OA11003A - Compositions and methods for ore beneficiation - Google Patents

Description

1 . 011003

Compositions and Methods for Ore Beneficiation

Background of the Invention

This invention is related to the beneficiation of sulfide and precious métal ores,preferably by froth flotation.

Froth flotation is one of the most widely used processes for beneficiating orescontaining valuable minerais; see e.g. "Flotation: Theory, Reagents and Ore Testing" byRonald D. Crozier, Pergammon Press 1992; also "Surface Chemistry of Froth Flotation" byJan Leja, Plénum Press, 1982. It is especially used for separating finely ground valuableminerais from their associated gangue or for separating valuable minerais from one another.In froth flotation, a froth or a foam is generally formed by introducing air into an aqueousslurry of the finely ground ore, typically in the presence of frothing or foaming agent. Achief advantage of séparation by froth flotation is that it is a relatively efficient operation ata substantially lower cost than many other processes. A wide variety of compounds are taught to be useful in froth flotation e.g. ascollectors, frothers, modifiers, depressants, dispersants, pH regulators, and variouspromoters and additives; e.g. see "Reagents for Better Metallurgy," edited by P.S.Mulukutla, published by the Society for Mining, Metallurgy and Exploration, Inc, 1994. Asingle compound may perform more than one function. The spécifie additives used in aparticular flotation operation are usually selected according to the nature of the ore, theconditions under which the flotation will take place, the minerai sought to be recovered andthe other additives which are to be used in combination therewith.

The use of various collectors e.g. for ore beneficiation is disclosed in U.S. 4,556,482;4,595,493; 4,587,013; 4,511,464; 4,605,519; 4,618,461; 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; and4,822,483. Alkylated diaryl oxide monosulfonate collectors are disclosed in U.S. 5,015,367.Dialkyl aryl monosulfonate collectors are disclosed in U.S. 5,173,176. A phosphate flotationprocess employing various aryl disulfonates is disclosed in U.S. 4,172,029. Depressantsfor silica or siliceous gangue are disclosed in U.S. 5,057,209. Both depressants andcollectors may be combinations of substances as in U.S. 4,514,292; 4,309,282; and5,171,427. The use of sulfonates as a substitute for, or along with, xanthate ordithiophosphate in copper sulfide ore flotation is disclosed in U.S. 3,827,557. An apatite 2 011003 flotation process employing combinations which include alkyl aryl sulfonate is disclosed inU.S. 3,405,802. Flotation of heavy métal oxides is disclosed in U.S. 2,861,687. Arylsulfonates useful as depressants for froth flotation of micaceous minerais are disclosed inU.S. 3,214,018. Use of dinonyl naphthalene disulfonic acid in solvent extraction of metalsis disclosed in U.S. 4,166,837 and U.S. 4,255,395. Ail patents, patent applications, booksand articles mentioned herein are hereby incorporated herein by reference.

Despite the large number of compounds and combinations of compounds, thoseskilled in the art are constantly searching for new ways to improve ore beneficiation.Frequently, froth flotation is a very large-scale operation, so that beneficiation improvementsof 0.5% or 1% may provide dramatic increases in plant économies. Accordingly, it is anobject of the instant invention to provide new compositions, effective to provide improvedbeneficiation of a particulate sulfide or precious métal ore in a froth flotation process. It isanother object to provide methods of using new compositions, effective to provide improvedbeneficiation of a particulate sulfide or precious métal ore in a froth flotation process.

Summary of the Invention

In accordance with these and other objects, the présent invention provides, in oneembodiment, a composition comprised of (a) a dialkyl aryl disulfonic acid selected from thegroup consisting of dialkyl naphthalene disulfonic acid, dialkyl benzene disulfonic acid,dialkyl diphenyloxide disulfonic acid, and dialkyl biphenyl disulfonic acid; and (b) a collecterselected from the group consisting of dialkyl dithiophosphinates, diaryl dithiophosphinates,dialkyl monothiophosphinates, diaryl monothiophosphinates, dialkylthionocarbamates, allylalkyl thionocarbamates, hydrocarboxycarbonyl thionocarbamates, hydrocarboxycarbonylthioureas, dialkyldithiophosphates, diaryldithiophosphates, dialkylmonothiophosphates,diarylmonothiophosphates, mercaptobenzothiazoles, alkyl xanthates, alkyl xanthate esters,alkyl xanthogen formates, alkyl dithiocarbamates, dialkyl sulfides, alkyl trithiocarbonates,dialkyl trithiocarbonates, cyanoethyl alkyl sulfides, alkyl thioethylamines, and mixtures andsalts thereof; wherein the amounts of said (a) and said (b) are effective to provide improvedbeneficiation of a particulate sulfide or precious métal ore in a froth flotation process. Inpreferred embodiments, said dialkyl aryl disulfonic acid is a collecter, and preferablycontains about 16 or more carbon atoms, more preferably from about 22 to about 34 carbonatoms. Even more preferably, said dialkyl aryl disulfonic acid is a dialkyl naphthalenedisulfonic acid, most preferably dinonyl naphthalene disulfonic acid (DNNDSA). Preferably, 3 011003 said composition contains less than 50%, more preferably less than 20%, of dialkyl arylmonosulfonic acid, by weight based on dialkyl aryl disulfonic acid. Preferably, the collectoris selected from the group consisting of hydrocarboxycarbonyl thionocarbamates,hydrocarboxycarbonyi thioureas, dialkyldithiophosphates, dialkylmonothiophosphates, dialkyldithiophosphinates, dialkylthionocarbamates, mercaptobenzothiazoles, and salts andmixtures thereof; most preferably, the collector is selected from the group consisting ofdiisobutyldithiophosphate and diisobutylmonothiophosphate. Preferably, said compositionfurther comprises a second collector different from said (a) or said (b). Preferably, the oreis a particulate sulfide ore.

The présent invention also provides, in another embodiment, a process comprising;(I) forming an aqueous slurry comprised of (a) particulate sulfide or precious métal ore and(b) a composition comprised of (i) a dialkyl aryl disulfonic acid selected from the groupconsisting of dialkyl naphthalene disulfonic acid, dialkyl benzene disulfonic acid, dialkyldiphenyloxide disulfonic acid, and dialkyl biphenyl disulfonic acid; and (ii) a collectordifferent from said (i); and (II) collecting beneficiated minerais by subjecting said slurry tofroth flotation conditions; wherein the amounts of said (i) and said (ii) are effective to provideimproved beneficiation of said particulate sulfide or precious métal ore. In preferredembodiments, said dialkyl aryl disulfonic acid is a collector, and preferably contains about14 or more carbon atoms, more preferably from about 22 to about 34 carbon atoms. Evenmore preferably, said dialkyl aryl disulfonic acid is a dialkyl naphthalene disulfonic acid,most preferably dinonyl naphthalene disulfonic acid (DNNDSA). Preferably, saidcomposition contains less than 50%, more preferably less than 20%, of dialkyl arylmonosulfonic acid, by weight based on dialkyl aryl disulfonic acid. Preferably, the collectoris selected from the group consisting of dialkyl dithiophosphinates, diaryl dithiophosphinates,dialkyl monothiophosphinates, diaryl monothiophosphinates, dialkylthionocarbamates, allylalkyl thionocarbamates, hydrocarboxycarbonyl thionocarbamates, hydrocarboxycarbonylthioureas, dialkyldithiophosphates, diaryldithiophosphates, dialkylmonothiophosphates,diarylmonothiophosphates, mercaptobenzothiazoles, alkyl xanthates, alkyl xanthate esters,alkyl xanthogen formates, and mixtures and salts thereof; more preferably, the collector isselected from the group consisting of rbonyl thionocarbamates, hydrocarboxycarbonylthioureas, dialkyldithiophosphates, dialkylmonothiophosphates, dialkyl dithiophosphinates,dialkylthionocarbamates, mercaptobenzothiazoles, and salts and mixtures thereof; mostpreferably, the collector is selected from the group consisting of diisobutyldithiophosphate 011003 - 4 - and diisobutylmonothiophosphate. Preferably, said composition further comprises a secondcollector different from said (i) or said (ii). Preferably, the ore is a particulate sulfide ore.

Detailed Description of the Invention

Sulfide and/or precious métal ores which may be beneficiated by the practice of theinstant invention include well-known sulfide or precious métal ores e.g. ores containingprecious metals such as platinum, palladium, gold, silver, rhodium, iridium, rhénium, etc.and minerais containing these precious metals. Chalcopyrite, covellite, bornite, energite,argentite, millerite, cobaltite, arsenopyrite, stibnite, orpiment, realgar, cinnabar, alabandite,chalcocite, galena, pyrite, sphalerite, molybdenite, and pentlandite are représentativeminerais that may be contained in sulfide ores.

Particulate sulfide or precious métal ores are generally formed by e.g. crushing orgrinding larger ore fragments to provide particulate sulfide or precious métal ores of flotationsize by means well known to those skilled in the art. The particle size of the particulatesulfide or precious métal ore will tend to vary from ore to ore and may dépend on severalfactors e.g. the nature of the deposit and libération characteristics. In general, particulatesulfide or precious métal ores should be predominately finer than about 50 mesh, preferablyin the range of about 50 mesh to about 400 mesh sizes, most preferably from about 65mesh to about 200 mesh. An aqueous slurry of particulate sulfide or precious métal oresmay be formed by intermixing the particulate sulfide or precious métal ore with water orother aqueous media in the usual manner. Frequently, the aqueous slurry contains othercompounds useful in froth flotation as described herein. The aqueous slurry typicallycontains from about 10% to about 60%, preferably about 25 to about 50%, most preferablyabout 30% to about 40%, of ore solids, by weight based on total weight. Unless otherwiseindicated, ail percentages mentioned herein are on a weight basis, based on total weight.

The particulate sulfide or precious métal ore may be slurried with a compositioncomprised of a diaikyl aryl disulfonic acid and a collector different from the dialkyl aryldisulfonic acid. The dialkyl aryl disulfonic acid of the instant invention may contain any arylgroup, preferably diphenyloxide, anthracene, benzene, naphthalene, phénol, and biphenyl,more preferably benzene, naphthalene, and biphenyl; most preferably naphthalene. Thearyl group generally has two alkyl substituents and two sulfonic acid, or sulfonate, - 011003 - 5 - substituents. As used herein "sulfonic acid" includes the sulfonate i.e. sait form of the acid.One, both or neither of the sulfonic acid substituents on an aryl group may be in thesulfonate form. For instance, in the représentative structures of dialkyl aryl disulfonic acidsshown below, the counterions to the SO3' groups may be H or known métal ions, e.g. Na+,K+, etc.:

Rr SO3;

The alkyl substituents e.g. R, and R2, may be any alkyl or branched alkyl group;preferably each alkyl group contains from 1 to about 16 carbons, more preferably about 4to about 12 carbons. The two alkyl substituents on each aryl group may be the same ordifferent. When the aryl group contains two or more aromatic rings, the alkyl groups maybe on the same ring or different rings. Also, when the aryl group contains two or morearomatic rings, the sulfonic acid groups may be on the same ring or different rings. Thedialkyl aryl disulfonic acid generally contains about 8 or more carbon atoms, preferablyabout 10 or more, more preferably about 14 or more, even more preferably about 16 ormore, most preferably about 22 or more. The dialkyl aryl disulfonic acid generally containsabout 46 or less carbon atoms, preferably about 34 or less, most preferably 28 or less. 011003

Preferably, the dialkyl aryI disulfonic acid is a collector. A most preferred dialkyl aryldisulfonic acid is dinonyt naphthatene disulfonic acid (DNNDSA). Dialkyl aryl disulfonic acidmay be obtained commercially or may be prepared by methods known to those skilled inthe art e.g. U.S. 4,943,656. Generally, dialkyl aryl monosulfonic acids, monoalkyl aryldisulfonic acids, and non-aryl sulfonic acids are less effective than the dialkyl aryl disulfonicacids. For instance, lignin sulfonates, Petroleum sulfonates, and monoalkyl arylmonosulfonic acids do not generally show the advantages of the instant invention.Accordingly, the compositions of the instant invention, comprised of a dialkyl aryl disulfonicacid and a collector different from the dialkyl aryl disulfonic acid, generally contain less than50% of dialkyl aryl monosulfonic acid, preferably less than 20%, by weight based on dialkylaryl disulfonic acid. Also, the compositions of the instant invention, comprised of a dialkylaryl disulfonic acid and a collector different from the dialkyl aryl disulfonic acid, generallycontain less than 50% of monoalkyl aryl disulfonic acid, preferably less than 20%, by weight

O based on dialkyl aryl disulfonic acid.

Collectors, different from the dialkyl aryl disulfonic acid, may be any collector orcombination of collectors known to those skilled in the art. Collectors enumerated in theaforementioned patents and methods for making those collectors are hereby incorporatedherein by reference. Preferably, the collectors are sulfide collectors. Useful collectorsinclude alkyl mercaptans, thiocarbanilides, dialkyl disulfides, aryl hydrocarbons, alkylhydrocarbons, 1,3-oxathiolane-2-thiones, 1,3-dithiolane-2-thiones, O- and S-(2-mercaptoalkyl)-mono- or dihydrocarbyl carbamodithioates, substitutedmercaptobenzothiazoles, mercaptobenzoxazoles, substituted mercaptobenzoxazoles, O,O'-,O,S'-, and S,S'-dithiodialkylene-bis(mono- or dihydrocarbyl) carbamothioates, omega-(hydrocarbylthio)alkylamines, S-(omega-aminoalkyl)hydrocarbyl thioate, N-(hydrocarbyl)-alpha, omega-alkanediamines, N-(omega-aminoalkyl)hydrocarbon amides, omega-(hydrocarbyloxy)alkylamines, omega-aminoalkyl hydrocarbonates, and epithiocompounds,alkylamines, alkyl sulfates, alkyl sulfonates, carboxylic acids, fatty acids, and mixtures andsalts thereof. Preferred collectors include dialkyl dithiophosphinates, diaryldithiophosphinates, dialkyl monothiophosphinates, diaryl monothiophosphinates,dialkylthionocarbamates, allyl alkyl thionocarbamates, hydrocarboxycarbonylthionocarbamates, hydrocarboxycarbonyl thioureas, dialkyldithiophosphates,diaryldithiophosphates, dialkylmonothiophosphates, diarylmonothiophosphates,mercaptobenzothiazoles, alkyl xanthates, alkyl xanthate esters, alkyl xanthogen formates,xanthates, alkyl dithiocarbamates, dialkyl sulfides, alkyl trithiocarbonates, dialkyl 7 011003 trithiocarbonates, cyanoethyl alkyl sulfides, alkyl thioethylamines, and mixtures and saltsthereof. More preferred collectors include hydrocarboxycarbonyl thionocarbamates,hydrocarboxycarbonylthioureas,dialkyldithiophosphates,dialkylmonothiophosphates,dialkyldithiophosphinates, dialkylthionocarbamates, mercaptobenzothiazoles, and mixtures andsalts thereof. Most preferred collectors are dialkyldithiophosphate anddialkylmonothiophosphate, particularly diisobutyldithiophosphate anddiisobutylmonothiophosphate. A feature of the instant invention is that a composition comprised of a dialkyl aryldisulfonic acid and a collecter different from the dialkyl aryl disulfonic acid may be preparedprior to using the composition for beneficiation. In some cases it may be advantageous topréparé the composition at the production site by combining a dialkyl aryl disulfonic acidand a collecter different from the dialkyl aryl disulfonic acid, or by intermixing a dialkyl aryldisulfonic acid and a collecter different from the dialkyl aryl disulfonic acid with particulatesulfide or precious métal ore, in any order, in order to respond to the vagaries of productionby adjusting the amounts of each component of the composition. In other cases, however,the need for on-site mixing equipment and the concomitant potential for batch-to-batchvariation may be undesirable. Consequently, it is an advantage of the instant invention thata composition comprised of a dialkyl aryl disulfonic acid and a collecter different from thedialkyl aryl disulfonic acid may be provided so that the need for on-site mixing or meteringis eliminated. In some cases, it may be preferred for the composition te also comprisewater, alcohol, pH adjuster, etc. to improve handling, shelf life, etc. of the composition. A feature of the instant invention is that the novel compositions may be single phasemixtures, e.g. aqueous solutions, or may be single phase mixtures when a small amountof a solvent e.g. alcohol is added. An advantage is obtained from the use of single phasemixtures because they are generally preferred for handling purposes. Another feature ofthe instant invention is that the instant compositions may be used in a wide pH range,unlike some other known collectors. Generally, the instant invention may be practiced atany pH, depending on the nature of the ore and the collecter. An advantage is obtainedfrom a wide pH operability range because less pH adjustment may be needed, thus savingcosts and reducing inconvenience. Another feature of the instant invention is that generallyno specialized equipment or process changes are required in order to practice the instantinvention in operating flotation plantSj which may also give the advantage of saving costsand reducing inconvenience. Another feature of the instant invention is that reduced frother - 011003 usage may resuit from the practice of the instant invention, which may also give theadvantage of saving costs and reducing inconvenience.

Beneficiation of particulate sulfide or precious métal ores may be practiced byforming an aqueous slurry comprised of particulate sulfide or precious métal ore and acomposition comprised of a dialkyl aryl disulfonic acid and a collector different from saiddialkyl aryl disulfonic acid by e.g. intermixing the particulate sulfide ore with saidcomposition, or by forming the composition in situ by intermixing particulate sulfide ore,dialkyl aryl disulfonic acid, and collector in any order. The aqueous slurry, comprised ofparticulate sulfide or precious métal ore and a composition comprised of a dialkyl aryldisulfonic acid and a collector different from said dialkyl aryl disulfonic acid, may be formedat any point in the process e.g. in the grinding mill, after the grinding mill, before sizeséparation e.g. cyclone, after size séparation, in the flotation machine, etc., or may beformed in stages as discussed below. Preferably, two or more collectors are used, eithersimultaneously or in any order. For instance, the composition may be comprised of adialkyl aryl disulfonic acid, a first collector different from the dialkyl aryl disulfonic acid, anda second collector different from said first or second collectors; said composition may alsobe formed in situ as above. Obviously, when the dialkyl aryl disulfonic acid is itself acollector, the other two collectors may be termed second and third collectors, respectively.The additional collector, if any, should also be used in an amount effective to provideimproved beneficiation of said particulate sulfide or precious métal ore. Other compoundsuseful in froth flotation e.g. collectors, frothers, modifiers, depressants, dispersants, pHregulators, promoters, additives etc. may also be added to the aqueous slurry. Beneficiatedminerais are generally collected by subjecting the aqueous slurry to froth flotationconditions. The process per se of collecting beneficiated minerais by froth flotation isgenerally known to those skilled in the art; see e.g. "Flotation; Theory, Reagents and OreTesting” by Ronald D. Crozier, Pergammon Press 1992.

The instant invention may be practiced by adding the instant compositions,comprised of dialkyl aryl disulfonic acid and collector different from said dialkyl aryldisulfonic acid, to particulate sulfide or precious métal ore in a single addition step or bystaged addition. By staged addition, it is meant that a part of the effective amount of thecomposition is added to the aqueous slurry of particulate sulfide or precious métal ore; frothconcentrate is collected; an additional portion of the composition is added; froth concentrateis again collected, and so on. This staged addition may be repeated several times to obtain 011003 - 9 - optimum recovery. The number of stages is generally limitée!, in practice, by practical andéconomie restraints. Staged addition may also be carried out by adding a particularcomposition of the instant invention at one stage, and a collector or a different compositionof the instant invention at another stage.

The amounts of dialkyl aryl disulfonic acid and collector different from said dialkylaryl disulfonic acid used in the processes and compositions of the instant invention areeffective to provide improved beneficiation of particulate sulfide or precious métal ore.Effective amounts of dialkyl aryl disulfonic acid and collector different from said dialkyl aryldisulfonic acid may generally be found by routine expérimentation. Improved beneficiationmay be evidenced by improved recovery e.g. when higher % recovery of value minerais isobtained using the instant invention than when the instant invention is not practiced.Spécifie examples of improved beneficiation are demonstrated in the Examples below.Generally, for compositions comprised of (a) dialkyl aryl disulfonic acid and (b) collectordifferent from said dialkyl aryl disulfonic acid, the weight ratio of (a) to (b) is in the range ofabout 5:95 to about 95:5. Preferably, the composition contains less (a) than (b), and mostpreferably the ratio of (a) to (b) is in the range of about 5:95 to about 45:55. Typicalamounts of dialkyl aryl disulfonic acid effective to provide improved beneficiation may rangefrom about 0.5 to about 100 grams per ton of dry ore (g/t), preferably about 5 to about 50g/t, same basis. Typical amounts of collector, different from said dialkyl aryl disulfonic acid,effective to provide improved beneficiation may range from about 1 to about 400 g/t,preferably about 5 to about 100 g/t, same basis.

Other objects and advantages provided by the compositions and processes of theinstant invention will become apparent from the following working Examples, which areprovided by way of further illustration only, to enable those skilled in the art to betterunderstand and practice the instant invention.

The following abbreviations may be used in the Examples: SIPX Sodium Isopropy xanthate SIBX Sodium isobutyl xanthate IPETC IsopropyI ethyl thionocarbamate EIXF Ethyl isopropyl xanthogen formate ESBDTP 50% solution of ethyl sec-butyl dithiophosphate in water - 10 - 011003 DIBDTP 50% solution of diisobutyl dithiophosphate in water DIBMTP 50% solution of diisobutylmonothiophosphate in water ECIBTC 75% solution of ethoxycarbonyl isobutyl thionocarbamate in isobutanol ECHTC 75% solution of ethoxycarbonyl hexyl thionocarbamate in isobutanol MIBC Methyl isobutyl carbinol MBT 50% solution of the sodium sait of mercaptobenzothiazole in water DNNDSA 40% solution of dinonyl napthalene disulfonic acid (about 35%) and residual byproducts (about 5%, primarily monononyl naphthalenemonosulfonic acid and dinonyl naphthalene monosulfonic acid) in isobutanol

Ail percentages herein are by weight, based on total weight, unless otherwiseindicated. SIPX, SIBX, IPETC, EIXF, ESBDTP, DIBDTP, DIBMTP, ECIBTC, ECHTC, MIBCand MBT may be obtained commercially. The DNNDSA solution is commercially availablefrom Cytec Industries, Inc. as Cycat® 500. Polypropylene glycol-based (PPG-based)frothers used in the Examples are those typically used in froth flotation and arecommercially available.

In the following Examples, compositions V, W, X, Y and Z are embodiments of theinstant invention. Composition V was obtained by intermixing 88 parts of ESBDTP collecterwith 12 parts of DNNDSA. Composition W was obtained by intermixing 88 parts of ECIBTCcollecter with 12 parts of DNNDSA. Composition X was obtained by intermixing 80 partsof DIBDTP collecter with 20 parts DNNDSA. Composition Y was obtained by intermixing70 parts of DIBDTP collecter, 20 parts of DNNDSA, and 10 parts of methanol. CompositionZ was obtained by intermixing 70 parts of DIBMTP collecter, 20 parts of DNNDSA, and 10parts of methanol. Minor amounts of NaOH solution were added to each composition toadjust pH to about 10.5.

Amounts of compositions V, W, X, Y and Z, as well as amounts of collecter andfrother, are given in the following Examples in units of grams per ton of dry ore (g/t). 11 >011003 EXAMPLES 1-4

One kilogram (kg) of a sulfide ore with a feed assay of 2.74% copper was groundin a Steel bail mill at about 50% solids to obtain a slurry with a granulometry of 27% +100mesh. Lime was added to the grinding mill to adjust the pH of the slurry. For each run, acollector from Table 1 was added at the dose shown to either the mill or to the flotationmachine after the slurry had been transferred thereto. The volume in the flotation machinewas adjusted to obtain a slurry of about 27% solids. The pH of the slurry was about 10.Collector SIBX at about 20 g/t and PPG-based frother at about 60 g/t were then added tothe slurry and conditioned for about 1 to 2 minutes. Air was passed through the flotationmachine and beneficiated minerais were collected by froth flotation for about 12 minutes.The beneficiated minerais were assayed for value metals such as Cu. The results shownin Table 1 demonstrate the amounts of composition X (DNNDSA and DIBDTP), as well ascomposition Y (DNNDSA and DIBDTP), that are effective to provide improved beneficiationof sulfide ore, as measured by the % Cu assay of the beneficiated minerais.

Table 1

Example # Collector Dosage, g/t Grade % Cu Assay, % Cu 1C IPETC/MIBC 40 13.2 61.1 2 Comp. X 40 10.3 78.4 3 Comp. Y 40 8.9 88.8 4C DIBDTP/ ECIBTC 40 12.9 63.8 DIBDTP/ECIBTC: 70 parts DIBDTP, 30 parts ECIBTC and 10 parts 2-ethyl hexanol

IPETC/MIBC: 50 parts IPETC, 50 parts MIBC C: Comparative 12 EXAMPLES 5-6 011003

Four liters of an aqueous slurry containing approximately 1670 grams of sulfide orewith a feed assay of 1.12 % Cu was added to a Notation cell. The granulometry of thisslurry was 23% + 65 mesh at 33% solids. The pH of this slurry was adjusted to about 11using lime. For each run, a collector from Table 2 was added at the dose shown along withcollecter SIBX at 12 g/t. A frother mixture containing PPG-based frother and MIBC (1:4ratio) at about 18 g/t was added to the slurry and conditioned for about 1 to 2 minutes. Airwas passed through the flotation machine and beneficiated minerais were collected by frothflotation for about 6 minutes. The beneficiated minerais were assayed for value metalssuch as Cu. The results shown in Table 2 demonstrate the amounts of composition X(DNNDSA and DIBDTP) that are effective to provide improved beneficiation of sulfide ore,as measured by the % Cu assay of the beneficiated minerais.

Table 2

Exemple # Collector Dosage g/t Grade % Cu Assay, % Cu 5C DIBDTP 12 11.4 89.4 6 Comp. X 12 10.4 90.3 C: Comparative 13 EXAMPLES 7-9 011003

About 1.19 kg of a sulfide ore with a feed assay of 1.18% copper was ground in asteel bail mill at about 73% solids to obtain a slurry with a granulometry of 28% +65 mesh.Lime was added to the grinding mill to adjust the pH of the slurry. For each run, thecollecter combination from Table 3 was added to the mill at the total dose shown; the dosesof the individual collectors in each combination are shown in parenthèses. The aqueousslurry was transferred to the flotation machine and the volume was adjusted to obtain aslurry of about 37% solids. The pH of the slurry was about 10.5. Frother mixture PPG-based frother/MIBC/pine oil (4/2/1 proportions) at about 20 g/t was then added to the slurryand conditioned for about 1 to 2 minutes. Air was passed through the flotation machine andbeneficiated minerais were collected by froth flotation for about 9 minutes. The beneficiatedminerais were assayed for value metals such as Cu. The résulte shown in Table 3demonstrate the amounts of composition Z (DNNDSA and DIBMTP) that are effective toprovide improved beneficiation of sulfide ore, as measured by the % Cu assay of thebeneficiated minerais.

Table 3

Example # Collecter(dose, g/t) Total Dosage,g/t Grade, % Cu Assay, % Cu 7 Comp. Z (20) SIPX (15) 35 10.4 90.3 8C DIBDTP/ECIBTC (20) SIPX (15) 35 19 81.4 9C DIBDTP/ MBT (3) SIPX (32) 35 17.9 81.0 DIBDTP/ECIBTC: 70 parts DIBDTP, 30 parts ECIBTC and 10 parts 2-ethyl hexanol

DIBDTP/MBT: 90 parts DIBDTP, 10 parts MBT C: Comparative 14 011003 EXAMPLES 10-11

About 1 kg of a sulfide ore with a feed assay of 1.16% copper was ground in a Steelbail mill at about 67% solids to obtain a slurry with a granulometry of 25% +65 mesh. Lime 5 was added to the grinding mill to adjust the pH of the slurry. For each run, a collector fromTable 4 was added at the dose shown to the mill along with collector mixtureDIBDTP/ECHTC (70/30 by weight) at about 18 g/t. The aqueous slurry was transferred tothe flotation machine and the volume was adjusted to obtain a slurry of about 37% solids.The pH of the slurry was about 11. PPG-based frother at about 60 g/t was then added to 10 the slurry and conditioned for about 1 to 2 minutes. Air was passed through the flotationmachine and beneficiated minerais were collected by froth flotation for about 7 minutes.The beneficiated minerais were assayed for value metals such as Cu. The results shownin Table 4 demonstrate the amounts of composition Z (DNNDSA and DIBMTP) that areeffective to provide improved beneficiation of sulfide ore, as measured by the % Cu assay 15 of the beneficiated minerais.

Table 4

Example # Collector Dosage g/t Grade % Cu Assay, % Cu 10C EIXF 18 15.3 85.8 11 Comp. Z 18 12.8 87.2 25 C: Comparative 15 EXAMPLES 12-14 011003 2.47 kg of a sulfide ore with a feed assay of 0.9% copper was ground in a Steel bailmill at about 62% solids to obtain a slurry with a granulometry of 23% +65 mesh. Lime wasadded to the grinding mill to adjust the pH of the slurry. For each run, a collector mixturefrom Table 5 was added at the dose shown to either the mill or to the flotation machineafter the slurry had been transferred thereto. The volume in the flotation machine wasadjusted to obtain a slurry of about 35% solids. The pH of the slurry was about 11.Collector SIPX at the dose shown in Table 5 and frother mixture PPG-based frother/MIBC(1/1) at about 20 g/t were then added to the slurry and conditioned for about 1 to 2 minutes.Air was passed through the flotation machine and beneficiated minerais were collected byfroth flotation for about 8 minutes. The beneficiated minerais were assayed for value metalssuch as Cu. The results shown in Table 5 demonstrate the amounts of composition X(DNNDSA and DIBDTP) and SIPX that are effective to provide improved beneficiation ofsulfide ore, even at lower total dose, as measured by the % Cu assay of the beneficiatedminerais.

Table 5

Example # Collector(dose, g/t) Total Dosage,g/t Grade, % Cu Assay, % Cu 12C IPETC (10) SIPX (28) 38 4.1 72.2 13 Comp. X (20) SIPX (15) 35 3.1 80.6 14C DIBDTP/ECIBTC (10) SIPX (28) 38 3.8 75.2 DIBDTP/ECIBTC: 70 parts DIBDTP, 30 parts ECIBTC and 10 parts 2-ethyl hexanol C: Comparative ,011003 16 - EXAMPLE 15 (Comparative) A blend was prepared by intermixing 80 parts of DIBDTP and 20 parts of 40%aqueous para-toluenesulfonic acid. An attempt was made to beneficate ore by the generalprocedure of Examples 1 -4, using said blend at 40 g/t in the place of the composition of theinstant invention, and using collector SIPX at 20 g/t in the place of collecter SIBX.Improved beneficiation was not obtained. This Example demonstrates that para-toluenesulfonic acid, a monoalkyl aryl monosulfonic acid, does not provide improvedbeneficiation under these conditions. EXAMPLES 16-18

One kilogram (kg) of a sulfide ore with a feed assay of 2.5% copper was ground ina Steel bail mill at about 50% solids to obtain a slurry with a granulometry of 27% +100mesh. Lime was added to the grinding mill to adjust the pH of the slurry. For each run, acollector from Table 6 was added at the dose shown to either the mill or to the flotationmachine after the slurry had been transferred thereto. The volume in the flotation machinewas adjusted to obtain a slurry of about 27% solids. The pH of the slurry was about 10.Collector SIBX at about 10 g/t and PPG-based frother at about 60 g/t were then added tothe slurry and conditioned for about 1 to 2 minutes. Air was passed through the flotationmachine and beneficiated minerais were collected by froth flotation for about 12 minutes.The beneficiated minerais were assayed for value metals such as Cu. The results shownin Table 6 demonstrate the amounts of composition X (DNNDSA and DIBDTP) that areeffective to provide improved beneficiation of sulfide ore, as measured by the % Cu assayof the beneficiated minerais. 17 011003

Table 6

Example # Collector Dosage, g/t Grade % Cu Assay, %Cu 16C IPETC/MIBC 40 15.25 80.63 17 Comp. X 40 7.7 83.4 18 DIBDTP/ ECIBTC Comp. X 9 31 7.1 86.4 10 DIBDTP/ECIBTC: 70 parts DIBDTP, 30 parts ECIBTC and 10 parts 2-ethyl hexanolIPETC/MIBC: 50 parts IPETC, 50 parts MIBCC: Comparative 18 011003 EXAMPLES 19-22

One kilogram (kg) of a sulfide ore with a feed assay of 2.5% copper was ground ina Steel bail mill at about 50% solids to obtain a slurry with a granulometry of 27% +100mesh. Lime was added to the grinding mill to adjust the pH of the slurry. For each run, acollector from Table 7 was added at the dose shown to the flotation machine after the slurryhad been transferred thereto. The volume in the flotation machine was adjusted to obtaina slurry of about 27% solids. The pH of the slurry was about 10. PPG-based frother atabout 60 g/t was then added to the slurry and conditioned for about 1 to 2 minutes. Air waspassed through the flotation machine and beneficiated minerais were collected by frothflotation for about 12 minutes. The beneficiated minerais were assayed for value metalssuch as Cu. The results shown in Table 7 demonstrate the amounts of DNNDSA and othercollector that are effective to provide improved beneficiation of sulfide ore, as measured bythe % Cu assay of the beneficiated minerais.

Table 7

Example # Collector Dosage, g/t Grade % Cu Assay, % Cu 19C EIXF 40 14.3 79.6 20 Comp. V 30 13.1 81.03 21 Comp. W 30 14.2 85.2 22C ESBDTP 30 13.1 74.7 C: Comparative

Claims (9)

1. 011003 - 19 - We Claim: A process comprising: S (I) forming an aqueous slurry comprised of (a) particulate sulfide or precious métal ore and (b) a composition comprised of (i) a dialkyl aryl disulfonic acid selected from the group consisting of dialkylnaphthalene disulfonic acid, dialkyl benzene disulfonic acid, dialkyl diphenyloxide disulfonicacid, and dialkyl biphenyl disulfonic acid; and 10 (ii) a collector selected from the group consisting of dialkyl dithiophosphinates, diaryl dithiophosphinates, dialkyl monothiophosphinates, diaryl monothiophosphinates,dialkylthionocarbamates, allyl alkyl thionocarbamates, hydrocarboxycarbonylthionocarbamates, hydrocarboxycarbonyl thioureas, dialkyldithiophosphates,diaryldithiophosphates, dialkylmonothiophosphates, diarylmonothiophosphates, 15 mercaptobenzothiazoles, alkyl xanthates, alkyl xanthate esters, alkyl xanthogen formates,xanthates, alkyl dithiocarbamates, dialkyl sulfides, alkyl trithiocarbonates, dialkyltrithiocarbonates, cyanoethyl alkyl sulfides, alkyl thioethylamines, alkyl mercaptans,thiocarbanilides, dialkyl disulfides, 1,3-oxathiolane-2-thiones, 1,3-dithiolane-2-thiones, O-and S-(2-mercaptoalkyl)-mono- or dihydrocarbyl carbamodithioates, substituted 20 mercaptoDenzothiazoles, mercaptobenzoxazoïes, substituted mercaptobenzoxazoles, O.O'-,O,S'-, and S,S'-dithiodialkylene-bis(mono- or dihydrocarbyl) carbamothiodtes, and mixturesand salts thereof; and (II) collecting beneficiated minerais by subjecting said slurry to froth flotation conditions;25 wherein the weight ratio of said (i) to said (ii) is in the range of 5:95 to 95:5, and wherein saidcomposition contains less than 20% dialkyl aryl monosulfonic acid, by weight based on saiddialkyl aryl disulfonic acid. 30
2. 2. A process as claimed in Claim 1, wherein said dialkyl aryl disulfonic acid contains at least about 14 carbon atoms.
3. 3. A process as claimed in Claim 1 wherein said composition further comprises a secondcollector different from said (i) or said (ii) in an amount effective to provide improved 35 beneficiation of said particulate sulfide or precious métal ore. - 20 - 011003 10 15 20
4. 4. A process as claimed in Claim 1 wherein said collector is selecied from tne groupconsisting of diisobutyldithiophosphate and diisobutylmonothiophosphate.
5. 5. A composition comprised of (a) a dialkyl aryl disulfonic acid selected from the group consisting of dialkylnaphthalene disulfonic acid, dialkyl benzene disulfonic acid, dialkyl diphenyloxide disulfonicacid, and dialkyl biphenyl disulfonic acid; and (b) a collector selected from the group consisting of dialkyl dithiophosphinates, diaryl dithiophosphinates, dialkyl monothiophosphinates, diaryl monothiophosphinates,dialkylthionocarbamates, allyl alkyl thionocarbamates, hydrocarboxycarbonylthionocarbamates, hydrocarboxycarbonyl thioureas, dialkyldithiophosphates,diaryldithiophosphates, dialkylmonothiophosphates, diarylmonothiophosphates, mercaptobenzothiazoles, alkyl xanthates, alkyl xanthate esters, alkyl xanthogen formates,xanthates. alkyl dithiocarbamates. dialkyl sulfides, alkyl trithiocarbonates, dialkyltrithiocarbonates, cyanoethyl alkyl sulfides. alkyl thioethylamines. alkyl mercaptans,thiocarbanilides. dialkyl disulfides, 1,3-oxathiolane-2-thiones, 1,3-dithiolane-2-thiones, O-and S-(2-mercaptoalkyl)-mono- or dihydrocarbyl carbamodithioates. substitutedmercaptobenzothiazoles, mercaptobenzoxazoles, substituted mercaptobenzoxazoles, O.O'-.O.S1-, and S,S'-dithiodialkylene-bis(mono- or dihydrocarbyl) carbamothioates, and mixturesand salts thereof; wherein the weight ratio of said (a) to said (b) is in the range of 5:95 to 95:5, and wherein saidcomposition contains less than 20% dialkyl aryl monosulfonic acid, by weight based on said 25 dialkyl aryl disulfonic acid.
6. S. A composition as claimed in Claim 5 wherein said dialkyl aryl disulfonic acid containsabout 16 or more carbon atoms. 30
7. 7. A composition as claimed in Claim 5 which further comprises a second collector different from said (a) or said (b) m an amount effective to provide improved beneficiation ofsaid particulate sulfide or precious métal ore.
8. 8. A composition as claimed m Claim 5 wherein said collector is selected from the group 35 consisting of hydrocarboxycarbonyl thionocarbamates, hydrocarboxycarbonyl thioureas, - 21 . 011003 dialkyldithiophosphates. dialkylmonothiophosphates. dtalkyl akhiophosphinates,dialkylthionocarbamates, mercaptobenzothiazoles, and salts and mixtures thereof. ' . .
9. 9. A composition as claimed in Claim 5 wherein said dialkyl aryl disulfonic acid is dinonyl» 5 naphthalene disulfonic acid and wherein said collecter is selected from the group consisting of diisobutyldithiophosphate and diisobutylmonothiophosphate.