IMPROVEMENTS IN THE MANUFACTURE OF SALTS OF BARIUM AND OTHER SALTS, WHICH IMPROVEMENTS ARE ALSO APPLICABLE TO THE EXTRACTION OF SILVER FROM ARGENTIFEROUS PYRITES.”
Year: 1876

page_text: LETTERS PATENT to Roger William Wallace, of the Chemical Works, New
Road, Battersea Park, in the County of Surrey, Manufacturing Chemist, and
Carl Friedrich Claus, of Great St. Helen's, in the City of London, Consulting
Chemist, for the Invention of "IMPROVEMENTS IN THE MANUFACTURE OF SALTS
OF BARIUM AND OTHER SALTS, WHICH IMPROVEMENTS ARE ALSO APPLICABLE TO
THE EXTRACTION OF SILVER FROM ARGENTIFEROUS PYRITES.”
PROVISIONAL SPECIFICATION left by the said Roger William Wallace and
Carl Friedricho Claus at the Office of the Commissioners of Patents on the 19th
July 1876.
ROGER WILLIAM WALLACE, of the Chemical Works, New Road, Battersea Park, in
the County of Surrey, Manufacturing Chemist, and CARL FRIEDRICH CLAUS, of Great
St. Helen's, in the City of London, Consulting Chemist. "IMPROVEMENTS IN THE
MANUFACTURE OF SALTS OF BARIUM AND OTHER SALTS, WHICH IMPROVEMENTS
ARE ALSO APPLICABLE TO THE EXTRACTION OF SILVER FROM AGENTIFEROUS
PYRITES."
This Invention relates to the production of hyposulphite of baryta, from which
we produce the other hyposulphites by double decomposition with their respective
sulphates. The hyposulphite we produce in the following manner :- -We first
prepare sulphide of barium by heating native sulphate of baryta together with
carbonaceous materials. Of this sulphide of barium we prepare a solution, and
inject into the same sulphurous acid gas obtained in any convenient manner, for
instance, by burning sulphide of hydrogen in contact with atmospheric air or from
the roasting of pyrites, or by blowing a current of air over burning sulphur. To
force the sulphurous acid into the liquid a blowing engine may be employed or a
steam injector.
The effect of the sulphurous acid gas upon the sulphide of barium solution is the
formation of hyposulphite of baryta, which precipitates in a crystalline white
powder, which we separate from the mother liquor by filtration, and wash it with
clean water. Mother liquor and washings contain a small quantity of hyposulphite
of baryta in solution, and in order that this may not be lost we use the same for
dissolving fresh quantities of sulphide of barium.
The precipitate of hyposulphite of baryta after being drained we either dry and
Price Ad

page_text: use it as such, or we use the same in the moist state for the decomposition of
alkaline sulphates or the sulphates of other bases forming soluble hyposulphites.
For instance, the reaction just above described may be made of the most important
use in the extraction of silver from roasted argentiferous pyrites. It is well known that
hyposulphite of soda has a more than 20 times greater dissolving power for chloride
of silver than the common salt usually employed.
In the process of chloridising, roasting of argentiferous pyrites, that is to say, in
the roasting of pyrites with common salt, a quantity of sulphate of soda is formed,
which enters into solution during the process of lixidation with water. Into this
liquor of the extracting vats containing sulphate of soda we mix an equivalent
quantity of the hyposulphite of baryta; the sulphate of baryta formed is separated
and the supernatant liquor containing the hyposulphite of soda is used for the
extraction of silver by dissolving the chloride of silver in the ore.
Native sulphate of baryta being almost invariably found near metalliferous
deposits, and the sulphurous acid being readily obtained from roasting of pyrites,
the cost of the use of hyposulphite of baryta is actually less than that of common
salt; besides this, it does not "foul" the liquors so soon as the salt does.
In preparing commercial hyposulphites from the hyposulphite of baryta the
sulphates are mixed with the same in equivalent quantities; the sulphate of baryta
formed is washed and filtered off and used as pigment, whilst the filtrate is boiled
down and crystallized in the usual manner, such (as for instance, hyposulphite of
soda); as to the other hyposulphites, such as that of alumina, zinc, and the like,
also used in the arts, these may be used in this manner most convenient for the
purpose.
Our Invention relates further to the manufacture of precipitated carbonate of
baryta and chloride of barium from materials not hitherto used for that purpose, and
the employment of which makes the production possible of these salts at a very low
cost, so that the same may be employed for purposes from which their cost of
production now excludes them.
We prepare carbonate of baryta by preciptating it by means of carbonate of
ammonia or gas liquor froin solutions of sulphide of barium. The precipitate is
washed with water, filtered, and dried, the drying being effected in closed vessels
(preferably by steam), in order to collect and absorb the sulphide of ammonium
given off by sulphuric acid.
The carbonate of baryta obtained is useful, for instance, for the manufacture of
cheap flint glass (it being free from iron), or as a glaze for pottery ware.
The filtrate consisting of a solution of sulphide of ammonium we distil by means
of steam, as with ordinary gas liquor, and the volatilized sulphide of ammonium
we convey into sulphuric acid or hydrochloric acid, whereby sulpbide of hydrogen
is liberated and sulphate or chloride of ammonium is formed.
Or we
The sulphide of hydrogen given off we convey into a burner (with the necessary
precautions against explosions) and burn the same in combination with atmospheric
air into sulphurous acid, which we employ for injecting, as described, into solutions
of sulphide of barium for the manufacture of hyposulphite of baryta.
concentrate the sulphide of ammonium filtrate by distillation at the most suitable
temperatures (in the manner known to manufacturers and now practised with weak
carbonate of ammonia solutions), and pass sulphurous acid gas diluted with air or
other gases through the same, whereby we obtain some sulphate of ammonia, but
also considerable quantities of hyposulphite of ammonia. This liquor we decompose
by sulphuric acid for the purpose of manufacturing commercial sulphate of
ammonia therefrom. Free sulphur is separated, and we collect and melt the same
into cakes, and sulphurous acid gas is given off, which we convey into the lead
chambers for the manufacture of sulphuric acid. This sulphurous acid gas being
unmixed with other gases and containing already two equivalents of oxygen in
combination and only requiring one more to form sulphuric acid enables tho
chambers to produce three times the quantity of sulphuric acid in the same cubic
space.

page_text: We also manufacture carbonate of baryta and byposulphite of soda by decomposing
the hyposulphite of baryta obtained as above with carbonate of soda.
Our Invention relates further to a method of manufacturing chloride of barium
from a material not hitherto used for that purpose, that is to say, by heating the
refuse resulting from the manufacture of acetic acid from acetate of lime and
hydrochloric acid (and which consists principally of chloride of calcium and tarry
matters), together with native sulphate of baryta and carbonaceous materials. By
this operation chloride of barium is formed, which dissolves out readily with water,
leaving behind undissolved sulphide of calcium, similar to that forming alkali waste
in the manufacture of alkali. If the solution should contain any sulphur compound
we destroy the same by the action of chlorine on the same, but generally there is
very little sulphur in the solution.
By lixiviating the flux with hot water a solution may be obtained strong enough
for crystallization. If cold water be used for lixiviating the liquor is boiled down
and crystallized by cooling. The mother liquor we use for dissolving. fresh
quantities of the crude chloride of barium.
Any sulphur compounds present in the liquor may also be destroyed by gently
heating or calcining the crude crystals of chloride of barium and redissolving and
recrystallizing the same.
SPECIFICATION in pursuance of the conditions of the Letters Patent filed by the
said Roger William Wallace and Carl Friedrich Claus in the Great Seal Patent
Office on the 19th January 1877.
ROGER WILLIAM WALLACE, of the Chemical Works, New Road, Battersea Park, in
the County of Surrey, Manufacturing Chemist, and CARL FRIEDRICH CLAUS, of Great
St. Helen's, in the City of London, Consulting Chemist. "IMPROVEMENTS IN
THE MANUFACTURE OF SALTS OF BARIUM AND OTHER SALTS, WHICH IMPROVEMENTS
ARE ALSO APPLICABLE TO THE EXTRACTION OF SILVER FROM ARGENTIFEROUS
PYRITES."
This Invention relates to the production of hyposulphite of baryta, from which
we produce the other hyposulphites by double decomposition with their respective
sulphates. The hyposulphite we produce in the following manner:-1
-We first
prepare sulphide of barium by heating native sulphate of baryta together with
carbonaceous materials. Of this sulphide of barium we prepare a solution and
inject into the same sulphurous acid gas obtained in any convenient manner, for
instance, by burning sulphide of hydrogen in contact with atmospheric air or from
the roasting of pyrites, or by blowing a current of air over burning sulphur. To
force the sulphurous acid into the liquid a blowing engine may be employed or a
steam injector.
The effect of the sulphurous acid gas upon the sulphide of barium solution is the
formation of hyposulphite of baryta, which precipitates in a crystalline white
powder, which we separate from the mother liquor by filtration, and wash it with
clean water. Mother liquor and washings contain a small quantity of hyposulphite
of baryta in solution, and in order that this may not be lost we use the same for
dissolving fresh quantities of sulphide of barium.
The precipitate of hyposulphite of baryta after being drained we either dry and
use it as such, or we use the same in the moist state for the decomposition of
alkaline sulphates, or the sulphates of other bases forming soluble hyposulphites.
For instance, the reaction just above described may be made of the most important
use in the extraction of silver from wasted argentiferous pyrites. It is well known
that hyposulphite of soda has a more than 20 times greater dissolving power for
chloride of silver than the common salt usually employed.
In the process of chloridising or washing of argentiferous pyrites, that is to say, in

page_text: the roasting of pyrites with common salt, a quantity of sulphate of soda is formed,
which enters into solution during the process of lixiviation with water. Into this
liquor of the extracting vats containing sulphate of soda we mix an equivalent
quantity of the hyposulphite of baryta ; the sulphate of baryta formed is separated,
the superabundant liquor containing the hyposulphite of soda is used for the
extraction of silver by dissolving the chloride of silver in the ore.
Native sulphate of baryta being almost invariably found near metalliferous
deposits, and the sulphurous acids being readily obtained from wasting of pyrites,
the cost of the use of hyposulphite of baryta is actually less than that of common
salt; besides this, it does not foul the liquors as soon as the salt does.
In preparing commercial hyposulphites from the hyposulphite of baryta the
sulphates are mixed with the latter in equivalent quantities, the sulphate of baryta
formed is washed and filtered off and used as pigment, whilst the filtrate is boiled
down and crystallized in the usual manner, such (as for instance, hyposulphite of
soda). As to the other hyposulphites, such as that of alumina, zinc, and the like,
also used in the arts, these may be employed in the manner most convenient
for the purpose.
Our Invention relates further to the manufacture of precipitated carbonate of
baryta and chloride of barium from materials not hitherto used for that purpose, and
the employment of which makes the production possible of these salts at a very
low cost, so that the same may be employed for purposes from which their cost of
production now excludes them.
We prepare carbonate of baryta by precipitating it by means of carbonate of
ammonia or gas liquor from solutions of sulphide of barium. The precipitate is
washed with water, filtered, and dried, this drying being effected in closed vessels
(preferably by steam), in order to collect and absorb the sulphide of ammonium
given off by sulphuric acid.
The carbonate of baryta obtained is useful, for instance, for the manufacture of
cheap flint glass (it being free from iron), or as a glaze for pottery ware.
The filtrate consisting of a solution of sulphide of ammonium we distil by means
of steam, as in the ordinary gas liquor, and the volatilised sulphide of ammonium
we convey into sulphuric acid or hydrochloric acid, whereby sulphide of hydrogen
is liberated and sulphate or chloride of ammonium is formed.
The sulphide of hydrogen given off we convey into a burner (with the necessary
precautions against explosions), and burn the same in combination with atmospheric
air into sulphurous acid, which we convey into the sulphuric acid chambers for the
manufacture of sulphuric acid therefrom, or we employ it, as stated above, for
injecting the same into solutions of sulphide of barium for the manufacture of
byposulphite of baryta. Or we also proceed in the following manner, namely, we
concentrate the sulphide of ammonium filtrate by distillation at the most suitable
temperatures (in the manner known to manufacturers and now practised with
weak carbonate of ammonia solutions), pass sulphurous acid gas, which may be
diluted with air or other gases, through the same, whereby we obtain some sulphate
of ammonia, but also considerable quantities of hyposulphite of ammonia.
liquor we decompose by sulphuric acid, for the purpose of manufacturing commercial
sulphate of ammonia therefrom. Free sulphur is then separated, and we collect and
melt the same into cakes, and sulphurous acid gas is given off, which we convey
into the lead chambers for the manufacture of sulphuric acid. This sulphurous
acid gas being unmixed with other gases and containing already two equivalents of
oxygen in combination, and only requiring one more to form sulphuric acid, enables
the chambers to produce three times the quantity of sulphuric acid in the same
cubic space.
This
We also manufacture carbonate of baryta and hyposulphite of soda by decomposing
the hyposulphite of baryta obtained as above with carbonate of soda.
Our Invention relates further to a method of manufacturing chloride of barium
from a material not hitherto used for that purpose, that is to say, by heating the
refuse resulting from the manufacture of acetic acid from acetate of lime and

page_text: hydrochloric acid (and which consists principally of chloride of calcium and tarry
matter), together with native sulphate of baryta and carbonaceous materials. By
this operation chloride of barium is formed, which dissolves out readily with water,
leaving behind undissolved sulphide of calcium similar to that forming alkali waste
in the manufacture of alkali. If the solution should contain any sulphur compound
we destroy the same by the action of chlorine on the same, but generally there is
very little sulphur in the solution.
By lixiviating the flux with hot. water a solution may be obtained strong enough
for cystallization. If cold water be used for lixiviating the liquor is boiled down
and crystallized by cooling. The mother liquor we use for dissolving fresh quantities
of the crude chloride of barium.
Any sulphur compounds present in the liquor may also be destroyed by gently
heating or calcining the crude crystals of chloride of barium and redissolving and
recrystallizing the same.
Having thus fully described our said Invention, and shown how the same may be
conveniently and advantageously carried into practise, we claim,—
First. The process of manufacturing hyposulphite of baryta from solutions of
sulphide of barium by exposing the latter to the action of sulphurous acid gas, as
above set forth.
Second. The preparation by double decomposition of commercial hyposulphites
from the hyposulphite of baryta manufactured as above set forth.
Third. The process of manufacturing carbonate of baryta from solutions of
sulphide of barium by the employment of gas liquor and the subsequent distillation
or blowing over of the sulphide of ammonium into sulphuric or hydrochloric acid,
in which process the sulphide of hydrogen is set free, so that it may be utilized in
the manner above described.
Fourth. The process consisting in the concentration of sulphide of ammonium by
fractional distillation, the production of hyposulphite of ammonium therefrom by
injecting sulphurous acid into it, and the recovery of sulphur and sulphurous acid
from such hyposulphite of ammonium by the action of sulphuric acid upon the same,
and the recovery and utilization of the sulphur and sulphurous acid as above
described.
Fifth. The process of manufacturing hyposulphite of soda and carbonate of
baryta, as above described.
Sixth. The manufacture of chloride of barium by treating the waste chloride of
calcium resulting from the manufacture of acetic acid, and together with sulphate
of baryta, as above described.
Seventh. The employment of hyposulphite of baryta for the extraction of silver
from argentiferous ores, as above described.
In witness whereof, I, the said Carl Friedrich Claus, for myself and on behalf
of the said Roger William Wallace, have hereunto set my hand and
seal, this Nineteenth day of January, in the year of our Lord One thousand
eight hundred and seventy-seven.
C. F. CLAUS. (L.S.)