Dialkylated aryl monosulfonate collectors useful in the flotation of minerals

Abstract

Dialkylated aryl monosulfonic acids or salts thereof or their mixture are useful as collectors in the flotation of minerals, particularly oxide minerals. Particularly useful are those sulfonic acids or salts in which the alkyl substituents are unsymmetrical. Collector compositions comprising these salts and sulfide collectors such as xanthates are useful in flotations conducted at natural pH of the slurry.

Description

BACKGROUND OF THE INVENTION

This invention is related to the use of chemical collectors in the recovery of minerals by froth flotation.

Flotation is a process of treating a mixture of finely divided mineral solids, e.g., a pulverulent ore, suspended in a liquid whereby a portion of the solids is separated from other finely divided mineral solids, e.g., silica, siliceous gangue, clays and other like materials present in the ore, by introducing a gas (or providing a gas in situ) in the liquid to produce a frothy mass containing certain of the solids on the top of the liquid, and leaving suspended (unfrothed) other solid components of the ore. Flotation is based on the principle that introducing a gas into a liquid containing solid particles of different materials suspended therein causes adherence of some gas to certain suspended solids and not to others and makes the particles having the gas thus adhered thereto lighter than the liquid. Accordingly, these particles rise to the top of the liquid to form a froth.

The minerals and their associated gangue which are treated by froth flotation generally do not possess sufficient hydrophobicity or hydrophilicity to allow adequate separation. Therefore, various chemical reagents are often employed in froth flotation to create or enhance the properties necessary to allow separation. Collectors are used to enhance the hydrophobicity and thus the floatability of different mineral values. Collectors must have the ability to (1) attach to the desired mineral species to the relative exclusion of other species present: (2) maintain the attachment in the turbulence or shear associated with froth flotation; and (3) render the desired mineral species sufficiently hydrophobic to permit the required degree of separation.

A number of other chemical reagents are used in addition to collectors. Examples of types of additional reagents used include frothers, depressants, pH regulators, such as lime and soda, dispersants and various promoters and activators. Depressants are used to increase or enhance the hydrophilicity of various mineral species and thus depress their flotation. Frothers are reagents added to flotation systems to promote the creation of a semi-stable froth. Unlike both depressants and collectors, frothers need not attach or adsorb on mineral particles.

Froth flotation has been extensively practiced in the mining industry since at least the early twentieth century. A wide variety of compounds are taught to be useful as collectors, frothers and other reagents in froth flotation. For example, xanthates, simple alkylamines, alkyl sulfates, alkyl sulfonates, carboxylic acids and fatty acids are generally accepted as useful collectors. Reagents useful as frothers include lower molecular weight alcohols such as methyl isobutyl carbinol and glycol ethers. The specific additives used in a particular flotation operation are selected according to the nature of the ore, the conditions under which the flotation will take place, the mineral sought to be recovered and the other additives which are to be used in combination therewith.

While a wide variety of chemical reagents are recognized by those skilled in the art as having utility in froth flotation, it is also recognized that the effectiveness of known reagents varies greatly depending on the particular ore or ores being subjected to flotation as well as the flotation conditions. It is further recognized that selectivity or the ability to selectively float the desired species to the exclusion of undesired species is a particular problem.

Minerals and their associated ores are generally categorized as sulfides or oxides, with the latter group comprising oxygen-containing species such as carbonates, hydroxides, sulfates and silicates. Thus, the group of minerals categorized as oxides generally include any oxygen-containing mineral. While a large proportion of the minerals existing today are contained in oxide ores, the bulk of successful froth flotation systems is directed to sulfide ores. The flotation of oxide minerals is recognized as being substantially more difficult than the flotation of sulfide minerals and the effectiveness of most flotation processes in the recovery of oxide ores is limited.

A major problem associated with the recovery of both oxide and sulfide minerals is selectivity. Some of the recognized collectors such as the carboxylic acids, alkyl sulfates and alkyl sulfonates discussed above are taught to be effective collectors for oxide mineral ores. However, while the use of these collectors can result in acceptable recoveries, it is recognized that the selectivity to the desired mineral value is typically quite poor. That is, the grade or the percentage of the desired component contained in the recovered mineral is unacceptably low.

Due to the low grade of oxide mineral recovery obtained using conventional, direct flotation, the mining industry has generally turned to more complicated methods in an attempt to obtain acceptable recovery of acceptable grade minerals. Oxide ores are often subjected to a sulfidization step prior to conventional flotation in existing commercial processes. After the oxide minerals are sulfidized, they are then subjected to flotation using known sulfide collectors. Even with the sulfidization step, recoveries and grade are less than desirable. An alternate approach to the recovery of oxide ores is liquid/liquid extraction. A third approach used in the recovery of oxide ores, particularly iron oxides and phosphates, is reverse or indirect flotation. In reverse flotation, the flotation of the ore having the desired mineral values is depressed and the gangue or other contaminant is floated. In some cases, the contaminant is a mineral which may have value. A fourth approach to mineral recovery involves chemical dissolution or leaching.

None of these existing methods of flotation directed to oxide ores are without problems. Generally, known methods result in low recovery or low grade or both. The low grade of the minerals recovered is recognized as a particular problem in oxide mineral flotation. Known recovery methods have not been economically feasible and consequently, a large proportion of oxide ores simply are not processed. Thus, the need for improved selectivity in oxide mineral flotation is generally acknowledged by those skilled in the art of froth flotation.

SUMMARY OF THE INVENTION

The present invention is a process for the recovery of minerals by froth flotation comprising subjecting an aqueous slurry comprising particulate minerals to froth flotation in the presence of a collector comprising aryl monosulfonic acids or salts thereof having at least two alkyl substituents or mixtures of such salts or acids under conditions such that the minerals to be recovered are floated and recovered. The recovered minerals may be the mineral that is desired or may be undesired contaminants. Additionally, the froth flotation process of this invention may utilize frothers and other flotation reagents known in the art. In a particular embodiment, the alkyl monosulfonate collector of this invention is substituted with at least two substituents, one being a C.sub.1-3 alkyl and the other an alkyl chain having greater than ten carbon atoms.

The practice of the flotation process of this invention results in improvements in selectivity and thus the grade of minerals recovered from oxide and/or sulfide ores while generally maintaining or increasing overall recovery levels of the mineral desired to be recovered. It is surprising that the use of aryl sulfonic acids or salts thereof having at least two alkyl substituents results in improvements in selectivity or recovery of mineral values when compared to the use of similar acids or salts having comparable numbers of carbon atoms but only a single substituent.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The flotation process of this invention is useful in the recovery of mineral values from a variety of ores, including oxide ores as well as sulfide ores and mixed ores. The oxide or oxygen-containing minerals which may be treated by the practice of this invention include carbonates, sulfates, hydroxides and silicates as well as oxides.

Non-limiting examples of oxide ores which may be floated using the practice of this invention preferably include iron oxides, nickel oxides, copper oxides, phosphorus oxides, aluminum oxides and titanium oxides. Other types of oxygen-containing minerals which may be floated using the practice of this invention include carbonates such as calcite, apatite or dolomite and hydroxides such as bauxite.

Non-limiting examples of specific oxide ores which may be collected by froth flotation using the process of this invention include those containing cassiterite, hematite, cuprite, vallerite, calcite, talc, kaolin, apatite, dolomite, bauxite, spinel, corundum, laterite, azurite, rutile, magnetite, columbite, ilmenite, smithsonite, anglesite, scheelite, chromite, cerussite, pyrolusite, malachite, chrysocolla, zincite, massicot, bixbyite, anatase, brookite, tungstite, uraninite, gummite, brucite, manganite, psilomelane, goethite, limonite, chrysoberyl, microlite, tantalite, topaz and samarskite. One skilled in the art will recognize that the froth flotation process of this invention will be useful for the processing of additional ores including oxide ores, wherein oxide is defined to include carbonates, hydroxides, sulfates and silicates as well as oxides.

The process of this invention is also useful in the flotation of sulfide ores. Non-limiting examples of sulfide ores which may be floated by the process of this invention include those containing chalcopyrite, chalcocite, galena, pyrite, sphalerite, molybdenite and pentlandite.

Noble metals such as gold and silver and the platinum group metals wherein platinum group metals comprise platinum, ruthenium, rhodium, palladium, osmium, and iridium, may also be recovered by the practice of this invention. For example, such metals are sometimes found associated with oxide and/or sulfide ores. Platinum, for example, may be found associated with troilite. By the practice of the present invention, such metals may be recovered in good yield.

Ores do not always exist purely as oxide ores or as sulfide ores. Ores occurring in nature may comprise both sulfur-containing and oxygen-containing minerals as well as small amounts of noble metals as discussed above. Minerals may be recovered from these mixed ores by the practice of this invention. This may be done in a two-stage flotation where one stage comprises conventional sulfide flotation to recover primarily sulfide minerals and the other stage of the flotation utilizes the process and collector composition of the present invention to recover primarily oxide minerals and any noble metals that may be present. Alternatively, both the sulfur-containing and oxygen-containing minerals may be recovered simultaneously by the practice of this invention.

A particular feature of the process of this invention is the ability to differentially float various minerals. Without wishing to be bound by theory, it is thought that the susceptibility of various minerals to flotation in the process of this invention is related to the crystal structure of the minerals. More specifically, a correlation appears to exist between the ratio of crystal edge lengths to crystal surface area on a unit area basis. Minerals having higher ratios appear to float preferentially when compared to minerals having lower ratios. Thus, minerals whose crystal structure has 24 or more faces (Group I) are generally more likely to float than minerals having 16 to 24 faces (Group II). Group III minerals comprising minerals having 12 to 16 faces are next in order of preferentially floating followed by Group IV minerals having 8 to 12 faces.

In the process of this invention, generally Group I minerals will float before Group II minerals which will float before Group III minerals which will float before Group IV minerals. By floating before or preferentially floating, it is meant that the preferred species will float at lower collector dosages. That is, a Group I mineral may be collected at a very low dosage. Upon increasing the dosage and/or the removal of most of the Group I mineral, a Group II mineral will be collected and so on.

One skilled in the art will recognize that these groupings are not absolute. Various minerals may have different possible crystal structures. Further the size of crystals existing in nature also varies which will influence the ease with which different minerals may be floated. An additional factor affecting flotation preference is the degree of liberation. Further, within a group, that is, among minerals whose crystals have similar edge length to surface area ratios, these factors and others will influence which member of the group floats first.

One skilled in the art can readily determine which group a mineral belongs to by examining standard mineralogy characterization of different minerals. These are available, for example, in Manual of Mineralogy, 19th Edition, Cornelius S. Hurlbut, Jr. and Cornelis Klein (John Wiley and Sons, New York 1977). Non-limiting examples of minerals in Group I include graphite, niccolite, covellite, molybdenite and beryl.

Non-limiting examples of minerals in Group II include rutile, pyrolusite, cassiterite, anatase, calomel, torbernite, autunite, marialite, meionite, apophyllite, zircon and xenotime.

Non-limiting examples of minerals in Group III include arsenic, greenockite, millerite, zincite, corundum, hematite, brucite, calcite, magnesite, siderite, rhodochrosite, smithsonite, soda niter, apatite, pyromorphite, mimetite and vanadinite.

Non-limiting examples of minerals in Group IV include sulfur, chalcocite, chalcopyrite, stibnite, bismuthinite, loellingite, marcasite, massicot, brookite, boehmite, diaspore, goethite, samarskite, atacamite, aragonite, witherite, strontianite, cerussite, phosgenite, niter, thenardite, barite, celestite, anglesite, anhydrite, epsomite, antlerite, caledonite, triphylite, lithiophilite, heterosite, purpurite, variscite, strengite, chrysoberyl, scorodite, descloizite, mottramite, brazilianite, olivenite, libethenite, adamite, phosphuranylite, childrenite, eosphorite, scheelite, powellite, wulfenite, topaz, columbite and tantalite.

As discussed above, these groupings are theorized to be useful in identifying which minerals will be preferentially floated. However, as discussed above, the collector and process of this invention are useful in the flotation of various minerals which do not fit into the above categories. These groupings are useful in predicting which minerals will float at the lowest relative collector dosage, not in determining which minerals may be collected by flotation in the process of this invention.

The selectivity demonstrated by the collectors of this invention permit the separation of small amounts of undesired minerals from the desired minerals. For example, the presence of apatite is frequently a problem in the flotation of iron as is the presence of topaz or tourmaline in the flotation of cassiterite. Thus, the collectors of the present invention are, in some cases, useful in reverse flotation where the undesired mineral is floated such as floating topaz or tourmaline away from cassiterite or apatite from iron.

In addition to the flotation of ores found in nature, the flotation process and collector composition of this invention are useful in the flotation of minerals from other sources. One such example is the waste materials from various processes such as heavy media separation, magnetic separation, metal working and petroleum processing. These waste materials often contain minerals that may be recovered using the flotation process of the present invention. Another example is the recovery of a mixture of graphite ink and other carbon based inks in the recycling of paper. Typically such recycled papers are de-inked to separate the inks from the paper fibers by a flotation process. The flotation process of the present invention is particularly effective in such de-inking flotation processes.

The aryl sulfonic acid or sulfonate collector of this invention comprises an aromatic core having from two to about five alkyl substituents and a sulfonic acid or sulfonate moiety. For purposes of this invention, the term sulfonate will include both the sulfonic acid moiety and the sulfonate moiety. It is preferred that the collector have two to three substituents and more preferred that it have two. The aromatic core preferably comprises phenol, benzene, napthalene, anthracene and compounds corresponding to the formula ##STR1## wherein X represents a covalent bond; --(CO)--; or R wherein R is a linear or branched alkyl group having one to three carbon atoms. It is preferred that the aromatic core is benzene, napthalene or biphenyl and more preferred that it is benzene or napthalene and most preferred that it is benzene.

The two or more alkyl substituents may be the same or may be different and may be ortho, para or meta to each other with para and meta being preferred and para being more preferred. The alkyl groups may be the same or different and may be substituted or unsubstituted and preferably contain from 3 to about 24 carbon atoms. More preferably each of the alkyl groups contains from about 6 to about 18 carbon atoms and most preferably about 8 to about 12 carbon atoms. The alkyl groups will contain a total of at least about 10, more preferably at least about 12 and most preferably at least about 16 carbon atoms. The maximum total number of carbon atoms in the alkyl groups is preferably no greater than about 32 and more preferably no greater than about 24. The alkyl groups can be linear, cyclic or branched with linear or branched being preferred. The alkyl substituted aryl sulfonates are available commercially or may be prepared by methods known in the art. For example, the alkyl substituted aryl sulfonate collectors may be prepared by alkylation of aryl centers using nucleophilic aromatic alkylation using alkyl halides, alcohols or alkenes as the alkylation agent with appropriate catalysts.

It is a critical feature of the present invention that the aryl sulfonate collectors contain at least two alkyl substituents. It will be recognized by one skilled in the art that methods of production of substituted aryl sulfonates will sometimes result in mixtures of non-substituted, mono-substituted, disubstituted and higher substituted aryl sulfonates. Such mixtures are operable in the practice of this invention. It is preferred that at least about 15 percent of the alkylated aryl sulfonates contain two or more alkyl substituents. More preferably at least about 35 percent of the alkylated aryl sulfonates contain at least two alkyl substituents and most preferably at least about 50 percent of the alkylated aryl sulfonates contain at least two alkyl substituents.

In a particularly preferred embodiment, the two or more alkyl groups are different. In this embodiment, it is preferred that one alkyl group is a C.sub.1-3 alkyl group and the second alkyl group is a C.sub.10-24 alkyl group. In the preparation of these unsymmetrical sulfonates, alpha-olefins, alkyl halides and alcohols having sufficient carbon atoms to provide the desired hydrophobicity are used as alkylating agents. Typically, groups having from 10 to 24, preferably from 16 to 24 carbon atoms are used. The species which is alklyated is typically toluene, cumene, ethyl benzene, xylene. The alklyated species is sulfonated by methods known in the art.

Other sulfonates useful in the collector composition include a central aromatic group having one alkyl substituent and one non-alkyl substituent. Examples of such sulfonates include monoalkylated diphenyloxide sulfonate.

Particular examples of unsymmetrically substituted monosulfonates include hexadecyl cumene sulfonic acid, octadecyl cumene sulfonic acid, octadecyl ethylbenzene sulfonic acid, octadecyl p-xylene sulfonic acid, octadecyl o-xylene sulfonic acid, and hexadecyl m-xylene sulfonic acid.

The aryl sulfonate collector of this invention is preferably a dialkylated or higher alkylated benzene sulfonate collector and corresponds to the following formula or to a mixture of compounds corresponding to the formula: ##STR2## wherein each R is independently in each occurrence a saturated alkyl or substituted saturated alkyl radical or an unsaturated alkyl or substituted unsaturated alkyl radical; m is at least two and no greater than five: each M is independently hydrogen, an alkali metal, alkaline earth metal, or ammonium or substituted ammonium. Preferably, the R group(s) are independently in each occurrence an alkyl group having from about three to about 24, more preferably from about 6 to about 18 carbon atoms and most preferably about 8 to about 12 carbon atoms with the proviso that the total number of carbon atoms in the alkyl groups is at least 10 and preferably at least 16 and no greater than about 32, preferably no greater than about 24. The alkyl groups can be linear, branched or cyclic with linear or branched radicals being preferred. In a preferred embodiment, the alkyl groups are different. The M.sup.+ ammonium ion radicals are of the formula (R').sub.3 HN.sup.+ wherein each R' is independently hydrogen, a C.sub.1 -C.sub. 4 alkyl or a C.sub.1 -C.sub.4 hydroxyalkyl radical. Illustrative C.sub.1 -C.sub.4 alkyl and hydroxyalkyl radicals include methyl, ethyl, propyl, isopropyl, butyl, hydroxymethyl and hydroxyethyl. Typical ammonium ion radicals include ammonium (N.sup.+ H.sub.4), methylammonium (CH.sub.3 N.sup.+ H.sub.3), ethylammonium (C.sub.2 H.sub.5 N.sup.+ H.sub.3), dimethylammonium ((CH.sub.3).sub.2 N.sup.+ H.sub.2), methylethylammonium (CH.sub.3 N.sup.+ H.sub.2 C.sub.2 H.sub.5), trimethylammonium ((CH.sub.3).sub.3 N.sup.+ H), dimethylbutylammonium ((CH.sub.3).sub.2 N.sup.+ HC.sub.4 H.sub.9), hydroxyethylammonium (HOCH.sub.2 CH.sub.2 N.sup.+ H.sub.3) and methylhydroxyethylammonium (CH.sub.3 N.sup.+ H.sub.2 CH.sub.2 CH.sub.2 OH). Preferably, each M is hydrogen, sodium, calcium, potassium or ammonium.

The collector can be used in any concentration which gives the desired selectivity and recovery of the desired mineral values. In particular, the concentration used is dependent upon the particular mineral to be recovered, the grade of the ore to be subjected to the froth flotation process and the desired quality of the mineral to be recovered.

Additional factors to be considered in determining dosage levels include the amount of surface area of the ore to be treated. As will be recognized by one skilled in the art, the smaller the particle size, the greater the surface area of the ore and the greater the amount of collector reagents needed to obtain adequate recoveries and grades. Typically, oxide mineral ores must be ground finer than sulfide ores and thus require very high collector dosages or the removal of the finest particles by desliming. Conventional processes for the flotation of oxide minerals typically require a desliming step to remove the fines present and thus permit the process to function with acceptable collector dosage levels. The collector of the present invention functions at acceptable dosage levels with or without desliming.

Preferably, the concentration of the collector is at least about 0.001 kg/metric ton, more preferably at least about 0.05 kg/metric ton. It is also preferred that the total concentration of the collector is no greater than about 5.0 kg/metric ton and more preferred that it is no greater than about 2.5 kg/metric ton. In general, to obtain optimum performance from the collector, it is most advantageous to begin at low dosage levels and increase the dosage level until the desired effect is achieved. While the increases in recovery and grade obtained by the practice of this invention increase with increasing dosage, it will be recognized by those skilled in the art that at some point the increase in recovery and grade obtained by higher dosage is offset by the increased cost of the flotation chemicals. It will also be recognized by those skilled in the art that varying collector dosages are required depending on the type of ore and other conditions of flotation. Additionally, the collector dosage required has been found to be related to the amount of mineral to be collected. In those situations where a small amount of a mineral susceptible to flotation using the process of this invention, a very low collector dosage is needed due to the selectivity of the collector.

It has been found advantageous in the recovery of certain minerals to add the collector to the flotation system in stages. By staged addition, it is meant that a part of the collector dose is added: froth concentrate is collected: an additional portion of the collector is added; and froth concentrate is again collected. The total amount of collector used is preferably not changed when it is added in stages. This staged addition can be repeated several times to obtain optimum recovery and grade. The number of stages in which the collector is added is limited only by practical and economic constraints. Preferably, no more than about six stages are used.

An additional advantage of staged addition is related to the ability of the collector of the present invention to differentially float different minerals at different dosage levels. As discussed above, at low dosage levels, one mineral particularly susceptible to flotation by the collector of this invention is floated while other minerals remain in the slurry. At an increased dosage, a different mineral may be floated thus permitting the separation of different minerals contained in a given ore.

In addition to the collector of this invention, other conventional reagents or additives may be used in the flotation process. Examples of such additives include various depressants and dispersants well-known to those skilled in the art. Additionally, the use of hydroxy-containing compounds such as alkanol amines or alkylene glycols has been found to useful in improving the selectivity to the desired mineral values in systems containing silica or siliceous gangue. In addition, frothers may be and typically are used. Frothers are well known in the art and reference is made thereto for the purposes of this invention. Examples of useful frothers include polyglycol ethers and lower molecular weight frothing alcohols. Additionally, the collectors of this invention may be used with hydrocarbon as an extender. Examples of hydrocarbon useful in this context include are those hydrocarbons typically used in flotation. Non-limiting examples of such hydrocarbons include fuel oil, kerosene and motor oil.

The collectors of this invention may also be used in conjunction with other collectors. For example, it has been found that in the flotation of sulfide mineral containing ores, the use of the collector of this invention with sulfide thiol collectors such as xanthates, dithiol phosphates and trithiol carbonates is advantageous. The use of a collector composition comprising both sulfide collectors and dialkyl aromatic sulfonate collectors is particularly advantageous when it is desired to conduct the flotation at natural or non-elevated slurry pH.

The collector of this invention may also be used in conjunction with a carboxylic acid or salt thereof, particularly C.sub.1-24 carboxylic acids or salts. Fatty acids or their salts are particularly preferred. Illustrative, but non-limiting examples of such acids include oleic acid, linoleic acid, linolenic acid, myristic acid, palmitic acid, strearic acid, palmitoleic acid, caprylic acid, capric acid, lauric acid and mixtures thereof. Preferred fatty acids include oleic acid, linoleic acid, linolenic acid and mixtures thereof. The fatty acids may be used in the acid form or may be used in salt form. As used herein, the term "acid" will include both the acid and salt form. A collector composition comprising the dialkyl aromatic monosulfonate collectors described above and an effective amount ofa carboxylate such as oleic acid or oleate is particularly useful when hard water is used in the flotation process. In the context of this invention, hard water is water having an equivalent conductivity of ionic strength equal to or greater than that of 50 ppm Na.sup.+ equivalents. By an effective amount is meant that amount of fatty acid which, when replacing an equal amount of dialkyl aromatic sulfonate, results in improved recovery of the desired mineral. The amount of carboxylate used is preferably at least about 1 weight percent, more preferably at least about 2 weight percent and most preferably at least about 3 weight percent. The maximum amount of fatty acid used is preferably no greater than about 70 weight percent, more preferably no greater than about 50 weight percent, and most preferably no greater than about 30 weight percent. As will be recognized by one skilled in the art, the optimum amount of carboxylate used will depend on the degree of hardness of the water used in flotation, the minerals to be recovered and other variables in the flotation process.

When using the diaryl aromatic sulfonate collector of this invention in conjunction with a carboxylate, the two components may be mixed together prior to the addition to the flotation system, or either may be added to the system separately.

The collectors of this invention may also be used in conjunction with other conventional collectors in other ways. For example, the aryl sulfonate collectors of this invention may be used in a two-stage flotation in which the sulfonate flotation recovers primarily oxide minerals while a second stage flotation using conventional collectors is used to recover primarily sulfide minerals or additional oxide minerals. When used in conjunction with conventional collectors, a two-stage flotation may be used wherein the first stage comprises the process of this invention and is done at the natural pH of the slurry. The second stage involves conventional collectors and is conducted at an elevated pH. It should be noted that in some circumstances, it may be desirable to reverse the stages. Such a two-stage process has the advantages of using less additives to adjust pH and also permits a more complete recovery of the desired minerals by conducting flotation under different conditions.

A particular advantage of the collector of the present invention is that additional additives are not required to adjust the pH of the flotation slurry. The flotation process utilizing the collector of the present invention operates effectively at typical natural ore pH's ranging from about 5 or lower to about 9. This is particularly important when considering the cost of reagents needed to adjust slurry pH from a natural pH of around 7.0 or lower to 9.0 or 10.0 or above which is typically necessary using conventional carboxylic xanthic collectors. As noted above, a collector composition comprising the collector of the present invention and a xanthate collector is effective at a lower pH than a xanthate collector used alone.

The ability of the collector of the present invention to function at relatively low pH means that it may also be used in those instances where it is desired to lower the slurry pH. The lower limit on the slurry pH at which the present invention is operable is that pH at which the surface charge on the mineral species is suitable for attachment by the collector.

Since the collector of the present invention functions at different pH levels, it is possible to take advantage of the tendency of different minerals to float at different pH levels. This makes it possible to do one flotation run at one pH to optimize flotation of a particular species. The pH can then be adjusted for a subsequent run to optimize flotation of a different species thus facilitating separation of various minerals found together.

The following examples are provided to illustrate the invention and should not be interpreted as limiting it in any way. Unless stated otherwise, all parts and percentages are by weight.

The following examples include work involving Hallimond tube flotation and flotation done in laboratory scale flotation cells. It should be noted that Hallimond tube flotation is a simple way to screen collectors, but does not necessarily predict the success of collectors in actual flotation. Hallimond tube flotation does not involve the shear or agitation present in actual flotation and does not measure the effect of frothers. Thus, while a collector generally must be effective in a Hallimond tube flotation if it is to be effective in actual flotation, a collector effective in Hallimond tube flotation will not necessarily be effective in actual flotation. It should also be noted that experience has shown that collector dosages required to obtain satisfactory recoveries in a Hallimond tube are often substantially higher than those required in a flotation cell test. Thus, the Hallimond tube work cannot precisely predict dosages that would be required in an actual flotation cell.

EXAMPLE 1 Hallimond Tube Flotation of Rutile, Apatite, Hematite and Silica

About 1.1 g of either the specified mineral or silica is sized to about -60 to +120 U.S. mesh and placed in a small bottle with about 20 ml of deionized water. The mixture is shaken 30 seconds and then the water phase containing some suspended fine solids or slimes is decanted. This desliming step is repeated several times.

A 150-ml portion of deionized water is placed in a 250-ml glass beaker. Next, 2.0 ml of a 0.10 molar solution of potassium nitrate is added as a buffer electrolyte. The pH is adjusted to the specified level with the addition of 0.10 N HCl and/or 0.10 N NaOH. Next, a 1.0-g portion of the deslimed mineral is added along with deionized water to bring the total volume to about 180 ml. The specified collector is added and allowed to condition with stirring for 15 minutes. The pH is monitored and adjusted as necessary using HCl and NaOH. All collectors indicated are first converted to the Na.sup.+ salt form before addition.

The slurry is transferred into a Hallimond tube designed to allow a hollow needle to be fitted at the base of the 180-ml tube. After the addition of the slurry to the Hallimond tube, a vacuum of 5 inches of mercury is applied to the opening of the tube for a period of 10 minutes. This vacuum allows air bubbles to enter the tube through the hollow needle inserted at the base of the tube. During flotation, the slurry is agitated with a magnetic stirrer set at 200 revolutions per minute (RPM).

The floated and unfloated material is filtered out of the slurry and oven dried at 100.degree. C. Each portion is weighed and the fractional recoveries of each mineral and silica are reported in Table I below. After each test, all equipment is washed with concentrated HCl and rinsed with 0.10 N NaOH and deionized water before the next run.

The recovery of each mineral and silica, respectively, reported is that fractional portion of the original mineral placed in the Hallimond tube that is recovered. Thus, a recovery of 1.00 indicates that all of the material is recovered. It should be noted that although the recovery of each mineral and silica, respectively, is reported together, the data is actually collected in four experiments done under identical conditions. It should further be noted that a low silica recovery suggests a selectivity to the the desired minerals. The values given for the various mineral recoveries generally are correct to .+-.0.05 and those for silica recovery are generally correct to .+-.0.03.

TABLE I__________________________________________________________________________Collector Dosage Fractional RecoveryRun (Na + Salt) pH (kg/kg) Rutile Apatite Hematite Silica__________________________________________________________________________ 1.sup.1 Benzene sulfonic acid 6.5 0.05 0.011 0.013 0.071 0.006 2.sup.1 Toluene sulfonic acid 6.5 0.05 0.038 0.058 0.114 0.009 3.sup.1 Xylene sulfonic acid 6.5 0.05 0.072 0.099 0.163 0.015 3a.sup.1 Isopropyl benzene sulfonic 6.5 0.05 0.066 0.088 0.145 0.013 acid 3b.sup.1 Ethyl benzene sulfonic acid 6.5 0.05 0.060 0.079 0.129 0.011 4.sup.1 2,4,6-Trimethyl Benzene 6.5 0.05 0.154 0.197 0.217 0.030 sulfonic acid 5.sup.1 Propyl benzene sulfonic acid 6.5 0.05 0.052 0.060 0.124 0.011 6.sup.1 di-Propyl benzene sulfonic 6.5 0.06 0.305 0.219 0.247 0.028 acid 6a.sup.1 Propyl toluene sulfonic acid 6.5 0.05 0.388 0.340 0.357 0.029 7.sup.1 Hexyl benzene sulfonic acid 6.5 0.05 0.247 0.094 0.115 0.037 8 di-Hexyl benzene sulfonic 6.5 0.05 0.693 0.457 0.478 0.036 acid 9.sup.1 Dodecyl benzene sulfonic 6.5 0.05 0.535 0.162 0.173 0.034 acid 9a Decyl toluene sulfonic acid 6.5 0.05 0.668 0.480 0.522 0.032 9b Dodecyl toluene sulfonic 6.5 0.05 0.776 0.584 0.603 0.038 acid 9c Dodecyl xylene sulfonic acid 6.5 0.05 0.844 0.615 0.664 0.04110 di-Dodecyl benzene sulfonic 6.5 0.05 0.904 0.887 0.814 0.047 acid11.sup.1 C.sub.24 benzene sulfonic acid 6.5 0.05 0.570 0.449 0.355 0.07411a C.sub.20-2 toluene sulfonic acid 6.5 0.05 0.987 0.980 0.903 0.06612 di-Dodecyl benzene sulfonic 0.05 4.0 0.956 0.701 0.684 0.087 acid13 di-Dodecyl benzene sulfonic 0.05 9.0 0.811 0.919 0.882 0.014 acid14 di-Dodecyl benzene sulfonic 0.025 6.5 0.863 0.817 0.753 0.040 acid15 di-Dodecyl benzene sulfonic 0.010 6.5 0.798 0.706 0.618 0.031 acid16 di-Dodecyl benzene sulfonic 0.005 6.5 0.611 0.422 0.350 0.023 acid16a C.sub.20-24 toluene sulfonic acid 0.05 4.0 1.000 0.801 0.755 0.09116b C.sub.20-24 toluene sulfonic acid 9.0 0.05 0.911 0.958 0.947 0.07216c C.sub.20-24 toluene sulfonic acid 6.5 0.025 0.935 0.922 0.850 0.06316d C.sub.20-24 toluene sulfonic acid 6.5 0.010 0.864 0.800 0.719 0.05816e C.sub.20-24 toluene sulfonic acid 6.5 0.005 0.642 0.510 0.401 0.04317.sup.1 Napthalene sulfonic acid 6.5 0.05 0.040 0.048 0.051 0.00318.sup.1 di-Propyl napthalene 6.5 0.05 0.347 0.240 0.283 0.047 sulfonic acid19.sup.1 Hexyl napthalene sulfonic 6.5 0.05 0.281 0.166 0.217 0.041 acid20 di-Hexyl napthalene sulfonic 6.5 0.05 0.777 0.548 0.574 0.043 acid21 di-Nonyl napthalene sulfonic 6.5 0.05 0.870 0.800 0.757 0.051 acid22 di-Nonyl napthalene sulfonic 4.0 0.05 0.897 0.743 0.632 0.093 acid23 di-Nonyl napthalene sulfonic 9.0 0.05 0.755 0.849 0.803 0.048 acid24 di-Nonyl napthalene sulfonic 6.5 0.025 0.774 0.705 0.684 0.048 acid25 di-Nonyl napthalene sulfonic 6.5 0.010 0.609 0.589 0.530 0.036 acid26 di-Nonyl napthalene sulfonic 6.5 0.005 0.483 0.364 0.303 0.024 acid27 di-Decyl benzene sulfonic 6.5 0.05 0.933 0.901 0.876 0.041 acid28 Mixture of di-octyl, 6.5 0.05 0.887 0.853 0.778 0.049 di-nonyl, di-decyl, and benzene sulfonic acids.sup.229 Mixture of di-hexyl and 6.5 0.05 0.814 0.703 0.700 0.039 di-dodecyl benzene sulfonic acids.sup.230 Mixture of di-dodecyl and 6.5 0.05 0.839 0.804 0.735 0.041 di-hexadecyl benzene sulfonic acids.sup.231 di-Hexadecyl 6.5 0.05 0.711 0.519 0.534 0.033 benzene sulfonic acid32 di-Dodecyl 6.5 0.05 0.835 0.749 0.699 0.048 napthalene sulfonic acid33 Mixture of di-octyl, 6.5 0.05 0.894 0.831 0.805 0.053 di-nonyl, di-decyl and napthalene sulfonic acids.sup.234 Ethyl-dodecyl 6.5 0.05 0.674 0.300 0.534 0.038 benzene sulfonic acid35 Hexyl-dodecyl 6.5 0.05 0.818 0.699 0.687 0.041 benzene sulfonic acid36 Octadecylcomene 6.5 0.025 Not 0.95 0.918 Not Avail- Avail- able able37 Octadecylcomene 6.5 0.0375 Not 0.980 0.969 Not Avail- Avail- able able38 Octadecylcomene 6.5 0.05 Not 0.99 0.98 Not Avail- Avail- able able39 Hexadecylcumene 6.5 0.25 Not 0.874 0.946 Not Avail- Avail- able able40 Hexadecylcumene 6.5 0.0375 Not 0.958 0.957 Not Avail- Avail- able able41 Hexadecylcumene 6.5 0.05 Not 0.979 0.948 Not Avail- Avail- able able42 Hexadecyl m-xylene 6.5 0.025 Not 0.093 0.287 Not Avail- Avail- able able43 Hexadecyl m-xylene 6.5 0.0375 Not 0.742 0.888 Not Avail- Avail- able able44 Hexadecyl m-xylene 6.5 0.05 Not 0.959 0.918 Not Avail- Avail- able able45 Octadecyl o-xylene 6.5 0.025 Not 0.884 0.745 Not Avail- Avail- able able46 Octadecyl o-xylene 6.5 0.0375 Not 0.980 0.918 Not Avail- Avail- able able47 Octadecyl o-xylene 6.5 0.05 Not 0.990 0.939 Not Avail- Avail- able able48 Octadecyl p-xylene 6.5 0.025 Not 0.299 0.093 Not Avail- Avail- able able49 Octadecyl p-xylene 6.5 0.0375 Not 0.853 0.745 Not Avail- Avail- able able50 Octadecyl p-xylene 6.5 0.05 Not 0.970 0.919 Not Avail- Avail- able able51 Octadecyl ethyl benzene 6.5 0.025 Not 0.206 0.694 Not Avail- Avail- able able52 Octadecyl ethyl benzene 6.5 0.0375 Not 0.577 0.847 Not Avail- Avail- able able53 Octadecyl ethyl benzene 6.5 0.05 Not 0.551 0.884 Not Avail- Avail- able able__________________________________________________________________________ .sup.1 Not an embodiment of the invention .sup.2 In these runs, the collector is a mixture of the components listed

The data in Table I above demonstrate various aspects of the invention. A comparison of Run 8 with Run 9 or of Run 10 with Run 11 demonstrates that the arrangement of carbon atoms present in the alkyl groups is important. Each pair of runs has the same total number of carbon atoms present, but the dialkylated version shows significantly improved results when compared to monoalkylated version. A comparison of Runs 1-7, 9, 11 and 17-19, which are not embodiments of the present invention, with the remaining runs, which are embodiments of the present invention, clearly show the importance of total carbon content of the substituents being greater than 12 as well as showing the importance of a degree of alkylation greater than one. Runs 28-30 and 33 show that mixtures of the collectors are effective. Run 34 demonstrates the effectiveness of a compound where one substituent is an ethyl group while the other is a dodecyl and Run 35 similarly demonstrates the effectiveness of compounds where one substituent is an hexyl group while the other is a dodecyl. In each case, the collector is more effective than a collector having more carbon atoms, but in a single substituent rather than split between two substituents. Additionally, comparing those runs where the alkyl groups are asymmetrical with those having similar numbers of carbon atoms in symmetrical alkyl groups, it is shown that asymmetrical alkyl groups provide improved performance.

EXAMPLE 2 Flotation of Various Oxide Minerals

The general procedure of Example 1 is followed with the exception that various oxide minerals are used in place of the ores specified in Example 1. All runs are conducted at a pH of 8.0. The collectors used are a

C.sub.12 dialkylated benzene sulfonate and a C.sub.20-22 toluene sulfonate, each at a dosage of 0.024 kg of collector per kilogram of mineral. The results are shown in Table II below.

TABLE II______________________________________ Fractional Mineral Recovery Fractional (C.sub.12 Mineral Dialkylated Recovery Benzene (C.sub.20-22 TolueneMineral Sulfonate) Sulfonate)______________________________________Silica (SiO.sub.2) 0.048 0.038Cassiterite (SnO.sub.2) 0.877 0.914Bauxite [Al(OH).sub.3 ] 0.813 --Calcite (CaCO.sub.3) 0.854 --Chromite (FeCr.sub.2 O.sub.4) 0.915 0.955Dolomite [CaMg(CO.sub.3).sub.2 ] 0.805 0.711Malachite [Cu.sub.2 CO.sub.3 (OH).sub.2 ] 0.773 0.887Chrysocolla [Cu.sub.2 H.sub.2 Si.sub.2 O.sub.5 (OH).sub.4 ] 0.540 0.655Hematite (Fe.sub.2 O.sub.3) 0.868 0.944Corundum (A.sub.2 O.sub.3) 0.900 --Rutile (TiO.sub.2) 0.946 0.989Apatite [Ca.sub.5 (Cl.sub.1 F)[PO.sub.4 ].sub.3 ] 0.897 0.943Nickel Oxide (NiO) 0.652 --Galena (PbS) 0.890 0.937Chalcopyrite (CuFeS.sub.2) 0.883 0.939Chalcocite (Cu.sub.2 S) 0.847 0.880Pyrite (FeS.sub.2) 0.667 0.433Tourmaline 0.940 --Sphalerite (ZnS) 0.843 0.903Pentlandite [Ni(FeS)].sup.1 0.789 0.854Barite (BaSO.sub.4) 0.844 --Molybdenite (MoS.sub.2) 0.935 0.988Cerussite (PbCO.sub.3) 0.905 0.956Calcite (CaCO.sub.3) 0.461 --Beryl (Be.sub.3 Al.sub.2 Si.sub.6 O.sub.18) 0.893 --Covellite (CuS) 0.793 0.868Zircon (ZrSiO.sub.4) 0.874 0.931Graphite (C) 0.944 0.970Topaz [Al.sub.2 SiO.sub.4 (F.sub.1 OH).sub.2 ] 0.910 0.966Scheelite (CaWO.sub.4) 0.822 --Anatase (TiO.sub.2) 0.904 --Boehmite (.gamma.AlO.OH) 0.776 --Diaspore (.alpha.AlO.OH) 0.815 --Goethite (HFeO.sub.2) 0.773 0.875______________________________________ .sup.1 Sample includes some pyrrhotite. .sup.2 Sample comprises powdered elemental metal of similar size to other mineral samples.

The data in Table II demonstrates the broad range of minerals which may be floated using the collector and process of this invention. The asymmetrical collector generally outperforms the symmetrical collector at constant dosage. Only in the flotation of silica, dolomite and pyrite (typically viewed as gangue consituents) does the symmetrical collector perform better.

EXAMPLE3 Sequential Flotation

This example uses the Hallimond tube flotation procedure outlined in Example 1. In each case, the feed material is a 50/50 weight percent blend of the components listed in Table III. The specific collectors used (in the sodium salt form) and the mineral recoveries obtained are also listed in Table III below. All runs are performed at a pH of 7.0.

TABLE III__________________________________________________________________________ Mineral Blend Mineral Recovery Dosage Component Component Component ComponentRun Collector (kg/kg) #1 #2 #1 #2__________________________________________________________________________ 1 di-Dodecyl benzene 0.025 Apatite Hematite 0.541 0.039 sulfonic acid 0.100 Apatite Hematite 0.887 0.405 1a C.sub.20-22 Toluene 0.025 Apatite Hematite 0.677 0.030 sulfonic acid 0.100 Apatite Hematite 0.940 0.445 2 di-Nonyl benzene 0.025 Apatite Hematite 0.497 0.027 sulfonic acid 0.100 Apatite Hematite 0.810 0.384 3 C.sub.20-22 Toluene 0.025 Rutile Bauxite 0.373 0.021 sulfonic acid 0.100 Rutile Bauxite 0.677 0.314 3a C.sub.20-22 Toluene 0.025 Rutile Bauxite 0.414 0.023 sulfonic acid 0.100 Rutile Bauxite 0.757 0.340 4 di-Nonyl napthalene 0.025 Rutile Bauxite 0.308 0.018 sulfonic acid 0.100 Rutile Bauxite 0.598 0.276 5 di-Dodecyl benzene 0.025 Topaz Cassiterite 0.437 0.073 sulfonic acid 0.100 Topaz Cassiterite 0.816 0.114 6 di-Nonyl napthalene 0.025 Topaz Cassiterite 0.399 0.067 sulfonic acid 0.100 Topaz Cassiterite 0.774 6.089 6a C.sub.20-22 Toluene 0.025 Topaz Cassiterite 0.503 0.086 sulfonic acid 0.100 Topaz Cassiterite 0.917 6.128 7 di-Dodecyl benzene 0.025 Rutile Kaolin 0.275 0.103 sulfonic acid 0.100 Rutile Kaolin 0.559 0.270 8 di-Nonyl Napthalene 0.025 Rutile Kaolin 0.229 0.095 sulfonic acid 0.100 Rutile Kaolin 0.518 0.233 8a C.sub.20-22 toluene 0.025 Rutile Kaolin 0.399 0.144 sulfonic acid 0.100 Rutile Kaolin 0.777 0.353 9 di-Dodecyl benzene 0.025 Hematite Pyrolusite 0.314 0.039 sulfonic acid 0.100 Hematite Pyrolusite 0.690 0.117 9a C.sub.20-22 Toluene 0.025 Hematite Pyrolusite 0.366 0.047 sulfonic acid 0.100 Hematite Pyrolusite 0.790 0.14410 di-Nonyl napthalene 0.025 Hematite Pyrolusite 0.298 0.031 sulfonic acid 0.100 Hematite Pyrolusite 0.673 0.11111 di-Dodecyl benzene 0.025 Magnetite Bauxite 0.286 0.114 sulfonic acid 0.100 Magnetite Bauxite 0.577 0.23712 di-Nonyl napthalene 0.025 Magnetite Bauxite 0.279 0.108 sulfonic acid 0.100 Magnetite Bauxite 0.569 0.20213 di-Dodecyl benzene 0.025 Apatite Dolomite 0.317 0.051 sulfonic acid 0.100 Apatite Dolomite 0.834 0.11314 di-Nonyl napthalene 0.025 Apatite Dolomite 0.299 0.048 sulfonic acid 0.100 Apatite Dolomite 0.810 0.10515 di-Dodecyl benzene 0.025 Molybdenite Chalcopyrite 0.513 0.084 sulfonic acid 0.100 Molybdenite Chalcopyrite 0.879 0.12916 di-Nonyl napthalene 0.025 Molybdenite Chalcopyrite 0.486 0.071 sulfonic acid 0.100 Molybdenite Chalcopyrite 0.832 0.11017 di-Dodecyl benzene 0.025 Printing Ink.sup.1 Clay, Paper Pulp 0.366 0.081 sulfonic acid 0.100 Printing Ink.sup.1 Clay, Paper Pulp 0.854 0.11518 di-Nonyl napthalene 0.025 Printing Ink.sup.1 Clay, Paper Pulp 0.403 0.074 sulfonic acid 0.100 Printing Ink.sup.1 Clay, Paper Pulp 0.897 0.099__________________________________________________________________________ .sup.1 Inks are carbon based materials of graphite form. Printed newsprin is soaked in water and caustic with a pH of 9.5 in a hallimond tube and then standard experiment is followed.

The data above demonstrate that various minerals subject to flotation in the process of the present invention may be effectively separated by the control of collector dosage. For example, while apatite and hematite can both be floated by the process of this invention, it is clear that apatite floats more readily at lower dosages than does hematite. Thus, the apatite can be floated at a first stage, low dosage float. This can be followed by flotation at higher collector dosages to float the hematite. An examination of the other runs in this examples demonstrates that similar separations are possible using other minerals. It should also be noted that the asymmetrical collector consistently outperforms the symmetrical collector.

EXAMPLE 4 Separation of Apatite and Silica

A series of 30-g samples of a -10 mesh (U.S.) mixture of 10 percent apatite (Ca.sub.5 (Cl,F)[PO.sub.4 ].sub.3) and 90 percent silica (SiO.sub.2) is prepared. Each sample of ore is ground with 15 g of deionized water in a rod mill (2.5 inch diameter with 0.5 inch rods) for 240 revolutions. The resulting pulp is transferred to a 300 ml flotation cell.

The pH of the slurry is left at natural ore pH of 6.7. After addition of the collector (in the sodium salt form) as shown in Table IV, the slurry is allowed to condition for one minute. Next, the frother, a polyglycol ether available commercially from The Dow Chemical Co. as Dowfroth.RTM. 420 brand frother, is added in an amount equivalent to 0.050 kg per ton of dry ore and the slurry is allowed to condition an additional minute.

The float cell is agitated at 1800 RPM and air is introduced at a rate of 2.7 liters per minute. The froth concentrate is collected by standard hand paddling for four minutes after the start of the introduction of air into the cell. Samples of the concentrate and the tailings are dried and analyzed as described in the previous examples. The results obtained are presented in Table IV below.

TABLE IV______________________________________ Phosphorus Dosage Recovery and (kg/metric GradeRun Collector ton) Rec Gr______________________________________ 1.sup.1 Dodecyl benzene sulfonic 0.150 0.172 0.121 acid 2.sup.1 Dodecyl benzene sulfonic 0.300 0.482 0.142 acid 2a.sup.1 C.sub.20-22 benzene sulfonic 0.150 0.491 0.124 acid 2b.sup.1 C.sub.20-22 benzene sulfonic 0.300 0.556 0.135 acid 3 di-Dodecyl benzene 0.150 0.882 0.142 sulfonic acid 4 di-Dodecyl benzene 0.300 0.940 0.118 sulfonic acid 4a C.sub.20-22 Toluene sulfonic 0.150 0.915 0.155 acid 4b C.sub.20-22 Toluene sulfonic 0.300 0.977 0.150 acid 5 di-Nonyl napthalene 0.150 0.633 0.147 sulfonic acid 6 di-Nonyl napthalene 0.300 0.840 0.144 sulfonic acid 7.sup.1 C.sub.24 benzene sulfonic acid 0.150 0.314 0.117 8.sup.1 C.sub.24 benzene sulfonic acid 0.300 0.580 0.137 9 Mixture of dioctyl, 0.150 0.904 0.145 di-nonyl, and di-decyl benzene sulfonic acids.sup.210 Mixture of di-octyl, 0.150 0.844 0.141 di-nonyl, and di-decyl napthalene sulfonic acids.sup. 211 di-Hexadecyl benzene 0.150 0.540 0.123 sulfonic acid12 di-Hexyl benzene sulfonic 0.150 0.658 0.148 acid12a Decyl Toluene sulfonic 0.150 0.688 0.154 acid12b Dodecyl Toluene sulfonic 0.150 0.773 0.137 acid13.sup.3 di-Hexyl benzene sulfonic 0.025 0.500 0.133 acid Dodecyl benzene sulfonic 0.125 acid13a.sup.3 Dodecyl toluene sulfonic 0.025 0.588 0.140 acid Dodecyl benzene sulfonic 0.125 acid14.sup.3 di-Hexyl benzene sulfonic 0.050 0.517 0.135 acid Dodecyl benzene sulfonic 0.100 acid14a.sup.3 Dodecyl toluene sulfonic 0.050 0.635 0.148 acid Dodecyl benzene sulfonic 0.100 acid15.sup.3 di-Hexyl benzene sulfonic 0.075 0.544 0.140 acid Dodecyl benzene sulfonic 0.075 acid15a.sup.3 Dodecyl toluene sulfonic 0.075 0.692 0.153 acid Dodecyl benzene sulfonic 0.075 acid16.sup.3 di-Hexyl benzene sulfonic 0.100 0.609 0.149 acid Dodecyl benzene sulfonic 0.050 acid16a.sup.3 Dodecyl toluene sulfonic 0.100 0.744 0.160 acid Dodecyl benzene sulfonic 0.050 acid17.sup.3 di-Dodecyl benzene 0.025 0.544 0.115 sulfonic acid Dodecyl benzene sulfonic 0.125 acid18.sup.3 di-Dodecyl benzene 0.050 0.636 0.119 sulfonic acid Dodecyl benzene sulfonic 0.100 acid19.sup.3 di-Dodecyl benzene 0.075 0.755 0.140 sulfonic acid Dodecyl benzene sulfonic 0.075 acid20.sup.3 di-Dodecyl benzene 0.100 0.843 0.148 sulfonic acid Dodecyl benzene sulfonic 0.050 acid21.sup.4 di-Dodecyl benzene 0.150 0.914 0.152 sulfonic acid21a.sup.4 C.sub.20-22 Toluene sulfonic 0.150 0.947 0.167 acid22.sup.4 di-Dodecyl benzene 0.125 0.908 0.150 sulfonic acid22a.sup.4 C.sub.20-22 Toluene sulfonic 0.125 0.947 0.161 acid23.sup.4 di-Dodecyl benzene 0.100 0.873 0.148 sulfonic acid23a.sup.4 C.sub.20-22 Toluene sulfonic 0.100 0.925 0.155 acid24.sup.5 di-Dodecyl benzene 0.150 0.850 0.140 sulfonic acid25.sup.6 di-Dodecyl benzene 0.150 0.837 0.138 sulfonic acid26.sup.7 di-Dodecyl benzene 0.150 0.776 0.137 sulfonic acid27.sup.8 di-Dodecyl benzene 0.150 0.610 0.135 sulfonic acid28.sup.1,8 Oleic Acid 0.150 0.606 0.13129.sup.3,5 di-Dodecyl benzene 0.125 0.876 0.141 sulfonic acid Oleic acid 0.02530.sup.3,6 di-Dodecyl benzene 0.129 0.867 0.140 sulfonic acid Oleic acid 0.02531.sup.3,7 di-Dodecyl benzene 0.129 0.844 0.139 sulfonic acid Oleic acid 0.02532.sup.3,8 di-Dodecyl benzene 0.129 0.830 0.138 sulfonic acid Oleic acid 0.025______________________________________ .sup.1 Not an embodiment of the invention. .sup.2 In these runs, the collector is a mixture of the components listed .sup.3 Mixture added together and then added to cell. .sup.4 Collector mixed with 0.150 kg/metric ton fuel oil #2 and both adde to cell. .sup.5 Ionic strength of water used equivalent to 100 ppm Na + impounded by conductivity cell. .sup.6 Ionic strength of water used equivalent to 250 ppm Na + impounded by conductivity cell. .sup.7 Ionic strength of water used equivalent to 500 ppm Na + impounded by conductivity cell. .sup.8 Ionic strength of water used equivalent to 1000 ppm Na + impounded by conductivity cell.

The data in Table IV demonstrate the effectiveness of the present invention. Runs 13-20 show the effect of mixing collectors of the present invention with similar monoalkylated species. Clearly the monoalkylated species is significantly less effective than the dialkylated species as shown by the steadily decreasing recoveries obtained when the monoalkylated species are added. For example, a comparison of Run 3 with Run 20 shows that replacing 0.050 kg/metric ton of di-dodecyl benzene sulfonic acid with a similar amount of dodecyl benzene sulfonic acid results in lower recovery. As more monoalkylated species is added, recoveries consistently decline. Runs 9 and 10 again demonstrate that mixtures of the collectors of this invention are effective. Additionally, Runs 21-23 show that the collector of the present invention may be used with hydrocarbons. The replacement of a portion of the collector with a hydrocarbon gives comparable results which is of economic benefit assuming the hydrocarbon is less expensive than the collector.

Runs 3 and 24-32 demonstrate the effect of hard water on the present invention and how the use of an oleic acid in conjunction with the dialkylated aromatic sulfonate collector counteracts this effect. The use of oleic acid and di-dodecylbenzene sulfonate together result in recoveries in hard water significantly improved over what either can obtain in hard water.

EXAMPLE 5 Flotation of Mixed Copper Sulfide Ore Containing Molybdenum

A series of 30-gram samples of a -10 mesh (U.S.) ore from Arizona containing a mixture of various copper oxide minerals and copper sulfide minerals plus minor amounts of molybdenum minerals is prepared. The grade of copper in the ore is 0.013 and the grade of the molybdenum is 0.00016. Each sample of ore is ground in a laboratory swing mill for 10 seconds and the resulting fines are transferred to a 300 ml flotation cell.

Each run is conducted at a natural ore slurry pH of 6.5. The collector (in the sodium salt form) is added at a dosage of 0.150 kg/ton of dry ore and the slurry is allowed to condition for one minute. Ore concentrate is collected by standard hand paddling between zero and four minutes. Just before flotation is initiated, a frother, a polyglycol ether available commercially from The Dow Chemical Company as Dowfroth.RTM. 250 brand frother, is added in an amount equivalent to 0.030 kg/ton of dry ore.

The float cell in all runs is agitated at 1800 RPM and air is introduced at a rate of 2.7 liters per minute. Samples of the concentrates and the tailings are then dried and analyzed as described in the previous examples. The results obtained are presented in Table V below.

TABLE V______________________________________ Dosage (kg/ metric Cu Cu Mo MoRun Collector ton) Rec Grade Rec Grade______________________________________ 1.sup.1 Dodecyl benzene 0.150 0.235 0.131 0.291 0.024 sulfonic acid 2 di-Dodecyl 0.150 0.790 0.163 0.862 0.044 benzene sulfonic acid 2a C.sub.20-22 Toluene 0.150 0.844 0.171 0.903 0.051 sulfonic acid 3 di-Nonyl 0.150 0.713 0.156 0.825 0.040 napthalene sulfonic acid 4.sup.1 C.sub.24 benzene 0.150 0.339 0.141 0.357 0.026 sulfonic acid 5 Mixture of di- 0.150 0.803 0.164 0.877 0.045 octyl, di-nonyl, and di-decyl benzene sulfonic acids.sup.2 6 di-Hexadecyl 0.150 0.517 0.135 0.533 0.031 benzene sulfonic acid 7 di-Hexyl benzene 0.150 0.557 0.161 0.560 0.034 sulfonic acid 7a Decyl Toluene 0.150 0.622 0.163 0.625 0.038 sulfonic acid 7b Dodecyl Toluene 0.150 0.680 0.171 0.671 0.041 sulfonic acid 8 di-Dodecyl 0.300 0.854 0.157 0.901 0.043 benzene sulfonic acid 8a Dodecyl Toluene 0.300 0.880 0.168 0.929 0.045 sulfonic acid 9 Mixture of di- 0.150 0.748 0.165 0.839 0.046 octyl, di-nonyl, and di-decyl napthalene sulfonic acids.sup.210.sup.3 di-Dodecyl 0.100 0.803 0.163 0.890 0.045 benzene sulfonic acid Sodium ethyl 0.050 xanthate10a.sup.3 C.sub.20-22 Toluene 0.100 0.845 0.166 0.904 0.047 sulfonic acid Sodium ethyl 0.050 xanthate11.sup.3 di-Dodecyl 0.050 0.810 0.165 0.903 0.046 benzene sulfonic acid Sodium ethyl 0.100 xanthate12.sup.14 Sodium ethyl 0.150 0.799 0.161 0.721 0.035 xanthate______________________________________ .sup.14 Not an embodiment of the invention .sup.2 The collector is a mixture of the component listed. .sup.3 Collectors are added to the cell at the same time. .sup.4 Run conducted at a pH of 9.5.

The data in the above table demonstrate the effectiveness of the present invention in the recovery of copper and molybdenum. Runs 10-12 demonstrate the effectiveness of collector compositions containing the dialkylated aromatic sulfonate and a xanthate collector are in recovering copper and molybdenum at lower pH. It should be noted that Run 12, not an embodiment of the invention, was conducted at a pH of 9.5 after attempts to conduct flotations at a pH of 6.5 resulted in essentially no recovery. However, when the xanthate replaces comparable amounts of di-dodecylbenzene sulfonate, good recoveries are obtained at the lower pH.

EXAMPLE 6 Flotation of Iron Oxide Ore

A series of 600-g samples of iron oxide ore from Michigan is prepared. The ore contains a mixture of hematite, martite, goethite and magnetite mineral species. Each 600-g sample is ground along with 400 g of deionized water (Runs 1-10) in a rod mill at about 60 RPM for 10 minutes. In Runs 11-17, water containing 300 ppm Ca.sup.+, 10 ppm Fe.sup.+++, 80 ppm SO4.sup.=, 20 ppm Cl.sup.- and 40 ppm Mg.sup.++ is used. The resulting pulp is transferred to an Agitair 3000 ml flotation cell outfitted with an automated paddle removal system. The collector (sodium salt form) is added and the slurry is allowed to condition for one minute. Next, an amount of a polyglycol ether frother equivalent to 40 g per ton of dry ore is added followed by another minute of conditioning.

The float cell is agitated at 900 RPM and air is introduced at a rate of 9.0 liters per minute. Samples of the froth concentrate are collected at four minutes after the start of the air flow. Samples of the froth concentrate and the tailings are dried, weighed and pulverized for analysis. They are then dissolved in acid, and the iron content determined by the use of a D.C. Plasma Spectrometer. Using the assay data, the fractional recoveries and grades are calculated using standard mass balance formulas. The results are shown in Table VI below.

TABLE VI______________________________________ Dosage (kg/metricRun Collector ton) Fe Rec Fe Grade______________________________________ 1.sup.1 Dodecyl benzene 0.300 0.151 0.397 sulfonic acid 2.sup.1 Dodecyl benzene 0.600 0.260 0.466 sulfonic acid 2a Dodecyl toluene 0.300 0.294 0.417 sulfonic acid 2b Dodecyl toluene 0.600 0.458 0.444 sulfonic acid 2c.sup.1 Decyl toluene 0.600 0.400 0.438 sulfonic acid 3 di-Dodecyl benzene 0.300 0.578 0.563 sulfonic acid 4 di-Dodecyl benzene 0.600 0.735 0.524 sulfonic acid 4a C.sub.20-22 Toluene 0.300 0.680 0.574 sulfonic acid 4b C.sub.20-22 Toluene 0.600 0.789 0.577 sulfonic acid 5 di-Nonyl napthalene 0.300 0.563 0.549 sulfonic acid 6 di-Nonyl napthelene 0.600 0.712 0.511 sulfonic acid 7.sup.1 C.sub.24 benzene 0.300 0.307 0.478 sulfonic acid 8.sup.1 C.sub.24 benzene 0.600 0.479 0.490 sulfonic acid 9 Mixture of di-octyl 0.600 0.758 0.530 and di-nonyl benzene sulfonic acids.sup.210 Mixture of di- 0.600 0.698 0.509 octyl, di-nonyl and di-decyl benzene sulfonic acids.sup.211 di-Dodecyl benzene 0.600 0.588 0.489 sulfonic acid12 di-Dodecyl benzene 0.300 0.401 0.500 sulfonic acid13.sup.1 Oleic Acid 0.300 0.488 0.47714.sup.1 Oleic Acid 0.600 0.337 0.43815 di-Dodecyl benzene 0.300 0.694 0.523 sulfonic acid Oleic Acid.sup.3 0.30016 Mixture of di-octyl 0.300 0.417 0.513 and di-nonyl benzene sulfonic acids.sup.217 Mixture of di-octyl 0.300 0.703 0.541 and di-nonyl benzene sulfonic acids.sup.2 Oleic Acid.sup.3 0.300______________________________________ .sup.1 Not an embodiment of the invention .sup.2 The collector is a mixture of the components listed. .sup.3 The two components are mixed together before addition to cell.

A comparison of Runs 4 and 11 and of Runs 3 and 12 show the effect of hard water on the collectors of the present invention. As examination of Runs 11-17 show the effect of mixtures of collectors of the present invention with oleic acid to overcome the detrimental effects of hard water. When oleic acid is mixed with the collectors of the present invention, results comparable to those obtained in deionized water are obtained even when using the very hard water used in those runs. Oleic acid itself used in hard water also results in poor recovery as shown in Runs 13 and 14. It is the mixtures shown in Runs 15 and 17 that demonstrate surprising results.

EXAMPLE 7 Separation of Apatite and Silica

The procedure outline in Example 4 is used with the exception that deionized water is replaced with water having 600 ppm Ca.sup.++, 20 ppm Fe.sup.+++, 140 ppm SO.sub.4.sup.=, and 50 ppm Mg.sup.++. The results obtained are shown in Table VII below:

TABLE VII______________________________________ Dosage Phosphorus Recovery (kg/metric and GradeRun Collector ton) Rec Grade______________________________________ 1.sup.1 Oleic Acid 0.025 0.249 0.141 2.sup.1 Oleic Acid 0.050 0.350 0.139 3.sup.1 Oleic Acid 0.075 0.538 0.136 4.sup.1 Oleic Acid 0.150 0.671 0.134 5 di-Dodecyl benzene 0.150 0.534 0.139 sulfonic acid 6 di-Dodecyl benzene 0.125 0.449 0.141 sulfonic acid 7 di-Dodecyl benzene 0.100 0.308 0.142 sulfonic acid 8 di-Dodecyl benzene 0.075 0.217 0.144 sulfonic acid 9.sup.2 Oleic Acid 0.025 0.637 0.135 di-Dodecyl benzene sulfonic acid 0.12510.sup.2 Oleic Acid 0.050 0.753 0.133 di-Dodecyl benzene sulfonic acid 0.10011.sup.2 Oleic Acid 0.075 0.814 0.132 di-Dodecyl benzene sulfonic acid 0.07512.sup.2 Oleic Acid 0.100 0.729 0.130 di-Dodecyl benzene sulfonic acid 0.05013.sup.3 Oleic Acid 0.075 0.790 0.133 di-Dodecyl benzene sulfonic acid 0.07514.sup.4 Oleic Acid 0.075 0.636 0.136 di-Dodecyl benzene sulfonic acid 0.07515.sup.2 Fatty Acid.sup.5 0.075 0.833 0.133 di-Dodecyl benzene sulfonic acid 0.07516.sup.3 Fatty Acid.sup.5 0.075 0.805 0.132 di-Dodecyl benzene sulfonic acid 0.07517.sup.4 Fatty Acid.sup.5 0.075 0.648 0.135 di-Dodecyl benzene sulfonic acid 0.07518.sup.6 Fatty Acid.sup.5 0.075 0.863 0.141 di-Dodecyl benzene sulfonic acid 0.07519.sup.6 Fatty Acid.sup.5 0.050 0.885 0.142 di-Dodecyl benzene sulfonic acid 0.010______________________________________ .sup.1 Not an embodiment of the invention. .sup.2 Two components mixed together before addition to cell. .sup.3 First component added to cell, conditioned for one minute followed by second component added to cell conditioned for one minute. .sup.4 Second component added to cell, conditioned for one minute followe by addition of first component added to cell conditioned for one minute. .sup.5 Mixture of oleic, linoleic and linoleic acids. .sup.6 Mixture added to grinding step.

The data in Table VII above shows that higher collector dosages are required in the presence of the hard water used in this example. The examples also demonstrate the benefits obtained when the collectors of the present invention are used with fatty acids. The benefits are most noticeable when the two types of acids are mixed together prior to being added to the float cell as in Runs 9-12 and 15 or are mixed and added to the grinding step as shown in Runs 18-19.

EXAMPLE VIII Flotation of Ink from Printed Paper

A special column flotation cell with a one inch diameter glass tube 16 inches tall with a porous frit at the bottom thorughwhich air can be introduced is used. Air is introduced through the porous frit at the rate of 3 liters/minute. One gram samples of printed material (70 percent newsprint and 30 percent magazine) is soaked in 50 cm.sup.3 of water containing sufficient sodium silicate to raise the slurry pulp pH to 9.5. The collector is added to the mixture and then it is mixed in a blender for 10 minutes. The collector concentration of 0.5 kg/metric ton of dried printed material. The contents are transferred to the column cell and sufficient water is added to bring the slurry level to the top of the cell. Air is then introuduced causing the liberated ink to rise to the top of the column where it is collected, weighed and anlayzed. Dried mats of the remaining deinked fiber in the cell are made and a brightness meaurement is conducted on a light meter using white light as a basis.

TABLE VIII______________________________________ Dry Weight of Product (g) Ink Concen-Run Collector Brightness Pulp trate______________________________________1 di-Hexyl Benzene 50.2 0.117 0.883 sulfonic acid2.sup.1 Dodecyl Benzene 44.7 0.183 0.817 sulfonic acid3 Dodecyl toluene 53.3 0.105 0.895 sulfonic acid4 Decyl toluene 52.1 0.110 0.890 sulfonic acid5 di-Dodecyl benzene 59.9 0.087 0.913 sulfonic acid6.sup.1 C.sub.24 benzene 48.3 0.260 0.740 sulfonic acid7 C.sub.20-22 toluene 61.3 0.080 0.920 sulfonic acid______________________________________ .sup.1 Not an embodiment of the invention

Claims

1. A process for the recovery of minerals by froth flotation comprising subjecting an aqueous slurry comprising particulate minerals selected from the group consisting of copper oxides, nickel oxides, titanium oxides, noble metals, sulfides, carbon based inks and mixtures thereof to froth flotation in the presence of a collector for the minerals comprising at least one aryl monosulfonic acid or salt thereof having at least two alkyl substituents or mixtures of such salts or acids under conditions such that the minerals are floated and recovered.

2. The process of claim 1 wherein the collector further comprises aryl sulfonic acids or salts with less than two alkyl substituents and wherein at least about 15 percent of the total acids or salts have at least two alkyl substituents.

3. The process of claim 1 wherein the collector further comprises aryl sulfonic acids or salts with less than two alkyl substituents and wherein at least about 35 percent of the total acids or salts have at least two alkyl substituents.

4. The process of claim 1 wherein the collector further comprises aryl sulfonic acids or salts with less than two alkyl substituents and wherein at least about 50 percent of the total acids or salts have at least two alkyl substituents.

5. The process of claim 1 wherein the aryl sulfonic acid or salt thereof comprises an aromatic core selected from the group consisting of phenol, benzene, napthalene, anthracene and compounds corresponding to the formula ##STR3## wherein X represents a covalent bond; --(CO)--; or R wherein R is a linear or branched alkylene group having one to three carbon atoms.

6. The process of claim 1 wherein the aryl sulfonic acid or salt thereof corresponds to the formula ##STR4## wherein each R.sup.1 is independently in each occurrence a saturated alkyl or substituted saturated alkyl radical or an unsaturated alkyl or substituted unsaturated alkyl radical, with the proviso that the total number of carbon atoms in the alkyl groups is at least 18 and no greater than about 32: m is at least two and no greater than five; each M is independently hydrogen, an alkali metal, alkaline earth metal, or ammonium or substituted ammonium.

7. The process of claim 6 wherein the total number of carbon atoms in the alkyl groups represented by R.sup.1 is at least 18 and no greater than 24.

8. The process of claim 6 wherein R.sup.1 is independently in each occurrence an alkyl group having from about 6 to about 16 carbon atoms.

9. The process of claim 8 wherein R.sup.1 is independently in each occurrence an alkyl group having from about 8 to about 12 carbon atoms.

10. The process of claim 6 wherein m is two.

11. The process of claim 1 wherein the particulate minerals are oxides selected from the group consisting of copper oxide, nickel oxide, and titanium oxide ores.

12. The process of claim 1 wherein the minerals are sulfides.

13. The process of claim 1 wherein the minerals are both sulfur-containing and oxygen-containing minerals.

14. The process of claim 1 wherein the minerals are at least one noble metal selected from the group consisting of gold, silver and platinum group metals.

15. The process of claim 1 wherein the process is conducted at the natural pH of the slurry.

16. The process of claim 1 wherein the flotation is conducted at a pH lower than the natural pH of the slurry.

17. The process of claim 1 wherein the flotation is conducted at a pH higher than the natural pH of the slurry.

18. The process of claim 1 wherein the total concentration of the collector is at least about 0.001 kg/metric ton and no greater than about 5.0 kg/metric ton.

19. The process of claim 1 wherein the collector is added to the slurry in at least about two stages and no more than about six stages.

20. The process of claim 1 wherein the collector further comprises a sulfide collector.

21. The process of claim 20 wherein the sulfide collector is selected from the group consisting of xanthates, dithiol phosphates and trithiol carbonates.

22. The process of claim 20 wherein the flotation process is conducted at the natural pH of the slurry.

23. A process for the recovery of minerals by froth flotation wherein an aqueous slurry comprising particulate minerals comprising carbon based inks and pulped paper is subjected to froth flotation in the presence of a collector for the carbon based inks comprising at least one aryl monosulfonic acid or salt thereof having at least two alkyl substituents or mixtures of such salts or acids and under conditions such that the carbon based inks are floated and recovered.

24. A process for the recovery of minerals by froth floatation comprising subjecting an aqueous slurry of particulate minerals comprising phosphorus containing ores to froth flotation in the presence of a collector for the phosphorus wherein said collector comprises at least one alkylated aryl monosulfonic acid or salt thereof of mixtures thereof wherein greater than about 15 percent of said acids or salts is didodecylbenzene monosulfonic acid or a salt thereof under conditions such that the minerals are floated and recovered.

25. The process of claim 24 wherein greater than about 50 percent of said acids or salts is didodecylbenezene sulfonic acid or a salt thereof.

26. A process for the recovery of minerals by froth flotation comprising subjecting an aqueous slurry comprising particulate minerals selected from the group consisting of copper oxides, nickel oxides, titanium oxides, noble metals, sulfides, carbon based inks and mixtures there of to froth flotation in the presence of a collector for the minerals comprising at least one aryl monosulfonic acid or salt there of having at least two alkyl substituents wherein one alkyl group is a C.sub.1-13 and one is a C.sub.10-24 alkyl or mixtures of such salts or acids under conditions such that the minerals are floated and recovered.

27. A process for the recovery of minerals by froth flotation comprising subjecting an aqueous slurry comprising particulate minerals selected from the group consisting of hematite, magnetite, martite, goethite, bauxite, corundum, boehmite, diaspore and mixtures thereof to froth flotation in the presence of a collector for the minerals comprising at least one aryl monosulfonic acid or salt thereof having at least two alkyl substituents or mixtures of such salts or acids, said froth flotation occurring without the presence of a cationic collector and under conditions such that the minerals are floated to form the froth and recovered.