CERTAIN IMPROVE- MENTS IN MANUFACTURING CHLORINE, PART OF WHICH ARE APPLICABLE FOR OBTAINING CERTAIN ACCESSORY PRODUCTS
Year: 1855

page_text: LETTERS PATENT to Germain Adolphe Thibierge, Apothecary, of Versailles,
Town in the French Empire, for the Invention of "CERTAIN IMPROVE-
MENTS IN MANUFACTURING CHLORINE, PART OF WHICH ARE APPLICABLE FOR
OBTAINING CERTAIN ACCESSORY PRODUCTS."
Sealed the 1st April. 1856, and dated the 13th October 1855..
PROVISIONAL SPECIFICATION left by the said Germain Adolphe Thibierge
at the Office of the Commissioners of Patents, with his Petition, on the
13th October 1855.
I, GERMAIN ADOLPHE THIBIERGE, do hereby declare the nature of the said
Invention for "CERTAIN IMPROVEMENTS IN MANUFACTURING CHLORINE, PART OF
WHICH ARE APPLICABLE FOR OBTAINING, CERTAIN ACCESSORY PRODUCTS," to be as
follows:
I manufacture chlorine without employing the peroxide of manganese, and
I obtain hydrogen and oxide of iron as accessory or secondary products. I
pass hydrochloric or muriatic acid gas over iron at a high temperature, and
I thus obtain protochloride of iron and hydrogen gas. I pass common air over
the protochloride of iron at a high temperature, and I thus obtain peroxide
of iron and chlorine gas. A quantity of hydrochloric or muriatic acid of

page_text: commerce is placed in a close stoneware vessel or retort, heated by a sand
bath, or by a bath containing a saline solution: The vapour or gaseous pro-
ducts are conducted by a tube of earthenware or lead into two large tubes of
earthenware, containing fragments of chloride of calcium, and united by a
bent earthenware or leaden tube. The hydrochloric acid gas is thus dried,
and is conducted by a tube of porcelain or fire clay into a large tube of about
four inches or more in diameter, and about ten feet long, which is capable of
resisting the action of the gas, and sustaining a high temperature. This tube
contains a quantity of fragments of cast iron, placed in perforated clay vessels.
This tube may be preserved from sudden changes of temperature by a metallic
envelope. The tube terminates in a porcelain or fire clay tube joined to a
leaden tube, which enters a gasometer in which the hydrogen gas is received.
All the joints must be carefully closed or luted. When a supply of hydro-
chloric acid gas can be obtained at a low price, às in some chemical manu-
factories, where large quantities are thrown into the atmosphere, it will be
advantageous to employ this gas, which is then conducted through the drying
tubes filled with chloride of calcium, and the retort is not then required. The
second part of the operation is conducted in a similar apparatus, except that
in lieu of the retort an apparatus for producing a current of air is employed,
such as an air pump or blowing machine. The air is dried by means of chlo-
ride of calcium, and passed slowly over or amongst the chloride of iron, formed
in the preceding operation, inclosed in perforated clay vessels, and heated
nearly red hot in tubes of refractory materials. Chlorine gas is thus produced
and conducted into a gasometer, or into a Woolf's bottle, or other vessel con-
taining water, or into chambers, for the production of chloride of lime or other
chloride. The construction of the apparatus and the materials of which it is
composed may be varied. I thus manufacture chlorine either in the gaseous
state or in solution, and I apply it in the manufacture of chlorides and chlo-
rates, and the production of metals; also in the production of oxygen from
the solution of chlorine by the action of heat or light, which oxygen may be
applied to the feeding of furnaces and the fusion of refractory substances.
The peroxide of iron may be employed for the production of iron and steel,
and the hydrogen may be used for the reduction of metals, and the fusion of
refractory substances, and for filling balloons, and other purposes.
み

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said Germain Adolphe Thibierge in the Great Seal Patent Office
on the 3rd April 1856.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, GERMAIN
ADOLPHE THIBIERGE, Apothecary, of Versailles, a Town in the French Empire,
send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Thirteenth day of October, in the year of our Lord
One thousand eight hundred and fifty-five, in the nineteenth year of Her
reign, did, for Herself, Her heirs and successors, give and grant unto me,
the said Germain Adolphe Thibierge, Her special licence that I, the said
Germain Adolphe Thibierge, my executors, administrators, and assigns, or
such others as I, the said Germain Adolphe Thibierge, my executors, adminis-
trators, 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 "CERTAIN IMPROVEMENTS IN MANUFACTURING CHLORINE, PART OF
WHICH ARE APPLICABLE FOR OBTAINING CERTAIN ACCESSORY PRODUCTS," upon the
condition (amongst others) that I, the said Germain Adolphe Thibierge, 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 per-
formed, 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 Germain Adolphe Thibierge, 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 thereof, that is to say:
I manufacture chlorine without employing the peroxide of manganese, and I
obtain hydrogen and oxide of iron as accessory or secondary products. I pass
hydrochloric or muriatic acid gas over iron at a high temperature, and I thus
obtain protochloride of iron and hydrogen gas. I pass common air over the
protochloride of iron at a high temperature, and I thus obtain peroxide of iron
and chlorine gas. The mode of proceeding is as follows:-A quantity of the
hydrochloric or muriatic acid of commerce is placed in a close stoneware or
glass vessel or retort. The hydrochloric acid gas or vapour is disengaged by

page_text: heating the retort by means of a sand bath or otherwise, or by introducing into
the retort a stream of concentrated sulphuric acid through a glass or metal
tube, contracted at its lower end. The gaseous products are conducted through
an earthenware or metal tube into a series of tubes or vessels of stoneware or
metal, connected by bent tubes, and containing fragments of chloride of
calcium, or an extended surface of concentrated sulphuric acid. The hydro-
chloric acid gas is thus dried, and is then conducted by a tube of earthenware
or metal into a strong tube of fire clay, or other material capable of resisting
the simultaneous action of the gas and a red heat, and containing fragments
of cast iron. This tube is heated in a furnace, and may be protected from
sudden changes of temperature by an envelope or casing of iron, or of fire clay
or tiles. This tube may be about four inches diameter and ten feet long.
About two-thirds of its length is filled with cast iron and heated in the
furnace. It is connected to a tube of earthenware or metal, which conducts
the gas into two drying vessels, arranged and charged in a similar manner to
those by which the gas is dried before it enters the heated tube. These
drying vessels may, however, be omitted when the hydrogen gas is not required
in a dry state. The gas may be stored in a gasometer. All the points of
junction must be carefully luted. To give a certain degree of flexibility to
the different parts of the apparatus, the cool parts of the tubes are connected
by tubes of caoutchouc. In soda manufactories, and other localities in which
a current of hydrochloric acid gas can be obtained at a low price, it may be
conducted at once into the drying apparatus, and then through the heated cast
iron. The retort for distilling or producing the hydrochloric acid gas is not
then required. The second operation consists in decomposing the chloride of
iron produced in the first operation by means of a current of atmospheric air.
This operation is performed in a similar apparatus to that employed for the
first operation, with the exception that in lieu of the retort or apparatus
furnishing a current of hydrochloric acid gas, an apparatus for supplying a
current of air is employed. This apparatus may be a blowing machine of any
description, or the current of air may be produced by applying exhausting
apparatus to the opposite end of the apparatus. The air is dried in the drying
vessels, and is then passed slowly over or amongst the chloride of iron formed
in the first operation, contained in a tube of refractory material and heated to
nearly a red heat by a furnace of any suitable construction. The chloride of
iron is thus decomposed, and oxide of iron and chlorine gas are obtained. The
chlorine gas may be dried by passing it through the drying vessels, if required,
and may then be conducted into a gasometer, or into a vessel or vessels con-
'taining water, or into chloride of lime chambers or elsewhere; according to the

page_text: purpose for which it may be required. The chlorine may be employed for
bleaching, and for preparing aqueous solution of chlorine, chlorurets, or chlo-
rides, and chlorates, and in the extraction of metals, and other purposes for
which chlorine is required. Oxygen gas may be obtained by decomposing the
aqueous solution of chlorine by heat or light, and this oxygen may be employed
for supporting combustion in furnaces or otherwise, for the production of
intense heat and the fusion of refractory substances. The peroxide of iron
may be employed in the production of iron and steel. The hydrogen gas may
be employed in the reduction of metals, the fusion of refractory substances, for
filling balloons, or for lighting and heating purposes.
Having thus described the nature of my said Invention, and in what manner
the same is to be performed, I wish it to be understood that what I claim is,
the manufacture of chlorine and hydrogen by means of the apparatus and
processes herein-before described by the action of hydrochloric acid upon
iron, and by the decomposition of the protochloride of iron so produced by
atmospheric air, as herein-before described.
In witness whereof, I, the said Germain Adolphe Thibierge, have here-
unto set my hand and seal, this Fifteenth day of March, in the year
of our Lord One thousand eight hundred and fifty-six.
G. A. THIBIERGE. (L.S.)
Witness,
Cu. ARMENGAUD, Ing* Civil,
No. 6, Rue Filles du Calvaire, à Paris.