U.S. patent number 3,655,044 [Application Number 05/004,356] was granted by the patent office on 1972-04-11 for separation of molybdenum sulfide from copper sulfide with depressants.
This patent grant is currently assigned to The Anaconda Company. Invention is credited to John F. Delaney.
United States Patent |
3,655,044 |
Delaney |
April 11, 1972 |
SEPARATION OF MOLYBDENUM SULFIDE FROM COPPER SULFIDE WITH
DEPRESSANTS
Abstract
Molybdenum sulfide is separated from a molybdenite-containing
copper ore concentrate by subjecting an aqueous pulp of the
concentrate to froth flotation in the presence of a collector for
molybdenum sulfide and a Nokes-type (e.g., arsenic trioxide/sodium
sulfide) depressant for copper sulfide, the aqueous pulp being
aerated with an inert gas to effect flotation of the molybdenum
sulfide constituent of the pulp while maintaining the emf of the
pulp above about minus 200 millivolts.
Inventors: |
Delaney; John F. (Tucson,
AZ) |
Assignee: |
The Anaconda Company (New York,
NY)
|
Family
ID: |
21710377 |
Appl.
No.: |
05/004,356 |
Filed: |
January 20, 1970 |
Current U.S.
Class: |
209/167;
428/331 |
Current CPC
Class: |
B03D
1/06 (20130101); Y10T 428/259 (20150115) |
Current International
Class: |
B03D
1/00 (20060101); B03D 1/06 (20060101); B03d
001/06 () |
Field of
Search: |
;209/166,167 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Chem. Abstracts, 68, 1968 .
Froth Flot, 50th Anniv., Vol., 1962, pg. 5, 570-572.
|
Primary Examiner: Lutter; Frank W.
Assistant Examiner: Halper; Robert
Claims
I claim:
1. The process for the separation and recovery of molybdenum
sulfide from copper ore concentrates containing both molybdenum
sulfide and copper sulfide which comprises conditioning an aqueous
pulp of the copper ore concentrates with a collector for molybdenum
sulfide and a Nokes-type depressant for copper sulfide, and
subjecting the conditioned pulp to froth flotation in which an
inert gas that will prevent any oxidation from occuring in the
conditioned aqueous pulp is employed as the froth producing medium
to effect recovery of a molybdenum concentrate in the flotation
overflow and recovery of a copper concentrate in the flotation
underflow while maintaining the emf of the aqueous pulp above a
predetermined value to maintain the effectiveness of said
depressant for copper sulfide.
2. The process according to claim 1 in which the emf of the aqueous
pulp is maintained above about -200 mv. when measured with a
platinum electrode with reference to a standard GP (calomel) glass
electrode.
3. The process according to claim 1 in which the depressant for
copper sulfide is a reaction product of two or more inorganic
compounds, said reaction product containing bivalent sulfur, a
caustic cation and, combined therewith, an element selected from
the group consisting of phosphorus, aresenic and antimony.
4. The process according to claim 3 in which the aqueous pulp
contains a sufficient amount of said depressant for copper sulfide
to maintain the emf of the pulp above about -200 mv. when measured
with a platinum electrode with reference to a standard GP (calomel)
glass electrode.
5. The process according to claim 1 in which the non-oxidizing
aerating gas is selected from the group consisting of nitrogen,
freon, the inert gases and mixtures thereof.
6. The process according to claim 1 in which the non-oxidizing
aerating gas comprises nitrogen.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to separation and recovery of molybdenum
sulfide from copper ore concentrates containing both molybdenum
sulfide and copper sulfide by froth flotation in the presence of a
collector for molybdenum sulfide and a depressant for copper
sulfide to effect recovery of a molybdenum concentrate in the
flotation overflow and recovery of a copper concentrate in the
flotation underflow.
2. Prior Art
Sulfidic copper ores frequently contain minor but economically
significant amounts of molybdenite (MoS.sub.2) which, when
separated from the copper ore, comprises an important source of
molybdenum. By way of example, a typical low-grade copper ore may
contain about 1 percent copper sulfides and about 0.1 to 0.5
percent molybdenum disulfide. Such copper ores are beneficiated by
conventional froth flotation to obtain an ore concentrate
containing typically about 30 percent copper sulfides, if the ore
is chalcopyritic, and about 1 percent molybdenum disulfide, the
molybdenite following the copper minerals in the flotation circuit.
The molybdenite content of the copper ore concentrate is then
advantageously separated therefrom by differential flotation to
obtain a molybdenum concentrate containing 90 percent or more
MoS.sub.2. As noted, sulfidic copper minerals and molybdenite are
normally floated by the same collectors. Therefore, in order to
effect differential flotation of molybdenite-containing copper
concentrates it is necessary either to depress the copper sulfides
while floating the molybdenite content of the concentrate or to
depress the molybdenite while floating the copper sulfide content
of the concentrate.
A process widely used in the industry for effecting the
aforementioned differential flotation of molybdenite comprises
conditioning an aqueous pulp of the molybdenite-containing copper
ore concentrate with a conventional collector for molybdenum
sulfide and with a Nokes-type depressant for copper sulfide
followed by froth flotation of the conditioned pulp with a
conventional flotation machine to obtain a molybdenum concentrate
as the flotation overflow (concentrate) and a copper concentrate as
the flotation underflow (tailing). Nokes-type reagents are complex
sulfidic compounds of phosphorus, arsenic or antimony and a
caustic. They are available commercially from a number of
suppliers, one such reagent being Anamol "D" which is a mixture of
arsenic trioxide and sodium sulfide. Nokes-type copper depressants
do not destroy the ability of conventional copper collectors to
collect and float copper minerals, they merely selectively mask or
hinder the collecting power of these collectors for copper
minerals. It has been found that the amount of depressant in the
pulp must be maintained above certain empirically determined levels
to be effective. If the amount of copper depressant reagent present
in the flotation pulp is insufficient to be effective, either
because an insufficient amount was initially used or because some
of the depressant initially present has been consumed or lost, the
collector employed to float both sulfide minerals initially will
allow the copper minerals to refloat and efficient separation of
the two will not be obtained. Flotation plant operators have
heretofore found that the amount of Nokes-type copper depressant
required to insure efficient differential flotation is on the order
of from 15 to 20 pounds of depressant per ton of copper ore
concentrates being treated. As Nokes-type reagents are relatively
expensive, the relatively large quantities of these reagents
heretofore required to effect efficient differential separation add
significantly to the cost of the molybdenum ultimately
produced.
After an extensive investigation into the causes for high Nokes
reagent consumption I have discovered that if certain essential
operating procedures and criteria are observed a relatively small
amount of Nokes-type copper depressant is required to effect
efficient differential separation of molybdenite from sulfidic
copper minerals. Specifically I have found that when a copper ore
concentrate is subjected to conventional froth flotation in the
presence of a Nokes-type reagent differential flotation of the
mineral values proceeds efficiently and effectively until a point
is reached at which the reagent appears to lose, rather abruptly,
almost all of its ability to depress copper minerals. At the same
time the electromotive force (emf) of the flotation pulp, as
measured by reference to a standard half-cell, progressively
declines, the aforementioned abrupt loss in depressant ability of
the Nokes reagent becoming manifest when the emf of the pulp
reaches the vicinity of minus 200 millivolts (-200 mv.). Both
phenomena appear to be the result of the progressive destruction or
inactivation of the Nokes reagent which, in turn, appears to be due
to the use of air or other oxidizing gases as the aerating medium
in the conventional flotation operation. Based on these findings
and discoveries I have devised the improved process for the
differential flotation of molybdenite-containing copper ore
concentrates that is hereinafter described.
SUMMARY OF THE INVENTION
The improved process of the invention comprises conditioning an
aqueous pulp of copper ore concentrates containing both molybdenum
sulfide and copper sulfide with a collector for molybdenum sulfide
and a Nokes-type depressant for copper sulfide. The conditioned
pulp is then subjected to froth flotation in which an inert gas (or
gases) is employed as the froth producing medium to effect
flotation of a molybdenum concentrate in the flotation overflow and
the recovery of a copper concentrate in the flotation underflow
while maintaining the emf of the pulp above a predetermined value
in order to maintain the effectiveness of the depressant for copper
sulfide. The amount of the aforesaid copper depressant in the
flotation pulp should be sufficient to maintain the emf of the pulp
above about -200 mv. when measured with a platinum electrode with
reference to a standard GP glass electrode (calomel electrode). The
froth producing gas should be one which will not oxidize or react
with the copper depressant and advantageously is selected from the
group consisting of nitrogen, or the inert gases such as helium and
argon, or a mixture of these gases. I presently prefer to employ
nitrogen as the aerating gas, although specially treated combustion
gases the flue gases containing only nitrogen and other inert gases
may also advantageously be used.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph showing the percentage of the copper content of
the pulp that is depressed (i.e., that appears in the flotation
underflow) as measured with respect to time when the pulp is
aerated with an oxidizing gas (air) and with a non-oxidizing gas
(nitrogen); and
FIG. 2 is a graph which illustrates the relationship between the
percentage of copper depressed and the emf of the flotation
pulp.
DETAILED DESCRIPTION
As previously described, sulfidic copper ores frequently contain
minor amounts of molybdenum sulfides. Conventional ore
beneficiation operations result in the preparation of a copper ore
concentrate that may typically contain up to about 30 percent by
weight copper sulfides (if the ore is chalcopyritic) and up to
about 1 percent by weight molybdenite (MoS.sub.2). The molybdenite
is advantageously separated from the copper ore concentrate by
differential flotation in which an aqueous pulp of the concentrate
is conditioned with a conventional collector for molybdenum sulfide
and with a depressant for copper minerals, the conditioned pulp
then being subjected to conventional froth flotation to obtain a
molybdenum sulfide concentrate as the flotation overflow and a
copper sulfide concentrate as the flotation underflow. The copper
depressant employed is advantageously one of a variety of
Nokes-type reagents. Nokes-type reagents were first described in
U.S. Pat. No. 2,492,936, dated Dec. 27, 1949, and may be defined
broadly as the reaction product of two or more inorganic compounds,
the reaction product containing bivalent sulfur, a caustic cation
(for example, sodium, potassium, calcium, ammonium or the like)
and, combined therewith, an element selected from the group
consisting of phosphorus, arsenic and antimony. These reagents are
well known in the art and are available commercially from a number
of sources.
Conventional froth flotation is usually carried out in
agitator-equipped flotation cells which use air as the froth
producing gas. The amount of Nokes-type reagent required to depress
copper minerals effectively during such conventional froth
flotation operations has heretofore been determined empirically by
plant operators to be in the order of from 15 to 20 pounds of
reagent per ton of copper concentrates being treated. As a result
of my investigations I have found that when a non-oxidizing gas is
used as the froth producing gas in place of air, and when the
electromotive force (emf) of the flotation pulp is maintained above
a predetermined value, the amount of Nokes-type reagent required to
depress copper minerals effectively is reduced to about one fifth
to one half of the amount heretofore required.
Specifically, I have found when a copper ore concentrate is
conditioned with a Nokes-type reagent and is subjected to
conventional froth flotation using air as the froth producing gas
that, after a certain period of time, the Nokes reagent rather
abruptly loses its ability to depress copper minerals and as a
result these minerals now appear in the flotation overflow (the
froth) as though no copper depressant were present in the pulp. I
have also found when using air as the froth producer that the emf
of the flotation pulp progressively decreases from a maximum
initial value to a final value that closely approaches the emf of
the unconditioned pulp. The length of time that the Nokes reagent
retains its ability to depress copper minerals depends directly on
the amount of reagent initially present in the pulp, and the rather
abrupt loss in the ability of the reagent to depress these minerals
appears to take place when the emf of the pulp reaches an
empirically predetermined value. These findings indicate that, in
the course of conventional froth flotation with air, Nokes reagents
are progressively decomposed or consumed until insufficient reagent
remains in the pulp to be effective.
When an inert gas that is non-reactive with respect to the highly
alkaline Nokes reagent is used as the froth producing gas, the emf
of the flotation pulp remains substantially constant, and the
Nokes-type reagent retains its ability to depress copper minerals,
throughout the duration of the flotation operation. Moreover, when
an inert gas is used as the froth producing medium, a substantially
smaller quantity of Nokes-type reagent may be used as a copper
depressant than is the case when air or some other oxidizing gas is
employed as the froth producer. The non-oxidizing gases useful in
the practice of the invention include, but are not necessarily
limited to, nitrogen; and other inert gases such as helium and
argon; and various mixtures of these gases. One convenient source
of this type of gas is flue gas or combustion gas which has been
cooled and cleaned to remove dust particles and treated to remove
free oxygen, carbon dioxide and/or carbon monoxide therefrom.
The emf of the flotation pulp is determined by techniques that are
well known in the art. In brief, the electrical potential of the
pulp is measured by reference to the potential of a conventional
standard half cell. The absolute value, in millivolts, of the emf
or potential of the pulp will depend on a number of factors which
include the type and composition of the copper ore concentrate, the
type and concentration of the Nokes reagent employed and the type
of standard half cell with reference to which the emf of the pulp
is being measured. However, for a given ore concentrate, Nokes
reagent and type of standard half cell the emf of the pulp is
essentially reproducible from sample to sample. Moreover, in such
cases the emf of the pulp at which approximate value the Nokes
reagent appears to lose its ability to depress copper minerals is
approximately the same from sample to sample, and this approximate
emf value can be empirically predetermined for any given ore
concentrate, Nokes reagent and standard half cell by known
techniques. By way of example, when a chalcopyrite copper
concentrate produced from Twin Buttes ore is conditioned with
Anamol "D," a commercially available Nokes-type reagent, the
reagent appears to lose its ability to depress copper minerals when
the emf of the flotation pulp decreases to about -200 to -250 mv.
when measured with a platinum electrode with reference to a
standard GP (calomel) glass electrode.
The following examples are illustrative but not limitative of the
practice of the invention.
EXAMPLE I
A series of flotation experiments were performed on freshly
produced Twin Buttes copper concentrates assaying approximately
31.9 percent copper and 0.51 percent molybdenum to extract a
molybdenite rougher concentrate by the use of Anamol "D," a
Nokes-type reagent, as the depressant for copper minerals. A single
portion of the ore concentrate was divided into four equal samples
having an average weight of about 740 grams. Each sample (herein
referred to as Samples A, B. C and D) was conditioned with the same
collector for molybdenite and with a different amount of the
aforementioned Nokes-type depressant for copper. These conditioned
flotation samples are set forth in Table 1.
---------------------------------------------------------------------------
TABLE 1
Sample Molybdenite Copper Initial Weight Collector Depressant emf
Sample (gms) (lbs/ton) (lbs/ton) (Mv) (negative)
__________________________________________________________________________
A 750 0.520 5.34 -460 B 730 0.535 7.66 -520 C 750 0.52 10.7 -560 D
733 0.533 16.5 -610
__________________________________________________________________________
each conditioned sample was then subjected to froth flotation in a
standard laboratory flotation machine for a total period of 16
minutes using air as the froth producing gas. The emf of the
conditioned flotation pulp prepared from each sample was determined
just before the start of each flotation experiment and thereafter
at two minute intervals throughout the duration of the experiment.
The flotation overflow (that is, the froth) was also collected at
two minute intervals and the mineral content thereof weighed and
assayed. At the conclusion of each experiment the flotation
underflow (that is, the tails) was collected and the mineral
content thereof weighed and assayed. The results of these four
flotation experiments are set forth in Table 2: ##SPC1##
EXAMPLE II
A second series of flotation experiments were performed on similar
freshly produced Twin Buttes copper concentrates, a single portion
of the ore concentrate being divided into two equal samples (herein
referred to as Samples E and F) having an average weight of about
510 grams. Each sample was conditioned with the same molybdenite
collector and each with a different, relatively small, amount of
Anamol "D," the Nokes-type copper depressant. These conditioned
flotation samples are set forth in Table 3:
---------------------------------------------------------------------------
TABLE 3
Sample Molybdenite Copper Initial Weight Collector Depressant emf
Sample (gms) (lbs/ton) (lbs/ton) (Mv)
__________________________________________________________________________
E 527 0.76 3.8 -370 F 493 0.81 6.5 -360
__________________________________________________________________________
each conditioned sample was then subjected to froth flotation in
the same laboratory flotation machine for a total period of 16
minutes using nitrogen as the froth producing medium. The emf of
the flotation pulp was measured, and the flotation overflow was
collected and assayed, as in Example I. At the conclusion of each
flotation experiment the underflow was collected and assayed as
before. The results of these two flotation experiments are set
forth in Table 4: ##SPC2##
The results of the flotation experiments described in Examples I
and II are combined and are presented graphically in FIGS. 1 and 2
of the drawings. FIG. 1 shows the effectiveness of various
concentrations of Anamol "D" as a copper depressant with respect to
time (duration of flotation) when air and when nitrogen are used as
the froth producing gas. FIG. 2 illustrates the progressive
decrease in the emf and depressing effect of the Nokes reagent on
copper minerals in the flotation pulp when air is employed as the
froth producing gas as contrasted with the relatively constant emf
and the effective depression of the copper minerals in the pulp
when nitrogen is employed for this purpose.
Referring to FIG. 1, it is evident that, when the froth producing
gas is air, the percent of copper depressed with respect to time is
a function of the amount or concentration of Nokes reagent
initially present in the flotation pulp. Moreover, it is evident
that for a certain length of time, depending on the initial
concentration of the Nokes reagent, the percent of copper depressed
is very high until, rather abruptly, the reagent appears to lose
its ability to depress copper minerals, whereupon the percent of
copper minerals depressed drops sharply. In contrast to this, when
the froth producing gas is nitrogen, the Nokes reagent retains its
ability to depress copper minerals without appreciable
deterioration throughout the flotation operation. Of particular
significance is the fact that when an inert gas is used as the
froth producer, the amount of Nokes reagent required to achieve and
maintain a very high degree of copper depression is markedly less
than the amount required when air is employed as the froth
producing gas.
Referring to FIG. 2, the contrast between the rapid decrease in the
emf of the flotation pulp when air is used as the froth producer
and the relatively stable emf of the pulp when nitrogen is employed
as the froth producing gas is readily apparent. Also, the
relationship between the emf of the pulp and the aforementioned
abrupt loss is depressant ability of the Nokes reagent is
apparent.
* * * * *