CA2098574A1 - Aryl monosulfonate collectors useful in the floatation of minerals - Google Patents

Abstract

Dialkylated aryl monosulfonic acids or salts thereof or their mixture are useful as collectors in the flotation of minerals, particularly oxide minerals. Collector compositions comprising these salts and oleic acid are particularly useful in hard water.
Collector compositions comprising these salts and sulfide collectors such as xanthates are useful in flotations conducted at natural pH
of the slurry.

Description

WO 9~/1 109~ 2 0 ~ ~ ~ 7 ~ PCr/US~ )9371 ARYL MONOSULFONATE COLLECTORS
USEFUL IN THE FLOTATION OF MINERALS

This invention iq related to the use of chemical collectorq in the recovery of minerals by froth flotation.
Froth flotation ha~ been extensively practiced ; 5 in the mining industry ~ince at least the early twentieth century. A wide variety of compounds are taught to be useful as collectors, frothers and other reagents in ~roth flotation. For example, xanthates, simple alkylamines, alkyl sulfates9 alkyl ~ulfonates, carboxylic acids and fatty acids are generally accepted as useful collectors. Reagents u~eful as frothers include lower molecular weight alcohols such as methyl isobutyl carbinol and glycol ether~. The specific additives used in a particular flotation operation are ~elected according to the nature of the ore, the conditions under which the flotation takes 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 vary greatly depending .. .v ~
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on the particular ore or ores being qubjected 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 comprised of oxygen-containing species such as carbonates, hydroxides, sulfates and silicates.
Thus, the group of minerals categorized as oxides generally includes 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 a~ 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 3electivity. Some of the recognized collectors such as the carboxylic acids, alkyl sulfates and alkyl ulfonates 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 quit~ poor. That is, the grade or the 3 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 . .

W092/11091 ~ 0 9 ~ ~ 7 ~ pcr/us9l/o937 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 exiqting commercial processes. After the oxide minerals are sulfidized, they are then subjected to flotation u~ing 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 reverYe flotation, the flotation of the ore having the desired mineral values is depressed and the gangue or other contaminant is floated. In some case , the contaminant is a mineral which may have value. A fourth approach to mineral recovery involves chemical disolution or leaching.
None of these existing methods of flotation directed to oxide ore~ 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. Rnown recovery methods have not been economically feasible and consequently, a large proportion of oxide ores are simply not processed.
Thus, the need for improved selectivity in oxide mineral flotation i~ generally acknowledged by those skilled in the art of froth flotation.
This invention is a process for the recovery of minerals by ~roth flotation characterized by the u~e of a collector comprising: ;

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(a) at least one aryl monosulfonic acid or salt thereof having at least two alkyl substituents or mixtures of such salts or acids, or (b) a qulfonic component comprising at least one alkylated aryl monosulfonic acid or ~alt thereo~ and a carboxylic component comprising at least one C1_24 carboxylic acid or salt thereof.
The recovered mineralq 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.
The practice of the flotation process of this invention re~ults in improvements in ~electivity and thu~ the grade of minerals recovered from oxide and/or sulfide ores while generally maintaining or increaqing overall recovery levels of the mineral desired to be recovered. The uqe of the aryl monosulfonic acid or salt thereof having at leaqt two alkyl qubstituents result-q in improvements in ~electivity or recovery of mineral values when compwered to the use of similar acids or salts having comparable numbers of carbon atoms but only a single qubstituent. The use of a collector containing the qulfonic component and the carboxylic component reQult~ in highly effecient flotation of minerals, particularly in those instance~ where hard water exists in the flotation environment.
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 , .
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', W092/~1091 2 0 9 ~ ~ r~ ~ PCT/US91/09371 and mixed ores. The oxide or oxygen-containing minerals which ~ay 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 or dolomite and hydroxides such as bauxite.
Non-limiting examples of specific oxide oreq which may be collected by froth flotation using the process of this invention include thoqe containing cassiterite, hematite, cuprite, vallerite, calcite~
talc, kaolin, apatite, dolomite, bauxite, spinel, corundum, laterite, azurite, rutile, magnetite, columbite, ilmenite, smithsonite, anglesite, scheelite, chromite, cerus~ite, pyrolusite, malachite, chrysocolla, zincite, massicot, bixbyite, anatase, brookite, tungstite, uraninite, gummite, brucite, manganite, psilomelane~ ~oethite, 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 was 3 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 .~

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WO 92/1 1091 PCr/VS91/09371 2a9~sr~
invention include tho~e containing chalcopyrite, chalcocite, galena, pyrite, sphalerite, molybdenite and ;~
pentlandite.
Noble metals ~uch as gold and silver and the platinum group metals wherein plaSinum group metals comprise platinum, ruthenium, rhodium, palladium, osmlum, 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.
Ore~ do not always exist purely as oxide ores or as sulfide ores. Ores occurring in nature may comprise both ~ulfur-containing and oxygen-containing minerals as well as ~mall 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.
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A particular feature of the process of this invention is the ability to differentially float various minerals. The susceptibility of various minerals to flotation in the process of this invention is thought to be related to the crystal structure of the minerals.

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More qpecifically, a correlation appears to exist between the ratio of crystal edge lengths to crystal surface area on a unit area basis. Minerals with higher ratios appear to float preferentially when compared to minerals with lower ratios. Thus, mineralq whose crystal structure have 24 or more faces (Group I) are generally more likely to float than minerals with 16 to 24 faces (Group II). Group III minerals comprising minerals with 12 to 16 faces are next in order of preferentially floating followed by Group IV minerals with 8 to 12 faceq.
In the process of this invention, generally Group I minerals float before Group II minerals which would float before Group III minerals which float before Group I~ minerals. By floating before or preferentially floating, it is meant that the preferred ~pecies 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 is collected and so on.
One skilled in the art recognizes that these groupings are not absolute. Variouq minerals may have different possible crystal structures. Further, the size of crystals existing in nature also varies which influences the ease with which different minerals are floated. An additional factor affecting flotation preference is the degree of liberation. Further, within 3~ a group, that is, among minerals whose crystals have similar edge length to surface area ratios, these factors and others influence which member of the group floated first.
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One skilled in the art can readily determine which group a mineral belongs to by examining standard mineralogy characterization of di~ferent minerals.
These are available, for example, in Manual of Mineralo~, 19th Edition, Cornelius S. ~urlbut, 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, ~mithsonite, ~oda 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, dia~pore, 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, de~cloizite, mottramite, brazilianite, olivenite, libethenite, adamite, phosphuranylite, childrenite, eosphorite, scheelite, powellite, wulfenite, topaz, columbite and tantalite.

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" .' ' . ' . ' W092/11091 2 a9~ PCT/~S91/09371 As diYcussed above, these groupings aretheorized to be useful in identifying which minerals float preferentially. However? as discussed above, the collector and process of this invention are useful in the flotation of various minerals which did not fit into the above categories. These groupings are useful in predicting which minerals 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 permits the separation of small amountq 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 ca~es, useful in reverse flotation where the undesired mineral is floated such as floating topaz or tourmaline away from ca~siterite 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 3Q contain minerals that may be recovered using the flotation process of the pre~ent invention. Another example is the recovery of a mixture of carbon based inks such as graphite ink and other inks in the recycling of paper. Typically such recycled papers are de~inked to separate the inks from the paper fibers by a .

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flotation process. The flotation process of the present invention is particularly ef`fective in such de-inking flotation processes.
The aryl monosulfonic acid or monosulfonate collector of this invention comprise 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 ~ulfonate include both the sulfonic acid moiety and the sulfonate moiety. It is preferred that the collector has two to three substituents and more preferred that it has two. The aromatic core preferably comprises phenol, benzene, napthalene, anthracene and compounds corresponding to the formula:
r ' X = ) (I) wherein X represents a covalent bond; --(C0)--; or R
wherein R is a linear or branched alkyl divalent moiety 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 24 carbon atoms. More preferably each of the alkyl groups contains from 6 to 18 carbon atoms and most preferably 8 to 12 carbon atoms. The alkyl groups contain a total of .. ' ,. ' . :.
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wos2/1109~ j 7 4 PCT/US91/0~371 at least 10, more preferably at least 12 and most preferably at least 16 carbon atoms. The maximum total number of carbon atoms in the alkyl groups is preferably no greater than 32 and more preferably no greater than 24. The alkyl groups can be linear, cyclic or branched with linear or branched being preferred. The alkyl ~ubstituted aryl sulfonate~ are available commercially or may be prepared by method~ known in the art. For example, the alkyl substituted aryl sulfonate collectors may be prepared by alkylation of aryl centers by nucleophilic aromatic alkylation using alkyl halides, alcohols or alkenes a~ the alkylation agent with appropriate catalysts.
It i3 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 methuds of production of substituted aryl sulfonates sometimes result in mixtures of non-substituted, mono-substituted, di-substituted and higher ~ubstituted aryl sulfonates. Such mixtures are operable in the practice of this invention. It is preferred that at least 15 percent of the alkylated aryl sulfonates contain two or more alkyl substituents. More preferably at least 35 percent of the alkylated aryl sulfonates contain at lea t two alkyl substituents and even more preferably at least 50 percent of the alkylated aryl sulfonates contain at least two alkyl 3o Substituentq.
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 C1_3 alkyl group and the second alkyl group is a C10-24 alkyl group. In the preparation of these unsymmetrical ' " . , W092/11091 ~ .5 14 ,~ PCT/US91/09371 sul~onates, alpha-olefins, alkyl halides and alcohols having sufficient carbon atoms to provide the desired hydrophobicity are used as alkylating agentq.
Typically, group~ having from 10 to 24, preferably from l6 to 24 carbon atomq are u~ed~ The species which i~
alklyated is typically toluene, cumene, ethyl benzene or xylene. The alklyated qpecie~ is ~ulfonated by methods known in the art.
Other sulfonateq u~eful in the collector composition include a central aromatic group having one alkyl substituent and one non-alkyl substituent.
Examples of su~h qulfonates include monoalkylated diphenyloxide sulfonate.
Particular examples of unsymmetrically sub~tituted monosulfonates include hexadecyl cumene ~ulfonic acid, octadecyl cumene sulfonic acid, octadecyl ethylbenzene sulfonic acid, octadecyl p-xylene sulfonic acid, octadecyl o-xylene ~ulfonic acid, and hexadecyl m-xylene sulfonic acid.
The aryl Aulfonate collector of this invention is preferably a dialkylated or higher alkylated benzene sulfonate collector and correspondq to the following formula or to a mixture of compounds corre~ponding to the formula:

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WO 92/1 1~ 0 9 ~ ~ 7 ~ PCr/US91/09371 -13- i ) m (II) ( SO3 M+ ) 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 i~ at least two and no greater than five;
eaoh M is independently hydrogen, an alkali metal, alkaline earth metal, or ammonium or ~ubstituted ammonium. Preferably, the R group(~) are independently in each occurrence an alkyl group which has ~rom three to 24, more preferably from 6 to 18 carbon atoms and most preferably 8 to 12 carbon atomq with the provi~o that the total number of carbon atoms in the alkyl - groups is at least 10, more preferably at least 12 and most preferably at least 16 and no greater than 329 pre~erably no greater than 24. The alkyl groups can be linear, branched or cyclic with linear or branched radicals being preferred. In one pre~erred embodiment, the R groups are different with one having from 1 to 3 carbon atoms and the other from 10 to 24 carbon atoms.
The M+ ammonium ion radicals were o~ the formula (R')3HN+ wherein each R' is independently hydrogen, a 3 C1-C4 alkyl or a C1-C4 hydroxyalkyl radical.
Illustrative C1-C4 alkyl and hydroxyalkyl radicals include methyl, ethyl, propyl, isopropyl, butyl, hydroxymethyl and hydroxyethyl. Typical ammonium ion radicals include am~onium (N+H~), methylammonium (CH3N+H3), ethylammonium (C2H5N~H3~, dimethylammonium , . .

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~ O ~ 8 5 7 ~-14-((CH3)2N+H2), methylethylammonium (CH3N+H2C2H5), trimethyla~monium ((CH3)3N+H), dimethylbutylammonium ((CH3)2N+HC4Hg), hydroxyethylammonium (HOCH2CH2N~H3) and methylhydroxyethylammonium (CH3N+H2CH2CH20H).
Preferably, each M was hydrogen, sodium, calcium, potassium or a~monium. The dialkylated sulfonic acid or salt i9 useful as a collector either alone or in conjunction with the carboxylic component.
Another sulfonic compound useful in conjunction with the carboxylic component is an alkylated diaryl oxide sul~onic acid collector known in the art and described in U. S. Patent 5,015,367. In a preferred e~bodiment, thiC collector is a diphenyl oxide collector and corresponds to the following formula or to a mixture of compounds corresponding to the formula:

(R)m (R)n ~0) ~ ~' 25(S03-M+)y (S03-M+)x 3~ wherein each R is independently a saturated alkyl or substituted saturated alkyl radical or an unsaturated alkyl or substituted unsaturated alkyl radical; each m and n is independently 0, 1 or 2; each M is independently hydrogen, an alkali metal, alkaline earth metal, or ammonium or sub~tituted ammonium and each x WO9~/11091 2 0 3 ~ ~ 7 ~-~ PCT/US91/09371 and y is individually O or 1 with the proviso that the sum of x and y is one. Preferably, the R group(s) is independently an alkyl group having from about 1 to about 24, more preferably from about 6 to about 24 carbon atoms, even more preferably about 6 to about 16 carbon atoms and most preferably about 10 to about 16 carbon atoms. The alkyl groups can be linear, branched or cyclic with linear or branched radicals being preferred. It i~ also preferred that m and n are each one. The M+ ammonium ion radicals are of the formula (R')3HN+ wherein each R' is independently hydrogen, a C1-C4 alkyl or a C1-C4 hydroxyalkyl radical.
Illustrative C1-C4 alkyl and hydroxyalkyl radicals include methyl, ethyl, propyl, i~opropyl, butyl, hydroxymethyl and hydroxyethyl. Typical ammonium ion radicals include ammonium (N+H4), methylammonium (CH3N+H3), ethylammonium (C2H5N+H3), dimethylammonium ((CH3)2N~H2), methylethylammonium (CH3N~H2C2H5), trimethylammonium ((CH3)3N~H), dimethylbutylammonium ((CH3)2N+HC4H9), hydroxyethylammonium (HOCH2CH2N~H3) and methylhydroxyethylammonium (CH3N+H2CH2CH20H).
Preferably, each M is hydrogen, sodium, calcium, potassium or ammonium.

The carboxylic component is a C1-24 carboxylic acid or salt thereof. Examples of useful materials include acetic acid, citric acid, tartaric acid, maleic acid, oxalic acid, ethylenediamine dicarboxylic acid, ethyleneamine tetracarboxylic acid and fatty acids.
Fatty acid~ or their salts were particularly preferred.
Illustrative 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. One W~92/11091 PCT/US91/09371 2~3~ ~ ~ 16-example of a mixture of fatty acids was tall oil.
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. R~ used herein, the terms "acid" and"carboxylate"
include both the acid and salt form.

The collector comprising the sulfonic component and the carboxylic component i9 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+ equivalents. An effective amount of carboxylic component is that amount which, when replacing an equal amount of sulfonate, re~ults in improved recovery of the desired mineral.
The amount of carboxylic component used is preferably at least 1 weight percent, more preferably at least 2 weight percent and most preferably at least 5 weight percent, based on the combined weight of the sulfonic and carboxylic components. The maximum amount of carboxylic component used is preferably no greater than 50 weight percent, more preferably no greater than 40 weight percent, and most preferably no greater than 30 weight percent. As will be recognized by one skilled in the art, the optimum amount of carboxylic component used depends on the degree of hardne~s of the water used in flotation, the minerals to be recovered and other variables in the flotation process.

The carboxylic component may be added to the flotation system prior to the addition of the sulfonate or they may be added simultaneously. It is preferred, however, that the sulfonic and carboxylic components be WO92/l10~1 2 ~ 3 ~ PCT/l)S~1/09371 formulated and then added to the flotation system. The collector composition may be formulated in a water based mixture or a hydrocarbon based mixture which depends on the particular application. When a water formulation is used, the sulfonic and/or the carboxylic component are in the salt form. When a hydrocarbon based formulation is used, one or both of the components are in the acid form. Typical hydrocarbon formulations include any saturated hydrocarbon, kerosene, fuel oil, alcohol, alkylene oxide compound, or organic solvents such as dodecene, dimethylsulfoxide, limonene and dicyclo-pentadiene.

The type of collector formulation and whether the acid or salt form is used also impacts the preferred ratio of sulfonake to carboxylate. When the salt form is used, the amount of carboxylate used was preferably at least 1 weight percent, more preferably at least 2 weight percent and most preferably at least 5 weight percent, based on the combined weight of the sulfonate and carboxylate component. The maximum amount of carboxylate used is preferably no greater than 60 weight percent, more preferably no greater than 40 weight percent, and most preferably no greater than 25 weight percent. When the acid form is used, the amount of carboxylic component used is preferably at least 1 weight percent, more preferably at least 5 weight percent and most preferably at least 10 weight percent, based on the combined weight of the sulfonic and carboxylic component. The maximum amount of carboxylic component used is preferably no greater than 70 weight percent, more preferably no greater than 50 weight percent7 and most preferably no greater than 30 weight percent.

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wog2/l~091 P~r/US9l/0937l 2 ~ i 7 ~1- 18-In preferred embodiments, both the sulfonic and carboxylic components are in either the salt form or the acid form. Mixed formulations where one is a salt and the other an acid are possible, but are generally not preferred. The acid form, or hydrocarbon based formulations, are generally preferred in those situations where pH regulators are used to raise the p~ -above 7. In tho~e instances where the flotation was conducted at a natural pH, it is typically preferred to use the salt form or water based formulations.

The collector can be used in any concentration which gives the desired selectivity and recovery of the desired mineral valuesO In particular, the concen-tration 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 sul~ide 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 typiaally require a desliming step to remove the fines prese~t and thus permit the process to function with acceptable collector dosage levels. The collector of the precent , ' . , .

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_19_ invenkion functions at acceptable dosage levels with or without desliming.
Preferably, the concentration of the collector was at least 0.001 kg/metric ton, more preferably at least 0.05 kg/metric ton. It is also preferred that the total concentration of the collector is no greater than 5.0 kg/metric ton and more preferred that it is no greater than 2.5 kg/metric ton. In general, to obtain optimum performance fro~ 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 thiq 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 ~lotation using the process of this in~ention is present, a ~e~y low collector dosage is needed due to the ~electivity of the collector.
It ha9 been found advantageous in the recovery 3 of certain minerals to add the collector to the flotation ~ystem 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 .

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preferably not changed when it is added in stages. This staged addition can be repeated several times to obtain .
optimum recovery and grade. The nu~ber 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 increa~ed dosa~e, a different mineral is floated thus permitting the separation of different minerals contained in a given ore.
In addition to the collector of this invention, ; 20 other conventional reagents or additives may be used in the flotation process. Examples of such additives include variou~ 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 is 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 3 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 hydrocarbons useful in this context include those hydrocarbons typically used in flotation.
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' , WO9~/11091 2 ~ 7 ~ PCT/US91/09371 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 de~ired to conduct the flotation at natural or non-elevated slurry pH.
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 Qecond stage flotation using conventional collectors recovers 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 3 may be dssirable to reverse the stages. Such a two--stage process has the advantage~ of using less additives to adjust pH and also permits a more complete recovery of the desired minerals by conducting flotation under different conditions.

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WO92~11091 PCT/US91/09371 2 ~ 3 3 ~ 22 A particular advantage of the collector of the present invention iq that additional additives are not required to adjust the pH of the flotation slurry. The flotation proce~s utilizing the collector of the present invention operate effectively at typical natural ore pH's ranging from 5 or lo~er to 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.
~5 The ability of the collector of the present invention to function at relatively low pH means that it may also be uqed 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 was 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 3 subsequent run to optimize flokation of a different species thus facilitating separation of various minerals found together.
The following examples are provided to illus-trate the invention and qhould not be interpreted as WO92/11091 2 0 9 3 ;i ~ ~ PCT/US91/09371 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 muqt be effective in a Hallimond tuoe flotation if it is to be effective in actual flotation, a collector effective in Hallimond tube flotation is not necessarily 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 required in an actual flotation cell.
Example 1 - Hallimond Tube Flotation of Rutile, Apatite, Hematite and Silica 1~1 g sample either the specified mineral or silica sized to about -60 to +120 U.S. mesh was placed in a small bottle with 20 ml of deionized water.
The mixture was shaken 30 seconds and then the water 3 pha~e containing some suspended fine solids or slimes was decanted. This desliming step was repeated several times.
A 150-ml portion of deionized water was placed in a 250-ml glass beaker. Next, 2.0 ml of a 0.10 molar 2 0 9 ~ ~ 1 4 -24-solution of potassium nitrate was added as a buffer electrolyte. The pH was 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 was added along with deionized water to bring the total volume to about 180 ml. The specified collector was added and allowed to condition with stirring for 15 minutes. The pH was monitored and adjusted as necessary using HCl and NaOH. All collectors indicated were converted to the Na+ salt form before addition.
The slurry was transferred into a Hallimond tube de~igned 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 was applied to the opening of the tube for a period of 10 minutes. This vacuum allowed air bubbles ~; to enter the tube through the hollow needle inserted at the base of the tube. During flotation, the slurry was agitated with a magnetic stirrer set at 200 revolutions per minute (RPM).
The floated and unfloated material was filtered out of the slurry and oven dried at 100C. Each portion was weighed and the fractional recoveries of each mineral and silica were reported in Table I below.
After each test, all equipment was washed with concentrated HCl and rinsed with 0.10 N NaOH and deionized water before the next run.
The recovery of each mineral and sîlica, respectively, reported was that fractional portion of the original mineral placed in the Hallimond tube that was recovered. Thus, a recovery of 1.00 indicated that all of the material was recovered. It should be noted WO ~t/11091 ~ r~ ~ PCT/US91/09371 that although the recovery of each mineral and silica, respectively, was reported together, the data was actually oollected in four experiments done under identical conditions. It should further be noted that a low silica recovery indicated a selectivity to the the 5 desired minerals. The values given for the various mineral recoveries generally were correct to 10. 05 and those for silica recovery were generally correct to +0.03-:

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'. '' ' ', , ' '' ~ , '' '' ' ' . : ' ': ' ' WO92/11091 rC~/US91/09371 209~57~ -34-The data in Table I above demonstrated various aspects o~ the invention. A comparison of Run 8 with Run 9 or of Run 10 with Run 11 demonstrated that the arrangement of carbon atoms present in the alkyl groups was important. Each pair of runs had the same total number of carbon atoms preqent, but the dialkylated version shows significantly improved reqults when oompared to monoalkylated version. A comparison of Runs 1-7, 9, 11 and 17-19, which were not embodiments of the present invention, with the remaining runs, which were 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 were effective. Run 34 demonstrates the effectiveness of a compcund where one substituent was an ethyl group while the other was a dodecyl and Run 35 similarly demonstrates the effectiveness of compounds where one substituent was an hexyl group while the other was a dodecyl. In each case, the collector was 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 were a~ymmetrical with those having similar numbers of carbon atoms in symmetrical alkyl groups, it was shown that asymmetrical alkyl groups provide improved performance.

WO 92/l l091 ~ 0 9 ~ ~ 7 ~ PCT/US91/0937l Example 2 - Flotation of Various Oxide Minerals The general procedure of Example 1 was followed with the exception that both the sulfonate and carboxylate components were pre-blended and then added to the slurry. Additionally, the ion concentrations are indicated for those runs where metal ions were deliberately added to the processing water for flotation. The ratio of metal ions added is five parts Na+, two partq Mg+~, and one part Fe+++ with the total amount of the~e ions added being determined by measuring the ionic strength of the water in equivalent Na~
concentration as measured by a conductivity cell.
The data in Table II demonstrate the broad range of minerals wnich may have been floated using the collector and process of this invention.

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W092/11091 ~ 0~ 5 ~ ~ PCT/US91/09371 The above information demonstrated the effect of ratio of sulfonate to carboxylate and also shows that the combination of sulfonate and carboxylate functions better than either alone.

Example 3 - Flotation of Various Oxide Minerals The general procedure of Example 1 was followed with the exception that various oxide minerals were used in place of the ores specified in Example 1. All runs were conducted at a pH of 8.o. The collec~ors u~ed were a C12 dialkylated benzene sulfonate and a C20-22 toluene sulfonate, each at a dosage of 0.024 kg of collector per kilogram of mineral. The results are shown in Table III
below.

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2a98~7.~ -~2-The data in Table III demonstrated the broad ranKe of minerals which may have been floated using the collector and process of this invention. The asymmetrical collector generally outperformed 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.

Example 4 - Flotation of minerals The procedure of Example 3 was followed with the exception that the collector used was 0.018 of C12 alkylated benzene sulfonic acid and 0.006 kg of oleic acid per kg of mineral. The sulfonic and oleic components were pre-blended prior to addition to the cell. In all runsS the ratio of metal ions added was five parts Na+, two parts Mg++, and one part Fe+++ with the total amount of these ions added being sufficient to result in measured ionic strength of the water being equivalent to Na+ of 1000 ppm as measured by a conductivity cell. The results obtained are shown in Table IV below.
:

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W092/11091 2 0 9 ~ ~ 7 '~ PCT/US91/09371 ' ~
-43- !

TABLE IV
. Fractional Mineral Mineral Recovery Silica (SiO2) _ 0,041 Ca3~iterite (sno2) 0.833 : 5 _ Bauxite [Al(OH)3] 0.663 Calcite (CaC03) 0.707 _ .
Chromite (FeCr204) o.839 :
10Dolomite [CaMg(C03)2] 0.666 :-~
Malachlte IC~zC0310~21 O.715 0.715 _ Hematite (Fe2o3) 0 417 ~ :
Corundum (A203) 0.739 _ 15 Rutile (Tio2) 0.915 _. _ : Apatite [Cas(Cl1F)[PO~]3] 0.804 Nickel Oxide (NiO) ~ 0.494 Galena (PbS) 0.862 20Chalcopyrite (CuFeS2) ~ O 8bO
Chalcocite (CuzS) 0.825 Pyrite (FeS2) _ _ 0~595 Tourmaline 0.884 _ _ _ _ Sp~ ri~o ~LnS~ 0~797 _ Pentlandite [Ni(FeS)]~ 0.746 ~ 7_BaS4) 0.725 Molybdenite (MoS2) 0.900 .
.
' ' , ~' ' ~

W092/1tO91 Pcrlus91/o937l 2 0 9 ~ ~ I 4 -44- j TABLE IV (Continued) _ _ .
Fractional Mineral Mineral Recovery _ _ Cerussite (PbC03) o.839 Calcite (CaC03) 0.355 Beryl (Be3Al2Si60l8) 0.8`18 Covellite (Cu~) 0.766 Zircon (ZrSiO4) 0.784 lOGraphite (C) 0.922 Topaz [Al2sio4(FloH)2] 0.875 Scheelite (CaW04) ~.794 _ Anatase (TiO2) 0.860 Boehmite (yAlO-OHj 0.611 15Diaspore (aAlO-OH) 0.7l8 Goethite (HFeO2) 0.733 ~ Sample includes some pyrrhotite.
~ Sample compri-~es powdered elemental metal of similar size to other mineral samples.
.' The data in Table IV demonstrated the broad range of minerals which may have been floated using the collector composition and process of this invention.

Example 5 Sequential Flotation This example u~ed the Hallimond tube flotation 3 prooedure outlined in Example 1. In each case, the feed material was a 50/50 weight percent blend of the components listed in Table V. The specific collectors used (in the sodium ~alt form) and the mineral recoveries obtained are also listed in Table V below.
All runs were performed at a pH of 7Ø

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~, '~ '' ' ' ' ' . ' , ' 2 ~ 9 ~ 48 The above data demonstrat0d that various minerals subject to flotation in the process of the pre~ent invention may be effectively separated by the control of callector 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 apatits 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 example demonstrate~ that similar separations are possible using other minerals. It should also be noted that the asymmetrical collector consistently outperforms the symmetrical collector.

Example 6 - Separation of Apatite and Silica A series of 30-g samples of a -10 mesh (U.S.) mixture of 10 percent apatite (Cas(Cl,F)[P04]3) and 90 percent silica (SiO2) was prepared. Each sample of ore was 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 was transferred to a 300 ml flotation cell.

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

Z

WO92/11091 2 0 9 ~ ~ 7 ~ PCT/US91/09371 The float cell was agitated at 1800 RPM and air is introduced at a rate of 2~7 liters per minute. The froth concentrate was 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 were dried and analyzed as described in the previous examples. The results obtained are presented in Table VI below.

3~

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Table VI
. Phosphorus Recovery and Dosage (kg/met- _ Run Collector ric tor) Rec Gr 1l Dodecyl benzer.e sul~onic 0.150 0.172 0.121 . .
2l Dodecyl benzene sulfonic û.3ûû 0.432 0.142 3~ C20-22 benazceinde sulfonic 0.150 0.491 0.124 _ 4l C20-22 benzene sulfonic 0. 300 0.556 0.135 di-Dodecyl benzene 0.150 0.882 0.142 _ - sulfonic acid 6 di-Dodecyl benzene 0.300 0.940 0.118 sulfonic acid .
7 C20-22 Toluene sulfonic 0.150 0.915 0.155 8 C20-22 Toluene sulfonic 0.300 0.977 0.150 9 di-Nonyl napthalene 0.150 o.633 0.147 _ ~sulfonic acid ~

:

WO92/11~9t PCT/US91/U9371 _5 1 _ ,' Table VI (Cont . ) . . _ Phosphorus Grade (kg/met- ~ .
Run Colleotor ric ton) Rec Gr di-Nonyl napthalene 0.300 0.840 0.144 sulfonic acid 11l C24 benzene sulfonic acid 0.150 0.314 0.117 121 Cz4 benzene sulfonic acid 0.300 0.580 0.137 13 Mixture of di-octyl, 0.150 0.904 0.145 di-nonyl, and di-decyl benzene sulfonic acids2 14 Mixture of di-octyl, 0.150 0.844 0.141 di-nonyl, and di-decyl napthalene sulfonic acid~2 ~
di-Hexadecyl benzene 0.150 0.540 0.123 sulfonic acid ~
16 di-Hexyl benzene sulfonic 0.150 0.658 0.148 acid _ 17 Decyl Toluene sulfonic 0.150 0.688 0.154 ac i d . ~ :
18 Dodecyl Toluene sulfonic 0.150 0.773 0.137 acid _ .

WO92/1109l PCT/US91/09371 2 O 9 ~

Table VI (Cont . ) Phosphorus Recoverv and Crade (kg/met-Run Collector ric ton) Rec Gr _ _ __ 3 di Hexyl beanczledneulfonic0.025 0.500 0.133 acid 0.125 203 acid 0.025 0.588 0.140 Dodecyl benzene qulfonic 0.125 _ _ _ 213di Hexyl beancziedne 5ulfonic 0.050 0.517 0.135 _ Dodecyl benzene aulfonic 0.100 _ _ 223Dodecyl toluene sulfonic 0.050 0.6350.148 ::
acid acid 0.100 _ 233 acid 0.075 0.5440.140 acid 0.075 ~
: ' " ' '' ~ , . . , j ~ .
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wo 92/l1091 PCI/US91/09371 209~7~

T~ble VI (Cont . ) _ .
Phosphorus Grade Dosage .
Run Collector ric ton) Rec Gr _ . _ ___ 243 acid 0.075 0.692 0.153 _ acid 0.075 _ 253 di ~exyl beancZi~'dne sulfonic 0.100 0.609 0.149 Dodecyl benzene sulfonic 0.050 _ 263 acid 0.100 0.7440.160 _ acid 0.050 ~
273di-Dodecyl benzene 0.025 0.5440.115 ..
sulfonic acid Dodecyl benzene sulfonic 0.125 .
283di-Dodecyl benzene 0.050 0.6360.119 sulfonic acid Dodecyl benzene sulfonic 0.100 .
' :: ' ' ~'' '.' , .
. :
..

WO92~1l09~ PCT/US91/~9371 2 ~ 9 ~

Table VI (Cont.) Phosphorus Recovery and Grade (kg/met-RunCollector ric ton) Rec Gr 293di-Dodecyl benzene 0.075 0.755 0.140 ~ulfonic acid acid 0.075 .
303di-Dodecyl benzene 0.100 0.843 0.148 :-~ulfonic acid Dodecyl benzene sulfonic 0.050 :. .
ac i d 314di-Dodecyl benzene 0.150 0.914 0.152 ~ :
sulfonic acid ~ ::.
324C20-~-2 roluene sulfonic 0.150 0.947 0.167 _ acid _. _ _ :
334di-Dodecyl benzene 0.125 0.908 0.150 sulfonic acid .
. _ 344C20-22 Toluene sulfonic 0.125 0.947 0.161 _ . .
354di-Dodecyl benzene 0.100 0.873 0.148 sulfonic acid .
: 364C20-22 Toluene sulfonic 0.100 0.925 0.155 ,: - . :'-,:
', ' ~ ' .
, ,. , . : , . , W ~ 92/11091 2 0 9 ~ ~ 7 ~ P ~ /US91/09371 Table VI (Con~.) __ Pho phorus Recovery and Grade Dosage -(kg/met-Run Collector ric ton) Rec Gr 375 di-Dodecyl benzene 0.150 0.850 0.140 sulfonic acid _ 38fi di-Dodecyl benzene 0.150 0.837 0.138 sulPonic acid 397 di-Dodecyl benzene 0.150 0.776 0.137 sulfonic acid _ 408 di-Dodecyl benzene 0.150 0.610 0.135 -~ulfonic acid _ 411,8 Oleic Acid 0.150 0.606 0.131 _ _ 4235 di-Dodecyl benzene 0.125 0.876 0.141 qulfonic acid Oleic acid 0.025 . . _ _ 433,6 di-Dodecyl benzene 0.129 o. 867 0.140 sulfonic acid Oleic acid 0.025 .

4~3,7 di-Dodecyl ben7ene 0.129 0.844 0.139 sulfonic acid Oleic acid 0.025 _ __ 453,8 di-Dodecyl benzene 0.129 0,830 0.138 sulfonic acid Oleic acid 0.025 lNot an embodiment of the invention.
2In these runs, the collector is a mixture of the components listed.
3Mixture added together and then added to cellO
4Collector mixed with 0.150 kg/metric ton fuel oil #2 and both added to cell.
5Ionic strength of water used equivalent to 100ppm Na+
impounded by conductivity cell.
6Ionic strength of water u ed equivalent to 250ppm Na+
impounded by conductivity cell.
7Ionic strength of water used equivalent to 500ppm Na~
impounded by conductivity cell.
8Ionic strength of water used equivalent to 1000ppm Na~
impounded by conductivity cell.

:. , ' :
, .

wos2/1~9l PCT/US91/09371 2 ~ 7 ~

The data in Table VI demonstrate the effectiveneqs of the present invention. Runs 13-20 show the effect of mixing collectors of the present invention with similar monoalkylated species. Clearly the monoalkylated qpecies 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 showed 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 demonstrated that mixtures of the collectorq 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 ; 20 which is of economic benefit assuming the hydrocarbon is less expensive than the collector.

Runs 3 and 2~-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 7 - Separation of Apatite and Silica The procedure of Example 6 was followed with the exception that the water used to prepare each sample contained 5 parts Na+, 4 parts Ca++, 2 part~ Mg+~, and 1 part Fe+++ in the appropriate amounts to produce the ionic strengthq indicated in the Table VII. The ionic strengths were measured in Na+ equivalents using a conductivity cell. The results obtained are shown in Table VII below.

; 20 , :

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. ~ . . ..

W092/11091 2 0 ~ 8 ~ 7 ~ PCT/US9i/09371 -65~

The data in Table VII demonstrate the effectiveness of the present invention. It is of particular interest to note that the collector composition resulted in efficient reoovery of the desired minerals in water containing high amounts of salt~. When compared with either the sulfonate or carboxylate component alone, the combination results in enhanced recoveries. The importance o~ preferred ratios of sulfonate to carboxylate is demonstrated in, for example, Runs 15-17 and Runs 2-4.

Example 8 - 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 was prepared. The grade of copper in the ore was 0.013 and the grade of the molybdenum was 0.00016. Each sample of ore was ground in a laboratory swing mill for 10 seconds and the resulting fines were transferred to a 300 ml flotation cell.

Each run was conducted at a natural ore slurry pH of 6.5. The collector (in the sodium salt form) was added at a dosage of 0.150 kg/ton of dry ore and the - 30 slurry was allowed to condition for one minute. Ore concentrate wa collected by standard hand paddling between zero and four minutes. Just before flotation was initiated, a frother, a polyglycol ether available commercially from The Dow Chemical Company as Dowfroth~

.

2~9~S7~ -66-250 brand frother, was added in an amount equivalent to 0.030 kg/ton of dry ore.

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

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WO92/11091 PCTtUS91/09371 2 0 9 ~ r~ 7 ~

TABLE VIII
_ Dosage (kg/
met-ric Cu Cu Mo Mo Run Collector ton) Rec Grade Rec Grade 1~Dodecyl benzene 0.150 0.2350.131 0.291 0.024 sulfonic acid ._ 2di-Dodecyl benzene 0.150 0.7900.163 0.862 0.044 sulfonic acid _ . _ 2aC20-22 Toluene 0.150 0.8440.171 o.ga3 0.051 sulfonic acid ~
_ 3di-Nonyl napthalene 0.150 0.7130.156 0.825 0.040 sulfonic acid _ 4~C24 benzene 0.150 0.3390.141 0.357 0.026 sulfonic acid 5Mixture of di- 0.150 0.8030.164 0.877 0.045 octyl, di-nonyl, and di-decyl benzene sulfonic acids~
__ _ _ _ _ 6 di-Hexadecyl0.150 0.517 0.135 0.533 0.031 benzene sulfonic acid _ _ _ _ . .
7 di-Hexyl benzene0.150 0.557 0.161 0.560 0.034 sulfonic acid _ _ 7a Decyl Toluene0.150 0.622 0.163 0.625 0.038 sulfonic acid ~ _ 7b Dodecyl Toluene0.150 0.680 0.171 0.671 0.041 sulfonic acid ~ -8 di-Dodecyl benzene 0.300 0.854 0.157 0.901 0.043 sulfonic acid _ _ _ . _ . .
8a Dodecyl Toluene0.300 0.880 0.168 o.g29 0.045 sulfonic acid . _ _ _ . ~ .

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WO 92/l 1091 PCI /US91/09371 2~9~57~ -68-TABLE V I I I (Cont ) Do age ~ ~
mreitC Cu Cu Mo Mo Run Collector ton) Rec Crade Rec Grade 9Mixture of di- 0.1500.7480.165 o.839 0.046 octyl, di-nonyl, and di-decyl napthalene sulfonic acids~ _ 10~di-Dodecyl benzene 0.100o.8Q30.163 0.890 0.045 sulfonic acid Sodium ethyl 0.050 xanthate _ ~ . .
lOa~C20-22 Toluene 0.1000.8450.166 0.904 0.047 :
sulfonic acid Sodium ethyl 0.050 xanthate _ ::
11~di-Dodecyl benzene 0.0500.8100.165 0.903 0.046 sulfonic acid Sodium ethyl 0.100 .
xanthate 12~Sodium ethyl 0.1500.7990.161 0.721 0.035 xanthate ~Not an embodiment of the invention ~The collector is a mixture of the components listed.
~Collectors are added to the cell at the same time.
~Run conducted at a pH of 9~5.
.

. . -W0~2~11091 2 ~ 9 ~ PCT/US91/09371 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 ~nd 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 9 - Flotation of Mixed Copper Sulfide Ore Containing Molybdenum The procedure in Example 9 was followed with the exception that the water used contained 600 ppm Ca~+, 20 ppm Fe~+, 140 ppm S04= and 50 ppm Mg++.

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

Samples of the concentrates and the tailings were then dried and analyzed as described in the previous .' ' ~ ..

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WO92/11091 ~ PCT/US91/0937!
2 0 9 3 ~ 1 70 examples. The results obtained are presented in Table IX
below.
TABLE IX
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Dosage (kg/
metric Cu Cu Mo Mo ~ \ _ _ _ _ Run Collector ~un, Rec Grade Rec Grade _ . .:
1 di-Dodecyl benzene 0.145 0.724 0.150 o.783 o.o38 monosulfonate Sodium Oleate 0.005 2 di-Dodecyi benzene 0.140 0. 777 0.161 o .848 0.043 monosulfonate Sodium Oleate 0.010 _ _ 3 di-Dodecyl benzene 0. 135 0.765 o . l 61 0.829 0.042 monosulYonate Sodium Oleate 0. 015 _ _ .
4 di-Dodecyl benzene 0.120 0. 708 0.153 0.767 0.038 monosulfonate Sodium Oleate 0.030 .
_ .
di-Dodecyl benzene 0. 105 0.605 0.137 0.657 0.028 monosulfonate Sodium Oleate 0. 045 6 di-Dodecyl 0. 140 o .837 0.176 0.900 0.048 diphenyloxide monosulfonate Sodium Oleate 0.010 : .

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WO 92/1 10~1 2 ~ PCl/US91/09371 -71- ?

The data in the above table demonstrate the effectiveness of the present invention in the recovery of copper and molybdenum. In particular, it shows that, in this system, the ratio of sulfonate to oleate collector that is most effective is ranges from 30:1 to 2:1.

Example 1_ - Flotation of Iron Oxide Ore A series of 600-g samples of iron oxide ore from Michigan was prepared. The ore contained a mixture of hematite, martite, goethite and magnetite mineral species. Each 600-g sample was ground along with 400 g of deionized water (Runs 1-10) in a rod mill at about 60 RPM for ~O minutes. In Runs 11-40, water containing 300 ppm Ca+, 10 ppm Fe+++, 80 ppm S04-, 20 ppm Cl- and 40 ppm Mg++ was used. The resulting pulp was transferred to an Agitair 3000 ml flotation cell outfitted with an automated paddle removal system. The collector was added and the slurry was allowed to condition for one minute.
Next, an amount of a polyglycol ether frother equivalent to 40 g per ton of dry ore was added followed by another minute of conditioning.

The float cell was agitated at 900 RPM and air was introduced at a rate of 9.0 liters per minute.
Samples of the froth concentrate were collected at four minutes after the start of the air flow. Samples of the froth concentrate and the tailings were dried, weighed and pulverized for analysis. They were 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 ~ere calculated using standard mass balance formulas. The results are shown in Table X below.

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w092/llO9l PCT/US91/09371 209~57~ -72-TABLE X
_ :
Dosage .
Run Collector (kg/metric ton) Fe Rec Fe Grade _.
1~ Dodecyl benzene 0.300 0.151 0.397 ; 5 sulfonic acid 2~ Dodecyl benzene 0.600 0.260 o.466 sulfonic acid _ 2a Dodecyl toluene 0.300 0.294 0.417 sulfonic acid 2bDodecyl toluene 0.600 0.458 0.444 sulfonic acid _ . . _ .
: 2c~Decyl toluene 0.600 0.400 0.438 :
sulfonic acid 3di-Dodecyl benzene 0.300 0.578 0.563 sulfonic acid _ di-Dodecyl benzene 0.600 0.735 0.524 .
sulfonic acid .
4aC20-22 Toluene 0.300 0.680 0.574 sulfonic acid _ _ .
4bC20-22 Toluene 0.600 0.789 0.557 sulfonic acid - 5di-Nonyl napthalene 0.300 0.563 0.549 sulfonic acid _ 6di-Nonyl napthelene 0.600 0.712 0.511 sulfonic acid ~, 7~C24 benzene 0.300 0.307 0.478 sulfonic acid 8~C24 benzene 0.600 0.479 0.490 sulfonic acid _ : 9Mixture of di-octyl 0.600 0.758 0.530 3o and di-nonyl benzene sulfonic acids~ _ . . . , ~ , .
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, WO 9 ~/1 1091 PCI /US9 1/09371 2~393~7~

TABLE X (Cont . ) Dosage Run Collector ~kg/metric ton) Fe Rec Fe Grade Mixture of di- 0.600 o.698 0.509 octyl, di-nonyl and di-decyl benzene . .
qulfonic acids~
11 di-Dodecyl benzene 0.600 0. 588 O .489 :
sulfonic acid 10 12di-Dodecyl benzene 0.300 0.401 0.500 sulfonic acid : .
_ 13~Oleic Acid 0.300 o.488 0.477 14~Oleic Acid 0.600 0. 337 O .438 ~ .
15di-Dodecyl benzene 0. 300 0.694 O .523 sulfonic acid Oleic Acid~ 0. 300 _ Mixture of di-octyl 0. 300 O .417 O .513 and di-nonyl benzene sulfonic acids~
17Mixture of di-octyl O.300 o.703- 0.541 : and di~nonyl benzene sulfonic acids~
Oleic Acid~ 0. 300 25 18~Di-dodecyl benzene 0.600 0. 504 0.483 ::
sulfonic acid _ _ 19Di-dodecyl benzene 0. 550 O . 663 0. 483 sulfonic acid Oi~c ~Gi~ 0.050 .
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W~92/11091 PCT/US91/09371 03~5 ~4 -74-TABLE X (Cont . ) Dosage Run Collector (kg/metric ton) Fe Rec Fe_Grade _ Di-dodecyl benzene 0.500 0.723 0.526 sulfonic acid Oleic acid~ 0.100 21 Di-dodecyl benzene 0.450 0.735 0.528 sulfonic acid Oleic acid~ 0.150 _ 22 Di-dodecyl benzene 0.400 0.663 0.510 sulfonic acid Oleic acid0 0.200 . .
23 Di-dodecyl benzene 0.300 0.582 0.487 sulfonic acid Oleic acid~ 0.300 __ _ 24 Di-dodecyl benzene 0.538 0.585 0.481 sulfonic acid Tall oil fatty 0.062 acid~
: 25 Di-dodecyl benzene 0.475 0.668 0.544 sul~onic acid Tall oil fatty 0.125 ~: 25 acid _ 26 Di-dodecyl behzene 0.300 0.602 0.548 sul~onic acid Tall oil fatty 0.300 acid~
_ _ _ .

W09~ ngl ~39~5 7~ PCT/US9~/09371 ~75 -TABLE X (Cont . ) Dosage .
Run Collector (kg/metric .
ton) Fe Rec Fe Grade . _ 27Di-dodecyl benzene o.538 0. 527 0.491 sulfonic acid Oxalic acid~ O. 062 28Di-dodecyl benzene O. 475 0.6470.529 sulfonic acid Oxalic acid0 0.12 5 29Di-dodecyl benzene 0.300 O. 556 o .488 sulfonic acid Oxalic acid~ 0. 300 3oDi-dodecyl benzene O. 538 0.5110.476 sulfonic acid Tartaric acid~ O . U62 31Di-dodecyl benzene O. 475 0.5870.532 sulfonic acid Tartaric acid~ 0.125 _ 32Di-dodecyl benzene 0.300 O. 530 0.519 sulfonic acid t Tartaric acid~ O. 300 33Di-dodecyl benzene 0. 538 0.5400.484 sulfonic acid .
Dodecanoic acid~ 0.062 34Di-dodecyl benzene 0. 475 0.6270.530 sulfonic acid 3o Dodecanoic acid~ 0 125 .

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WO92/1~091 PCT/US91/09371 2~9~7~ -76- ~`

TABLE X (Cont.) _ . _ ..
Dosage RunCollector(kg/metric ton) Fe Rec Fe Grade 35Di-dodecyl benzeneO. 300 0.5630.544 sulfonic acid Dodecanoic acid~ 0.300 3~Tall oil fatty acid 0.6000.437 0.454 : 37~ Tall oil fatty acid O. 300 0.314 0.432 38~ Oxalic acid 0.600<0.1 __ _ _ 39~ Tartaric acid 0.600<0.1 __ . _ _ 40~ Dodecanoic acid 0.600O. 288 0.434 _ ~
~Not an embodiment of the invention ~The collector i~ a mixture of the components listed.
~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. An examination of Runs 11-40 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 or oleate was 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 runsO
Oleate 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.

Wog~ ogl 2~3a ~ PCT/US9l/09371 Example 11 - Separation of Apatite and Silica The procedure outlined in Example 6 was used with the exception that deionized water was replaced with water having 600 ppm Ca++, 20 ppm Fe~+, 140 ppm S04=, and 50 ppm Mg+~. The results obtained are shown in Table 5 VII below:
TABLE XI
Phosphorus Recovery Dosage and Grade Run Collector(kg/metric ton) Rec Grade 11Oleic Acid 0.025 0. 249 0.141 21Oleic Acid 0.050 0O350 0.139 31 -Oleic Acid 0.075 0.538 0,136 15 41Oleic Acid 0.150 0.671 0. 134 5di-Dodecyl benzene 0.150 0.5 34 0. l39 sulfonic acid _ _ 6di-Dodecyl benzene 0.125 0.449 0.141 sulfonic acid 7di-Dodecyl benzene 0.100 0.308 0.142 sulPonic acid _ 8di- Dodecyl benzene 0.075 0.217 0.144 sulfonic acid : :
_ _ _ 92Oleic Acid 0.025 0. 637 0.135 di-Dodecyl benzene sulfonic acid 0.125 __ .
102Oleic Acid 0.050 0.753 0.133 di-Dodecyl benzene sulfonic acid 0.100 _ _ _ _ _ 112Oleic Acid 0.075 0.814 0.132 3o di-Dodecyl benzene sulfonic acid 0.075 _ _ _ 122Oleic Acid 0~100 0.729 0.130 di-Dodecyl benzene sulfonic acid 0.050 _ , .:

Wo92tl109l PCT/US91/09371 2 a 9 ~ 78-TABLE XI (cont.) Phosphorus Recovery Dosageand Grade Run Collector (kg/metric ton) Rec Grade 133 Oleic Acid 0.075 0.790 0.133 di-Dodecyl benzene sulfonic acid 0.075 l . _ _ _ 14~ Oleic Acid 0.075 o.636 0.136 di-Dodecyl benzene sulfonic acid 0.075 _ _ 152 Fatty Acid~ 0.075 o.833 0.133 di-Dodecyl benzene sulfonic acid 0.075 .
163 Fatty Acid5 0.075 0.805 0.132 di-Dodecvl benzene sulfonic acid 0.075 174 Fatty Acid5 0.075 0.648 0.135 di-Dodecyl ben~ene sulfonic acid 0.075 18~ Fatty Acid5 0.075 o.863 00141 di-Dodecyl benzene sulfonic acid 0.075 ,, _ _ 1 9DFatty Acid5 0.050 0.885 0.142 di-Dodecyl benzene sulfonic acid 0.010 25lNot an embodiment of the invention.
2Two components mixed ~ogether before addition to cell.
3First component added to cell, conditioned for one minute followed by second component added to cell conditioned for one minute.
4Second component added to cell, conditioned for one minute followed by addition of first component added to cell 30conditioned for one minute.
5Mixture of oleic, linoleic and linoleic acids.
6Mixture added to grinding step.

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W092~11091 2 0 g " ~ 7 f~ pcr/~s~l/o~37l The data in Table XI 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 12 - 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 thorugh which air can be introduced was used.
Air was 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) were soaked in 50 cm3 of water containing sufficient sodium silicate to raise the slurry pulp pH to 9.5. The collector was added to the mixture and then it was mixed in a blender for 10 minutes. The collector concentration was 0.5 kg/metric tor. of dried printed material. The contents were transferred to the column cell and sufficient water is added to bring the slurry level to the top of the cell. Air was 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 de-inked fiber in the cell were made and a brightness meaurement was conducted on a light meter using white light as a basis~

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WO92/l1091 PCI/US91/09371 r -80 -2 0 ~

TABLE XI I
Dry Weight of Product (g) 5 Run Collector Bri~htness Ink PU 1 P Crncen-1di-Hexyl Benzene 50.2 0.117 o.883 sulfonic acid 21 Dodecyl Benzene 44. 7 0 . 183 0 . 817 sulfonic acid _ _ 3 Dodecyl toluene 53.3 0.105 o.895 sulfonic acid _ _ _ 4 Decyl toluene 52.1 0.110 0.890 sulfonic acid . ~ _ .
,, 5 di-Dodecyl benzene 59.9 0.087 0.913 sulfonic acid .
61 C24 benzene 48.3 0.260 0.740 sulfonic acid .
_ _ 7 C20-22 toluene 61.3 0.080 0.920 sulfonic acid .
1Not an embodiment of the invention .:

'

Claims (12)

AMENDED CLAIMS
[received by the International Bureau on 24 June 1992 (24.06.92);
original claim 1 amended; remaining claims unchanged (3 pages)]

1. A process for the recovery of minerals by froth flotation wherein an aqueous slurry of particulate minerals is subjected to froth flotation characterized by the use of a collector comprising (a) at least one aryl monosulfonic acid or salt thereof having at least two aryl substituents or mixtures of such salts or acids, or (b) a sulfonic component having at least one dialkylated benzene monosulfonic acid or a salt thereof and a carboxylic component comprising at least one C1-24 carboxylic acid or salt.

2. The process of Claim 1 wherein the collector comprises aryl monosulfonic acids or salts thereof wherein at least about 15 percent of such acids or salts have at least two alkyl substitutents

3. The process of Claim 1 or 2 wherein the aryl monosulfonic acid or salt thereof corresponds to the formula wherein each R1 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 12 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.

4. The process of Claim 3 wherein R1 is independently in each occurrence an alkyl group having from about 8 to about 12 carbon atoms.

5. The process of Claim 1 wherein the process is conducted at the natural pH of the slurry.

6. The process of Claim 1 wherein the collector further comprises a sulfide collector.

7. The process of Claim 6 wherein the sulfide collector is selected from the group consisting of xanthates, dithiol phosphates and trithiol carbonates.

8. The process of Claim 1 wherein the C1-24 carboxylic acid comprises a fatty acid or salt thereof.

9. The process of Claim 8 wherein the fatty acid or salt is selected from the group consisting of oleic acid or salt, linoleic acid or salt, linolenic acid or salt and mixtures thereof.

10. A collector composition comprising (1) at least one dialkylated benzene monosulfonic acid or salt thereof or mixtures of such salts or acids and (2) a fatty acid or salt thereof.

11. The composition of Claim 10 wherein the fatty acid or salt thereof is selected from the group consisting of oleic acid or salt thereof, linoleic acid or salt thereof, linolenic acid or salt thereof and mixtures thereof.

12. The process of Claim 1 wherein the recovered mineral comprises ink and the aqueous slurry comprises pulped paper.