IMPROVEMENTS IN THE PRODUCTION OF OZONE, AND IN THE APPLICATION OF THE SAME TO VARIOUS USEFUL PURPOSES
Year: 1873

page_text: LETTERS PATENT to John Henry Johnson, of 47, Lincoln's Inn
Fields, in the County of Middlesex, Gentleman, for the Invention
of "IMPROVEMENTS IN THE PRODUCTION OF OZONE, AND IN THE APPLICATION
OF THE SAME TO VARIOUS USEFUL PURPOSES."-A communication from
abroad by Pierre Isidore David, of Paris, in the Republic of France.
PROVISIONAL SPECIFICATION left by the said John Henry Johnson
at the Office of the Commissioners of Patents, with his Petition, on
the 2nd October 1873.
I, JOHN HENRY JOHNSON, of 47, Lincoln's Inn Fields, in the
County of Middlesex, Gentleman, do hereby declare the nature of the
said Invention for "IMPROVEMENTS IN THE PRODUCTION OF OZONE, AND IN THE
APPLICATION OF THE SAME TO VARIOUS USEFUL PURPOSES," a communication to
me from abroad by Pierre Isidore David, of Paris, in the Republic of
France. to be as follows:-

page_text: at a costly rate, whereas in order to apply the ozone commercially it is
requisite that it should be abundantly and economically produced.
It is proposed according to this Invention to apply ozone to the
decolorization or bleaching of organic matters in such a manner as to
effect their decolorization by the gaseous method whilst obviating the
wetting of the matters operated upon.
It is well known that chlorine employed for bleaching or decoloriza-
tion acts only indirectly, that it has no other effect than to produce
ozone (nascent oxygen) by gradually decomposing, in order to enter
into combination with its hydrogen the water with which it is placed in
contact or which is naturally contained in the materials to be decolorized,
and that it is the ozone or oxygen then liberated which causes by
oxygenation the decolorization. The use of chlorine is therefore
unavoidably accompanied by the inconvenient production of chlorhydric
acid, which so attacks the materials that they would be soon destroyed
if the precaution were not taken (as has hitherto been done) of neutral-
izing this acid by an alkaline bath.
Now in order to obviate the necessity for this and the previous baths,
which possess the disadvantage of increasing the labour and expense
and extending the time required for the operation, and more particularly
of not being susceptible of application without great difficulties to a
number of articles, such as, for example, cotton in laps, bobbins and
cops from spinning machines, fabrics of a very light texture, such as net
and lace, stitched and bound books, papiers, and the like, it is proposed
to effect the decolorization or bleaching by the application of ozone
(nascent oxygen, ozonized oxygen) resulting from chemical reactions
effecting the decolorization by the gaseous method, which avoids all'
preliminary wetting and any deterioration by chlorhydric acid.
The following processes are proposed for producing and applying
ozone :-
First Process, by Chlorine, Carbonic Acid Gas, and Ammoniac.-Chlorine
in a gaseous state is produced in a closed receptacle by one of the
ordinary means, such as, for example, the action of an acid on chloride
of lime diluted with water. The chlorine obtained is introduced by a
tube into a receptacle containing the materials to be decolorized, the
sides of which receptacle are transparent in order to facilitate the action
of the light. After a lapse of time, which varies with the nature of the

page_text: materials to be decolorized, there is projected by another tube into the
receptacle containing the materials a rapid current of carbonic acid gas
obtained by the ordinary means. The apparatus in which the carbonic
acid is produced communicates by a tube with another apparatus con-
taining liquid ammonia. The ammoniacal fumes or vapours enter the
carbonic acid gas and are conducted by it into the receptacle. The
presence of the ammoniac and carbonic gases neutralizes the chlorhydric
acid whilst maintaining and accelerating the decolorization. The fumes
or vapours of the ammonia are regulated by augmenting or diminishing
the surface of exhalation according to the quantity of chlorine employed,
taking as a basis the chemical equivalents.
Second Process, by Permanganate of Lime and Sulphuric Acid.-This
permanganate is obtained by the reaction of bi-oxide of manganese on
lime by means of heat. It is placed in a closed receptacle which com-
municates by a tube with another receptacle containing the materials to
be decolorized. By gradually pouring sulphuric acid through a tube on
to the permanganate of lime ozonized oxygen is evolved, which passes
into the other apparatus and produces the decolorization.
Third Process, by Phosphorus and Acetic Acid.-The means of pro-
ducing ozone by phosphorus in a moist atmosphere is well known, but
as by this means a very small quantity is produced it cannot be applied
commercially. It is proposed to increase considerably the production of
ozone by this process by causing air which has bubbled up through
acetic acid contained in an adjacent receptacle to bubble up through the
water which contains the half submerged phosphorus. The receptacle
which contains the phosphorus communicates by a tube with the
receptacle which contains the materials to be decolorized, and the
decolorization is effected. The bubbling action is obtained by means of
an exhaust or blast fan.
Fourth Process, by Alum, Chalk, and Sulphuric Acid.-A. saturated
solution of alum is prepared by elevating the temperature to about 140
degrees or 160 degrees Fahrenheit; to this is added carbonate of lime in
powder, in the proportion of about equal weight to that of the alum; a
quantity of sulphuric acid, about equal to that of the alum or chalk, is
then poured over the whole, effervescence is produced, and the gas
which is evolved is conducted through a tube into a receptacle containing
the materials to be decolorized and effects their decolorization,

page_text: in these latter processes as in the former it is preferred nav
receptacle for the materials to be decolorized should have transparent
sides in order to facilitate the action of the light.
After having withdrawn the decolorized materials from the receptacle
it is desirable to expose them for a time (which will vary with the nature 5
of the materials) in the open air, when the smell which is characteristic
of ozone will be speedily removed.
The herein-before described processes wherein the wetting of the
materials to be treated is obviated are specially applicable to the following
purposes:
-
First. The decolorization of raw or worked textile materials, even
those presenting themselves under forms which do not admit of
immersion in a liquid.
Second. The bleaching of books, papers, and engravings, before and
after printing.
Third. The modification of alcoholic liquids with a view A, to improve
them by giving age to them by means of oxidation; B, to change them
into vinegar or acetic acid; C, to arrest their putrid fermentation or to
remove their unpleasant flavour.
Fourth. The clarification of oils and fatty matters.
Fifth. The rendering more healthy the wards of hospitals and other
places subject to deleterious effluvia.
Sixth. The improving the condition of the air in apartments by the
expansion therein of ozone (nascent oxygen, or ozonized or ozonified
oxygen).
1
1

page_text: WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Second day of October, in the year
of our Lord One thousand eight hundred and seventy-three, in the
37th year of Her reign, did, for Herself, Her heirs and successors, give
and grant unto me, the said John Henry Johnson, Her special
license that I, the said John Henry Johnson, my executors, adminis-
trators, and assigns, or such others as I, the said John Henry Johnson,
my executors, administrators, or assigns, should at any time agree with,
and no others, from time to time and at all times thereafter during the
term therein expressed, should and lawfully might make, use, exercise,
and vend, within the United Kingdom of Great Britain and Ireland,
the Channel Islands, and Isle of Man, an Invention for "IMPROVEMENTS IN
THE PRODUCTION OF OZONE, AND IN THE APPLICATION OF THE SAME TO VARIOUS
USEFUL PURPOSES," a communication to me from abroad by Pierre Isidore
David, of Paris, in the Republic of France, upon the condition (amongst
others) that I, the said John Henry Johnson, my executors or admini-
strators, by an instrument in writing under my hand and seal, should
particularly describe and ascertain the nature of the said Invention, and
in what manner the same was to be performed, and cause the same to
be filed in the Great Seal Patent Office within six calendar months next
and immediately after the date of the said Letters Patent.
NOW KNOW YE, that I, the said John Henry Johnson, do hereby
declare the nature of the said Invention, and in what manner the
same is to be performed, to be particularly described and ascertained
in and by the following statement, that is to say :-
The said Invention has for its object the production of ozone, and the
application of the same to the bleaching of textile materials and paper,
the declorization of oils, and other useful purposes.
For the production of ozone chemical reactions are preferred to
physical processes, as the latter produce it in very small quantities and
at a costly rate, whereas in order to apply the ozone commercially it is
requisite that it should be abundantly and economically produced.
According to this Invention ozone is applied to the decolorization or
bleaching of organic matters in such a manner as to effect their
decolorization by the gascous method whilst obviating the wetting of
the matters operated upon.

page_text: It is well known that chlorine employed for bleaching or decolorization
acts only indirectly, that it has no other effect than to produce ozone
(nascent or ozonized oxygen) by gradual decomposition in order to enter
into combination with its hydrogen of the water with which it is placed
in contact or which is naturally contained in the materials to be
decolorized, and that it is the ozone or oxygen then liberated which
effects the decolorization. The use of chlorine is therefore accompanied
by the inconvenient production of chlorhydric acid which so attacks the
materials that they would be speedily destroyed if the precaution were
not taken (as has hitherto been done) of neutralizing this acid by an
alkaline bath.
Now in order to obviate the necessity for this and the previous baths,
which process the disadvantage of increasing the labour and expense
and extending the time required for the operation, and more particularly
of not being susceptible of application without great difficulties to a
number of articles (such, for example, as cotton in laps, bobbins and
cops of spinning and weaving machinery, skins for glove making during
the manufacture and manufactured gloves, fabrics of a very light
texture such as net and lace, stitched and bound books, papers, and the
like); the decolorization or bleaching is effected according to this
Invention by the application of ozone (nascent or ozonized oxygen)
resulting from chemical reactions, and producing such decolorization
or bleaching by the gaseous method, by which means all preliminary
wetting is dispensed with and consequent deterioration by chlorhydric
acid is prevented.
The following processes are employed according to this Invention for
producing and applying ozone:-
1st Process, by Chlorine, Carbonic Acid Gas, and Ammonia.-Chlorine
in a gaseous state is produced in a closed receptacle by one of the ordinary
means, such, for example, as by the action of an acid on chloride of lime
diluted with water. The chlorine obtained is introduced by a tube into
a receptacle containing the materials to be decolorized, the sides of
which receptacle are transparent in order to facilitate the action of the
light. After a lapse of time, which varies with the nature of the
materials to be decolorized, there is projected by another tube into
the receptacle containing the materials a rapid current of carbonic acid
gas obtained by one of the ordinary means, such, for example, as by the

page_text: reaction of an acid on a carbonate. The apparatus in which the carbonic
acid is produced, say, a cask, for example, communicates by a tube with
another apparatus containing liquid ammonia; the ammoniacal fumes
or vapours combine with the carbonic acid gas and are conducted by it
into the receptacle; the presence of the ammoniacal gas and the carbonic
gas neutralizes the chlorhydric acid whilst accelerating the decolorization.
The fumes or vapours from the ammonia are regulated by augmenting
or diminishing the surface of evaporation according to the quantity of
chlorine employed, taking as a basis the relation of the chemical
equivalents.
2nd Process, by Permanganate of Lime and Sulphuric Acid.-This
permanganate is obtained by the reaction of bi-oxide of manganes on
lime with the employment of heat. In order to perform this operation
either the bi-oxide or the peroxide of manganese may be employed. One
part by weight of peroxide of manganese in powder and three parts by
weight of quicklime in powder are taken and mixed together and heated
to the ordinary red heat for about three hours. After the operation has
been continued at the red heat for about an hour a rapid current of
carbonic acid (obtained by the reaction of an acid on a carbonate, say,
chalk, for example), is directed into the mixture, and the supply of such
carbonic acid is continued until the operation is completed. The object
and effect of the carbonic acid are to superoxidize the mixture in
order to obtain at the time of the reaction a much larger quantity of
active oxygen. The mixture is stirred from time to time during the
operation in order to prevent its adhering to the sides of the receptacle.
The permanganate is then placed in a closed receptacle which com-
municates by a tube with another receptacle containing the materials to
be decolorized. By gradually pouring commercial sulphuric acid through
a tube on to the permanganate of lime ozonized oxygen is evolved, which
passes into the other apparatus and produces the decolorization. In
order to accelerate the evolution of the ozonized oxygen there is added
to the permanganate and the sulphuric acid about an equal quantity of
vegetable acid to that of the sulphuric acid employed. Nitric acid, oxalic
acid, and acetic acid are suitable for the purpose, but acetic acid is pre-
ferable as being more economical.
3rd Process, by Phosphorus and Acetic Acid.-The means of producing
ozone by phosphorus in a moist atmosphere are well known, but the
small quantity so obtained precludes its being commercially applied.

page_text: The production of ozone by this process is considerably increased
according to this Invention by causing air which has bubbled up or
passed through acetic acid (wood vinegar and the like) contained in an
adjacent receptacle to bubble up or pass through the water which
contains the phosphorus. The receptacle containing the phosphorus
communicates by a tube with the receptacle which contains the materials
to be decolorized, and the gas being conducted therein the decolorization
is effected. The bubbling action is obtained by means of an exhaust or
blast fan.
4th Process, by Alum, Chalk, and Sulphuric Acid.-A saturated
solution of alum is prepared by elevating the temperature to about 140°
or 160° Fahrenheit; to this is added carbonate of lime in powder in the
proportion of about equal weight to that of the alum employed; a
quantity of sulphuric acid, about equal to that of the alum or chalk, is
then poured over the whole; effervescence is produced, and the gas which 1
is evolved is conducted through a tube into a receptacle containing the
materials to be decolorized, and effects their decolorization.
In all these processes it is preferred that the receptacle for the
materials to be decolorized should be provided with transparent sides in
order to facilitate the action of the light.
After having withdrawn the decolorized materials from the receptacle
it is desirable to expose them for a time (which will vary with the nature
of the materials under treatment) in the open air, when the smell which
is characteristic of ozone will be speedily removed.
By these processes, in some of which the use of chlorine is dispensed
with, the formation of chlorhydric acid is entirely obviated, and the
deterioration of the materials under treatment is prevented.
The herein-before described processes, wherein the wetting of the
materials to be treated is obviated, are specially applicable to the
following purposes :-
First. The decolorization of raw or worked textile materials, even
those which from their form do not admit of immersion in a liquid.
Second. The bleaching of books, papers, and engravings before and
after printing.
Third. The treatment of alcoholic liquids with a view to improve a
them by giving age to them by means of oxidation, to convert them

page_text: into vinegar or acetic acid, and to arrest their putrid fermentation or
remove their unpleasant flavour.
Fourth. The decolorization of oils and fatty matters.
Having now described and particularly ascertained the nature of the
said Invention, and the manner in which the same is or may be used or
carried into effect, I would observe in conclusion that what I consider to
be novel and original, and therefore claim as the Invention secured to
me by the herein-before in part recited Letters Patent is,―
First. The employment of ammoniacal gas and of carbonic acid gas
for the purpose of neutralizing the hydrochloric acid formed when textile
materials, paper, or other organic substances are bleached by means of
chlorine.
Second. The preparation of permanganate of lime and the employ-
ment of the same in the manner and for the purposes herein-before
described.
Third. The employment of acetic acid in conjunction with air,
together with the employment of phosphorus, in the manner herein-
before described, in order to obtain an increased production of ozone.
Fourth. The employment of alum, chalk, and sulphuric acid for
effecting the decolorization of textile materials, paper, or other organic
substances, in the manner and for the purposes herein-before described.
In witness whereof, I, the said John Henry Johnson, have to
this my Specification set my hand and seal, this Thirtieth day of
March, One thousand eight hundred and seventy-four.