U.S. patent number 3,669,869 [Application Number 04/862,861] was granted by the patent office on 1972-06-13 for electrolytic cells.
This patent grant is currently assigned to A. Johnson & Company (London) Limited. Invention is credited to Derek Arthur Burton.
United States Patent |
3,669,869 |
Burton |
June 13, 1972 |
ELECTROLYTIC CELLS
Abstract
An electrolytic cell with spaced-apart electrodes in a row so
constructed that the inter-electrode spaces are in series so that
the electrolyte flows through them in succession. Preferably the
electrodes are at least 1 centimeter thick and the inter-electrode
spaces communicate with one another only by way of holes through
the electrodes. The electrodes may be wedge-shaped.
Inventors: |
Burton; Derek Arthur
(Basingstoke, EN) |
Assignee: |
A. Johnson & Company (London)
Limited (London, EN)
|
Family
ID: |
10441988 |
Appl.
No.: |
04/862,861 |
Filed: |
October 1, 1969 |
Foreign Application Priority Data
|
|
|
|
|
Oct 1, 1968 [GB] |
|
|
46,628/68 |
|
Current U.S.
Class: |
204/268;
204/288 |
Current CPC
Class: |
C25B
11/036 (20210101) |
Current International
Class: |
C25B
9/06 (20060101); B01k 003/04 () |
Field of
Search: |
;204/252,245,255,257,263,275,269,263,268 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Douglas; Winston A.
Assistant Examiner: Feeley; H. A.
Claims
I claim:
1. A bipolar electrolytic cell comprising a housing the interior of
which is closed off from the atmosphere, a vertical row of
spaced-apart electrodes in the housing which comprise upper and
lower electrodes and between them at least one bipolar intermediate
electrode which has an anode and a cathode integral with one
another and a lower face inclined to the horizontal, the lower face
of the upper electrode also being inclined to the horizontal, an
inlet into the housing at the bottom of the housing for the supply
of electrolyte liquid, an outlet from the housing at the top of the
housing for the discharge of treated liquid and means including
sealing devices engaging the electrodes for causing liquid to flow
in an always ascending path from the inlet to the outlet in which
it passes in succession through all the spaces between the
electrodes in the row, in each case across the faces of the two
electrodes on opposite sides of the space.
2. A cell according to claim 1 wherein the electrodes are at least
1 centimeter thick and said means comprises portions of some of the
electrodes defining holes through those electrodes, and seals
around the edges of the electrodes between them and the inside
surface of the housing.
3. A cell according to claim 1 in which the housing comprises
sections equal in number to the electrodes, each electrode being
encircled by its own housing section, and seals for preventing
leakage between adjacent sections.
4. A cell according to claim 1 in which each intermediate electrode
has its upper and lower faces inclined in opposite senses to the
horizontal.
5. A cell according to claim 1 in which said upper electrode is a
bipolar electrode which has an anode and a cathode integral with
one another (and is also a lower electrode in a second vertical row
of spaced-apart electrodes, which row comprises an upper electrode
having its lower face inclined to the horizontal and at least one
bipolar intermediate electrode which has an anode and a cathode
integral with one another and a lower face inclined to the
horizontal, means for causing liquid to flow in a second always
ascending path on its way from the inlet to the outlet in which it
passes in succession through all the spaces between the electrodes
in the second row, in each case across the faces of the two
electrodes on opposite sides of the space, and means for dividing
the stream of liquid to be treated into two streams of which one
follows one of said paths and the other follows the other of said
paths.
6. A cell according to claim 5 in which the two rows of electrodes
lie in a straight line and the housing is tubular, the cell further
comprising a second tubular housing surrounding and spaced from the
first tubular housing, partitions extending along the housings and
dividing the space between them into two chambers and portions of
the inner housing defining two openings from one chamber into the
first inter-electrode spaces in the rows of electrodes and two
openings from the last inter-electrode spaces in the rows of
electrodes into the other chamber.
7. A cell according to claim 5 in which each bipolar electrode has
its upper and lower faces inclined in opposite senses to the
horizontal.
Description
This invention relates to electrolytic cells.
It is already known to make an electrolytic cell comprising a row
of electrodes with spaces between them through which the
electrolyte is caused to flow, in each case across the faces of the
two electrodes on opposite sides of the space, each electrode being
made throughout of electrically conductive material. A potential
difference is applied between the end electrodes of the row, one of
which acts as an anode and the other as a cathode, whilst each of
the other electrodes, or the other electrode if the row comprises
only three electrodes, has one face which acts as an anode and an
opposite face which acts as a cathode and is therefore known in the
art as a "bipolar" electrode, the cell being known as a "bipolar"
cell. Such cells may, for example, be used in the electrolysis of
sodium chloride solution or sea water to form sodium hypochlorite
and hydrogen. In one known cell of this kind the electrodes consist
of sheet titanium, 1/16th of an inch thick, with a thinner cladding
of platinum on one face and because they are so thin the spacing
between them must not be much less than 1/10th of an inch, for fear
that they will bow and touch one another.
In the use of such cells for the electrolysis of sea water,
by-products are formed and these create difficulties, a major one
of which is the deposition of magnesium hydroxide within the cell
which causes constriction or blockage of the paths through which
the electrolyte must flow. Sometimes such an electrical leakage
path is created by the deposit between two adjacent electrodes that
the local heating caused by the electrical leakage results in
damage to the electrode material.
In most hitherto known cells of the kind discussed above, the
stream of electrolyte entering the cell splits up into several
parallel paths, some of it flowing between one anode and the
adjacent cathode, some flowing between another anode and the
adjacent cathode, and so on. The individual streams join to form
again a single stream, downstream of the gaps between the
electrodes. If the electrolysis is to take place adequately in a
single pass of the electrolyte through the cell, the rate of flow
of electrolyte in each gap will be small, which makes the cell
particularly prone to having magnesium hydroxide deposited on its
electrodes. Instead, the electrolyte could be recirculated, i.e.
passed through the cell repeatedly, at high velocity, which would
mitigate the problem of deposition of magnesium hydroxide but
increase the cost of the necessary ancillary equipment.
It is also known to have a bipolar electrolytic cell comprising a
housing the interior of which is closed off from the atmosphere, a
vertical row of spaced-apart electrodes in the housing which
comprise upper and lower electrodes and between them some bipolar
intermediate electrodes each of which has horizontal upper and
lower faces, an inlet into the housing at the bottom of the housing
for the supply of electrolyte liquid, an outlet from the housing at
the bottom of the housing for the discharge of treated liquid and
means for causing liquid to flow in a path from the inlet to the
outlet in which it passes in succession through all the spaces
between the electrodes in the row, in each case across the faces of
the two electrodes on opposite sides of the space, the bipolar
intermediate electrodes essentially comprising an aluminum anode
plate, an iron cathode plate, an insulating sheet between the two
plates, means for uniting the plates and openings in the plates and
the sheet.
Such a cell and also a cell according to the present invention can
be so constructed that when it is operated, passing the electrolyte
once only through the cell, there will be less deposit magnesium
hydroxide than when operating in a similar manner, and with the
same throughput of electrolyte, a cell in which the electrolyte
flows in parallel paths, with the same size, number and
construction of electrodes and the same electrode spacing. This is
largely on account of the greater velocity of the electrolyte
across the electrode faces. However this known cell and a cell in
accordance with the invention can also be operated with
recirculation of the electrolyte.
In this known cell and a cell according to the invention, because
the electrolyte flows through the interelectrode spaces in
succession, it is always warmer and hence more conductive when
passing through one space than it was when passing through the
preceding space, so the downstream end of the cell operates more
efficiently than the upstream end. The temperature rise is
cumulative, a feature which is absent from the known cells with
parallel flow paths for the electrolyte. Also it appears that the
evolved hydrogen, which passes through the inter-electrode spaces
in succession in contrast to what happens in the known cells,
assists in keeping the electrodes free from magnesium hydroxide
deposit, on account of its scouring action.
In the known cell, however, the composite construction of the
bipolar intermediate electrodes adds to the cost. Also the fact
that the spaces between the electrodes are bounded above and below
by horizontal surfaces and the inlet and outlet are both at the
bottom of the housing means that there are very large parts of the
path of the electrolyte where it flows horizontally and another
very large part where it flows downwardly. Thus liberated hydrogen
can remain stagnant in the housing. This reduces the electrical
efficiency of the apparatus and the hydraulic pressure drop across
the cell is increased so that the power required to pass the
requisite volume of electrolyte through the cell is increased.
According to the present invention there is provided a bipolar
electrolytic cell comprising a housing the interior of which is
closed off from the atmosphere, a vertical row of spaced-apart
electrodes in the housing which comprise upper and lower electrodes
and between them at least one bipolar intermediate electrode which
has an anode and a cathode integral with one another and a lower
face inclined to the horizontal, the lower face of the upper
electrode also being inclined to the horizontal, an inlet into the
housing at the bottom of the housing for the supply of electrolyte
liquid, an outlet from the housing at the top of the housing for
the discharge of treated liquid and means for causing liquid to
flow in a never descending path from the inlet to the outlet in
which it passes in succession through all the spaces between the
electrodes in the row, in each case across the faces of the two
electrodes on opposite sides of the space.
The or each bipolar intermediate electrode of a cell according to
the invention has the anode integral with the cathode, that is to
say there is not a body of electrically insulating material with
electrically conductive material applied as a layer on the outside
of the body, such as is known per se. The electrically conductive
material used for the bipolar intermediate electrodes in a cell
according to the invention could, however, be made up by mixing an
electrically conductive substance with an electrically insulating
substance. For example it could be plastics material reinforced
throughout with carbon fibers. The electrodes could instead be made
wholly of graphite or they could be made of graphite or metal with
a cladding which protects the graphite or metal from the
electrolyte and is more resistant than it to chemical action such
as occurs in use of the cell.
Another disadvantage of all the known cells described above is that
when they are used for the production of sodium hypochlorite the
influent electrolyte is simultaneously in contact with one side of
each electrode and the effluent sodium hypochlorite is
simultaneously in contact with the other side of each electrode, so
that in the case of the or each electrode other than the end
electrodes the electrolyte and sodium hypochlorite afford
electrical leakage paths between the opposite faces of the
electrode. Also, the electrolyte and hypochlorite afford electrical
leakage paths across the spaces between adjacent electrodes. The
resultant electrical leakage results in an increase in the amount
of electrical energy that must be used to produce a given amount of
sodium hypochlorite. Of course, such electrical leakage paths
cannot be avoided but substantial improvements can be made in this
respect over the known cells with very thin electrodes and
consequently short leakage paths and over the known cells with
horizontal composite electrodes of iron and aluminum if, in
accordance with a further development of the invention, the
electrodes are made at least 1 centimeter thick, the spaces between
them are interconnected only by holes through the electrodes and
seals are provided around the edges of the electrodes, between them
and the inside surface of a housing containing them. It is
desirable also to line the holes with tightly fitting tubes of
electrically insulating material, for example plastics material.
With such thick electrodes, the electrode spacing can be made 0.08
inch or less.
Preferably, the end electrodes in the row each have one flat face
which is perpendicular to the axis of the row and another flat face
which is inclined by an angle other than 90.degree. to that axis.
It is also preferable for each intermediate electrode to have two
opposite flat faces inclined in opposite senses to said axis.
According to a further development of the invention a cell
according to the invention as defined above may have said upper
electrode constructed as a bipolar electrode which has an anode and
a cathode integral with one another and is also a lower electrode
in a second vertical row of spaced-apart electrodes, which row
comprises an upper electrode having its lower face inclined to the
horizontal and at least one bipolar intermediate electrode which
has an anode and a cathode integral with one another and a lower
face inclined to the horizontal, the cell having means for causing
liquid to flow in a second never descending path on its way from
the inlet to the outlet in which it passes in succession through
all the spaces between the electrodes in the second row, in each
case across the faces of the two electrodes on opposite sides of
the space, and means for dividing the stream of liquid to be
treated into two streams of which one follows one of said paths and
the other follows the other of said paths.
Preferably, the two rows of electrodes lie in a straight line and
are disposed within a tubular housing which is in turn surrounded
by another tubular housing, there being a space between the two
housings divided by two partitions, extending along the housing,
into two chambers. One of these chambers is an electrolyte inlet
chamber and the other a treated liquid outlet chamber. There are
two openings from the inlet chamber into the first inter-electrode
spaces in the rows of electrodes and two openings into the outlet
chamber from the last inter-electrode spaces in the rows of
electrodes. This is a space-saving way of constructing a cell
having two rows of electrodes operating in parallel.
In an embodiment of the invention which is particularly
advantageous as regards ease of positioning of the electrodes, the
electrodes are disposed in a housing which is composed of sections
equal in number to the electrodes. Each electrode is assembled with
its own housing section encircling it, a comparatively simple
operation, after which the housing sections are assembled together
with seals to prevent leakage between adjacent sections.
Examples in accordance with the invention are described below with
reference to the accompanying drawings, in which:
FIG. 1 shows a side view of the interior of an electrolytic
cell,
FIG. 2 shows a plan view of the cell,
FIG. 3 shows a side view of the interior of a second electrolytic
cell,
FIG. 4 shows a plan view of the second cell,
FIG. 5 shows a detail of the second cell, and
FIG. 6 shows a side view, exploded, of part of the interior of a
third electrolytic cell.
The cell shown in FIGS. 1 and 2 has a vertical row of five
wedge-shaped electrodes, each at least 1 centimeter thick at the
thinnest part. These electrodes are an anode 4 at the lower end of
the row, a cathode 13 at the upper end of the row and three bipolar
electrodes 3 each of which acts as a cathode at its lower face and
as an anode at its upper face. These bipolar electrodes and every
bipolar electrode mentioned below have an anode and a cathode
integral with one another. All the electrodes are made of graphite
and are circular as seen in plan, although they could have other
shapes as seen in plan, the electrodes 4 and 13 being similar to
one another and each having one flat face which is perpendicular to
the longitudinal axis of the row of electrodes and an opposite flat
face which is inclined to that axis by an angle other than
90.degree.. The electrodes 3 are similar to one another and each
has two opposite flat faces which are inclined in opposite senses
to the aforementioned axis. Each electrode 3 has its thickest part
lying between the thinnest parts of the two adjacent electrodes.
Each electrode 3 has a hole 15 through it from one flat face to the
opposite one and near the thinnest part of the electrode. Each of
the electrodes 4 and 13 has a hole 16 through it from one flat face
to the opposite one and near the thinnest part of the electrode. In
this example and the other examples described below, the holes
could be lined with tightly-fitting tubes of electrically
insulating material, but this is not shown.
The electrodes are spaced apart and prevented from moving sideways
with respect to one another by pegs 16a of polytetrafluoroethylene.
There are four pegs 16a between each two electrodes and parts of
them project into holes (not shown) in the electrodes. The
electrodes are enclosed within a tubular housing 5 made of
polyvinyl chloride and are encircled by O-rings 2 which are
squashed between the electrodes and the inner surface of the
housing 5. Thus there are four enclosed spaces between adjacent
ones of the electrodes and each space communicates with the or each
adjacent one only by way of one of the holes 15.
Instead of the pegs 16a, there could be a ring of polyvinyl
chloride between each two adjacent electrodes, the ring touching
the inside of the housing 5 all round the periphery of the
ring.
At each end of the housing 5 there is a gasket 6 and a rigid end
plate 7 of electrically insulating material and the end plates are
interconnected by bolts 14 provided with nuts 8, so that they clamp
and render fluid-tight the assembly which is between them. An inlet
tube 17 is fastened to the lower plate 7 and holes pass through
this plate and the lower gasket 6 so that electrolyte can
continuously enter the tube 17 and flow in a straight line through
these holes and the hole 16 in the anode 4 into the space between
the anode 4 and the adjacent electrode 3. The electrolyte then
flows through all the spaces, between adjacent ones of the
electrodes, in succession, in each case across the flat faces of
the two electrodes on opposite sides of the space. An outlet tube
11 is fastened to the upper plate 7 and holes pass through this
plate and the upper gasket 6 so that electrolyte can continuously
flow in a straight line out of the space between the cathode 13 and
the upper electrode 3, through these holes and the hole 16 in the
cathode 13. Connecting conductors 10 and 12 pass through holes 18
in the end plates 7 and are screwed into the anode 4 and cathode
13, respectively.
Each electrode could be modified by providing the graphite with a
cladding which protects the graphite from the electrolyte and is
more resistant than the graphite to chemical action such as occurs
in use of the cell. Instead of using graphite, the electrodes could
be made of a metal, for example copper or aluminum, which is
provided with a cladding which protects it from the electrolyte and
is more resistant than the metal to chemical action such as occurs
in use of the cell. Suitable materials for use as the cladding in
these cases are titanium for the cathode 13 and the lower sides
(below the O-rings) of the electrodes 3 and titanium covered with a
layer of platinum for the anode 4 and the upper sides (above the
O-rings) of the electrodes 3. Security of the cladding may be
provided by screwing it on to the electrodes and/or sticking it on
with conductive adhesive.
Another possibility is to make each electrode of a plastics
material, for example an epoxy or polyester resin, reinforced with
carbon fibers.
The above observations concerning possible materials for the
construction of the electrodes apply also to the examples described
below.
There could be any odd number greater than three of the electrodes
3, or only one. The housing 5 could be of polypropylene and it and
the pegs 16a could be of some other material which is inert to the
electrolyte.
Electrolytic cells constructed as described above may be used for
the production of sodium hypochlorite by electrolysis of brine
solution or sea water and of course they have other uses too.
An electrolytic cell according to the invention could have a row of
only three or only four electrodes. There is described below and
illustrated in FIGS. 3 to 5 of the accompanying drawings an
electrolytic cell in accordance with the invention comprising two
rows of electrodes, one row of 4 and one row of 3. One electrode is
both the last in one row and the first in the other so that there
are six electrodes in all. Within each row the electrolyte flows
through both or all the inter-electrode spaces in succession, that
is to say the spaces are connected in series. The two series
arrangements of inter-electrode spaces are in parallel.
The cell has a row of four electrodes 20 to 23 and a row of three
electrodes 23 to 25, each electrode being at least 1 centimeter
thick at the thinnest part. The electrodes 20 and 25 are the same
in shape as the electrodes 4 and 13 of FIG. 1 except that they do
not have the holes 16. The electrodes 21 to 24 are the same in
shape as the electrodes 3 in FIG. 1, except that only the
electrodes 21, 22 and 24 have the holes 15 through them. The
reference numerals 2 and 16A in FIGS. 3 and 4 have the same
significance as they do in FIGS. 1 and 2.
The electrodes of FIGS. 3 and 4 are enclosed within a tubular
housing 26 made of polyvinyl chloride which is formed with four
slits 27, 28, 29 and 30, each of which is horizontal when the axis
of the housing 26 is vertical and is as shown in FIG. 5 for the
case of the slit 30. These slits are adjacent the first and last
inter-electrode spaces in the rows of electrodes. The slits 27 and
29 form inlets for brine solution or sea water to flow into the
inter-electrode spaces from a chamber 31. The slits 28 and 30 form
outlets for treated liquid to flow out of the inter-electrode
spaces into a chamber 32. A further tubular housing 33 of polyvinyl
chloride surrounds the housing 26 and the chambers 31 and 32 are
formed between the inner surface of the housing 33 and the outer
surface of the housing 26. The chambers are separated by walls 34
extending along the housings.
End plates 35 of electrically insulating material are provided at
the ends of the housings 26 and 33 and they are formed with
recesses which receive O-rings 36 which seal the housings with
respect to the end plates. The end plates are interconnected by
bolts 37 provided with nuts 38. An inlet tube 39 projects into a
hole in the lower plate 35 and communicates with the chamber 31 and
an outlet tube 40 projects into a hole in the upper plate 35 and
communicates with the chamber 32. Connecting conductors 41 and 42
pass through holes in the end plates 35 and are screwed into the
electrodes 20 and 25, respectively. O-rings 43 surround and seal
the inner ends of the holes through the plates 35.
There could be more than two paths connected in parallel, each path
comprising a number of inter-electrode spaces connected in series,
and whether or not this is so there could be more than the
illustrated numbers of electrodes in the rows.
Finally, FIG. 6 shows a cell which is like the cell shown in FIGS.
1 and 2 but differs from the latter in the respects indicated
below. Some details have been omitted from FIG. 6. The reference
numerals in FIG. 6 which appear also in FIGS. 1 and 2 have the same
significance.
There are only two electrodes 3 and the row of electrodes lies
within a housing made up of individual sections 44 and 45, one
section 44 for the anode 4, another for the cathode 13 and one
section 45 for each of the electrodes 3. If there were more or less
than two electrodes 3 there would be a corresponding number of
sections 45 so that standard parts can be used to build the
housings of cells of differing sizes. Each section 44 has a groove
46 on one side and each section 45 has a groove 46 on each side.
These grooves receive O-rings 47 which are squashed between the
sections to provide good seals between them, by tightening screws
48 which are screwed into the lower plate 7 and press on the lower
section 44. There are actually three screws 48, spaced equally
around the axis of the cell, but only one is shown. The electrodes
are first individually assembled with the O-rings 2 and the
sections 44 and 45, which is easier than positioning the electrodes
in a long tubular housing as is necessary in the construction shown
in FIGS. 1 and 2, and then these assemblies are put together, with
the O-rings 47 and spacer rings 49 of polytetrafluoroethylene
between adjacent electrodes.
Of course, the idea of building a housing of individual sections,
as shown in FIG. 6, could also be applied to the construction
according to FIGS. 3 to 5. In all the examples shown in the
drawings there is a never descending path for fluid from the inlet
to the housing at the bottom of the housing to the outlet of the
housing at the top of the housing.
* * * * *