MXPA99002739A - Compositions and methods for ore beneficiation - Google Patents

Abstract

Novel compositions comprised of a dialkyl aryl disulfonic acid and a collector different from the dialkyl aryl disulfonic acid are provided, said compositions being useful for beneficiation of ores. Novel methods for using compositions comprised of a dialkyl aryl disulfonic acid and a collector different from the dialkyl aryl disulfonic acid to beneficiate ores are also provided.

Description

COMPOSITIONS AND METHODS FOR MINERAL BENEFIT BACKGROUND OF THE INVENTION This invention is related to the benefit of sulfide minerals and precious metals, preferably by foam flotation. Foam flotation is one of the most widely used processes for the benefit of minerals that contain valuable minerals; see for example "Flotation: Theory, Reagents and Ore Testing" by Ronald D. Crozier, Pergammon Press 1992; also "Surface Chemistry of Froth Flotation" by Jan Leja, Plenu Press, 1982. This is especially used for the separation of valuable finely ground minerals from their associated gangue and for the separation of valuable minerals from each other. In foam flotation, a foam is generally formed by the introduction of air into an aqueous suspension of the finely ground mineral, typically in the presence of the foaming agent. A major advantage of foam flotation separation is that this is a relatively efficient operation at a substantially lower cost than many other processes. ref. 29478 It is shown that a wide variety of compounds are useful in foam flotation, for example, as collectors, foamers, modifiers, depressants, dispersants, pH regulators, and various promoters and additives; for example see "Reagents for Better Metallurgy", edited by P.S. Mulukutla, published by the Society for Mining, Metallurgy and Exploration, Inc., 1994. A simple compound can perform more than one function. The specific additives used in a particular flotation operation are usually selected according to the nature of the mineral, the conditions under which the flotation will take place, the mineral to be recovered and the other additives that will be used in combination with East. The use of various collectors for example for mineral benefit is described in U.S. Patent Nos. 4,556,482 4, 595, 493, 4,587, 013; 4, 511, 464 4, 605, 519 4, 618, 61 4, 676, 890; 4, 684, 459, 4, 699, 711, 4, 702, 822, 4,732,668; 4, 735, 711 4, 780, 557 4, 789, 392, 4,797,202; 4,793,852; and 4,822,483. The alkylated diary oxide monosulfate collectors are described in U.S. Patent No. 5,015,367. The dialkylaryl monosulfate collectors are described in U.S. Patent No. 5,173,176. A phosphate flotation process employing various aryl disulfonates is described in US Patent No. 4,172,029. Depressants for silica or siliceous gangue are described in U.S. Patent No. 5,057,209. The depressants and collectors can be combinations of substances as in U.S. Patent Nos. 4,514,292; 4,309,282; and 5,171,427. The use of sulfonates as a substitute for, or in conjunction with, xanthate or dithiophosphate in the flotation of copper sulfide ore is described in US Patent No. 3,827,557. An apatite flotation process employing combinations including alkylaryl sulfonate is described in US Patent No. 3,405,802. The flotation of heavy metal oxides is described in U.S. Patent No. 2,861,687. The aryl sulfonates useful as depressants for the flotation by foam of micaceous minerals are described in US Pat. No. 3,214,018. The use of dinonylnaphthalenedisulfonic acid in metal solvent extraction is described in U.S. Patent No. 4,166,837 and U.S. Patent No. 4,255,395. All patents, patent applications, books and articles mentioned herein are incorporated by reference only. Despite the large number of compounds and combinations of compounds, those skilled in the art are constantly looking for new ways to improve mineral benefit. Frequently, foam flotation is a very large-scale operation, so that profit improvements of 0.5% or 1% can provide dramatic increases in the economy of plants. Accordingly, an object of the present invention is to provide novel compositions, effective to provide the improved benefit of a particulate mineral of sulfur or precious metal in a foam flotation process. Yet another object is to provide methods for using new, effective compositions to provide the enhanced benefit of a particulate mineral of sulfur or precious metal in a foam flotation process.

BRIEF DESCRIPTION OF THE INVENTION In accordance with these and other objects, the present invention provides, in one embodiment, a composition comprised of a) a dialkylarylsulfonic acid selected from the group consisting of dialkylnaphthalenedisulfonic acid, dialkylbenzenedisulfonic acid, dialkyldiphenyloxy disulfonic acid, and dialkylbiphenyldisulfonic acid; and b) a collector selected from the group consisting of dialkyl dithiophosphonates, diaryl dithiophosphonates, dialkyl monothiophosphonates, diaryl monothiophosphonates, dialkyl thionocarbamates, allyl alkyl thionocarbamates, hydrocarboxycarbonyl thionocarbamates, hydrocarboxycarbonyl thioureas, dialkyl dithiophosphates, diaryl dithiophosphate. dialkyl monothiophosphates, diaryl monothiophosphates, mercaptobenzothiazoles, alkyl xanthates, alkyl xanthate esters, alkylxanthogen formates, alkyl dithiocarbamates, dialkyl sulphides, alkyl tri-thiocarbonates, dialkyl tri-thiocarbonates, cyanoethylalkyl sulphides, alkyl -thioethylamines, and mixtures and salts thereof; wherein the amounts of (a) and (b) are effective to provide improved benefit of a particulate mineral of sulfur or precious metal in a foam flotation process. In preferred embodiments, said dialkylarylisulfonic acid is a collector, and preferably contains about 16 or more carbon atoms, more preferably from about 22 to about 34 carbon atoms. Still more preferably, said dialkylaryldisulfonic acid is a dialkylnaphthalenedisulfonic acid, more preferably dinonylnaphthalenedisulfonic acid (DNNDSA). Preferably, said composition contains less than 50%, more preferably less than 20%, of dialkylarylmonosulfonic acid, by weight, based on dialkylaryldisulfonic acid. Preferably, the collector is selected from the group consisting of hydrocarboxycarbonyl thionocarbamates, hydrocarboxylic thioureas, dialkyldithiophosphates, dialkyl monothiophosphates, dialkyldithiophosphonates, dialkylthiocarbamates, mercaptobenzothiazoles, and salts and mixtures thereof; more preferably, the collector is selected from the group consisting of diisobutyldithiophosphate and diisobutyl monothiophosphate.

Preferably, said composition further comprises a second collector different from (a) or (b). Preferably, the mineral is a particulate sulfide mineral. The present invention also provides, in yet another embodiment, a process comprising: I) the formation of an aqueous suspension comprised of a) particulate mineral of sulfide or precious metal and b) a composition comprised of i) a dialkylaryldisulfonic acid selected from the group consisting of consists of dialkylnaphthalenedisulfonic acid, dialkylbenzene disulfonic acid, dialkyldiphenyloxy disulfonic acid, and dialkyl biphenyldisulfonic acid; and ii) a collector different from (i); and II) the collection of minerals benefited by holding said suspension to flotation conditions by foam; wherein the amounts of (i) and (ii) are effective to provide enhanced benefit of the particulate sulfide or precious metal ore. In the preferred embodiments, said dialkylaryldisulfonic acid is a collector, and preferably contains about 14 or more carbon atoms, more preferably from about 22 to about 34 carbon atoms. Still more preferably, dialkylaryldisulfonic acid is a dialkylnaphthalenedisulfonic acid, more preferably dinonylnaphthalenedisulfonic acid (DNNDSA). Preferably, the composition contains less than 50%, more preferably less than 20%, of dialkylarylmonosulfonic acid, by weight, based on dialkylaryldisulfonic acid. Preferably, the collector is selected from the group consisting of dialkyl dithiophosphonates, diaryl dithiophosphonates, dialkyl monothiophosphonates, diaryl monothiophosphonates, dialkyl thionocarbamates, allyl alkyl thionocarbamates, hydrocarboxycarbonyl thionocarbamates, hydrocarboxycarbonyl thioureas, dialkyldithiophosphates, diaryldithiophosphates, dialkyl monothiophosphates, diarylmonothiophosphates, mercaptobenzothiazoles. , alkyl xanthates, alkyl xanthate esters, alkyl xanthogen formates, and mixtures and salts thereof; more preferably, the collector is selected from the group consisting of carbonyl thionocarbamates, hydrocarboxycarbonyl thioureas, dialkyldithiophosphates, dialkyl monothiophosphates, dialkyl dithiophosphonates, dialkylthiocarbamates, mercaptobenzothiazoles, and salts and mixtures thereof; more preferably, the collector is selected from the group consisting of diisobutyldithiophosphate and diisobutyl monothiophosphate. Preferably, the composition further comprises a second collector different from (i) or (ii). Preferably, the mineral is a particulate sulfide mineral.

DETAILED DESCRIPTION OF THE INVENTION The sulfide and / or precious metal minerals that may be benefited by the practice of the present invention include well-known sulfide or precious metal ores, for example, minerals containing precious metals such as platinum, palladium, gold, silver, rhodium, iridium, rhenium, etc., and minerals that contain these precious metals. Chalcopyrite, covelite, bornita, energita, argentita, millerite, cobaltite, arsenopyrite, stibnite, orpiment, realgar, cinnabar, alabandite, chalcocite, galena, pyrite, sphalerite, molybdenite and pentlandite are representative minerals that can be contained in sulfide minerals .

Particulate sulphide or precious metal minerals are generally formed by, for example, grinding or grinding larger mineral fragments to provide sulfide or precious metal particulates of floating size by means well known to those of experience. in the technique. The particle size of the particulate mineral of the sulfide or precious metal will tend to vary from one mineral to another, and may depend on various factors, for example, the nature of the deposit and the release characteristics. In general, the particulate sulfide or precious metal minerals should be predominantly finer than about 50 mesh, preferably in the range of about 50 mesh to about 400 mesh sizes, more preferably about 65 mesh to about 200 mesh. Aqueous particulate minerals of sulfur or precious metal can be formed by mixing the particulate mineral sulfide or precious metal with water or other aqueous media, in the usual manner. Frequently, the aqueous suspension contains other compounds useful in foam flotation as described herein. The aqueous suspension typically contains from about 10% to about 60%, preferably from about 25% to about 50%, more preferably from about 30% to about 40%, of mineral solids, by weight, based on the total weight. Unless stated otherwise, all percentages mentioned herein are on a weight basis, based on the total weight. The sulfide or precious metal particulate mineral can be suspended with a composition comprised of a dialkylaryldisulfonic acid, and a different collector of dialkylaryldisulfonic acid. The dialkylaryldisulfonic acid of the present invention may contain any aryl group, preferably diphenyloxide, anthracene, benzene, naphthalene, phenol, and biphenyl, more preferably benzene, naphthalene, and biphenyl; more preferably still naphthalene. The aryl group generally has two alkyl substituents and two sulfonic acid substituents, or sulfonate. As used herein "sulfonic acid" includes the sulfonate, for example, the salt form of the acid. One, both or none of the sulfonic acid substituents on an aryl group can be in the sulfonate form. For example, in the representative structures of the dialkylarylisulfonic acids shown below, the counterions to the S03 ~ groups can be hydrogen or known metal ions, for example, Na +, K +, etc. : The alkyl substituents, for example Ri and R2 can be any alkyl or branched alkyl group; preferably, each alkyl group contains from 1 to about 16 carbon atoms, more preferably from about 4 to about 12 carbon atoms. The two alkyl substituents on each aryl group can be the same or different. When the aryl group contains two or more aromatic rings, the alkyl groups may be on the same ring or on different rings. Also, when the aryl group contains two or more aromatic rings, the sulfonic acid groups can be on the same ring or on different rings. The dialkylaryldisulfonic acid generally contains about 8 or more carbon atoms, preferably about 10 or more, more preferably about 14 or more, still more preferably about 16 or more, most preferably about 22 or more. The dialkylaryldisulfonic acid generally contains about 46 or less carbon atoms, preferably about 34 or less, more preferably 28 or less. Preferably, dialkylaryldisulfonic acid is a collector. A more preferred dialkylaryldisulfonic acid is dinonylnaphthalenedisulfonic acid (DNNDSA). The dialkylaryldisulfonic acid can be obtained commercially or can be prepared by methods known to those of skill in the art, for example in U.S. Patent No. 4,943,656. In general, dialkylarylmonosulfonic acids, monoalkylaryldisulfonic acids, and non-arylsulfonic acids are less effective than dialkylaryldisulfonic acids. For example, lignin sulfonates, petroleum sulfonates, and monoalkylarylmonosulfonic acids generally do not show the advantages of the present invention. Accordingly, the compositions of the present invention, comprised of a dialkylaryldisulfonic acid and a different collector of dialkylaryldisulfonic acid, generally contain less than 50% of the dialkylarylmonosulfonic acid, preferably less than 20%, by weight, based on the dialkylaryldisulfonic acid. Also, the compositions of the present invention, comprised of a dialkylaryldisulfonic acid and a different collector of dialkylaryldisulfonic acid, generally contain less than 50% of the monoalkylaryldisulfonic acid, preferably less than 20%, by weight based on the dialkylaryldisulfonic acid. Collectors, other than dialkylaryldisulfonic acid, can be any collector or combination of collectors known to those of skill in the art. The collectors listed in the aforementioned patents and the methods for making those collectors are incorporated by reference herein. Preferably, the collectors are sulfide collectors. Useful collectors include alkylmercaptans, thiocarbanilides, dialkyl disulfides, aryl hydrocarbons, alkyl hydrocarbons, 1,3-oxathiolan-2-thiones, 1,3-dithiolan-2-thiones, carbamodithioates of 0- and S- (2-mercaptoalkyl) -mono- or dihydrocarbyl, substituted mercaptobenzothiazoles, mercaptobenzoxazoles, substituted mercaptobenzoxazoles, carbamothioates of 0.0'-, 0, S'- and S, S'-dithiodialkylene-bis (mono- or dihydrocarbyl), omega- (hydrocarbyl) alkylamines, S- (omega-animoalkyl) hydrocarbyl, N- (hydrocarbyl) -alpha, omega-alkanediamines, N- (omega-aminoalkyl) hydrocarbon-amides, omega- (hydrocarbyloxy) alkylamines, omega-a-hydrocarbonates, and epithiocompounds , alkylamines, alkyl sulfates, alkyl sulfonates, carboxylic acids, fatty acids, and mixtures and salts thereof. Preferred collectors include dialkyl dithiophosphonates, diaryl dithiophosphonates, dialkyl monothiophosphonates, diaryl monothiophosphonates, dialkyl thionocarbamates, allyl alkyl thionocarbamates, hydrocarboxylcarbonyl thionocarbamates, hydrocarboxylcarbonylthioureas, dialkyl dithiophosphates, diaryl dithiophosphates, dialkyl monothiophosphates, diaryl monothiophosphates, mercaptobenzothiazoles, alkyl xanthates, alkyl xanthate esters, alkyl xanthogen formates, xanthates, alkyl dithiocarbamates, dialkyl sulphides, alkyl tri-thiocarbonates, dialkyl tri-thiocarbonates, cyanoethylalkyl sulphides, alkylthioethylamines, and mixtures and salts of the same. The most preferred collectors include hydrocarboxylcarbonyl thionocarbamates, dialkyl hydroxycarbonyl thioureas, dialkyl dithiophosphates, dialkyl monothiophosphates, di thiophosphonates, dialkyl, dialkyl thionocarbamates, mercaptobenzothiazoles, and mixtures and salts thereof. The most preferred collectors are dialkyl dithiophosphate and dialkyl monothiophosphate, particularly diisobutyl dithiophosphate and diisobutyl monothiophosphate. It is a feature of the present invention that a composition comprised of a dialkylaryldisulfonic acid and a different collector of dialkylaryldisulfonic acid can be prepared, before using the composition for the benefit. In some cases, it may be advantageous to prepare the composition at the production site by the combination of a dialkylaryldisulfonic acid and a different collector of dialkylaryldisulfonic acid, or by mixing a dialkylaryldisulfonic acid and a different collector of dialkylaryldisulfonic acid with the particulate mineral of sulfur or precious metal, in any order, in order to respond to the whims of production by adjusting the quantities of each component of the composition. In other cases, however, the need for mixing equipment at the site and the concomitant potential for variation from batch to batch may be undesirable. Accordingly, an advantage of the present invention is that a composition comprised of a dialkylaryldisulfonic acid and a different collector of dialkylaryldisulfonic acid can be provided, so that the need for mixing or for in-site dosing is eliminated. In some cases, it may be preferred for the composition that it also comprises water, alcohol, pH adjuster, etc., to improve the handling, shelf life, etc., of the composition. A feature of the present invention is that the novel compositions can be simple phase mixtures, for example aqueous solutions, or can be simple phase mixtures when a small amount of a solvent, for example alcohol, is added. An advantage is obtained from the use of the simple phase mixtures because they are generally preferred for handling purposes. Yet another feature of the present invention is that the present compositions can be used over a wide pH range, in a manner contrary to some other known collectors. In general, the present invention can be practiced at any pH, depending on the nature of the mineral and the collector. An advantage is obtained from a wide range of pH operability because lower pH adjustment may be necessary, thereby saving costs and reducing inconvenience. Yet another feature of the present invention is that specialized changes in the equipment or process are not generally required in order to practice the present invention in the operation of flotation plants, which can also give the advantage of saving costs and reduce the inconvenience. Yet another feature of the present invention is that the reduced use of the foamer may result from the practice of the present invention, which may also give the advantage of saving costs and reducing inconvenience. The benefit from the sulfide or precious metal particulate minerals can be practiced by forming an aqueous suspension comprised of sulfide particulate mineral or precious metal and a composition comprised of a dialkylaryldisulfonic acid and a different collector of dialkylaryldisulfonic acid, for example by mixing the particulate sulfide mineral with said composition, or by forming the composition itself by mixing the particulate sulfide mineral, the dialkylaryldisulfonic acid, and the collector, in any order. The aqueous suspension, comprised of sulphide or precious metal particulate mineral and a composition comprised of a dialkylaryldisulfonic acid and a different collector of dialkylaryldisulfonic acid, it can be formed at any point in the process, for example in the grinding mill, after the grinding mill, before separation by size, for example by cyclone, after separation by size, in the flotation machine, etc. , or it can be formed in stages as discussed below. Preferably, two or more collectors are used, either simultaneously or in any order. For example, the composition can be comprised of a dialkylaryldisulfonic acid, a first collector different from dialkylaryldisulfonic acid, and a second collector different from the first or second collectors.; said composition can also be formed in si t u as described above. Obviously, when dialkylaryldisulfonic acid is itself a collector, the other two collectors can be referred to as second and third collectors, respectively. The additional collector, if any, must also be used in an effective amount to provide enhanced benefit of particulate sulfide ore or precious metal. Other compounds useful in foam flotation, for example collectors, foamers, modifiers, depressants, dispersants, pH regulators, promoters, additives, etc., can also be added to the aqueous suspension. The beneficiated minerals are generally collected or collected by subjecting the aqueous suspension to flotation conditions by foam. The process per se of collecting or collecting beneficiated minerals by foam flotation is generally known to those of skill in the art; see for example "Flotation: Theory, Reagents and Ore Testing" by Ronald D. Crozier, Pergammon Press 1992. The present invention can be practiced by adding the present compositions, comprised of dialkylaryldisulfonic acid and the different collector of dialkylaryldisulfonic acid, to the particulate mineral sulphide or precious metal, in a simple addition step or by stepwise addition. By stepwise addition, it is understood that a part of the effective amount of the composition is added to the aqueous suspension of the sulfide or precious metal particulate mineral; the concentrate in foam is collected; an additional portion of the composition is added; the foam concentrate is collected again, and so on. The stepwise addition can be repeated several times to obtain optimal recovery. The number of stages is generally limited, in practice, by practical and economic restrictions. The stepwise addition can also be carried out by the addition of a particular composition of the present invention in one step, and a collector or a different composition of the present invention in a further step. The amounts of dialkylaryldisulfonic acid and the different collector of the dialkylaryldisulfonic acid used in the processes and compositions of the present invention are effective to provide improved benefit of the sulfide or precious metal particulate mineral. The effective amounts of the dialkylaryldisulfonic acid and the different collector of the dialkylaryldisulfonic acid can generally be found by routine experimentation. The improved benefit can be evidenced by the improved recovery, for example, when a higher percentage of recovery of the valuable minerals is obtained, using the present invention, than when the present invention is not practiced. Specific examples of improved benefit are demonstrated in the following examples. In general, compositions comprised of a) dialkylaryldisulfonic acid and b) a different collector of dialkylaryldisulfonic acid, the weight ratio of (a) to (b) being in the range of about 5:95 to about 95: 5. Preferably, the composition contains less than (a) that of (b), and more preferably the ratio of (a) to (b) is in the range of about 5:95 to about 45:55. Typical amounts of dialkylaryldisulfonic acid, effective to provide improved benefit, may be in the range of about 0.5 to about 100 grams per tonne of dry ore (g / t), preferably about 5 to about 50 g / t, on the same basis . Typical amounts of the collector, other than dialkylarylisulfonic acid, effective to provide improved benefit, may be in the range of about 1 to about 400 g / t, preferably about 5 to about 100 g / t., on the same basis. Other objects and advantages provided by the compositions and processes of the present invention will become apparent from the following working examples, which are provided by way of illustration only, to enable those skilled in the art to better understand and practice the present invention. The following abbreviations may be used in the Examples: SIPX sodium isopropylxantate SIBX sodium isobutylxanthate IPETC ethylthionocarba isopropyl abate EIXF ethylisopropyl xanthogen formate ESBDTP 50% solution of ethyl sec-butylthiophosphate in water DIBDTP 50% solution of dithiophosphate diisobutyl in water DIBMTP 50% solution of diisobutyl monothiophosphate in water ECIBTC 75% solution of ethoxycarbonyl isobutyl thionocarbamate in isobutanol ECHTC 75% solution of ethoxycarbonylhexyl thionocarbamate in isobutanol MIBC methyl isobutylcarbinol MBT 50% solution of mercaptobenzothiazole sodium salt in water DNNDSA 40% solution of dinonylnaphthalenedisulfonic acid (approximately 35%) and residual byproducts (approximately 5%, mainly monononylnaphthalenesulfonic acid and dinonylnaphthalene monophonic acid) in isobutanol All percentages herein are by weight, based on the total weight, unless otherwise indicated. SIPX, SIBX, IPETC, EIXF, ESBDTP, DIBDTP, DIBMTP, ECIBTC, ECHTC, MIBC and MBT can be obtained commercially. The DNNDSA solution is commercially available from Cytec Industries, Inc., as Cycat® 500. The polypropylene glycol-based (PPG-based) foaming agents used in the Examples are those typically used in foam flotation and are commercially available. In the following Examples, compositions V, W, X, Y and Z are embodiments of the present invention. Composition V was obtained by mixing 88 parts of the ESBDTP collector with 12 parts of DNNDSA. Composition W was obtained by mixing 88 parts of the ECIBTC collector with 12 parts of DNNDSA. Composition X was obtained by mixing 80 parts of the DIBDTP collector with 20 parts of DNNDSA. Composition Y was obtained by mixing 70 parts of the DIBDTP collectors, 20 parts of DNNDSA, and 10 parts of methanol. Composition Z was obtained by mixing 70 parts of the DIBMTP collector, 20 parts of DNNDSA, and 10 parts of methanol. Minor amounts of NaOH solution were added to each composition to adjust the pH to about 10.5. The amounts of the compositions V,, X, Y and Z, as well as the amounts of the collector and the foamer, are given in the following examples in units of grams per tonne of dry ore (g / t).

EXAMPLES 1-4 One kilogram (kg) of a sulfide mineral with a feed test of 2.74% copper was crushed in a steel ball mill at approximately 50% solids, to obtain a suspension with a granulometry of more than 27% mesh 100. Limestone was added to the grinding mill to adjust the pH of the suspension. For each run, a collector from Table 1 was added to the dose shown for each mill or to the flotation machine after the suspension had been transferred thereto. The volume in the flotation machine was adjusted to obtain a suspension of approximately 27% solids. The pH of the suspension was about 10. The SIBX collector at about 20 g / t and the PPG-based foamer at about 60 g / t were then added to the suspension and conditioned for about 1 to 2 minutes. Air was passed through the flotation machine and the beneficiated minerals were collected by foam flotation, for approximately 12 minutes. The beneficiated minerals were evaluated for valuable metals such as copper. The results shown in Table 1 demonstrate the amounts of composition X (DNNDSA and DIBDTP), as well as composition Y (DNNDSA and DIBDTP), which are effective to provide improved benefit of the sulfide mineral, as measured by the test of % of Cu of the beneficiated minerals.

DIBDTP / ECIBTC: 70 parts of DIBDTP, 30 parts of ECIBTC and 10 parts of 2-ethylhexanol IPETC / MIBC: 50 parts of IPETC, 50 parts of MIBC C: Comparative EXAMPLES 5-6 To a flotation cell was added four liters of an aqueous suspension containing approximately 1670 grams of sulfide ore with a feed test of 1.12% copper. The granulometry of this suspension was more than 23% 65 mesh to 33% solids. The pH of this suspension was adjusted to approximately 11 using limestone. For each run, a collector from Table 2 was added to the dose shown, together with the SIBX collector at 12 g / t. A foaming mixture containing the foamer based on PPG and MIBC (ratio 1: 4) at about 18 g / t was added to the suspension and conditioned for approximately 1 to 2 minutes. Air was passed through the flotation machine and the beneficiated minerals were collected by foam flotation for approximately 6 minutes. The beneficiated minerals were evaluated for valuable metals such as copper. The results shown in Table 2 demonstrate the amounts of composition X (DNNDSA and DIBDTP) that are effective in providing the improved sulfide mineral benefit, as measured by the% Cu assay of the beneficiated minerals.

C: Comparative EXAMPLES 7-9 Approximately 1.19 kg of a sulfide mineral was crushed with a 1.18% copper feed test, in a steel bead mill at approximately 73% solids to obtain a suspension with a granulometry of 28% greater than 65 mesh. limestone to the grinding mill to adjust the pH of the suspension. For each run, the combination of the collector from Table 3 was added to the mill, at the total dose shown; the doses of the individual collectors in each combination are shown in parentheses. The aqueous suspension was transferred to the flotation machine and the volume was adjusted to obtain a suspension of approximately 37% solids. The pH of the suspension was approximately 10.5. The PPG / MIBC / pine oil based foaming mixture (proportions 4/2/1) at about 20 g / t was then added to the suspension, and conditioned for about 1 to 2 minutes. Air was passed through the flotation machine and the beneficiated minerals were collected by foam flotation for approximately 9 minutes. The beneficiated minerals were evaluated for valuable metals such as copper. The results shown in Table 3 demonstrate the amounts of composition Z (DNNDSA and DIBMTP) that are effective to provide improved sulfide mineral benefit, as measured by the% Cu assay of the beneficiated minerals.

Table 3 DIBDTP / ECIBTC: 70 parts of DIBDTP, 30 parts of ECIBTC and 10 parts of 2-ethylhexanol DIBDTP / MBT: 90 parts of DIBDTP, 50 parts of MBT C: Comparative E JEMPLOS 10 - 11 Approximately 1 kg of a sulfide mineral with a feed test of 1.16% copper was crushed in a steel bead mill at approximately 67% solids to obtain a suspension with a granulometry of 25% greater than 65 mesh. Limestone was added crusher to adjust the pH of the suspension. For each run, a collector from Table 4 was added to the dose shown to the mill, together with the DIBDTP / ECHTC collection mix (70/30 by weight) at approximately 18 g / t. The aqueous suspension was transferred to the flotation machine and the volume was adjusted to obtain a suspension of approximately 37% solids. The pH of the suspension was approximately 11. The PPG based foamer at approximately 60 g / t was then added to the suspension and conditioned for approximately 1 to 2 minutes. Air was passed through the flotation machine and the beneficiated minerals are collected by foam flotation for approximately 7 minutes. The beneficiated minerals were evaluated for valuable metals such as copper. The results shown in Table 4 demonstrate the amounts of composition Z (DNNDSA and DIBMTP) that are effective to provide the improved sulfide mineral benefit, as measured by the% Cu test of the beneficiated minerals.

C: Comparative EXAMPLES 12-14 2. 47 kg of a sulphide mineral with a 0.9% copper feed test was crushed in a steel ball mill to approximately 62% solids to obtain a suspension with a granulometry of 23% greater than 65 mesh. It was then added limestone to the grinder mill to adjust the pH of the suspension. For each run a collector mix of Table 5 was added to the dose shown, either to the mill or to the flotation machine after the suspension had been transferred thereto. The volume in the flotation machine was adjusted to obtain a suspension of approximately 35% solids. The pH of the suspension was approximately 11. The SIPX collector at the dose shown in Table 5 and the foaming mixture, based on PPG / MIBC (1/1) at about 20 g / t, were then added to the suspension and conditioned for approximately 1 to 2 minutes. Air was passed through the flotation machine and the beneficiated minerals were collected by foam flotation for approximately 8 minutes. The beneficiated minerals were evaluated for valuable metals such as copper. The results shown in Table 5 demonstrate the amounts of composition X (DNNDSA and DIBDTP) and SIPX that are effective to provide the improved sulfide mineral benefit, even at the lowest total dose, as measured by the% Cu of the beneficiated minerals.

Table 5 DIBDTP / ECIBTC: 70 parts of DIBDTP, 30 parts of ECIBTC and 10 parts of 2-ethylhexanol C: Comparative EXAMPLE 15 (Comparative) A mixture was prepared by mixing 80 parts of DIBDTP and 20 parts of 40% aqueous para-toluenesulfonic acid. An attempt was made to benefit the ore by the general procedure of Examples 1-4, using said mixture at 40 g / t in place of the composition of the present invention, and using the SIPX collector at 20 g / t instead of the SIBX collector. The improved benefit was not obtained. This Example demonstrates that para-toluenesulfonic acid, a monoalkylarylmonosulfonic acid, does not provide improved benefit under these conditions.

EXAMPLES 16-18 One kilogram (kg) of a sulfide mineral with a 2.5% copper feed test was crushed in a steel ball mill at approximately 50% solids to obtain a suspension with a granulometry of 27% greater than 100 mesh. Then limestone was added to the grinding mill to adjust the pH of the suspension. For each run, a collector from Table 6 was added to the dose shown, either to the mill or to the flotation machine after the suspension had been transferred to it. The volume of the flotation machine was adjusted to obtain a suspension of approximately 27% solids. The pH of the suspension was about 10. The SIBX collector at about 10 g / t and the PPG-based foamer at about 60 g / t were then added to the suspension, and conditioned for about 1 to 2 minutes. Air was passed through the flotation machine and the beneficiated minerals were collected by foam flotation for approximately 12 minutes. The beneficiated minerals were evaluated for valuable metals such as copper. The results shown in Table 6 demonstrate the amounts of composition X (DNNDSA and DIBDTP) that are effective to provide the improved benefit of the sulfide mineral, as measured by the% copper assay of the beneficiated minerals.

DIBDTP / ECIBTC: 70 parts of DIBDTP, 30 parts of ECIBTC and 10 parts of 2-ethylhexanol IPETC / MIBC: 50 parts of IPETC, 50 parts of MIBC C: Comparative EXAMPLES 19-22 One kilogram (kg) of sulfur ore with a 2.5% copper feed test was crushed in a steel ball mill to approximately 50% solids to obtain a suspension with a granulometry of 27% greater than 100 mesh. Then added limestone to the grinding mill to adjust the pH of the suspension. For each run, a collector from Table 7 was added, at the dose shown, to the flotation machine after the suspension had been transferred thereto. The volume in the flotation machine was adjusted to obtain a suspension of approximately 27% solids. The pH of the suspension was approximately 10. The foamer based on PPG was then added at approximately 60 g / t, to the suspension, and conditioned for approximately 1 to 2 minutes. Air was passed through the flotation machine and the beneficiated minerals were collected by foam flotation for approximately 12 minutes. The beneficiated minerals were evaluated for valuable metals such as Cu. The results shown in Table 7 demonstrate the amounts of DNNDSA and another collector, which are effective to provide the improved sulfide mineral benefit, as measured by the% Cu assay of the beneficiated minerals.

Table 7 Comparative It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (9)

CLAIMS Having described the invention as above, the content of the following "l" is claimed as property:

1. A process, characterized in that it comprises: I) the formation of an aqueous suspension comprised of a) particulate mineral of sulphide or precious metal and b) a composition comprising: i) a dialkylaryldisulfonic acid selected from the group consisting of dialkylnaphthalenedisulfonic acid, dialkylbenzene disulfonic acid, dialkyldiphenyloxyldisulfonic acid, and dialkylbiphenyldisulfonic acid; and ii) a collector selected from the group consisting of dialkyl dithiophosphonates, diaryl dithiophosphonates, dialkyl monothiophosphonates, diaryl monothiophosphonates, dialkyl thionocarbamates, allyl alkyl thionocarbamates, hydrocarboxylcarbonyl thionocarbamates, hydrocarboxycarbonyl thioureas, dialkyl dithiophosphates, diaryl dithiophosphates, monothiophosphates of dialkyl, diaryl monothiophosphates, mercaptobenzothiazoles, alkyl xanthates, alkyl xanthate esters, xanthogenous alkyl formates, xanthates, alkyl dithiocarbamates, dialkyl sulphides, alkyl tri-thiocarbonates, dialkyl tri-thiocarbonates, cyanoethylalkyl sulphides , alkylthioethylamines, alkylmercaptans, thiocarbanilides, dialkyl disulfides, 1,3-oxothiolan-2-thiones, 1,3-dithiolan-2-thiones, carbamodithioates of O- and S- (2-mercaptoalkyl) -mono- or dihydrocarbyl, mercaptobenzothiazoles substituted, mercaptobenzoxazoles, substituted mercaptobenzoxazoles, carba otioat 0.0'-, 0, S'-, and S, S '-dithiodialkylene-bis (mono- or dihydrocarbyl), and mixtures and salts thereof. II) the collection of beneficiated minerals by subjecting said suspension to flotation conditions by foam; wherein the weight flotation of (i) to (ii) is in the range of 5:95 to 95: 5, and wherein the composition contains less than 20% dialkylarylmonosulfonic acid, by weight, based on dialkylaryldisulfonic acid .

2. A process according to claim 1, characterized in that the dialkylaryldisulfonic acid contains at least about 14 carbon atoms.

3. A process according to claim 1, characterized in that the composition further comprises a second collector different from (i) or (ii), in an amount effective to provide improved benefit of the particulate mineral of sulfur or precious metal.

4. A process according to claim 1, characterized in that the collector is selected from the group consisting of diisobutyl dithiophosphate and diisobutyl monothiophosphate.

5. A composition, characterized in that it is comprised of: a) a dialkylaryldisulfonic acid selected from the group consisting of dialkylnaphthalenedisulfonic acid, dialkylbenzenedisulfonic acid, dialkyldiphenyloyldisulfonic acid, and dialkylbiphenyldisulfonic acid; and b) a collector selected from the group consisting of dialkyl dithiophosphonates, diaryl dithiophosphonates, dialkyl monothiophosphonates, diaryl monothiophosphonates, dialkyl thionocarbamates, allyl alkyl thionocarbamates, hydrocarboxycarbonyl thionocarbamates, hydrocarboxycarbonyl thioureas, dialkyl dithiophosphates, diaryl dithiophosphates, monothiophosphates dialkyl, diaryl monothiophosphates, mercaptobenzothiazoles, alkyl xanthates, alkyl xanthate esters, alkyl xanthogen formates, xanthates, alkyl dithiocarbamates, dialkyl sulfides, alkyl tri-thiocarbonates, dialkyl tri-thiocarbonates, cyanoethylalkyl sulfides, alkylthioethylamines, alkylmercaptans, thiocarbanilides, dialkyl disulfides, 1,3-oxathiolan-2-thiones, 1,3-dithiolan-2-thiones, carbamodithioates of O- and S- (2-mercaptoalkyl) -mono- or dihydrocarbyl, substituted mercaptobenzothiazoles , mercaptobenzoxazoles, substituted mercaptobenzoxazoles, carba otioa 0.0'-, 0, S'-, and S, S'-dithiodialkylene-bis (mono- or dihydrocarbyl), and mixtures and salts thereof; wherein the weight ratio of (a) to (b) is in the range of 5:95 to 95: 5, and wherein the composition contains less than 20% dialkylarylmonosulfonic acid, by weight, based on dialkylaryldisulfonic acid .

6. A composition according to claim 5, characterized in that the dialkylaryldisulfonic acid contains approximately 16 or more carbon atoms.

7. A composition according to claim 5, characterized in that it further comprises a second collector different from (a) or (b), in an amount effective to provide improved benefit of the particulate mineral of sulfur or precious metal.

8. A composition according to claim 5, characterized in that the collector is selected from the group consisting of hydrocarboxylcarbonyl thionocarbamates, hydrocarboxylcarbonyl thioureas, dialkyl dithiophosphates, dialkyl monothiophosphates, dialkyl dithiophosphonates, dialkyl thionocarbamates, mercaptobenzothiazoles, and salts and mixtures thereof. the same.

9. A composition according to claim 5, characterized in that the dialkylaryldisulfonic acid is dinonylnaphthalenedisulfonic acid, and wherein the collector is selected from the group consisting of diisobutyl dithiophosphate and diisobutyl monothiophosphate.