chlorine or chlorates, it is not
limited to such use. The electrodes herein contemplated may be used
in electrochemical reactions wherever a corrosion-resistant
electrode pair having long life is required and the service is such
that the pH of the electrolyte is greater than about 3.5 and less
than about 10.0. Thus, the electrolyte in the cell may be a salt of
a metal which may be electrodeposited and the electrolyte
electrolyzed between the coated silicon anode and a silicon
cathode. Alternatively, the electrode pair herein described may be
used for the electrolytic oxidation of organic compounds. The
electrode pair herein contemplated may further be understood by
reference to the following Examples.
EXAMPLE I
A silicon bipolar electrode was prepared containing 0.5 weight
percent boron as dopant. The electrical properties of the cathode
surface of the bipolar electrode were tested, and thereafter the
electrode is utilized as a bipolar electrode.
The electrode was prepared by placing 2700 grams of Ohio Ferro
Alloys Corporation silicon pieces having a nominal silicon content
of 100 weight percent, and an actual silicon content of 99.5 weight
percent, and 63 grams of Fisher Scientific Company fused sodium
tetraborate in a Number 10 graphite crucible. The crucible was
placed in an electric resistance furnace and heated to
1540.degree.C for 11/2 hours. The resulting molten silicon was then
poured into a graphite mold that had been preheated to
1000.degree.C. The molten silicon in the mold was slowly cooled to
300.degree.C over a period of 4 hours.
An electrode measuring 5 inches by 3/4 inch by 1/4 inch was cut
from the ingot. This electrode was tested as a cathode in an
aqueous solution of 450 grams per liter of sodium chlorate, 150
grams per liter of sodium chloride, and 5 grams per liter of sodium
dichromate. The pH of the electrolyte solution was 7, and the
temperature of the electrolyte solution was 40.degree.C. The
cathode voltage was measured against a standard calomel electrode,
and was found to be:
Current Density Voltage (Amperes per square foot) (Volts)
______________________________________ 50 1.87 100 1.87 200 1.89
______________________________________
Thereafter, a ruthenium oxide-titanium oxide surface is applied to
one surface of the silicon electrode.
This is accomplished by etching the surface and applying a
ruthenium trichloride under-coating to the surface. The
under-coating solution is prepared by dissolving 2 grams of
ruthenium trichloride in 18 grams of ethyl alcohol. Three coats of
the under-coating are applied with heating to 350.degree.C for 10
minutes after all three coats.
Then an outer-coating solution is applied above the undercoating.
The outer-coating is prepared by dissolving 18.1 grams of titanium
trichloride in 51.5 grams of a 15 weight percent aqueous solution
of hydrochloric acid. Two grams of this solution were mixed with 1
gram of methyl alcohol, 0.5 grams of 30 percent hydrogen peroxide,
and 1.2 grams of a solution prepared from 1 gram of ruthenium
trichloride and 4 grams of methyl alcohol. Three coats of this
outer-coating solution are applied on top of the under-coating. The
electrode is heated to 350.degree.C for 10 minutes after each first
two coats and heated to 450.degree.C for 30 minutes after the third
coat. Thereafter the electrode is utilized as a bipolar electrode
between two monopolar electrodes. The cells are divided into
diaphragm cells by asbestos paper diaphragms on minus 80 mesh
Teflon (TM) felt mats. A brine containing 315 grams per liter is
fed into the two anolyte compartments, a cell liquor containing 150
grams per liter of sodium chloride and 100 grams per liter of
sodium hydroxide is fed into the catholyte chambers. Electrolysis
is commenced and gas is seen to be evolved from both surfaces of
the silicon bipolar electrode.
EXAMPLE II
A ferro-silicon bipolar electrode was prepared containing 0.5
weight percent boron as dopant. The electrical properties of the
cathode surface of the bipolar electrode were tested, and
thereafter the electrode is utilized as a bipolar electrode.
The electrode was prepared by placing 1800 grams of Ohio Ferro
Alloys Corporation ferro-silicon pieces having a nominal silicon
content of 85 weight percent, a nominal iron content of 15 weight
percent, an actual silicon content of 88.2 weight percent, and an
actual iron content of 11.2 weight percent, and 42 grams of Fisher
Scientific Company fused sodium tetraborate in a Number 10 graphite
crucible. The crucible was placed in an electric resistance furnace
and heated to 1540.degree.C for 1 hour. The resulting molten
ferro-silicon was then poured into a graphite mold that had been
preheated to 1000.degree.C. The molten ferro-silicon in the ingot
mold was slowly cooled to 300.degree.C over a period of 4
hours.
An electrode measuring 5 inches by 3/4 inch by 1/4 inch was cut
from the ingot. This electrode was tested as a cathode in an
aqueous solution of 450 grams per liter of sodium chlorate, 150
grams per liter of sodium chloride, and 5 grams per liter of sodium
dichromate. The pH of the electrolyte solution was 7, and the
temperature of the electrolyte solution was 40.degree.C. The
cathode voltage was measured against a standard calomel electrode,
and was found to be:
Current Density Voltage (Amperes per square foot) (Volts)
______________________________________ 50 1.78 100 1.84 200 1.88
______________________________________
Thereafter, a ruthenium oxide-titanium oxide surface is applied to
one surface of the silicon electrode.
This is accomplished by etching the surface and applying a
ruthenium trichloride under-coating to the surface. The
under-coating solution is prepared by dissolving 2 grams of
ruthenium trichloride in 18 grams of ethyl alcohol. Three coats of
the under-coating were applied with heating to 350.degree.C for 10
minutes after all three coats.
Then an outer-coating solution is applied above the undercoating.
The outer-coating is prepared by dissolving 18.1 grams of titanium
trichloride in 51.5 grams of a 15 weight percent aqueous solution
of hydrochloric acid. Two grams of this solution were mixed with 1
gram of methyl alcohol, 0.5 grams of 30 percent hydrogen peroxide,
and 1.2 grams of a solution prepared from 1 gram of ruthenium
trichloride and 4 grams of methyl alcohol. Three coats of this
outer-coating solution are applied on top of the under-coating. The
electrode is heated to 350.degree.C for 10 minutes after each first
two coats, and to 450.degree.C for 30 minutes after the third coat.
Thereafter the electrode is utilized as a bipolar electrode between
two monopolar electrodes. The cells are divided into diaphragm
cells by asbestos paper diaphragms on minus 80 mesh Teflon felt
mats. A brine containing 315 grams per liter is fed into the two
anolyte compartments, a cell liquor containing 150 grams per liter
of sodium chloride and 100 grams per liter of sodium hydroxide is
fed into the catholyte chambers. Electrolysis is commenced and gas
is seen to be evolved from both surfaces of the silicon bipolar
electrode.
EXAMPLE III
A ferro-silicon bipolar electrode was prepared containing 0.15
weight percent boron as dopant. The electrical properties of the
cathode surface of the bipolar electrode were tested, and
thereafter the electrode is utilized as a bipolar electrode.
The electrode was prepared by placing 1800 grams of Ohio Ferro
Alloys Corporation ferro-silicon pieces having a nominal silicon
content of 75 weight percent, a nominal iron content of 25 weight
percent, an actual silicon content of 80.8 weight percent, and an
actual iron content of 19.2 weight percent, and 42 grams of Fisher
Scientific Company fused sodium tetraborate in a Number 10 graphite
crucible. The crucible was placed in an electric resistance furnace
and heated to 1540.degree.C for 11/4 hours. The resulting molten
ferro-silicon was then poured into a graphite mold that had been
preheated to 1000.degree.C. The molten ferro-silicon in the ingot
mold was slowly cooled to 300.degree.C over a period of 4
hours.
An electrode measuring 5 inches by 3/4 inch by 1/4 inch was cut
from the ingot. This electrode was tested as a cathode in an
aqueous solution of 450 grams per liter of sodium chlorate, 150
grams per liter of sodium chloride, and 5 grams per liter of sodium
dichromate. The pH of the electrolyte solution was 7, and the
temperature of the electrolyte solution was 40.degree.C. The
cathode voltage was measured against a standard calomel electrode,
and was found to be:
Current Density Voltage (Amperes per square foot) (Volts)
______________________________________ 50 1.77 100 1.80 200 1.84
______________________________________
Thereafter a ruthenium oxide-titanium oxide surface is applied to
one surface of the silicon electrode.
This is accomplished by etching the surface and applying a
ruthenium trichloride under-coating to the surface. The
under-coating solution is prepared by dissolving 2 grams of
ruthenium trichloride in 18 grams of ethyl alcohol. Three coats of
the under-coating were applied with heating to 350.degree.C for 10
minutes after all three coats.
Then an outer-coating solution is applied above the undercoating.
The outer-coating is prepared by dissolving 18.1 grams of titanium
trichloride in 51.5 grams of a 15 weight percent aqueous solution
of hydrochloric acid. Two grams of this solution were mixed with 1
gram of methyl alcohol, 0.5 grams of 30 percent hydrogen peroxide,
and 1.2 grams of a solution prepared from 1 gram of ruthenium
trichloride and 4 grams of methyl alcohol. Three coats of this
outer-coating solution are applied on top of the under-coating. The
electrode is heated to 350.degree.C for 10 minutes after each first
two coats and heated to 450.degree.C for 30 minutes after the third
coat. Thereafter, the electrode is utilized as a bipolar electrode
between two monopolar electrodes. The cells are divided into
diaphragm cells by asbestos paper diaphragms on minus 80 mesh
Teflon (TM) felt mats. A brine containing 315 grams per liter is
fed into the two anolyte compartments, a cell liquor containing 150
grams per liter of sodium chloride and 100 grams per liter of
sodium hydroxide is fed into the catholyte chambers. Electrolysis
is commenced and gas is seen to be evolved from both surfaces of
the silicon bipolar electrode.
EXAMPLE IV
A ferro-silicon bipolar electrode was prepared containing 0.5
weight percent boron as dopant. The electrical properties of the
cathode surface of the bipolar electrode were tested, and
thereafter the electrode is utilized as a bipolar electrode.
The electrode was prepared by placing 700 grams of Ohio Ferro
Alloys Corporation ferro-silicon pieces having a nominal silicon
content of 65 weight percent, a nominal iron content of 35 weight
percent, an actual silicon content of 69.8 weight percent and an
actual iron content of 30.2 weight percent, and 16.25 grams of
Fisher Scientific Company fused sodium tetraborate in a Number 4
graphite crucible. The crucible was placed in an electric
resistance furnace and heated to 1540.degree.C for 1 hour. The
resulting molten ferro-silicon was then poured into a graphite mold
that had been preheated to 1000.degree.C. The molten ferro-silicon
in the ingot mold was slowly cooled to 300.degree.C over a period
of 4 hours.
An electrode measuring 5 inches by 3/4 inch by 1/4 inch was cut
from the ingot. This electrode was tested as a cathode in an
aqueous solution of 450 grams per liter of sodium chlorate, 150
grams per liter of sodium chloride, and 5 grams per liter of sodium
dichromate. The pH of the electrolyte solution was 7, and the
temperature of the electrolyte solution was 40.degree.C. The
cathode voltage was measured against a standard calomel electrode
and was found to be:
Current Density Voltage (Amperes per square foot) (Volts)
______________________________________ 50 1.71 100 1.75 200 1.85
______________________________________
Thereafter a ruthenium oxide-titanium oxide surface is applied to
one surface of the silicon electrode.
This is accomplished by etching the surface and applying a
ruthenium trichloride under-coating to the surface. The
under-coating solution is prepared by dissolving 2 grams of
ruthenium trichloride in 18 grams of ethyl alcohol. Three coats of
the under-coating are applied with heating to 350.degree.C for 10
minutes after all three coats.
Then an outer-coating solution is applied above the under-coating
solution. The outer-coating is prepared by dissolving 18.1 grams of
titanium trichloride in 51.5 grams of a 15 weight percent aqueous
solution of hydrochloric acid. Two grams of this solution are mixed
with 1 gram of methyl alcohol, 0.5 grams of 30 percent hydrogen
peroxide, and 1.2 grams of a solution prepared from 1 gram of
ruthenium trichloride and 4 grams of methyl alcohol. Three coats of
this outer-coating solution are applied on top of the
under-coating. The electrode is heated to 350.degree.C for 10
minutes after each first two coats, and to 450.degree.C for 30
minutes after the third coat. Thereafter, the electrode is utilized
as a bipolar electrode between two monopolar electrodes. The cells
are divided into diaphragm cells by asbestos paper diaphragms on
minus 80 mesh Teflon felt mats. A brine containing 315 grams per
liter is fed into the two anolyte compartments, a cell liquor
containing 150 grams per liter of sodium chloride and 100 grams per
liter of sodium hydroxide is fed into the catholyte chambers.
Electrolysis is commenced and gas is seen to be evolved from both
surfaces of the silicon bipolar electrode.
EXAMPLE V
A ruthenium oxide coated ferro-silicon bipolar electrode was
prepared containing 0.5 weight percent boron as dopant. The
electrical properties of the cathode surface of the bipolar
electrode were tested, and thereafter the electrode is utilized as
a bipolar electrode.
The electrode was prepared by placing 1200 grams of Ohio Ferro
Alloys Corporation ferro-silicon pieces having a nominal silicon
content of 85 weight percent, a nominal iron content of 15 weight
percent, an actual silicon content of 88.2 weight percent, and an
actual iron content of 11.8 weight percent, 600 grams of Ohio Ferro
Alloys Corporation silicon, and 42 grams of Fisher Scientific
Company fused sodium tetraborate in a Number 10 graphite crucible.
The crucible was placed in an electric resistance furnace and
heated to 1540.degree.C for 11/2 hours. The resulting molten
ferro-silicon was then poured into a graphite mold that had been
preheated to 1000.degree.C. The molten ferro-silicon in the ingot
mold was slowly cooled to 300.degree.C over a period of 4
hours.
An electrode measuring 5 inches by 3/4 inch by 1/4 inch was cut
from the ingot. A ruthenium oxide-titanium oxide exterior surface
was applied to both 5 inches by 3/4 inch surfaces of the bipolar
electrode. This was accomplished by etching the surface and
applying a ruthenium trichloride under-coating to the surface. The
under-coating solution was prepared by dissolving 2 grams of
ruthenium trichloride in 18 grams of ethyl alcohol. Three coats of
the under-coating were applied with heating to 350.degree.C for 10
minutes after all three coats.
Then an outer-coating solution was applied above the undercoating
solution. The outer-coating was prepared by dissolving 18.1 grams
of titanium trichloride in 51.5 grams of a 15 weight percent
aqueous solution of hydrochloric acid. Two grams of this solution
were mixed with 1 gram of methyl alcohol, 0.5 grams of 30 percent
hydrogen peroxide, and 1.2 grams of a solution prepared from 1 gram
of ruthenium trichloride and 4 grams of methyl alcohol. Three coats
of this outer-coating solution were applied on top of the
under-coating. The electrode was heated to 350.degree.C for 10
minutes after each first two coats, and to 450.degree.C for 30
minutes after the third coat. This electrode was tested as a
cathode in an aqueous solution of 450 grams per liter of sodium
chlorate, 150 grams per liter of sodium chloride, and 5 grams per
liter of sodium dichromate. The pH of the electrolyte solution was
7, and the temperature of the electrolyte solution was 40.degree.C.
The cathode voltage was measured against a standard calomel
electrode and was found to be:
Current Density Voltage (Amperes per square foot) (Volts)
______________________________________ 50 1.25 100 1.29
______________________________________
Thereafter the electrode is utilized as a bipolar electrode between
two monopolar electrodes. The cells are divided into diaphragm
cells by asbestos paper diaphragms on minus 80 mesh Teflon (TM)
felt mats. A brine containing 315 grams per liter is fed into the
two anolyte compartments, a cell liquor containing 150 grams per
liter of sodium chloride and 100 grams per liter of sodium
hydroxide is fed into the catholyte chambers. Electrolysis is
commenced and gas is seen to be evolved from both surfaces of the
silicon bipolar electrode.
EXAMPLE VI
A bipolar chlorate electrolyzer was prepared having a silicon
bipolar electrode dividing the electrolyzer into two separate
electrolytic cells, and having silicon electrodes facing the
bipolar electrode.
The silicon electrodes were prepared by melting silicon powder, and
fused sodium tetraborate (Na.sub.2 B.sub.4 O.sub.7) in a graphite
crucible. Sufficient sodium tetraborate was added to the charge to
provide an electrode containing one weight percent boron. The
charge was heated to 1500.degree.C for 16 hours. Thereafter, the
molten silicon containing boron was poured into a graphite mold
that had been heated to 1000.degree.C. After the silicon had
solidified and cooled, the ingot was cut into 3 pieces.
The silicon member intended for use as an anode and one surface of
the silicon member intended for use as a bipolar electrode were
coated to provide a ruthenium oxide-titanium dioxide surface.
This was accomplished by etching the surface and applying a
ruthenium trichloride under-coating to the surface. The
under-coating solution was prepared by dissolving 2 grams of
ruthenium trichloride in 18 grams of ethyl alcohol. Three coats of
the under-coating were applied with heating to 350.degree.C for 10
minutes after all three coats.
Then, an outer-coating solution was applied above the undercoating.
The outer-coating was prepared by dissolving 18.1 grams of titanium
trichloride in 51.5 grams of a 15 weight percent aqueous solution
of hydrochloric acid. Two grams of this solution were mixed with 1
gram of methyl alcohol, 0.5 grams of 30 percent hydrogen peroxide,
and 1.2 grams of a solution prepared from 1 gram of ruthenium
trichloride and 4 grams of methyl alcohol. Three coats of this
outer-coating solution were applied on top of the under-coating.
The electrode was heated to 350.degree.C for 10 minutes after each
first two coats, and to 450.degree.C for 30 minutes after the third
coat.
The silicon member intended for use as a bipolar electrode was then
cemented into a plastic fitting.
The uncoated silicon member was inserted at one end of a plastic
rectangular box, and the coated silicon member intended for use as
an anode was inserted at the opposite end of the plastic
rectangular box. The member intended for use as a bipolar
electrode, in its plastic fitting, was cemented into the
rectangular plastic box with the ruthenium dioxide coated surface
thereon facing the uncoated silicon member, and the uncoated
surface facing the ruthenium dioxide coated silicon member. The
bipolar electrode was spaced one inch from each of the monopolar
electrodes.
A solution of brine containing 310 grams per liter of sodium is
placed in the cell and electrolysis is commenced. Chlorine is seen
to be evolved from the anode, hydrogen from the cathode.
The silicon cathode was removed from the electrolytic cell and
tested as a cathode. The electrolyte used for testing the cathode
contained 450 grams per liter of sodium chlorate, 150 grams per
liter of sodium chloride, and 5 grams per liter of sodium chromate
(Na.sub.2 Cr.sub.2 O.sub.7). At a current density of 200 Amperes
per square foot, the voltage versus a standard calomel reference
electrode was 1.89 volts. At a current density of 100 Amperes per
square foot, the voltage versus a standard calomel electrode is
1.87 volts. At a current density of 50 Amperes per square foot, the
voltage versus a standard calomel reference electrode is 1.84
volts.
The hydrogen overvoltage of the silicon cathode was calculated to
be 0.44 volt at 200 Amperes per square foot.
It is to be understood that although the invention has been
described with reference to specific details of particular
embodiments thereof, it is not to be so limited as changes and
alterations therein may be made which are within the full intended
scope of this invention as defined by the appended claims.
* * * * *