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WO2000009268A1 - Flottation d'especes minerales au sulfure avec des huiles - Google Patents

Flottation d'especes minerales au sulfure avec des huiles Download PDF

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Publication number
WO2000009268A1
WO2000009268A1 PCT/US1999/018055 US9918055W WO0009268A1 WO 2000009268 A1 WO2000009268 A1 WO 2000009268A1 US 9918055 W US9918055 W US 9918055W WO 0009268 A1 WO0009268 A1 WO 0009268A1
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WO
WIPO (PCT)
Prior art keywords
collector
oil
oils
flotation
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1999/018055
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English (en)
Inventor
Tom L. Young
Michael G. Greene
Kathy Bauer
Sharon K. Young
Norman R. REBER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Reber Bonnie J
Versitech Inc
Original Assignee
Reber Bonnie J
Versitech Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Reber Bonnie J, Versitech Inc filed Critical Reber Bonnie J
Priority to US09/762,619 priority Critical patent/US6827220B1/en
Priority to MXPA01001590A priority patent/MXPA01001590A/es
Priority to AU54732/99A priority patent/AU761765B2/en
Priority to CA2340363A priority patent/CA2340363C/fr
Publication of WO2000009268A1 publication Critical patent/WO2000009268A1/fr
Anticipated expiration legal-status Critical
Priority to US10/974,140 priority patent/US7461745B2/en
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/012—Organic compounds containing sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/008—Organic compounds containing oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/014—Organic compounds containing phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/02—Froth-flotation processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; Specified applications
    • B03D2203/02—Ores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; Specified applications
    • B03D2203/02—Ores
    • B03D2203/025—Precious metal ores

Definitions

  • This invention relates to the beneficiating or concentrating of ores.
  • 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.
  • froth flotation 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 been used in collecting one or more of the oxide minerals such as fluorspar, iron ore, chromite, scheelite, CaCO 3 , Mg CO 3 , apatite, or ilmenite.
  • alkali metal salts of fatty acids or soaps derived from natural oils by the process known as saponification.
  • 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.
  • neutralized fatty acids are soaps that act as non-selective flotation collectors.
  • sulfur such as xanthates, thionocarbamates, dithiophosphates, and mercaptans
  • sulfur based collectors are often toxic, have repugnant odors or both.
  • Amine compounds are used to float KC1 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 KC1.
  • 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.
  • 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, these collectors can be very expensive. Therefore, a need exists for new collectors that are effective but not toxic or odiferous.
  • 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, and ruthenium by froth flotation in the presence of a collector as well as a collector for beneficiation of sulfide minerals, precipitates, or metallic species by froth flotation.
  • 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.
  • 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.
  • a collector for beneficiation of sulfide minerals or precipitates from ores, concentrates, residues, tailings, slags, or wastes is provided.
  • the collector includes at least one sulfur- containing sulfide mineral flotation promotor; 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.
  • 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.
  • remediation processes to remove unwanted materials or may be used in mining processes to recover valuable minerals.
  • triglycerides esters of fatty acids and long chain alcohols
  • essential oils of both terpene and aromatic chemistries. Any of these oils may be used alone, in mixtures of these oils, or in combination with other collectors.
  • the method includes the steps of (1) providing an aqueous slurry of the mineral sulfi de-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.
  • a collector for beneficiation of sulfide minerals or precipitates from ores, concentrates, residues, tailings, slags, or wastes is provided.
  • the collector includes at least one sulfur- containing sulfide mineral flotation promotor; 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.
  • the mineral sulfide-containing material is selected from the group consisting of chalcocite, chalcopyrite, bornite, galena, sphalerite, pentlandite, molybdenite, and other sulfide minerals 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.
  • the method may be carried out in the same steps except acting upon metallic species such as gold, silver, copper, palladium, platinum, iridium, osmium, rhodium, and ruthenium by froth flotation in the presence of a collector.
  • metallic species such as gold, silver, copper, palladium, platinum, 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.
  • 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.
  • 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
  • the mixture produced in Part (b) will have between about 1% to 75% solids by weight.
  • 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.
  • a natural oil such as cottonseed, may be used as the only collector or it may be used with other collector compounds.
  • the concentration of the natural oil used according to the subject invention can range from about 1 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.
  • 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 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 throughout the world. The oils run in price from $0.40 per/kilogram to over $125 per/kilogram.
  • blends of these oils with each other and with standard collectors frequently exhibit synergistic or enhanced effects, in that 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.
  • sulfur species such as pyrite are not as readily floated by these non-sulfur-containing collectors.
  • 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.
  • Saturated or highly saturated oils such as coconut oil, contain triglycerides made from a zero or a low percentage of fatty acids with double bonds.
  • Linseed oil contains a high percentage of linolenic acid oil, an 18 carbon fatty acid with three double bonds (expressed as C I8 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 (C 22 i) species of canola oil.
  • Some canola oil is also hydrogenated (hydrogen reacted with the double bonds) before being sold.
  • 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 (C 2 j).
  • 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.
  • 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% C )8 ⁇ (oleic acid), 15% C ] 82 (linoleic acid), 1% C ] 8 3 (linolenic acid), and 62% saturated fatty acids.
  • sperm whale oil is 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 contains at least 1 double bond.
  • Sperm whale oil is of course no longer available due to whaling restrictions. However, its replacements, jojoba oil (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.
  • the natural oils used in this invention include triglycerides that contain only fatty acids having a carbon number less than 20.
  • 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, 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.
  • 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.
  • Te ⁇ ene chemistry is defined as compounds that can be assembled from two or more moles of isoprene (C 5 H 8 ) and the alcohol, aldehyde, and ketone derivatives of such compounds.
  • a te ⁇ ene compound can be defined as a monote ⁇ ene, sesquite ⁇ ene, or dite ⁇ ene compound based on whether it contains 2, 3, or 4 isoprene units, respectively.
  • the compounds can be further defined as being acyclic, monocyclic, bicyclic or tricyclic depending on whether the te ⁇ ene contains, respectively, 0, 1, 2, or 3 ring structures (only dite ⁇ enes are tricyclic).
  • Tricyclic dite ⁇ enes are generally solids.
  • Aromatic chemistry for essential oils is the chemistry of derivatives of benzene.
  • the two most common aromatic components of essential oils are cinnamaldehyde and eugenol. These are obtained from cinnamon and clove oil. Their structures are shown in Figure 2.
  • the essential oils used in the method of this invention include either a te ⁇ ene compound or an aromatic compound. More preferably, the essential oil includes a te ⁇ ene derivative having a functional group selected from an alcohol, an ether, an aldehyde, or 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 and citronella.
  • esters and alcohols have indicated, other oxygen-containing compounds such as aldehydes, ketones, and ethers of sufficient carbon number to be water-insoluble function as collectors for sulfide minerals. These compounds may or may not have carbon-carbon double bond(s).
  • 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 promoters.” 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the natural oils make up preferably between 20% and 80% by weight of the blend
  • the flotation promotors make up preferably between the remaining 80% and 20% by weight of the blend.
  • 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.
  • 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.
  • This example is 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% 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 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- 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.
  • 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.
  • PbS galena
  • 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 standard collector is a mixture of 33%o 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 (0.0150 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.
  • SIPX sodium isopropyl xanthate
  • 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.
  • 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.
  • 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 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 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. 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.
  • molybdenum recoveries 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%> belter recovery than another compound in single tests will have an average higher molybdenum recovery on multiple tests.
  • 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 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
  • 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 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 conditioned for two minutes with 1.5 gram/ton of sodium isopropyl xanthate (SIPX). The slurry was floated three more minutes.
  • SIPX sodium isopropyl xanthate
  • 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- isopropropyl thionocarbamate.
  • 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.
  • 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.

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  • Fats And Perfumes (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Cette invention se rapporte à l'utilisation de composés sans soufre comme collecteurs dans la flottation par mousse de certains composés minéraux au sulfure et métalliques. Ces composés sans soufre peuvent provenir de sources naturelles, telles que les huiles végétales, ou de sources commerciales de synthèse. Ces collecteurs sans sulfure peuvent être utilisés seuls, combinés et mélangés à d'autres collecteurs connus contenant du soufre d'usage commercial. Ces collecteurs sans soufre sont compatibles avec les agents moussants traditionnels.
PCT/US1999/018055 1998-08-11 1999-08-09 Flottation d'especes minerales au sulfure avec des huiles Ceased WO2000009268A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US09/762,619 US6827220B1 (en) 1998-08-11 1999-08-09 Flotation of sulfide mineral species with oils
MXPA01001590A MXPA01001590A (es) 1998-08-11 1999-08-09 Flotacion de especies minerales de sulfuro con aceites.
AU54732/99A AU761765B2 (en) 1998-08-11 1999-08-09 Flotation of sulfide mineral species with oils
CA2340363A CA2340363C (fr) 1998-08-11 1999-08-09 Flottation d'especes minerales au sulfure avec des huiles
US10/974,140 US7461745B2 (en) 1998-08-11 2004-10-26 Flotation of sulfide mineral species with oils

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US9617598P 1998-08-11 1998-08-11
US60/096,175 1998-08-11

Related Child Applications (2)

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US09762619 A-371-Of-International 1999-08-09
US10/974,140 Continuation US7461745B2 (en) 1998-08-11 2004-10-26 Flotation of sulfide mineral species with oils

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CO (1) CO5100956A1 (fr)
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WO2003045566A1 (fr) * 2001-11-25 2003-06-05 Roe-Hoan Yoon Procedes d'augmentation de la vitesse de flottation
US6799682B1 (en) 2000-05-16 2004-10-05 Roe-Hoan Yoon Method of increasing flotation rate
WO2004098782A1 (fr) * 2003-05-07 2004-11-18 Ekof Flotation Gmbh Utilisation d'alkylesters d'acides gras en tant qu'agents auxiliaires de flottation
FR2855987A1 (fr) * 2003-06-16 2004-12-17 Atofina Composition de mercaptans utilisable dans un procede de flottation de minerais
FR2857278A1 (fr) * 2003-06-16 2005-01-14 Atofina Compositions de mercaptans utilisables dans un procede de flottation de minerais
US6855260B1 (en) 1999-06-07 2005-02-15 Roe-Hoan Yoon Methods of enhancing fine particle dewatering
US6959815B2 (en) 2002-01-28 2005-11-01 The Governors Of The University Of Alberta Selective reactive oily bubble carriers in flotation processes and methods of generation and uses thereof
WO2006095325A3 (fr) * 2005-03-11 2007-07-19 Boc Group Inc Procedes d'enrichissement de minerai flottant
AU2008200740B2 (en) * 2001-11-25 2011-09-01 Roe-Hoan Yoon Methods of increasing flotation rate
CN103331212A (zh) * 2013-07-12 2013-10-02 武汉工程大学 一种碳酸盐磷矿反浮选捕收剂及其制备方法
WO2016138627A1 (fr) * 2015-03-03 2016-09-09 Rhodia Operations Procédé de récupération de particules fines dans une suspension aqueuse
US9885095B2 (en) 2014-01-31 2018-02-06 Goldcorp Inc. Process for separation of at least one metal sulfide from a mixed sulfide ore or concentrate
CN108262174A (zh) * 2018-03-28 2018-07-10 广东省资源综合利用研究所 一种白钨矿捕收剂及其制备方法和应用

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CN104772220A (zh) * 2015-03-11 2015-07-15 铜陵鑫腾矿业科技有限公司 一种氧化铜矿浮选剂

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US1208171A (en) * 1914-03-14 1916-12-12 Minerals Separation American Syndicate 1913 Ltd Concentration of sulfid ores.
US2120217A (en) * 1937-12-18 1938-06-07 Benjamin R Harris Ore flotation
US4507198A (en) * 1982-12-20 1985-03-26 Thiotech, Inc. Flotation collectors and methods
US5544760A (en) * 1994-10-20 1996-08-13 Benn; Freddy W. Flotation of lead sulfides using rapeseed oil
WO1997025149A1 (fr) * 1996-01-11 1997-07-17 Allied Colloids Limited Procede de recuperation de mineraux et compositions utiles a ce procede

Cited By (25)

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Publication number Priority date Publication date Assignee Title
US7820058B2 (en) 1999-06-07 2010-10-26 Mineral And Coal Technologies, Inc. Methods of enhancing fine particle dewatering
US6855260B1 (en) 1999-06-07 2005-02-15 Roe-Hoan Yoon Methods of enhancing fine particle dewatering
US6799682B1 (en) 2000-05-16 2004-10-05 Roe-Hoan Yoon Method of increasing flotation rate
US10144012B2 (en) 2000-05-16 2018-12-04 Mineral And Coal Technologies, Inc. Methods of increasing flotation rate
US6871743B2 (en) 2000-05-16 2005-03-29 Mineral And Coal Technologies, Inc. Methods of increasing flotation rate
AU2002246613B2 (en) * 2001-11-25 2007-11-15 Roe-Hoan Yoon Methods of increasing flotation rate
AU2008200740B2 (en) * 2001-11-25 2011-09-01 Roe-Hoan Yoon Methods of increasing flotation rate
WO2003045566A1 (fr) * 2001-11-25 2003-06-05 Roe-Hoan Yoon Procedes d'augmentation de la vitesse de flottation
US6959815B2 (en) 2002-01-28 2005-11-01 The Governors Of The University Of Alberta Selective reactive oily bubble carriers in flotation processes and methods of generation and uses thereof
WO2004098782A1 (fr) * 2003-05-07 2004-11-18 Ekof Flotation Gmbh Utilisation d'alkylesters d'acides gras en tant qu'agents auxiliaires de flottation
AP1909A (en) * 2003-06-16 2008-10-28 Atofina Composition formed of mercaptans which can be used in a process for the floatation of ores.
FR2855987A1 (fr) * 2003-06-16 2004-12-17 Atofina Composition de mercaptans utilisable dans un procede de flottation de minerais
US7014048B2 (en) 2003-06-16 2006-03-21 Arkema Composition formed of mercaptans which can be used in a process for the flotation of ores
AU2004202612B2 (en) * 2003-06-16 2009-08-20 Atofina Composition formed of mercaptans which can be used in a process for the flotation of ores
AU2004202612B8 (en) * 2003-06-16 2009-12-17 Atofina Composition formed of mercaptans which can be used in a process for the flotation of ores
EP1504820A1 (fr) * 2003-06-16 2005-02-09 Arkema Composition de mercaptans utilisable dans un procédé de flottation de minerais
FR2857278A1 (fr) * 2003-06-16 2005-01-14 Atofina Compositions de mercaptans utilisables dans un procede de flottation de minerais
WO2006095325A3 (fr) * 2005-03-11 2007-07-19 Boc Group Inc Procedes d'enrichissement de minerai flottant
CN103331212A (zh) * 2013-07-12 2013-10-02 武汉工程大学 一种碳酸盐磷矿反浮选捕收剂及其制备方法
US9885095B2 (en) 2014-01-31 2018-02-06 Goldcorp Inc. Process for separation of at least one metal sulfide from a mixed sulfide ore or concentrate
US10370739B2 (en) 2014-01-31 2019-08-06 Goldcorp, Inc. Stabilization process for an arsenic solution
US11124857B2 (en) 2014-01-31 2021-09-21 Goldcorp Inc. Process for separation of antimony and arsenic from a leach solution
WO2016138627A1 (fr) * 2015-03-03 2016-09-09 Rhodia Operations Procédé de récupération de particules fines dans une suspension aqueuse
CN108262174A (zh) * 2018-03-28 2018-07-10 广东省资源综合利用研究所 一种白钨矿捕收剂及其制备方法和应用
CN108262174B (zh) * 2018-03-28 2020-07-10 广东省资源综合利用研究所 一种白钨矿捕收剂及其制备方法和应用

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PE20000920A1 (es) 2000-09-18
CA2719881C (fr) 2013-06-11
MXPA01001590A (es) 2002-04-08
CA2340363A1 (fr) 2000-02-24
CO5100956A1 (es) 2001-11-27
AU5473299A (en) 2000-03-06
CA2340363C (fr) 2012-01-10
ZA200101154B (en) 2003-05-09
AR020151A1 (es) 2002-04-10
AU761765B2 (en) 2003-06-12
CA2719881A1 (fr) 2000-02-24

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