IMPROVEMENTS IN OBTAINING SULPHATE OFTASHDROCHLORICCID
Year: 1874

page_text: LETTERS PATENT to Emil Königs and James Henderson, both of
Irvine, in the County of Ayr, North Britain, Manufacturing
Chemists, for the Invention of "IMPROVEMENTS IN OBTAINING SULPHATE
Scaled the 10th November 1874, and dated the 16th May 1874
PROVISIONAL SPECIFICATION left by the said Emil Königs and
James Henderson at the Office of the Commissioners of Patents,
with their Petition, on the 16th May 1874.
We, EMIL KÖNIGS and JAMES HENDERSON, both of Irvine, in the
County of Ayr, North Britain, Manufacturing Chemists, do hereby
declare the nature of the said Invention for "IMPROVEMENTS IN OBTAINING
SULPHATE OF SODA OR OF POTASH, HYDROCHLORIC ACID, AND CHLORINE," to be as
follows, that is to say:-
This Invention relates to improvements and modifications in processes
of the kind described in the Specifications of Letters Patent, Nos. 853,

page_text: *1305, of 1781, and No. 571 of 1872, granted to Emil Königs, one of the
present applicant, and No. 1642 of 1871, granted to both the present
applicants.
It consists, firstly, in using iron salts or iron itself, or even an iron
apparatus, in effecting the decomposition, or any iron compound capable
of acting in the chemical action which takes place when chlorides of
sodium or potassium admixed with it is exposed in a heated state to
the alternate or continuous action of sulphurous acid and air or air
and steam, as described in 'the carlier Specifications herein-before
referred to.
Instead of artificially mixing salt with materials containing iron
mixtures that occur in nature such as chloride of sodium and ferru-
ginous clay may be employed and treated in the same manner as and
acted on similarly to artificial mixtures, as described in the carlier
Specifications, the iron in these natural mixtures insuring the reaction
wanted.
Iron residues, solid or liquid, from manufactures, such as the mixture
of chloride of iron and alkaline salts produced in precipitating copper
with iron, may be employed either to mix in a dry, state with chloride
of sodium or as a liquid to moisten the chloride of sodium before forming
this material into pieces, which are to be exposed to the action of
sulphurous acid and air, or sulphurous acid, air, and steam.
A small quantity of iron or iron compound is sufficient to insure the
perfect decomposition of the chlorides, and it is for some purposes (such
as the manufacture of soda ash from sulphate of soda or carbonate of
potash from sulphate of potash) not necessary to free the resulting
sulphate from iron, as it can be produced according to this process with
no more than one per centum of iron in it, and even less.
gases of
In other modifications volatilised chloride of iron or the chlorine pro-
duced from this substance is made to act on the mixed
sulphurous acid, steam, and air to produce a gaseous mixture that will
promote the decomposition of even pure alkaline chlorides without
mixing these chlorides with iron or substances containing iron, or using
natural mixtures of alkaline chlorides which already contain iron.
Thus the vapor of chloride of iron is admitted into a chamber or other
receptacle heated to from 600 to 900 degrees Fahrenheit, and at the

page_text: same time at other openings of the chamber sulphurous acid obtained.
from pyrites, burners, or otherwise, and air and steam are admitted..
The masses exposed in the chamber to the action of the gases are either.
chloride of sodium or chloride of potassium, preferably formed into
pieces before being charged into the chamber or other receptacle.. The
chloride of iron employed is by preference produced by the action of
hydrochloric acid gas on iron oxide at temperatures between 400 and
700 degrees Fahrenheit when chloride of iron is volatilised.
By another modification of the process a mixture of hydrochloric gas and
air is passed over or through oxide of iron at a temperature of between
600 and 900 degrees Fahrenheit, and the resulting gases are passed
admixed with sulphurous acid from any source and with steam or air
and steam over or through chloride of sodium or chloride of potassium
at a. temperature of 300 degrees Fahrenheit and upwards, care being
taken not to fuse the salt.
:
By another modification the gases, sulphurous acid, air and steam,
and hydrochloric acid gas are passed together over or through red hot
iron oxide, and after this over or through chloride of sodium or of
potassium at a temperature of 300 degrees Fahrenheit or upwards.
By another modification the gases from the muffles or close furnaces,
in which burnt copper ore and salt are calcined, are mixed with the
gases from pyrites, burners, or sulphurous acid of any kind, and these
mixed gases are moistened and passed over or through chloride of;
sodium or of potassium at a temperature of 300 degrees Fahrenheit or,
upwards, care being taken not to fuse the mass.
:
:
Another modification is to evaporate the alkaline and iron salts pro-"
duced in the copper process to dryness, and mix them with the burnt
ore in a sufficient quantity to replace wholly or in part the common salt
used in the process herein-before described. By this means the gases
obtained are richer in chlorine than those produced with common salt,
and are mixed with steam and sulphurous acid or with air and steam
and sulphurous acid, and are passed over or through chloride of sodium®
or of potassium.
By using a smaller proportion of sulphurous acid and steam in some
cases chlorine is produced when acting on large masses and the hiszelno

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said Emil Königs and James Henderson in the Great
Seal Patent Office on the 14th November 1874.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, EMIL
KÖNIGS, of Irvine, in the County of Ayr, North Britain, Manufac-'
turing Chemist, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Sixteenth day of May, in the year of
our Lord One thousand eight hundred and seventy-four, in the thirty-
seventh year of Her reign, did, for Herself, Her heirs and successors,
give and grant unto me, the said Emil Königs and to James Hen-
derson, since deceased, Her special licence that we, the said Emil Königs
and James Henderson, our executors, administrators, and assigns, or such
others as we, the said Emil Königs and James Henderson, our 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 “IMPROVEMENTS IN
OBTAINING SULPHATE OF SODA OR OF POTASH, HYDROCHLORIC ACID, AND CHLORINE,”
upon the condition (amongst others) that we, the said Emil Königs
and James Henderson, our executors or administrators, by an instru-
ment in writing under our, or thoir, or one of their hands and seals,
should particularly describe and ascertain the nature of the said Inven-
tion, 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

page_text: Patent.
NOW KNOW YE, that I, the said Emil Königs, do hereby declaro
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 in writing, that is to say:
34
The said Invention relates to improvements and modifications in pro-
cesses of the kind described in the Specifications of Letters Patent,
Nos. 853, 1305, of 1871, and No. 571, of 1872, granted to Emil Königs,
O and No. 1642, of 1871, granted to Emil Königs and James Henderson.
The present Invention consists, firstly, in using iron salts or iron
itself, or even an iron apparatus, in effecting the decomposition or any
iron compound capable of acting in the chemical action which takes
place when chlorides of sodium or potassium admixed with it is exposed
in a heated state to the alternate or continuous action of sulphurous acid
and air or air and steam, as described in the earlier Specifications herein-
before referred to.
Instead of artificially mixing salt with materials containing iron,
mixtures that occur in nature, such as chloride of sodium and ferru-
ginous clay or rock salt, which is generally of this nature, may be
employed and treated in the same manner as and acted on similarly to
artificial mixtures, as described in the earlier Specifications, the iron in
these natural mixtures insuring the reaction wanted.
Iron residues, solid or liquid, from manufactures, such as the mixture
of chloride of iron and alkaline salts, obtained by calcining burnt pyrites
with common salt, and afterwards washing cut the soluble salts
and precipitating the copper with iron, may be employed either to mix
in a dry state with chloride of sodium or as a liquid to moisten the
chloride of sodium before forming this material into pieces, which are to
be exposed to the action of sulphurous acid and air, or sulphurous acid,
air, and steam.
A small quantity of iron or iron compound is sufficient to insure the
perfect decomposition.of the chlorides, and it is for some purposes (such
as the manufacture of soda ash from sulphate of soda or carbonate of

page_text: :
potash from sulphate of potash) not necessary to free the resulting
sulphate from iron, as it can be produced according to this process witli
no more than 1 per centum of iron in it, and even less.
In other modifications volatilised chloride of iron, or the chlorine
produced from this substance, is made to act on the mixed gases of
sulphurous acid, steam, and air to produce a gaseous mixture that will
promote the decomposition of even pure alkaline chlorides. without
mixing these chlorides with iron or substances containing iron, or using
natural mixtures of alkaline chlorides. which already contain iron. Thus
the vapor of chloride of iron is to be admitted into a chamber or
receptacle heated to from 600 to 900 degrees Fahrenheit, and at the same
țime at other openings of the chamber sulphurous acid obtained from
pyrites, burners, or otherwise, and air and steam are admitted. The masses
exposed in the chamber or chambers to the action of the gases are either
chloride of sodium or chloride of potassium formed into pieces before
being charged into the chamber or receptacle. The chloride of iron
employed is by preference produced by the action of hydrochloric acid
gas on iron oxide at temperatures between 400 and 700 degrees Fahren-
heit when chloride of iron is volatilised.
By another modification of the process a mixture of hydrochloric
acid gas and air is passed over or through oxide of iron at a temperature
between 600 and 900 degrees Fahrenheit, and the resulting gases are
passed admixed with sulphurous acid from any source, and with steam'
or air and steam, over or through chloride of sodium or chloride of
potassium at a temperature of 300 degrees Fahrenheit and upwards,
care being taken not to fuse the salt.
'
:
By another modification the gases, sulphurous acid, air and steam,
and hydrochloric acid gas are passed together over or through red hot
iron oxide, and after this over or through chloride of sodium or of
potassium at a temperature of 300 degrees Fahrenheit or upwards.
By another modification the gases from the muffles or close furnaces,;
in which burnt copper ore and salt arc calcined, are mixed with the
gases from pyrites, burners, or sulphurous acid of any kind, and these
mixed gases are moistened and passed over or through chlorido of
sodium or of potassium at a temperature of 300 degrees Fahrenheit or
upwards, care being taken not to fuse the mass..

page_text: 1. Another modification is to evaporate the alkaline and iron salts pro-
duced in the copper process to dryness, and mix them with the burnt
ore in a sufficient quantity to replace wholly or in part the common salt
used in the process herein before described. By this means the gases:
obtained are richer in chlorine than those produced with common salt,
and are mixed with steam and sulphurous acid.or with air and steam
and sulphurous acid, and are passed over or through chloride of sodium
or of potassium.
By using a smaller proportion of sulphurous acid and steam in some
cases chlorine is produced when acting on large masses, and the hydro-
chloric acid gas is freer from moisture, and can be converted into
chlorine with greater certainty and ease than that produced in tho
ordinary way.
:
In the various processes herein-before described a series of communi-
cating chambers or receptacles may be employed, so as to exhaust the
action of the gases on the chlorides; and when it is found that the
sulphurous acid produced by the pyrites, burners, or sulphur ovens is:
not of sufficiently high temperature to effect with certainty and economy
the decomposition of the common salt or the chloride of potassium in
the chambers, the sulphurous acid and other mixed gases may. be
passed through the close muffle furnaces in which the burnt copper orc
is being calcined with common salt or chloride of iron, or a mixture of
the two chlorides; and this process may, if necessary, and without
detriment to the copper process, be carried on at a greatly higher tem-
perature, in order to heat the mixed gases to the proper temperature to:
insure the regular, economical, and complete decomposition of the
chloride of sodium or of potassium in the chambers. Or the process
may be varied in this manner: The mixed, gases produced from the
close muffle furnaces in which burnt copper ore and common salt arc
being calcined (as in the well-known Henderson process for extracting
copper from its ores) are first passed through the first and newly,
charged chamber of a series of chambers in which common salt or
chloride of potassium is being exposed to the action of sulphurous acid
or sulphurous acid, steam, and air.
The action of the gases from the copper furnaces is very energetic, and
the temperature can be raised or lowered to suit the requirements of the

page_text: chambers in which the chlorides of sodium or of potassium are being
decomposed, so as to dispense wholly or in part with the use of fuel for
heating the said chambers externally. In a series of chambers filled with
alkaline chloride by this modification the materials in the first or newly
charged chamber would be heated up and partly decomposed by the
gases from the copper furnaces alone, which after passing through the
first chamber would join the sulphurous acid from the burners at the
entrance to the second chamber, and mixed with the sulphurous acid
ness onwards through the others

page_text: reaction before admitting sulphurous acid, in the manner and for the
purposes herein-before described.
In witness whereof, I, the said Emil Königs, on behalf of myself
and the administrators of the late James Henderson, have here-
unto set my hand and seal, this Eleventh day of November,
in the year of our Lord One thousand eight hundred and seventy-
four.
Witness,
EDMUND HUNT,
Patent Agent,
Glasgow.
EMIL KÖNIGS. (L.S.)