[0001] Diaphragm electrolytic cells have been used widely in the production of chlorine
and caustic from brine. It is conventional in such cells to employ elongated, hollow
finger-shaped cathodes with graphite anodes interdigited between the cathodes. The
asbestos diaphragm is customarily deposited in situ on the cathode so as to divide
the interior of the cell into a catholyte and an anolyte compartment. Among recent
developments have been new, long lasting metal anodes, along with preformed membranes
made of polymeric materials which may be either semipermeable (allow only ions to
permeate them) or hydraulically-permeable (allowing the electrolyte to permeate them).
In spite of the increase of life of these preformed membranes, as well as a number
of additional advantages, there is still the problem of fitting these membranes between
the cathodes and the anodes in the cell to form fluid tight catholyte and anolyte
compartments. These membranes must be fitted over either the anodes or the cathodes
and do not naturally adhere to the electrodes as do the asbestos diaphragms which
have, for the most part, been formed in situ on one electrode or the other.
[0002] As would be expected, those skilled in the art have sought an answer to this particular
problem. U.S. Patent No. '3,980,544 discloses complex clamping means, requiring major
modifications in the electrolytic cells now in use. Any deviation of any of the metal
clamp parts disclosed in this patent presents a possibility for a leak. -U.S. Patent
No. 3,878,082 discloses and claims resilient means for holding the diaphragm in place,
but does not-detail how the. open edges of the diaphragm or membrane sheet are to
be sealed. U.S. Patent No. 3,923,630 discloses a cylindrical, continuous sheet of
preformed membrane positioned about a cylindrical electrode and held in place by being
glued or sealed to upper and lower membrane supports. In actual practice, it is extremely
difficult to completely seal the entire edge of these membrane sheets for the fifty
or more electrodes included in each electrode section, and this task is multiplied
many times when one considers that a large plant for producing chlorine and caustic
may have several thousand electrodes.
[0003] The present invention comprises a solution to the above problems and resides in an
electrolytic cell comprising a cathode spaced from an anode by a membrane, the improvement
comprising a first membrane support plate cast in situ to embed a portion of said
membrane, and a second membrane support plate cast in situ to embed another portion
of said membrane.
[0004] The present invention is more clearly illustrated in the accompanying drawings, wherein
Figure 1 is a perspective view of an electrolytic cell partially in section and shown
in a partially assembled state,
Figure 2 is an enlarged, cross-sectional view taken on line II-II of Figure 1,
Figure 3 is an enlarged, cross-sectional view taken on line III-III of Figure 1 and
at right angles to Figure 2, and
Figure 4 is a cross-sectional view taken on lineIV-IV of Figure 1.
[0005] In practicing the present invention, a conventional cell frame 10 is constructed
with an inner raised member 11 extending around the entire inner perimeter of the
cell frame. The raised member 11 is so formed as to provide ledges 12 which likewise
extend around the interior of the perimeter of the cell frame ' on either side of
the raised member 11. The raised member 11 may be an integral part of the cell frame
10, and is so shown in the accompanying drawings. The cell frame itself may be composed
of cement, a poured plastic such as polymeric resins, mixtures of polymeric resins
with various types of fillers, or any material which is sufficiently strong, relatively
non-electrically conducting and nonreactive with the cell environment.
[0006] In the embodiment shown in the drawings, an elongated footing strip 14 (see Figure
2) of polymeric resin having raised slots 15 molded therein is glued to the raised
member 11 along the bottom 16 of the cell frame. Slots 15 are aligned with openings
18 in the cell frame so as to permit electrolyte to flow in through the bottom 16
of the cell frame and through the anolyte compartment 39. Chlorine passes out of the
anolyte compartment 39 through slots 15 in the top 19 of the cell frame, as hereinafter
described. An identical footing strip 14 with identical slots 15 is glued to the top
19 of the cell frame. Here the slots 15 are also aligned with openings 18 in the top
of the cell frame and provide vents for the chlorine formed in the anolyte compartment
of the cell.
[0007] A series of hollow finger-shaped cathodes 20, made of wire mesh, are bolted to a
steel cathode backboard 21. Cathodes 20 are spaced from one another but in parallel:-alignment
with each other. Outlets 17 are provided in the backboard 21 for hydrogen and for
cell effluent from the catholyte compartment (hereinafter fully defined). The cathode
backboard 21, with the cathodes attached, is laid on its back and continuous elongated
preformed membrane sheet 22 is laid over the cathodes 20 in a serpentine shape, as
best seen in Figure 4. This preformed membrane sheet performs broadly the function
generally ascribed to a "diaphragm" in the electrolytic cell. It may be composed of
an inert, flexible material which is fluid permeable or one which permits only the
passage therethrough of ions (referred to in the art as semipermeable membranes).
Such membranes are well known in the art and may be composed of any one of many polymeric,
synthetic resins. A preferred composite membrane comprises a perfluorosulfonic acid
resin supported by a polyfluoroolefin fabric, and is sold commercially by E.I. duPont
de Nemours and Company under its trademark "Nafion".
[0008] The preformed membrane sheet 22 is of sufficient width to overhang along its serpentine
edges 28 both top and bottom ends 24 of the cathodes 20 (see Figure 2). Elastomeric,
foamed pieces (not shown) may be used to hold the serpentine shaped membrane 22 in
position, while the entire backboard 21, with cathodes 20 attached, is tipped on end,
as shown in Figure 1. This assembly is then moved into the cell frame 10 so that the
cathodes are positioned between the raised slots 15 positioned at the top and bottom
of the cell frame. The cathode backboard 21 rests in the cell frame on the ledges
12, and is attached to the cell frame 10 by bolts 25 positioned along the perimeter
of the backboard.
[0009] A molding board (not shown) is seated temporarily in that portion of the ledge 12
which runs along the bottom 16 of the cell frame opposite the cathode backboard 21.
A lower membrane support plate 26 is cast in situ by pouring a casting material along
the bottom footing strip 14 (note Figure 2). Sufficient casting material is poured
along the footing to embed the serpentine edges 28 of the membrane sheet 22 in the
casting material. The tops of slots 15, however, should not be covered, -since this
would prevent the introduction of the brine into the cell. Also, in the embodiment
shown, the ends of the cathodes 20 were not embedded in the support plate 26. The
lower membrane support plate 26 should be cast in a single pour. If the pour is stopped
after the level of the casting material reaches bottom 29 of the serpentine edges
28 of the membrane sheet 22, the already hardened material would prevent the casting
material of the second pour from filling in on the backside 27 of the membrane sheet
to further embed the serpentine edges 28 (see Figure 2).
[0010] An inorganic or organic cementitious material, a polymeric synthetic resin or a material
which is the same as or similar to the composition of the cell frame, may be employed
as the casting material. This casting material must wet the membrane to form a fluid-tight
seal therewith. Furthermore, the casting material should not be attacked by the environment
of the electrolytic cell and must be castable at a temperature that does not melt
or weaken the membrane sheet. Obviously, the casting material must be sufficiently
fluid in the casting state to flow up and around the serpentine edges 28 of the membrane
sheet to embed the same in the resulting membrane support plate 26. Vinyl ester resins
have been found to be useful as a casting material for the support plates, particularly
the reaction product of an unsaturated monocarboxylic acid and a polyepoxide in about
equivalent amounts. Fillers, such as sand, may be added to the casting material to
provide a heat sink and thus minimize shrinkage upon cooling. After the lower membrane
support plate 26 has hardened, the cell frame 10 is reversed so that it rests on the
top 19 of the cell frame. At this point an upper membrane support plate (not shown)
is cast in exactly the same manner as that heretofore described in connection with
the lower membrane support plate 26. The straight (non-serpentine) edges 30 of the
membrane sheet 22 which parallel the two sides 31 and 32 of the cell frame, may be
sealed in place by laying the cell frame on its back so that it rests on the cathode
backboard 21. Casting material 34 is then poured along the interior of the two sides
31 and 32, as shown in Figure 4. In the particular embodiment shown, edges 30 of membrane
22 are wedged between backboard 21 and cell frame sides 31 and 32. Clamps or other
types of seals may, of course, be used to provide a fluid-tight seal for the edges
30. The cell is completed by inserting in the cell frame 10 a plurality of anodes
35 held in parallel alignment with one another by means of an anode backboard 36,
as shown in Figure 4. It will be further apparent from Figure 4 that each of the anodes
35 is interposed or interdigited between each of the cathodes 20.
[0011] Again referring to Figure 4, it is seen that the membrane support assembly, consisting
of the membrane sheet 22 and the upper (not shown) and lower membrane support plates
26 divide the interior of the cell into fluid-tight catholyte compartment 38 and an
anolyte compartment 39. The trough portion 40 of the membrane sheet is held in place
by the embedment of the serpentine edges 28 in the upper and lower membrane support
plates, but is otherwise entirely free of mechanical means that could perforate the
relatively fragile membrane sheet 22.
[0012] It will be apparent from the above detailed description that the present invention
provides means for securely holding the serpentine-shaped membrane sheet 22 in a fluid-tight
arrangement which is economical to produce and one which can be readily adapted to
electrolytic cells for producing chlorine and caustic which are currently in general
industrial use. The trough portions 40 of the membrane sheet 22, which run the entire
length of the cathodes, are free from clamps of any kind and are merely held at the
edges by the cast-in-place membrane support plates. The improved membrane support
assembly is so constructed that both the anodes and the cathodes may be removed from
the cell frame without disturbing the membrane sheet 22.
[0013] Numerous variations in the embodiment of the invention illustrated in the accompanying
drawings will be apparent to those skilled in the art without departing from the scope
of the present invention as described in the claims. For example, the "continuous"
membrane sheet may in fact be made up of a plurality of short membrane sheets spliced
to one another either by gluing or heat sealing. The exact construction of the cell
frame 10, or the particular shape of the cathodes and anodes employed in the cell
form no part of the present invention, and may be varied widely. For example, hollow,
expanded mesh anodes may be employed in place of the solid anodes shown, and punched
plate cathodes may be employed in place of the wire mesh cathodes shown.
1. An electrolytic cell comprising a cathode spaced from an anode by a membrane, characterized
by a first membrane support plate cast in situ to embed a portion of said membrane,
and a second membrane support plate cast in situ to embed another portion of said
membrane.
2. The cell of Claim 1, characterized in that said first membrane support plate is
cast in situ for embedding an edge of the membrane, and said second membrane support
plate is cast in situ for embedding a generally opposite edge of the membrane.
3. An electrolytic cell for the production of chlorine and caustic from aqueous alkali
metal chloride solutions comprising a plurality of cathodes spaced from one another
and a plurality of anodes interposed between said cathodes and spaced therefrom, characterized
by a membrane support assembly which comprises a continuous, elongated sheet of preformed
membrane positioned in serpentine fashion between the anodes and the cathodes so as
to separate all opposing surfaces of anodes and cathodes, a first membrane support
plate cast in situ embedding one serpentine-shaped edge of said membrane, and a second
membrane support plate cast in situ embedding the other serpentine-shaped edge of
said membrane, said membrane support assembly dividing said electrolytic cell into
separate anolyte and catholyte compartments.
4. The cell of Claim 3, characterized by means for sealing the non-serpentine edges
of the membrane sheet which comprise a sealant cast in situ to embed all of the non-serpentine
edges of said membrane sheet.
5. The cell of Claim 3 or 4, characterized in that said membrane sheet is a composite
membrane composed of a perfluorosulfonic acid resin supported by a polyfluoroolefin
fabric.
6. The cell of Claim 3, characterized in that said membrane supports are composed
of a polymeric material that wets said membrane sheet so as to form a liquid impermeable
seal with the embedded portion thereof.
7. A method for supporting a preformed membrane in an electrolytic cell, characterized
by the step of casting in situ support plates about the open edges of the membrane.
8. Method of Claim 7, wherein said electrolytic cell is constructed for the production
of chlorine and caustic from aqueous alkali metal chloride solutions and comprises
a plurality of cathodes spaced from one another, a plurality of anodes interposed
in the spaces between said cathodes and separated therefrom, said membrane comprising
a continuous elongated preformed membrane sheet separating the anodes and the cathodes
from one another so as to provide separate anolyte and catholyte compartments within
said cell, said method being characterized by the steps of positioning said membrane
sheet in serpentine shape between said anodes and cathodes so as to separate all opposing
surfaces of said anodes and cathodes, casting a first of said membrane support plates
about one serpentine-shaped edge of said membrane sheet so as to fixedly embed said
edge in said support plate, and casting a second of said membrane support plates about
the other serpentine--shaped edge of said membrane so as to fixedly embed said other
edge in said support plate, said membrane support assembly thus forming separate anolyte
and catholyte compartments within said electrolytic cell.
9. The method of Claim 8 characterized in that said membrane sheet is constructed
of a polymeric synthetic resin.
10. The method of Claim 8 characterized in that said membrane sheet is constructed
of a perfluorosulfonic acid resin supported by a polyfluoro-olefin fabric.
11. The method of any one of Claims 7 to 10, characterized by casting the edges of
said membrane sheet in an inorganic or organic cementitious material or a polymeric
synthetic resin.
12. The method of Claim 8 characterized by casting in situ a sealant around non-serpentine
edges of the.membrane to embed at least a portion of such edges in the sealant and
to adhere the edges to at least a wall portion of the cell.
13. The method of any one of Claims 7 to 12, characterized in that each of the membrane
support plates is cast to fully embed both sides of the membrane sheet.
14. The method of Claim 13 characterized in that each of the membrane support plates
is cast in a single pour.