Improvements in the Manufacture of Hydrogen Peroxide and in Apparatus therefor.
Year: 1897

page_text: PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Hydrogen Peroxide and in
Apparatus therefor.
We, SIGMUND ROSENBLUM, of 28, Victoria Street, Westminster, Consulting
Chemist, SAMUEL RIDEAL, of 28, Victoria Street, Westminster, Consulting Chemist,
and THE COMMERCIAL OZONE SYNDICATE, LIMITED, having its offices at 31, Lombard
Street, in the City of London, do hereby declare the nature of this invention
to be as follows:-
This invention relates to the manufacture of hydrogen peroxide, and consists of
improved methods for its production and in improved apparatus therefor.
Hydrogen peroxide is at present manufactured by acting on the peroxide of an
alkaline earth by an acid, and is liable to contain several impurities. The cost of
this process has militated against its wide commercial application.
It is well known that ozone, when it acts upon certain organic liquids in the
presence of water yields traces of hydrogen peroxide. We have found that by
atomizing at the ordinary temperature the mixture of liquids by means of ozone
(prepared preferably by Yarnold's method), the yield of hydrogen peroxide is
enormously increased, and according to our invention, the manufacture of hydrogen
peroxide is rendered possible on a commercial scale free from impurities.
Of the organic liquids we find that the terpene series of the hydrocarbons,
preferably turpentine, give good results, and we further find that the addition of a
small quantity of acid such as sulphuric acid, or of a salt such as sodium phosphate,
increases the yield, whereas alkali has a deleterious effect on the yield."
The hydrogen peroxide produced is soluble in water and is therefore present in
it and can be separated by any convenient means from the organic liquid employed,
which as a rule is not miscible in water. The small quantity or trace of organic com-
pounds above described which remains suspended in or dissolved in the water and may
cause it to be cloudy or turbid can easily be removed by shaking with ether, benzene or
other suitable solvent, and in this way a perfectly clear and pure solution of the
hydrogen peroxide is obtained.
When ether is used as a solvent a small amount of it remains in the hydrogen
peroxide solution and tends to render it more stable. In this
way solutions
containing "several volumes" of hydrogen peroxide can be obtained.
We prefer to carry out the intimate mixture between the two liquids and the
ozone by means of an apparatus constructed substantially as follows:-The
apparatus consists of a vessel with means for introducing the two liquids and with
suitable means for the introduction of ozone. This vessel is provided with a dis-
charge pipe or pipes so arranged and constructed that the two liquids are forced
thereout in an ozonized and "atomized" spray into a covered vessel. This second
vessel may be provided with means for the passage of ozone through the spray
and may be provided with a return pipe to the first vessel so that the operation
may be repeated again if required.

page_text: As the two liquids to be initially treated have different specific gravities care
must be taken that they discharge together. This may be effected by having three
discharge tubes arranged concentrically, one being lengthened so as to deliver the
heavier liquid whilst the second is arranged so as to dip into the lighter and the
third affords a means for the passage of the ozone to the nozzle or orifice of
the discharge pipe. By this means the two liquids are forced to the nozzle and are
sprayed by means of the ozone in a finely divided condition. The two innermost
concentric tubes may if thought more desirable be substituted by one which is
branched and adjusted so as to deliver a mixture of the two liquids to the discharge
orifice, and the vessel may if desired be divided so as to contain the two liquids
separately; or the two liquids may be intimately mixed mechanically or made to
form an emulsion before being sprayed by means of the ozone.
J. C. MEWBURN & ELLIS,
55 and 56, Chancery Lane, London, Chartered Patent Agents.
Improvements in the Manufacture of Hydrogen Peroxide and in "
Apparatus therefor.
We, SIGMUND ROSENBLUM, formerly of 28, Victoria Street, Westminster,
now of Imperial Chambers, Cursitor Street, City of London, Consulting Chemist,
SAMUEL RIDEAL, of 28, Victoria Street, Westminster, Consulting Chemist, and The
COMMERCIAL OZONE SYNDICATE, LIMITED, having its offices at 31, Lombard Street,
in the City of London, do hereby declare the nature of this invention and in what
manner the same is to be performed, to be particularly described and ascertained in
and by the following statement: —
This invention relates to the manufacture and application of hydrogen peroxide
and consists of improved methods for its production and its applications and in
improved apparatus therefor.
Hydrogen peroxide is at present manufactured by acting on the peroxide of an
alkaline earth, preferably barium peroxide by an acid. The cost of this process
is very considerable and has militated against a wide industrial application of the
product, and as the latter when prepared by above process is very liable to contain
numerous impurities it has been hitherto impossible to apply it for medical and
many sanitary uses.
It is well-known that ozone when acting in the presence of water upon certain
organic chemical compounds will produce traces of hydrogen peroxide. Of such
compounds the terpene series of the hydro-carbons have been found to yield to
above reaction more easily than others. We have found, however, that besides
these there is a whole series of organic compounds, especially the so-called un-
saturated ones amongst which may be classed many of the aldehydes and ketones,
the camphors, the carbo-hydrates of the formula (C10H16x) (otherwise called terpenes
and polyterpenes) nearly all the ethereal or essential oils, which mainly consist of
terpenes and polyterpenes, and also a large number of resins and balsams, will
when acted upon by ozone in the presence of water yield hydrogen peroxide in a
smaller or lesser degree.
The chemical change which takes place in the abovo stated order of reactions is
not yet clearly known, but we presume that in the case of the above enumerated
unsaturated organic compounds an addition of ozone takes place and peroxides of
these compounds are formed. These peroxides when acted upon by water are

page_text: decomposed into hydrogen peroxide and into the original unsaturated or only
partially oxidised compounds.
However, the yield of hydrogen peroxide in all the above stated reactions if carried
out in the ordinary way is an extremely small one and would be of no value for
industrial or medical purposes. But we have found that by employing a method
in conjunction with suitable apparatus, hereinafter to be described, the yield of
hydrogen peroxide in any of the above stated reactions can be enormously increased
and thus the utilization of these reactions for the production of hydrogen peroxide
on a large scale be made possible and practicable.
Of all the above stated organic compounds which will yield hydrogen peroxide
when acted upon by ozone in the presence of water, we have selected on account
of their comparatively low cost, the terpene and polyterpene series of the hydro-
carbons as the most suitable ones for our purpose and for the same reason we
prefer to use oil or spirits of turpentine whenever a large yield of hydrogen
peroxide at a low cost is desired.
Any of the above enumerated organic compounds we may use for our purpose,
either single or in suitable mixtures of various proportions, or dissolved in suitable
solvents.
There are numerous methods by which we can manufacture hydrogen peroxide
by the action of ozone and water or ozone and steam upon the above mentioned
organic compounds. For instance hydrogen peroxide may be prepared by leading
ozone and vapourised turpentine into water or in the place of turpentine one or
more of the above mentioned organic compounds in a vapourised condition may be
substituted.
Or as an alternative hydrogen peroxide may be formed by leading steam
and ozone into turpentine or one or more of the organic compounds
menfioned above which if necessary can be in suitable solutions. The method
however we prefer to adopt in the manufacture of hydrogen peroxide on a com-
mercial scale consists in atomising an emulsion or mixture of the original liquid or
suitably dissolved organic compound or compounds with water by means of ozone,
or if preferred steam may be substituted for water as will be more fully, described
hereafter, and in carrying this principle into effect we prefer to employ the
apparatus shown in the accompanying drawings, of which
Figure 1 is a central vertical section, Figure 2 is an enlarged view of a portion
of Figure 1, and Figure 3 is a plan of Figure 2. Figures 4 and 5 illustrate a
modification of the apparatus illustrated by Figures 2 and 3 and hereinafter
described in detail.
A is a cylindrical casing carried by supports A¹. Below it is a cylindrical vessel B
having a hermetic cover B¹. Within the vessel is a duplex stirrer C constituted by
two sets CC of stirring arms or frames, the set C being carried upon a tubular
shaft C3 and the set C² carried upon a shaft C received concentrically within the
shaft C³. Two sets of stirring frames are rotated by means of bevel or other
gearing in opposite directions. In the present example the shaft C³ carries at its
upper end a bevel wheel C5, and the shaft C is provided with a bevel wheel C6;
these two bevel wheels are geared together by an intermediate wheel C7 which
rotates the wheels C C and the shafts connected thereto in opposite directions,
being it elf driven by means of a shaft C8 supported in bearings C on the top of
the cover B¹. The lower ends of the shafts C³ C+ run in or upon the footstep
bearing Co. B2 is a pipe for the admission of the turpentine or other suitable
organic liquid mixed or not with water into the vessel B and B is a drain cock
placed at the bottom of the vessel to enable the latter to be drained when desired.
B is a pipe situated at the lower part of the vessel B which may be curved to form a
coil and is perforated to allow of the passage of the ozone in small jets through
the liquid above it as shown.
In the casing A and beneath the top cover A2 is provided a hollow conical
mounting A3 supporting a circular dish D having a vertical annular flange D¹. In
the dish D is another dish D2 somewhat shallower than the former.
D³ is a

page_text: space below the dish D³ communicating on the one hand with perforations D* made
through the latter near its circumference and tubular spindles 15 hereinafter again
referred to, and on the other hand with the upper portion of the interior of the
vessel B by way of a pipe E controlled by a valve E¹.
A pipe in which is a valve F1 extends upwards from a point near the bottom
of the interior of the vessel B through the cover B¹, the hollow conical mount-
ing A³ and the bottom of the dish D2 to afford communication between the vessel B
and the space D in the dish D2 which is closed by a cover D' perforated with
tapered conical holes DB having their smaller ends uppermost. Tubular spindles I)5
are screwed into the bottom of the dish D³ and have coned upper ends which extend into
the holes Ds. There is a passage way through the holes Ds around the tapered upper
ends of the tubular spindles D³, which latter constitute passages for the ozone, as
hereinafter described, from the space D³ to points just below the level of the
top of the cover D7: they can be screwed up or down to regulate the area of the
annular passage around them.
G is a pipe controlled by a valve G₁ affording communication between the
chamber A and the interior of the vessel B; H is a drain pipe for draining the
chamber A. The operation is as follows:-The turpentine or other suitable
organic compound or mixture or suitable solution of such compounds is delivered
into the vessel B through the pipe B2 in conjunction with a suitable proportion
of water to form an emulsion, or the water may be introduced into the vessel
separately. An emulsion is formed by rotating the stirring frames or arms C¹ C²
in opposite directions, and ozone, which should preferably be free from moisture
or carbonic acid gas, is then delivered into the vessel B through the perforated
pipe D under any suitable pressure, say 7 lbs., to the square inch. The ozone
passes in an upward direction through the emulsion, thereby ozonising it and
collects at the top of the vessel B thereby producing surface pressure which forces
the emulsion of turpentine and water up the pipe into the space D6, while some
of the ozone controlled by a cock E¹ passes up the pipe E into the space D³.
A portion of the ozone escapes from the space 13 through the perforations D'
into the interior of the chamber A, while the remainder passes through the
spindles D³ and draws the emulsion of turpentine and water from the space D6
through the tapering annular spaces of the passages Ds. The emulsion meeting
the ozone at the nozzles of the spindles D5 is atomised and in the form of a very
fine spray is delivered with the gas into the interior of the chamber A, where it is
met by the additional ozone which enters the vessel through the perforations D'
The turpentine water and ozone thus become intimately mixed with the result
that hydrogen peroxide is formed and simultaneously absorbed by the water. The
mixture of turpentine and water containing hydrogen peroxide in solution falls to
the bottom of the chamber A, whence it can be either withdrawn through the
pipe H or conveyed through the pipe G back again to the vessel B for re-treatment.
The excess of ozone escapes from the chamber A by way of the exit valve A*, and
as it always carries with it uncondensed vapours of turpentine it is passed through
suitable condensers in order to remove the turpentine.
It may sometimes be desirable to manufacture hydrogen peroxide "in situ" for
its direct application to articles which are required to be oxidised or bleached.
Again we have found under some conditions the substitution of steam for water
gives in certain cases more satisfactory results. For the manufacture of hydrogen
peroxide under these conditions we prefer to employ the apparatus shown in
Figures 4 and 5, which respectively are modified forms of that shown in Figures 2
and 3, and in which like letters represent like parts.
From Figures 4 and 5 it will be seen that the spindles Ds instead of opening
into tapered holes in the plate D7 open into tapered passages made in nozzles 19
which are screwed into that plate, and which in turn extend into tapered holes D10
in a cover D. Between the plates D' and D is a space D¹ into which by
way of a pipe G steam is admitted for a purpose hereinafter explained, passing out
in an upward direction around the nozzles D9 through the holes D10.

page_text: The action is as follows:-
A turpentine or other suitable organic compound either in a liquid or a
vapourised form is forced through the pipe F into the space De. Ozone, which
should be free from moisture or carbonic acid gas, enters by the pipe E into the
space D³. Steam enters the space D12 through the pipe G. The ozone passes
from the space D³ through the spindles D5, nozzles D9 and holes D10, drawing up
the turpentine from the space D5 through the annular passage-way D8 surrounding
each nozzle D5, and out through the nozzles D2 and holes D10 in company with
the ozone; steam from the space D 12 passes up the annular passages surrounding
the nozzles D³, the turpentine, ozone, and steam being delivered from the holes Dio
in an atomised or vapourised condition into the vessel A shown in Figure 1. If
it is desired to manufacture the hydrogen peroxide "in situ" then the turpentine,
ozone and steam may be delivered from the openings D¹º directly on to the article
to be bleached or otherwise treated.
The chamber B if desired may be jacketted with steam or hot water and the
several jets of fluid need not be delivered concentrically with one another but may
be otherwise arranged in any desired manner so long as they mingle ultimately
at some common point of issue.
It is clear from the above description of the process that the oil of turpentine
or any other suitable organic compound used in our process is not actually and
entirely consumed in it but plays only an intermediary role in the reaction, so
that if the whole process were carried out cautiously and quantitatively none or
only a very small loss of the organic compound used would be experienced.
In practice, however, we find that a small loss of the organic compound used
occurs and also that in the case of several of the organic compounds here described
a chemical change known as polymerisation takes place. We, therefore, prefer
to dissolve or dilute the polymerised compounds in or with the particular com-
pounds originally used, before using it over again in our process, and we have found
that a higher yield of hydrogen peroxide is the result of such procedure. Thus the
compound which we employ in our process can, as is shown in the above, be used
over again nearly indefinitely.
The whole process can, if desired, be made self-working or automatic and is
carried out at the ordinary temperature. The concentration of the hydrogen
peroxide produced depends upon the length of the time the reaction is allowed to
continue in our apparatus, e.g., after the reaction has gone on for only 5 to 6 hours
solutions of three "volumes" of hydrogen peroxide are produced.
Such or stronger solutions can, if a very high concentration of hydrogen peroxide
is desired, be enriched in their contents of hydrogen peroxide by evapora-
tion in vacuo.
As the hydrogen peroxide is soluble in water it is therefore found to be entirely
present in the water used in this process.
When the process is considered to be finished, .e., when the desired concentra-
tion is attained, the aqueous solution of hydrogen peroxide is by any convenient
means separated from the organic liquid employed, which as a rule is lighter
and not miscible with the water. The aqueous solution of hydrogen peroxide so
obtained usually still contains a trace of the organic compound employed or of any
intermediary compounds which may have formed during the reaction and as neither
of these are soluble in water they will usually give to the aqueous solution of the
hydrogen peroxide a turbid appearance. We have found, however that if
this turbid solution after having been separated, is treated with ozone
for quite a short time the traces of organic compounds contained therein will
be decomposed or so altered in their composition that the solution is rendered
perfectly clear.
The hydrogen peroxide produced by this process is more stable than when
produced by any other process, and we have noticed that if it is exposed to the
action of atmosphere it shows a tendency to absorb further quantities of oxygen.
As the hydrogen peroxide obtained by our process is free from any bodies which

page_text: may be injurious to the human organism, it can therefore be used in suitable
concentrations, solutions or mixtures, or with suitable additions for internal and
external theurapeutical purposes, also as a general antiseptic, disinfectant,
deodorant, preservative against putrefaction etc., also for the production of
absolutely pure oxygen for inhalations and for many other sanitary purposes.
It is well known that hydrogen peroxide on account of its being able to give off
one atom of active or available oxygen in a nascent form is a very strong oxidising
and bleaching agent. But its present high cost has hitherto not allowed its wide
application in these directions. As the hydrogen peroxide produced by our
process is of a very low cost it will become possible to apply it whenever a strong
oxidising or bleaching agent is required. As for instance for the bleaching of
silks, yarns, feathers, ivory, bones, sugar syrups, oils, wood, cotton, wool, for the
removal of stains, removal of the last traces of "hypo" in photography, of chlorine
and sulphur dioxide in the old bleaching processes, and so on. For all these
purposes the aqueous hydrogen peroxide produced by our process can be used
directly according to methods which may be found most convenient and practicable
for the particular purpose.
"
But we have also devised a new process by means of which hydrogen peroxide
when required for several of the above stated purposes can be generated directly
on the objects to be oxidised or bleached and therefore its action as being "in situ”
be made much more effective and considerably less costly. This new process is
carried out as follows:-The object to be oxidised or bleached, for example cotton,
is dipped into an emulsion of any of the already mentioned organic compounds,
preferably turpentine with water and is then exposed to the action of ozone in a
suitable receptacle vessel or chamber. The hydrogen peroxide resulting from the
reaction is thus produced directly on the fibre, and we have found that even articles
which are very difficult to bleach by the best ordinary processes will be entirely
bleached in a very short time by means of this process.
Or the same process can also be carried out as follows:-
The articles to be bleached are dipped into the liquid organic compound, say
turpentine, and then placed in a chamber into which ozone and low pressure
steam are allowed to enter. Hydrogen peroxide is formed on the fibre and
the article is bleached quickly and efficiently.
The apparatus or chambers in which any of the above stated bleaching or
oxidising processes are carried out are supplied with outlet-pipes leading into
similar condensing apparatus, as previously described, the object of which is
to condense the fumes of the organic compound or compounds used and thus
obviate their loss.
Articles bleached by way of the above described modifications of our process
retain a faint odour of the organic compound which has been used for the production
of hydrogen peroxide, but this odour is easily removed from the article by a short
exposure to hot steam and ozone. In order not to waste hydrogen peroxide we
have found that all articles to be bleached, should before bleaching be freed from
fatty matters, dirt, &c., by any of the ordinary methods adapted for this purpose.
We have found that the usually deleterious action upon the fibre experienced in
most bleaching processes does not take place in our process.
" can be modified
The above described production of hydrogen peroxide "in situ
in numerous ways according to the purpose for which it is required.
Having now particularly described and ascertained the nature of this said
invention and in what manner the same is to be performed, we declare that what
we claim is:-
1. The manufacture of hydrogen peroxide by leading ozone and one or more of
the organic compounds above described in a vapourised condition into water.
2. The manufacture of hydrogen peroxide by leading steam and ozone into one
or more of the organic compounds above described.
3. The manufacture of hydrogen peroxide by mixing together ozone, steami

page_text: and one or more of the organic compounds above described in a vapourised
condition.
4. The manufacture of hydrogen peroxide by intermingling a jet of ozone with
a spray of one of the terpene series of hydrocarbons such as oil or spirits of
turpentine in the presence of water or steam.
5. The manufacture of hydrogen peroxide by intermingling a jet of ozone with
a spray of a suitable organic compound or a mixture of such compounds in the
presence of water or steam.
6. Purifying and clarifying hydrogen peroxide manufactured as above from
traces of organic compounds employed, by atomising it in a jet of ozone.
7. The manufacture of hydrogen peroxide "in situ" consisting in dipping the
article to be oxidised or bleached in an emulsion of one or more of the above
mentioned organic compounds and water and then exposing it to the action of
ozone.
8. The manufacture of hydrogen peroxide “in situ" consisting in dipping the
article to be oxidised or bleached into une or more of the above described organic
compounds and then exposing it to the action of ozone and steam in a suitable
chamber.
9. Removing from articles bleached or oxidised by hydrogen peroxide manu-
factured in situ" traces of the organic compound used by exposing them to the
action of a jet of steam and ozone.
10. In apparatus for the manufacture of hydrogen peroxide the combination
with a vessel B of a device for intermingling a suitable organic liquid and water
in the form of spray with ozone.
11. In apparatus for the manufacture of hydrogen peroxide the device for
intermingling a jet of ozone and a spray of a suitable organic liquid and water
substantially as described.
12. In an apparatus for the manufacture of hydrogen peroxide the device for
producing jets of ozone, steam and suitable organic compound in a vapourised
condition substantially as described.
13. In the manufacture of hydrogen peroxide the apparatus substantially as
described and illustrated in Figure 1 or Figures 2 and 3 or Figures 4 and 5 of the
enclosed drawings.