Improvements in the Treatment of Bluestone and other Sulphurised Ores.
Year: 1895

page_text: This Print is in accordance with the Original Specification as it stands after
Amendment (undu Section 18 of the Patents, &c Act, 1883) as allowed by
the decision of the Cluef Examiner of the 30th day of March 1898
Date of Application, 7th May, 1895
Complete Specification Left, 9th Mar, 1896-Accepted, 7th Aug.,
1896
Improvements in the Treatment of Bluestone and other Sulphurised
Ores.
I, JOHN COPE BUTTERFIELD of 13 Victoria Street, in the City of
Westminster, FIC, FCS, Analyst do hereby declare the nature of this
invention to be as follows
The invention relates more especially to the treatment of the complex ores of
Bluestone" wluch oies occur in
lead, zinc, copper and non technically known as
Anglesea, Ireland, the south of Fiance, Austiaha and other localities associated
with gold, silver, antimony, aisenic de, in such a manner that the precious metals
cannot be extracted therefrom owing to the presence of one or all of the above
metals I am aware that various wet methods have been proposed (and abandoned)
for the treatment of oies of this nature, but by the following method I can success-
fully treat very complex minerals the pincipal objects which I have in view being
to eliminate and at the same time obtain the metal or metals which interfere with
the extraction of the gold and silver and also to iender the sulphur with which
the metals were previously combined saleable. obtaining besides other valuable
bye-products
In carrying this invention into practice the oies are first finely ground to
powder by any suitable machinery, I prefer to first produce the ore by means of a
stone-crusher to coarse powder and afterwards grind it by edge-runncis or other
suitable machinery to a sufficiently fine state of division to pass through a 70 mesh
Bieve
The finely ground ore is then placed in tanks of jacketted enamelled cast on
and heated by steam which I find is not attacked by the chemicals employed in the
pincess, each tank 18 heated in a suitable manner to the requisite temperature.
Any suitable number of tanks may be arranged in a series and conveniently, though
not necessarily, six tanks one above the other may be said to constitute one battery.
Each tank is supplied with its proper quantity of ore and to the first of the series
I add a strong hot solution of perchloride of non about 70° T to 80° T which
immediately attacks the 01e,
the perchloride of non being reduced by the sulpludes
of copper, lead, antimony etc all of which metals are converted into chlorides
whilst the iron salt is robbed of its available chloine and converted into ferrous
chloride The sulphur gangue and gold are left as au insoluble residue at the
bottom of the tanks The solution 18 now run whilst hot into No 2 tank in which
is another supply of ore and a fresh quantity of the perchlonde in as hot a condition
as possible is now run on to No 1 tank in order to decompose any ore remaining
unacted upon and also to wash away the soluble salts of the metals produced with
which the residue is wetted.

page_text: The
This operation I repeat as often as necessary passing the solutions from one tank
to the other until the gangue is practically tire fiom soluble chlorides
solutions ansing from the above fieatment are allowed to settle in deep tanks
called settlers in which the gangue sulphur ele, along with some portion of the
chloride of lead will deposit at the bottom and the liquid become clean and when
such condition is reached the liquid is run off into a large tank and allowed to
settle (which will take from 24 to 30 hours) in order to deposit the chlode of
lead After the lapse of a suitable time the clear liquid is run off into another
tank in which is placed scrap non and the tank is left at rest until by the action of
the metallic non on the chloides of copper, antimony, ete, the whole of the copper
or other metals in solution are precipitated in the state of mud as metallic copper
etc, the non passing into solution
When the above re-action has taken place the cleat super natent liquid is un
into a large vessel consisting of either teak wood with indiarubber joints, or india
ubber asbestos sheeting, which prevents the teak from leaking, as I have found by
experience that by the action of the feito and ferric chloride, the wood 19 made
to contract and thus cause leakage-which is avoided by using the indiai ubber or
asbestos joint-01 a stoneware tank made up in sections and contained in an Hon
framework the sections of which are cemented together by means of a cement
made from Portland cement, tar and albumen, or an enamelled cast on tank may
be made in sections each section being provided with a flange and the joint
between each made with the cement, indiarubber or asbestos as above described
and afterwards bolted together on the outside in the usual manner To the bottom
of each tank a lenden oi non pipe covered with indiarubber is carried--the sand
pipe being twisted into a flat spiral at the bottom (or nearly 50) of the tank On
the under surface of this pipe a number of small holes are made and connection
established by means of a flexible pipe with a blast engine capable of supplying air
(at a pressure of 50 to 60 lbs to the inch) either heated up to 100 or 150° 1, or
the solution of ferrous chlonde may be heated by means of a coil of lead india-
rubber covered pipe, passing round the inner peuphery of the vessel, through
which steam is allowed to travel,-and by the condensation of which, the solution
attains a temperature of 120 or 130°, and it is highly cssential that the
temperature be kept at or above this point, as the success of the operation is
dependent upon the temperature at which the solution is aerated, and the operation
is completed far more expeditiously if these strengths and temperatures are adhered
to than otherwise By the continual blowing of the air obtained from a blast
engine or otherwise at a pressure of from 40 to 60 lbs per uch, the ferrous
chloride is oxidised and converted into hydrated ferric oxide (FeO 3 OH,) and
FeCl (fenic chloride) thus

page_text: The solution during the blowing operation is apt to froth to a very great extent
and in order to avoid this and subsequent loss I add to every 500 gallons of solution
about pint of petroleum oil which most effectually prevents the excessive fiothing
without injury to the chemical re-action taking place
,-so as to
The precipitated metals c.g, copper, antimony, etc obtained by the action of the
metallic on upon the various chlondes arc washed free from fenous salts, and
filtered through either a piess or by an ordinary filtration--the precipitated metal
s then taken and dned at a very low temperature, say on a steam bath,-
avoid oxidation and when diy the metal is compressed by hydraulic pressure into
cakes and afterwards melted into ingots at the lowest possible temperature or when
dealing with copper the precipitated metal is placed in an earthenware ietoit which
is heated by gas or other wise and exposed to the free action of the oxidizing influence
of the an, by which the metallic copper is converted into black oxide which can be
used as a basis for the production of the venous salts of copper when treated with
the necessary acids q, mitne or sulphuric etc
"
In the case of antimony the pressed cakes are taken and dropped into a covered
ciucible in which a slag or cinder has already been melted consisting of carbonate
of soda, carbonate of potash sulphate of soda and bolax
The crucible is prefer-
ably heated by gas and provided with a cup and cone arrangement of feeding by
which the metal can be thrown into the crucible without admission of air When
the metal is melted and a sufficient quantity of cinder or flux has been added the
contents of the crucible are poured into a deep and heated cast iron mould of any
desired shape, it being necessary to cover the whole of the metal with at least
6 inches of fluid slag so as to ensure the crystallization of the metal or what 18
technically known as stairing
"
By the above method antimony ones containing gold can be treated so as to
obtain both metals but if it is preferred the antimony may be converted into red
sulphide of antimony known technically as "golden sulphide" by taking the
solution obtained by acting upon the antimony oies with chloride of iron allowing
the solution to settle as described and passing sulphuretted hydrogen obtained by
any of the ordinais methods used to give off gas eg acting upon non sulphide
with HCl or H.SO, or actually by treating the pure forms of stibnite with
hot IICI, the SII, is conducted into the solution of ferrous, ammonium chlonde
(obtained by the process above described) and the antimony is precipitated
as SbS, whilst the iron chloride is not affected-(so long as the solution is kept
acid) the red sulphide of antimony is then allowed to settle, the solution of ferrous
chloride is boiled to evolve the SH, contained and afterwards blown in the manuer
already described, whilst the SbS, is washed with warm OH, free from the slightest
trace of ferrous salt (otherwise it will not preserve its colour) filter pressed and
dued and sold to the indiarubber factomes
2
19
The gangue consisting of sulphur sand gold and minerals not acted upon by the
feric chloide is air diied then heated to dull redness in iron or clay retorts which
are connected with large condensers of buck work in which the arsenic and sulphur
are condensed and afterwards refined, the residue from the retorts 18 then mixed
with sufficient line or carbonate of lime, sulphate or sulphide of lead and fluor spar
to produce a fusible cinder by the latter uniting with the silica present in the
residue, whilst the lead compounds unite with the compounds or minerals containing
the gold, silver antimony etc thereby forming a regulus of lead, antimony, gold and
silver. The slag is detached and used over again in another operation whilst the
regulus is ground up for subsequent treatment
The regulus is ground to pass through an 80 mesh sieve and treated in a series
of small tanks of enamelled iron with hot ferric chloride which acts upon the lead
antimony cte in the manner already described, the lead being separated by cooling
and subsequent removal as chloride of lead which is converted afterwards into
sulphate by using sulphuric acid or soda sulphate The sulphate of lead so
produced is economised in the smelting for regulus as above described the antimony

page_text: 18 precipitated by metallic non washed free from non salts and afterwards dried
compressed by hydraulic pressure and melted at a dull red heat
The residue remaining after the treatment of the regulus, contains the gold.
silver etc, mixed with sulphur te this is heated in a small etoit the sulphur
driven off and the residuuin of gold bearing material is run with the addition of
metallic lead or sulphide of lead, sulphate of lead and scrap non producing a
button of lead which contains the whole of the gold and silver originally piesent
in the ore and which by my method of treatment has become concentrated so that
very poor ores of lead, and antimony containing gold can be most successfully
treated in this manne
The lead so obtained is "cupelled in an ordinary test known to all metallurgists
and the gold and silver refined by ordinary methods
Dated this 7th day of Mar 1895
BOULT & WADE,
Agents for the Applicant
Improvements in the Treatment of Bluestone and other Sulphurised
Ores.
I, JOHN COPE BUTTLRFIELD of 13 Victoria Street, in the City of
Westminster, FIC, FCS, Metallurgical Engmeer, do hereby declare the nature
of this invention and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement
-
The invention relates more especially to the treatment of the complex ores of
lead, zinc, copper and non technically known as Bluestone" which ones occur in
Anglesea, Ireland the south of France, Australia and other localities associated
with gold, silver, antimony, arsenic etc in such a manner that the precious metals
cannot be extracted therefiom owing to the presence of one or all of the above
metals I am aware that various wet methods have been proposed (and abandoned)
for the treatment of ones of this nature, but by the following method I can
successfully treat very complex minerals, the principal objects which I have in
view being to eliminate and at the same time obtain the metal or metals which
interfere with the extraction of the gold and silver and also to render the sulphur
with which the metals were previously combined saleable, obtaining besides other
valuable bye-products
In carrying this invention to practice the ores are first finely ground to powder å
by any suitable machinery, I prefer to first reduce the one by means of a stone-
crusher to coarse powder and afterwards grind it by edge-1 unners
suitable machinery to a sufficiently fine state of division to pass through a 70 mesh
or other
gleve.
The finely ground ore is then placed in tanks of jacketted enamelled cast iron 4
and heated by steam which I find is not attacked by the chemicals emploved
in the process, each tank is heated in a suitable manner to the requisite
temperature Any suitable number of tanks may be arranged in a series and
conveniently, though not necessarily six tanks one above the other may be
said to constitute one battery Each tauk is supplied with its proper quantity 4
of ore and to the first of the series I add a strong hot solution of perchloride
of iron about 70° T to 80° T which immediately attacks the ore, the perchloride of
iron being reduced by the sulphides of copper, lead, antimony etc all of which
metala are converted into chlorides whilst the iron salt is robbed of its available
chlorine and converted into ferrous chloride The sulphur gangue and gold are 6

page_text: left as an insoluble residue at the bottom of the tanks The solution is now
run whilst hot into No 2 tank m which is another supply of ore and a fresh
quantity of the perchloude in as hot a condition as possible is now run on to
No 1 tank in order to decompose any ore remaining unacted upon and also to
wash away the soluble salts of the metals produced with which the residue is
wetted
This operation I repeat as often as necessary passing the solutions from one
tank to the other until the gangue is practically free from soluble chlorides
The solutions asing from the above treatment are allowed to settle in deep
tanks called settlers in which the gaugue, sulphur ete, along with some portion
of the chloride of lead will deposit at the bottom and the liquid become clear and
when such condition is reached the liquid is tun off into a large tank and allowed
to settle (which will take from 24 to 30 hours) in order to deposit the chloride of
lead After the lapse of a suitable time the clear liquid is iun off into another
tank in which is placed scrap on and the tank is left at rest until by the
action of the metallic iron on the chlorides of copper, antimony, etc, the whole
of the copper or other metals in solution are precipitated in the state of mud as
metallic copper etc, the iron passing into solution
To
When the above re-action has taken place the clear supernatent liquid is 1un into
a large vessel consisting of either teak wood with indiarubber joints, or indiarubber
asbestos sheeting, which prevents the teak from leaking, as I have found by
experience that by the action of the ferio and feric chloride, the wood is made to
contract and thus cause leakage--which 19 avoided by using the indiarubber or
asbestos joint-or a stoneware tank made up in sections and contained in an
iron famework-the sections of which are cemented together by means of a
cement made from Portland cement, tar and albumeu, or an enamelled cast iron
tank may be made in sections, each section being provided with a flange and the
joint between each made with the cement, indiarubber or asbestos as above
descubed and afterwards bolted together on the outside in the usual manner
the bottom of each tank a leaden or on pipe covered with indian ubber is carried
-the said pipe being twisted into a flat spiral at the bottom (or nearly so) of the
tank On the under surface of this pipe a number of small holes are made and
connection established by means of a flexible pipe with a blast engine capable of
supplying an (at a pressure of 50 to 60 lbs to the uch) either heated up to
100 or 150° F, or the solution of ferrous chloride may be heated by means of a
coil of lead udia ubber covered pipe, passing round the inner periphery of the
vessel, though which steam is allowed to travel, and by the condensation of which,
the solution attains a temperature of 120 or 130° F, and it is highly essential that
the temperature be kept at or above this point as the success of the operation is
dependent upon the temperature at which the solution is aerated, and the operation
19 completed far more expeditiously if these strengths and temperatures are adhered
to than otherwise By the continual blowing of the air obtained from a blust
engine or otherwise at a pressure of from 40 to 60 lbs per inch, the ferrous
chloride is oxidised and converted into hydrated fenic oxide (Fe,O, 3 OH.)
and Fe.Cl. (fcuc chloude) Thus
6 FeCl2 + 0 + 3 OB₂ =¡(Fе, (₂ 3 (119) +2
(hydrated ferne oxide)
(an)
and provided the blowing is continued for some 60 hours or longer until nearly the
whole of the FeCl, is oxidised at the temperature and strength of solution as
18 formed The solution of perchloride with
given no oxy chloide of iron
suspended oxide is then passed through a filter press provided with asbestos filter
cloths (linen cloths are destroyed by the action of the perchloride) and press plates
made of enamelled cast non which are found to withstand the corrosive action of
the iron chloride
The oxide of iron is then either washed with hot water in the press or in wooden
vats until all soluble iron salts are removed and the washing water no longer gives

page_text: any blue coloration with either ferro- or ferri cyanide of potassium-when
thoroughly washed the oxide can be sold as paint material, or by a gentle
calcination at a dull red heat in a muffle furnace it may be converted into valious
shades of Indian red or scarlet pigment, the colour depending upon the degree of
heat applied
The solution during the blowing operation is apt to froth to a very great extent
and in order to avoid this and subsequent loss I add to every 500 gallons of solution
about pint of petroleum oil which most effectually prevents the excessive frothing
without injury to the chemical re-action taking place
The precipitated metals eg, copper, antimony, etc obtained by the action of the
metallic ron upon the various chlondes are washed free from ferrous salts, and
filtered through either a press or by an ordinary filtration--the precipitated metal
is then taken and dried at a very low temperature, say on a steam bath,--so as to
avoid oxidation and when dry the metal is compressed by hydraulic pressure into
cakes and afterwards melted into ingots at the lowest possible temperature or
when dealing with copper the precipitated metal is placed in an earthenware retort
which is heated by gas or otherwise and exposed to the free action of the oxidising
influence of the air, by which the metallic copper is converted into blach oxide
which can be used as a basis for the production of the vanous salts of
treated with the necessary acids eg, nitric or sulphuric etc
copper
when
In the case of antimony the pressed cakes are taken and dropped into a covered
crucible in which a slag or cinder has already been melted consisting of carbonate
of soda, carbonate of potash sulphate of soda and borax The crucible is preferably
heated by gas and provided with a cup and cone arrangement of feeding by which
the metal can be thrown into the crucible without admission of air When the
metal is melted and a sufficient quantity of cinde o flux has been added the
contents of the crucible are poured into a deep and heated cast on mould of any
desired shape, it being necessary to cover the whole of the metal with at least six
inches of fluid slag so as to ensure the crystallization of the metal, or what is
technically known as "starring"
By the above method antimony ores contaming gold can be treated so as to
obtain both metals but if it is preferred the antimony may be converted into ied
sulphide of antimony known technically as "golden sulphide" by taking the
solution obtained by acting upon the antimony ores with chloride of 11on allowing
the solution to settle as described and passing sulphuretted hydrogen obtained by
any of the ordinary methods used to give off gas, eg, acting upon iron sulplude
with HC or H,SO,, or actually by treating the purer forms of stibnite with
hot HCI--the SH, is conducted into the solution of ferrous antimony chloride
(obtained by the process above descubed) and the antimony 15 precipitated
as SbS, whilst the iron chlode is not affected-(so long as the solution is kept
acid) the red sulphide of antimony is then allowed to settle, the solution of ferrous
chloride is boiled to evolve the SH, contained and afterwards blown in the manner
already described, whilst the SbS, is washed with warm OH, free from the
slightest trace of ferrous salt (otherwise it will not pieseive its colour) filter pressed
and dried and sold to the indiarubber factories
The gangue consisting of sulphur sand gold and nunerals not acted upon by the
feric chloride is air dried then heated to dull redness in 11on or clay retorts which
are connected with large condensers of brick work in which the arsenic and sulphur
are condensed and afterwards refined, the residue from the retorts is then mixed
with sufficient lime or carbonate of lime, sulphate or sulphide of lend and fluor spar
to produce a fusible cinder by the latter uniting with the silica present in the
residue, whilst the lead compounds unite with the compounds or minerals containing
the gold, silver antimony etc thereby forming a regulus of lead. antimony, gold
and silver The slag is detached and used over again in another operation whilst
the regulus is ground up for subsequent treatment
The regulus is ground to pass through an 80 mesh sieve and treated in a series
of small tanks of enamelled iron with hot ferric chloride which acts upon the lend

page_text: antimony ete in the manner already descubed, the lead being separated by cooling
and subsequent removal as chlode of lead which 18 converted afterwards into
sulphate by using sulphuric acid or soda sulphate The sulphate of lead so
produced is economised in the smelting for regulus as above described the
antimony is precipitated by metallic iron washed fice from non salts and afterwards
died compressed by hydraulic pressure and melted at a dull red heat
The residue remaining after the treatment of the regulus, contains the gold,
silver etc, mxed with sulphur etc-this is heated in a small etort the sulphur
diven off and the residuuin of gold beaning matenal is run with the addition of
metallic lead or sulphide of lead, sulphate of lead and scrap iron, producing a
button of lead which contains the whole of the gold and silver origmally present in
the one and which by my method of treatment has become concentrated so that
very poor oies of lead, and antimony containing gold can be most successfully
tieated in this manner
The lead so obtained 18 cupelled" in an ordinary test known to all metallurgists
and the gold and silver refined by ordinary methods
Having now particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be performed, I declare that what I
claim 18.-
1 In the treatment of ores the employment of iron perchlorido to separate the
lead, copper, gold and antimony from each other in the manner substantially as
described
2 The regeneration of the feous chloride resulting from the above reaction
into perchloride of non for further use with the formation of oxide of iron as a
bye product by means of hot air substantially as described
3 The complete process for the treatment of ores and the separation and recovery
of the metals which they contain substantially as described
Dated this a day of Maten 1896
JC BUTTERFIELD,
Boult & Wade,
Agents for the Applicant.
JC BUTTERFIELD,
Boult & Wade,
Agents for the Applicant.