IMPROVEMENTS IN TREATING ORES AND SUBSTANCES CONTAINING ANTIMONY, AND IN APPARATUS EMPLOYED THEREIN." PROVISIONAL SPECIFICATION
Year: 1881

page_text: LETTERS PATENT to John Hargreaves, of Widnes, in the County of Lancaster,
Chemist, and Thomas Robinson, of the same Place, Iron Founder, for an
Invention of "IMPROVEMENTS IN TREATING ORES AND SUBSTANCES CONTAINING
ANTIMONY, AND IN APPARATUS EMPLOYED THEREIN."
PROVISIONAL SPECIFICATION left by the said John Hargreaves and
Thomas Robinson at the Office of the Commissioners of Patents on the
12th April 1881.
JOHN HARGREAVES, of Widnes, in the County of Lancaster, Chemist, and
THOMAS ROBINSON, of the same Place, Iron Founder. "IMPROVEMENTS IN
TREATING ORES AND SUBSTANCES CONTAINING ANTIMONY, AND IN APPARATUS
EMPLOYED THEREIN.'
"
The Invention relates more especially to the treatment of antimonious ores and
substances containing sulphur, and contaminated with lead and arsenic or mixed
with a large amount of gangue.
The main objects are to obtain economically and quickly metallic antimony
relatively free from admixture or contamination, to eliminate the sulphur in an
available condition, to recover and re-use hydrochloric acid employed in the treatment,
and to provide suitable apparatus.
In carrying the Invention into practice,- First, finely divided ores or substances
containing antimony are subjected in a suitable vessel, or suitable vessels, to the
action of heated hydrochloric acid of specific gravity not less than 1.06. The
temperature of the acid is gradually raised during the treatment, and finely
divided ores or substances added until as much antimony as possible has been
dissolved.
"
Second. The solution of chloride of antimony after being allowed to settle is
decanted or run into a vat or vats, and any excess of or free hydrochloric acid is
partially neutralized with lime, magnesia, or other convenient alkaline substance,
for the purpose of reducing the quantity of iron or zinc required for precipitating
the antimony, and for diminishing the amount of antimonuretted hydrogen evolved
during precipitation.
Third. The neutralized solution above mentioned when settled and clear is
decanted or run into a tank or tanks maintained at a suitable temperature by
means of heat applied direct to the said solution or externally to the tank or tanks,

page_text: and antimony is precipitated by the addition of metallic iron or zinc to the said
solution.
The precipitate obtained as above described is drained, pressed, dried, and fused
with alkali and carbon in a crucible in any usual or desired manner.
The antimonious ores or substances when not naturally in a sufficiently fine
state of division should be ground or pulverized until they will pass through a
sieve having meshes of about two millimetres in diameter.
When the said ores or substances contain much gangue of such a nature as to
neutralize the hydrochloric acid the treatment should be carried on in a series of
vessels having openings, through which the undissolved gangue may be removed
from time to time.
It is desirable that a partial vacuum should be maintained in the vessel or vessels
mentioned under the first part of the process, so that the sulphuretted hydrogen
generated may pass freely away.
The hydrochloric acid used in dissolving the antimonious ores and substances
should be as strong as possible, and suitable acid may be conveniently obtained as
a bye product in the manufacture of sulphate of soda; as however such acid usually
contains arsenic the said arsenic should be precipitated by means of sulphide of
antimony before the acid is used.
The precipitate obtained in the third part of the process is preferably washed
with a solution of chloride of antimony, hydrochloric acid, and water, in order to
remove any metallic iron, zinc, lead, or other impurities which would render the
metallic antimony less valuable.
Sulphuretted hydrogen evolved in the reaction under the first part of the process
is treated as follows:-
The said sulphuretted hydrogen is passed through cooling pipes, scrubbers, or
condensers of any usual or desired construction, in which chloride of antimony and
hydrochloric acid carried over are condensed and recovered, and the said sulphuretted
hydrogen freed, as above set forth, from chloride of antimony, and hydrochloric
acid is passed through a series of chambers containing oxide of iron for decomposing
the gas and absorbing the sulphur; or the said sulphuretted bydrogen is passed
directly into the hot sulphurous acid flue leading from the pyrites burners to vitriol
chambers, or to the converting cylinders of the Hargreaves & Robinson direct action
sulphate of soda plant.
The hydrochloric acid employed under the first part is recovered for re-use in
manner following:-The chloride of iron solution formed under the third part is
evaporated to dryness, and then roasted in a muffle furnace in the presence of air
and water vapour. The chlorine combined with the iron is liberated as hydrochloric
acid, and is again used for dissolving antimonious ores or substances.
When the ores or substances are sufficiently free from arsenic they may be treated
under the first part as follows:--The sulphuretted hydrogen evolved whilst the
antimonious ores or substances are being dissolved is oxidized by binoxide of
manganese or perchloride of iron added to the solution, or by means of air blown
therethrough. The sulphur is precipitated, and the chloride of antimony is treated,
as set forth under the second and third parts..
Apparatus suitable for carrying our Invention into practice is constructed
advantageously as follows:-The vessels under the first part are of stone or are
made of or lined with metallic antimony, or an alloy thereof, and are provided with
a loosely fitting cover, or a cover having a safety valve. From the said cover or
from the side of the vessel a pipe leads to the series of chambers or to the
sulphurous acid flue mentioned under the head treating of the utilization of the
sulphuretted hydrogen evolved. The said vessels are provided with suitable means
for heating their contents, either externally or internally. The vat or vats under
the second part are of wood or any convenient material. The tanks under the
third part are of stone, wood, or other suitable material, and are provided with loose
cowls or hoods for carrying off the antimonuretted hydrogen evolved.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed
by the said John Hargreaves and Thomas Robinson in the Great Seal Patent
Office on the 11th October 1881.
JOHN HARGREAVES, of Widnes, in the County of Lancaster, Chemist, and
THOMAS ROBINSON, of the same Place, Ironfounder. "IMPROVEMENTS IN
TREATING ORES AND SUBSTANCES CONTAINING ANTIMONY, AND IN APPARATUS
EMPLOYED THEREIN."
"
The Invention relates more especially to the treatment of antimonious ores and
substances containing sulphur, and also those contaminated with lead and arsenic
or mixed with a large amount of gangue. It is also applicable to all kinds of
antimonious ores or substances in which the antimony is or can be made to become
soluble in hydrochloric acid.
The main objects are to obtain economically and quickly metallic antimony
relatively free from admixture or contamination to eliminate the sulphur in an
available condition to recover and re-use hydrochloric acid employed in the treat-
ment, and to provide suitable apparatus.
In carrying the Invention into practice, first, finely divided ores or substances
containing antimony are subjected in a suitable vessel or suitable vessels to the
action of heated hydrochloric acid of specific gravity not less than 106. The
temperature of the acid is gradually raised during the treatment, and finely divided
ores or substances added until as much antimony as possible has been dissolved
by the acid. In this part of the operation, the sulphur present in the form of
sulphide of antimony is liberated in the form of sulphuretted hydrogen.
Second. The solution of chloride of antimony after being allowed to settle is
decanted or run into a vat or vats, and any excess of hydrochloric acid is partially
neutralized with lime, magnesia, or other convenient alkaline substance for the
purpose of reducing the quantity of iron or zinc required for precipitating the
antimony, and for diminishing the amount of antimonuretted hydrogen evolved
during precipitation.
Third. The neutralized solution above mentioned when settled and clear is
decanted or run into a tank or tanks and maintained at a suitable temperature,
say, by means of heat applied direct to the said solution, or externally to the tank
or tanks when necessary, and antimony is precipitated by the addition of metallic
iron or zinc to the said solution.
The precipitate obtained as above described is drained, pressed, dried, and fuseḍ
with alkali and carbon in a crucible in any usual or desired manner.
Referring to the first part, we would point out:-(A.) The antimonius ores or
substances when not naturally in a sufficiently fine state of division should be
ground or pulverized until they will pass through a sieve having meshes about two
millimeters in diameter.
The fineness of division should be such that everything will pass through a
sieve of two millimeters in opening, and by preference finer and down to an
impalpable powder.
(B.) When the said ores or substances contain much gangue of such a nature as
to neutralize the hydrochloric acid, such as carbonate of lime, the treatment should
be carried on in a series of vessels, having openings through which the undissolved
gangue may be removed from time to time, by which means the basic materials
in the ores other than antimony are used to neutralize the excess of acid present in
the antimony solution.
(C.) It is desirable that a partial vacuum should be maintained in the vessel or

page_text: vessels in which the ores or substances are dissolved, so that the sulphuretted
hydrogen generated may pass freely away without entering the atmosphere so as
to annoy the workmen.
(D.) The hydrochloric acid used in dissolving the antimonious ores and substances
should be as strong as possible, and suitable acid may be conveniently obtained as
a bye-product in the manufacture of sulphate of soda. As however such acid
usually contains arsenic, the said arsenic should be precipitated by means of
sulphide of antimony before the acid is used. We find however that in some
instances the previous precipitation of the arsenic in the acid may be dispensed
with when the presence of sulphide of arsenic in the insoluble residue is not
objectionable.
(F.) The precipitated antimony obtained in the third part of the process is
preferably washed with a solution of chloride of antimony, hydrochloric acid, and
water in order to remove any metallic iron, zinc, lead, or other impurities which
would render the metallic antimony less valuable.
(F.) Sulphuretted hydrogen evolved in the reaction is treated as follows:-
-The
said sulphuretted hydrogen is passed through cooling pipes, scrubbers, or condensers
of any usual or desired construction in which the whole or part of the chloride of
antimony and hydrochloric acid carried over are condensed and recovered, and
the said sulphurretted hydrogen freed, as above set forth, from chloride of antimony,
and hydrochloric acid is passed through a series of chambers containing oxide of
iron for decomposing the gas and absorbing the sulphur; or the said sulphuretted
hydrogen is passed directly into the hot sulphurous acid flue leading from the
pyrites burners to vitriol chambers, or to the converting cylinders of the Hargreaves
and Robinson direct action sulphate of soda plant.
(G). The hydrochloric acid employed under the first part is recovered for re-use
in manner following:-The chloride of iron solution formed under the third part is
evaporated to dryness and then roasted in a muffle furnace in the presence of air
and water vapour.
The chlorine combined with the iron, together with any free
bydrochloric acid is liberated as hydrochloric acid and again used for dissolving
antimonious ores or substances.
(H). When the ores or substances are sufficiently free from arsenic they may be
treated as follows:-
The sulphuretted hydrogen evolved whilst the antimonious ores or substances
are being dissolved is oxidized or acted upon by binoxide of manganese or
perchloride of iron added to the solution, or by means of air blown therethrough
when a solution of iron is present. The sulphur is precipitated and the chloride of
antimony is treated as set forth under the second and third parts.
(I). Apparatus suitable for carrying our Invention into practice is constructed
advantageously as follows:-The dissolving vessels are of stone, or are made of or
lined with metallic antimony or an alloy thereof, and are provided with a loosely
fitting cover or a cover having a safety valve or equivalent arrangement to allow
exit of gases in case of suddenly developed internal pressure. We may here
remark that in actual working we find the following arrangement to be the most
convenient and practical. In the latter mentioned fixed cover of the dissolving
vessel we make an opening of about 6 inches diameter through which the ore is
charged, and the said opening is closed by a cover or valve which is surrounded
or covered by finely powdered ore or substance so as to form a lute and close up
any leakage around about the valve. In the event of a suddenly developed
pressure the said small valve or cover is lifted and the gases allowed to escape into
the air. From the said cover or from the side of the said dissolving vessel a pipe
leads to the series of chambers or to the sulphurous acid flue mentioned under the
head F in the third part, which refers to the utilization of the sulphuretted
hydrogen evolved. The said dissolving vessels are provided with suitable means
for heating their contents either externally or internally. The vat or vats under
the second part are of wood or any convenient material. The tanks under the
third part are of stone, wood, or other suitable material, and are or may be

page_text: provided with loose cowls or hoods for carrying off the antimonuretted bydrogen
evolved.
Having now described and particularized our said Invention in such manner that
others will be enabled to carry our improvements into effect, we claim,-
First. Obtaining chloride of antimony by treating ores and substances with
suitable hydrochloric acid, substantially in the manner and for the purpose herein
set forth under the first head.
Second. Treating sulphuretted hydrogen liberated under the first part whilst
producing chloride of antimony, and the means to avoid nuisance from escape of
the sulphuretted hydrogen, all substantially as described under C and F for the
purpose set forth.
Third. Recovering hydrochloric acid for re-use, substantially by the treatment
described herein under G.
Fourth. The manner of treatment described under H for the purpose set forth.
Fifth. Neutralizing the free hydrochloric acid in the chloride of antimony
solution, substantially as set forth under the second head and under B.
Sixth. Precipitating metallic antimony from the said chloride of antimony by
the addition of metallic iron or zinc to the said solution obtained, substantially as
described under the first and second heads, all substantially as herein set forth
under the third head.
Seventh. The treatment of the precipitated antimony in the manner and for the
purpose set forth under E.
Eighth. The processes and apparatus constructed, arranged, and combined to act
conjointly, substantially as herein described for the purposes set forth.
Ninth. The use of a covered vessel or vessels, substantially as described under I,
for the purpose set forth.
In witness whereof, I, the said John Hargreaves, have hereunto set my hand
and seal, this Seventh day of October, in the year of our Lord One
thousand eight hundred and eighty one.
TATT11
JOHN
TT
(94)