CA2719881A1 - Flotation of sulfide mineral species with oils - Google Patents

Abstract

This invention is directed to the use of non-sulfur containing compounds as collectors in the froth flotation of certain mineral sulfide and metallic compounds. These non-sulfur-containing compounds may be from natural sources, such as vegetable oils, or synthesized commercial sources. These non-sulfide collectors can be used singularly, in combinations, an in mixtures with known commercial sulfur containing collectors. These non-sulfur-containing collectors are compatible with common frothers.

Description

FLOTATION OF SULFIDE MINERAL
SPECIES WITH OILS

BACKGROUND OF THE INVENTION

This invention relates to the beneficiating or concentrating of ores. In particular, this invention relates to collectors useful in ore beneficiating.
Flotation is a process for concentrating minerals from their ores. Flotation processes are well known in the art and are probably the most widely used method for recovering and concentrating minerals from ores. In a flotation process, the ore is typically crushed and wet ground to obtain a pulp. Additives such as flotation or collecting agents and frothing agents are added to the pulp to assist in subsequent flotation steps in separating valuable minerals from the undesired, or gangue, portion of the ore. The flotation or collecting agents can comprise liquids such as oils, other organic compounds, or aqueous solutions. Flotation is accomplished by aerating the pulp to produce froth at the surface. Minerals, which adhere to the bubbles or froth, are skimmed or otherwise removed and the mineral-bearing froth is collected and further processed to obtain the desired minerals.
The basic technique behind froth flotation is to use chemicals to increase the hydrophobicity of the mineral to be beneficiated to form a concentrate.
Meanwhile, chemicals are added, as necessary, to decrease the hydrophobicity of unwanted (gangue) minerals, so that these minerals report to the slurry and are discarded as tail. The main alternative technique in froth flotation is "reverse flotation." This consists of floating the gangue minerals as a concentrate and keeping the mineral of interest in the slurry.
Chemicals that promote hydrophobicity of a mineral are called that mineral's "promoter" or "collector." Collectors based on fatty acids have long

2 been used in collecting one or more of the oxide minerals such as fluorspar, iron ore, chromite, scheelite, CaCO3, Mg C03, apatite, or ilmenite.
Also, early work used alkali metal salts of fatty acids, or soaps derived from natural oils by the process known as saponification. When an oil containing triglycerides is treated with a caustic solution under certain harsh processing conditions, the triglycerides disassociate into the alkali metal salts of the component fatty acids. The dissociation of the triglycerides into neutralized fatty acids is the saponification process. These neutralized fatty acids are soaps that act as non-selective flotation collectors.
Compounds containing sulfur, such as xanthates, thionocarbamates, dithiophosphates, and mercaptans, will selectively collect one or more sulfide minerals such as chalcocite, chalcopyrite, galena, or sphalerite.
Unfortunately, sulfur based collectors are often toxic, have repugnant odors or both. Amine compounds are used to float KCl from NaCl and for silica flotation. Petroleum-based oily compounds such as diesel fuels, decant oils, and light cycle oils, are often used to float molybdenite. Those oils are also used as an "extender oil"
that reduces the dosage of other more expensive collectors in the amine flotation of KCI.
Previous work on sulfide minerals has indicated that molecules containing sulfur are useful compounds for the froth flotation of sulfide minerals. These collectors'are usually grouped into two categories: water-soluble and oily (i.e., hydrophobic) collectors. Water-soluble collectors such as xanthates, sodium salts of dithiophosphates, and mercapto benzothiazole have good solubility in water (at least 50 gram per liter) and very little solubility in alkanes. Oily collectors, such as zinc salts of dithiophosphates, thionocarbamates, mercaptans, and ethyl octylsulfide, have negligible solubility in water and generally good solubility in alkanes.

Currently used collectors for most sulfide minerals are sulfur-based chemicals such as xanthates, thionocarbamates, dithiophosphates, or mercaptans.
These chemicals have problems with toxicity and/or repugnant odors. In addition,

3 these collectors can be very expensive. Therefore, a need exists for new collectors that are effective but not toxic or odiferous.
BRIEF SUMMARY OF THE INVENTION
This invention is directed to a method of beneficiating a mineral sulfide-containing material or a metallic species of gold, silver, copper, palladium, platinum, iridium, osmium, rhodium, or ruthenium by froth flotation in the presence of a collector as well as a collector for beneficiation of sulfide minerals, precipitates, or metallic species. In both aspects, the collector includes at least one oil which is either an essential oil or a natural or synthesized oil comprising triglycerides containing fatty acids of only 20 carbons or less, or an ester made from a fatty acid and an alcohol.
In the method aspect of the invention, the method includes the steps of (1) providing an aqueous slurry of the mineral sulfide-containing or metal-containing material, (2) adding a selective collector to the slurry, the collector comprising at least one oil selected from the group consisting of (a) a natural oil or synthesized oil comprising triglycerides containing fatty acids of only 20 carbons or less, or an ester made from a fatty acid and an alcohol; and (b) an essential oil; (3) selectively floating the mineral sulfide; and then (4) recovering the mineral.
In the collector aspect of the invention, a collector is provided for beneficiation of sulfide minerals or precipitates from ores, concentrates, residues, tailings, slags, or wastes.
The collector includes at least one sulfur-containing sulfide mineral flotation promoter; and at least one oil selected from the group consisting of (1) a natural or synthesized oil comprising at least one triglyceride, or at least one ester made from a fatty acid and an alcohol; and (2) an essential oil.
This invention has an advantage that the specified triglyceride, specialty, or essential oil will selectively float sulfide minerals by itself or mixed with other collectors.
This and other advantages will be apparent from the detailed description of the invention that follows.
DETAILED DISCLOSURE OF THE INVENTION
The subject invention provides materials and methods useful in the recovery of minerals. These materials and methods are specifically applicable to froth flotation procedures; whereby, minerals are removed and recovered from complex mixtures of ores, residues, concentrates, slags and wastes. The subject invention can be used in remediation processes to remove unwanted materials or may be used in mining processes to recover valuable minerals. Specifically exemplified herein is the use of certain triglycerides, esters of fatty acids and long chain alcohols, and essential oils of both

4 terpene and aromatic chemistries. Any of these oils may be used alone, in mixtures, or in combination with other collectors.
In the method aspect of the invention, the method includes the steps of (1) providing an aqueous slurry of the mineral sulfide-containing or metal-containing material, (2) adding a selective collector to the slurry, the collector comprising at least one oil selected from the group consisting of (a) a natural oil or synthesized oil comprising triglycerides containing fatty acids of only 20 carbons or less, or an ester made from a fatty acid and an alcohol; and (b) an essential oil; (3) selectively floating the mineral sulfide; and, then (4) recovering the mineral.
In the collector aspect of the invention, a collector is provided for beneficiation of sulfide minerals or precipitates from ores, concentrates, residues, tailings, slags, orwastes.
The collector includes at least one sulfur-containing sulfide mineral flotation promoter; and at least one oil selected from the group consisting of (1) a natural or synthesized oil comprising at least one triglyceride, or at least one ester made from a fatty acid and an alcohol; or (2) an essential oil.
Preferably the mineral sulfide-containing material is selected from the group consisting of chalcocite, chalcopyrite, bornite, galena, sphalerite, pentlandite, molybdenite, and other sulfide materials containing silver, gold, platinum, palladium, iridium, rhodium, and osmium, either in the crystal structure or in association as an independent mineral species, and combinations thereof.

This material may be derived from ores, concentrates, precipitates, residues, tailings, slag, or wastes.
Alternatively, the method may be used for acting upon metallic species such as gold, silver, copper, palladium, platinum,

5 iridium, osmium, rhodium, and ruthenium by froth flotation in the presence of a collector. The metallic species may be from material derived from any ore, concentrate, residue, tailings, slag, or waste:
The oils used according to the subject invention can be readily obtained and used by a person trained in the teaching of this patent. The natural oils identified in this invention are obtained directly or indirectly from plants or animals.

In a specific embodiment, the process of the subject invention can comprise the following steps:

a) pulverizing a mineral-containing material to appropriate fine-sized particles;
b) mixing the pulverized particles with water to produce a slurry;
c) agitating the mixture and adjusting its pH as necessary to produce a conditioned slurry;
d) adding a sufficient amount of a naturally occurring oil or a mixture thereof to the slurry with conditioning to render the surfaces of the particles containing the desired minerals hydrophobic;
e) agitating the resultant slurry under conditions and for a time sufficient to obtain a sufficiently homogenous mixture;
f) adding a frothing agent to the homogenous mixture in an amount sufficient to cause frothing of the homogenous mixture upon injecting air or other gases;
g) injecting air or other gas into the mixture to form bubbles in the resultant composition in an amount and under conditions sufficient to cause the hydrophobic particles to become attached to the bubbles and cause the resultant bubbles with attached particles to rise and form froth; and h) separating the froth fraction and recovering the desired mineral.

In a specific embodiment of the subject invention, the mixture produced in Part (b) will have between about 1%o to 75% solids by weight. In Part (c) of the WO 00/09268 PCT/US99/180'

6 process, the pH may be adjusted to anywhere in the 5 to about 13 pH range, with particularly good results in the 7 to 10 pH range. With regard to Part (d), a natural oil, such as cottonseed, may be used as the only collector or it may be used with other collector compounds. In a preferred embodiment, the concentration of the natural oil used according to the subject invention can range from about I
gram per ton of ore to about 1,000 grams per ton of ore. The temperature range of the use of these compounds goes from 5 to 75 degrees Centigrade with most normal operations in the 15 to 40 degree Centigrade range. Preferably, the flotation conditions should be kept mild enough to prevent significant disassociation of the triglycerides, or other components, contained in the natural oils into fatty acids, and to prevent the subsequent saponification into fatty acid soaps. The selectivity of the flotation when using oils according to this invention is evidenced by the selective recovery of the minerals, and substantiates this observation. A
skilled artisan trained in the teachings of this patent can adjust the concentration and conditions to achieve optimization of the process for a particular mineral once a collector compound has been identified as useful for that mineral species.
Gold, silver and platinum metal group metals (platinum, palladium, rhodium, and iridium) are often associated with sulfide minerals. These metals may be also effectively collected by the oils described in this patent either alone or in combination with another collector.
The invention is specifically exemplified for the recovery of certain sulfide minerals. A skilled artisan, having the benefit of the instant disclosure, could readily adapt the process for the recovery and/or removal of a broad range of sulfide minerals, silver, gold or platinum group metals.
It was found, however, that there are unexpected benefits of using certain organic compounds containing no sulfur, no nitrogen and no phosphorous for selective froth flotation of certain sulfides. These molecules contain oxygen in a variety of functional groups such as triglycerides and esters. These groupings occur in many natural oils, such as cottonseed, corn, palm, safflower, jojoba, and clove. Surprisingly many of these oils are non-toxic and are used in foodstuffs

7 throughout the world. The oils run in price from $0.40 per kilogram to over $125 per kilogram.
It was also unexpected that blends of these oils with each other and with standard collectors frequently exhibit synergistic or enhanced effects, in that a mixture of a sulfur containing collector with a non-sulfur containing collector may perform better than either of the components alone, and mixtures of multiple components may perform better than a two-component blend. This invention is uniquely suited to such mineral species as chalcocite, chalcopyrite, bornite, galena, and sphalerite. However, sulfur species such as pyrite are not as readily floated by these non-sulfur-containing collectors.

Most natural plant and animal oils are triglycerides of mixtures of fatty acids. A triglyceride is simply the reaction product of a carboxylic acid and glycerol. The general formula for a triglyceride is shown in Figure 1.
Triglycerides are generally made from fatty acids with typically 10 to 24 carbon atoms and from 0 to 3 double bonds in their chains. Some triglycerides are made from hydroxyl fatty acids that have an alcohol group somewhere in the chain.
An example of this is castor oil. Another oil, oiticicia, has three double bonds and a ketone functionality in its composition.

O R' O R"
Figure 1. General Formula for Triglyceride Saturated or highly saturated oils, such as coconut oil, contain triglycerides made from a zero or a low percentage of fatty acids having double bonds.
Linseed oil contains a high percentage of linolenic acid oil, an 18 carbon fatty acid with

8 PCTIUS99/180 three double bonds (expressed as C18:3). The composition of some common natural oils is shown in Table 1. The iodine value is a measure of the unsaturation of the oil. The saturated fat column is for the percentage of saturated fat when the exact chain length is unspecified. A given type of oil composition will vary with the variety of plant, the growing conditions and the treatment of the oil after pressing. For instance, there are both high and low erucic acid (C22:1) species of canola oil. Some canola oil is also hydrogenated (hydrogen reacted with the double bonds) before being sold.
It was unexpectedly found, however, that oils containing triglycerides that have fatty acids with 20 carbon atoms or less, perform much better than oils, such as canola oil, that contain triglycerides with fatty acids having 22 carbons or more, such as erucic acid (C22:1). Moreover, since oils containing triglycerides of fatty acids with twenty carbon atoms or less do not contain free fatty acids, they do not behave as either fatty acids or soaps of fatty acids. The selective nature of these oils in flotation was surprising because fatty acids and fatty acid salts (i.e., soaps) are very non-selective.

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WO 00/09268 PCT/US99/180' Other sources of triglycerides are animal oils. Commercially available animal oils have a limited range of unsaturation values. A highly unsaturated lard oil will have triglycerides containing 46% C18:1 (oleic acid), 15% C1B.2 (linoleic acid), 1% C18:3 (linolenic acid), and 62% saturated fatty acids.
5 There are some unique natural oils. Sperm whale oil contains esters made from long chain fatty acids and long chain fatty alcohols instead of esters of the fatty acid and glycerol as in triglycerides. Both the fatty acid and long chain alcohol usually contain at least 1 double bond. Sperm whale oil is, of course, no longer available due to whaling restrictions. However, its replacements, jojoba oil

10 (vegetable) and orange roughy oil (fish), have the same basic chemistry as sperm whale oil. The only differences between them are in the carbon numbers (chain length) of the various components of the oils.
Chemical manufacturers can synthesize a long chain ester from a fatty acid and a long chain alcohol. One example of a "synthesized oil" or "synthetic oil" is 2-butyloctyl oleic acid ester. This compound contains one unsaturated site in the fatty acid molecule. The carbon numbers of the largest fractions of these oils are shown in Table 2.

Table 2. Carbon Numbers of Major Components of Specialty Oils of Material of Specified Carbon Number Oil 30 32 34 36 38 40 42 44 Sperm Whale 21 23 20 12 Jojoba 6 31 50 8 Orange Roughy 11 16 25 23 15 5 2-butyloctyl oleic 100 T
acid ester Preferably, the natural oils used in this invention include triglycerides that contain only fatty acids having a carbon number less than 20. Also, it is preferred that the triglycerides include an alcohol, an ether, an aldehyde, or a ketone functional group, or an aromatic group. A preferred group of natural oils includes cottonseed, corn, linseed, rice bran, safflower, soybean, avocado, jojoba, menhaden, lard, castor, cod liver, tung, oiticicia, apricot, sunflower, pistachio,

11 herring, and coconut oils. A more preferred group of natural oils includes cottonseed, corn, linseed, rice bran, safflower, soybean, avocado, jojoba, menhaden, lard, castor, cod liver, tung, and oiticicia. A still more preferred group of natural oils includes cottonseed, corn, linseed, rice bran, safflower, soybean, avocado, jojoba, menhaden, lard, and castor oils. An even more preferred group of natural oils includes cottonseed, corn, linseed, rice bran, safflower, and soybean. The most preferred natural oil is cottonseed oil.
Another class of naturally occurring oils is called "essential oils" or "volatile oils." These are fragrant oils derived from various plant species.
Since ancient Egyptian times, they have been used for their fragrance and reputed medicinal properties. The chemistry of most of these compounds is based on either terpene chemistry or aromatic chemistry.

Terpenes are defined as compounds that can be assembled from two or more molecules of isoprene, (C5H8) and the alcohol, aldehyde, and ketone derivatives of such compounds. A terpene compound can be defined as a monoterpene, sesquiterpene, or diterpene compound based on whether it contains 2, 3, or 4 isoprene units, respectively. Within each of these classifications the compounds can be further defined as being acyclic, monocyclic, bicyclic or tricyclic depending on whether the terpene contains, respectively, 0, 1, 2, or 3 ring structures (only diterpenes are tricyclic). Tricyclic diterpenes are generally solids.
Aromatic chemistry for essential oils refers to the chemistry of derivatives of benzene. The two most common aromatic components of essential oils are cinnamaldehyde and eugenol. These are olbtained from cinnamon and clove oil.
Their structures are shown in Figure 2.

12 O
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Cinnamaldehyde Eugenol Figure 2. Structure of Eugenol and Cinnamaldehyde Most essential oils have one single major terpene or aromatic component or are a mixture of closely related terpenes or aromatics. Table 3 shows the composition of some representative essential oils. Note that any particular oil's composition can vary with variety, weather, etc.

Table 3. Major Constituent of Representative Essential Oils Major Component Oil Plant Source Name % Chemical Family Citronella Cymbopogon Citronellal: 33 Aldehyde and winterianus Citronellol: 16 Alcohols of acyclic Geraniol: 24 monoterpene Limonene Citrus (Orange) Limonene 95 Monocyclic monoterpene Eucalyptus Eucalyptus globus Cinole 90 Bicyclic monoterpene ether Sandalwood Sandalwood Mixture 80 Sesquiterpenes Clove Clove Eugenol 85 Aromatic Preferably, the essential oils used in the methods of this invention include either a terpene compound or an aromatic compound. More preferably, the essential oil includes a terpene derivative having a functional group selected from an alcohol, and ether, an aldehyde and a ketone. Specific preferred essential oils include limonene, citronella, eugenol, eucalyptus globus, camphor, and clove oil.
A more preferred group of essential oils includes limonene 4nd citronella.
As work with the triglycerides, esters and alcohols has indicated, other oxygen-containing compounds such as aldehydes, ketones, and ethers of sufficient

13 carbon number to be water-insoluble function as collectors for sulfide minerals.
These compounds may or may not have carbon-carbon double bond(s).
The literature has shown that emulsified collectors can give better results than unemulsified collectors. Emulsification should also allow the combining of inexpensive water-soluble xanthates and sodium sulfide into the oils. Other water-soluble collectors that may be amenable to emulsification into oil include sodium dithiophosphates and mercaptobenzothiazole.
The invention also includes the use of the plant and animal oil collectors blended with known commercial collectors. Commercial collectors are also known as "flotation promotors" and are identified herein as "sulfur-containing flotation promotors." These common commercial promotors are usually separated into two classes of chemicals based on their water solubility. Water soluble sulfur containing collectors, or promotors, used in the froth flotation of sulfide minerals include such well-known collectors as xanthates and dithiophosphates. These are usually used as sodium or potassium salts of the respective organic acids. An example of a water-soluble collector would be sodium isopropyl xanthate. The other class of sulfur containing collectors would be water insoluble collectors.
These collectors are generally referred to as oily collectors, because they are liquids that are insoluble in water. These collectors include thionocarbamates, mercaptans, organic sulfides, and the zinc salts of dithiophosphates. Even though these compounds are chemical reaction products, they are called oils.
Another grouping of collectors commonly used in froth flotation of substances such as coal, sulfur, and molybdenite are petroleum-based products that are truly oils. These oils generally consist of kerosene, vapor, diesel, fuel, turbine, light cycle, and carbon black oil. These petroleum oils are generally called "extender oils" and generally exhibit poor collecting ability and very poor selectivity when used by themselves. To distinguish these "petroleum-based collectors" from other described collectors, the term "oily collector" used in this text means a synthesized organic chemical compound containing sulfur such as the group of "sulfur-containing flotation promotors" described above.

14 This invention also includes the use of any of these aforementioned natural, synthetic or essential oils in combination. The essential oils are found to be very potent collectors. As such they are ideally suited for use in small amounts in combination with other oils or with other sulfide-containing flotation promotors.
Good results have been obtained when using the essential oils in amounts of less than 10% by weight blended with other collectors. Preferably, less than 2% by weight is used.
Also, any of the natural oils including the higher carbon fatty acid-containing triglycerides, and in particular, the preferred natural oils alone or in combination with other preferred oils, may be used blended with any number of sulfur-containing flotation promotors. In such blends, the natural oils make up preferably between 20% and 80% by weight of the blend, and the flotation promotors make up preferably between the remaining 80% and 20% by weight of the blend. Optionally, a frother may be added to that blend, preferably in an amount between about 10% and 40% by weight of the composition. Frothers are commercially available compositions that are used to develop a froth or foam on top of a slurry that has been aerated. A particular suitable frother is one such as that sold by NALCO under the designation 9743. Methyl isobutyl carbonol (MIBC), also known as methyl amyl alcohol, is one of the most widely used frothers in the mining industry.
The collectors and blends of collectors in accordance with the methods of this invention can be used in standard froth flotation processes known by those skilled in the art and modified by the teachings of this patent as illustrated in the following examples.

EXAMPLES

The following are examples that illustrate procedures for practicing the invention. These examples should not be construed as limiting the invention, but are provided to further illustrate the teachings of the invention. All percentages are by weight and all collector mixture proportions are by volume unless otherwise noted.

Example I.

This example illustrates the effectiveness of cottonseed oil as a collector for molybdenite and chalcopyrite. The ore had a head grade of 0.259% Cu and 0.0064% Mo. The ore charge of 1.0 kilogram was ground at 60% solids to 60%
5 passing (P60) a 150 micron (100 mesh) screen. The ground ore slurry was adjusted to a pH of 10.5 with lime. The ore was ground with 10 gram/ton (0.020 pound/ton) of secondary collector. A Denver laboratory flotation machine was used. The ore slurry charge was diluted with water to 29 percent solids, and 6 grams per ton of the main collector, sodium ethyl xanthate, and 25 gram/ton (0.05 10 pound/ton) of the OrePrep F-533 frother were added. The flotation was carried out for a total of six minutes with a two minute break for conditioning at the halfway point. During the conditioning break, 4 gram/ton dosage of the sodium ethyl xanthate was added.
The cottonseed oil was used by itself in place of the standard decant oil-

15 light cycle oil-mercaptan (tertiary dodecyl mercaptan) secondary collector.
Also, a 33% each mixture of cottonseed oil, zinc di (1,3 dimethylbutyl) dithiophosphate, and the tertiary dodecyl mercaptan was tested. For comparison a 33% each mixture of decant oil, the zinc dithiophosphate and the mercaptan was tested.
The dosage of the main and secondary collector was 10 grams collector per ton of ore (g/t) for all tests. As shown in Table 4, cottonseed oil by itself improved the recovery of both molybdenum recovery and copper grade over the standard collector. The cottonseed mixture had a similar copper recovery as the decant oil mixture while improving copper grade.

WO 00/09268 PCT/US99/180'

16 Table 4. Chalcopyrite Ore containing MoS2 Flotation Main Secondary Cu Cu Mo Collector Collector Recovery Grade Recovery Xanthate Cottonseed Oil 94.5% 3.68 82.2%
Xanthate Standard 93.9% 2.96 79.1%
Xanthate Decant Oil Mixture 97.0% 2.85 87.3%
Xanthate Cottonseed Mixture 96.2% 4.25 83.7%
Example H.

This example shows that cottonseed oil can be used to collect some galena (PbS). It can be used either alone in place of the main collector, sodium isopropyl xanthate, or in a mixture with a mercaptan (tertiary dodecyl mercaptan) collector in place of the main collector.
The ore was ground to a P80 of around 240 microns. The ore charge was 2.0 kilograms and had a head assay of 70 gram/ton Ag, 0.70% Pb, and 1.32% Zn.
Fifty gram/ton of zinc sulfate and fifteen gram/ton of dextrin were added to the grind. The flotation was conducted in a Denver laboratory flotation machine with a 5-liter cell. The float was conducted at the natural pH of the ore, 7.5 to 8.
Before the first float, the slurry was conditioned with 30 gram/ton of the collector and 80 gram/ton of the frother for two minutes. The ore was floated for three minutes, then conditioned with 10 gram/ton collector and 16 gram/ton of frother.
The results are shown in Table 5, and demonstrate the enhanced effects for a blend of the natural oil and the mercaptan flotation promotor in comparison to the use of each alone.

17 Table 5. Lead-Zinc-Silver Sulfide Ore Flotation for Lead Grade Recovery into Pb Concentrate Collector Pb As Weight Ag Pb Zn Fe Xanthate 2.18 1.23 23.6% 74.9% 79.5% 18.0% 82.9%
Cottonseed Oil 6.38 0.49 5.1% 51.4% 50.6% 17.2% 15.7%
Mercaptan 7.08 0.76 5.7% 42.9% 49.1% 19.3% 14.7%
50% Mercaptan + 3.21 0.78 13.8% 53.9% 64.5% 21.1% 38.6%
50% Cottonseed The ore was then conditioned for two minutes with 125 gram per ton of copper sulfate. A further 10 gram/ton of collector and 32 gram/ton of frother were added and conditioned in for two minutes. The first zinc float was conducted for three minutes. Finally, another 50 gram/ton of frother was added. The results of these zinc floats are shown in Table 6.

Table 6. Lead-Zinc-Silver Sulfide Ore Flotation for Zinc Grade Recovery into Zn Concentrate Collector Zn Weight Ag Pb Zn Fe Xanthate 8.63 9.5% 16.5% 7.1% 42.1% 6.3%
Cottonseed Oil 9.13 6.6% 13.9% 20.4% 48.1% 10.1%
Mercaptan 12.20 5.6% 16.7% 19.8% 46.4% 6.2%
50% Mercaptan + 11.54 5.0% 9.1%1 7.1%1 45.6% 3.8%
50% Cottonseed Example III.

Apricot, sunflower, pistachio, cottonseed, and jojoba oils were tested on chalcopyrite ore containing molybdenum sulfide. The head assays of the ore were 0.704% Cu and 0.0119% Mo. The ore charge of 2.0 kilograms was ground at 65%
solids to 90% passing a 212 micron (65 mesh) screen. The ore charge was diluted with water to 27% solids and placed in a Denver laboratory flotation cell. The ore was conditioned for two minutes by agitation at 2000 rpm. The ore was floated for one minute by allowing air to be drawn in by the impeller. Subsequently, the ore was conditioned for two minutes, floated for two minutes, conditioned for two minutes, and finally floated for three minutes. The standard collector is a mixture WO 00/09268 PCT/US99/180'

18 of 33% of the allyl ester of isopropyl xanthate, 33% of 2-ethylhexanol, and 33% of sodium diisobutyl di-thiophosphate collector.
The standard reagent addition is as follows. Enough lime is added to the ball mill to adjust to a pH of 10.4. At the same time, 7.7 gram/ton (0.0154 pound/ton) of the standard collector or oil being tested, 7.5 gram/ton (0.0 pound/ton) of diesel fuel are added. During the first conditioning step, 20 g/t (0.040 lb/ton) of frother is added. During the second conditioning step, 8 g/t (0.016 pound/ton) of sodium isopropyl xanthate (SIPX), 2.5 g/t (0.005 lb/t) of frother, and 5 g/t (0.010 lb/ton) of the standard reagent or oil are added.
During the third and final conditioning step, 4g/t (0.008 lb/ton) of SIPX, (0.005 lb/t) of frother, and 5 g/t (0.010 lb/ton) of the standard reagent or oil are added.
The results for the final combined concentrates are presented in Table 7, sorted by copper recovery. Every oil listed above the sunflower oil gave essentially the same copper and molybdenum recovery as the standard reagent.

Table 7. Chalcopyrite Ore containing MoS2 Flotation Cu Recovery Recovery Tested Oil Grade Cu Mo Standard 5.04 92.4% 84.6%
Cottonseed 3.62 91.9% 84.4%
Pistachio 2.92 91.9% 88.3%
Sunflower 2.97 91.8% 84.7%
Apricot 2.70 91.7% 79.6%
Jojoba 2.69 91.5% 86.5%
Example IV.

There are two primary types of cotton in the United States, Pima long staple cotton and short staple cotton. The oils derived from both were tested on a copper-molybdenum ore with a head grade of 0.663% Cu and 0.0134% Mo. The ore was floated as in Example III. The results of the test are shown in Table 8.

19 Table 8. Comparison of Cottonseed Oils Grade Recovery Cottonseed Oil Source Cu Cu Mo Pima Long Staple 5.36 94.8% 84.7%
Short Staple 5.23 90.9% 83.9%
Standard Collector 5.76 90.6% 82.1%
Example V.

This example shows the selectivity of cottonseed against calcite. Pure calcite crystals were crushed and screened for the fraction passing a 355 micron (42 mesh) screen. A sample size of 812 grams was obtained. The sample was slurried in a 2.5 liter cell of a Denver laboratory flotation machine. The ore was conditioned for two minutes with 123 gram/ton cottonseed oil and 26.2 gram/ton frother. The slurry was floated for two minutes and then conditioned again for two minutes with 61.5 gram/ton cottonseed oil and 10.5 gram/ton frother. The slurry was floated again for two minutes. During both flotations, a slime-stabilized froth was obtained. The results of the test are shown in Table 9.
Table 9. Recovery of Calcite from Pure Calcite Sample Float Concentrate Recovery 1 10.70%
2 1.88%
Combined 12.58%

Example VI.

This example shows cottonseed's selectivity against silica. Pure quartz crystals were crushed and screened for the fraction passing a 150 micron (100 mesh) screen. A sample size of 1000 grams was obtained. The sample was slurried in a 2.5 liter cell of a Denver laboratory flotation machine. The ore was conditioned for two minutes with 123 gram/ton cottonseed oil and 26.2 gram/ton frother. The slurry was floated for two minutes and then conditioned again for two minutes with 61.5 gram/ton cottonseed oil and 10.5 gram/ton frother. The slurry was floated again for two minutes. During both flotations, a small amount of slime-stabilized froth was obtained. The total recovery was less than 2% of the total silica.

Example VII.

A number of triglyceride, specialty, and essential oil collectors were tested 5 on chalcopyrite ore containing molybdenite. The head assays of the ore were 0.579% Cu and 0.010% Mo. The ore charge of 1.0 kilograms was ground at 65%
solids to 90% passing a 212 micron (65 mesh) screen.
The standard flotation procedure was as follows. Enough lime (0.9 grams) was added to the grind for the flotation slurry to have a pH of 10.4. The following 10 reagents were added to the grind, 5.5 gram/ton of the standard thiophosphate copper collector, 7.7 gram/ton of diesel fuel, molybdenum collector, and 10 gram/ton of Nalco 9743 frother. A Denver laboratory flotation cell was used.
The ore charge was diluted with water to 27% solids. The ore was floated for two minutes. The slurry was then conditioned for one minute with 6.5 gram/ton of 15 frother and 8 gram/ton of sodium isopropyl xanthate. The slurry was floated for two more minutes, then conditioned for one more minute with half of the dosage of the previous conditioning step, and floated for a final three minutes. All concentrates were collected into one pan for a single concentrate for the whole flotation.

20 The oils were tested by using them as the only collector. Only lime, 10 grams/ton of frother and 24 gram/ton of the oil being tested were added to the grind. No xanthate or other collector was added to the conditioning step, only the listed frother dosage.
The results for the triglyceride tests are presented in Table 10. As tested, no triglyceride was as good a collector for copper as the standard collector system.
Due to the low molybdenum grade of the head ore, molybdenum recoveries often have a large standard deviation in repeated tests on the same ore. Generally, compounds that show a 5% better recovery than another compound in single tests will have an average higher molybdenum recovery on multiple tests.

21 Table 10. Results of Triglycerides Flotation Number of Double Bonds, % Assay Con Recovery Collector 0 1 2 3 5 Cu I Mo Cu Mo Standard 4.94 0.071 88.3% 79.2%
Cottonseed 27 30 43 0 3.82 0.063 87.3% 84.7%
Lard Oil 31 48 12 1 5.61 0.094 85.4% 80.9%
Corn 13 29 57 1 5.64 0.084 85.3% 81.6%
PBO Lard 38 46 15 1 5.01 0.082 85.2% 83.4%
Linseed 9 19 15 57 4.91 0.080 85.1% 80.2%
Tung 85 5.71 0.088 85.1% 78.2%
Menhaden 18 18 37 13 14 8.52 0.144 84.5% 80.7%
Safflower 21 79 3.75 0.071 84.2% 83.9%
Herring 14 49 23 7.88 0.122 84.0% 78.9%
Avocado 70 15 1 6.38 0.111 84.0% 85.0%
Oiticicia 75 4.63 0.074 83.8% 78.2%
Soybean 16 24 54 7 5.14 0.094 83.7% 80.2%
Peanut 15 45 40 0 8.33 0.142 82.8% 81.3%
Casto 12 88 7.20 0.122 82.2% 77.95/o Canola 8 59 22 11 8.43'0. 130 82.0% 80.6%
Rice Bran 64 2 32 2 8.0210.142,' 81.5% 78.7%0 Coconut 94 4 21 1 7.3810.133174.1%1 75.0%0 Notes: Has a ketone functionality; has a alcohol functionality The results of the testing of specialty and essential oils are shown in Table 11. The bicyclic compounds equaled or surpassed the standard for copper and molybdenum recovery.

22 Table 11. Results of Specialty and Essential Oil Testing Grade Recovery Oil Chemical Family Cu 1 Mo Cu Mo Eucalyptus globus Bicyclic Ether 5.25 0.088 88.8% 87.8%
Standard Thiophosphate -4.94 0.071 88.3% 79.2%
Camphor Bicyclic Ketone 5.32 0.082 87.9% 85.7%
2-butyloctyl oleic Mono-unsaturated 5.62 0.092 87.3% 86.0%
acid ester Ester Jojoba Di-unsat. Ester 5.11 0.088 85.7% 84.8%
Limonene Cyclic 4.87 0.082 84.7% 81.2%
monoterpene Example VIII.

A number of triglyceride, specialty, and essential oil collectors were tested on a molybdenum sulfide ore. The head assay of the ore was 0.0638% Mo. The ore charge of 1.0 kilogram was ground at 65% solids to 90% passing a 425 micron (35 mesh) screen.
The flotation procedure is as follows. The 100 gram/ton of oil was added to the grind. A Denver laboratory flotation cell was used. The ore charge was diluted with water to 27% solids. To the two minute conditioning step, 40 g/t frother was added. The ore was floated for 1 minute. The slurry was then conditioned for one minute, floated for two minutes, conditioned for one minute, and finally floated for six minutes. Each concentrate was collected separately and assayed separately. One test was conducted with frother alone to test the free flotability of the ore. The standard collector used at the mine was diesel fuel.
The results of the flotation of molybdenum sulfide for the triglycerides are shown in Table 12. The percentage of fatty acids in the triglycerides with the shown number of double bonds is listed. All of these oils did better than the free-flotability test.

23 Table 12. Results of Triglycerides on Molybdenum Recovery Number of Double Bonds, % 1 s Concentrate Overall Collector 0 1 2 3 5 Grade Recovery Grade Recovery Oiticicia 75 2.19 68.9% 0.892 72.5%
Peanut 15 45 40. 0 0 1.15 57.9% 0.602 71.9%
Coconut 94 4 2 9.42 60.1% 1.355 67.5%
Menhaden 18 18 37 13 14 4.14 59.0% 0.938 66.8%
Pfau 1JJ 31 48 12 1 3.11 54.9% 0.736 64.9%
Rice Bran 64 2 32 2 2.21 48.7% 0.763 61.4%
Cottonseed 27 30 43 0 4.44 51.1% 1.084 60.1%
Tung 85 3.57 54.8% 0.989 59.1%
Sunflower 12 24 64 3.21 48.8% 0.736 58.1%
None 0 0 0 0 0 3.38 53.9% 0.870 57.8%
Corn Oil 31 48 12 1 4.15 54.2% 1.013 57.7%
Linseed 9 19 15 57 2.61 48.4% 0.570 56.2%
Diesel 0 0 0 0 0 1.38 53.3% 0.565 56.1%
Notes: Has a ketone functionality The results of specialty and essential oils are shown in Table 13. All of these oils did better than the free-flotability test.

Table 13. Results of Testing Specialty and Essential Oils on Molybdenite First Concentrate Overall Collector Type Grade Recovery Grade Recovery 2-butyloctyl oleic Mono-unsaturated 0.73 71.6% 0.589 80.2%
acid ester' Ester Jojoba Di-unsat. Ester 0.96 68.5% 0.507 78.1%
Clove Oil Aromatic 2.08 73.5% 0.817 77.9%
limonene oil Cyclic monoterpene 2.24 75.0% 0.902 76.7%
Citronella Acylic 2.00 69.8% 0.598 74.6%
monoterpenes Eucalyptus, globus Bicyclic Ether 2.77 67.0% 0.759 71.6%
Camphor Bicyclic Ketone 4.41 61.0% 1.056 64.9%
None 3.38 53.9% 0.870 57.8%
Diesel 1.38 53.3% 0.565 56.1%
Note: Oil synthesized from natural products and used as a sperm whale oil replacement

24 Example IX.

In this example the synergistic effect of various oils and a sodium isopropyl xanthate is shown. A chalcocite ore with a head assay of 0.602% Cu and 0.0 16%
Mo was used. The ore charge of 1.0 kilogram was ground at 65% solids to 90%
passing a 212 micron (65 mesh) screen.
The standard flotation procedure is as follows. Enough lime (1.9 grams) was added to the grind for the flotation slurry to have a pH of 10.8. To this grind 30 g/ton (0.060 lb/ton) of either the standard collector, Cytec S-8399, believed to be a blend of dithiophosphate and thionocarbamate available from Cytec, Inc., Wayne, New Jersey, U.S.A., or the natural oil collector being tested was added.
The grind charge was transferred to a Denver laboratory flotation cell. The ore charge was diluted with water to 27% solids. The ore was conditioned for two minutes with 20 gram/ton of Oreprep F-533, a blended alcohol frother. The ore was floated for three minutes. The slurry was then conditioned for three minutes with 10 gram/ton of frother and 1.5 gram/ton of sodium isopropyl xanthate (SIPX). The slurry was floated three more minutes. The concentrates were collected separately except for the avocado oil and Cytec S-8399.
The results are shown in Table 14. These results show that limonene oil has the best synergy with SIPX despite not collecting much chalcocite by itself as shown in the recovery in the first concentrate (1" Con). All the oils performed better as a secondary collector than the regular thiophosphate based Cytec S-8399.

Table 14. Results of Tests with Oils and SIPX
Overall 15 Con Copper Mo Copper Mo Calc Head Collector Grade Recovery Recovery Grade Recovery Recovery Cu Mo Limonene 5.50 92.2% 71.7% 2.02 9.98% 59.00% 0.599 0.0162 Safflower 5.23 92.2% 68.2% 1.11 6.26% 55.24% 0.604 0.0168 Coconut 5.77 92.1% 72.2% 1.95 8.67% 49.50% 0.608 0.0179 Eucalyptus 6.00 92.0% 65.9% 2.48 8.09% 39.14% 0.619 0.0154 Avocado 5.63 91.9% 65.9% 0.660 0.0157 Corn 4.90 91.9% 69.0% 2.13 11.42% 52.23% 0.571 0.0164 Cottonseed 5.57 91.7% 71.0% 2.76 12.66% 56.19% 0.590 0.0165 Tung 4.83 91.2% 67.1% 1.39 4.61% 42.21% 0.604 0.0167 S-8399 3.69 90.6% 69.5% 0.599 0.0148 Example X.

In this example, the various combinations of oils and standard collectors 5 are shown. A chalcocite ore with a head assay of 0.543% Cu and 0.014% Mo was used. The ore charge of 1.0 kilograms was ground at 65% solids to 90% passing a 212 micron (65 mesh) screen.
The standard flotation procedure was as follows. Enough lime (1.9 grams) was added to the grind for the flotation slurry to have a pH of 10.8. To this grind 10 30 g/ton (0.060 lb/ton) of either the standard collector, Cytec S-8399, or the natural oil collector being tested was added. The grind charge was transferred to a Denver laboratory flotation cell. The ore charge was diluted with water to 27%
solids. The ore was conditioned for two minutes with 20 gram/ton of Oreprep F-533 frother. The ore was floated for three minutes. The slurry was then 15 conditioned for two minutes with 1.5 gram/ton of sodium isopropyl xanthate (SIPX). The slurry was floated three more minutes.
The mixtures tested are shown in Table 15. The mercaptan used was tertiary dodecyl mercaptan. The zinc dithiophosphate used was zinc di- (1,3 dimethylbutyl) -dithiophosphate. The thionocarbamate used was n-ethyl, o-20 isopropropyl thionocarbamate.

WO 00/09268 PCT/US99/1805' Table 15. Composition of Mixture Tested Staple. Percentage Zinc Glycol Type of of dithio- Thiono- Still Collector Cottonseed Cottonseed Mercaptan phosphate carbamate Bottoms Mixture 1 Pima Long 40 40 10 10 0 Mixture 2 Short 40 40 10 10 0 Mixture 3 Short 20 20 20 20 20 Mixture 4 Short 50 10 30 10 0 The results of the flotation tests are summarized in Table 16. The results show that cottonseed interacts well with the mercaptan, zinc dithiophosphate and thionocarbamate collectors.

Table 16. Test results for Various Mixtures Overall Results Calc. Head Collector Grade Cu Mo Cu Mo fixture 3 1.48 0.4% 72.1% .532 p.0144 Mixture 14.99 9.6% 59.4% .562 .0144 Mixture 2 5.48 8.8% 57.8% .544 P.0 14 -8399 1.88 8.6% 55.0% .525 p.0137 Mixture 415.75 8.1% 57.9% .583 p.0142 Example XI.

Pure mineral samples of chalcopyrite, chalcocite and galena were floated with cottonseed and limonene oils.
The flotation procedure was as follows: 500 gram charges of mineral were crushed to minus 1.7 millimeter (10 mesh) then ground with 50 gram per ton of collector to around 90% passing 212 micron (65 mesh). A charge was then placed in a Denver laboratory flotation cell with enough water to make the slurry 27%
by weight solids. The slurry was then conditioned with 18 grams/ton of an alcohol frother for two minutes. The ore was floated for two minutes. The slurry was then conditioned for one minute and floated for three minutes. Each concentrate was collected and weighed separately. One test was conducted with frother alone to test the free flotability of the mineral. The results are shown below.

Table 17. Results of Pure Mineral Flotation Chalcocite Chalcopyrite Collector Con 1 Con 2 Total Con 1 Con 21 Total None --- 1.20% 1.20% 4.90% 3.31% 8.20%
Cottonseed 2.51% 1.87% 4.38% 58.75% 5.74% 64.49%
Limonene 3.59% 2.05% 5.64% 19.15% 4.70% 23.85%
Galena Collector Con 1 Con 2 Total None 18.98% 2.55% 21.54%
Cottonseed 90.95% 5.57% 96.52%
Limonene 18.53% 2.07% 20.60%

The cottonseed oil collected a good proportion of the pure mineral chalcopyrite. Comparing the results of cottonseed on chalcopyrite to the results of the "no collector" test shows that the cottonseed was responsible for collecting the chalcopyrite and that it is a better collector than the limonene oil.
Of course, it should be understood that changes and modifications can be made to the preferred embodiments described above without departing from the scope of the present invention. It is therefore intended that the foregoing detailed description be regarded as illustrative rather than limiting, and that it be understood that it is the appended claims including all equivalents, which are intended to define the scope of this invention.

Claims (21)

1. A method for beneficiation of a mineral sulfide-containing material by air-injection froth flotation in the presence of a selective collector, the method comprising:
a) providing an aqueous slurry of the mineral sulfide-containing material;

b) adding a selective collector to the slurry in an amount less than about 100g/ton of the mineral sulfide-containing material, the selective collector comprising:

1) at least one natural or synthesized oil consisting of an ester made from a fatty acid and an alcohol;

2) an essential oil; and

3) a sulfur-containing sulfide mineral flotation promoter selected from the group consisting of xanthates, thionocarbamates, dithiophosphates, mercaptans, and combinations thereof;
c) selectively floating the mineral sulfide by injecting air and selectively allowing the mineral sulfides to adhere to the air bubbles; and d) recovering the mineral.

2. The method according to claim 1, wherein said mineral sulfide-containing material is selected from the group consisting of chalcocite, chalcopyrite, bornite, sphalerite, pentlandite, molybdenite, and other sulfide minerals containing silver, gold, platinum, palladium, iridium, rhodium, or osmium, either in the crystal structure or in association as an independent mineral species, and combinations thereof.

3. The method according to claim 1, wherein said mineral sulfide-containing material is derived from ores, concentrates, precipitates, residues, tailings, slags, or wastes.

4. The method according to claim 1, wherein the essential oil comprises a compound selected from the group consisting of a terpene compound, an aromatic compound, and a combination thereof.

5. The method according to claim 1, wherein the essential oil comprises a terpene derivative having a functional group selected from the group consisting of an alcohol, an ether, an aldehyde, and a ketone.

6. The method according to claim 1, wherein said oil and said sulfur-containing sulfide mineral flotation promoter are emulsified.

7. The method according to claim 1, wherein said selective collector further comprises a frother.

8. The method according to claim 1, wherein said selective collector further comprises a petroleum-based flotation promoter.

9. The method according to claim 1, wherein said natural oil is jojoba; and the essential oil is selected from the group consisting of limonene, citronella, eugenol, eucalyptus globus, camphor, and clove oil.

10. The method according to claim 1, wherein said synthetic oil is 2-butyloctyl oleic acid ester; and said essential oil is selected from the group consisting of limonene, citronella, eugenol, eucalyptus globus, camphor, and clove oil.

11. The method according to claim 1, wherein the selective collector comprises jojoba.

12. The method according to claim 1, wherein the essential oil comprises limonene or citronella.

13. The method according to claim 12, wherein the essential oil comprises citronella.

14. The method according to claim 1, wherein the selective collector comprises a synthesized oil.

15. The method according to claim 14, wherein the selective collector comprises 2-butyloctyl oleic acid ester.

16. The method according to claim 1, wherein the selective collector comprises a blend of two or more of said natural or synthetic oils and essential oils.

17. The method according to claim 1, wherein the selective collector is added in an amount less than about 50 g/ton of material.

18. The method according to claim 1, wherein the selective collector is added in an amount less than about 30 g/ton of material.

19. The method according to claim 1, wherein the selective collector is added in an amount less than about 10 g/ton of material.

20. The method according to claim 1, further comprising separating the floated mineral sulfide and subjecting the mineral sulfide to a second flotation by repeating (b) and (c).

21. A method for beneficiation of a metallic species of gold, silver, copper, palladium, platinum, iridium, osmium, rhodium or ruthenium by air-injection froth flotation in the presence of a selective collector, the method comprising:
a) providing an aqueous slurry of a material containing the metallic species, the material being derived from any ore, concentrate, residue, slag, or waste;

b) adding a selective collector to the slurry in an amount less than about 100g per ton of material containing metallic species, the selective collector comprising:

1) at least one natural or synthesized oil consisting of an ester made from a fatty acid and an alcohol;

2) an essential oil; and 3) a sulfur-containing sulfide mineral flotation promoter selected from the group consisting of xanthates, thionocarbamates, dithiophosphates, mercaptans, and combinations thereof;
c) selectively floating the metallic species by injecting air and selectively allowing the mineral sulfides to adhere to the air bubbles; and d) recovering the metallic species.