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Патент USA US2105901

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2,105,901
Patented Jan. 18, 1938’
2,105,901
FROTH FLOTATIQN METHOD
Frederic ‘ A.. Brinker, Denver, C010.
No Drawing.
Application March 20, 1935, 7
Serial No. 11,998
16 Claims. ,
(01. 209-167)
This invention relates to the froth ?otation
process for the recovery of minerals and has to
do particularly with the differential separation of
copper sul?des from other sul?des and from
5 gangue.
On some ores it is dif?cult to recover the maxi
mum amount,‘ of copper sul?de from the ore. This -
is particularly true for many copper ores that
contain zinc and/or iron sul?des to which a
cyanide compound, such as zinc or sodium cyanide
has-been added to inhibit the zinc and/or iron
sul?des to permit the differential ?otation of the
copper sul?de either with or without lead sul?de.
While it is true that other workers have‘found
some copper ores in which copper sul?des are
_ g
_
.
_
also discovered that, while any of the well known
promoters such as xanthate and the di-substl
tuted dithiophosphate otherwise known .as “aero
?oat” give good results in any of the above condi
tions, thiocarbanilid on most ores gives better‘
results.
I
It is preferable'to add the sulfuric acid after
the addition of the cyanide compound.
The
cyanide'compound may be added either to the
grinding mill or to the ground ore pulp prior to 10
the ?otation operation. The sulfuric acid and the
?otation promoter may be added ‘together, or one
may be added prior to the other. Better results
seem to be obtained on most ores' where using
thiocarbanilid by‘adding the sulfuric acid after'
not inhibited by cyanide, I have found that such the promoter has been added to the ?otation pulp.
The sulfuric acid may be added as a concentrated
ores have some characteristic which permits ?oat
acid,
or as a dilute acid. But where the strong
ing of the copper sul?de without further treat
ment after addition of cyanide. For example, ' acid is used it is added separately from thiocaré 20
26? ores containing considerable amounts of oxidized banilid when employed. so as to avoid solution
{materials or soluble salts usually may be so effects which strong sulfuric acid has upon thio
handled.
However, there are many other ores,
especially those which are relatively free from
oxidized constituents and soluble salts and ores
25 which appear to exert reducing effects possibly
by reason of their sul?de content, wherein the‘
addition of cyanide in amount sumcient to inhibit
effectively zinc and/or iron sul?des resultsin the
inhibition of so much copper sul?de as to be
05
economically undesirable.
This may vary from
carbanilid. ‘ The cyanide used may be sodium
cyanide, zinc cyanide or any other cyanide com
pound soluble or even slightly soluble as well
known in the flotation art, to perform a function
supposedly of forming a nonsactivating or in
hibiting coating on certain sul?des such as iron
and zinc sul?des.
25"
I
The invention may, therefore, be stated as re=
siding in the use of sulfuric acid as an activator 30v
smaller percentages up to nearly all the copper > or reactivator for the froth ?otation of copper
I have discovered that in treating ores of the
last mentioned types, sulfuric acid produces an
activating or reactivating condition for these
copper sul?des where they are di?icult to float
as a result of a previous addition of a cyanide
compound. Where a cyanide compound has been
added for the purpose of inhibiting zinc and/or
iron sul?de, it will ordinarily have been for the
‘purpose of recovering copper sul?de, .or both
copper and lead sulfides. In this instance, the
cyanide will also inhibit some of the copper sul
?des. These are then reactivated by the sulfuric
acid, which however will not reactivate substan
tial proportions of the iron and/oi" zincsul?des.
Where lead sul?de is present, it may be separated
from the copper, zinc or iron sul?des by pre
liminary ?otation, or the sulfuric acid may be
50 added in the presence of the lead sul?de to reac
tivate the copper sul?des so that the lead and
copper sul?des are recovered together. I have
further discovered that where a cyanide com
pound has been added for the purpose of inhibit
55 ing nickeliferous pyrrhotite, the cyanide will in
hiblt also some of the copper sul?des when present
with this nickeliferous pyrrhotite. In this case
sulfuric acid isadded to reactivate 'the copper
sul?des for their: subsequent ?otation and separa
I have
60 tion from the nickellferous pyrrhotlte.
sul?des where they have been inhibited by cyanide
compounds, as where such cyanide compounds
have been employed to depress zinc or iron sul
?des as above mentioned; The invention like
wise includes the separation of copper sul?des
from zinc and/or iron sul?des by employing a
cyanide compound to depress the zinc and/or
iron sul?des, and sulfuric acid to activate the
copper sul?des and permit froth ?otation of the 40
copper sul?des.
’
The invention further includes such use of the“
cyanide and sulfuric acid in ores containing both
copper and lead sul?des along with zinc and/or
iron sul?des, both where the sulfuric acid is added 45
after the ?otation of the lead sul?des, the copper
sul?des being ?oated after the addition of the sul
furic acid, and where the sulfuric acid is added
before the flotation of the lead sul?de, so that the 50
copper and lead sul?des are froth ?oated to
gether, the zinc and/or iron sul?des being left'lin
the tailings in each case. As above stated the
preferred promoter or collecting agent of those
above mentioned to be used in this connection is 55
thiocarbanilid, from the standpoint of either the
copper sul?des or the lead sul?des.
To illustrate the application of theiinventlon,
the following examples are given of the treatment
of ores wherein copper sul?des are depressed upon 60
2
2,105,901‘
addition of cyanide to inhibit iron and zinc sul
Therefore, prior to the ?otation operation in
Example 1.—An ore containing 5% copper sul
which the copper sul?des are separated. from
the iron sul?des, sulfuric acid is added to the ore
?de, 10% zinc sul?de, 70% iron sul?de and the .pulp to reactivate the copper sul?des inhibited
rest gangue, was ground with water to liberate
the different sul?des from each other and from
the gangue and then introduced into the ?otation
machine with the addition of I21; pound per ton
of ore of sodium cyanide. A small amount @100
10 pound per ton) of thiocarbanilid in solution in
ortho-toluidine was added together with su?icient
‘by the ‘cyanide.-
' ‘ frothing agent and one to three poundsof sul
it is necessary to add additional sulfuric acid to ‘
This ore pulp is next subjected
to a froth ?otation treatment in which a ?ota
tion collector, such as xanthate or thiocarbanilid,
and a ?otation frother are added and the copper
sul?de removed as a froth copper concentrate,
thereby making a sharp separation between the
copper sul?de and the iron sul?de. Sometimes
'furic acid per ton of ore, to produce a’ copper
sul?de froth concentrate which was removed by
reactivate the last of the inhibited copper sul
?de. After this separation, the iron sul?de may
15 ?otation and which contained but little iron and ' be either ‘rejected as tailing or ?oated by well
15
zinc sul?des. The iron and zinc sul?des may be known methods to make an .iron froth concen
separated by another froth ?otation process or trate.
rejected as tailing. Instead of the thiocarbanilid
Example 5.—In an ore containing copper sul
solution thiocarbanilid per se or xanthate or other ?de and nickeliferous pyrrhotite where it is de
20 promoter may be used.
sired to make a sharp separation by the froth 20
Example 2.-An ore containing 15 to 20 per cent ?otation process between the copper sul?des and ,
combined lead, copper, zinc and iron‘ sul?des with nickeliferous pyrrhotite, the same method is used.
gangue was ground in water and then introduced Here also the cyanide compound is a well known
into the ?otation machine with 1/g pound of so-. inhibitor for nickeliferous pyrrhotite but if suf?
25 dium' cyanide per ‘ton of ore together with su?i ‘ cient cyanide is used to give the best results for
cient frothing and collecting agents to produce
the inhibiting of the nickeliferous pyrrhotite, some
copper sulfides are inhibited by the cyanide,
thereby resulting in a higher tailing loss of copper
sul?de. Therefore, prior to the ?otation oper
ation in which the‘ copper sul?des are separated 30
from the nickeliferous pyrrhotite, sulfuric acid is
added to the ore pulp to reactivate the copper‘
sul?des inhibited by the cyanide. This ore pulp
is next subjected to the froth ?otation treatment
a lead sul?de froth concentrate. . Upon froth ?o
tation this concentrate contained most of the
lead sul?de with a small amount of copper sul?de
30 and very little zinc and iron sul?des. Here most
of this copper sul?de was inhibited by the cy
anide. After this froth concentrate was removed,
one tothree pounds per ton of ore of sulfuric
acid was added and su?icient frothing and col
35 lecting agents to produce a copper sul?de froth
in which a ?otation collector, such as xanthate
or thiocarbanilid, and a ?otation frother are
added and the copper sul?de removed as afroth
concentrate. Upon froth ?otation, substantially
all the copper sul?de came over in the concen
trate. The zinc‘ and iron sul?des were rejected
in the tailing.- To recover the zinc sul?de from
40 the tailing, this may next be ?oated by the addi
copper concentrate, thereby making a sharp. sep
aration between the copper sul?de and the nickel
iferous pyrrhotite. Sometimes it is necessary here 40
also to add additional sulfuric acid to reactivate
the last of the inhibited copper sul?de. 'After this
tion of any soluble copper compound, such as cop
per sulfate, and sufficient frothing and collecting
agents.
‘
'
separation, the nickeliferous pyrrhotite may be
Example 3.—-An ore containing 15 to 20‘per
45 cent combined lead, copper, zinc and iron'sul
?des contained in gangue, was ground in water
and then introduced in the ?otation machinewith
?oated by well known methods to make a nickel
iferous froth concentrate.
In the above examples the amounts of sulfuric
acid added were. based on sulfuric acid of 1.84.
1/2 pound per ton of ore of sodium cyanide and
sp. gr; Some reactivation of copper sul?des,
_ two to three pounds of sulfuric acid per ton of - after they have been inhibited by cyanide, re
50 ore and suf?cient frothing and'collecting agents sults from the addition of other acids, such as
to produce a lead-copper concentrate. In this hydrochloric acid, nitric acid, phosphoric acid, 60
case, the addition of the sulfuric acid reactivated but these acids are not so effective as sulfuric
,the copper sul?de, while the iron and zinc sul?des acid which is preferred. In Examples 2 and 3,
1were ,inhibited. The copper was then froth any of the promoters or collecting agents‘ here
55 ?oated and zinc and iron sul?des were rejected inbefore mentioned may be used, including thio
55
in the tailing. The lead sul?de, of course, came carbanilid, a solution thereof, disubstituted di'thio
over with the copper sul?de. With this proce
' dure also the zinc may be ?oated from the tailing
phosphate and xanthate, thiocarbanilid being
preferred because of its better results as hereto
fore stated.
60
Example 4.—In an ore containing copper sul-’
On some ores containing gold and/or silver, 60
?de and iron sul?de whereit ‘is desired to make the addition of the cyanide (soluble form‘) re
a sharp separation by the froth ?otation process sults in solution of some of the gold and/or sil
between the copper sul?des and the iron sul?des, ver, and it'is advisable to remove this gold and/or
the ore is ground with water to liberate the sul
silver-bearing solution from the ore for recov
65 ?des from each other and from the gangue pres
ery of contained gold and/or silver.
- 65
as in Example 2 if desired.
*
. ent in the ore and a cyanide compound is added
. In the treatment of some ores containing re-'
either to the grinding mill so as to be present
fractory compounds of gold and/or silver and
having a high sul?de content, the reducing con
dition resulting from the high'sul?de content to
during the grinding, or the cyanide compound is
'’ added to the ground ore ,pulp prior to the ?ota
70 tion operation. This cyanide compound is a well
known inhibitor for iron sul?des but if sufficient
cyanide is used to give the best results for the
inhibiting of the iron sul?des, some copper sul
?des also are inhibited by the cyanide, thereby
resulting in a higher tailing loss of copper sul?de.
gether with the cyanide. is bene?cial for the so
lution of the gold and/or silver in.the ground
ore pulp as well as for the inhibiting of the iron
*
and/or zinc sul?des and substantial amounts of
copper sul?des. The solution containing the sol
uble gold and/or silver is separated from the
, 2,105,901
ground ore for subsequent recovery of contained
gold and/or, silver values? After said solution
has been removed from the ground ore, the ore is
repulped and the copper sul?des that were in
hibited in the presence of the cyanide are reacti
vated by the addition of sulfuric acid and recov
ered as a froth concentrate.
Y
In practicing this invention, such factors as
collectors, frothing agents, pulp densities and the
from the ore, supplying cyanide compound there
by depressing the copper sul?de and iron and
zinc sul?des present, supplying frothing and
promoting agents to the pulp, subjecting the pulp
to froth ?otation and recovering'a lead sul?de‘
froth concentrate, adding sulfuric acid to 'the
pulp thereby activating the copper sul?de with
out substantial activation of iron and zinc sui
?des present, and subjecting the pulp to froth
?otation to remove copper sul?de froth concen
10 like, will be controlled by prevailing practices as
well known to those skilled in the art. Thus, in
of the zinc and iron class with the tailings.
5. A method for the froth ?otation of sul?de
ores containing lead and copper sul?des and sul
?des of the class zinc ‘and iron sul?des wherein 15
the copper sul?des will be depressed at least in
the ?eld, pulp densities vary ordinarily between
20% and 40% solids according to theofe, the
equipment and other local factors. -The pro
15 portions here given meet the requirements of
these variations.
It is to be understood that these disclosures
are merely illustrative of the generic invention
part by cyanide in a ?otation pulp, comprising
preparing a ?otation pulp from the ore, adding
a cyanide compound to the pulp thereby inhib
iting zinc and iron sul?des present, adding sul
and therefore they are not to. be taken as nec
20 essarily limiting.
I claim:
'
>
'
‘
‘~ 1. A method for the froth ?otation separation
of sul?de‘ ores containing copper sul?de and sul
?des of the class zinc and iron sul?des,comprising
preparing a ?otation pulp from the ore, supply
10
trate and. rejecting substantially all the sul?des
' furic acid to the pulp to reactivate the depressed
copper sul?des, supplying a frothing and vpro
ing a cyanide compound thereby inhibiting ?o
tation of. the sul?des of said class, supplying sul
furic acid thereby activating depressed copper
sul?de, supplying a frothing and a promoting
agent, subjecting the pulp to froth ?otation, and '
removing a copper sul?de concentrate substan
tially free from sul?des of said class and rejecting
substantially all the sul?des of said zinc and iron
class with the tailings.
2. A method for the froth ?otation‘separation
of sul?de ores containing lead and copper sul
?des and sul?des of the class-zinc and iron sul
?des, comprising preparing a ?otation pulp, add
ing cyanide to the pulp thereby depressing cop
40 per sul?des and sul?des of said class, supplying
frothlng and promoting agents to the pulp, sub
jecting the pulp to froth ?otation and removing
the lead sul?de as a froth concentrate, adding
sulfuric acid to the pulp thereby activating the
45 copper sul?de without substantial activation of
zinc sul?des of said class, and removing a copper
sul?de froth concentrate by subjecting the pulp
' to froth ?otation'and rejecting substantially all
moting agent, and subjecting the pulp to the
froth ?otation and recovering a lead and cop
per sul?de froth concentrate and rejecting sub 26
stantially all the sul?des of the zinc and iron
class with the tailings.
‘
'
6. A method according to claim 3 wherein the
sul?des in the ore are copperand zinc sul?des
only.
30
‘
7. A method according to claim 3 wherein the
sul?des in the ore are copper and iron sul?des
only.
',
8. A method according to claim 3 wherein-the
sul?des in the ore are copper sul?de and nick
eliferous pyrrhotite only.
35
_
9. A method according to claim 3 wherein thi
ocarbanilid is employed as the promoting agent
and is added separately from the sulfuric acid.
10. A method according to claim 3 wherein
the metals of the class containing gold and sil
ver are dissolved by the cyanide added and the
resulting solution containing these metals is sep
arated from the ground ore and subjected to
treatment for recovery of its gold and silver 45
content.
>
11. A method according to claim 1 wherein
the pulp is free from iron sul?des.
12. A method according to claim 1 wherein 50
the pulp is free from zinc sul?des.
the sul?des of the zinc and iron class with the
13. A method according to claim ,5 wherein
50 tailings.
3. A method for the ‘froth ?otation separation , the ore is free from iron sul?des.
of sul?de ores comprising preparing a ?otation
14. A method according to claim 5 wherein
' pulp containing copper sul?des and sul?des ofv
the class consisting of zinc and. iron sul?des
copper sul?des are of the character which
55 where
will be depressed by cyanide, adding cyanide to
the pulp thereby depressing iron and zinc sul
the ore is free from zinc sul?des.
'
15. A ?otation method according to claim 5 55
wherein thiocarbanilid is employed as the pro
moting agent and is added separately from the
acid. .
?des present, supplying sulfuric acid to the pulp, sulfuric
16. A method for the froth ?otation of sul?de
thereby reactivating depressed copper sul?des ’ ores
containing lead sul?de and sul?des of the
60 without reactivation of substantial proportions of class zinc and iron sul?des, comprising prepar
iron and zinc sul?des present, supplying frothing ing a ?otation pulp from the ore, adding a cy
and promoting agcnts to the pulp, and subject
anide compound and sulfuric acid to the pulp,
ing the same to froth ?otation to produce a cop
per sul?de froth concentrate and rejecting sub
stantially all the sul?des of the zinc and iron
65
class with the tailings.
4. A method for the froth'?otation separation
of sul?de ores containing lead and copper sul
?des and sul?des of the class consisting of iron
and zinc sul?des wherein the ore is of such char
70 acter that the copper sul?des will be depressed
by cyanide compounds, preparing a ?otation pulp
thereby inhibiting the ?otation of zinc and iron
sul?des present, supplying a frothing agent and 85
thiocarbanilid as a promoting agent and sub
jecting the pulp to froth ?otation and recov
ering a lead sul?de froth concentrate substan
tially free from iron and zinc sul?des and sub
stantially rejecting sul?des of said zinc and iron 70
class with the tailings.
‘-
’
FREDERIC A. BRINKER.
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