IMPROVEMENTS IN OR APPERTAINING TO THE TREAT-
Year: 1883

page_text: LETTERS PATENT to James Beveridge of Runcorn in the county of Chester
for an Invention of " IMPROVEMENTS IN OR APPERTAINING TO THE TREAT-
PROVISIONAL SPECIFICATION left by the said James Beveridge at the
Office of the Commissioners of Patents on the 6th October 1883.
JAMES BEVERIDGE of Runcorn in the County of Chester
"IMPROVEMENTS IN
OR APPERTAINING TO THE TREATMENT OF ORES (OR OTHER SUBSTANCES) CONTAINING
ANTIMONY BY THE WET PROCESS
Part first:-
"
My process is applicable to the ores and substances containing compounds of
antimony which are soluble in hydrochloric acid.--Preferably I use ores containing
about twenty per cent more or less of antimony. in the form of sulphide (Sb, S.)
and treat the finely pulverized ore in hydrochloric acid of convenient strength with
the aid of heat, obtained either by the injection of steam into the contents of the
containing vessel, or by the outward application of heat to the vessel itself, The
hydrochloric acid acting on the Sb, S, forms trichloride of antimony (Sb Cl,) and
sulphuretted hydrogen (H, S) as is well known. The chloride of antimony remains
in solution in the liquid whilst the sulphuretted hydrogen is liberated in the form
of a gas and is led away through earthenware pipes for further use as described
under parts three and four of this specification.
The vessels which I at present propose to employ for dissolving the antimonial
compounds contained in the ores or substances, are earthenware pots of as large
cubical capacity as possible (those made by Doulton & Co Lambeth Potteries, suit
the purpose admirably) and in order to protect them from rough usage etcetera,
each of them may be inserted into a larger pot made of cast or wrought iron, the
space between the walls of the two pots being filled up with any convenient
mixture, preferably of silicate of soda and asbestos or cement or iron filings and
'

page_text: salammoniac. The compound pot thus formed is set in brickwork, like an ordinary
wash house boiler and is heated by a fire placed underneath. Or a much better
method is to heat them in a steam; in a chloride of calcium, or in an oil bath, as
is usually done. In all cases the pots are covered with a hood of wood or of stone
or of brickwork, means being provided for the escape of the sulphuretted hydrogen
gas. To every cubic foot of hydrochloric acid of specific gravity 1·14 I add a
quantity of ore representing 5 pounds weight of real metallic antimony.
Part second.
The solution thus obtained contains chloride of antimony equivalent to
about 5 pounds weight (more or less) of metallic antimony per cubic foot of liquor
together with a large quantity of free hydrochloric acid and is either syphoned or
otherwise drawn off by means of a suction apparatus into a vessel made preferably
of stone, where it is allowed to settle till clear. It is then removed to another
vessel also of stone (or it may be made of wood) and there is added to it from 4 to
51, times its volume of water which precipitates about 95 per cent (more or less)
of the total antimony operated upon in this part of the process as oxychloride of
antimony, this substance appearing as a white flocculent precipitate which settles
with difficulty and only after continued standing. In order to quickly separate
the precipitated oxychloride of antimony from the liquid, I raise the temperature
of the liquid containing the precipitate by the injection of steam or other convenient
means till it reaches about 140 degrees or 155 degrees Fahrenheit when the
Sb. OCI separates out in the form of a fine crystalline powder which rapidly settles
to the bottom of the vessel. After the liquor (which is practically weak hydro-
chloric acid) is perfectly clear it is run off into a convenient vessel to be further
treated as described under the third part of this specification The above operation
of precipitating and crystallizing Sb. O Cl is repeated several times until a quantity
of precipitate has accumulated in the precipitating vessel where it is washed with
water to get rid of free acid dried and smelted with alkali flux and carbon in the
ordinary way to procure the metal or otherwise treated for the manufacture of
the salts of antimony.
Part Third.
The weak acid which is run off from the precipitating vessel after the
oxychloride of antimony has been precipitated by the aid of heat as described
under part second contains a small quantity of antimony in solution which I
recover in the following manner namely I treat the said acid liquor with a part
of the sulphuretted bydrogen gas evolved from the pots as described under part
first whereby the antimony is precipitated in an insoluble state as sulphate of
antimony. For this purpose the sulphuretted hydrogen gas may be injected into
the acid liquor by any suitable apparatus, such as a pump or steam jet, or the weak
acid may be allowed to flow through an apparatus resembling in principle the
ordinary gas scrubber used in the purification of coal gas whilst the gas itself is
passing through the said scrubber. In practice I prefer to use a tower constructed
of wood, stone or bricks, packed in a convenient manner with prisms of wood or
other material not acted on by weak H Cl. The sulphuretted hydrogen gas ascends
this tower, whilst the weak acid is allowed to flow down it. The antimony
contained in the weak acid is thus precipitated as Sb, S. The extent of the flow
of weak acid liquor is regulated according to the work such a tower is capable of
performing, that is to say, the liquor coming from the tower should after filtration
be perfectly clear, and should not on the addition of an alkaline suphide, give a
precipitate of sulphide of antimony. The flow of weak acid liquor should be
regulated to obtain this result.
The sulphide of antimony is separated from the weak acid by any convenient
means such as settling, and decanting the clear liquor, or by any of the many
methods of filtration. The clear liquor which separates from the sulphide of
antimony is practically weak hydrochloric acid of about degrees -Twaddle,
containing in solution sulphuretted hydrogen gas, and is run into a separate vessel
or vessels for further treatment. The precipitated sulphide of antimony is, washed

page_text: with water, and partially dried by means of a hydroextractor or filter press. It
may be then redissolved as in the first part, or heated to form the black sulphide.
In order to free the weak hydrochloric acid from H, S gas, I inject air through
the liquid by any convenient means, such as an air pump or a steam jet, until it is
nearly all or wholly expelled. I then add a small quantity of chlorine in the form
of gas or bleaching powder, or bleaching powder solution preferably the latter or
other xidising substances so that no trace of sulphuretted hydrogen may remain
in the weak acid.
The weak acid thus purified is pumped on to the "condensers" of alkali works
and is used instead of water for the condensation of hydrochloric acid gas.
Part fourth.
The sulphuretted hydrogen liberated as described under part first may, after
being used as described under part third, be further utilized in many ways. For
example it may be burnt in air for the production of sulphuric acid or absorbed by
a caustic alkali and the sulphide of the alkali made therefrom or it may be absorbed
by moist alkali waste in any convenient apparatus thus producing sulphydrate of
calcium. This sulphydrate of calcium may be decomposed by the joint action
of hyposulphite of calcium and hydrochloric acid producing calcium chloride and
sulphur thus.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said James Beveridge in the Patent Office on the 3rd April 1884.
JAMES BEVERIDGE, of Runcorn, in the County of Chester "IMPROVEMENTS IN
OR APPERTAINING TO THE TREATMENT OF ORES (OR OTHER SUBSTANCES) CONTAINING
ANTIMONY BY THE WET PROCESS"
Part First.
My process is applicable to the ores and substances containing compounds of
antimony which are soluble in hydrochloric acid. Preferably I use ores containing
about twenty per cent more or less of antimony in the form of sulphide (Sb, S.)
and treat the finely powdered ore in hydrochloric acid of convenient strength with
the aid of heat, obtained either by the injection of steam into the contents of the
containing vessel or by the outward application of heat to the vessel itself. The
hydrochloric acid acting on the Sb, S, forms trichloride of antimony (Sb Cl,) and
sulphuretted hydrogen (H, S) as is well known. The chloride of antimony remains
in solution in the liquid, whilst the sulphuretted hydrogen is liberated in the form
of a gas and is led away through earthenware pipes for further use as described
under parts three and four of this Specification.
The vessels which I at present propose to employ for dissolving the antimonial
compounds contained in the ores or substances are earthenware pots of as large a
cubic capacity as possible (those made by Doulton & Co, Lambeth Potteries, suit
the purpose admirably) and in order to protect them from rough usage etcetera
each of them may be inserted into a larger pot made of cast or wrought iron, the
space between the walls of the two pots being filled up with any convenient
mixture, preferably of silicate of soda and asbestos, or cement, or iron filings and
sal-ammoniac. The compound pot thus formed is set in brickwork like an
ordinary wash-house boiler and is heated by a fire placed underneath. . Or a much
better method is to heat them in a steam, in a chloride of calcium, or in an oil bath
as is usually done. In all cases the pots are covered with a hood of wood or of
stone or of brick work, means being provided for the escape of the sulphuretted
hydrogen gas. To every cubic foot of hydrochloric acid of Sp. Gr. 1·14 I add a
quantity of ore representing 5 pounds weight of real metallic antimony.
In practice I find that hydrochloric acid of 28° to 30° Twaddle with the
equivalent quantity of ore as above mentioned gives chloride of antimony liquor
of 42° Twaddle (cold), and that it invariably contains somewhere about 5 pounds
of antimony per cubic foot as also a large excess of free acid, in many cases
amounting to 75 per cent of the total H Cl present. The gangue or residue left
undissolved in the pot contains, if the operation has been conducted properly, less
than 1 per cent of metallic antimony, but too large a quantity of trichloride of
antimony to allow it to be thrown away without being washed. I therefore wash
the residue in the pot twice with weak acid liquor from the precipitating vessels as
described under part second, the first of such washings being added to the strong
antimony liquor, whilst the second washings are passed down the sulphuretted
hydrogen tower as in part third. In all cases I find it is necessary to heat the
acid and ore together up to the boiling point, about 220° Fahrenheit.
I find that the foregoing apparatus is well adapted for dissolving the ore, but
would recommend the use of Messrs Hargreaves and Robinson's Antimony steam
jacket pans as described in their specification N° 5809 dated 6th December 1882,
which are admirably adapted for this purpose.
Part Second.
The solution thus obtained contains chloride of antimony equivalent to about

page_text: together with a large quantity of free hydrochloric acid, and is either syphoned or
otherwise drawn off by means of a suction apparatus into a vessel made preferably
of stone, when it is allowed to settle till clear. It is then removed to another
vessel also of stone (or it may be made of wood) and there is added to it from
4 to 5 times its volume of water which precipitates about 95 per cent (more or
less) of the total antimony operated upon in this part of the process as oxychloride
of antimony, this substance appearing as a white flocculent precipitate which
settles with difficulty and only after continued standing. In order to quickly
separate the precipitated oxychloride of antimony from the liquid I raise the
temperature of the liquid by the injection of steam or other convenient means till
it reaches about 115 degrees or 155 degrees Fahrenheit, when the oxychloride
separatus out in the form of a fine crystalline powder which rapidly settles to the
bottom of the vessel. After the liquor (which is practically weak hydrochloric
acid) is perfectly clear it is run off into a convenient vessel to be further treated
as described under the third part of this specification. The above operation of
precipitating and crystallizing oxychloride is repeated several times until a quantity
of precipitate has accumulated in the precipitating vessel where it is washed with
water to get rid of free acid, dried and smelted with alkali flux and carbon in the
ordinary way to procure the metal, or otherwise treated for the manufacture of the
salts of antimony.
In practice I find that working with liquors of the above strength (that is
5 pounds antimony per cubic foot) and adding thereto 5 volumes of water, I get a
precipitation of about 95 per cent as above explained, and that the precipitate
varies in composition within narrow limits. It generally contains somewhere
about 70 per cent real Sb and from 15 to 20 per cent Cl, the remainder being
oxygen. The précipitate is remarkably free from other impurities.
To reduce the oxychloride to metal with carbon and alkali flux as aforementioned,
I find the following flux to act well:
200 parts common salt (NaCl)
100
carbonate of soda.
To every 100 parts of precipitate I use 100 parts of flux and 14 to 16 parts of coal.
All must be intimately mixed together.
This mixture may be smelted at a bright red heat in crucibles or on the bed of a
reverberatory furnace. The metal thus obtained is exceptionally pure.
Sb, O, is prepared from the oxychloride by boiling it in a clear solution of
carbonate of soda, and washing by decantation in the ordinary way.
Part third.
The weak acid which is run off from the precipitating vessel after the
oxychloride of antimony has been precipitated by the aid of heat as described
under part second, contains a small quantity of antimony in solution which I
recover in the following manner, namely:-I treat the said acid liquor with a part
of the sulphuretted hydrogen gas evolved from the pots as described under part
first, whereby the antimony is precipitated in an insoluble state as sulphide of
antimony. For this purpose the sulphuretted hydrogen gas may be injected into
the acid liquor by any suitable apparatus such as a pump or steam jet, or the
weak acid may be allowed to flow through an apparatus resembling in principle
the ordinary gas scrubber used in the purification of coal gas whilst the
sulphuretted hydrogen gas itself is passing through the said scrubber. In practice
I prefer to use a tower constructed of wood, stone or bricks packed in a
convenient manner with prisms of wood or other material not acted on by
weak H Cl. The sulphuretted hydrogen gas ascends this tower whilst the weak
acid is allowed to flow down it. The antimony contained in the weak acid is thus.
precipitated as Sb, S.. The extent of the flow of weak acid is regulated according
to the work such a tower is capable of performing, that is to say the liquor coming
from the tower should after filtration be perfectly clear and should not on the
addition of an alkaline sulphide give a precipitate of sulphide of antimony. The
flow of weak acid liquor should be regulated to obtain this result;
.

page_text: The sulphide of antimony is separated from the weak acid by any convenient
means such as settling and decanting the clear liquor or by any of the many
methods of filtration. The clear liquor which separates from the sulphide of
antimony is practically weak hydrochloric acid of about 5 degrees Twaddle
containing in solution sulphuretted hydrogen gas, and is run into a separate vessel
or vessels for further treatment. The precipitated sulphide of antimony is
washed with water and partially dried by means of a hydro-extractor or filter
press. It may be then redissolved as in the first part or heated to form the black
sulphide.
.
In order to free the weak hydrochloric acid from sulphuretted hydrogen gas, I
inject air through the liquid by any convenient means such as an air pump or a
steam jet until it is nearly all or wholly expelled. I then add a small quantity of
chlorine in the form of gas or bleaching powder or bleaching powder_solution,
preferably the latter, or other oxydising substance so that no trace of H, S may
remain in the weak acid.
The weak acid thus purified is pumped on to the "Condensers" of alkali works
and is used instead of water for the condensation of hydrochloric acid gas.
In practice I find that the best method of freeing weak acid liquor obtained
under part second from antimony is by passing it down a square tower built of
Yorkshire flag-stones (in construction similar to the ordinary alkali works
condenser) and fitted with prisms of wood. This apparatus is the least liable to
cause nuisance by escape of gas, etcetera. The flow is regulated according to the
foregoing directions and plainly it is advantageous that the dissolving pots be so
charged with acid and ore that a regular and constant supply of sulphuretted
hydrogen gas be passed into the tower.
Moreover I find that recently precipitated sulphide of antimony is slightly
soluble in solutions containing H, S gas, and therefore I prefer in practice to run
the liquor and precipitate from the tower direct into a large wooden tank along
the bottom of which a perforated 3-inch ebonite pipe is laid and which is
connected with a large blowing engine. I then pump air through the liquid
contained in the tank until all or nearly all the H, S has been expelled, and then I
pass the contents through a coarse woollen cloth stretched over the sides and
bottom of a tight wooden tank. The precipitate of sulphide of antimony on the
filter after it is drained is washed with water, partially dried in a hydro-extractor
and fused with flux in crucibles to form the black sulphide (Sb, S.). The black
sulphide of antimony thus obtained is remarkably pure.
To the clear weak acid I find it necessary to add a little bleaching powder
Bolution in order to ensure perfect freedom from H, S gas before I use it on the
HCI Condensers."
. Having now described my invention and the best mode known to me of
carrying it into effect, I wish it to be understood that what I claim as new under
the Letters Patent is: The treatment of antimonial ores and the manufacture
therefrom of metallic antimony or merchantable compounds of antimony sub-
stantially in the manner herein described, and also the following special parts of
the process taken separately:-
1st. The speedy separation of oxychloride of antimony in the crystalline form by
the addition of an excess of water to the solution of trichloride of antimony, and
heating the mixture to from 115° to 155° Fahrenheit.
2nd. The recovery of the hydrochloric acid and also the residual antimony
remaining from the trichloride of antimony solution by the process described,
which consists substantially in treating the trichloride solution with sulphuretted
hydrogen in scrubbing towers or their mechanical equivalent, separating the
sulphide of antimony that precipitates, aerating the residual acid so as to expel the
remaining sulphuretted hydrogen, removing the last traces of sulphuretted hydrogen
by means of chlorine or a hypochlorite, and using the purified weak acid in
condensers of alkali works instead of water.
.:

page_text: 3rd. In the process of treating antimonial ores in the wet way, dissolving out
the antimony by means of hydrochloric acid with the aid of heat, and passing the
sulphuretted hydrogen given off up scrubbing towers down which descends a stream
of the residual weak acid left after most of the antimony has been precipitated from
it, substantially as hereinbefore described.
I also believe the pots substantially as described in the first part of my
specification to be new, but I do not desire to claim them as a necessary part of
my invention,
In witness whereof I the said James Beveridge have hereunto set my hand
and seal this twenty second day of February in the year of our Lord one thousand
eight hundred and eighty four.
JAMES BEVERIDGE (L.S.)