A PROCESS AND APPARATUS FOR PRODUCING JOINTLY OR SEPARATELY OXYGEN AND CHLORINE PROM THE SAME CHEMICAL SUBSTANCE AND IN THE SAME APPARATUS
Year: 1866

page_text: LETTERS PATENT to Jules Théodore Anatole Mallet, of 29, Boulevart
St. Martin, Paris, in the Empire of France, Civil Engineer, for the
Invention of "A PROCESS AND APPARATUS FOR PRODUCING JOINTLY OR
SEPARATELY OXYGEN AND CHLORINE PROM THE SAME CHEMICAL SUBSTANCE AND
IN THE SAME APPARATUS."
Sealed the 28th May 1867, and dated the 3rd December 1866.
PROVISIONAL SPECIFICATION left by the said. Jules Théodore Anatole
Mallet at the Office of the Commissioners of Patents, with his Petition,
on the 3rd December 1866.
I, JULES THÉODORE ANATOLE MALLET, of 29, Boulevart St. Martin, Paris,
in the Empire of France, Civil Engineer, do hereby declare the nature of the
said Invention for "A PROCESS AND APPARATUS FOR PRODUCING JOINTLY OR
SEPARATELY OXYGEN AND CHLORINE FROM THE SAME CHEMICAL, SUBSTANCE, AND
IN THE SAME APPARATUS," to be as follows:-
My Invention consists in a process and apparatus for producing at will,
conjointly or separately, oxygen and chlorine from the same chemical substance.
This chemical substance is the sub-chloride of copper (Cu³CI) which is trans-

page_text: formed through the action of the oxygen of the air into an oxychloride, this
again loses its oxygen at a dark red heat and returns to the state of sub-chloride
and so forth. The apparatus I make use of are cast-iron retorts lined
internally with fire-clay or other suitable lining for preserving the metal from
the influence of the chemical matter and gases; these retorts have openings
at their bottom parts suitably closed or stopped, at which point there is also
an extension forming an exit tube. The retorts are placed horizontally in a
furnace and supported by sets of rollers, which allow of the retorts having
a rotary motion on their axis with the least possible friction. The exit tube
is connected to another tube by means of a stuffing box, so that the system of
retorts may rotate without any loss of gas. The oxychloride above alluded to
is mixed in the proportions of about one to twenty, per cent. of its weight
with an inert substance, such as kaolin, sand, or fire-brick, which always
remains in the retort. When the retort is not drawn out from the furnace and
allowed to cool slowly therein it may be made wholly of ceramic material,
earthenware, for instance; when it is desired to produce oxygen only the retort
being in the furnace and heated is caused to rotate continuously, so as to
agitate the substance and impart the same temperature to every point in the
retort, in which case only a low temperature is required, say a dark red heat.
The oxygen gas which evolves is caused to pass through a washing vessel, and
is collected for use on the gas ceasing to be disengaged; if large quantities of
gas are to be produced a sufficient number of retorts are provided for a con-
tinuous operation; the heated retort is hoisted by a winch or other suitable
device out of the furnace, laid aside, and replaced by another, and so forth;
when, on the contrary, but a small quantity of gas is required the retorts are.
then allowed to cool in the furnace.
I will now describe in what manner the revivification is effected. When
the retort is cooled to a temperature much below 212 degrees Fahrenheit, say,
from 120 to 140 degrees, the opening opposite to the exit tube being opened
I produce a draught of air through the latter by means of a chimney. or blowing
engine, the retort still continuing to rotate on its rollers as above described.
The air must be moist and may be rendered so by the addition of steam, the
simplest method being to add water to the material before injecting the air in
the proportion of from 12 to 15 per cent. of its weight. The action of the
oxygen of moist air on the sub-chloride will rapidly transform the latter into
oxychloride, and if the current of air is. sufficient the revivification may be
effected within three or four hours. The heat developed by reaction or that
retained by the retort absorbs any excess of water, and the retort is then ready
to be again heated. For moistening the matters I may use the water from

page_text: the washers as it is always warm and often contains some acid, which in this
manner is restored to the matters. The rotary motion of the retort should
during the distilling and revivifying operations be continuous and uniform,
and may be obtained by any suitable motive power. If during the revivifica-
tion without changing the apparatus or material or varying the manner of
operating I substitute for the water above mentioned a certain amount of
hydrochloric acid of commerce, say from 25 to 30 per cent. of the weight
of the material without rendering the latter turbid, and the air is caused to
pass through as before, there will be formed in the material through the
action of the oxygen a mixture of oxychloride and chloride, CuCl, so that by
distillation a mixture may be obtained of chlorine and oxygen containing the
more chlorine the greater the amount of oxide that has been added. The
chlorine is absorbed in alkaline solutions or in a solution of lime, or lime in
powder, and the oxygen is collected in a gasometer or otherwise. If it were
desired to obtain chlorine only the coppery matter must be completely trans-
formed into chloride, CuCl, and a proportion of from 50 to 60 per cent. of
acid added thereto, which cannot be accomplished at once, but only as the
heat developed by the reaction or retained by the retort eliminates a portion
of the water; should gaseous hydrochloric acid be easily obtained this might
be used instead of the liquid acid or together with the current of air, or after
the latter has acted.
The advantage of the arrangements just above mentioned is to avoid all
loss of material, to facilitate and quicken the distillation and revivification, and
also to prevent all noxious odours or vapors being emitted by the materials
should they be withdrawn from the retorts before being completely cooled.
The simultaneous or separate production. of two such gases as chlorine and
oxygen in the same apparatus, and as it were by the same process, is a very
great advantage, the chlorine being applicable for bleaching or preparing
chlorides for decolorizing purposes, and oxygen for heating and lighting
purposes. For obtaining a continuous action there should be three sets of
retorts, those in the fire, those which are cooling, and those used for the
revivification, each of these operations requiring four hours at least, hence it
is evident that each retort will undergo a complete operation within twelve
hours. If oxygen only is to be obtained about three cubic yards is produced
for about every two hundred pounds of the material employed. By using for
he revivification 25 or 30 per cent. of hydrochloric acid of commerce from
two to three cubic yards of chlorine and one and a half cubic yards of oxygen
may be obtained, and if lastly the whole of the material be transformed into
chloride from five to six cubic yards of chlorine may be obtained, say from

page_text: 100 to 120 pounds of chloride of lime in a solid form if such product is sought
to be produced. The end intended by the rotary motion of the retort being
constantly to agitate the material therein the same result might be attained
by having the retort stationary, and fitting therein an agitator of any suitable
form, in which case the retorts may be placed either in a horizontal, vertical,
or inclined position.
My Invention thus consists in a process, and apparatus for producing
conjointly or separately oxygen and chlorine without making any change in
the apparatus used for the purpose, or in the material or chemical substance
in the retort, or method of operation.
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said Jules Théodore Anatole Mallet in the Great Seal Patent
Office on the 1st June 1867.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I,. JULES
THEODORE ANATOLE MALLET, of 29, Boulevart St. Martin, Paris, in the
Empire of France, Civil Engineer, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Third day of December, in the year of our Lord
One thousand eight hundred and sixty-six, in the thirtieth year of Her reign,
did; for Herself, Her heirs and successors, give and grant unto me, the said Jules
Théodore Anatole Mallet, Her special licence that I, the said Jules Théodore
Anatole Mallet, my executors, administrators, and assigns, or such others as
as I, the said Jules Théodore Anatole Mallet, my executors, administrators, and
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 "A PROCESS AND APPARATUS FOR PRODUCING JOINTLY OR SEPARATELY OXYGEN
AND CHLORINE FROM THE SAME CHEMICAL SUBSTANCE AND IN THE SAME APPARATUS,"
upon the condition (amongst others) that I, the said Jules Théodore Anatole
Mallet, my executors or administrators, by an instrument in writing under
my, or their, or one of their hands and seals, 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
sáid Letters Patent.

page_text: NOW KNOW YE, that I, the said Jules Théodore Anatole Mallet, do hereby
declare the nature of my 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) :-
My Invention refers to a new process and apparatus for producing at will
conjointly or separately oxygen and chlorine by using the same substance.
This substance is the sub-chloride of copper (Cu Cl) which is by the action of
the oxygen of the air transformed into an oxychloride; this oxychloride .loses
its oxygen at the dark red heat, passes again to the state of sub-chloride, and
so forth. The apparatus which I make use of are cylindrical cast-iron retorts
with an inside of fire-clay, porcelain, or grit lining, or any suitable inside
coating so as to preserve the metal from the action of the material therein and
gases. Even the inside pieces unless the clay is of sufficient compactness
not to get imbibed at the contact of the material are to be coated with an
enamel unattackable by chloride of copper, one, for instance, with base of
borate, silicate, phosphate of copper, or any other which may be alike efficient.
At the bottom of the retorts are plug-shut openings, and in the elongation of
the figure axis there is an exit tube. The retorts are placed horizontally in a
furnace and supported by a system of rollers which allow of their rotation
round their axis with the least possible friction. The exit tube is connected
to another tube through a stuffing box so that the retort system can rotate
without loss of gas; (the stuffing box may be packed with amianth.) The
oxychloride before, mentioned is mixed with 15 to 20 per cent. of inert
material, such as kaolin, porcelain, sand, or powdered fire-bricks; it is placed
in the retort and never got out of it when in regular working. So much
being said, if it is desired to produce oxygen alone the retort being in the
furnace is heated by being continually and slowly rotated so as to stir the
material and give every portion of it the same temperature; in this manner
the heat minimum (dark red) is requisite. The oxygen gas evolved passes
through a washing vessel, and is collected for one purpose or another when
the evolving thereof has subsided (after about two hours). When large
amounts of gas are to be produced and a sufficient number of retorts are to be
had for a continuous working the heated retort is removed by means of any
suitable apparatus, such as a windlass or crane, through the furnace top, put
aside, replaced by another, and so forth. When, on the contrary, but little
gas is requisite and no other retorts but those in the furnace are to be had
they are there allowed to get cool without being removed.
I will actually describe in what manner the revivifying operation is pro-
ceeded with. When the retort is comparatively cooled even when marking 302

page_text: or 392 degrees Fahrenheit, still continuing on its rotation, jets of water or of
steam are projected on it, which has the immediate effect of lowering the
temperature to 212 degrees or below, and a draft of air is directed on it from
a chimney, or forced on it by a blower or pump, when the color of the material
is changed and the material itself is completely converted or transformed into
.oxychloride within two or three hours if the current is sufficiently strong and
care has been had in case of the material becoming too dry to inject water or
steam. It is obvious that though the amount of forced air is to be rather
considerable care must be taken not to impart the same velocity, whereby part
of the material might be carried away. The heat preserved by the retort and
that developed by the reaction will expel the excess of water and the retort
may be heated again for the production of oxygen. The rotation of the
retort is to be kept continuous and uniform during all the operations, which
continuity may be obtained through any motive power. While revivification
is proceeded with the material, the apparatus, the mode of operation are not
to undergo any change; instead of either water or steam chlorhydric acid is
injected either in the liquid state or at the state of vapor or gas, and its
action is combined with that of the air current; or, again, after the revivi-
fication has been effected, as for the oxygen, the hydrochloric acid is added in
either a liquid or gaseous state, care being taken if the acid is liquid not to
inject it all at once in order to prevent the material from being liquified, and
by maintaining the retort at a sufficient temperature to eject or eliminate the
excess of water by the combined successive or simultaneous action of the
water steam the air and chlorhydric acid there will be obtained according to
the amount of this last agent a mixture of oxychloride and chloride, CuCl,
or chloride alone liable to yield when distilled a mixture of oxygen and
chlorine or chlorine alone if the quantity of acid has proved sufficient. The
chlorine is retained in alkaline dissolutions in solution of lime or by powdered
lime, and the oxygen, if any, is collected into a gasometer or otherwise. The
necessary amount of acid to saturate the whole oxychloride and transform it
into chloride CuCl being when the liquid acid of trade is used equal to from
50 to 60 per cent. the weight of the material, it is evident that it must be
thrown in little by little as the water which constitutes the 60 to 70 degrees
per cent. of the acid is ejected it is proper to maintain the retort at about
175 to 212 degrees Fahrenheit, which is very easy if it has been kept in the
furnace, which may still be done in case it was removed by having a supple-
mental furnace or shell heated by the waste heat, or by steam or other means;
or, again, by having the retorts heated directly by steam when gaseous acid is
used, and chiefly the acid gases from the soda ovens consequently at a high

page_text: temperature, this precaution is needless. I have heretofore mentioned rotating:
retorts only, but as their rotation is merely intended for the constant agitation
of the material I can attain the same end. by having stationary retorts and
applying a suitable agitator of any form, in which case the retorts may be
either horizontal, vertical, or inclined.
The advantage of the above-described arrangements is to prevent entirely
the waste occasioned by manipulation, to quicken the distillation, and remove
any noxious odour which would proceed from the material were it taken out
of the retorts previous to their being completely cooled. The simultaneous
production of two gases, such as chlorine and oxygen, in the same apparatus,
and by using as it were the same mode of operation may prove very advan-
tageous, as by making use of the chlorine for bleaching purposes, or for
preparing, decoloring, or disinfecting chlorides, and the oxygen for heating and
lighting purposes, the production of these two gases may be made adequate to
daily requirements. For continuous working three sets of retorts may be
employed, viz., those in the furnace, those which are cooling, and those
serving for the revivification, a complete operation requiring from eight to
twelve hours, it is obvious that each retort may perform two or three
operations every twenty-four hours. If oxygen only is to be produced abe
one hundred and five cubic feet for 440 pounds may be obtained.
If chlo
only is to be produced there will be obtained only 120 or 140 cubic fee
220 pounds, say, 80 to 90 pounds of chlorine and solid lime. By proceeding
with this simultaneous production intermediate variable quantities may be
had proportionately to the amount of the acid used. The decomposition of the
material for producing chlorine and oxygen may be facilitated by injecting
steam into the retort during the distilling operation; the steam should then
be superheated, and the retort should not in this case be heated to redness,
so as to avoid the decomposition of water at the contact of the material and
the hydrochloric acid formed, in which case the difference between the
distilling and the revivifying temperatures being less it will not be necessary
to take the retorts out of the furnace, and the cast-iron shell may then be
either entirely or partially suppressed. It is obvious besides that a mixture
of gas and water, steam being obtained at the issuing from the retort, any
suitable arrangement may be made for condensing the latter and freeing
the gases.
Having described the nature of my Invention, and the manner of per-
forming the same, I declare that what I claim as my Invention to be protected
by the herein-before in part recited Letters Patent is the process and apparatus,
as described, whereby are produced at will, conjointly or separately, oxygen

page_text: and chlorine without any change or alteration being made in the apparatus or
material in the retorts or in the mode of operation.
In witness whereof, I, the said Jules Theodore Anatole Mallet, have
hereunto set my hand and seal, this Twenty-ninth day of May, in
the year of our Lord One thousand eight hundred and sixty-seven.
J. T. A. MALLET. (L.S.)