IMPROVED METHODS OF OBTAINING OXYGEN AND CHLORINE GASES
Year: 1862

page_text: PROVISIONAL SPECIFICATION left by Christopher Binks at the Office of
the Commissioners of Patents, with his Petition, on the 17th November
1862.
I, CHRISTOPHER BINKS, of Parliament Street, Westminster, do hereby
declare the nature of the said Invention for "IMPROVED METHODS OF OBTAINING
OXYGEN AND CHLORINE GASES," to be as follows:-
My improvements consist, firstly, in causing by any convenient means or
kinds of apparatus or appliances a mixture of hydrochloric acid gas and
oxygen gas, or a mixture of hydrochloric acid gas and atmospheric air, or
atmospheric air mixed with a larger proportion of oxygen gas than the pro-
portion contained in atmospheric air in its natural condition to be brought in
contact with concentrated or strong sulphuric acid either under ordinary
temperatures or under temperatures higher than ordinary ones, in order to
effect the decomposition of the bydrochloric acid with the liberation of its
chlorine in the form of gas. In conducting this operation I prefer to use the
hydrochloric acid gas, the oxygen gas, and the atmospheric air in their dry
state, that is, (as regards the hydrochloric acid gas,) free from the vapour
of water usually accompanying that acid when produced from the materials
and by the methods commonly resorted to, and (as regards the oxygen and
the atmospheric air) free from hygrometric or other moisture; and in order
to give to the air. and the- gases this dryness, I resort to any of the well-
known methods used for abstracting hygrometric water, or water derived from
any other source, from air or gases.

page_text: But it will be understood that although advantageous to operate with these
elements in their dry state, a condition of perfect freedom from moisture is
not essential to my process, for the presence of a small proportion of water
only detracts to a greater or less extent, according to its relative proportion,
from the relative proportion of chlorine obtained ultimately. In applying
heat to aid or facilitate the reactions that follow on contact of the said
materials with each other, I proceed by heating the sulphuric acid and
throwing into or upon it the gas, or air, or gaseous mixture thereof as
aforesaid, using such gas or gaseous mixture at ordinary temperatures. Or
the same object can be obtained by previously heating the gas or the gaseous
mixture and applying this to the acid whilst the latter is in the first
instance of ordinary temperatures; or I apply heat to both the gaseous
materials and the acid previously to bringing them into contact.
My object in thus applying concentrated sulphuric acid as the reagent
for effecting the decomposition of hydrochloric acid through the conjoint
agency of gaseous oxygen is twofold, first, in order to bring into play
the power of sulphuric acid to induce (in certain cases and under certain
conditions) the formation of water from its elements previously existing in
some substances in other form of combination, and secondly, to make use
of the strong affinity of sulphuric acid for water, whereby in this case the
water after its formation is returned by the acid, the latter being always
kept so strong that the possibility of any reformation of hydrochloric acid
through after or secondary reactions is obviated.
When in the above
operations the sulphuric acid (through the gradual accumulation in it of the
water formed) becomes too weak efficiently to accomplish the decomposition
of the hydrochloric acid, it is then reconcentrated by ordinary methods and
reapplied in these operations. The above process I at pleasure vary as
to the kind and order of operations in manner as follows, keeping in view
the same or similar kinds of reactions and results as above:-For the liquid
sulphuric acid used in the operations just described I substitute the vapour
of sulphuric acid, and cause this vapour when mixed with oxygen gas or with
atmospheric air, or both, to be brought in contact with dry hydrochloric acid
gas, and I conduct the operation by bringing these elements into contact under
ordinary atmospheric temperatures, relying for fulfilment of the decomposing
actions upon the heat naturally evolved on contact, or on the normal action
of the sulphuric acid vapour in eliminating water and retaining it as above
described; or I at pleasure aid the reactions by the application to the
materials of artificial heat.
Secondly, my Invention consists in projecting into or otherwise bringing in

page_text: contact with liquid hydrochloric acid (by means of any convenient apparatus]
or appliances) strongly heated oxygen gas or atmospherie air, or a mixture
thereof, in order to effect the decomposition of the acid and liberation from
it of gaseous chlorine. The steam and proportion of vapourized undecomposed
acid that in the operation do or may accompany the evolved chlorine I separate
therefrom in the usual manner by well-known apparatus or contrivances.
Thirdly, my Invention consists in the following improved methods of effecting
the well-known reactions between gaseous bydrochloric acid and oxygen gas
when these reactions are applied in the production of chlorine, namely, I
cause the oxygen or the atmospheric air, or mixtures thereof, to be strongly
.heated previously to being mixed or brought in contact with the hydrochloric
acid, using the latter at ordinary temperatures in the first instance, that is,
previously to intermixture I cause a jet or stream of the heated oxygen to
be projected into the hydrochloric acid, the latter being kept in excess of the
oxygen. I prefer to cause a jet of the hot oxygen to be thrown into the centre
of a flowing stream or current of hydrochloric acid gas held in pipes or tubes
for conveying the products into water, for condensation of the water formed,
and absorption of the excess of hydrochloric acid, with consequent liberation
of the chlorine in the form of gas. This method I use instead of the ordinary
one of diffusing the oxygen through the hydrochloric acid gas, and then
applying heat externally to the vessels or apparatus containing the mixture.
I sometimes find it desirable so far to vary this operation as to add to the
water used for condensation and separating the products materials for
absorbing or combining with the excess or undecomposed portion of the
hydrochloric acid gas, but which will not absorb or retain the liberated chlorine.
For heating the oxygen previously to intermixture with the hydrochloric
acid the usual plan of applying heat externally to tubes through which it
flows may be employed, but in some cases I prefer to procure the requisite
heat for it by one or other of the following methods, namely, first, I mix
a small proportion of hydrogen gas with an excess of the oxygen previously
to the heating of the tubes used to carry the oxygen, and then apply heat
externally to the tubes; second, I cause an ignited jet of mixed hydrogen
and oxygen gases to be placed in the centre of a flowing current of the
oxygen contained in pipes or tubes, whereby the requisite high temperature
s given to the oxygen before contact with the hydrochloric acid.
Fourthly, the object of my Invention is to facilitate and economise the
production of oxygen gas, and it consists, first, in projecting into or otherwise
ringing in contact with water (by means of any suitable apparatus or con-
rivances) chlorine gas so strongly heated as to effect on such contact the

page_text: .
decomposition of the water, the result of a combination between its hydrogen
and the chlorine forming hydrochloric acid, (which is retained by the excess
of water present,) and thus liberating its oxygen in the form of gas. I vary this
operation when desirable by adding to the water so acted upon any or certain
materials capable of combining with the hydrochloric acid formed or capable
of aiding the decomposing action of the chlorine, and of such materials I
prefer to employ magnesia or one or other of the oxides of manganese. The
hydrochlorates so formed and retained in the water can be applied to useful
purposes, or be used for the reproduction of the chlorine for its reapplication
to these purposes. Second, this part of my Invention consists in projecting into
steam strongly heated chlorine, using the steam in excess of the chlorine, and
bringing the products of the resulting decompositions along with the excess of
.steam in contact with cold water for condensation of the steam in excess, and
absorption of the hydrochloric acid formed, with concurrent separation of the
oxygen in the form of gas. I prefer for this purpose to use a stream or current
of water in order to avoid too great an accumulation of the acid in it, and
consequent reaction with the acid and the liberated oxygen, or I obviate this
.secondary action by adding to the water substances capable of absorbing or
The mode of heating the
combining with the hydrochloric acid formed.
chlorine previously to its contact with the steam may be one or other of those
above described with reference to the heating of oxygen when that gas is used
.for the production of chlorine; or I heat chlorine to be used for the decom-
position of steam for the production of oxygen by igniting, heating, or burning
a mixture of chlorine and hydrogen gases when in contact with or surrounded
by an excess of chlorine, and for this purpose I prefer to cause a jet of mixed
hydrogen and chlorine heated up to combination point to be placed concen
trically either a pipe or tube, through which the decomposed chlorine is made
.to flow, and then be brought in contact with the steam to be decomposed
The small proportion of hydrochloric acid generated by combustion of the chlo
rine and the hydrogen passed along with the heated chlorine in excess, and i
finally separated by passing the whole products of the operation through water
or otherwise bringing them in contact with water, those products by steam
I vary thi
in excess undecomposed hydrochloric acid and gaseous oxygen.
operation, where desirable, by using superheated steam of the temperatures re
quisite to effect its decomposition on contact with the chlorine, using the latte
at ordinary temperatures on contact with the superheated steam; or I prefe
in some cases to heat the chlorine as well as to superheat the steam befor
bringing them into contact, or to project a stream of heated chlorine int
boiling water.

page_text: Fifthly, it is well known that when the higher oxides of manganese, such
as the anhydrous, sesqui, and the per oxides, are under certain conditions
brought in contact with dry chlorine, there result the formation of a chloride
of the metal, and the liberation of the previously combined oxygen in the
form of gas. It is also well known that other oxides similarly treated yield
like results.
Now my Invention as to this part consists in applying, by any suitable means
or apparatus, heated chlorine (previously freed from all moisture) to the
manganese or other excess, whilst the latter are used in the first instance
at ordinary temperatures; or I heat both the oxides and the chlorine instead'
of heating the oxides, or the vessels or apparatus containing them, and thus
causing the chlorine to be brought in contact with them under its ordinary
temperatures.
The evolved oxygen gas is collected by any and well-known means, and
the chloride of manganese is applied to useful purposes or treated for its
recovery in the form of oxides for their reapplication by methods described
by me in the Specification of Letters Patent granted to me the 19th May
1860, No. 1240.