U.S. patent number 3,767,542 [Application Number 05/186,082] was granted by the patent office on 1973-10-23 for reduction of electrolytic cell voltage by anode vibration.
This patent grant is currently assigned to Diamond Shamrock Corporation. Invention is credited to Richard C. Carlson.
United States Patent |
3,767,542 |
Carlson |
October 23, 1973 |
REDUCTION OF ELECTROLYTIC CELL VOLTAGE BY ANODE VIBRATION
Abstract
The operating voltage of an electrolytic cell in which gaseous
evolution occurs at the anode is reduced by applying high speed
mechanical vibration to the anode.
Inventors: |
Carlson; Richard C. (Euclid,
OH) |
Assignee: |
Diamond Shamrock Corporation
(Cleveland, OH)
|
Family
ID: |
22683586 |
Appl.
No.: |
05/186,082 |
Filed: |
October 4, 1971 |
Current U.S.
Class: |
205/528; 204/261;
204/273 |
Current CPC
Class: |
C25B
1/36 (20130101); C25B 15/00 (20130101); C02F
1/46109 (20130101); C02F 1/4674 (20130101); C02F
1/34 (20130101); C02F 2001/46142 (20130101); C02F
2001/46123 (20130101) |
Current International
Class: |
C02F
1/461 (20060101); C25B 1/00 (20060101); C25B
1/40 (20060101); C25B 15/00 (20060101); C02F
1/467 (20060101); C02F 1/34 (20060101); C01b
007/06 () |
Field of
Search: |
;204/261,273,98,128,162S,163S,129 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
1,284,288 |
|
Oct 1970 |
|
SU |
|
1,111,392 |
|
Feb 1956 |
|
FR |
|
Other References
Modern Electroplating by Lowenheim, 2nd Ed., 1963, pages
18-19..
|
Primary Examiner: Williams; Howard S.
Assistant Examiner: Andrews; R. L.
Claims
I claim:
1. An improvement in the method of electrolyzing alkali metal
halide solutions by passing a current between an anode and an
opposed cathode, said current being sufficient to cause gaseous
evolution at the anode, which improvement consists essentially of
causing said anode to vibrate rapidly and continuously by the
direct application of mechanical force to the anode structure.
2. In a method of electrolyzing an aqueous alkali metal halide by
passing current through said aqueous halide between an anode and an
opposed cathode at an anode current density of greater than 8
amperes per square inch, the improvement which consists essentially
of reducing the operating voltage by causing said anode to vibrate
continuously at a rate of from 6,000 vibrations per minute up to
ultrasonic by the direct application of mechanical force to the
anode structure.
Description
BACKGROUND OF THE INVENTION
A variety of electrochemical reactions is known wherein electrical
current is passed through an aqueous electrolyte between an anode
and an opposed cathode, the current being such as to result in the
generation of a gas or gasses at the anodic surface. Electrowinning
of metals from aqueous solution, the electrolysis of water and the
production of chlorine, caustic and the chemical compounds thereof
are but a few examples of such reactions. As the applied anode
current density in these processes is increased, the rate of
production and the amount of gaseous evolution increase, as does
the operating cell voltage. At least initially, this increase in
voltage is, for all practical purposes, in direct relation to the
increase in current density. However, it has been noted at the
higher current densities desirable in order to increase the
production rate of a given electrolytic cell that the voltage
begins to increase at a rate greater than theoretical, resulting in
an increase in power consumption per unit of product.
Attempts have been made to counteract this undesirable rate of
increase in voltage. For example, following the suggestion of
certain prior art, the electrolyte has been subjected to ultrasonic
vibrations with, unfortunately, no detectable effect.
STATEMENT OF THE INVENTION
Therefore it is an object of the present invention to provide a
method for reducing the operating voltage of an electrochemical
cell, which method is especially effective when the cell is
operated at relatively high current densities.
This and further objects of the present invention will become
apparent to those skilled in the art from the specification and
claims which follow.
In a method for conducting an electrolytic reaction wherein, upon
passing an electric current through an aqueous electrolyte between
an anode and an opposed cathode, gaseous evolution occurs at the
anode, the improvement has now been found which consists
essentially of reducing the operating voltage by directly
subjecting the anode to high speed mechanical vibrations.
DESCRIPTION OF THE DRAWING
The FIGURE is a graph illustrating the improved performance of the
present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As described above, the invention is applicable to those
electrochemical reactions wherein an electric current is passed
through an aqueous electrolyte at a voltage sufficient to achieve
the desired reaction and result in the evolution of a gas or gasses
at the anodic surface. Generally the gas evolved either is desired
product (e.g., chlorine) or is required for a subsequent chemical
reaction resulting in the desired product (e.g., chlorine reacting
to chlorate). However, the invention functions equally as well
where the gas evolved is an unavoidable by-product, the desired
reaction occurring predominantly at the cathodic surface (e.g.,
oxygen at the anode in electrowinning).
The advantage of the instant invention is most marked at relatively
high current densities wherein the rate of production is such that
considerable quantities of gas are evolved and rapid decomposition
of the electrolyte occurs at the anodic surface. These conditions
of high current density have become increasingly common-place in
recent years with the advent of dimensionally stable anodes that
are not subject to the usual decomposition and attrition of, for
example, graphite at increased current densities.
The action to which the anode is subjected is stated as being "high
speed mechanical vibration". As suggested by this phrase, together
with the word "directly," it is intended that the anode itself,
especially the working face thereof, be caused to vibrate,
preferably at a rate in excess of 6,000, especially in excess of
9,000 vibrations per minute and up to speeds which may be
considered ultrasonic (e.g., 20,000 vibrations/second). The
vibrations are applied directly to the anode and/or its supporting
and connecting framework up to and including the current lead in
(busbar). Vibrations applied to other of the cell components, such
as the cell supports or sidewalls, or to the electrolyte have been
found to have substantially no effect.
The means for inducing the mechanical vibration is of little or no
consequence to the invention, although obviously important from a
practical standpoint. It has been found that in order to be
effective the vibrations must be continually applied, that is, upon
cessation of the vibrations the operating voltage immediately
increases to its prior, excessive, value. For this reason the
vibrating means should be chosen for its durability and simplicity
of operation and maintenance. Typical of such are those vibrators
in which compressed air is used to impart unbalanced rotation to
balls or rollers which in turn induce vibrations in members in
contact therewith.
Illustrative of the present invention is its effect upon the
electrolysis of an aqueous alkali metal halide solution in a cell
employing a dimensionally stable anode and a flowing mercury
cathode. The cell used is a horizontal-type mercury cell employing
an anode suspended above a steel cathode base plate, the assembly
being enclosed to contain the electrolyte and products of
electrolysis. The dimensionally stable anode is constructed
primarily of titanium, is supported by an anode frame and is
connected to a copper busbar. An anode riser leads from the busbar
connection to the interior of the cell, the active working face of
the anode consisting of a plurality of elongated rod-like elements
positioned in a plane parallel to the flowing mercury surface and
connected by welding through secondary conductors to the anode
riser. The surface of these titanium rods is coated with an
electrically-conductive electrocatalytically active material, in
this case a titanium dioxide-ruthenium oxide deposit. The
anode-cathode gap is established at 0.136 inch. A 305 grams/liter
sodium chloride solution is employed as the electrolyte at an
average cell temperature of 76.degree.C.
The Figure shows the relationship between applied anode current
density and the operating cell voltage at the above-described
conditions. The first line (1) charts the theoretical straight line
relationship between voltage and current density for the given
conditions. Line 3 is a plot of the anode current density versus
the actual cell voltage obtained, measured from anode face to
mercury. Line 2 is again a plot of the measured voltage at the
various current densities, all conditions being the same as those
of Line 3 with the exception that mechanical vibration is
employed.
Vibration is effected by placing a commercially-available
compressed air-driven vibrator (Vibrolator Model BDR-16, Martin
Engineering Co.) directly on the anode busbar. The vibrator
operates within the range of 9,000-11,000 vibrations per minute.
The location of the vibrator on the copper busbar is a matter of
convenience, attachment to the anode per se and the anode frame
having been found to give equivalent results.
The substantial reduction in voltage obtained by the application of
vibrational force is readily seen from the attached figure,
reductions of up to 300 millivolts having been observed.
While the invention has been described with reference to certain
preferred embodiments thereof, it is not to be so limited since
changes and alterations may be made therein while remaining within
the scope of the appended claims.
* * * * *