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5,837,210 Method for processing gold-bearing sulfide ores involving preparation of a sulfide concentrate

5,837,210

*Nov. 17, 1998

[11]

[45]

111111111111111111111111111111111111111111111111111111111111111111111111111

US005837210A

Patent Number:

Date of Patent:

United States Patent [19]

Simmons et al.

[73] Assignee: Newmont Gold Company, Denver,

Colo.

[75] Inventors: Gary L. Simmons, Albuquerque, N.

Mex.; John C. Gathje, Longmont,

Colo.

[54] METHOD FOR PROCESSING GOLDBEARING

SULFIDE ORES INVOLVING

PREPARATION OF A SULFIDE

CONCENTRATE

[ *] Notice: The term of this patent shall not extend

beyond the expiration date of Pat. No.

5,653,945.

OTHER PUBLICATIONS

Burger, "Froth Flotation Developments: This Industry

Workhorse Goes From Strength to Strength,"E&MJ (Sep.

1983) pp. 67-75.

Onstott et aI., "By-Product Molybdenum Flotation From

Copper Sulfide Concentrate With Nitrogen Gas In Enclosed

Wemco Nitrogen Flotation Machines," Preprint No. 84-65

(1984) Society of Mining Engineers ofAIME, Feb. 26-Mar.

1, 1984.

Berglund et aI., "Influence of Different Gases In Flotation of

Sulphide Minerals," Proceedings ofAn Engineering Society

Foundation Conference on Advances in Coal and Mineral

Processing Using Flotation (1989) pp. 71-76, Society for

Mining, Metallury and Exploration, Inc., Littleton, Colorado,

Dec., 1989.

FOREIGN PATENT DOCUMENTS

References Cited

Related U.S. Application Data

Appi. No.: 735,783

Filed: Oct. 23, 1996

[57] ABSTRACT

Provided is a method for processing a gold-bearing sulfide

ore which involves maintaining the ore in a substantially

oxygen free environment, preferably beginning with comminution

of the ore and ending when a desired final

concentrate, enriched in sulfide minerals, is obtained by

flotation. In one embodiment, nitrogen gas is used to substantially

prevent contact between the ore and air during

comminution of the ore and during flotation operations. It is

believed that oxygen gas present in air detrimentally affects

the recovery of sulfide minerals in a flotation concentrate

through surface oxidation of sulfide mineral particles. The

use of a gas such as nitrogen can significantly reduce the

potential for such surface oxidation. Additionally, gases

separated from an oxygen plant may be beneficially used,

with an oxygen gas stream being used, for example, for

pressure oxidation of sulfide mineral materials, and with a

nitrogen gas stream being used in comminution and/or

flotation operations, resulting in advantageous use of a

nitrogen gas by-product stream which has previously been

vented to the atmosphere as waste.

(List continued on next page.)

Primary Examiner~teven Bos

Attorney, Agent, or Firm-Holme Roberts & Owen

5/1906 Lovett ... ... 209/39

5/1991 Fair et al. 423/26

12/1991 Kerr et al. 423/26

5/1995 Kelebek et al. 252/61

8/1997 Gathje et al. 423/26

U.S. PATENT DOCUMENTS

Continuation-in-part of Ser. No. 423,839, Apr. 18,1995, Pat.

No. 5,653,945.

Int. C1.6 B03D 1/00; COlO 7/00;

C22B 11/00

U.S. CI 423/26; 423/27; 423/29;

209/166; 209/167

Field of Search 423/26,27,29,

423/DIG. 15; 209/39, 166, 167

821,516

5,013,359

5,074,993

5,411,148

5,653,945

[56]

[21]

[22]

[63]

[51]

[52]

[58]

2608462 6/1988 France 209/39

833320 5/1981 U.S.S.R 209/39 40 Claims, 24 Drawing Sheets

MINERAL

MATERIAL

FEED

102

GAS

SOURCE

ill

FLOTATION

CONCENTRATE

116

FLOTATION

TAIL

118

5,837,210

Page 2

OlliER PUBLICATIONS

Martin et aI., "Complex Sulphide Ore Processing With

Pyrite Flotation by Nitrogen," International Journal of Mineral

Processing, 26 (1989) pp. 95-110, Elsevier Science

Publishers B.Y., Amsterdam, no month.

Jones, "Some Recent Developments in the Measurement

and Control of Xanthate, Perxanthate, Sulphide, and Redox

Potential in Flotation," International Journal of Mineral

Processing, 33 (1991) pp. 193-205, Elsevier Science Publishers

B.Y., Amsterdam, no month.

Berglund, "Pulp Chemistry in Sulphide Mineral Flotation,"

International Journal of Mineral Processing, 33 (1991) pp.

21-31, Elsevier Science Publishers B.Y., Amsterdam, no

month.

Klymowsky et aI., "The Role of Oxygen in Xanthate Flotation

of Galena, Pyrite and Chalcopyrite," CIM, Bulletin

for Jun., pp. 683-688 (1970), Jun.

Rao et aI., "Possible Applications of Nitrogen Flotation of

Pyrite," Minerals, Materials and Industry (ed. M.T.Jones),

Institute of Mining and Metallurgy, pp. 285-293 (1990), no

month.

Rao et aI., "Adsorption ofAmyl Xanthate at Pyrrhotite in the

Present of Nitrogen and Implications in Flotation," Can.

Metall. Q., vol. 30, No.1, pp. 1-6 (1990), no month.

Xu et aI., "Sphalerite Reverse Flotation Using Nitrogen,"

Proc. Electrochem Soc., vol. 92-17, Proc. Int. Symp. Electrochem.

Miner. Met. Process. III, 3rd, pp. 170-190 (1992),

no month.

Van Deventer et aI., "The Effect of Galvanic Interaction of

the Behavior of the Froth Phase During the Flotation of a

Complex Sulfide Ore," Minerals Engineering, vol. 6, No. 12,

pp. 1217-1229 (1993), no month.

Author unknown, title unknown, Chapter IV, Gases and

Aeration, pp. 63-70, date unknown.

Plaskin et aI., "Role of Gases in Flotation Reactions,"

Academy of Sciences, U.S.S.R. Moscow, date unknown.

Kongolo et aI., "Improving the efficiency of sulphidization

of oxidized copper ores by column and inert gas flotation,"

Proceedings of COPPER 95-COBRE 95 International Conference,

vol. II, The Metallurgical Society of CIM, pp.

183-196, 1995, no month.

Rao and Finch, "Galvanic Interaction Studies on Sulphide

Minerals," Canadian Metallurgical Quarterly, vol. 27, No.4,

pp. 253-259 (1988), no month.

u.s. Patent Nov. 17, 1998

MINERAL

MATERIAL

FEED

102

108

COMMINUTION

104

Sheet 1 of 24

GAS

SOURCE

110

5,837,210

106

FLOTATION

112

FLOTATION

TAIL

118

114

FLOTATION

CONCENTRATE

116

Fig. 1

u.s. Patent Nov. 17, 1998

PARTICULATE

MINERAL

MATERIAL

+ 110

FLOTATION

112

FLOTXTION

TAIL

118

114

116

Sheet 2 of 24

AIR

132

OXYGEN

PLANT 130

128

Ir

PRESSURE

OXIDATION

124

t

OXIDIZED

MATERIAL

126

5,837,210

Fig. 2

u.s. Patent Nov. 17, 1998

FIRST

MINERAL MATERIAL

FEED

138

Ir

Sheet 3 of 24

SECOND

MINERAL MATERIAL

FEED

~ 140

MIXING

142

144

5,837,210

FLOTATION 116

112

114

PRESSURE

OXIDATION

124

128

OXYGEN

PLANT 130

,

FLOTATION

TAIL

118

Fig. 3

OXIDIZED

MATERIAL

126

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u.s. Patent Nov. 17, 1998 Sheet 10 of 24 5,837,210

102

116

4

8

118 Fig. 10

Ir

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1\ 10

106

ACID

TREATMENT \

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\ SOURCE

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118 Fig. 11

u.s. Patent Nov. 17, 1998 Sheet 11 of 24 5,837,210

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u.s. Patent Nov. 17, 1998

102

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Sheet 14 of 24 5,837,210

COMMINUTION

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/ SEPARATION

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Fig. 15

u.s. Patent

250 l

248

Nov. 17, 1998

102

Sheet 15 of 24 5,837,210

DEOXYGENATION

\ 104

110

/

COMMINUTION

108 1 GAS --..

SOURCE

~

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(114

+

FLOTATION 116

\

~118 112

240~

,

OXYGENATION

242 ~_

LEACH

246

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Fig. 16

u.s. Patent Nov. 17, 1998 Sheet 16 of 24 5,837,210

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u.s. Patent Nov. 17, 1998 Sheet 17 of 24 5,837,210

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u.s. Patent Nov. 17, 1998 Sheet 20 of 24 5,837,210

.. PAX

+ 8-703

... AP 5100

e AP 412

25 30

•

10 15 20

Float Time (min)

5

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u.s. Patent Nov. 17, 1998 Sheet 21 of 24 5,837,210

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u.s. Patent Nov. 17, 1998 Sheet 23 of 24 5,837,210

30

10 5 10

Float Time (min)

22

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-<> De-Ox H20

Fig. 25

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---.

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Float Time (min)

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u.s. Patent Nov. 17, 1998 Sheet 24 of 24 5,837,210

FIRST

MINERAL MATERIAL

FEED

SECOND

MINERAL MATERIAL

FEED

-138 ---140

'r

.r

- 108\ ACID

COMMINUTION PRETREATMENT

\

Ii L104

,r

106

~ 114)

PRESSURE

.. OXIDATION )

FLOTATION T

I 124

~112 1

116

1

126 Ir

118

Fig. 28

5,837,210

2

SUMMARY OF THE INVENTION

The present invention involves a method for processing

gold-bearing sulfide ores to facilitate gold recovery without

the burden of pressure oxidizing or roasting a whole ore and

without the substantial loss of gold value associated with

preparation of an ore concentrate by conventional flotation.

It has been found that air, which is used as the flotation gas

25 in conventional flotation, detrimentally affects flotation

separation of gold-bearing sulfide minerals, and that significantly

enhanced flotation performance may be obtained by

maintaining the sulfide ore in an environment substantially

free of air until a desired final flotation concentrate is

30 obtained.

It is believed that oxygen gas present in air tends to

oxidize the surface of certain gold-bearing sulfide mineral

particles, with the effect that flotation of those sulfide

35 mineral particles is reduced, resulting in a significant

amount of sulfide mineral which fails to float during

flotation, and, therefore, remains with the gangue.

By using a flotation gas that is deficient in oxygen gas

relative to air, however, the problems associated with the use

40 of air can be reduced. The result is an increased recovery of

sulfide materials in the concentrate, and correspondingly, an

increase in the recovery of gold in the concentrate. It is also

believed that the presence of oxygen promotes increased

galvanic interaction, which tends to depress sulfide minerals

45 during flotation.

In one embodiment, the gold-bearing sulfide minerals in

a sulfide ore are maintained in an environment that is

substantially free of oxygen beginning with comminution of

the ore and ending with recovery of a desired final sulfide

50 mineral concentrate. An oxygen deficient gas can be introduced

prior to or during comminution to displace any air that

may be present in the ore feed and to prevent air from

entering during comminution. Oxygen in the air that would

otherwise be present during comminution is, thereby, press

vented from oxidizing newly exposed sulfide mineral surfaces

created during comminution. Although comminution

in an atmosphere of the oxygen deficient gas is preferred, an

alternative to reduce detrimental effects of oxygen is to seal

the entire comminution process to prevent air from entering

60 into the process during comminution. With this alternative,

only oxygen initially in feed to comminution will be present,

so that damage to the mineral material will be limited.

In addition to reducing oxygen levels during comminution

and flotation, the use of an oxygen deficient gas tends

65 to decrease galvanic interaction, with a corresponding

increase in floatability of sulfide minerals. In one

embodiment, galvanic interaction is further reduced by

through a slurry of ore particles which have been treated

with reagents and the particles of the ore which are less

hydrophilic tend to attach to and rise with the air bubbles,

thereby permitting separation of the ore into two fractions.

5 Flotation has been used to prepare concentrates of goldbearing

sulfide minerals which are rich in the sulfide minerals

and relatively free of gangue material. One problem

with flotation of many gold-bearing sulfide ores, however, is

that a significant amount of the gold-bearing sulfide mineral

10 often reports to the wrong flotation fraction, representing a

significant loss of gold.

There is a significant need for an improved method for

processing many gold-bearing sulfide ores that avoids the

high costs associated with oxidatively treating whole ores

15 without the significant loss of gold associated with concentrating

sulfide ores by flotation.

FIELD OF THE INVENTION

CROSS-REFERENCE TO RELATED

APPLICATIONS

BACKGROUND OF THE INVENTION

1

METHOD FOR PROCESSING GOLDBEARING

SULFIDE ORES INVOLVING

PREPARATION OF A SULFIDE

CONCENTRATE

This application is a continuation-in-part of U.S. Pat.

application Ser. No. 08/423,839 filed Apr. 18, 1995, now

U.S. Pat. No. 5,653,945 the entire contents of which are

incorporated herein.

The present invention involves a method for processing

gold-bearing sulfide ores to facilitate recovery of gold from

the sulfide ore. In particular, the present invention involves

flotation processing of gold-bearing sulfide ores in a manner

that reduces problems associated with conventional flotation

to produce an ore concentrate. The present invention also 20

involves the flotation processing in combination with oxidative

treating, such as pressure oxidation, and use of

by-product gas from an oxygen plant used to supply oxygen

gas for the oxidative treating.

Significant amounts of gold are found in sulfide ores, in

which the gold is associated with sulfide mineralogy. The

gold is difficult to recover from such sulfide ores, because

the gold is typically bound in sulfide mineral grains in a

manner that renders the ore refractory to many traditional

gold recovery techniques, such as direct cyanidation of the

ore. Therefore, sulfide ores are commonly treated to chemically

alter the sulfide mineral to permit dissolution of the

gold during subsequent gold recovery operations.

One technique for treating a gold-bearing sulfide ore in

preparation for gold recovery is to subject the ore to an

oxidative treatment to oxidize sulfide sulfur in the sulfide

minerals, thereby rendering the gold more susceptible to

recovery. One method for oxidatively treating a sulfide ore

is pressure oxidation, in which a slurry of the ore is subjected

to oxygen gas in an autoclave at elevated temperature and

pressure to decompose the sulfide mineral, freeing the gold

for subsequent recovery. Other oxidative treating methods

include roasting and bio-oxidation of the ore in the presence

of air or oxygen gas.

Treating whole ores by pressure oxidation or by oxidative

roasting is expensive. Part of the expense is due to energy

consumed in heating gold-barren gangue material in the

whole ore, and especially the energy required to heat water

in which the gangue material is slurried in the case of

pressure oxidation. Also, process equipment for treating a

whole ore must be sized to accommodate the throughout of

gangue material, in addition to the throughput of the goldbearing

sulfide minerals, thereby significantly adding to the

cost of process equipment. Moreover, side reactions may

occur involving gangue material which can detrimentally

affect the oxidative treating or can produce hazardous materials

which require special handling.

One way to reduce the high energy and process equipment

costs associated with oxidative treating of a whole ore, as

well as the potential for problems associated with side

reactions, would be to remove gangue material from the ore

prior to the oxidative treatment. For example, one method

that has been used to remove gangue material from goldbearing

sulfide ores is flotation. In flotation, air is bubbled

5,837,210

3 4

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow diagram showing one embodiment of the

present invention;

FIG. 2 is a flow diagram showing another embodiment of

the present invention;

FIG. 3 is a flow diagram showing yet another embodiment

of the present invention;

FIG. 4 is a graph of the grade of concentrate recovered

from flotation versus grind size Examples 1-6;

FIG. 5 is a graph of the grade of tails from flotation versus

grind size Examples 1-6;

FIG. 6 is a graph of concentrate weight percent recovery

from flotation versus grind size for Examples 1-6;

FIG. 7 is a graph of gold recovered in concentrate from

flotation versus grind size for Examples 1-6;

FIG. 8 is a flow diagram for one embodiment of the

present invention relating to a pilot plant for Example 7; and

FIG. 9 is a graph of gold recovery in concentrate from

flotation versus grind size for Example 8;

FIG. 10 is a flow diagram of one embodiment of the

present invention including acid pretreatment;

FIG. 11 is a process flow diagram of one embodiment of

the present invention showing recycle of flotation gas;

FIG. 12 is a sectional elevation showing features of one

embodiment of a flotation apparatus of the present invention;

FIG. 13 is a sectional elevation of another embodiment of

a flotation apparatus of the present invention;

FIG. 14 is a process flow diagram of a comminution

circuit of one embodiment of the present invention;

FIG. 15 is a process flow diagram of one embodiment of

the present invention including magnetic separation prior to

flotation;

FIG. 16 is a process diagram of one embodiment of the

present invention including a leach of flotation tails and

including the use of deoxygenated water;

FIG. 17 is a process flow diagram of one method of the

present invention having multiple flotation stages with comminution

occurring between flotation stages;

FIG. 18 is a graph with plots of sulfide sulfur recovery

versus pH for Examples 9-28;

FIG. 19 is a graph including plots of gold recovery versus

pH for Examples 9-28;

FIG. 20 is a graph including plots of incremental gold

recovery and incremental sulfide sulfur recovery for

Examples 9-28;

FIG. 21 is a graph including plots of gold recovery versus

flotation time for Examples 29-35;

FIG. 22 is a graph of gold recovery versus flotation time

for Examples 29-35;

FIG. 23 is a graph including plots of gold recovery and

oxidation-reduction potential versus flotation time for

Example 36;

oxidation, although another oxidative treatment such as an

oxidizing roast or bio-oxidation may be used instead. Such

oxidative treating often requires a source of purified oxygen

gas, which is often produced by separation from air in an

5 oxygen plant. A by-product gas from such an oxygen plant

is deficient in oxygen gas and rich in nitrogen gas. The

by-product gas is, therefore, an ideal source of gas for use

during comminution and/or flotation of a gold-bearing sulfide

ore. This by-product gas is normally vented to the

10 atmosphere in current gold processing operations and is,

therefore, wasted.

reducing the amount of iron introduced into the system

and/or by removing iron from the system. Iron contamination

in the system may be reduced by using comminution

media made of stainless steel or hardened steel, rather than

the normal mild steel, and/or by using a nonmetallic liner for

comminution equipment. Iron may be removed from the

system prior to flotation by magnetic separation. It has been

found that reducing galvanic interaction can significantly

improve recovery of gold-bearing sulfide minerals during

flotation, especially when flotation is conducted with an

oxygen deficient flotation gas.

Possible sources of the oxygen deficient gas include

by-product gas from an oxygen plant, a dedicated nitrogen

plant, combustion exhaust gases, and on-site delivery of

compressed or liquified gases. In one embodiment to reduce 15

the consumption of the oxygen deficient gas, flotation gas is

recycled in the flotation operation.

When using an oxygen-deficient flotation gas according to

the present invention, adjustment of other flotation operating

parameters have been found to be unusually important to 20

maximizing flotation performance. In that regard, it has been

found that the flotation should be operated at an acidic pH,

preferably below about pH 6. Also, use of a lead-containing

activator significantly enhances flotation performance, as

does the use of deoxygenated water during comminution and 25

flotation. These additional enhancements are particularly

important because it has been found that the gold is often

most associated with the mineralogical/morphological sulfide

species that are generally the hardest to float. Therefore,

for example, a flotation enhancement that increases sulfide 30

mineral recovery by just one percentage point may increase

gold recovery in the concentrate by a proportionately larger

amount. This is because the incremental sulfide mineral

particles that tend to float with each enhancement include

those most likely to contain significant quantities of gold. 35

Conversely, the sulfide minerals that are easiest to float, such

as coarse grain pyrite, often contain little gold.

Another embodiment according to the present invention

includes a leach of flotation tails to recover gold remaining 40

in the tail that is not associated with sulfide minerals. For

some sulfide ores, this may be a significant quantity of gold.

The tail leach generally involves a cyanide leach. A major

advantage of the present invention is that the flotation tail is

relatively clean of sulfide minerals. This is important to 45

effective cyanide leaching of the tail because of the significant

loss of cyanide that would occur if significant quantities

of sulfide minerals were present in the tail.

In a still further embodiment according to the present

invention, a significant operational enhancement is obtained 50

by performing a regrind operation intermediate between two

flotation stages. This permits a more coarse initial grind to

be used for an initial stage of flotation to recover a significant

quantity of the sulfide mineral particles. The regrind

then permits additional liberation of sulfide minerals that 55

may be locked in middling particles. Such staged processing

would not be possible with conventional air flotation

because of the detrimental effects of oxygen during conventional

grinding and flotation.

In one aspect, the present invention involves the advan- 60

tageous utilization, in the processing of gold-bearing sulfide

ores, of gases which may be separated from air. In one

embodiment, a flotation operation, conducted substantially

in the absence of oxygen gas, is combined with oxidative

treating to decompose sulfide minerals, freeing gold for 65

possible subsequent dissolution using a gold lixiviant, such

as a cyanide. The preferred oxidative treating is pressure

5,837,210

TABLE 11

0.08

Twin Creeks

0.03

Gold Loss (%) per 1.0% Loss

Iron Sulfide

Lone Tree

TABLE 12

Morphology

Iron Sulfide

Coarse Grained

Pyrite

25 'Not applicable.

2Average content from 5 high grade samples from fine grained/amorphous

material.

Gold Content

Iron Sulfide (ppm by wt.) Grain

15

Morphology Lone Tree Twin Creeks Size

Coarse Grained Pyrite 2 2 Coarse

Blastic Pyrite 25 NA' Coarse

Medium Grained Pyrite 48 9 Medium

Fine Grained/Framboidal Pyrite 103 58 Fine

20 Amorphous/Framboidal Pyrite NA' 96 Fine to very

fine

Framboidal Pyrite 1902 271 Very fine

Marcasite 34 16 NA

Orpiment NA 28 NA

Finer grain size and finer morphological character of a

sulfide mineral renders the sulfide mineral generally more

susceptible to the detrimental effects from the presence of

oxygen in a flotation system. To obtain a high recovery of

gold in a flotation concentrate it is, therefore, extremely

important that the flotation be operated in a manner to

maximize the flotation of those mineralogical morphologies

that are most difficult to float. To illustrate this problem,

calculated gold losses are shown in Table 12 in flotation

tailings for each one percent equivalent loss of sulfide

mineral to the tail for the various species. As seen in Table

12, if one percent of the iron sulfide of the Lone Tree ore is

lost to the tail, and that one percent is framboidal pyrite, then

the corresponding loss of gold to the tail is over three

percent, or a loss of gold that is proportionately more than

three times the loss of iron sulfide material. As seen for Twin

Creeks, the loss of framboidal pyrite results in a loss of gold

that is proportionately more than ten times the loss of the

iron sulfide. To further illustrate, experience on the Lone

Tree, Twin Creeks and other ores indicates gold recoveries

in only the 50 to 80 percent range with conventional flotation

50 recoveries of sulfide minerals in the 75 to 95 percent range.

For the Twin Creeks ore, 87 to 90 percent flotation gold

recovery in the concentrate is not achieved until sulfide

sulfur recovery exceeds about 97 percent. By promoting the

flotation of the most difficult-to-float mineralogical/

morphological species of the sulfide minerals, the present

invention addresses the need for extremely high sulfide

mineral recoveries in the flotation concentrate to obtain

acceptable gold recoveries.

6

Nevada, U.S.A. As shown in Table 11, the pyritic species

represent a variety of mineralogical/morphological types. A

common theme, however, is that the gold content of the iron

sulfides generally tends to increase as the grain size and/or

5 morphologic character becomes finer. Coarse grained pyrite

contains very low levels of gold, whereas fine grained,

amorphous and framboidal pyrite all contain much higher

levels of gold. The pyritic species shown in Table 11 are

arranged in decreasing coarseness of grain size.

10

5

FIG. 24 is a graph including plots of gold recovery and

oxidation-reduction potential versus flotation time for

Example 37;

FIG. 25 is a graph including plots of weight recovery

versus flotation time for Example 38;

FIG. 26 is a graph including plots of gold-recovery versus

flotation time for Example 38;

FIG. 27 is a graph including plots of sulfide sulfur

recovery versus flotation time for Example 38;

FIG. 28 is a process flow diagram of one embodiment of

the present invention using gas generated in an acid pretreatment

step as a flotation gas.

The present invention provides a method for processing a

gold-bearing sulfide mineral material, such as a gold-bearing

sulfide ore, to facilitate recovery of the gold from the

mineral material. The method involves preparation of a

flotation concentrate in a manner that reduces problems

associated with conventional flotation. It has, surprisingly,

been found that the problems associated with concentrating

a gold-bearing sulfide ore by conventional flotation may be

significantly reduced by the use of a flotation gas which

comprises a lower volume fraction of oxygen gas than is

present in ambient air. Preferably, the flotation gas should be

substantially free of oxygen gas. When air is used as a

flotation gas, the oxygen gas in the air appears to detrimentally

affect the floatability of the sulfide minerals. This may 30

be due to a surface oxidation of sulfide mineral particles

caused by the presence of the oxygen gas. The surface

oxidation would tend to depress the sulfide mineral particles

during flotation. Furthermore, the detrimental effects of

oxygen gas may be further reduced by maintaining the ore 35

in an environment that is substantially free of oxygen gas

during comminution, mixing, pumping and all other processing

steps until a final flotation concentrate has been

obtained. For example, when multiple flotation steps are

used, it is desirable to maintain the ore in an environment 40

that is substantially free of oxygen gas between the flotation

steps.

By reducing the apparently detrimental effects of oxygen

gas, it is possible to recover a greater amount of the sulfide

mineral in the flotation concentrate. The present invention, 45

therefore, facilitates the recovery of gold from sulfide mineral

material which may have previously been discarded as

waste, either with the gangue in a flotation tailor as subgrade

ore previously believed to be uneconomical for gold recovery.

Enhanced concentration, according to the present

invention, of sulfide minerals into the flotation concentrate

provides a particular advantage with respect to gold recovery

from gold-bearing sulfide minerals. This is because it has

been found that gold in a refractory sulfide ore is often 55

predominantly associated with sulfide mineral

mineralogical/morphological species that are most difficult

to effectively float. Therefore, the increase in gold recovery

in the concentrate with the present invention will often be a

substantially greater percentage increase than the percentage 60

increase in recovery of sulfide minerals.

As an example of concentration of gold in difficult-tofloat

mineralogical/morphological species, a detailed mineralogical

characterization is shown in Table 11 of auriferous

pyritic species found in two refractory sulfide ore 65

samples. One ore sample is from the Lone Tree Mine and the

other ore sample is from the Twin Creeks Mine, both in

DETAILED DESCRIPTION OF IRE

PREFERRED EMBODIMENT

7

5,837,210

8

(l)Not applicable.

(2)Average content from 5 high grade samples from fine grained/amorphous

material

Morphology Lone Tree Twin Creeks

Blastic Pyrite 0.41 NA(l)

Medium Grained 0.80 0.36

Pyrite

Fine 1.71 2.29

Grained/Amorphous

Pyrite

Amorphous/Framboidal NA(l) 3.79

Pyrite

Framboidal Pyrite 3.15(2) 10.7

Marcasite 0.45 0.63

Orpiment NA 1.11

One embodiment in accordance with the present invention

is shown in FIG. 1. With reference to FIG. 1, a gold-bearing

mineral material feed 102 is provided for processing. The

mineral material feed 102 may be any gold-bearing material

comprising one or more sulfide mineral with which the gold

is predominantly associated, and from which the gold is

difficult to recover. The sulfide mineral could include one or

more mineralogy including pyrite, marcasite, arsenopyrite,

arsenous pyrite and pyrrhotite. The mineral material feed

102 is typically a whole ore, but may be a residue from other

processing or a previously discarded tail.

The mineral material feed 102 is subjected to comminution

104 to obtain a particulate mineral material 106 having

mineral particles of a size suitable for flotation. The particulate

mineral material 106 is preferably sized such that at

least 80 weight percent of particles in the particulate mineral

material are smaller than about 100 mesh, more preferably

smaller than about 150 mesh, and still more preferably

smaller than about 200 mesh. The size at which 80 weight

percent of a material passes is often referred to as a P80 size.

Any suitable grinding and/or milling operation may be used

for the comminution 104. Wet grinding and/or milling

operations are generally preferred due to their relative ease

and low cost compared to dry operations.

The comminution 104 is conducted in the presence of a

blanketing gas 108 which is obtained from a gas source 110.

During, or prior to, the comminution 104, the mineral

material feed 102 is mixed with the blanketing gas 108,

which contains oxygen gas, if at all, at a lower volume

fraction of oxygen gas than is present in ambient air, to

reduce problems that could be caused by the presence of air

during the comminution 104. During the comminution 104,

it is preferable to maintain a positive pressure of the blanketing

gas 108 into any grinding and/or milling apparatus to

assist mixing of the mineral material feed 102 with the

blanketing gas 108, and to displace any air which may have

been present with the mineral material feed 102.

After the comminution 104, the particulate mineral material

106 is subjected to flotation 112 to separate sulfide

minerals, with which the gold is associated, from non-sulfide

gangue material. During flotation, a slurry of the particulate

mineral material 106 is aerated with a flotation gas 114 from

the gas source 110. Any suitable flotation apparatus may be

used for the flotation 112, such as a one or more of a

conventional flotation cell or a flotation column. Preferably,

however, the flotation apparatus is such that a small positive

pressure of the flotation gas 114 may be maintained in the

Iron Sulfide

TABLE 12-continued

Gold Loss (%) per 1.0% Loss

Iron Sulfide

apparatus to prevent the entry of air into the apparatus. The

flotation gas 114 has oxygen gas, if at all, at a reduced

volume fraction relative to the volume fraction of oxygen

gas in ambient air, to reduce the problems associated with

5 using air as a flotation gas. Although not required, the

flotation gas 114 will normally be of substantially the same

composition as the blanketing gas 108 used in the comminution

104. Additionally, normal reagents may be added

during or prior to the flotation 112 to assist in flotation

10 separation. Such reagents may include frothing agents,

activators, collectors, depressants, modifiers and dispersants.

Preferably, the flotation 112 is conducted at ambient

temperature and a natural pH produced by the mineral

material. Operating conditions such as pH may, however, be

15 adjusted as desired to optimize flotation separation for any

particular mineral material.

Exiting from the flotation 112 is a flotation concentrate

116, which is recovered from the flotation froth and which

is enriched in sulfide minerals, and consequently is also

20 enriched in gold. Also exiting from the flotation 112 is a

flotation tail 118, which is enriched in non-sulfide gangue

materials, and consequently contains low levels of gold. The

flotation concentrate 116 may be further processed to

recover the gold by any suitable technique, if desired.

25 Alternatively, the flotation concentrate 116 may be sold as a

valuable commodity for processing by others to recover the

gold.

As noted previously, the flotation gas 114 and the blanketing

gas 108 each comprise oxygen gas, if at all, at a

30 volume fraction that is less than the volume fraction of

oxygen gas in ambient air. Preferably, however, the amount

of oxygen gas in the flotation gas 114 and/or blanketing gas

108 is less than about 15 volume percent, and more preferably

less than about 5 volume percent. Most preferably, both

35 the flotation gas 114 and the blanketing gas 108 are substantially

free of oxygen gas.

To aid in the understanding of the present invention, but

not to be bound by theory, it is believed that oxygen gas, if

present in any appreciable quantity, tends to oxidize the

40 surface of particles of certain gold-bearing sulfide minerals,

which can have the effect of depressing flotation of the

gold-bearing sulfide mineral particles during the flotation

112. By reducing the amount of oxygen gas that comes into

contact with a mineral material, it is believed that any

45 surface oxidation effect is reduced, resulting in enhanced

flotation of sulfide mineral particles and a corresponding

increase in the amount of sulfide mineral, and therefore gold,

recovered in the flotation concentrate 116. Therefore, it is

preferred that the flotation gas 114 and the blanketing gas

50 108 consist essentially of components which could not

oxidize the surface of gold-bearing sulfide mineral particles.

It is preferred that the flotation gas 114 and the blanketing

gas 108 predominantly comprise one or more gases other

than oxygen gas. Suitable gases include nitrogen, helium,

55 argon and carbon dioxide. Preferably, one or more of these

gases should comprise greater than about 95 volume percent

of the flotation gas 114 and the blanketing gas 108, and more

preferably greater than about 98 volume percent. Still more

preferable is for the blanketing gas 108 and the flotation gas

60 114 to consist essentially of one or more of these gases.

Nitrogen gas is particularly preferred because of its relatively

low cost. Carbon dioxide is less preferred because it

forms an acid when dissolved in water, which could corrode

process equipment or produce conditions less conducive to

65 optimum flotation.

The blanketing gas 108 and/or the flotation gas 114 may

be introduced into process apparatus in any appropriate

5,837,210

9 10

5

enriched stream from an oxygen plant. The nitrogen plant

may be based on separation of air into a nitrogen-enriched

stream and an oxygen-enriched stream by membrane

separation, cryogenic separation or otherwise.

Another possibility for the gas source 110 is a burner or

other combustion device to produce combustion exhaust

gases that are substantially depleted in oxygen. For example,

the gas source 110 could be exhaust from an electrical power

generator used to generate power for a mine or mineral

10 processing facility. When using combustion exhaust gases as

the blanketing gas 108 and/or the flotation gas 114, it is

preferred that the fuel combusted to produce the gases be a

clean-burning fuel such as natural gas, propane or another

liquified petroleum gas, or an alcohol such as methanol or

15 ethanol. Although less preferred, other fuels could be used

such as coal or fuel oils, including diesel fuel.

Yet another possibility for the gas source 110 is gas

generated during acid pre-treatment of a mineral material

feed 102 comprising carbonate minerals. Carbon dioxide gas

20 is generated from decomposition of the carbonate minerals.

The carbon dioxide may be used as the blanketing gas 108

and/or the flotation gas 114. Such an embodiment is shown

in FIG. 10. As shown in FIG. 10, the mineral material feed

102 is subjected to comminution 104 to form the particulate

25 mineral material 106. The particulate mineral material 106 is

then subjected to an acid pre-treatment 150 where acid 152

is added to the particulate mineral material 106 to decompose

carbonate minerals present in the particulate mineral

material 106. The particulate mineral material 106 remain-

30 ing following the acid pre-treatment is subjected to flotation

112, to form the flotation concentrate 116 and the flotation

tail 118. During the acid pre-treatment 150, a gas that is

enriched in carbon dioxide and deficient in oxygen is

produced, which is used as the blanketing gas 108 and the

35 flotation gas 114. An alternative to acid pretreatment of the

mineral material feed 102 is to use gases produced during

acid pretreatment of another carbonate-containing mineral

material, such as a whole ore, prior to pressure oxidation.

Such an embodiment is shown in FIG. 28.

A still further possibility for the gas source 110 is to have

liquid or compressed nitrogen, carbon dioxide or another gas

delivered to the site. On-site generation of the flotation gas

114 and the blanketing gas 108 is, however, preferred.

In one preferred embodiment of the present invention, the

flotation gas 114 is made up, at least in part, of recycled gas

from the flotation 112. One such embodiment is shown in

FIG. 11, where a recycle gas 156 from the flotation 112 is

used as part of the flotation gas 114. In this manner, make-up

50 flotation gas 114 from the gas source 110 may be kept to a

minimum. This recycling of gas from the flotation 112

provides the benefits of reducing the amount of make-up gas

that needs to be supplied by the gas source 110 and reduces

emission of oxygen-deficient gas from the flotation 112.

55 Reducing the emission of oxygen-deficient gas from the

flotation 112 is particularly important when the flotation 112

is conducted in an enclosed structure where people are

present, so that ambient air in the structure does not become

seriously deficient in oxygen. In that regard, oxygen moni-

60 tors should be placed in any such enclosed structure to

ensure that sufficient oxygen is present for human needs.

FIG. 12 shows features of one embodiment of a flotation

apparatus 160 that may be used with the present invention to

accomplish recycling of flotation gas. As shown in FIG. 12,

65 the flotation apparatus 160 has a sealed flotation tank 162,

above which is mounted a motor 164 for rotating a shaft 166

extending down into the flotation tank 162 to drive an

manner. Such gases may be fed under positive pressure or

may be induced into the apparatus by creating a suction

which pulls the gas in. Preferably, however, the apparatus is

designed to substantially prevent introduction of air into

comminution and flotation apparatus.

In one embodiment, the possible detrimental effects of

any surface oxidation of sulfide mineral particles that may

be present in a mineral material feed may be counteracted by

the addition of a sulfidizing agent, to at least partially replace

the oxidized coating with a sulfide coating. Any material

capable of reacting to form the desired sulfide coating of the

mineral particle could be used. Suitable sulfidizing agents

include alkali metal sulfides and bisulfides, such as Na2S,

NaHS, etc. Such sulfidizing agents could be added just

before or during any stage of the flotation 112.

With the present invention, greater than about 80 weight

percent of sulfide minerals from the particulate mineral

material 106 may be recovered in the flotation concentrate

116, and preferably greater than about 90 weight percent of

those sulfide minerals are recovered in the flotation concentrate

116.

One major advantage of the process of the present invention

is that, in addition to permitting a high recovery of

gold-bearing sulfide minerals in the flotation concentrate

116, it permits a high rejection of gangue material into the

flotation tail 118. Relative to the use of air as a flotation gas,

the present invention permits the same recovery of gold to

be obtained in a concentrate of smaller weight. This provides

a significant economic advantage because less gangue material

is present in the concentrate, from which the gold must

ultimately be separated to produce a purified gold product,

if desired.

The gas source 110 may be any source providing a

suitable flotation gas 114 and blanketing gas 108. One

preferred gas source 110 is a facility in which nitrogen gas

is separated from air, with the separated nitrogen gas being

used as the blanketing gas 108 and the flotation gas 114.

Several processes are known for separating nitrogen from

air, including cryogenic separation and membrane separa- 40

tion.

One particularly preferred gas source 110 is an oxygen

plant, which is commonly found at existing facilities where

gold-bearing sulfide ores are processed. An oxygen plant is

typically required, for example, when a pressure oxidation 45

operation or an oxidative roasting operation is used in the

processing of gold-bearing sulfide ores. In the oxygen plant,

oxygen is separated from air, such as by cryogenic separation

or membrane separation, and the separated oxygen gas

is used in the pressure oxidation or oxidative roasting

operation. A by-product of such an oxygen plant is an

effluent gas stream which is enriched in nitrogen gas and is

suitable for use as the blanketing gas 108 and/or the flotation

gas 114. This by-product stream has previously been vented

to the atmosphere and has, therefore, been wasted. With the

present invention, however, the by-product stream may be

beneficially used to produce the flotation concentrate 116, in

addition to using the oxygen gas product stream for the

pressure oxidation or oxidative roasting operation.

Another possibility for the gas source 110 is a nitrogen

plant dedicated to producing a nitrogen-enriched gas for use

as the blanketing gas 108 and/or the flotation gas 114. A

nitrogen plant differs from an oxygen plant in that the main

product stream is a nitrogen-enriched gas stream and the

by-product stream is an oxygen-enriched gas stream. The

oxygen-enriched gas stream from a nitrogen plant, however,

is normally of much lower purity in oxygen than an oxygen5,837,210

10

11

impeller 168. When the flotation apparatus 160 is operating,

a vapor headspace 170 exists above a liquid column 172.

Gas from the vapor headspace 170 is withdrawn via a

conduit 174 by a blower 176 to be forced through a conduit

178 for use as flotation gas. The flotation gas from conduit 5

178 is forced through an annular conduit 180 to the vicinity

of the impeller 168 so that the flotation gas may be

adequately distributed and dispersed throughout the liquid

column 172. Make-up flotation gas is provided via conduit

182 to compensate for any system losses of flotation gas.

FIG. 13 shows features of another embodiment of the

flotation apparatus 160 for effecting recycle of flotation gas.

In the embodiment shown in FIG. 13, the flotation apparatus

160 is designed such that a blower is not used. Instead, the

conduit 174 collects gases from the overhead vapor space 15

170 and cycles the gas to the annular conduit 180 for use as

a flotation gas. The action of the impeller 168 causes a

vacuum in the annular conduit 180 creating sufficient suction

to draw the flotation gas through the conduit 174 at a

sufficiently high rate. This type of flotation apparatus 160 20

design, therefore, is self-inducing with respect to the introduction

of flotation gas and does not require a blower or

other gas compression device. Cycling of the flotation gas

without the use of a blower is important because the recycled

flotation gas will normally contain a significant amount of 25

acid or corrosive mists or corrosive gases that could significantly

corrode interior surfaces of a blower.

Referring again to FIG. 1, as noted previously, the flotation

112 may be performed at a natural pH. It has been

found, however, that it is preferred that the flotation 112 be 30

conducted at an acidic pH, and preferably at an acidic pH

that is lower than about pH 6. Even more preferred is a

flotation pH range of from about pH 3 to about pH 6, and

most preferred is a pH range of from about pH 5 to about pH

6. Control of the pH may be accomplished by the addition 35

of an acid or a base as necessary to adjust the pH to within

the desired range. For example, sulfuric acid and/or any

other acid could be added to the flotation 112 to lower the pH

and lime, sodium carbonate, caustic or any other base could

be added during the flotation 112 to raise the pH. Acid for 40

reducing the pH could come from other mineral processing

steps, such as pressure oxidation or bio-oxidation, as discussed

below. Furthermore, acidification could be accomplished

by introducing sulfur dioxide into the flotation 112.

In its dissolved state in water, sulfur dioxide forms sulfurous 45

acid. The sulfur dioxide could be provided by exhaust gas

from a sulfur burner.

As noted previously, various reagents may be used during

the flotation 112. It has been unexpectedly found, however,

that copper-based activators generally do not perform as 50

well as lead-based activators used during the flotation 112.

Lead-based activators should contain lead in an oxidation

state of +2. One preferred activator is lead nitrate. Another

preferred activator is lead acetate. One benefit of using a

lead-based activator, relative to the use of a copper-based 55

activator such as copper sulfate, is that higher recoveries are

experienced in the flotation concentrate 116 for both sulfide

minerals and gold. Also, if the flotation tail is subjected to

cyanide leaching, as discussed below, the use of a lead-based

activator provides the additional advantage of lowering 60

cyanide consumption during the leaching operation relative

to a copper-based activator. An added advantage is that

cyanide consumption for eventual cyanide leaching of gold

contained in the flotation concentrate 116, such as after

pressure oxidation, will be lower with the use of a lead- 65

based activator compared to the use of a copper-based

activator.

12

Another reagent that has been found to be particularly

useful in the flotation 112 is a xanthate collector. The

appropriate xanthate collector may be provided by addition

to the flotation 112 of a xanthate salt such as potassium amyl

xanthate or sodium isopropyl xanthate. The enhanced performance

through use of a xanthate collector reagent is

significantly greater than would normally be expected, especially

when compared to the performance of other widely

used collector reagents.

When the mineral material feed 102 contains a significant

amount of organic carbon, the organic carbon can significantly

detrimentally interfere with recovery of gold and

sulfide minerals in the flotation concentrate 116. To reduce

the detrimental effects of organic carbon, when present in

the mineral material feed 102, it has been found to be

advantageous to add an aromatic oil to the flotation 112. One

example of such an aromatic oil is moly collecting oil,

commonly referred to as MCO.

As discussed above, the comminution 104 is conducted in

the presence of the blanketing gas 108. With reference now

to FIG. 14, one embodiment of a comminution circuit is

shown. As shown in FIG. 14, the mineral material feed 102

is fed to a first comminution unit 186, such as a sag mill. In

the first comminution unit 186, the mineral material particles

in the mineral material feed 102 are reduced in size. Output

from the first comminution unit 186 passes through a

trommel screen 188 in a sealed discharge box 190. Blanketing

gas 108 is fed into the discharge box 190 so that the

blanketing gas will flow back through the first comminution

unit 186 in counter-flow with the mineral material feed 102,

to ensure removal of air from the mineral material feed 102.

Material exiting the discharge box goes to a tank 192 for

delivery to a cyclone separator 194 via a pump 196. The

cyclone separator 194 classifies the mineral material by

particle size into an overflow 198 of smaller-size particles

and an underflow 200 of larger-size particles. The underflow

200 is then fed to sealed feed box 201 of a second comminution

unit 202, such as a ball mill, to further reduce the size

of mineral material particles in the underflow 200. Discharge

from the second comminution unit 202 passes through a

trommel screen 204 in a sealed discharge box 206. Blanketing

gas 108 is fed into both the feed box 201 and the

discharge box 206. Material exiting the discharge box 206

goes to a tank 208 where it is combined with the overflow

198 from the cyclone separator 194. Discharge from the tank

208 goes to a cyclone separator 210 via a pump 212. The

cyclone separator 210 makes a size separation of particles

into an overflow 214 comprising smaller-size particles and

an underflow 216 comprising larger-size particles. The

underflow 216 from the cyclone separator 210 is fed to the

second comminution unit 202 along with the underflow 200

from the cyclone separator 194. The overflow 214 from the

cyclone separator 210 goes to the tank 218 where particulate

mineral material in the overflow 214 may be held for feed to

flotation processing.

It should be noted that, as shown in FIG. 14, all process

equipment is sealed except for feed into the comminution

unit 186. Furthermore, the blanketing gas 108 is introduced

at various points in the comminution system to ensure that

minimal air makes its way into the system. As shown in FIG.

14, the blanketing gas 108 is specifically fed to the discharge

box 190 of the first comminution unit 186, to the tanks 192,

208 and 218; to the cyclone separators 194 and 210; and to

the feed box 201 and the discharge box 206 of the second

comminution unit 202.

In addition to maintaining the comminution environment

in the absence of any significant quantities of air, it is

5,837,210

13 14

enter into the system. With the present invention, however,

when it is not practical or economic to use a blanketing gas,

enhanced performance may still be obtained by sealing all

equipment involved with comminution processing so that

5 substantially the only oxygen entering into the comminution

processing enters with the mineral material feed 102 to be

processed. In that regard, such a comminution system could

be substantially as described with respect to FIG. 14, with all

process equipment sealed to prevent the entry of air and with

10 no blanketing gas 108 being fed to the process equipment.

Oxygen already present in the mineral material feed 102

would be consumed through oxidation of surfaces of sulfide

mineral particles exposed during comminution. Once all of

that original oxygen had been consumed, however, the

continued detrimental effects of oxygen would be substan-

15 tially eliminated. Although this mode of operation is not as

preferable as using the blanketing gas 108, it is preferred to

a system that it is open to the introduction of air, as is

commonly practiced.

To further reduce the amount of oxygen introduced in the

20 system to reduce the detrimental effects of surface oxidation

of sulfide minerals and of galvanic interactions, it is preferred

that process water used to slurry mineral material for

comminution processing and/or flotation processing has

been deoxygenated. Deoxygenation of process water can

25 significantly enhance recovery in the concentrate of sulfide

minerals and gold during flotation processing. The deoxygenation

may be performed in any convenient manner, such

as by bubbling an inert stripping gas, such as nitrogen or

carbon dioxide, through the process water to remove oxygen

30 from the process water or by adding an oxygen scavenger to

the water to tie-up the oxygen. It has been found that a

flotation tank works well for deoxygenation, with nitrogen

or carbon dioxide being introduced into the vessel to perform

the oxygen stripping function. Alternatively, the inert

35 stripping gas could be sparged into a tank containing the

process water. Preferably, the process water should be

deoxygenated to a dissolved oxygen level that is less than

about 1.0, and more preferably less than about 0.5, parts per

million of oxygen by weight.

Also, with the present invention it is possible to use

recycled water as process water. When recycled water is

used, however, it is important that an activator be used

during flotation processing. This is because any cyanide in

the recycle water that is available for reaction with sulfide

45 sulfur or sulfide minerals will tend to depress flotation of the

sulfide minerals and, accordingly, reduce the recovery of

gold in the concentrate. The activators, however, counter the

depressing effect that cyanide has on flotation. Also, the

recycle water may be treated with a material such as

50 ammonium bisulfite, sulfur dioxide, a peroxide, Caro's acid

or any other known cyanide destruction technology used to

destroy the cyanide prior to using the recycle water for

flotation.

As noted with respect to FIG. 1, one preferred gas source

55 110 for the blanketing gas 108 and the flotation gas 114 is an

oxygen plant. FIG. 2 shows one embodiment of the present

invention in which both the oxygen gas product stream and

the nitrogen gas by-product stream from an oxygen plant are

both used to process gold-bearing sulfide mineral material.

60 Referring to FIG. 2, particulate mineral material 110 is

subjected to the flotation 112 to produce the flotation concentrate

116 and the flotation tail 118, as previously

described. The flotation gas 114 is a nitrogen gas enriched

by-product stream from an oxygen plant 130, in which air

65 132 is separated into an oxygen enriched gas stream

(treating gas 128) and nitrogen enriched gas stream

(flotation gas 114).

Eq. 1

auriferous pyrite surface (cathode):

Vz02+H20+2e-~20H- Eq.2

For example, during grinding, galvanic cells are created

every time an auriferous pyrite mineral surface comes into

contact with grinding media, mill liners, abraded tramp iron

or any other metal sulfide at a lower or higher rest potential.

These galvanic interactions create hydroxide coatings on

sulfide mineral surfaces, depressing their floatability.

According to the present invention, such detrimental galvanic

interactions can be hindered by reducing the amount

of oxygen present during comminution through use of the

blanketing gas 108.

It has been found, however, that, in addition to reducing

the amount of oxygen present during the comminution

operation, improved flotation results may be obtained by

further limiting iron contamination of the mineral material

being processed. The combination of reducing the amount of

iron introduced into the mineral material and the use of the

blanketing gas 108 provides an increase in gold recovery in 40

the flotation concentrate that would be unexpected based on

the contributions of each alone.

One way to reduce the amount of iron available for

galvanic interactions during the comminution processing is

to use comminution media made of a hardened steel or a

corrosion-resistant steel, such as stainless steel or a high

chromium alloy steel. Although ceramic comminution

media could be used, ceramic comminution media are

typically not of sufficient density for effective comminution.

Another way to reduce detrimental galvanic effects from

iron is to provide all comminution equipment, such as

grinders and mills, with non-metallic liners, and preferably

with rubber liners.

A further, and preferred method for reducing detrimental

galvanic interactions caused by iron during flotation is to

perform a magnetic separation step after comminution and

prior to flotation. Referring to FIG. 15, an embodiment is

shown including a magnetic separation step after comminution.

As shown in FIG. 15, the mineral material feed 102

is first subjected to comminution 104, followed by magnetic

separation 230 to remove particles of magnetic material 232

from the mineral material 106.

As an alternative to the embodiments discussed thus far,

it should be noted that many of the advantages of the present

invention may be obtained even without the use of the

blanketing gas 108. In that regard, most conventional comminution

circuits utilize equipment that freely permits air to

important to the performance of subsequent flotation operations

that the effects of galvanic interaction be reduced as

much as possible during comminution of the mineral material

feed 102. Such galvanic interactions are due to different

electrochemical activities at different material surfaces. The

combination of a cathodic surface (i.e., pyrite, pyrrhotite,

etc.) and an anodic surface (i.e., iron from comminution

media or from steel walls of mill liners) results in the

creation of galvanic cell during the comminution processing.

Galvanic cells also exist between different sulfide minerals

that may be present in the mineral material feed, with the

sulfide mineral with the higher rest potential acting as the

cathode and the sulfide mineral with the lower rest potential

acting as the anode. For example, the galvanic interaction

between grinding iron and various forms of auriferous pyrite

can be represented by the following reactions:

grinding iron surface (anode):

15

5,837,210

16

The flotation concentrate 116, which is enriched in goldbearing

sulfide minerals, is subjected to pressure oxidation

124 to decompose sulfide minerals, producing an oxidized

material 126 from which the gold could be recovered by

dissolution using any suitable gold lixiviant, such as a

cyanide. The pressure oxidation 124 involves treating a

slurry of the flotation concentrate 116 in an autoclave at a

temperature of greater than about 1500 C. and an elevated

pressure in the presence of an overpressure of a treating gas

128, which is rich in oxygen. It should be noted that other

oxidative treating steps could be used instead of the pressure

oxidation 124. For example, an oxidative roasting or biooxidation

could be used to produce the oxidized material

126 using the treating gas 128.

A further embodiment in accordance with the present

invention is shown in FIG. 3 which uses the product and

by-product gas streams from an oxygen plant to process a

gold-bearing sulfide mineral material provided in two separate

feed streams. Referring to FIG. 3, a particulate first

mineral material feed 138 is subjected to the flotation 112 to

produce the flotation concentrate 116 and the flotation tail

118, as previously described. The flotation gas 114 is a gas

stream enriched in nitrogen from the oxygen plant 130. A

particulate second mineral material feed 140 is combined

with the flotation concentrate 116 in a mixing step 142. The

combined stream 144, in the form of a slurry, is subjected to

the pressure oxidation 124 to produce the oxidized material

126, from which gold could be recovered.

One advantage of the embodiment shown in FIG. 3 is that

it permits the processing of multiple ores having different

characteristics. For example, the first mineral material feed

138 may comprise a lower grade gold-bearing sulfide ore

than the second mineral material feed, which may comprise

a higher grade gold-bearing sulfide ore. The higher grade ore

may be suitable for pressure oxidation in a whole ore form,

whereas the lower grade ore must be upgraded to a concentrate

form to be suitable for pressure oxidation.

Alternatively, the second mineral material feed may comprise

a gold-bearing sulfide ore which has a significant

amount of carbonate material which would require acid to be

added prior to pressure oxidation 124, and which could,

therefore, cause high operating costs compared to ores with

low carbonate levels detrimentally interfere with proper

operation of the pressure oxidation 124. A high sulfide sulfur

content in the flotation concentrate 116, however, tends to

produce additional acid during pressure oxidation to at least

partially offset the acid consuming effect of carbonate material

in the second mineral material feed. Most of the carbonate

material that may have been present in the first

mineral material feed, if any, would ordinarily have been

removed during the flotation 112.

With the present invention, most of the gold reports to the

flotation concentrate. Gold in the concentrate, which is

typically substantially all associated with one or more sulfide

mineral, may then be freed for recovery operations by

oxidative processing, such as pressure oxidation, oxidative

roasting or bio-oxidation. Many mineral material feeds,

however, contain a significant amount of gold that is not

associated with a sulfide mineral. For example, it is not

uncommon for a gold-bearing refractory sulfide ore to also

contain some gold in association with oxidized minerals. Up

to 50%, and in some instances even more, of the gold in a

refractory sulfide ore may be associated with minerals other

than sulfide minerals. Also, refractory sulfide ores that have

been stockpiled for a significant amount of time, and therefore

exposed to air for a significant amount of time, may

contain even larger amounts of gold that are no longer held

by the sulfide minerals. This is because a significant amount

of a sulfide mineral may become oxidized so that a significant

quantity of the gold is no longer associated with the

sulfide mineral. For example, a refractory sulfide ore stock-

S piled for several months may oxidize to a degree where 20%

to 30% or more of the gold is no longer associated with

sulfide minerals.

It has been found that the present invention works very

well for the treatment of mineral material feeds having both

10 gold associated with sulfide minerals and gold not associated

with sulfide minerals. Gold that is not associated with sulfide

minerals, and especially gold associated with oxidized

minerals, may be recovered following flotation processing

by leaching of the flotation tail. Although any compatible

15 leaching operation may be used, a preferred leaching operation

is cyanide leaching. One embodiment of the present

invention involving a leach of the flotation tail is shown in

FIG. 16.

With reference to FIG. 16, a mineral material feed 102 is

20 provided having both gold that is associated with a sulfide

mineral and gold that is not associated with a sulfide

mineral. The mineral material feed 102 is subjected to

comminution 104 to prepare the particulate mineral material

106, which is then subjected to flotation 112. Following the

25 flotation 112, the flotation tail 114 is subjected to oxygenation

240 followed by a leach 242 of the flotation tail 114.

Preferred for the leach 242 is a carbon-in-pulp cyanide

leach, although a carbon-in-Ieach cyanide leach could be

used instead. Exiting from the leach 242 is loaded carbon

30 244 that is loaded with gold. Also exiting from the leach 242

is a leach tail 246 that is depleted in gold. The loaded carbon

244 may be processed in any known manner for recovery of

the gold.

With continued reference to FIG. 16, the comminution

35 104 and the flotation 112 are performed in the presence of

the blanketing gas 108 and the flotation gas 114,

respectively, supplied from the gas source 110. As also

shown in FIG. 16 process water 248 is subjected to deoxygenated

prior to using the process water 248 in the process.

40 Therefore, according to the embodiment shown in FIG. 16,

the process water 248 is first deoxygenated in the deoxygenation

step 250 and, following the flotation 112, the water

with the flotation tail 118 is then oxygenated in the oxygenation

step 240 prior to the leach 246. The oxygenation 240

45 may be accomplished in any manner suitable for increasing

the amount of oxygen dissolved in the liquid of the slurry of

the flotation tail 118. Typically, the slurry of the flotation tail

118 is subjected to sparging or bubbling with air or an

oxygen-enriched gas. Oxygenation 240 may be conducted

50 using air or an oxygen-enriched gas, such as would be

suitable for pressure oxidation processing, as previously

discussed. Although the embodiment described with respect

to FIG. 16 includes deoxygenation of process water, such

deoxygenation is not required. The use of deoxygenated

55 process water does, however, tend to improve gold recovery

from the process.

The ability to successfully leach the flotation tail 118, as

shown in FIG. 16, results from the efficient separation of

sulfide minerals into the concentrate during the flotation 112.

60 If a significant amount of sulfide mineral were to report to

the flotation tail 118, then performance of the leach 242

could be significantly impaired because sulfide sulfur from

the sulfide mineral would consume cyanide during a cyanide

leach and the gold in the flotation tail associated with the

65 sulfide mineral would not be leachable. With the present

invention, however, cyanide consumption is reduced during

the leach 242 because of the efficient reporting of sulfide

5,837,210

17 18

0.063 OZ/st(l)

0.05 OZ/st(l)

1.75 wt. %

1.66 wt. %

1440 ppm. by wt.

TABLE 1

EXAMPLES

LONE TREE SUBGRADE SULFIDE ORE

REPRESENTATIVE HEAD ANALYSIS

Gold

Silver

Total Sulfur

Sulfide Sulfur

Arsenic

(l)ounces per short ton of ore

For each example, the ore sample is ground to the desired

size. A first portion of the ore sample is subjected to flotation

in a laboratory-scale flotation cell using air as the flotation

gas. A second portion of the ore sample is subjected to

flotation under the same conditions, except using a flotation

gas which consists essentially of nitrogen gas. During each

flotation test, a flotation froth is collected from the top of the

flotation cell to recover a flotation concentrate which is

enriched in sulfide minerals, and which is, therefore, also

enriched in gold. The flotation tail is that material which is

not collected in the froth. For each flotation test, the flotation

conditions are substantially as follows: A natural pH and

addition of potassium amyl xanthate and mercaptoben-

Examples 1-6

Examples 1-6 demonstrate the use of nitrogen gas as a

flotation gas during flotation of a gold-bearing sulfide ore to

produce a sulfide enriched concentrate which could be

further processed to recover gold, if desired.

For each of Examples 1-6, an ore sample is provided from

Santa Fe Pacific Gold Corporation's Lone Tree Mine in

Nevada. The ore samples are of a low grade sulfide ore

which would be unsuitable for economic pressure oxidation

in a whole ore form. A representative assay of an ore sample

is shown in Table 1.

the cleaner flotation 292 and the cleaner scavenger flotation

294. Use of the blanketing gas 108 and the flotation gas 114

substantially prevents problems that could occur if comminution

and/or flotation operations were conducted in the

5 presence of air. Furthermore, because the detrimental effects

from air are reduced, it is possible to have the second

comminution step 284 intermediate between the first flotation

stage 256 and the second flotation stage 290 without

destroying the floatability of sulfide minerals in the reground

10 mineral material 286. The second comminution step 284

significantly improves performance of the flotation circuit.

This is because it will not be necessary to comminute all of

the mineral material feed 102 to a very fine size that may be

required for liberating gold-bearing sulfide minerals from

15 middling particles in the first comminution step 254. Having

a coarser grind for the particulate mineral material 106 is

significantly less expensive than comminuting all of the

mineral material feed 102 to a size small enough to liberate

gold-bearing sulfide mineral fragments from middling. Also,

20 a coarser comminution to produce the particulate mineral

material 106 simplifies operation of the first flotation stage.

Middling particles from the first flotation stage 256 are, then

further comminuted in the second comminution step 284 to

liberate the locked gold-bearing sulfide mineral fragments

25 for recovery in the second flotation stage 290.

The present invention is further described by the following

examples, which are intended to be illustrative only and

are not intended to limit the scope of the present invention.

minerals to the flotation concentrate 116 and the relative

absence of sulfide minerals in the flotation tail 118.

Another significant advantage of the process of the

present invention is that it permits interim regrinding of

particulate mineral material between flotation stages (to

enhance gold recovery in the concentrate). Such intermediate

grinding can significantly enhance recovery of gold in

sulfide minerals fragments locked in middling particles. By

comparison, with conventional flotation using air as the

flotation gas, such intermediate grinding would further

reduce the floatability of the particulate mineral material due

to the detrimental effects of oxygen.

FIG. 17 shows a process diagram for one embodiment

according to the present invention involving regrinding of

particulate mineral material intermediate between flotation

stages. As shown in FIG. 17, a mineral material feed 102 is

subjected to a first comminution step 254 to produce a

particulate mineral material 106, which is then subjected to

a first flotation stage 256. The first flotation stage 256

includes rougher flotation 258 and rougher scavenger flotation

260. In the rougher flotation 258, the particulate mineral

material 106 is separated by flotation into a rougher concentrate

262, which forms part of a final concentrate 264,

and a rougher tail 266, that is fed to the rougher scavenger

flotation 260. The rougher scavenger flotation produces a

rougher scavenger concentrate 268 and a rougher scavenger

tail 270. The rougher tail 266, the rougher scavenger concentrate

268 and the rougher scavenger tail 270 often

include a substantial amount of middling particles. Such

middling particles include gold-bearing sulfide mineral frag- 30

ments locked with gangue material, such as silica.

Additionally, the rougher scavenger tail 270 will typically

include a substantial amount of very fine slime particles.

To remove the slime particles and to permit recovery of

the sulfide mineral fragments from middling particles, the 35

rougher scavenger tail 270 is subjected to a size separation

274, such as may be accomplished using a screen or a

classifying cyclone. A first fraction 276, comprising the

smaller-size slime particles becomes part of a final tail 278.

For example, a 500 mesh screen may be used in the size 40

separation 274 with all particles passing through the screen

being sent to the final tail 278 as slimes.

Asecond fraction 280 from the size separation 274, which

comprises larger-size particles, is sent to a second comminution

step 284 along with the rougher scavenger concen- 45

trate 268. In the second comminution step 284, particles are

comminuted to a smaller size to break up middling particles

and liberate gold-bearing sulfide mineral fragments. The

reground mineral material 286 is sent to a second flotation

stage 290 for concentration of the sulfide mineral fragments 50

liberated from middling particles. The second flotation stage

290 includes cleaner flotation 292 and cleaner scavenger

flotation 294. In the cleaner flotation 292, a cleaner concentrate

296 is produced, which is sent to form part of the final

concentrate 264. The cleaner flotation 292 also produces a 55

cleaner tail 298 which is sent to the cleaner scavenger

flotation 294. In the cleaner scavenger flotation 294, a

cleaner scavenger concentrate 300 is prepared, which is

recycled to the second comminution step 284 for further

processing. The cleaner scavenger flotation 294 also pro- 60

duces a cleaner scavenger tail 302 that is sent to form part

of the final tail 278.

Also shown in FIG. 17 is the gas source 110 that supplies

blanketing gas 108 to the first comminution step 254, the

second comminution step 284 and the size separation 274. 65

The gas source 110 also provides flotation gas 114 to the

rougher flotation 258, the rougher scavenger flotation 260,

5,837,210

19

zothiazole as collectors, copper sulfate for activation of

sulfides and MIBC as a frother. Flotation times range from

20 to 30 minutes.

The results for examples 1-6 are shown tabularly in Table

2 and graphically in FIGS. 4-7 and reveal a significant

increase in the amount of gold recovered in the concentrate

when nitrogen gas is used as the flotation gas, especially at

smaller grind sizes.

20

used as a flotation gas, with the detrimental chemical process

counteracting the normally beneficial effects of a smaller

grind size. It was observed that when air is used as the

flotation gas, the pH of the slurry in the flotation cell drops

5 rapidly for several minutes, sometimes falling by as much as

0.5-2 pH units. Therefore, it appears that oxygen in the air

may be oxidizing the surface of sulfide mineral particles,

producing sulfuric acid and lowering the slurry pH. Such

surface oxidization of the sulfide mineral particles could

TABLE 2

LONE TREE SUBGRADE BATCH TESTS

Concentrate Concentrate Gold Reporting

Grind Grade Tail Grade Recovery to Concentrate

P80 oz gold/st(2) oz gold/st(3) wt. %(4) %(5)

Example Mesh(1) air nitrogen air nitrogen air nitrogen air nitrogen

1 100 0.31 0.35 0.019 0.020 15 15 75 75

2 150 0.28 0.31 0.021 0.016 15 16 71 79

3 200 0.33 0.29 0.021 0.016 15 19 74 81

4 270 0.22 0.25 0.022 0.012 20 24 72 86

5 325 0.23 0.20 0.022 0.016 20 25 73 81

6 400 0.14 0.14 0.029 0.012 29 33 67 85

(1)80 weight percent of material passing the indicated size

(2)ounces of gold per short ton of concentrate

(3)ounces of gold per short ton of tail

(4)weight percent of ore sample feed reporting to concentrate

(5)% of gold in ore sample feed reporting to concentrate

Example 7

This example further demonstrates the beneficial use of

nitrogen gas in the flotation of gold-bearing sulfide ores, and

the use of a rougher-scavenger-cleaner arrangement of flotation

to enhance recovery of concentrate.

A flotation pilot plant is operated using a low grade sulfide

ore from the Lone Tree Mine, as previously described with

Examples 1-6. The pilot plant flow is shown in FIG. 8.

With reference to FIG. 8, the ore sample 166 is subjected

to comminution 168 in a ball mill to a PSO size of 270 mesh.

The ground ore, in a slurry 170, is introduced into a rougher

flotation step 172. In the rougher flotation step 172, an initial

flotation separation is made with a rougher concentrate 174

being collected with the flotation froth and a rougher tail 176

being sent to a scavenger flotation step 178, material collected

in the flotation froth of the scavenger flotation step

178 is repulped and introduced, as a slurry 179, to a cleaner

flotation step 180, where a final flotation separation is made

to produce a cleaner concentrate 182 from the froth and a

cleaner tail 184. The cleaner tail 184 is combined with a

scavenger tail 186, from the scavenger flotation step 178, to

produce the final tail 188. The rougher concentrate 174 and

the cleaner concentrate 182 are combined to form a final

concentrate 190. In this example, the rougher flotation step

172 is accomplished in a single dual compartment flotation

cell, the scavenger flotation step 178 is accomplished in a

30 render them less responsive to flotation. As the grind

becomes smaller, the surface area available for oxidation of

the sulfide minerals increases significantly and, accordingly,

any beneficial effect from more complete liberation of

sulfide mineral due to the smaller grind size is offset by

35 increased surface oxidation, further depressing flotation of

the sulfide mineral particles. Nitrogen gas, however, would

not oxidize the surface of sulfide minerals and, therefore,

permits better flotation of sulfide mineral particles, resulting

in a higher recovery of sulfide minerals at the smaller grind

40 sizes, as would normally be expected.

FIG. 4 graphically shows the grade of the flotation concentrate

(measured as ounces of gold per short ton of

concentrate material) as a function of the grind size. As seen

in FIG. 4, no identifiable effect on the grade of the concentrate

is apparent from using nitrogen gas relative to using air

in the flotation. FIG. 5, however, shows that the flotation tail,

at smaller grind sizes, contains a significantly lower gold

value when using nitrogen gas as a flotation gas than when

using air. Therefore, when using nitrogen gas, more of the

gold-bearing sulfide minerals are recovered in the

concentrate, apparently without any detrimental effect to the

grade of the concentrate recovered. FIG. 6 shows that the

amount of material recovered in the concentrate may be

significantly higher when using nitrogen gas as a flotation

gas than when using air, especially at the smaller grind sizes.

FIG. 7 shows that gold recovery in the concentrate may be 45

increased by almost 15% at a PSO grind of 270 mesh, when

using nitrogen gas as a flotation gas as opposed to air, again

without detrimental effect to the grade of concentrate recovered.

It should be noted that at a PSO grind of 100 mesh, there 50

is no significant difference in flotation performance when

using nitrogen gas as opposed to air as the flotation gas. It

is, therefore, surprising and unexpected that the performance

using nitrogen gas would improve so markedly relative to air

at the smaller grind sizes. Typically, it is expected that 55

flotation performance should improve with a smaller grind

size due to a more complete liberation of sulfide minerals

from non-sulfide gangue material. As seen in FIG. 7,

however, the gold recovery in the concentrate when using air

as the flotation gas is flat, at best. When using nitrogen gas, 60

however, gold recovery generally increases with decreased

grind size due to increased sulfide mineral particle

liberation, as would normally be expected.

One way to explain the unexpectedly poor flotation performance

when using air, to assist in the understanding in the 65

present invention but not to be bound by theory, is that some

detrimental chemical process may be occurring when air is

21

5,837,210

22

Examples 9-28

These examples demonstrate the importance of flotation

pH and the choice of activators for use during flotation with

the present invention.

A series of laboratory flotation tests are performed using

Lone Tree low grade gold-bearing sulfide ore samples. Prior

to flotation, each sample is ground to a p80 size of about 60

microns. One series of tests are performed using a nitrogen

atmosphere in the grind and nitrogen flotation gas with

10 varying flotation pH using lead nitrate as an activator. A

second series of tests are performed using air as the grinding

atmosphere and air as the flotation gas at varying flotation

pH's and using lead nitrate as an activator. A third series of

tests are performed using nitrogen as the grinding environ-

15 ment and nitrogen flotation gas with varying flotation pH

and using copper sulfate as an activator. The pH is adjusted

by either the addition of sulfuric acid or calcium hydroxide,

as required. Also, other normal flotation reagents are used in

each test. Conditions for the grind and flotation for each

20 example are shown in Table 5 and specific reagents used

with each example are shown in Table 6.

Results of the flotation are shown tabularly in Table 7 and

graphically in FIGS. 18-20. FIG. 18 has plots of sulfide

series of three dual compartment flotation cells, and the

cleaner flotation step 180 is accomplished in a series of three

dual compartment flotation cells. As shown in FIG. 8,

nitrogen gas 192 is supplied from gas tank 194 and is fed to

each of the comminution step 168, the rougher flotation step 5

172, the scavenger flotation step 178 and the cleaner flotation

step 180. The nitrogen gas 192 is used as the flotation

gas in each of the flotation steps and is used as a blanketing

gas to prevent air from oxidizing ore particles during the

comminution 168. The nitrogen gas is also used to blanket

all other process equipment, not shown, such as pumps and

mixing tanks. Gold-bearing sulfide minerals in the ore

sample 166 are, therefore, maintained in a substantially

air-free environment through the entire pilot plant, until the

gold-bearing sulfide minerals have been recovered in a

desired concentrate product.

The results of the pilot plant are shown in Table 3, which

shows that the final concentrate 190 from the pilot plant is

of a higher quality than the concentrates shown in Examples

1-6. Addition of the scavenger flotation step 178 and the

cleaner flotation step 180 in the pilot plant significantly

improves the grade of concentrate finally recovered, without

any appreciable loss of gold recovery.

TABLE 3

LONE TREE PILOT PLANT

Example

Grind

P80

Mesh(1)

Final Concentrate Tail Grade Final Concentrate

Grade oz Recovery

oz gold/st(2) gold/st(3) wt %(4)

Gold Reporting

to Final

Concentrate

% gold

recovery(5)

7 270 0.57 .0095 9.4 86.4

(1)80 weight percent of material passing the indicated size

(2)ounces of gold per ton of respective concentrate

(3)ounces of gold per short ton of final tail

(4)weight percent of ore sample feed reporting to respective concentrate

(5)% of gold in concentrate relative to feed for the respective floatation step

40

TABLE 4

Twin Creeks SUBGRADE SULFIDE ORE

REPRESENTATIVE HEAD ANALYSIS

The results of Example 8 are graphically shown in FIG.

9 which shows a plot of gold recovery in the concentrate as

a function of grind size. As seen in FIG. 9, the use of

nitrogen gas generally results in a significantly higher recovery

of gold in the concentrate compared to the use of air as

a flotation gas.

Example 8

Laboratory tests are performed on samples of a low grade

gold-bearing sulfide ore from Santa Fe Pacific Gold Corporation's

Twin Creeks Mine in Nevada. A representative

analysis of an ore sample is shown in Table 4. For each test,

a sample is ground to the appropriate size and a portion of

each sample is then subjected to flotation using air as a

flotation gas and another portion is subjected to flotation

using nitrogen as a flotation gas. Substantially the same

flotation conditions are used as described for Examples 1-6.

sulfur recovery in the flotation concentrate versus flotation

pH for each of the three test series. FIG. 19 has plots of gold

recovery in the flotation concentrate versus flotation pH for

each of the three test series. As seen in Tables 5-7 and FIGS.

45 18 and 19, grinding and flotation using nitrogen gas provides

significantly enhanced performance relative to air for all but

the highest pH's. Furthermore, gold recoveries in the concentrate

are best at acidic pH's, and particularly at pH's

below about 6. Moreover, quite surprisingly, lead nitrate as

50 an activator consistently shows a significantly higher gold

recovery in the concentrate than the more standard activator

of copper sulfate.

FIG. 20 includes a plot of the difference in percentage

gold recoveries in the concentrate using nitrogen versus air

55 for various flotation pH's and a plot of the difference in

percentage recovery of sulfide sulfur in the concentrate

using nitrogen versus air for various flotation pH's. A

dramatic effect of pH is revealed in FIG. 20 at lower pH's.

For example, at pH 6, gold recovery in the concentrate

60 increases by greater than 15 percentage points for nitrogen

versus air with less than a 5 percentage point increase in

sulfide sulfur recovery. These results further indicate that

gold is often associated with sulfide mineral types that are

particularly difficult to recover in a concentrate using con-

65 ventional flotation with air as a flotation gas. These difficultto-

float sulfide mineral types float extremely well, however,

with the use of nitrogen, especially when a lead-containing

0.085 OZ/st(1)

0.28 OZ/st(1)

6.45 wt. %

6.27 wt. %

1630 ppm by wt.

Gold

Silver

Total Sulfur

Sulfide Sulfur

Arsenic

(l)ounces per short ton of ore

5,837,210

23

activator is used at an advantageously acidic pH. These

results, especially at pH's below about 6, are particularly

surprising.

24

TABLE 7-continued

Recovery in Concentrate

Examples 29-35

This example demonstrates the importance of the choice

of collector reagent in performing the flotation of the present

25 invention.

Laboratory flotation tests are performed on samples of

Twin Creeks low grade gold-bearing sulfide ore at a pH of

from about pH 5 to about pH 6 using various collector

TABLE 5

Grind

P-80 size Floatation

Example Atmosphere (microns) Floatation Gas pH

9 nitrogen 62 nitrogen 3

10 nitrogen 62 nitrogen 4

11 nitrogen 60 nitrogen 5

12 nitrogen 60 nitrogen 6

13 nitrogen 60 nitrogen 7

14 nitrogen 60 nitrogen 8

15 nitrogen 60 nitrogen 9

16 nitrogen 60 nitrogen 10

17 nitrogen 60 nitrogen 11

18 air 60 air 3

19 air 60 air 6

20 air 60 air 8

21 air 60 air 9

22 air 60 air 10

23 air 60 air 11

24 nitrogen 64 nitrogen 4

25 nitrogen 64 nitrogen 5

26 nitrogen 64 nitrogen 6

27 nitrogen 64 nitrogen 7

28 nitrogen 64 nitrogen 8

5

10

15

20

Example Gold (%) Sulfide Sulfur (%)

13 82.6 97.5

14 81.1 95

15 76.5 95.9

16 67.7 88.6

17 30.8 67.7

18 77.7 93.9

19 70.1 94

20 63.8 88.2

21 65.2 89.2

22 65.8 89.4

23 59.6 88.1

24 84.8 96.3

25 81.6 96.9

26 77.8 96.7

27 82.4 96.4

28 70.8 90.4

TABLE 6

Reagents (Ib/ton)

Calcium

Example Sodium Silicate MIBC(l) DF250(2) Sulfuric Acid Hydroxide PAX(3) Lead Nitrate Copper Sulfate

9 0.1 0.14 0.24 8.86 0 0.5 0.2 0

10 0.1 0.12 0.27 4.22 0 0.5 0.2 0

11 0.1 0.14 0.25 2.1 0 0.5 0.2 0

12 0.1 0.14 0.2 1.3 0 0.5 0.2 0

13 0.1 0.1 0.1 0 0.27 0.5 0.2 0

14 0.1 0.12 0.15 0 2.49 0.5 0.2 0

15 0.1 0.11 0.11 0 3.24 0.5 0.2 0

16 0.1 0.1 0.07 0 3.96 0.5 0.2 0

17 0.1 0.11 0.11 0 5.56 0.5 0.2 0

18 0.1 0.2 0.21 6.56 0 0.5 0.2 0

19 0.1 0.15 0.16 0 1.16 0.5 0.2 0

20 0.1 0.15 0.13 0 2.84 0.5 0.2 0

21 0.1 0.15 0.14 0 3.44 0.5 0.2 0

22 0.1 0.16 0.14 0 4.54 0.5 0.2 0

23 0.1 0.15 0.13 0 5.82 0.5 0.2 0

24 0.1 0.20 0.20 4.15 0 0.5 0 0.2

25 0.1 0.19 0.19 2.17 0 0.5 0 0.2

26 0.1 0.18 0.18 0.85 0 0.5 0 0.2

27 0.1 0.16 0.13 0 0.3 0.5 0 0.2

28 0.1 0.18 0.11 0 2.34 0.5 0 0.2

(l)Methyl isobutyl carbanol

(2)Polyethylene glycol

(3)Potassium amyl xanthate

TABLE 7

Recovery in Concentrate

Example Gold (%) Sulfide Sulfur (%)

9 86.7 96.8

10 86.7 95.3

11 85 97.3

12 86 97.3

reagents in cost equivalent amounts. A list of the different

collector reagents, companies that supply the reagents and

60 the amount of each collector reagent used are shown in Table

8. Nitrogen gas is used in the grind and as the flotation gas.

Particles are sized at a P80 size of about 46 microns and

flotation is conducted in a slurry with 30% solids. The ore

samples are of a low grade gold-bearing sulfide ore having

65 about 0.072 ounces per ton of gold and about 5.58 weight

percent sulfide sulfur. Other reagents used during the flotation

tests are shown in Table 9.

5,837,210

Other Reagents (Ib/ton)

TABLE 9

Sodium

Example Sulfuric Acid MIBC DF250 Lead Nitrate Silicate

(l)potassium amyl xanthate

(2)ethyl octyl sulfide, dialkyl dithiophosphate, polyglycol alkyl ether

(3)alkyl thionocarbonate

(4)Na-mercapto-benzothiazole and Na-di-iso-amyl dithiophosphate

(5)Na di-iso butyl dithiophosphate

(6)t-dodecyl mercaptan

(7)xanthogen formate

Example 38

This example demonstrates the important effect with the

25 present invention of using deoxygenated process water.

Samples of a Twin Creeks low grade gold-bearing sulfide

ore are subjected to laboratory flotation. Samples contain

about 0.072 ounces per ton of gold and about 5.58 weight

percent of sulfide sulfur. Grinding is performed in a nitrogen

atmosphere for each sample and flotation is performed using

nitrogen as the flotation gas. Both samples are sized at a P80

size of about 46 microns. One sample is slurried with regular

tap water for the flotation. The other sample is slurried with

tap water that has been deoxygenated by bubbling nitrogen

gas through the water for a sufficient time to remove most of

the oxygen previously dissolved in the water.

20

26

Samples of Lone Tree subgrade gold-bearing sulfide ore

are subjected to laboratory flotation. Both samples are

comminuted to a P80 size of approximately 270 mesh.

Following comminution, one sample is subjected to mag-

S netic separation to remove magnetic iron particles prior to

flotation while the other sample is not.

Results are shown graphically in FIG. 24, which includes

a plot of percent gold recovery in the flotation concentrate

10 versus flotation time and a plot of oxidation-reduction

potential in the flotation slurry versus flotation time. As seen

in FIG. 24, gold recovery is significantly higher for the

sample subjected to the magnetic separation. The effect is

15 particularly pronounced at shorter flotation times, but even

after 30 minutes of flotation, the sample having been subjected

to magnetic separation exhibits gold recovery that is

approximately ten percentage points higher than the sample

with no magnetic separation.

0.50

0.14

0.17

0.30

0.50

0.18

0.17

Amount lb/ton

30

0.12 0.25 0.3 1.0

0.11 0.07 0.3 1.0

0.07 0.07 0.3 1.0

0.09 0.09 0.3 1.0

0.04 0.04 0.3 1.0

0.17 0.17 0.3 1.0

35

0.11 0.11 0.3 1.0

Source

TABLE 8

Kerly Mining, Inc.

Minerals Reagents Inc.

Cytec Industries, Inc.

Cytec Industries, Inc.

Cytec Industries, Inc.

Phillips 66 Company

Minerec Mining Chemicals

Collector

PAX(l)

S-703(2)

AP-5100(3)

AP-412(4)

AP-3477(5)

CO-200(6)

Minerec A(7)

29

30

31

32

33

34

35

Example

29 7.76

30 4.8

31 4.37

32 5.0

33 5.04

34 5.74

35 5.49

25

Results of the flotation tests are shown in FIGS. 21 and

22, which plot percent gold recovery in the concentrate

versus flotation time for the various collector reagents. As

shown in FIGS. 21 and 22, potassium amyl xanthate performs

anomalously better than the other collectors with the

flotation of the present invention.

Examples 39-57

Samples of Lone Tree subgrade gold-bearing sulfide ore

are subjected to laboratory flotation. Each sample is ground

to a P80 size of approximately 270 mesh in a nitrogen

atmosphere. Flotation is conducted with a nitrogen flotation

gas. Following flotation for each sample, the flotation tail is

subjected to a carbon-in-Ieach cyanidation to recover gold

remaining in the flotation tail.

Results are shown in Table 10, where it is seen that the

leach of the flotation tail significantly contributes to gold

recovery according to the process of the present invention.

These examples demonstrate the benefit of a tail leach

55 with the present invention.

Results of flotation for each sample are shown in FIGS.

40 25-27. FIG. 25 includes a plot of weight recovery in the

concentrate versus flotation time for each sample, and shows

that flotation with the deoxygenated water attains a greater

weight recovery in the flotation concentrate. FIG. 26

includes a plot of gold recovery in the concentrate versus

45 flotation time for each sample, and shows that at the longer

flotation times, gold recovery is higher using the deoxygenated

water. FIG. 27 includes a plot of sulfide sulfur recovery

in the concentrate versus flotation time, and shows that, at

longer flotation times, sulfide sulfur recovery in the concen-

50 trate is higher using the deoxygenated water.

Example 36

Example 37

This example demonstrates a surprising effect of perform- 65

ing a magnetic separation on a ore sample prior to flotation

according to the present invention.

This example demonstrates the importance of grind media

on operation of the flotation of the present invention.

Laboratory flotation is conducted on Lone Tree low grade

gold-bearing sulfide ore samples using nitrogen during the

grind and during flotation as the flotation gas. All samples

were ground to a P80 size of about 44 microns. One sample

is comminuted using stainless steel rods while the other

sample is comminuted using conventional mild steel balls.

Results of the flotation are shown graphically in FIG. 23,

which includes a plot of percent gold recovery versus

flotation time for each sample and a plot of oxidation

reduction potential versus flotation time for each sample. As

shown in FIG. 23, the sample milled with stainless steel rods

exhibits substantially higher gold recovery at all flotation

times. More importantly, a high gold recovery is achieved in

a much shorter flotation time for the sample milled with the

stainless steel rods than for the sample milled with the mild

steel balls. This distinction is significant because it indicates

that flotation times may be reduced with the use of stainless

steel or other comminution media, such as a high chromium 60

alloy hardened steel, that would introduce less reactive iron

into the flotation system.

5,837,210

27 28

2. The method of claim 1, wherein:

said flotation gas comprises less than about 5 volume

percent oxygen gas.

3. The method of claim 1, wherein:

said flotation gas comprises greater than about 95 volume

percent of gas selected from the group consisting of

nitrogen gas, carbon dioxide gas, helium gas, argon gas

and combinations thereof.

4. The method of claim 1, wherein:

said flotation gas comprises combustion exhaust.

5. The method of claim 1, wherein:

relative to said mineral material feed, said flotation concentrate

is enriched in, and said flotation tail is depleted

in, substantially each and every sulfide mineral present

in said mineral material feed prior to said flotation.

6. The method of claim 1, wherein:

said flotation is substantially not selective to flotation of

said pyrite, marcasite, arsenopyrite, arsenous pyrite and

pyrrhotite, so that said flotation concentrate is enriched,

relative to said mineral material feed, in substantially

any of said pyrite, marcasite, arsenopyrite, arsenous

pyrite and pyrrhotite present in said mineral material

feed.

7. The method of claim 1, wherein:

after said flotation, said flotation tail is subjected to

leaching to remove from said flotation tail gold that is

not associated with a sulfide mineral.

8. The method of claim 7, wherein:

said leaching comprises cyanide leaching of gold from

said flotation tail.

9. The method of claim 1, wherein:

said liquid medium comprises deoxygenated water.

10. The method of claim 9, wherein:

said deoxygenated water comprises less than about 1.0

part per million by weight of oxygen.

11. The method of claim 9, wherein:

said deoxygenated water, prior to said flotation, had been

prepared by passing a gas through water to remove

oxygen from said water.

12. The method of claim 1, wherein:

prior to said flotation, said mineral material feed is

subjected to wet comminution to reduce the particle

size of said mineral material;

water used during said wet comminution comprising

deoxygenated water.

13. The method of claim 12, wherein:

said comminution is conducted in an environment that is

substantially free of air.

14. The method of claim 1, wherein:

before said flotation, said mineral material feed is subjected

to comminution to reduce the particle size of said

mineral material feed;

said comminution being conducted in equipment sealed to

substantially prevent air from being drawn into said

equipment.

15. The method of claim 14, wherein:

said comminution comprises processing said mineral

material through a sealed comminution unit having an

inlet and an outlet;

a blanketing gas being introduced into at least one of said

inlet and said outlet;

said blanketing gas comprising no greater than about 10

volume percent oxygen.

5

45

20

65

40

10

15

5.7 93.0

9.1 90.7

10.3 83.2

11.4 87.0

9.2 88.2

12.3 86.8

12.8 88.3

8.9 88.8

4.3 86.7

9.8 93.4

5.4 90.9

4.6 90.2

3.9 91.8

3.5 82.3

5.8 84.2

1.5 85.9

6.1 82.7

5.4 92.5

4.0 84.7

Gold Recovery from Total

Flotation Tail Gold Recovery

TABLE 10

87.3

81.6

72.9

75.6

79.0

74.5

75.5

79.9

82.4

83.6

85.5

85.6

87.9

78.8

78.4

84.4

76.6

87.1

80.7

Gold Recovery(1)

Form Flotation

Concentrate

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

57

Example

25 The present invention has been described with reference

to specific embodiments of the present invention. According

to the present invention, however, any of the features shown

in any embodiment may be combined in any way with any

other feature of any other embodiment. For example, any 30

feature shown in anyone of FIGS. 1-3,8, 10-17 and 28 can

be combined with any other feature shown in any of those

figures. Furthermore, while various embodiments of the

present invention have been described in detail, it is apparent

that modifications and adaptations to those embodiments 35

will occur to those skilled in the art. It is to be expressly

understood that such modifications and adaptations are

within the scope of the present invention, set forth in the

following claims.

What is claimed is:

1. A method for flotation processing of a gold-bearing

mineral material feed that is refractory to gold recovery due

to association of gold in the mineral material with one or

more iron-containing sulfide mineral species, the method

comprising the steps of:

subjecting to flotation in a liquid medium said mineral

material feed in particulate form, said mineral material

feed comprising at least one iron-containing sulfide

selected from the group consisting of pyrite, marcasite,

arsenopyrite, arsenous pyrite, and pyrrhotite, said flo- 50

tation including passing bubbles of a flotation gas

through said liquid medium;

during said flotation, a first portion of said mineral material

feed rising through said liquid medium with said

bubbles and said first portion being collected from a 55

flotation froth as a flotation concentrate, a second

portion of said mineral material feed being collected as

a flotation tail;

said flotation concentrate being enriched, relative to said 60

mineral material feed, in said iron-containing sulfide

and in gold;

said flotation tail being depleted, relative to said mineral

material feed, in said iron-containing sulfide and in

gold;

wherein, said flotation gas comprises no greater than

about 10 volume percent of oxygen gas.

(1)Assumes 96% of gold in concentrate removed in elL leach following

pressure oxidation.

5,837,210

29 30

5

40

25

35

* * * * *

subjected to further flotation to produce a second

flotation concentrate enriched, relative to said first

flotation tail, in said at least one iron-containing sulfide

and in gold and to produce a second flotation tail

depleted, relative to said first flotation tail, in said at

least one iron-containing sulfide and in gold;

after said first flotation stage and prior to said second

flotation stage, said first flotation tail being subjected to

comminution to reduce the size of particles in said first

flotation tail.

30. The method of claim 29, wherein:

after said comminution and prior to said second flotation

stage, said first flotation tail is subjected to size separation

to separate said first flotation tail into two

fractions, a first fraction of smaller-size particles and a

second fraction of larger-size particles, said second

fraction being subjected to said second flotation stage

and said first fraction not being subjected to said second

flotation stage.

31. The method of claim 1, wherein:

said flotation is conducted in a sealed flotation apparatus

having a vapor headspace above said liquid medium;

gas is withdrawn from said vapor headspace and recycled

for introduction into said liquid medium to form at least

a part of said flotation gas.

32. The method of claim 31, wherein:

said flotation apparatus comprises means for dispersing

said flotation gas in said liquid medium, said means for

dispersing creating a vacuum to suck said gas from said

vapor headspace to introduce said gas into said liquid

medium.

33. The method of claim 22, wherein:

said lead-containing activator includes lead in a +2 oxidation

state.

34. The method of claim 22, wherein:

said flotation tail, after said step of flotation, is subjected

to cyanide leaching to recover gold from said flotation

tail.

35. The method of claim 34, wherein:

during said cyanide leaching of said flotation tail, consumption

of cyanide is lower using said lead-containing

activator relative to use of a copper-containing activator

during said step of flotation.

36. The method of claim 22, wherein:

said flotation concentrate, after said step of flotation, is

subjected to cyanide leaching to remove gold from said

flotation concentrate.

37. The method of claim 36, wherein:

during said cyanide leaching of said flotation concentrate,

consumption of cyanide is lower using said leadcontaining

activator relative to use of a coppercontaining

activator during said step of flotation.

38. The method of claim 22, wherein:

said liquid medium of said flotation comprises at least

some recycled process water.

39. The method of claim 38, wherein:

said recycled process water includes cyanide.

40. The method of claim 39, wherein:

said lead-containing activator at least partially counters a

depressing effect of said cyanide on said at least one

iron-containing sulfide.

10

50

said lead-containing activator comprises at least one of

lead nitrate and lead acetate.

24. The method of claim 1, wherein:

a copper-containing activator contacts said mineral material

feed during said flotation.

25. The method of claim 1, wherein:

a xanthate collector contacts said mineral material feed 45

during said flotation.

26. The method of claim 1, wherein:

during said flotation, said liquid medium is at an acidic

pH.

27. The method of claim 1, wherein:

during said flotation, said liquid medium is at a pH of

smaller than about pH 6.

28. The method of claim 1, wherein:

during said flotation, said liquid medium is at a pH of 55

from about pH 3 to about pH 6.

29. The method of claim 1, wherein:

said flotation comprises a first flotation stage of said

mineral material feed to produce a first flotation concentrate

enriched, relative to said mineral material feed, 60

in said at least one iron-containing sulfide and in gold

and to produce a first flotation tail depleted, relative to

said mineral material feed, in said at least one ironcontaining

sulfide and in gold;

said flotation further comprising a second flotation stage 65

wherein at least a portion of said first flotation tail is

16. The method of claim 15, wherein:

said blanketing gas comprises greater than about 95

volume percent of gas selected from the group consisting

of nitrogen gas, carbon dioxide gas, helium gas,

argon gas and combinations thereof.

17. The method of claim 14, wherein:

beginning with said comminution and ending with said

flotation, said mineral material feed is processed in an

environment that is substantially free of oxygen gas.

18. The method of claim 1, wherein:

before said flotation, said mineral material feed is subjected

to comminution to reduce the particle size of said

mineral material feed;

said comminution being performed in the interior of a 15

vessel having a nonmetallic interior lining to reduce the

potential for contamination of said mineral material by

Iron.

19. The method of claim 1, wherein:

before said flotation, said mineral material feed is sub- 20

jected to comminution in the presence of grinding

media to reduce the particle size of said mineral material;

said grinding media comprising at least one of a corrosion

resistant steel and a hardened steel alloy.

20. The method of claim 19, wherein:

said grinding media comprises at least one of stainless

steel and chromium alloy steel.

21. The method of claim 1, wherein:

30

before said flotation, said mineral material feed is subjected

to magnetic separation to remove particles of

magnetic iron to reduce galvanic interaction involving

iron during said flotation.

22. The method of claim 1, wherein:

a lead-containing activator contacts said mineral material

feed during said flotation.

23. The method of claim 22 wherein:


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