Note: Descriptions are shown in the official language in which they were submitted.
1330125
-1- PC-3140A/
.. . .
..... .. .
POLYAMINES AS PYRRHCYllTE DEPRESSANT
IN A FL(~ATION PROCESS
.
The present invention is concerned with flotation and, more particularly, ~ -
with selective flotation of sulfidic minerals.
S BACKGROUND OF TÆ INVENTION
Ores and various concentrates of ores which contain valuable metals such
as nicke1, copper, zinc, lead, etc. as simple or complex sulfides together with small
amounts of the precious metals gold and silver platinum group metals present in various
forms including distinct sulfidic, selenic and telluric species are almost universally
concentrated by froth flotation using xanthates or other sulfur-containing collectors.
The various schemes of froth flotation employed are generally quite complex having
been developed in order to maximize grade and recovery of the valuable metals present
and to maximize discarding of rock and mineral species of little commercial value. ln ;
addition to strictly sulfide minerals, certain oxide or carbonate species of metals such as
copper can also be floated. ln floating these oxide or carbonate minerals such as ~ ~ -
cuprite, malachite, azurite, chrysocolla, etc., ground mineral surfaces can be sulfided
B :
.~
~ r
1 330 1 25
-2- PC-3140A/
by reagents such as sodium sulfide carried in the liquid continuum of the flotation pulp
or can be rendered amenable to flotation by overdosing with a collector such as a
xanthate. For purposes of this specification and claims the term "floatable non-ferrous
metal-containing mineral" is intended to include, but not be limited to, the mineral
S species chalcopyrite, chalcocite, pentlandite, niccolite, millerite, staMite, cuprite,
malachite, galena, stibnite, heazlewoodite, argentite, covellite, sperrylite, ciMabar,
cubanite, cobaltite, skutterudite and smaltite.
After concentration, sulfidic minerals are most often subjected to
pyrometallurgical oxidation, a bi-product of which is sulfur dioxide. Good practice, as
well as governmental orders, requires that sulfur dioxide released to the atmosphere be
minimized. Sources of sulfur often present in ore bodies are the minerals pyrrhotite,
pyrite and marcæite. Pyrrhotite has a composition roughly Fe~S9 and is symbolized
hereinafter as Px. In many ores Px carries with it very little material of economic ~ - `
value but does contain sulfur which contributes to the sulfur dioxide burden. Px can be
either strongly ferromagnetic, in which cæe it can be separated by magnetic separation,
or paramagnetic in which case magnetic separation is not practical. In the past,procedures such as the Inco-developed cyanide process, Canadian Patent No. 1,062,819
and the SOJair process Canadian patent No. 1,238,430 have been developed to
maximize rejection of Px during flotation. These processes in general have been
successful but often require extensive conditioning of mineral pulps to be reasonably
operable. ~ ~ ~
DlSCOVERY ~ - .
Our discovery involves the use of a class of reagents which permits
selective flotation of a floatable non-ferrous metal-containing mineral while depressing
the flotation of Px, but at the same time permining excellent grade and recovery of non- : -
ferrous metal values.
:~` ' ~' .' ~.
, ~ ::, .
.:
''''' ""'""'' '
B ~:
1 330 1 25
-3- PC-3140A
:, '.
DESCRIPTION OF INVENTION
In its broadest aspect, the present invention contemplates
a process or method of flotation of at least one non-ferrous metal-
containing mineral (as defined hereinbefore) in the presence of Px
which comprises treating a ground mineral mixture as a pulp in an
aqueous alkaline continuum with a polyamine preponderantly non-
heterocyclic in nature and having limited or nil collecting capacity.
The polyamine $s used prior to, during or after grinding in an amount
of at least about 0.05 gram per kilogram. (For purposes of this
specification and claims the kilogram weight refers to the dry weight
of solids in a flotation pulp and, more particularly, in the range of
about 0.10 to about 0.50 g/Kg.) Following polyamine addition, the
pulp may be cond:Ltioned aerobically or anaerobically for periods
ranging from O to 30 minutes. The pulp is then floated so that, in
the presence of a collector, a frother and a gas phase distributed
throughout the pulp, the non-ferrous metal-containing mineral floats
selectively as compared to the Px.
More specifically, the present invention has been tested
and found operable with ore pulps containing Px and the non-ferrous
20 metals copper and nickel specifically in the form of chalcopyrite ~-~
(Cp) and pentlandite (Pn) as well as sperrylite and other associated
mineral sulfide, selenide, arsenide and telluride species. In
flotation, the aqueous phase of the pulp has a p~ preferably in the ~ -
range of about 8 to 11 and, perhaps, ideally at about 9.2.
The present invention has also been tested and found
operable with ore pulps containing Px, Cp and Pn and in which the ore
has undergone a natural or induced process of oxidative conditioning
or leaching prior to or during flotation, such that the ore has been
exposed to oxygen as well as to oxidation products of the sulfide ion
such as sulfite or thiosulfate and to cations of copper, nickel, iron
or other metals to such an extent and in such a manner as to
detrimentally affect the selective separation of Cp and Pn from Px.
Ore having undergone such a process is hereinafter referred to as
'~oxldized ore`'. It is within the contemplation of the present
invention to treat an oxidized ore in which at least one non-ferrous
1 33 0 1 25
-4_ PC-3140A
metal-containlng mineral is to be separated from an iron-bearing
sulfide other than Px, such as pyrite or marcasite.
In carrying out the method or process of the present
invention the generally accepted techniques of mineral flotation are
employed. Thus, mineral species are in the form of ground particles
having an average size in the range of about 62 to 210 micrometers.
This size range avoids excessively fine slime producing material and
excessively coarse material which is not amenable to selective
flotation. For most practical purposes xanthogenates (xanthates) are
used as collectors, such materials being very efficient and
economical. The present invention has been tested and found
operative when the principle sulfide mineral collector is a xanthate,
a dithiophosphate or a thionocarbamate. Phosphinic acid,
mercaptobenzothiazole, dixanthogen formate and the like may also be -~ -
employed. The collectors are added in the usual amounts, e.g. of the
order of 0.04 gram of potassium amyl xanthate (KAX) per kilogram.
Frothers such as alcohols, methyl isobutyl carbinol, pine oil and ~ -
proprietary frothers such as those of the DOWFROT~ group can be used
and the gas phase is normally air bubbles distributed in the pulp by
a commercial flotation machine although nitrogen or nitrogen enriched
air can be used as the gas phase.
The essence of the present invention as specifically tested
ls the use of a polyamine to depress Px while allowing Cp and Pn and
other mineral sulfide, selenide and telluride species containing
valuable non-ferrous base and precious metals to float. In practice
up to the present time it has been found that polyamines containing
at least two amine moieties, at least two of which are separated by
two or three carbon atoms are operable. The present invention may
most advantageously be represented by ethylenediamine,
diethylenetriamine and triethylenetetramine. Other related
structures which have demonstrated selective depressant properties
include tetraethylenepentamine, pentaethylenehexamine,
2-[(2-aminoethyl)amino]ethanol, N-methyl ethylenediamine, 1,2
dismino 2 methylpropane, and Tris-(2-aminoethyl) amide. Structures
based upon propylene dismine show weak to absent depressant
properties snd are not very useful for the purpose of this invention.
'~"; '`~" '
.:,, . ,:,
- ` 1 330 1 25
_5_ PC-3140A
Unsuccessful structures include primary, secondary and
tertiary alkyl monamines and alkyl polyamines wherein the alkyl
group separating the amines has chain length four or larger. Also
unsuitable are molecules with R or R' unsubstituted moietles of
carbon chain length two or greater. These possess collecting
properties. Hydrophilic moieties larger than those contalning 2
carbon atoms (e.g. propanolyl) are also detrlmental to depressant
performance.
The depressant action of the above structures appears to
be related to the ability to form metal chelates. Thus, the most
favorable structure is that which allows two nitrogen atoms to
coordinate around a metal ligand in a five-membered ring (i.e., an
NCCN structure). Based upon this model a monamine will not be
effective and substituted amines will not be as effective (due to
15 steric hinderance) as unsubstituted amine groups. Nitrogen-oxygen -
chelating compounds (e.g. ethanolamine, NCCO) appear to be
ineffective. The NCCN depressants as described above are effective
only when the amlno group is predominantly non-protonated (i.e. at a
pH of approximately 8 eo 9 or higher, depending upon the basicity of
the amine being applied). Experimental confirmation of this model
has been obtained.
One interesting compound known for its chelating properties
i8 ethylenediamine tetraacetic acid. This compound is slow to
chelate in the NCCN configuration due to steric hindrance and tends,
instead, to form six-membered OCNCO rings around metal ligands.
Consequently, this compound is ineffective as a selective pyrrhotite
depressant as defined herein. The NCCN structure defined above
stands apart from the polymeric amine depressants described by
Griffith (e.g. U.S. Patents 4,078,993 and 4,139,455) in that amine
depressant structures for pyrrhotite in the abovementioned patents
depend upon the presence of tertiary amines with no required
geometrical relationship between amine moieties whereas the current
invention relies upon a specific configuration of two or more amine -;~
groups (which are most advantageously primary, but which may also be
secondary or tertiary) such that ethylene diamine chelate rings may
form.
16~ 3 0 1 2 5 PC-3140A ;-~ ~
It is within the contemplation of thls inventlon to use
amines and saturated or unsaturated cycllc structures whlch could
also confer the geometry required for chelatlon in an NCCN or NXXN
configuration. Among these are n, n+1 amino substltutions of
aromatlc and cyclic compounds (e.g. 1,2 diaminobenzene) or
aminomethyl substitution on nltrogen-containing aromatic rings such
as in 2 aminomethyl piperidine in which the surfactant properties are
conferred by coordination of a ligand between two nitrogen atoms in a
five-membered ring, as well as aliphatic amines capable of forming an
unsaturated five-membered ring (e.g. HN=CH-CH2-NH2). Nitriles have
an unfavorable geometry due to the displacement of the unshared
electron pair on the triple-bonded nitrogen.
In order to give those skilled in the art a better
appreciation of the advantages of the invention the following
15 examples are given. `
EXAMPLE I
- :-
A Sudbury, Ontario, Canada nickel-copper ore suitable for
rod mill feed was subjected to laboratory tests. This ore consists ~ ~-
psimarily of a matrix of silicates and pyrrhotite containing the ore -~
minerals pentlandite and chalcopyrite. 1250 grams of ore in a pulp
of 65Z solids with the aqueous liquld of the pulp (or slurry) having ~ -,` ~~an initial pH of about 9.2 were ground in a laboratory rod mill for ''
8.8 minutes per kilogram of solid. The ground pulp was floated in a `~
Denver~ D1 laboratory flotation machine using air as the gaseous
phase with about 0.04 g/Kg of ~AX as collector (0.01 g/Kg being added "~
to the grind and 0.03 g/Kg being added to the flotation cell) and
about .025 glKg of DOWFROTH~ 1263 as frother. Flotation was carried
out for a total of 19 minutes with samples of concentrate being `~
collected for the periods 0-3, 3-6, 6-10, 10-14 and 14-19 minutes.
30 The pH of the flotation feed was in the range of 9.0 to 9.5. For ' ;
comparative purposes illustrative of standard practice without the `
use of amine the data in Table 1 is given. In each of the tables in `
this specification the amount of pyrrhotite is calculated according --
to Inco standard practice by subtracting from the total sulfur assay
, .. ..
1 330 1 25
-7- PC-3140A -
the amount of sulfur which is contained in chalcopyrite and
pentlandite:
Px = [S - Cu* 1.0145 - Ni* 0.9652] * 2.549
Likewise, pentlandite isi calculated according to standard Inco
practice by subtracting from the nickel assay the amount of nickel
normally present as solid solution in pyrrhotite:
Pn = (Ni - 0.008* Px) * 2.7778
TABLE 1
Sudbury Ore, Standard Test
Assay S Distribution
Wt. ~ Cu Ni S Pn Px Cu Ni Pn Px
Calc Head100.0 0.85 0.83 7.981.9316.12100.00100.00100.00 100.00
Cumulatl~e
Concentrates
15 0 min 3.4 7.50 10.0532.9027.03 39.7430.1041.5047.60 8.40
3 min 8.3 7.03 6.49 33.4316.90 51.0868.9065.6072.80 26.40
6 min13.5 5.34 4.68 33.1111.67 59.0984.9076.6081.60 49.60
10 min17.6 4.33 3.87 32.729.3662.6789.6082.6085.20 68.50 - - -
14 min19.8 3.94 3.57 32.428.4963.6891.5085.4086.80 78.10 ~- ; -
20 ~ails80.2 0.09 0.15 1.960.324.39 8.5014.6013.2021.90
The data set forth in Tables 2, 3 and 4 represent the
practice of the present invention in which about 0.23 gtKg (of ore
solids) diethylene triamine, 0.23 g/Kg ethylene diamine, and 0.46
g/Kg 2-[(2-aminoethyl)amino] ethanol, respectively, are added during ;~
the grinding stage prior to flotation. A comparison of Tables 2, 3
and 4 with Table l shows that the addition of diethylene triamine,
ethylene diamine or 2-[(2-aminoethyl)amino] ethanol to the grind
results in less Px reporting to the concentrate at any given recovery
of Pn. None of the depressants show deleterious effects upon Cp or
Pn recoveries.
1 330 1 25
-8- PC-3140A
TABLE 2
Sudbury Ore, 0.23 g/Kg Diethylene Trlamlne
Assay S Dlstributlon
Wt. S Cu Nl S Pn PxCu Nl Pn Px
5Calc Uesd100.0 0.91 0.85 8.17 2.00 16.37100.00 100.00 100.00 100.00
Cumulatlve
Concentrates
O mln3.011.00 13.70 34.3037.49 25.28 36.2048.3056.20 4.60
3 mln5.411.98 10.13 33.1527.49 28 60 70 8064 2074 10 9 40
106 mln7.510.42 8,06 32.3721.61 35 73 85 7071 1081 10 16 40
lO mln10.18,24 6,39 31,8216,78 44,08 91,0075,8084,60 27,20
14 mln11,87,13 5,64 31,3614,60 47,64 92.3078,3086,20 34,50
Talls88.20,08 0,21 5,06 0,31 12,17 7,7021,7013,80 65,50
.,;,' ' ',
TABLE 3
",. ~ .
15 &dbury Ore, 0.23 g/Kg Ethylene Dlamlne
'' - ',;". '
Assay S Dlstrlbutlon '~
Wt. S Cu Nl S Pn Px Cu Nl Pn Px
. :: , . .-: -.
Calc Head100.0 0.85 0.877.99 2.06 16.05100.00 100,00 lOO.OO lOO,OO -
:,, . :,,,
Cumulative
20Concentrates
O min 2,9 6,99 15,0033,20 41.01 29,6523,9050,10 57.80 5.40
3 min 4.9 9,37 11,2432.54 30,53 31,0754,3063,60 73.00 9.50
6 mln 6.7 9.92 8.9632.04 24.13 33.9878.9069.60 79.20 14.30
10 min 9.1 8.34 7.1531.47 18.96 41.0489.3074.80 83.80 23.20 - , `~2514 min10.7 7,29 6,3030,64 16.53 43,7691,6077,40 85.70 29,10
,, : - .
Talls 89,3 0,08 0,225,29 0,33 12,748.4022.60 14,30 70.90
. .
';''.'
1 3301 25
-9_ PC-3140A
TABLE 4
Sudbury Ore, 0.46 glKB 2-¦(2-amlnoethyl)amlno] ethanol
Assay % Dls~rlbution
Wt. ~ Cu Ni S Pn PxCu Nl Pn Px
5Calc Head100.0 0.87 0.81 8.11 1.8B 16.43100.00 100.00 100.00 100.00
Cumulative
Concentrates
0 mln 4.5 9.23 10.20 33.30 27.54 35.9247.2056.50 65.60 9.80
3 min 6.9 9.50 7.76 32.59 20.69 39.4175.2066.50 76.20 16.60
106 min 9.0 8.41 6.52 31.36 17.17 42.1786.2072.30 81.90 23.00
10 min11.7 6.78 5.36 30.75 13.84 47.6590.4077.40 85.90 33.80
14 min14.2 5.67 4.60 30.43 11.63 51.5992.1080.90 87.90 44.50 -
~ails85.8 0.08 0.18 4.42 0.26 10.627.9019.10 12.10 55.50 ~ -
Ea~UMPLE II
Samples of Inco pyrrhotite re~ection feed were sub~ected to
treatment with diethylene triamine to illustrate the beneficial ~ -
effècts of these amine depressants on oxidized feed material.
Pyrrhotite re~ection fèed is derived from various stages of magnetic
separation, flotation and thickening of Sudbury nickel-copper ore and
20 is typically considered to be an oxidized stream showing poor --
selectivity when sub~ected to flotation.
Samples of Px re~ection feed were allowed to settle,
whereupon water was decanted to produce a slurry of about 55% solids
for regrinding. The slurry was ground for 5 minutes per kilogram of
dry solids, then repulped to 37X solids with process water prior to
flotation. No collector or frother were used. Flotation
concentrates were collected for the periods 0-3, 3-6, 6-10, 10-14 and
14-19 minutes. The flotation pH was about 9.3. For comparative
purposes illustrative of standard practice without the use of amines `
the data in Table 5 is given. This may be compared with Table 6, in
which 0.11 g/Kg (of dry solids) diethylene triamine (DETA) is added
to the regrind. Addition of DETA in this amount results in massive
depression of pyrrhotite (from 65.8% recovery in the standard test to
10.4X recovery in the test with DETA), although slight depression of
Pn was observed.
:' ~
1 330 1 25
_lo- PC-3140A
TA8EE 5
Px Re~ectlon Feed, Standard Test
Assay ~ Dlstrlbutlon
Wt. S Cu Nl S Pn Px Cu Nl Pn Px
Calc Head 100.0 0.70 1.44 10.41 3.53 21.18 loo.oo loo.oo loo.oo loo.oo
Cumulatlve . ~ . -. 'i
Concentrates
,,j .
O mln 7.5 4.33 9.88 29.8012.54 40.46 46.30 51.60 s6.60 14.40
3 mln 12.8 3.91 7.31 30.1311.32 48.73 71.20 65.10 69.80 29.50
lo 6 mln 16.6 3.36 6.16 30.359.74 s3.53 79.60 71.20 75.10 42.1010 mln 19.7 2.97 s.49 30.558.62 S6.67 s3.20 75.00 78.00 s2.70
14 mln 23.7 2.s9 4.82 30.397.49 S8.90 87.00 79.30 81.10 6S.80
Tails 76.3 0.12 0.39 4.22 0.35 9.49 13.00 20.70 T8.90 34.20
TABLE 6
15 Px Re~ectlon Feed, 0.11 g/Kg Dlethylene Trlamlne : .. ..
Assay S Dlstrlbution .- -
Wt. % Cu Ni S Pn PxCu Ni Pn Px
Cslc Head 100.0 0.68 1.40 10.47 3.4221.48loo.oo Too.oo loo.oo loo.oo
Cumulative
Concentrates
O min6.0 7.47 10.2025.00 27.90 19.3166.4043.90 49.30 5.40
3 min7.5 6.87 10.1824.64 27.s3 20.0176.2054.70 61.30 7.00
6 min8.6 6.35 9.74 23.88 26.60 20.4880.7059.90 67.10 8.20
10 min9.4 6.00 9.33 23.28 25.46 20.8482.9062.40 69.80 9.10
2s14 mlnlo.S 5.54 8.70 22.35 23.69 21.2485.5064.90 72.50 10.40 p
Tails89.5 o.ll 0.55 9.08 l.oS 21.5114.5035.10 27.50 89.60
EXAMPLE III '
Pyrrhotite rejection feed was floated in an experiment '~
ldentical to that of Example II, except that pentaethylene hexamine
was used as the amine depressant in place of DETA, at an addition
rate of 0.45 g/Kg of dry solids. Table 7 illustrates the results
obtained by flotation according to standard practice. The effects of
addlng pentaethylene hexamine are shown by the data of Table 8, in -
which the recovery of pentlandite is higher and the recovery of
pyrrhotite much lower than that observed in the standard test.
: " 1 330 1 25
PC-3140A
TABLE 7
Px Re~ectlon Feed, Standard Test
Assay S Distributlon
Wt. S Cu Ni S Pn Px Cu Ni Pn Px
5Calc Head100.0 0.57 1.23 9.202.9918.94100.00100.00 100.00 100.00
Cu~ulative
Concentrates
0 min 3.2 5.61 8.37 31.0022.27 43.9231.6022.00 24.00 7.50
3 min 7.8 4.48 5.95 29.0715.46 47.8860.9037.70 40.20 19.70
10 6 min10.6 3.87 5.07 28.2512.98 49.5371.8043.80 46.00 27.80
10 min15.6 2.92 4.32 29.0610.76 55.9179.3054.80 56.00 46.00
14 min23.1 2.11 3.59 28.918.6459.4285.2067.50 66.80 72.60
Tails76.9 0.11 0.52 3.261.296.75 14.8032.5033.20 27.40
TABLE 8
Px Re~ection Feed, 0.45 g/~g Pentsethylene Hexamine
Asssy S Distribution
~ Wt. S Cu Ni S Pn PxCu Ni Pn Px
Calc Head100.0 0.60 1.27 9.27 3,09 18,97100.00 100,00 100.00 100.00
Cumulati~e
Goncentrates
0 min 3.0 5.44 5.25 17.90 14.17 18.6427.2012.40 13.70 2.90
3 min 5.0 5.73 5.01 18.10 13.50 19.0048.2019.90 21.90 5,00
6 min 6.3 5.62 4.67 17.64 12.56 18.9259.3023.30 25.60 6.30
10 min11.1 4,21 5.72 22.12 15.18 31.4578.3050.20 54.50 18.40
2514 min14.7 3.43 5.66 22.34 14.95 34.1684.3065.60 70.90 26.40
Tails85.3 0.11 0.51 7.02 1.05 16.3615.7034.40 29.10 73.60
EXAMPLE IV
- ~
A sample was obtained from a stockpile of ore from the
Sudbury area. The stockpile originally consisted of a materisl
similar to that described in Example I except that the ore had been
allowed to lie dormant for cner a month, and had undergone extenslve
oxidatlon. The sample was treated according to a procedure identical
to that of Exa~ple I. The data presented in Table 9 illustrates the
flotatlon performance of the oxidized ore, and can be compared to the ~:
:: ~, ~::: :
~: ~ :;: ,' ':
-: : ~: -
11323 l 25 PC-3140A
data of Table 10, which illustrates the effect of adding 0.45 g/Kg
diethylene triamine (DETA~ to the grind. When DETA is added to the
grind the recovery of Px is lower at any given recovery of Pn than
that which is observed under standard conditions without DETA.
TABLE 9
Oxidized Ore, Standard Test
Assay % Distributlon
Wt. % Cu Ni S Pn PxCu Nl Pn Px
Calc Hesd100.0 0.46 1.13 13.73 2.45 31.02100.00100.00 100.00 100.00
10Cumulative
Concentrates ;~ -
O min 2.3 5.31 4.73 35.40 11.7064.8725.909.5010.~80 4.70
3 min 5.5 4.15 5.01 34.99 12.4666.1849.5024.5028.10 11.80
6 min 9.0 3.33 5.19 35.07 12.8968.0264.7041.3047.30 19.70
1510 min13.5 2.49 4.65 34.44 11.3669.9372.7055.6062.70 30.50
14 mln 21.1 1.74 3.64 33.78 8.48 72.6679.6067.9073.10 49.50 -
Talls 78.9 0.12 0.46 8.36 0.84 19.8720.4032.1026.90 50.50
...... .............. ............... ...................... ....... ........ ........ ......... ........ ... .... .................... ,~ ,,.
TABLE 10 ~ -
Oxidized Ore, 0.45 g/K8 Diethylene Triamine ,, -
Assay S Dlstrlbutlon
Wt. ~ Cu Nl S Pn PxCu Ni Pn Px
Calc Head100.0 0.46 1.15 14.57 2.47 33.11100.00100.00100.00 100.00
Cumulative :
Concentrates
25 0 min 2.3 5.19 6.01 34.40 15.37 59.4825.8011.80 14.10 4.10 - -
3 min 3.3 4.41 6.06 33.86 15.49 59.9932.2017.50 20.90 6.00
! i6 mln 4.7 4.23 6.92 33.55 17.95 57.5643.4028.10 34.00 8.10
10 mln 7.1 3.77 6.98 33.71 18.08 58.9958.9043.10 52.20 12.70 -
14 min10.9 2.87 5.67 33.01 14.35 62.7768.8053.70 63.50 20.70 ;~ ~
30 Tails 89.1 0.16 0.60 12.30 1.01 29.4631.2046.30 36.50 79.30 ~ -
EXAMPLE V :
A cample of Sudbury area nickel ore suitable for rod mill
feed and simllar to that ore described in Example I was floated
- 1 330 1 25
-13- PC-3140A
.' ~:.
according to the procedure described in Example I, except that the
addition of potassium amyl xanthate was cut back to 0.01 g/Kg, added
to the grind, while 0.03 g/Kg of Cyanamid~ AER0~ 3477 dithiophosphate
was used in flotation. Table 11 illustrates the flotation results
obtained according to this practice, while the data of Table 12 shows
the effect of adding diethylene triamlne 0.23 g/Kg to the grindlng
stage. The addition of diethylene triamine results in lower recovery
of Px at any given recovery of Pn, although Pn is quite strongly
depressed.
0 TABLE 11
Sudbury Ore, Xanthste and Dlthlophosphste a5 Collector
Assay % Dlstribution
Wt. S Cu Nl S Pn PxCu Ni Pn Px
Cslc Head100.0 0.83 0.85 7.98 2.0116.10 100.00100.00 100.00 100.00
15Cu~ulative
Concentrates
.,' :"
O mln 1.4 4.52 13.3031.70 36.1436.39 7.8022.4025.80 3.20
3 mln 4.1 9.07 7.76 32.55 20.6640.41 44.8037.5042.40 10.30 ----
6 mln 6.9 9.40 5.69 31.01 14.8443.28 77.2045.8050.70 18.40
10 mln 8.98.214.9131.10 12.6145.98 87.1051.0055.60 25.30
14 min 10.5 7.22 4.47 30.48 11.3448.04 90.3054.8059.00 31.20
Talls 89.5 0.09 0.43 5.36 0.9212.37 9.7045.2041.00 68.80
TABLE 12
Sudbury Ore, Xsnthate and Dlthlophosphate
a~ Collector ~ith 0.23 g/Kg Dlethylene Trlamine '~ -
Assay S Distributlon
~t. S Cu Nl S Pn Px Cu Ni Pn Px
Calc Bead 100.0 0.930.838.03 1.95 16.00100.00 100.00 100.00 100.00
Cumulative
Concentrates
O mln1.6 16.10 8.8829.7024.40 12.2226.9016.7019.50 1.20
3 mln2.6 16.45 8.0628.9922.14 11.5345.1024.9029.00 1.80
6 mln3.3 15.75 7.3927.7120.28 11.7055.5029.3034.20 2.40
10 min3.7 15.48 7.0027.1219.17 11.8961.1031.0036.20 2.70
3514 mln4.0 15.20 6.6226.4618.13 11.8665.1031.9037.10 3.00
Talls96.0 0.34 0.597.261.28 16.18 34.9068.1062.90 97.00
.~: : ,:
~ 1 330 1 25
-14- PC-3140A
EXAMPLE VI
: - '
A sample of Sudbury area nlckel ore suitable for rod mill
feed similar to that ore described in Example I was floated according
to the procedure described in Example I, except that the addition of
potassium amyl xanthate was cut back to 0.01 g/Kg, added to the
grind, while 0.03 g/Kg of Cyanamid~ S5415 th1onocarbamate was used in
flotation. Table 13 illustrates the flotation results obtained -
according to this practice, while the data of Table 14 shows the
effect of adding diethylene triamine 0.23 g/Kg of dry solids to the
10 grinding stage. As seen in the test with dithiophosphate, the - ~
addition of diethylene triamine results in lower recovery of Px at
any given recovery of Pn, although Pn is quite strongly depressed.
IABEE 13
- . , -. ` '' , ,,:
Sudbury Ore~ Xanthate and Thionocarbamate as Collector
Assay % Distribution
Wt. S Cu Ni S Pn PxCu Ni Pn PX
Calc Head100.00 0.89 0.87 7.98 2.05 15.90100.00 100.00 100.00 100.00 -~
Cumulative ~ '
Concentrates
200 min 1.4 4.09 11.00 30.40 29.67 39.856.6018.20 20.70 3.60
3 min 3.6 7.93 7.77 31.66 20.66 41.0931.6032.00 35.90 9.20 ,~ ::
6 d n 6.2 9.24 5.91 31.97 15.46 43.0864 3042 50 46 90 16 90 `~
10 min 8.2 8.80 5.22 31.74 13.49 45.3180 6049 40 53 90 23 30
14 min 10.2 7.50 4.86 31.37 12.41 48.6285.9057.50 62.00 31.30 - ` ~ , -
25Tails 89.8 0.14 0.41 5.31 0.87 12.1614.1042.50 38.00 68.70
' ' ~''.''.
~, ' ~ ' '''
~' ." " ~ `'~
- ` ; ~ :;
, :: :: ::
. ~ ' . .
~' ..
'' ', '" .
` 1 330 1 25
-15- PC-3140A
TABLE 14
Sudbury Ore, Xanthate and Thion~carbamate as
Collector Wlth 0.23 g/Kg Diethylene Triamine
Assay ~ Dlstribution
Wt. % Cu Nl S Pn Px Cu Nl Pn Px
Calc Head100.0 0.97 0.88 8.33 2.09 16 55100.00 100.00 100.00 100.00
Cumulative
Concentrates
0 min 1.4 15.00 7.00 27.50 19.13 14.0921.1010.80 12.50 1.~0
3 mln 2.4 15.696.58 26.85 18.0211.6838.70 17.90 20.80 1.70
6 mln 3.4 14.61 6.42 26.60 17.50 14.2351.6025.00 28.90 3.00 - --
10 mln 4.0 13.82 6.01 25.23 16.38 13.7956.3026.90 31.10 3.30 -
14 mln 4.6 13.15 5.56 23.85 15.14 13.1261.8028.80 33.20 3.60
Tails95.4 0.39 0.66 7.59 1.46 16.7238.2071.20 66.~30 96.40
15EXAMPLE VII - - ~ ;~
In U.S. Patent No. 4,684,459 ('459 patent) it is di6closed
that certain diamines have collector properties in the flotation of
certain ores, particularly chalcopyrite pentlandite ores.
Specifically, in Table I, col. 11 of the '459 patent it is disclosed
that N,N-dibutyl-1,2-ethane diamine (NDBED):
C4Hg ~ Hl ~C4H9 -
-CI-C-N\
H ¦ ¦ H
~- ~ H H ~;~
has collector properties as to a copper-nickel ore ~hich are
equivalent to those of sodium amyl xanthate an arch-typical l ;
collector. Data presented in this patent in terms of fractional
recovery after 12 minutes (R-12) are set forth in Table 15.
1 330 1 25
-16- PC-3140A ~- -
TABLE 15
Cu Ni Gangue Pyrrhotite ~' :
Na Amyl Xanthate 0.939 0.842 0.039 0.333
NDBED 0.926 0.849 0.042 0.473
Na Amyl Xanthate + 0 957 0 883 0 062 0.466
Table 15 shows that N,N dibutyl-1,2-ethane diamine collects rather
than depresses pyrrhotite. As to pyrrhotite, it is disclosed to be a --
better collector than sodium amyl xanthate.
Contrary to the action of NDBED, the compounds employed in
the process of the present invention exhibit essentially no collector
characteristics especially in the presence of xanthate collector. -
Values comparative to those in Table 15 were obtained floating
copper/nickel ore using potassium amyl xanthate, N-methyl ethylene
15 diamine (NMED, the two materials together and, to establish a - -
baseline for these tests a flotation using no reagent other than a
frother. Contrary to what was said in the previous sentence, the
numerical values taken from Table I of the '459 patent are not
directly comparable to numerical values set forth in this Example. - ~
20 However, the trends of the numerical values can be compared. ~ ~ ;
Table 16 sets forth the amounts in g/Kg of ore of frother,
xanthate and NMED in the tests made for this Example.
TABLE 16
Test Frother KAX* NMED**
A 0.025 -- -- ;
B 0.025 0.043 -- - - -
C 0.025 0.043 0.5
D 0.025 -- 0.5
I*KAX additions 0.01 g/Kg to grind, 0.033 g/Kg staged addition to
flotation - -
**This reagent was added to the grind
Overall results in terms of cumulative fraction in concentrates of
tests A through D are set forth in Table 17. - ~-
, ~'':
,''
-17-1 3 3 0 1 2 5 PC-3140A
TABLE 17
Test Copper Nickel Rock Pyrrhotite
A 0.462 0.05 0.009 0.134
B 0.929 0.807 0.034 0.755
C 0.926 0.729 0.028 0.258
D 0.790 0.431 0.011 0.051
A comparison of data in Table 17 with date in Table 15 shows as a
trend that recoveries of copper, nickel and pyrrohtite are
significant and substantial in both tables. Use of a diamine alone
as employed in the prior art (Table 15) results in recoveries of
copper, nickel and pyrrhotite similar to those encountered wlth
xanthate. When both were used together as reported in Table 15,
recovery of all three copper, nickel and pyrrhotite were enhanced.
In contrast when a compound within the restricted special group of .- ;
compounts employed in the present invention is used alone, it
exhibits nowhere near the collecting characteristics of a xanthate.
When used together with a xanthate, the copper and nickel recoveries
exhibited by xanthate alone are essentlally maintained, but two
thirds less pyrrhotite reports to the mineral concentrate. Thus by -
20 employing a restricted group of amine compounds in a flotation - -
process, the present invention provides mineralogical and
metallurgical flotation results not heretofore obtained and not ~ -~
taught by the relevant prior art.
While in accordance with the provisions of the statute,
25 there is illustrated and described herein specific embodiments of the -~
invention, those skilled in the art will understand that changes may
~- be made in the form of the invention covered by the claims and that
certain features of the invention may sometimes be used to advantage
without a corresponding use of the other features. It is to be noted
that reference herein to "Inco practice" and the like refers to
practices and the like employed at the facilities of Inco Limited in
the Sudbury district of the Province of Ontario, Canada.
: . .. .~ : . ,:
, : . ~:.:.. .-
