U.S. patent number 3,884,777 [Application Number 05/429,998] was granted by the patent office on 1975-05-20 for electrolytic process for manufacturing chlorine dioxide, hydrogen peroxide, chlorine, alkali metal hydroxide and hydrogen.
This patent grant is currently assigned to Hooker Chemicals & Plastics Corp.. Invention is credited to Jeffrey D. Eng, Cyril J. Harke.
United States Patent |
3,884,777 |
Harke , et al. |
May 20, 1975 |
Electrolytic process for manufacturing chlorine dioxide, hydrogen
peroxide, chlorine, alkali metal hydroxide and hydrogen
Abstract
Chlorine dioxide, hydrogen peroxide, chlorine, alkali metal
hydroxide and hydrogen are produced from alkali metal chloride,
alkali metal chlorate, sulfuric acid and water, utilizing an
electrolytic cell having anode and cathode compartments separated
by two intermediate buffer compartments, the boundaries between the
anode and cathode compartments and the buffer compartments being of
cation-active permselective membranes which are resistant to attack
by the medium and the buffer compartments being separated by a
suitable anion-active permselective membrane. On electrolysis, with
sulfuric acid fed to the anode compartment, chloride and chlorate
fed to the buffer compartment adjacent to the cathode compartment
and water fed to the cathode compartment there are produced
hydrogen and alkali metal hydroxide in the cathode compartment,
chlorine dioxide and chlorine in the buffer compartment adjacent to
the anode compartment and persulfuric acid in the anode
compartment. The persulfuric acid is hydrolyzed to produce hydrogen
peroxide. Hydrogen peroxide, alkali metal hydroxide, chlorine and
chlorine dioxide are useful pulp mill chemicals especially suited
for pulping wood and bleaching wood pulp.
Inventors: |
Harke; Cyril J. (Burnaby,
British Columbia, CA), Eng; Jeffrey D. (North
Vancouver, British Columbia, CA) |
Assignee: |
Hooker Chemicals & Plastics
Corp. (Niagara Falls, NY)
|
Family
ID: |
23705635 |
Appl.
No.: |
05/429,998 |
Filed: |
January 2, 1974 |
Current U.S.
Class: |
205/472; 204/257;
204/296; 423/478; 423/585; 205/517; 205/556; 205/620 |
Current CPC
Class: |
C25B
1/28 (20130101); C25B 1/46 (20130101); C25B
1/29 (20210101); C25B 1/26 (20130101) |
Current International
Class: |
C25B
1/00 (20060101); C25B 1/26 (20060101); C25B
1/28 (20060101); C25B 1/46 (20060101); C01b
011/02 (); C01d 001/06 (); B01k 003/00 () |
Field of
Search: |
;204/82,84,101,103,95
;423/478,585 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Edmundson; F. C.
Attorney, Agent or Firm: Casella; Peter F. Studley; Donald
C.
Claims
What is claimed is:
1. A method of manufacturing chlorine dioxide, hydrogen peroxide,
chlorine, hydrogen and substantially alkali metal chloride-free
aqueous alkali metal hydroxide from aqueous alkali metal chloride,
aqueous alkali metal chlorate, sulfuric acid and water which
comprises electrolyzing in a cell having an anode compartment with
an anode therein, a cathode compartment with a cathode therein and
intermediate buffer compartments, B.sup.1 and B.sup.2, the anode
compartment being separated from B.sup.1 by a cation-active
permselective membrane, M.sup.c.sup.-1, the cathode compartment
being separated from B.sup.2 by a cation-active permselective
membrane, M.sup.c.sup.-2, and B.sup.1 and B.sup.2 being separated
from each other by an anion-active permselective membrane, M.sup.a,
solutions resulting from feeding sulfuric acid to the anode
compartment, alkali metal chloride and alkali metal chlorate to
B.sup.2, and water to the cathode compartment so that with the
passage of electric current through the cell hydrogen ions
selectively pass from the anode compartment to B.sup.1 through
M.sup.c.sup.-1, chloride and chlorate anions selectively pass from
B.sup.2 to B.sup.1 through M.sup.a, and alkali metal cations
selectively pass from B.sup.2 to the cathode compartment through
M.sup.c.sup.-2, sulfuric acid is oxidized at the anode to produce
persulfuric acid in the anode compartment, chloride and chlorate
ions react to produce chlorine and chlorine dioxide in B.sup.1, and
water and alkali metal cation react at the cathode to produce an
aqueous substantially alkali metal halide-free alkali metal
hydroxide and hydrogen in the cathode compartment, recovering the
persulfuric acid solutions, chlorine dioxide, chlorine, hydrogen
and aqueous hydroxide produced and reacting the persulfuric acid
solution with water to produce sulfuric acid and hydrogen
peroxide.
2. A method according to claim 1 wherein the alkali metal chloride,
the alkali metal chlorate and the alkali metal hydroxide are sodium
chloride, sodium chlorate and sodium hydroxide respectively, the
M.sup.c.sup.-1 and M.sup.c.sup.-2 cation-active membranes are of
the same cation-exchange material, the cell is operated at a
temperature below about 60.degree.C. and the persulfuric acid
solution recovered from the anode compartment is reacted with at
least about 2 moles of water per mol of persulfuric acid in the
solution.
3. A method according to claim 2 wherein the material of the
anion-active membrane is selected from the group consisting of
quaternary ammonium group-substituted fluorocarbon polymers and
quaternary ammonium-substituted polymers derived from heterogeneous
polyvinyl chloride, the cation-active membranes are selected from
the group consisting of hydrolyzed copolymers of perfluorinated
olefin and a fluorosulfonated perfluorinated vinyl ether,
fluorinated polymers having pendant side chains containing sulfonyl
groups which are attached to carbon atoms bearing at least one
fluorine atom, with sulfonyl groups on one surface being in
-(SO.sub.2 NH).sub.n M form where M is H,NH.sub.4, alkali metal or
alkaline earth metal and n is the valence of M, and the sulfonyls
of the polymer on the other membrane surface being in
-(SO.sub.3).sub.p Y form wherein Y is a cation and p is the valence
of the cation and when Y is H, M is also H, or being -SO.sub.2 F,
and sulfostyrenated perfluorinated ethylene propylene copolymers,
the sulfuric acid charged to the anode compartment is aqueous
sulfuric acid containing above about 80 percent thereof of sulfuric
acid by weight and the sodium chloride and sodium chlorate are
charged as aqueous solutions.
4. A method according to claim 3 wherein the anode is of a
persulfuric acid-inert noble metal, the cathode is a material
selected from the group consisting of platinum, iridium, ruthenium,
rhodium, graphite, iron and steel, the hydrolyzed copolymer is
derived from tetrafluoroethylene and fluorosulfonated
perfluorovinyl ether of the formula
FSO.sub.2 CF.sub.2 CF.sub.2 OCF(CF.sub.3)CF.sub.2 OCF=CF.sub.2
and an equivalent weight of about 900 to 1,600, the fluorinated
polymer with different side materials is a perfluorinated copolymer
of tetrafluoroethylene and FSO.sub.2 CF.sub.2 CF.sub.2
OCF(CF.sub.3)CF.sub.2 OCF=CF.sub.2 in a molar ratio of about 7:1, M
and Y are both sodium and n and p are both 1, and the
sulfostyrenated perfluorinated ethylene propylene copolymer is
about 16 to 18 percent styrenated and has from about two-thirds to
thirteen-sixteenths of the phenyl groups therein monosulfonated,
the thicknesses of the cation-active membranes and the anion-active
membrane are between about 0.02 to 0.5 mm., the concentration of
sulfuric acid in the sulfuric acid feed solution to the anode
compartment is about 93 to 97% by weight, the concentrations of
sodium chlorate and sodium chloride in the feed to B.sup.2 are from
about 1 N to the saturation solubility for each salt in water, and
the sulfuric acid, sodium chloride and sodium chlorate are fed to
the cell in molar proportioned rates of about 2:1:1.
5. A method according to claim 4 wherein the cell operates at a
temperature of from about 20.degree. to 35.degree.C., the
hydrolyzed copolymer is utilized and has an equivalent weight of
from about 1,100 to 1,400, the cation-active and anion-active
membranes are mounted on networks of material(s) selected from the
group consisting of polytetrafluoroethylene, asbestos,
perfluorinated ethylene-propylene copolymer, polypropylene,
titanium, tantalum, niobium and noble metals, which have area
percentage(s) of openings therein from about 8 to 80 percent and
the persulfuric acid solution recovered from the anode compartment
is reacted with water at a temperature of about 60.degree. to
100.degree.C. to produce hydrogen peroxide.
6. A method according to claim 5 wherein the cell operates at a
voltage of about 2.3 to 5 volts and a current density of about 0.5
to 4 amperes per square inch of electrode surface, the anode is of
platinum or platinum on titanium, the cathode is of mild steel and
the substantially sodium chloride-free hydroxide solution contains
about 60 to 250 grams per liter of sodium hydroxide.
7. A method according to claim 6 wherein the cell operates at a
voltage of about 2.5 to 4 volts, a current density of about 1 to 3
amperes per square inch of electrode surface and a temperature of
about 30.degree. to 35.degree.C., the membranes are from about 0.1
to 0.4 mm. thick, and are mounted on a network of
polytetrafluoroethylene filaments with the area percentage of
openings in the network being from 10 to 70 percent, and the
concentration of sodium hydroxide in the aqueous hydroxide solution
recovered from the cathode compartment is about 80 to 120 grams per
liter.
8. A method according to claim 7 wherein the cation-active
membranes are of the hydrolyzed copolymer having an equivalent
weight of about 1,250, the cell operates at about 3 volts and a
current density of about 2 amperes per square inch of electrode
surface, the anode is of platinum, the concentrations of sodium
chlorate and sodium chloride in the feed solution to B.sup.2 are
each 3 N, the hydroxide solution recovered from the cathode
compartment contains about 100 grams per liter of sodium hydroxide,
and the aqueous sulfuric acid distilland is recycled to the
sulfuric acid feed to the anode compartment.
9. A method according to claim 8 wherein the anion-active membrane
is a quaternary ammonium substituted fluorocarbon polymer.
10. A method according to claim 8 wherein the anion-active membrane
is a quaternary ammonium substituted polymer derived from a
heterogeneous polyvinyl chloride.
11. A method of manufacturing chlorine dioxide, hydrogen peroxide,
chlorine, substantially alkali metal chloride-free aqueous alkali
metal hydroxide and hydrogen from alkali metal chloride, alkali
metal chlorate, sulfuric acid and water which comprises
electrolyzing with a direct current, in a cell having an anode in
an anode compartment, a cathode in a cathode compartment and a
plurality of intermediate buffer compartments, with the anode
compartment being separated from a buffer compartment by a
cation-active permselective membrane, the cathode compartment being
separated from a buffer compartment by a cation-active
permselective membrane and at least one buffer compartment being
separated from another by an anion-active permselective membrane,
electrolytes resulting from feeds of sulfuric acid to the anode
compartment, alkali metal chloride and alkali metal chlorate to a
buffer compartment nearer to the cathode compartment than another
buffer compartment, and water to the cathode compartment, so that
with the passage of direct electric current through the cell
hydrogen ions selectively pass from the anode compartment to an
adjacent buffer compartment through the cation-active permselective
membrane, chloride and chlorate ions selectively pass from a buffer
compartment nearer to the cathode compartment to another buffer
compartment through an anion-active permselective membrane, and
alkali metal cations selectively pass from a buffer compartment to
the cathode compartment through a cation-active permselective
membrane, sulfuric acid is converted to persulfuric acid in the
anode compartment, chloride and chlorate ions react to produce
chlorine and chlorine dioxide in a buffer compartment nearer to the
anode compartment than the buffer compartment into which chloride
and chlorate are fed, and water and alkali metal cations are
converted to aqueous, substantially alkali metal halide-free alkali
metal hydroxide and hydrogen in the cathode compartment, and
removing from the electrolytic cell the persulfuric acid solution,
chlorine dioxide, chlorine, aqueous alkali metal hydroxide and
hydrogen produced.
Description
The present invention is directed to the preparation of chlorine
dioxide, hydrogen peroxide, chlorine, aqueous alkali metal
hydroxide solution which is substantially free of alkali metal
halide, and hydrogen. More particularly, the invention is of such a
process which utilizes a relatively simple four compartment
electrolytic cell having anion-active and cation-active membranes
separating compartments thereof.
Chlorine dioxide, hydrogen peroxide, chlorine, and salt-free
aqueous alkali metal hydroxide are chemicals that are frequently
employed in pulp mill operations, especially for the pulping of
wood chips and bleaching of wood pulps. It has long been desired,
for reasons of economy and convenience, to prepare these chemicals
together at a single site, preferably adjacent to the pulp mills.
However, the known methods of producing each of these chemicals
require comparatively costly and complex apparatuses and
multiplicities of reaction stages, so that single-site productions
of these reagents has heretofore proved impractical. For example,
in the well known Day-Kesting process for making chlorine and
chlorine dioxide, aqueous alkali metal chloride is electrolyzed to
the chlorate, which is treated with hydrogen chloride to form
chlorine and chlorine dioxide, which are separated by treatment
with water in an absorption tower. This process, however, employs a
very slow countercurrent contact of chlorate solution and hydrogen
chloride so that, in addition to an electrochemical cell, the
procedure requires a costly array of cascading reactors with a
large storage tank for holding the chlorate solution prior to its
reaction with hydrogen chloride [see the article by W. H. Rapson,
Canadian Journal of Chemical Engineering Vol. 36, p. 6 (1958)].
Furthermore, this process does not produce hydrogen peroxide or a
substantially salt-free alkali metal hydroxide, i.e., aqueous
sodium hydroxide containing less than about one percent of alkali
metal chloride.
The foregoing disadvantages of typical prior art processes are
overcome by the present invention, which provides a novel method,
utilizing a relatively simple reaction apparatus, for co-producing
chlorine dioxide, hydrogen peroxide, chlorine, substantially
chloride-free alkali metal hydroxide solution and hydrogen, from
aqueous alkali metal chlorate, aqueous alkali metal chloride,
sulfuric acid, water and electric power. This method comprises
electrolyzing in a cell having an anode compartment with anode
therein, a cathode component with cathode therein and intermediate
buffer compartments, B.sup.1 and B.sup.2, the anode compartment
being separated from B.sup.1 by a cation-active permselective
membrane, M.sup.c.sup.-1, the cathode compartment being separated
from B.sup.2 by a cation-active permselective membrane,
M.sup.c.sup.-2, and B.sup.1 and B.sup.2 being separated from each
other by an anion-active permselective membrane, M.sup.a, solutions
resulting from feeding sulfuric acid to the anode compartment and
alkali metal chloride and alkali metal chlorate to B.sup.2, so that
with the passage of electric current through the cell hydrogen ion
selectively diffuses or passes from the anode compartment to
B.sup.1 through M.sup.c.sup.-1, chloride and chlorate anions
selectively diffuse or pass from B.sup.2 to B.sup.1 through M.sup.a
and alkali metal cations selectively diffuse or pass from B.sup.2
to the cathode compartment through M.sup.c.sup.-2, sulfuric acid is
oxidized at the anode to produce a sulfuric acid solution of
persulfuric acid in the anode compartment, hydrogen chloride and
aqueous chlorate anions are reacted to produce chlorine and
chlorine dioxide in B.sup.1, and water and aqueous alkali metal
cation are reacted at the cathode to produce aqueous, substantially
alkali metal chloride-free alkali metal hydroxide and hydrogen in
the cathode compartment, after which the persulfuric acid solution,
chlorine dioxide, chlorine, hydrogen and aqueous alkali metal
hydroxide are removed from the cell compartments. Subsequently, the
aqueous persulfuric acid solution is converted to sulfuric acid and
hydrogen peroxide.
The invention will be readily understood by reference to
descriptions of the embodiments thereof herein, taken in
conjunction with the drawing of means for carrying out a preferred
embodiment of the process.
In the Drawing:
The FIGURE is a schematic diagram of a four-compartment
electrochemical cell for converting water, alkali metal chloride,
alkali metal chlorate and sulfuric acid to chlorine dioxide,
chlorine, aqueous alkali metal hydroxide, hydrogen and persulfuric
acid. The FIGURE also includes hydrolysis means for converting the
persulfuric acid to hydrogen peroxide by reaction with water in the
form of steam.
In the FIGURE the points of addition and withdrawal of typical and
preferred reactants and products are illustrated. Although the
production of sodium hydroxide solutions, using sodium chloride and
sodium chlorate reactants is illustrated, other alkali metal
cations, such as potassium, may also be employed. Furthermore,
although the hydrolysis means illustrated is a steam distillation
apparatus, it will be appreciated that other suitable vessels or
apparatuses for reacting the persulfuric acid solution with water
can also be used.
In the FIGURE electrolytic cell 11 includes outer wall 13, anode
15, cathode 17 and conductive means 19 and 21 for connecting the
anode and the cathode to sources of positive and negative
electrical potentials, respectively. Inside the walled cell a
cation-active permselective membrane M.sup.c.sup.-1 23,
anion-active permselective membrane M.sup.a 25, and cation-active
permselective membrane M.sup.c.sup.-2 27, divide the volume into an
anode or anolyte compartment 29, a buffer compartment B.sup.1 31, a
buffer compartment B.sup.2 33, and a cathode or catholyte
compartment 35. Aqueous sulfuric acid is fed to the anode
compartment through line 37. Aqueous sodium chlorate and aqueous
sodium chloride are fed to B.sup.2 through line 39 and water is fed
to the cathode compartment through line 41. During electrolysis
sulfuric acid in the anode compartment is oxidized at the anode to
form persulfuric acid which is withdrawn as an aqueous sulfuric
acid solution through line 43. Also during electrolysis, hydrogen
ions selectively diffuse or pass from the cathode compartment
through cation-active membrane M.sup.c.sup.-1 into buffer
compartment B.sup.1 while chlorate and chloride anions selectively
pass from buffer compartment B.sup.2 through anion-active membrane
M.sup.a into buffer compartment B.sup.1. In B.sup.1 the aqueous
hydrogen chloride introduced by the aforementioned diffusion
processes reacts with the chlorate anions to produce chlorine
dioxide and chlorine, which are withdrawn through line 45. Under
the electric potential of the electrolysis process sodium cations
selectively diffuse from buffer compartment B.sup.2 through
cation-active membrane M.sup.c.sup.-2 into the cathode compartment
where they are reacted with water to form hydrogen, which is
withdrawn through line 47, and aqueous sodium hydroxide, which is
withdrawn through line 49. The aqueous sulfuric acid solution of
persulfuric acid which is recovered from the anode compartment is
fed to a steam distillation apparatus 51 and is hydrolytically
distilled with steam fed to the apparatus through line 53. The
resulting steam distillate, an aqueous hydrogen peroxide solution,
is withdrawn from the steam distillation apparatus through line 55
and the steam distilland, an aqueous sulfuric acid, is withdrawn
from the apparatus through line 57.
In the present process the overall electrolytic cell reaction is
represented by Equation (1),
(1) 4H.sub.2 SO.sub.4 + 2MClO.sub.3 + 2MCl + 2H.sub.2 O .fwdarw.
2H.sub.2 S.sub.2 O.sub.8 + 2ClO.sub.2 + Cl.sub.2 + 2H.sub.2 +
4MOH
wherein M represents an alkali metal cation such as sodium or
potassium. The hydrolytic conversion of persulfuric acid to
hydrogen peroxide proceeds by the known reaction represented by
Equation (2).
(2) 2H.sub.2 S.sub.2 O.sub.8 + 4H.sub.2 O .fwdarw. 2H.sub.2 O.sub.2
+ 4H.sub.2 SO.sub.4
In initiating the electrolytic process of the invention the anode
compartments of the cell are charged with sufficient sulfuric acid,
in aqueous solution, as to initiate the electrolytic oxidation of
the H.sub.2 SO.sub.4 to H.sub.2 S.sub.2 O.sub.8, while the buffer
compartments are charged with sufficient alkali metal chlorate
and/or alkali metal chloride, also in aqueous solution, to avoid
depletion and concentration polarization. Additionally, an aqueous
solution containing about 0.1 to 1 percent of alkali metal
hydroxide is charged into the cathode compartments. Advantageously,
the cell is filled so as to provide a small free space, e.g., about
1 to 10 percent, preferably 1 to 5 percent of the cell volume,
above the compartments so as to facilitate collection and
withdrawal of the gaseous products, chlorine dioxide, chlorine and
hydrogen. On connection of the conductive means to sources of
positive and negative electrical potentials to initiate a direct
current electrolysis, sulfuric acid, alkali metal chlorate and
alkali metal chloride are fed to the cell at rates sufficient to
establish concentrations which will effect the electrolysis
according to Equation (1). Typically, these will be in molar
proportioned rates, of about 2:1:1, with the usual variance from
these of about .+-.20 percent, preferably .+-.10 percent and most
preferably about .+-.2 percent. During electrolysis water is
charged at a sufficient rate to maintain the desired caustic
concentration.
The cell is operated at a temperature above the freezing point of
the liquid contents of the cell, i.e., above about 2.degree. to
5.degree.C. and below about 60.degree.C. or the temperature at
which the rate of electrolytic formation of persulfuric acid from
sulfuric acid is about equal to the rate of hydrolytic
decomposition of the peracid. Preferably, the cell is operated at a
temperature of about 5.degree. to 40.degree.C., more preferably at
about 20.degree. to 35.degree.C. and most preferably at about
30.degree. to 35.degree.C.
The sulfuric acid charged to the anode compartment is generally
aqueous sulfuric acid containing at least about 80 percent by
weight sulfuric acid and is preferably "concentrated" sulfuric
acid, "aqueous" sulfuric acid containing about 90 to 100 percent,
usually 93 to 97 percent sulfuric acid. If desired and useful,
stronger, even non-aqueous sulfuric acids and sometimes, even
oleums can be successfully employed.
The alkali metal chloride and alkali metal chlorate are generally
charged in aqueous solution or solutions at concentrations of from
about 1 Normal up to about the saturation solubility of the salts.
Preferably the concentrations of the aqueous alkali metal chlorate
charged are about 3 N. The chlorate and chloride salts may be
charged in individual feed streams to compartment B.sup.2 but
preferably the salts are charged in the same feed solution.
The sulfuric acid solution of persulfuric acid produced in the
anode compartment is reacted with water at about 60.degree. to
100.degree.C., preferably at about 100.degree.C., to produce
hydrogen peroxide, in accord with known processes for the
hydrolytic conversion of persulfuric acid to hydrogen peroxide. At
least about two molar portions of water per mol of persulfuric acid
are employed in the hydrolysis in accord with the stoichiometry of
Equation (2) above. Advantageously, the water is charged in excess,
e.g., 10 to 300 percent or 20 to 100 percent. Preferably, the water
which is charged to the hydrolysis operation is in the form of
steam. In an especially preferred embodiment of the invention the
persulfuric acid solution is subjected to steam distillation to
prepare hydrogen peroxide, the distillation being effected in a
steam distillation apparatus comprising a still and a condenser of
the types conventionally used for the manufacture of hydrogen
peroxide from persulfuric acid. In accord with this preferred
embodiment of the invention the hydrogen peroxide is recovered from
the steam distillation apparatus as an aqueous steam distillate,
with the concentration of the hydrogen peroxide in the distillate
being determined by the amount of water used in the steam
distillation. The proportion of water may be regulated to produce
the peroxide in best form for use, e.g., in bleaching, especially
of woodpulps. The distilland remaining is aqueous sulfuric acid
which can be concentrated, if desired, by addition of stronger
sulfuric acid, oleum or sulfur trioxide, and may then be recycled
to the sulfuric acid feed stream to the anode compartment of the
present electrolytic cell. Alternatively, it may be sent to that
compartment directly.
The chlorine and chlorine dioxide produced in buffer compartment
B.sup.1 are recovered as a gaseous mixture. If desired, these
products can be separated by contacting the mixture with water to
preferentially dissolve the chlorine dioxide. Advantageously this
separation can be effected by contacting the chlorine
dioxide-chlorine mixture with a countercurrent stream of water in a
conventional absorption tower of the type utilized for separation
of chlorine dioxide and chlorine in the previously discussed
Day-Kesting process. If desired, the chlorine dioxide and chlorine
may remain together and be employed in such mixture. Of course, the
separate or mixed products are useful as bleaching agents,
especially for woodpulps.
The aqueous alkali metal hydroxide solution recovered from the
cathode compartment generally contains about 60 to 250 g./l.,
usually about 80 to 120 g./l. of alkali metal hydroxide and is free
or substantially free of alkali metal chloride, i.e., the product
solution generally contains less than about 1 percent alkali metal
chloride and under most preferred operating conditions, less than
about 0.1 percent. Thus, the aqueous caustic product is often
suitable, without further purification, for many applications
wherein substantially salt-free aqueous alkali metal hydroxides or
caustic is desirable or necessary, for example, in pulping wood
chips, neutralizing acids, peroxide bleaching, making caustic
sulfites and regenerating ion-exchange resins.
The present electrolytic cells operate at a voltage of about 2.3 to
5 volts, preferably about 2.5 to 4 volts, and most preferably,
about 3 volts. The current density in the cell is about 0.5 to 4,
preferably about 1 to 3, more preferably about 3 amperes per square
inch of electrode surface. The current efficiency of the present
cell is generally at least about 70 percent, and, under preferred
operating conditions, is about 75 to 80 percent or greater. The
caustic efficiency of the electrolytic cell is generally greater
than about 75 percent and, under preferred operating conditions may
be 85 to 90 percent or greater.
The membranes utilized in the invention to divide the electrolytic
cell into compartments and to provide selective ion diffusion are
preferably mounted in the cell on networks or screens of supporting
material such as polytetrafluoroethylene, perfluorinated
ethylene-propylene copolymer, polypropylene, asbestos, titanium,
tantalum, niobium or noble metals. Preferably,
polytetrafluoroethylene screening is used.
The cation-active and anion-active permselective membranes used are
of known classes of proprietary organic polymers, initially often
being thermoplastics, which are substituted with a multiplicity of
ionogenic substituents and which, in thin film form, are permeable
to a certain type of ion. Certain ions, apparently by means of ion
exchange with the ionogenic substituents on the polymer film, are
able to pass through the polymer membrane, while other ions, of
opposite sign, are not able to do so.
Cation-active permselective membrane materials which selectively
permit passage or diffusion of cations generally contain a
multiplicity of sulfonate or sulfonic acid substituents or, in some
instances, carboxylate or phosphonate substituents. Cation-active
membranes can be prepared by introducing the cation-exchanging
substituent, e.g., sulfonate, into a thin film of polymer, e.g.,
phenol formaldehyde polymer, by chemical reaction, e.g.,
sulfonation. Other polymers which can be sulfonated in this manner
to obtain cation-active membrane materials include polystyrene,,
styrene-divinyl benzene copolymer, polyvinyl chloride, vinyl
chloride-styrene copolymers, polyethylene, and styrene-butadiene
rubbers. Alternatively a homo- or copolymer containing the
cation-exchanging group(s) can be prepared by polymerizing a
monomer substituted with the group(s). For example, phenol sulfonic
acid can be substituted for some or all of the phenol normally used
as a reactant in preparing a phenol formaldehyde polymer to obtain
polysulfonated phenol formaldehyde polymer. In another example of
this type of procedure, acrylic, methacrylic or maleic acid or its
anhydride can be polymerized or copolymerized, e.g., with divinyl
benzene, to obtain a cation-active membrane material in which the
cation exchanging substituents on the polymer base are carboxylate
groups.
Anion-active permselective membranes permit selective passage or
diffusion of anions and are impermeable or substantially
impermeable to cations. In such membranes, the anion exchanging
substituents on the polymer base are generally quaternary ammonium
substituents wherein the substituent groups on the nitrogen atoms
can be lower alkyl groups, i.e., alkyl groups of 1 to 6 carbon
atoms, such as methyl, ethyl, t-butyl and isopropyl; aralkyl
groups, such as benzyl; aryl groups such as phenyl or tolyl; or
heterocyclics, such as hydrocarbyl-nitrogen ring-containing
compounds, e.g., those containing pyridine groups. Anion-active
membrane materials can be made by conventional aminations of thin
films of polymer base, e.g., phenol-formaldehyde polymer,
polyethylene, polyvinyl chloride and the like, followed by
quaternizing of the amino substituents by conventional reaction
with an alkylating agent, e.g., a lower alkyl halide, such as
methyl iodide or dilower alkyl sulfate such as dimethyl sulfate.
Alternatively, thin films of polymer bases such as polystyrene,
polyethylene and styrene-divinyl benzene copolymers can be
haloalkylated, for example, by conventional chloromethylation, to
introduce the group -CH.sub.2 Cl, and thereafter may be reacted
with a tertiary amine, such as trimethyl amine, to produce the
quaternary ammonium substituted anion-active membrane.
Additionally, polymer bases which contain replaceable halogen
substituents such as polyvinyl chloride, chlorinated polyethylene,
and chlorinated rubber, can be condensed with polyalkylene
polyamines, such as tetraethylene pentamine, to produce
anion-active polymeric membranes. The cation-active and
anion-active polymeric membranes used for selective diffusion of
ions are further classified as homogeneous, i.e., polymers visually
appearing to be of only one phase, or as heterogeneous, i.e.,
polymers visually appearing to include more than one phase because
of the presence of a matrix material in which the ion exchange
polymer is embedded in powdered form.
The preparation and structure of cation and anion-active
permselective membranes are discussed in greater detail in the
chapter entitled "Membranes" in the "Encyclopedia of Polymer
Science and Technology", published by J. Wiley and Sons, New York,
1968, at Vol. 8, pages 620 to 638, and in the chapter entitled
"Synthetic Resin Membranes" in Diffusion and Membrane Technology,
by S. B. Tuwiner, published by Rheinhold Publishing Corporation,
New York, 1962, at pages 200 to 206, the pertinent subjects matter
of which references are hereby incorporated by reference.
In addition to the examples of anion-active permselective membranes
listed above, the following proprietary compositions are
anion-active permselective membranes, and may also be considered as
representative of preferred membranes of such type: AMFion 310
series - anion type quaternary ammonium substituted flurocarbon
polymer, manufactured by American Machine and Foundry Co.; and
Ionac types MA 3148, MA 3236 and MA 3475-quaternary ammonium
substituted polymers derived from heterogeneous polyvinyl chloride,
manufactured by the Ritter-Pfaudler Corp., Permutit Division.
In addition to the examples of cation-active permselective
membranes previously discussed, the following proprietary
compositions are representative examples of cation-active
permselective membranes which may be used in practicing the present
invention: Ionac MC 3142, MC 3235, and MC 3470 XL types --
polysulfonate-substituted heterogeneous polyvinyl chloride,
manufactured by the Ritter-Pfaudler Corp., Permutit Division;
Nafion XR type hydrolyzed copolymer of perfluorinated olefin and a
fluorosulfonated perfluorovinyl ether, manufactured by E. I. DuPont
de Nemours and Company, Inc.; Nafion XR, modified - Nafion XR
treated on one side with ammonia to convert SO.sub.2 R groups to
SO.sub.2 NH.sub.2, which are then hydrolyzed to SO.sub.2 NHNa; RAI
Research Corporation membranes such as types 18ST12S and 16ST13S -
sulfostyrenated perfluorinated ethylene propylene copolymers.
Preferred cation-active permselective membranes of the invention
are the hydrolyzed copolymer of perfluoroolefins and
fluorosulfonated perfluorovinyl ether, the -SO.sub.2 NHNa
modifications thereof and the sulfostyrenated
perfluoroethylene-propylene copolymers.
The sulfostyrenated perfluoroethylene-propylene polymers useful as
cation-active membranes in a preferred embodiment of the invention
are generally those which have two-thirds to eleven-sixteenths of
the phenyl groups therein monosulfonated and which are about 16 to
18 percent styrenated. To manufacture the sulfostyrenated
perfluoroethylene propylene copolymer membrane materials, a
standard perfluoroethylene-propylene copolymer (hereinafter
referred to as FEP), such as is manufactured by E.I. DuPont de
Nemours & Company, Inc., is styrenated and the styrenated
polymer is then sulfonated. A solution of styrene in methylene
chloride or benzene at a suitable concentration in the range of
about 10 to 20 percent is prepared and a sheet of FEP polymer
having a thickness of about 0.02 to 0.5 mm., preferably 0.05 to
0.15 mm., is dipped into the solution. After removal it is
subjected to radiation treatment, using a cobalt.sup.60 radiation
source. The rate of application may be in the range of about 8,000
rads/hr. and a total radiation application is about 0.9 megarad.
After rinsing with water the phenyl rings of the styrene portion of
the polymer are monosulfonated, preferably in the para position, by
treatment with chlorosulfonic acid, fuming sulfuric acid or
SO.sub.3. Preferably, chlorosulfonic acid in chloroform is utilized
and the sulfonation is completed in about one-half hour.
Examples of useful membranes made by the described process are the
RAI Research Corporation products previously mentioned, 18ST12S and
16 ST13S, the former being 18 percent styrenated and having
two-thirds of the phenyl groups monosulfonated and the latter being
16 percent styrenated and having thirteen-sixteenths of the phenyl
groups monosulfonated. To obtain 18 percent styrenation a solution
of 171/2 percent of styrene in methylene chloride is utilized and
to obtain 16 percent styrenation a solution of 16 percent of
styrene in methylene chloride is employed.
The especially preferred cation-active permselective membranes of
the invention are of a hydrolyzed copolymer of perfluorinated
hydrocarbon, e.g., an olefin, and a fluorosulfonated perfluorovinyl
ether. The perfluorinated olefin is preferably tetrafluoroethylene,
although other perfluorinated hydrocarbons of 2 to 5 carbon atoms
may also be utilized, of which the monoolefinic hydrocarbons are
preferred, especially those of 2 to 4 carbon atoms and most
especially those of 2 to 3 carbon atoms, e.g., tetrafluoroethylene,
hexafluoropropylene. The sulfonated perfluorovinyl ether which is
most useful is that of the formula FSO.sub.2 CF.sub.2 CF.sub.2
OCF(CF.sub.3)CF.sub.2 OCF=CF.sub.2. Such a material, named as
perfluoro-[2-(2-fluorosulfonylethoxy)-propyl vinyl ether], referred
to henceforth as PSEPVE, may be modified to equivalent monomers
which are represented by the formula FSO.sub.2 CFR.sup.1 CF.sub.2
O(CFYCF.sub.2 O).sub.n CF=CF.sub.2, wherein R.sup.1 is a radical
selected from the group consisting of fluorine and perfluoroalkyl
radicals having from 1 to 10 carbon atoms, Y is a radical selected
from the group consisting of fluorine and the trifluoromethyl
radical, and n is an integer from 1 to 3, inclusive. However, it is
most preferred to employ PSEPVE.
The method of manufacture of the hydrolyzed copolymer is described
in Example XVII of U.S. Pat. No. 3,282,875 and an alternative
method is mentioned in Canadian Pat. No. 849,670, which also
discloses the use of the finished membrane in fuel cells,
characterized therein as electrochemical cells. The disclosures of
such patents are hereby incorporated herein by reference. In short,
the copolymer may be made by reacting PSEPVE or equivalent with
tetrafluoroethylene or equivalent in desired proportions in water
at elevated temperature and pressure for over an hour, after which
time the mix is cooled. It separates into a lower perfluoroether
layer and an upper layer of aqueous medium with dispersed desired
polymer. The molecular weight is indeterminate but the equivalent
weight is about 900 to 1,600 preferably 1,100 to 1,400, e.g.,
1,250, and the percentage of PSEPVE or corresponding compound is
about 10 to 30 percent, preferably 15 to 20 percent and most
preferably about 17 percent. The unhydrolyzed copolymer may be
compression molded at high temperature and pressure to produce
sheets or membranes, which may vary in thickness from 0.02 to 0.5
mm. These are then further treated to hydrolyze pendant -SO.sub.2 F
groups to -SO.sub.3 H groups, as by treating with 10 percent
sulfuric acid or by the methods of the patents previously
mentioned. The presence of the -SO.sub.3 H groups may be verified
by titration, as described in the Canadian patent. Additional
details of various processing steps are described in Canadian Pat.
No. 752,427 and U.S. Pat. No. 3,041,317, also hereby incorporated
by reference.
Because it has been found that some expansion accompanies
hydrolysis of the copolymer it is preferred to position the
copolymer membrane after hydrolysis onto a frame or other support
which will hold it in place in the electrolytic cell. Then it may
be clamped or cemented in place and will be true, without sags. The
membrane is preferably joined to the backing tetrafluoroethylene or
other suitable filaments prior to hydrolysis, when it is still
thermoplastic, and the film of copolymer covers each filament,
penetrating into the spaces between them and even around behind
them, thinning the films slightly in the process, where they cover
the filaments.
The aminated and hydrolyzed improvements or modifications of the
polytetrafluoroethylene PSEPVE copolymers are made, as previously
mentioned, by treatment with ammonia of one side of the copolymer,
before hydrolysis thereof, and then hydrolyzing with caustic or
other suitable alkali. Acid forms may also be utilized. The final
hydrolysis may be conducted after the membrane is mounted on its
supporting network or screen. The membranes so made are fluorinated
polymers having pendant side chains containing sulfonyl groups
which are attached to carbon atoms bearing at least one fluorine
atom, with sulfonyl groups on one surface being in -(SO.sub.2
NH).sub.n M form, where M is H, NH.sub.4, alkali metal or alkaline
earth metal and n is the valence of M, and the sulfonyls of the
polymer on the other membrane surface being in -(SO.sub.3).sub.p Y
form or -SO.sub.2 F, wherein Y is a cation and p is the valence of
the cation, with the requirement that when Y is H,M is also H. In
use the sulfonamide side faces the cathode.
A complete description of methods for making the above improved
membrane is found in French Pat. No. 2,152,194 of E.I. DuPont de
Nemours and Company, Inc., corresponding to U.S. Pat. application
Ser. No. 178,782, filed Sept. 8, 1971 in the name of Walther Gustav
Grot, which disclosures are hereby incorporated herein by
reference.
The membranes of hydrolyzed copolymer of perfluorinated olefin and
fluorosulfonated perfluorovinyl ether and the one-side hydrolyzed
aminated modifications thereof described are far superior in the
present processes to various other cation-active membrane
materials. The RAI type membranes are also generally superior to
those previously known. The preferred membranes last for much
longer time periods in the medium of the cell electrolytes and do
not become brittle when subjected to long term contact with
chlorine, chlorine dioxide and persulfuric acid. Considering the
savings in time and fabrication costs, the present membranes are
more economical. The voltage drops through the membranes are
acceptable and do not become inordinately high, as they do with
many other cation-active membrane materials, when the caustic
concentration in the cathode compartment increases to above about
200 g./l. of caustic. The selectivity of the membrane and its
compatibility with the electrolyte do not decrease detrimentally as
the hydroxyl concentration in the catholyte liquor increases, as
has been noted with other cation-active membrane materials.
Furthermore, the caustic efficiency of the electrolysis does not
diminish as significantly as it does with other membranes when the
hydroxyl ion concentration or the alkalinity in the catholyte
increases. Thus, these differences in the present process make it
practicable, whereas previously described processes have not
attained commercial acceptability. While the more preferred
copolymers are those having equivalent weights of 900 to 1,600,
with 1,100 to 1,400 being most preferred, some useful resinous
membranes employable in present methods may be of equivalent
weights from 500 to 4,000. The medium equivalent weight polymers
are preferred because they are of satisfactory strength and
stability, enable better selective ion exchange to take place and
are of lower internal resistances, all of which are important to
the present electrochemical cell's improved operation.
The improved versions of the TFE - PSEPVE copolymers, made by
chemical treatment of surfaces thereof to modify the -SO.sub.3 H
group thereon, may have the modification only on the surface or
extending up to as much as halfway through the membrane. The depth
of treatment will usually be from 0.001 to 0.2 mm., e.g., 0.01 mm.
Caustic and other efficiencies of the invented processes, using
such modified versions of the present improved membranes, can
increase about 3 to 20 percent, often about 10 to 20 percent, over
the unmodified membranes.
The membranes M.sup.c.sup.-2 and M.sup.c.sup.-2 may, if desired, be
composed of different cation-active permselective membrane
materials but preferably both are of the same polymer.
The walls of membranes used in the present process will normally be
from 0.02 to 0.5 mm. thick, preferably 0.1 to 0.4 mm. thick. When
mounted on a polytetrafluoroethylene, asbestos, titanium or other
suitable network, for support, the network filaments or fibers will
usually have a thickness of 0.01 to 0.5 mm., preferably 0.05 to
0.15 mm., corresponding to up to the thickness of the membrane.
Often it will be preferable for the fibers to be less than half the
film thickness but filament thicknesses greater than that of the
film may also be successfully employed, e.g., 1.1 to 5 times the
film thickness. The networks, screens or cloths have an area
percentage of openings therein from about 8 to 80 percent,
preferably about 10 to 70 percent and most preferably about 20 to
70 percent. Generally the cross-sections of the filaments will be
circular but other shapes, such as ellipses,, squares and
rectangles, are also useful. The supporting network is preferably a
screen or cloth and although it may be cemented to the membrane it
is preferred that it be fused to it by high temperature, high
pressure compression before hydrolysis of the copolymer. Then, the
membrane-network composite can be clamped or otherwise fastened in
place in a holder or support.
The electrodes of the cell and the conductive means connected
thereto can be made of any electrically conductive material which
will resist the attack of the various cell contents. In general,
the cathodes are made of graphite, iron, lead dioxide, iron in
graphite, lead dioxide on graphite, steel or noble metal, such as
platinum, iridium, ruthenium or rhodium. Of course, when using the
noble metals, they may be deposited as surfaces on conductive
substrates, e.g., copper, silver, aluminum, steel, iron.
Preferably, the cell cathode is of mild steel, although graphite,
especially high density graphite, i.e., graphite having a density
of about 1.68 to 1.78 grams per milliliter may also be used,
particularly in a bipolar configuration. The conductive means
attached to the cathode may be aluminum, copper, silver, steel or
iron, with copper being much preferred. The anode should be
resistant to attack by persulfuric acid and accordingly should
often be of persulfuric acid-inert noble metal. The anode
preferably is platinum or platinum-clad tantalum, with platinum
being much preferred. The conductive means attached to the anode,
is also desirably protected against the persulfuric acid in the
cathode compartment and preferably is tantalum encased in
platinum.
The material of construction of the cell body is conventional,
including steel, concrete, stressed concrete or other suitably
strong material, lined with mastics, rubbers, e.g., neoprene,
polyvinylidene chloride, FEP, chlorendic acid based polyester,
polypropylene, polyvinyl chloride, polytetrafluoroethylene, or
other suitable plastics, usually being in tank or box form.
Substantially self-supporting structures, such as rigid polyvinyl
chloride, polyvinylidene chloride, polypropylene or phenol
formaldehyde resins may be employed, preferably reinforced with
molded-in fibers, cloths or webs, such as asbestos fibers.
While the compartments of the present cell will usually be
separated from each other by flat membranes and will usually be of
substantially rectilinear or parallelepipedal construction, various
other shapes, including curves, e.g., cylinders, spheres,
ellipsoids; and irregular surfaces, e.g., sawtoothed or plurally
pointed walls, may also be utilized. In accord with conventional
electrochemical practice, pluralities of individual cells of the
invention can be employed in multi-cell units, often having common
feed and product manifolds and being housed in unitary structures
or in a filter press assembly, or the like.
For satisfactory and efficient operation of the present cell the
volumes of the buffer compartments B.sup.1 and B.sup.2 will be
about the same and the combined volume of both buffer compartments
will normally be from 1 to 100 percent that of the sum of the
volumes of the anode and cathode compartments, preferably from 5 to
70 percent, and the anode and cathode compartment volumes will be
approximately the same.
The present process provides efficiently, without excessive costly
reaction equipment being needed, important woodpulp bleaching
reagents, hydrogen peroxide, chlorine dioxide and chlorine together
with aqueous caustic which is useful in pulping wood chips. Even
the hydrogen produced can be used as a fuel to heat materials for
bleaching or pulping. Since the present process requires at most
only two or three reaction vessels, it can be readily set up at a
single location, which advantageously should be near
pulp-manufacturing and pulp-bleaching facilities, so as to take
advantage of its efficient production of the described pulping
chemicals. However, it is also useful for off-site production,
too.
The following examples illustrate but do not limit the invention.
All parts are by weight and all temperatures are in .degree.C.,
unless otherwise indicated.
EXAMPLE 1
A four-compartment electrolytic cell, as illustrated in the FIG.,
is utilized to produce chlorine, chlorine dioxide, aqueous,
substantially salt-free sodium hydroxide, hydrogen and persulfuric
acid, which is subsequently hydrolyzed to hydrogen peroxide. The
anode is of platinum mesh which is communicated with a positive
direct current electrical source through a platinum-clad tantalum
conductor rod. The cathode is of mild steel, and is communicated
with a negative direct current sink through a copper conductor rod.
The anode and cathode are each about two inches wide and about
thirty inches high. The cell walls are of asbestos-filled
polypropylene.
The two cation-active permselective membranes M.sup.c.sup.-1 and
M.sup.c.sup.-2, are Nafion membranes manufactured by E. I. duPont
de Nemours and Company, Inc. and sold as their XR-type membranes.
The membranes are 7 mils thick (about 0.2 mm.) and are joined to a
backing or supporting network of polytetrafluoroethylene (Teflon)
filaments of a diameter of about 0.1 mm., woven into cloth which
has an area percentage of openings therein of about 22 percent. The
membranes are initially flat and are fused onto the Teflon cloth by
high temperature, high compression processing, with some of the
membrane portions actually flowing around the filaments during the
fusion process to lock onto the cloth without thickening the
membrane between the cloth filaments.
The material of Nafion-XR permselective membranes contain a
multiplicity of sulfonate substituents and is a hydrolyzed
copolymer of tetrafluoroethylene and FSO.sub.2 CF.sub.2 CF.sub.2
OCF(CE.sub.3)CF.sub. 2 OCF=CF.sub.2 which has an equivalent weight
in the 900 to 1,600 range, about 1,250.
The anion-active permselective membrane M.sup.a is derived from a
heterogeneous polyvinyl chloride polymer containing a multiplicity
of quaternary ammonium substituents. The anion-active membrane is
Ionac type MA-3475R membrane (manufactured by Ritter-Pfaudler
Corporation, Permutit Division), having a thickness of about 14
mils (0.4 mm.), which is mounted on a Teflon cloth similar to that
employed as a supporting network for the cation-active
permselective membranes.
The cell electrodes are in contact with the cation-active
permselective membranes, with the "flatter" side of the membranes
facing and contacting the electrodes. In some experiments spacings
of about 0.01 to 5 mm. between the electrodes and the membranes are
utilized and satisfactory results are obtained but the present
arrangement, with no spacings, is preferred. The interelectrode
distance and the total width of the two buffer compartments,
B.sup.1 and B.sup.2, are about 6 mm. and the volume ratio of anode
compartment:buffer compartment B.sup.1 :buffer compartment B.sup.2
: cathode compartment is about 10:0.5:0.5:10.
The cell is filled with water to about 99 percent of usual
capacity, a small open volume, about 5 percent, being left at the
top of the cell to facilitate collection of gaseous products from
buffer compartment B.sup.1 and the cathode compartment. In small
amounts sulfuric acid is introduced into the anode compartment,
sodium chloride is charged to buffer compartments B.sup.1 and
B.sup.2 and sodium hydroxide is introduced into the cathode
compartment, to provide about a 1 percent concentration of these
electrolytes in the indicated compartments and thereby to provide
conduction of electric current through the cell. The cell is
externally cooled by circulating water to maintain the cell
contents at a temperature of about 30 to 35.degree.C. during
electrolysis
Electrolysis is initiated by passage of direct current through the
cell, concentrated aqueous sulfuric acid (containing about 93
percent sulfuric acid) is continuously fed to the anode
compartment, an aqueous solution containing about 3 equivalents per
liter, i.e., 3 N, of sodium chlorate and about 3 equivalents per
liter of sodium chloride is fed continuously to buffer compartment
B.sup.2 and water is continuously added to the cathode compartment.
The rates of addition of sulfuric acid, chlorate and chloride are
adjusted so that the mol ratio of acid, chlorate, and chloride feed
rates is about 2:1:1. Water is charged continuously to the cathode
compartment at a rate sufficient to maintain the liquid level in
the cell substantially constant. During electrolysis the voltage
drop in the cell is about 3 volts and the current density is about
2 amperes per square inch of electrode surface.
A sulfuric acid solution of persulfuric acid is continuously
withdrawn as product from the anode compartment. This solution is
subjected to distillation with steam at 100.degree.C. in
stoichiometric excess, in a conventional glass steam distillation
apparatus, including a still pot equipped with an inlet tube for
introducing steam below the surface of liquid in the pot, agitation
means, a water-cooled condenser and a distillate receiver. The
steam distillate recovered from the steam distillation is aqueous
hydrogen peroxide containing about 4 percent of the peroxide. The
distilland recovered from the steam distillation still pot is about
50 percent aqueous sulfuric acid which is adjusted to the
concentration of the sulfuric acid feed stream for the anode
compartment by addition of oleum and then is combined with the
sulfuric acid feed stream for recycling to the electrolytic
cell.
A gaseous mixture of chlorine dioxide and chlorine containing about
0.63 parts of chlorine dioxide per part of chlorine is continuously
withdrawn as product from buffer compartment B.sup.1. The mixture
is introduced into the base of a conventional chlorine dioxide
absorption tower or column of the type illustrated in FIG. 4 of the
Canadian Journal of Chemical Engineering, Vol. 36 (1958), page 3,
and is contacted with a downwardly flowing counter-current stream
of water at ambient temperature to remove chlorine dioxide as about
a 3 percent aqueous solution which is recovered from the base of
the tower, the purified chlorine gas being recovered from the top
of the tower. When desired, the aqueous chlorine dioxide product
solution is cooled enough so as to precipitate chlorine dioxide as
a solid hydrate containing about 16 percent chlorine dioxide, which
can be recovered by filtration or decantation.
Gaseous hydrogen and aqueous sodium hydroxide are continuously
withdrawn as products from the cathode compartment during
electrolysis. The aqueous caustic product contains about 80 grams
per liter of sodium hydroxide and less than about 0.1 percent
sodium chloride. The cell operates at a caustic efficiency of about
90 percent and a current efficiency of about 75 percent.
In modifications of the above laboratory cell for large scale
operation the thicknesses of the cation-active permselective
membranes can be increased to 10 to 14 mils, at which thicknesses
the caustic efficiency increases but the voltage drop also
increases. Accordingly, although cation-active membranes of greater
thicknesses are operative in the present process, it is preferred
to employ the 7 mil membranes. Cation-active membranes which are 4
mils thick are also used and are satisfactory although caustic
efficiency is decreased slightly.
The cation-active membranes of the present experiment do not show
any deterioration in appearance or operating efficiency or adverse
selectivity toward ion diffusion, even after operation in
electrolytic processes in contact with oxidizing chemicals such as
chlorinde and chlorates, for as long as three years. They withstand
the present cell's harsh environment very well and require fewer
replacements than other non-preferred membranes. More frequent
replacements of the anion-active membranes may be needed but the
process efficiency is satisfactory because only one-third of the
membranes used by this method are anion-active.
EXAMPLE 2
The procedure of Example 1 is repeated substantially as described
except that the anion-active permselective membrane employed is an
AMFion 310 series anion type membrane (manufactured by American
Machine and Foundry Co.) This membrane, which has a thickness of
about 6 mils (about 0.17 mm.), is a proprietary fluorocarbon
polymer containing a multiplicity of quaternary ammonium
substituents as anion-exchanging groups. The cell using this
anion-active membrane is operated continuously with substantially
no or little membrane deterioration and with excellent operating
results, substantially similar to those obtained in Example 1.
EXAMPLE 3
The procedure of Example 1 is followed and essentially the same
results are obtained, utilizing as cation-active membranes RAI
Research Corporation membranes identified as 18ST12S and 16St13S,
respectively, and DuPont "improved" membranes made by the method
previously described, instead of the hydrolyzed copolymer of
tetrafluoroethylene and sulfonated perfluorovinyl ether. The former
of the RAI products is a sulfostyrenated FEP in which the FEP is 18
percent styrenated and has two-thirds of the phenyl groups thereof
monosulfonated, and the latter is 16 percent styrenated and has
thirteen-sixteenths of the phenyl groups monosulfonated. The
membranes stand up well under the described operating conditions
and after operation for several weeks are significantly better in
appearance and operating characteristics, e.g., physical
appearance, uniformity, voltage drop, than other cation-active
permselective membranes available (except the hydrolyzed copolymers
of perfluoro-olefins and fluorosulfonated perfluorovinyl ethers of
the type utilized in Example 1).
When utilizing the RAI Research Corporation membranes described
above, the anion-active membranes are also changed, to Amberlite
resins of the same thickness, also supported on
polytetrafluoroethylene and polypropylene screening. The Amberlites
utilized are made by Dow Chemical Corp., and are ammonium and
quaternary ammonium functionalized styrenes grafted onto polymeric
bases, such as those of FEP, TFE, PVE, PE, nylon and polypropylene.
In other experiments, such anion-active permselective membranes are
employed with cation-active membranes other than the RAI products,
including the Ionacs and Nafions and the electrodes are both
platinum, in one series, or platinum-clad tantalum, in another. In
some such instances, two or four additional buffer compartments are
employed, inserted between B.sup.1 and B.sup.2 and maintained in
the same order as B.sup.1 and B.sup.2. The reactions described
produce the desired products, with the sodium hydroxide being even
lower in chloride content when additional buffering compartments
are utilized. However, the Amberlite resins do not appear to resist
deterioration by the electrolyte as well as the Ionac and Nafion
(and modified Nafion) resins previously discussed.
The invention has been described with respect to working examples
and illustrative embodiments but it is not to be limited to these
because it is evident that one of skill in the art will be able to
utilize substitutes and equivalents without departing from the
spirit of the invention or going beyond its scope.
* * * * *