U.S. patent number 3,873,437 [Application Number 05/305,063] was granted by the patent office on 1975-03-25 for electrode assembly for multipolar electrolytic cells.
This patent grant is currently assigned to Diamond Shamrock Corporation. Invention is credited to Dale R. Pulver.
United States Patent |
3,873,437 |
Pulver |
March 25, 1975 |
Electrode assembly for multipolar electrolytic cells
Abstract
An electrode assembly adapted for arrangement between the
terminal monopolar electrodes of a multipolar electrolytic cell
includes a compartment wall, an anode carried by a lateral surface
of the wall and provided with means for movement of the anode in a
direction toward an opposed cathode surface to maintain a narrow
gap between the electrodes and improve the cell power efficiency; a
cathode carried by the opposed lateral surface of the same
compartment wall and optionally provided with means for movement in
a direction toward an opposed anode surface for maintenance of a
narrow spacing of the electrodes. The electrode assembly provides
for the construction of electrolytic cells of the membrane or
diaphragm or diaphragm-less types which are useful for production
of chlorine and caustic and for various other products of
electrolytic processes.
Inventors: |
Pulver; Dale R. (Bay Village,
OH) |
Assignee: |
Diamond Shamrock Corporation
(Cleveland, OH)
|
Family
ID: |
23179163 |
Appl.
No.: |
05/305,063 |
Filed: |
November 9, 1972 |
Current U.S.
Class: |
204/254; 204/268;
204/280; 204/282; 204/284; 204/288; 205/511 |
Current CPC
Class: |
C25B
11/00 (20130101) |
Current International
Class: |
C25B
11/00 (20060101); B01k 003/04 (); C01d
001/06 () |
Field of
Search: |
;204/268,254,282,286,253,255,256,254,268,288,289,284,267 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Edmundson; F. C.
Attorney, Agent or Firm: Tinkler; Timothy E.
Claims
I claim:
1. A generally planar bipolar electrode assembly adapted for
closely spaced parallel series arrangement intermediate to the
terminal monopolar electrodes of a multipolar electrolytic cell
having side, bottom and end walls, comprising:
an electrically non-conducting, liquid tight partition, at least
one rigid electrical conductor extending through said partition and
beyond each lateral surface thereof;
a dimensionally stable anode and a cathode connected to the rigid
conductor on opposite sides of and parallel to the partition;
movable, resilient, electrically conductive means connecting the
non-working lateral surface of one electrode to the rigid
conductor, the movable, resilient means being capable of causing
movement of the lateral working surface of the electrode in a
direction toward the working lateral surface of an opposed
electrode of opposite charge of an adjacent bipolar assembly while
maintaining intraelectrode electrical integrity.
2. The electrode assembly according to claim 1 wherein the anode
comprises a number of segments and electrically conductive,
resilient, movable means are connected to a non-working lateral
surface of each anode segment and to the rigid conductor.
3. The electrode assembly according to claim 1 wherein the movable
electrically conductive means is a unitary resilient member
connected to the non-working lateral surface of the anode and to a
plurality of rigid electrically conductive members.
4. The electrode assembly according to claim 1 wherein movable,
resilient, electrically conductive means connect both the anode and
cathode to the rigid conductor.
5. The electrode assembly according to claim 4 wherein the anode
and cathode respectively are segmented.
6. The electrode assembly according to claim 1 wherein the movable
electrically conductive means is a plurality of resilient members
connected to the non-working lateral surface of the cathode and to
a plurality of rigid electrically conductive members.
7. The electrode assembly according to claim 1 wherein the cathode
is constructed of a plurality of segments and a movable, resilient,
electrically conductive means is connected to each segment and to a
rigid conductor.
8. The electrode assembly according to claim 1 wherein at least one
electrically non-conducting spacer is carried by the working
lateral surface of the anode or the cathode.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an electrode assembly for construction of
multipolar electrolytic cells capable of operating at optimum power
efficiencies and requiring a minimum of maintenance over extended
periods of time. More particularly this invention relates to
bipolar electrode assemblies for construction of multipolar
electrolytic cells of commercial size wherein the electrodes are
large and must be maintained in closely spaced uniform planar
relationship to each other for the cell to operate at optimum power
efficiency and at low maintenance requirements. The electrode
assembly of this invention is particularly adapted for
electrochemical conversion of aqueous sodium chloride to chlorine
and caustic in a diaphragm or membrane cell. It should be
understood however that the electrode assembly of this invention is
not limited to the construction of cells for the production of
chlorine and caustic only for it may be used in cells for other
electrochemical operations such as, for example, the manufacture of
alkali and alkaline earth metal hypochlorites, chlorates,
perchlorates, and various organic compounds.
2. Description of the Prior Art
It has been customary in the prior art to use multipolar
electrolytic cells for various chemical reactions as this type of
cell enables the cell to be constructed in compact form and
eliminates the exposed busbar and metallic connections required for
the introduction and withdrawal of the electric current to and from
the electrodes of monopolar cells. The exposed parts and
connections of monopolar cells are subject to attack by gases
evolved during electrolysis and other chemicals of the cell
environment which cause corrosion and contamination of the
electrolyte.
In the general use of prior multipolar cells, bipolar electrodes
are positioned intermediate to the terminal monopolar electrodes in
any desired manner in closely spaced compact position, sealed at
their edges to the cell side and bottom walls to prevent leakage
between the adjacent cell compartments which are separated by
partitions. Electrical connections are made only to the terminal
monopolar electrodes and the electrolyte is circulated in contact
with the electrodes in each of the individual compartments. The sum
total of the voltage of the intermediate bipolar electrodes is
equal to the voltage between the monopolar electrodes. In one type
of prior art, multipolar cell the bipolar electrodes are
constructed as a single sheet of titanium which serves as the
compartment partition. One side of the titanium sheet is uncoated
and acts as a cathode and the other side has at least a partially
active surface coating and operates as the anode portion of the
bipolar electrode. This assembly is positioned so that the anode
surface of one titanium sheet is positioned adjacent the cathode
position of an opposed assembly and any desired number of
assemblies may be arranged between the monopolar terminal
electrodes. A similar electrode assembly for multipolar cells which
has also been previously used is a graphite plate assembly which
functions in the same manner as titanium sheets, the plates serving
as compartment partitions with one lateral surface of the plate
operating as the anode and the opposed lateral surface acting as a
cathode. Such graphite bipolar electrode assemblies are still in
use but because of their limited resistance to erosion and chemical
attack have been, and are being, replaced by the metallic sheet
type bipolar assemblies. Another type of bipolar electrode assembly
presently in use comprises a number of metallic solid or foraminous
anode and cathode sheets which are positioned in opposed closely
spaced manner within an electrolytic cell, each pair being
separated by partitions and the total number of assemblies being
arranged between terminal monopolar electrodes.
As previously mentioned, the graphite type electrodes are subject
to erosion which results in contamination of the electrolyte and
reduction of power efficiency. The increased voltage required to
overcome the resistance of the larger quantity of the electrolyte
present between the constantly increasing spaces between the
electrodes caused by the continuous erosion reduces power
efficiency. The titanium sheets which serve as the cell partition
and provide a cathode on one lateral surface and an anode on the
opposed lateral sheet surface have the disadvantage of being
subject to corrosion of the cathode surface by the formation of
titanium hydride, with resultant deterioration of the cathode
surface, disintegration of the entire sheet and failure of the
cell. The bipolar assemblies, wherein opposed sheets are positioned
within individual compartments intermediate monopolar terminal
electrodes, suffer from the disadvantage of the difficulty of
maintenance of a closely spaced electrode gap across the entire
lateral surface of the electrodes. Consequently, the establishment
of a desired predetermined minimum voltage drop between the
electrodes by maintaining a minimum distance between the entire
cathode and anode surfaces to reduce the internal resistance loss
in the electrolyte layer is virtually impossible. Even if the
closely spaced electrodes are fabricated to close tolerance flat,
uniformly planar sheets and mounted at a predetermined minimum
operating distance from each other in a rigid frame, the varying
operating parameters of electrolytic processes such as temperature,
agitation of the electrolyte and variable stress in different areas
of the lateral surface induced by inherent mechanical
characteristics cause variations in the spacing of the electrodes.
Such variations in spacing cause objectionably high current density
at random areas of the working surfaces of the electrodes or
electrode segments, resultant inefficient cell operation and, if
not corrected, ultimate premature failure of the electrodes.
SUMMARY OF THE INVENTION
It is a primary object of the present invention to provide a
bipolar electrode assembly for multipolar electrolytic cells in
which the lateral surface spacing between the opposed electrode
surfaces may be established and maintained at a predetermined
uniform minimum distance.
It is a further object of this invention to provide bipolar
electrode assemblies for multipolar electrolytic cells whereby the
cells constructed with such bipolar electrodes arranged
intermediate terminal monopolar electrodes are capable of operating
at optimum power efficiency and minimum maintenance over extended
time periods.
It is a still further object of this invention to provide bipolar
electrode assemblies for multipolar electrolytic cells which cells,
constructed from such bipolar assemblies arranged between monopolar
terminal electrodes, are capable of producing, by electrochemical
processes, products such as caustic and chlorine, alkali and
alkaline earth metal hypochlorites, chlorates, perchlorates and
various organic compounds.
It is a further object of this invention to minimize the close
tolerance requirements in fabrication of the planar surfaces of
large electrodes required for such bipolar electrode
assemblies.
Broadly, this invention comprises at least one bipolar electrode
assembly adapted for arrangement intermediate to the terminal
monopolar electrodes of a multipolar electrolytic cell. The
assembly includes an electrically non-conductive partition at least
one rigid electrical conductor mounted in and extending beyond each
lateral surface of the partition, a dimensionally stable anode and
a cathode, respectively connected to the rigid conductor in opposed
parallel relation to the partition at opposed surfaces of the
conductor, and movable conductive means connecting the non-working
lateral surface of at least one electrode to a portion of the rigid
conductor facing the non-working lateral surface of said electrode
for adjustable movement of the working surface of the electrode in
a direction toward the working lateral surface of an opposed
electrode of an adjacent bipolar assembly. The assembly is useful
for constructing a bipolar electrolytic cell having monopolar
electrodes positioned in each of the two terminal compartments of
the cell and at least one bipolar electrode assembly of the
invention arranged intermediate said terminal monopolar electrodes
and means for connecting the terminal electrodes to the respective
positive and negative poles of an electrical power source. Such a
cell may be used for various electrolytic processes wherein either
a diaphragm or a diaphragm-less type cell is required.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatical view of one type of bipolar electrode
assembly of this invention showing a number of resilient members as
the electrically conductive means for movement of the anode, the
resilient members being shown connected to several individual rigid
electrical connectors.
FIG. 2 is a view similar to FIG. 1 illustrating the anode
constructed in segment form, all other parts being similar to FIG.
1.
FIG. 3 is a view similar to FIG. 1 but additionally including a
diaphragm positioned over the cathode and a number of electrically
conductive resilient members for movement of the cathode, such
assembly being adaptable for use in diaphragm type multipolar
electrolytic cells.
FIG. 4 is another view of the bipolar electrode assembly of this
invention wherein the electrically conductive means for adjustably
moving the anode consists of a unitary resilient member connected
to the surface of the number of rigid electrically conductive
members and a rigid bar connected to one surface of the cathode and
a portion of the surface of a number of electrically conductive
rigid members.
FIG. 5 is another view of the bipolar electrode assembly of this
invention showing a number of resilient members as the electrically
conductive means for movement of the cathode only.
FIG. 6 is a view similar to FIG. 5 showing the cathode in segmented
form.
FIG. 7 is another view similar to FIG. 3 illustrating the anode and
cathode, respectively, constructed of segments.
Referring to the drawings, the electrode assembly is shown
generally at numeral 10 and comprises an electrically
non-conductive partition 11, which may be constructed of any
suitable non-conducting material such as polyvinyl chloride,
polyethylene, polyvinylidene chloride and various other plastics
and the like. Rigid electrically conductive metal stud members or
studs 12 extend through the partition and beyond both opposed
lateral surfaces thereof and may be any suitable electrically
conductive metal resistant to the corrosive conditions of the cell
environment such as titanium, titanium sheathed copper and
tantalum. The rigid conductive members 12 may be of various
configurations provided they perform the function of conducting the
current between the electrodes of the cell assembly and are usually
designed of a geometrical configuration to provide maximum
current-carrying efficiency. The movable electrically conductive
members 15 for movement of the electrodes may be constructed of any
suitable electrically conductive metal which is resistant to the
cell environment and which is sufficiently resilient to permit
movement of the electrodes. Generally, the means 15 for movement of
the electrodes are constructed of metal such as titanium,
titanium-sheathed brass, steel and nickel but any suitably
resilient material resistant to the cell environment may be used.
The shape of the electrically conductive members for adjustably
moving the electrodes can vary with the design of the cell and may
be a plurality of resilient members connected to individual rigid
conductors extending through the partitions or may be in the form
of a unitary resilient member connected to a number of the
electrical conductors. The means for movement of the anodes are a
plurality of resilient members connected to a plurality of rigid
members 12 in FIGS. 1 to 3, inclusive and FIGS. 6 and 7, and a
unitary resilient member connected to a plurality of rigid members
12, in FIG. 4. The means for adjustable movement of the cathode are
shown as a plurality of resilient members in FIGS. 3, 5, 6 and
7.
The anodes 13 comprise an electrically conductive substrate with a
surface coating thereon of a solid solution of at least one
precious metal oxide and at least one valve metal oxide. The
electrically conductive substrate may be any metal which is not
adversely affected by the cell environment during use and also has
the capability, if a breakdown in the surface coating develops of
preventing detrimental reaction of the electrolyte with the
substrate. The size of the anodes and anode segments may vary
provided foraminous or solid anodes of suitable close tolerance
flatness for forming the structural bipolar electrode assembly are
used. Generally, the substrate is selected from the valve metals
including titanium, tantalum, niobium and zirconium. Expanded mesh
titanium sheet is preferred at the present time.
In the solid solutions an interstitial atom of a valve metal oxide
crystal lattice host structure is replaced with an atom of precious
metal. This solid solution structure distinguishes the coating from
physical mixtures of the oxides since pure valve metal oxides are,
in fact, insulators. Such substitutional solid solutions are
electrically conductive, catalytic and electrocatalytic.
In the above-mentioned solid solution host structure the valve
metals include titanium, tantalum, niobium and zirconium while the
implanted precious metals encompass platinum, ruthenium, palladium,
iridium, rhodium and osmium. Titanium dioxide-ruthenium dioxide
solid solutions are preferred at this time. The molar ratio of
valve metal to precious metal varies between 0.2-5:1, approximately
2:1 being presently preferred.
If desired, the solid solutions may be modified by the addition of
other components which may either enter into the solid solution
itself or admix with same to attain a desired result. For instance,
it is known that a portion of the precious metal oxide, up to 50%,
may be replaced with tin dioxide without substantial detrimental
effect on the overvoltage. Likewise, the defect solid solution may
be modified by the addition of cobalt compounds particularly cobalt
titanate. Solid solutions modified by the addition of cobalt
titanate, which serves to stabilize and extend the life of the
solid solution, are described more completely in co-pending
application Ser. No. 104,743 filed Jan. 7, 1971, now abandoned.
Other partial substitutions and additions are encompassed. Another
type of dimensionally stable anode coating which may be used with
good results in the practice of this invention consists of mixtures
of chemically and mechanically inert organic polymers and solid
solutions of valve metal and precious metal oxides as at least a
partial-coating on the electrically conductive substrate.
Particularly useful materials in such anode coatings are the
above-described solid solutions in admixture with fluorocarbon
polymers such as polyvinyl fluoride, polyvinylidene fluoride and
the like coated on at least part of the surface of an electrically
conductive substrate consisting of the above-described valve metals
and other suitable metals. Such anode coatings and preparation
thereof are disclosed and more completely described in co-pending
application Ser. No. 111,752 filed Feb. 1, 1971.
One other type of dimensionally stable anode capable of
satisfactory use in this invention consists of a valve metal
substrate bearing a coating of precious metals or precious metal
alloys, particularly platinum and alloys thereof on at least part
of its surface.
The above-mentioned preferred solid solution coatings are described
in more detail in British Pat. No. 1,195,871.
The cathodes 14 may be foraminous as shown and may be any metal
capable of sustaining the corrosive cell conditions. A useful metal
is generally selected from the group consisting of stainless steel,
nickel, titanium, steel, lead and platinum. In some cases the
cathodes may be coated with the solid solutions above-described for
coating the dimensionally stable anodes. When the assembly is
designed for movement of the anode only, the cathodes may be either
directly attached to a number of rigid electrically conductive
members 12 as shown in FIGS. 1 and 2 or to a unitary rigid member
17, as illustrated in FIG. 4. The working face of the cathode is
covered by a diaphragm or membrane 19, when the multipolar cell is
to be used as a diaphragm or membrane cell.
When the electrode assembly is utilized for construction of a
multipolar electrolytic cell, the cell casing may be any of the
usual types of construction materials such as polyvinyl fluoride,
polyvinylidene fluoride, various other reinforced plastics and any
other materials which are inert to the environment of the
particular cell electrolytes and resultant products of the process.
To construct a multipolar electrolytic cell, monopolar electrodes
are positioned at each of the terminal compartments at the ends of
the casing and, for example, may be connected to the end walls of
the casing. At least one bipolar electrode assembly is then
arranged intermediate the terminal monopolar electrodes with the
adjacent anodes and cathodes spaced as close as possible without
causing a short circuit. However, any desired number of bipolar
electrode assemblies may be arranged in the tank dependent upon the
production volume and design features of the particular cell.
It will be noted from the above description that anodes and
cathodes of adjacent bipolar electrode assemblies are positioned in
closely spaced parallel, substantially face-to-face relation.
Because of such closely spaced positioning of the electrodes
electrically non-conductive spacers may be and preferably are
interwoven through or positioned within the openings of foraminous
electrodes or electrode segments to prevent electrical contact of
the opposed electrode or segment surfaces. When flat or cylindrical
elements are used as spacers they are generally interwoven through
alternate openings on the outer edges of the lateral surfaces of
the electrodes or electrode segments, but may also be interwoven
through other openings in the foraminous electrodes. The
electrically non-conductive spacers should be constructed of
materials inert to the cell environment and may have any suitable
geometric configuration. Generally, the spacers are polyvinylidene
chloride, polyvinyl chloride, chlorinated polyvinylfluoride,
polyvinylfluoride, tetrafluoroethylene and the like and may be of
solid or hollow, cylindrical, flat or other suitable configuration.
Other types of spacers capable of satisfactory use are electrically
non-conductive strips provided with projections adapted to be
tightly engaged within the electrode openings and button-type
members such as semi-spherical elements arranged on opposite sides
of the electrode openings and joined by an engaging member such as
a stem extending through the electrode openings. The spacers are
preferably arranged to prevent electrical contact by shorting
between the opposed electrode surfaces and, at the same time,
provide maximum flow of the electrolyte solution through the
openings in the electrodes.
The bipolar electrode assembly of this invention offers many
advantages over the prior art electrodes utilized in multipolar
electrolytic cells. The electrically conductive means for moving
the electrodes assure maximum power efficiency by maintaining the
smallest possible space for electrolyte flow between the electrodes
plus assuring a low IR of the current passage through the
electrolyte. The flexibility of movement of the electrodes
resulting from the electrically conductive means for movement of
the electrodes maintains even large size electrodes in a flat or
planar position thus assuring uniform spacing of electrodes as well
as compensating for wear rates of individual sections of said
electrodes. The bipolar electrode assembly also affords a great
flexibility in construction of multipolar electrolytic cells in
that any number of the assemblies may be mounted intermediate the
monopolar terminal electrodes at each end of the cell thus
providing for variable production rates, ease of construction and
disassembly of said cells for cleaning or other maintenance
services. The bipolar electrode assembly may be used for any size
multipolar cell and enables the use of large size electrodes with
excellent power efficiency. The construction of the cells is simple
in that the electrode assemblies have been preconstructed and it is
merely necessary to position the desired number of assemblies
intermediate the terminal monopolar electrodes and connect the
terminal electrodes to negative and positive poles of an electrical
power source. Also, large size cells can be economically
constructed since the precise tolerances in fabricating the planar
surfaces of electrodes required by prior art cell construction to
obtain maximum power efficiency are not required as the bipolar
electrode assemblies of the present invention provide such close
tolerance without precise surface fabrication.
* * * * *