WO2018197476A1

WO2018197476A1 - Collectors for beneficiation of phosphate from phosphate containing ores

Info

Publication number: WO2018197476A1
Application number: PCT/EP2018/060455
Authority: WO
Inventors: Alexej Michailovski; Sylvia Von Krog; Tamara KUELZER; Adrian Mauricio VILLANUEVA BERINDOAGUE
Original assignee: Basf Se
Priority date: 2017-04-25
Filing date: 2018-04-24
Publication date: 2018-11-01

Abstract

The present invention relates to a collector composition for beneficiation of phosphates from phosphate containing oresand their use inflotation processes and to a method for beneficiation of phosphates using said collector composition.

Description

Collectors for beneficiation of phosphate from phosphate containing ores DESCRIPTION The present invention relates to a collector composition for beneficiation of phosphates from phosphate containing ores, their use in flotation processes and to a method for beneficiation of phosphates using said collector composition.

BACKGROUND OF THE INVENTION

A majority of phosphate fertilizer supply is produced by processing sedimentary phosphate ores. The global depletion of easily accessible high-grade phosphate deposits leads to a rising demand of beneficiation technologies in phosphate ore processing, in order to make low-grade phosphate rock accessible as phosphate source. In principle, the phosphate containing ores are processed to achieve an apatite concentrate, which is further processed to phosphoric acid and then into fertilizers. Typically, flotation processes, either direct and/or reverse flotation processes are applied for the beneficiation of phosphate containing ores and often several flotation stages are required. The froth flotation as separation technology in principle makes use of differences in hydrophobicity between the valuable desired material and the waste gangue impuri- ties. For phosphate ores, the type of phosphate deposit affects the flotation performance. For sedimentary deposits of phosphate ores, the desired phosphate concentration can be achieved by flotation of silicate impurities from the finely ground phosphate containing ores (reverse flotation) when the gangue impurities essentially consist of siliceous materials. For sedimentary phosphates with high carbonates, however, beneficiation of phosphate ores by separation of carbonate from phosphate presents especial difficulties since it requires a reagent selective between two chemically similar surfaces (apatite vs. calcite) (H. Sis et al., Minerals Engineering, 16 (2003) 577 - 585).

Both, direct apatite flotation (e.g. from igneous ores) and reverse flotation (flotation of the car- bonate and/or silicate impurities contained in the phosphoric rock) typically use fatty acid based collector systems as reagents to increase the differences in hydrophobicity between the desired and undesired material. The main primary collectors are based on partly unsaturated fatty acids (C12-C18), which are employed at pH 4-5, with phosphoric acid as depressant. Since fatty acids are badly soluble in water at that pH, secondary collectors are used, typically anionic or nonionic surfactants, to improve selectivity and recovery.

Surfactants are amphiphilic interface-active compounds which comprise a hydrophobic molecular moiety and also a hydrophilic molecular moiety and, in addition, can have charged and uncharged groups. Surfactants are orientedly absorbed at interfaces and thereby reduce the inter- facial tension so that these can form, in solution, association colloids above the critical micelle- formation concentration, meaning that substances which are per se water-insoluble are solubil- ized. On account of these properties, surfactants are used, for example, for wetting such as fibers or hard surfaces. Typical files of application are detergents and cleaners for textiles and leather, as formulation of paints and coatings and also for example in the flotation process of non-sulfidic ores.

Especially in reverse flotation, the effect of a secondary collector on flotation performance is crit- ical due to the low solubility and limited self-emulsification ability of fatty acids at low pH, which in turn is required to achieve selectivity between carbonates and phosphates (e.g. calcite and apatite). A common class of high performance flotation additives for phosphate beneficiation are alkyl phenol ethoxylates (APEOs), powerful emulsifying additives with a hazardous environmental profile whose application is restricted or banned in many jurisdictions. Other suitable second- ary collectors are sulfonate compounds. With these compounds a typical P2O5 grade of up to 30 wt% can be achieved starting with a typical sedimentary ore containing approx. 15 to 20 wt% P2O5. In particular, in the fertilizer industry however, P2O5 content larger than 30 % is often required. Nonionic surfactants based on alkoxylated alcohols as secondary collector are commonly not able to achieve the desired selectivity.

WO 2010070088 describes mixtures of surfactants comprising branched short-chained and branched long-chained components, which are alkoxylation products of alkanols. The short- chained alkanols contain 8 to 12 carbon atoms, C2-10 alkoxy groups and a degree of branching of at least 1. The long-chained alkanols contain 15 to 19 carbon atoms, C2-10 alkoxy groups and a degree of branching of at least 2.5.

US 86571 18 discloses a collector for the separation of phosphate by flotation of carbonates contained in non-sulfurous minerals, particularly phosphoric rock, preferably apatite. The collector comprises phosphoric ester.

WO 2016041916 discloses the use of branched fatty alcohol-based compounds selected from the group of fatty alcohols with 12-16 carbon atoms having a degree of branching of 1 -3, and their alkoxylates with a degree of ethoxylation of up to 3, as secondary collector for the froth flotation of non-sulfidic ores in combination with a primary collector selected from the group of am- photeric and anionic surface-active compounds. The use for reverse flotation is not disclosed.

EP 0270933 discloses the use of branched fatty alcohols and their alkoxylates. The described compositions in EP 0270933 are only suitable to achieve a grade of less than 31 % which may cause problems because of high dosing.

SUMMARY OF THE INVENTION

In the light of the prior art the technical problem underlying the present invention was the provision of collector compositions that overcome the disadvantages of those compositions known in the art. The collector compositions of the present invention are at least binary or ternary compositions that are suitable for direct and/or reverse flotation processes, show increased selectivity, offer the possibility of dose reduction and can be used for beneficiation of phosphate from phosphate containing ores. The process for flotation enables short process times and overcomes the disadvantages known in the art. The problem is solved by the features of the independent claims. Preferred embodiments of the present invention are provided by the dependent claims.

The invention therefore relates to a collector composition for beneficiation of phosphates from phosphate containing ores comprising

i. a component A,

ii. at least one component B, and

iii. at least one component C,

wherein the component A comprises saturated or unsaturated fatty acids or derivatives thereof having 12 to 22 carbon atoms, wherein the component B comprises non-ionic surfactants comprising alkoxylated branched alcohols, wherein the component C comprises non-ionic surfactants or anionic surfactants comprising alkoxylated branched alcohols or sulfur-containing surfactants, and wherein the component C is different to component B. In a preferred embodiment the component A is selected from the group consisting of a saturated or unsaturated fatty acid with 12 to 22 carbon atoms or mixtures thereof, a fatty acid blend with > 90% C16-C18 fatty acids and with an average unsaturation degree of 0.5-3, oleic acid, tall oil, resins, fatty acid peptides of the formula Cn-iHbn-iCO-NH-R with R being a residue of natural or artificial amino acids comprising glycine, sarcosine or taurine.

In a preferred embodiment the alkoxylated branched alcohols of component B comprise alcohols with 9 to 18 carbon atoms.

In a preferred embodiment the component C is selected from the group consisting of sulfonated fatty acids, dialkyl sulfosuccinates, di- or tetraalkyl sulfosuccinamates, sodium dodecyl sulfate, dioctyl sulfosuccinate, alkyl ether sulfates, alkyl benzenesulfonates, alkoxylated branched alcohols with alcohols with 6 to 20 carbon atoms, alkyl sulfates of the formula C_nH2n+iOS03^" with n=12 to 22. In a preferred embodiment the degree of alkoxylation of component B is in the range of 0.1 to 15.

In a preferred embodiment the degree of alkoxylation of the branched alkoxylated alcohol of component C is in the range of 1 to 30.

In a preferred embodiment the degree of branching of the alkoxylated branched alcohols of component B and/or component C is in average in the range of 1 to 5.

In a preferred embodiment the HLB value of component B is in average in the range of 5 to 15.

In a preferred embodiment the HLB value of component C is in average in the range of 8 to 18.

In a preferred embodiment the amount of component A in weight-% (wt%) in relation to the total collector composition is in the range from 50 wt% to 99.9 wt%. In a preferred embodiment the amount of component B in weight-% (wt%) in relation to the total collector composition is in the range from 0.1 wt% to 50 wt%.

In a preferred embodiment the amount of component C in weight-% (wt%) in relation to the total collector composition is in the range from 0.1 wt% to 40 wt%.

In a preferred embodiment the collector composition comprises one or more modifiers and/or one or more frothers and/or one or more depressants. A further aspect of the invention relates to the use of a collector composition for beneficiation of phosphates from phosphate containing ores, wherein the collector composition comprises i. a component A, and

ii. at least one component B,

wherein the component A comprises saturated or unsaturated fatty acids or derivatives thereof having 12 to 22 carbon atoms, and wherein the component B comprises non-ionic surfactants comprising alkoxylated branched alcohols.

In a preferred embodiment the collector composition is used for beneficiation of phosphates from phosphate containing ores, wherein the collector composition comprises

i. a component A,

ii. at least one component B, and

iii. at least one component C,

wherein the component A comprises saturated or unsaturated fatty acids or derivatives thereof having 12 to 22 carbon atoms, wherein the component B comprises non-ionic surfactants com- prising alkoxylated branched alcohols, wherein the component C comprises non-ionic surfactants or anionic surfactants comprising alkoxylated branched alcohols or sulfur-containing surfactants, and wherein the component C is different to component B.

In a preferred embodiment the collector composition is used for direct flotation of phosphates by collecting phosphate in the froth.

In a preferred embodiment the collector composition is used for reverse flotation of phosphates by collection of impurities from phosphate containing ores in the froth. In a preferred embodiment the collector composition is used for beneficiation of phosphates by flotation from sedimentary phosphate containing ores and/or from igneous phosphate containing ores.

In a preferred embodiment the collector composition is used for beneficiation of phosphates from phosphate containing ores, wherein the component A is selected from the group consisting of a saturated or unsaturated fatty acid having 12 to 22 carbon atoms or mixtures thereof, a fatty acid blend with > 90% Ci6 to Cie fatty acids with an unsaturation degree of 0.5 to 3, oleic acid, tall oil, resins, fatty acid peptides of the formula Cn-iHbn-iCO-NH-R with R being a residue of natural or artificial amino acids comprising glycine, sarcosine or taurine. In a preferred embodiment the collector composition is used for beneficiation of phosphates from phosphate containing ores, wherein the alkoxylated branched alcohols of component B comprise alcohols having 9 to 18 carbon atoms. In a preferred embodiment the collector composition is used for beneficiation of phosphates from phosphate containing ores, wherein the component C is selected from the group consisting of sulfonated fatty acids, dialkyl sulfosuccinates, di- or tetraalkyl sulfosuccinamates, sodium do- decyl sulfate, dioctyl sulfosuccinate, alkyl ether sulfates, alkyl benzenesulfonates, alkoxylated branched alcohols with alcohols having 6 to 20 carbon atoms, alkyl sulfates of the formula C_nH₂n₊iOS0₃- with n=12 to 22.

In a preferred embodiment the collector composition is used for beneficiation of phosphates from phosphate containing ores, wherein the degree of alkoxylation of component B is in the range of 0.1 to 15.

In a preferred embodiment the collector composition is used for beneficiation of phosphates from phosphate containing ores, wherein the degree of alkoxylation of the branched alkoxylated alcohol of component C is in the range of 1 to 30. In a preferred embodiment the collector composition is used for beneficiation of phosphates from phosphate containing ores, wherein the degree of branching of the alkoxylated branched alcohols of component B and/or component C is in average in the range of 1 to 5.

In a preferred embodiment the collector composition is used for beneficiation of phosphates from phosphate containing ores, wherein the HLB value of component B is in average in the range of 5 to 15.

In a preferred embodiment the collector composition is used for beneficiation of phosphates from phosphate containing ores, wherein the HLB value of component C is in average in the range of 8 to 18.

In a preferred embodiment the collector composition is used for beneficiation of phosphates from phosphate containing ores, wherein the amount of component A in weight-% (wt%) in relation to the total collector composition is in the range from 50 wt% to 99.9 wt%.

In a preferred embodiment the collector composition is used for beneficiation of phosphates from phosphate containing ores, wherein the amount of component B in weight-% (wt%) in relation to the total collector composition is in the range from 0.1 wt% to 50 wt %. In a preferred embodiment the collector composition is used for beneficiation of phosphates from phosphate containing ores, wherein the amount of component C in weight-% (wt%) in relation to the total collector composition is in the range from 0.1 wt% to 40 wt%. The invention further relates to a flotation process for beneficiation of phosphates from phosphate containing ores comprising the collector composition of the present invention.

In a preferred embodiment the flotation process according to the present invention is direct flo- tation of phosphates comprising the steps

Comminution of ores,

Optionally, conditioning of ores with depressants and/or activators,

pH adjustment,

Collector addition,

- Flotation,

Collection of phosphate in the froth.

In a preferred embodiment the flotation process according to the present invention is reverse flotation of phosphates by collection of impurities from phosphate containing ores in the froth comprising the steps

Comminution of ores,

Optionally, conditioning of ores with depressants and/or activators,

pH adjustment,

Collector addition,

- Flotation,

Collection of carbonate and/or other impurities in the froth,

Optionally, removal of silicate minerals by additional reverse flotation stage using in particular cationic collector,

Recovering of phosphates from the cell product.

In a preferred embodiment in the flotation process according to the present invention the phosphate containing ores are pretreated to remove silicates.

In a preferred embodiment in the flotation process according to the present invention one or more modifiers and/or one or more frothers and/or one or more depressants are used.

In a preferred embodiment in the flotation process according to the present invention the collector composition comprises

i. a component A,

ii. at least one component B, and

iii. at least one component C,

wherein the component A comprises saturated or unsaturated fatty acids or derivatives thereof having 12 to 22 carbon atoms, wherein the component B comprises non-ionic surfactants comprising alkoxylated branched alcohols, wherein the component C comprises non-ionic surfac- tants or anionic surfactants comprising alkoxylated branched alcohols or sulfur-containing surfactants, and wherein the component C is different to component B.

In a preferred embodiment in the flotation process according to the present invention the component A is selected from the group consisting of a saturated or unsaturated fatty acid having 12 to 22 carbon atoms or mixtures thereof, a fatty acid blend with > 90% Ci6 to Cie fatty acids with an unsaturation degree of 0.5 to 3, oleic acid, tall oil, resins, fatty acid peptides of the formula Cn-i H2n-iCO-NH-R with R being a residue of natural or artificial amino acids comprising glycine, sarcosine or taurine.

In a preferred embodiment in the flotation process according to the present invention the alkox- ylated branched alcohols of component B comprise alcohols having 9 to 18 carbon atoms.

In a preferred embodiment in the flotation process according to the present invention the com- ponent C is selected from the group consisting of sulfonated fatty acids, dialkyl sulfosuccinates, di- or tetraalkyl sulfosuccinamates, sodium dodecyl sulfate, dioctyl sulfosuccinate, alkyl ether sulfates, alkyl benzenesulfonates, alkoxylated branched alcohols with alcohols having 6 to 20 carbon atoms, alkyl sulfates of the formula C_nH2n+iOS03^" with n=12 to 22. In a preferred embodiment in the flotation process according to the present invention the degree of alkoxylation of component B is in the range of 0.1 to 15.

In a preferred embodiment in the flotation process according to the present invention the degree of alkoxylation of the branched alkoxylated alcohol of component C is in the range of 1 to 30.

In a preferred embodiment in the flotation process according to the present invention the degree of branching of the alkoxylated branched alcohols of component B and/or component C is in average in the range of 1 to 5. In a preferred embodiment in the flotation process according to the present invention the HLB value of component B is in average in the range of 5 to 15.

In a preferred embodiment in the flotation process according to the present invention the HLB value of component C is in average in the range of 8 to 18.

In a preferred embodiment in the flotation process according to the present invention the amount of component A in weight-% (wt%) in relation to the total collector composition is in the range from 50 wt% to 99.9 wt%. In a preferred embodiment in the flotation process according to the present invention the amount of component B in weight-% (wt%) in relation to the total collector composition is in the range from 0.1 wt% to 50 wt %.

In a preferred embodiment in the flotation process according to the present invention the amount of component C in weight-% (wt%) in relation to the total collector composition is in the range from 0.1 wt% to 40 wt%. In a preferred embodiment in the flotation process according to the present invention for direct flotation for beneficiation of phosphates from phosphate containing ores, the collector composition comprises in weight-% (wt%) in relation to the total collector composition an amount of 60 wt% to 75 wt% of component A and an amount of 5 wt% to 35 wt% of component B and an amount of 5 wt% to 20 wt% of component C.

In a preferred embodiment in the flotation process according to the present invention for reverse flotation for beneficiation of phosphates from phosphate containing ores, the collector composition comprises in weight-% (wt%) in relation to the total collector composition an amount of 60 wt% to 75 wt% of component A and an amount of 5 wt% to 35 wt% of component B and an amount of 5 wt% to 20 wt% of component C.

DETAILED DESCRIPTION OF THE INVENTION In a first aspect the invention relates to a collector composition for beneficiation of phosphates from phosphate containing ores comprising

i. a component A,

ii. at least one component B, and

iii. at least one component C,

wherein the component A is a saturated or unsaturated fatty acid or derivative thereof having 12 to 22 carbon atoms or mixtures thereof, wherein the component B is a non-ionic surfactant comprising alkoxylated branched alcohols, wherein the component C is a non-ionic surfactant or anionic surfactant comprising alkoxylated branched alcohols or sulfur-containing surfactants, and wherein the component C is different to component B. The component A in particular falls under the term "primary collector", the component B and/or C in particular falls under the term "secondary collector".

Surprisingly, it was found that alcohol alkoxylates containing branched alcohol moieties with a branching degree of at least 1 are significantly more suitable to achieve high selectivity in froth flotation for beneficiation of phosphates when used as surfactant in combination with fatty acids. This can be achieved by using the non-ionic surfactants alone or as a blend with sulfonate emulsifiers. It is especially pronounced when ethoxylated Tridecanol A or Tridecanol N, or other branched oxo-alcohols, or ethoxylated Guerbet alcohols, are used as surfactant respectively as main components of surfactant (> 10% of the surfactant by weight, respectively > 2% of the overall collector composition by weight). The use of such blends allows a significant increase in flotation selectivity, allowing concentrates with more than 30wt% P2O5, for example 31 -33wt% P2O5 to be achieved without additional loss of apatite into the flotation slurry compared to the state of the art. A further advantage of the present invention is that for example the use of a combination of two different components A and B in reverse phosphate flotation makes phosphate containing sedimentary ores accessible to phosphate beneficiation processes. Furthermore, it is an advantage that a ternary collector composition comprising at least the components A, B and C can effi- ciently be used for direct and/or reverse flotation of phosphate containing ores in order to increase the flotation selectivity and/or recovery. In particular surprising was that a combination of two different non-ionic surfactants as collectors (components B and C) in reverse phosphate flotation leads to improved grades of P2O5. Surprisingly, the combination of non-ionic surfactants (components B and C) as collectors is suitable for direct and/or reverse flotation and improves the flotation performance with regard to improved grades and/or recoveries of P2O5. Unexpected was also that the use of a combination of two non-ionic surfactants (components B and C) for the flotation of igneous and/or sedimentary phosphate ores leads to improved grades of P₂0₅.

As used herein, the term "phosphoric rock" or "phosphoric ore" relates to the ore sources, which in particular comprises phosphates. Phosphates are the desired or valuable material or mineral, which can be part of sedimentary phosphate deposits or igneous phosphate deposits. "Phosphate rock" or "phosphoric ore" falls under the general term of "non-sulfidic ores".

As used herein, the term "impurities" relates to undesired material or mineral as component in phosphoric rock. The undesired material is also named gangue or waste. Impurities may comprise for example carbonates (e.g. calcite, dolomite), silicates, and/or scheelite. Impurities can also comprise silicate minerals such as quartz, feldspar or syenite minerals, layered silicates (micas, clays) or organic materials. The typical composition of phosphates preferably comprises different subtypes of apatite structure, such as for example fluoroapatite, hydroxoapatite, car- bonatoapatite, chloroapatite or their combinations, also known as frankolyte.

As used herein, the term "flotation" relates to the separation of minerals based on differences in their hydrophobicity and their different ability to adhere or attach to air bubbles. Aim of flotation as mineral processing operation is to selectively separate certain materials. In particular, the flotation is used for beneficiation of phosphates from phosphate containing ores. Flotation comprises froth flotation methods like for example direct flotation or reverse flotation. Direct flotation of phosphates refers to methods where in particular phosphates are collected in the froth and the impurities remain in the slurry. Reverse flotation or inverse flotation of phosphates relates to methods where the impurities as undesired materials are collected in the froth and the phosphates remain in the slurry as cell product. In particular, reverse flotation of phosphates is similar to direct flotation of carbonates. Cell product has the similar meaning as cell underflow or slurry and means the product remaining in the cell in particular in reverse flotation processes. Froth product means the product obtained in the froth in particular in direct flotation processes. The term "concentrate" has the meaning of flotation product and refers to the material obtained as cell product (valuable material) in reverse flotation processes as well as to froth product as the material obtained in the froth (valuable material) in direct flotation processes. The term tailings or flotation tailings is understood economically and means the undesired product, impuri- ties which are removed in direct or reverse flotation processes.

As used herein, the term "collector" relates to substances with the ability to adsorb to an ore particle and to make the ore particle hydrophobic in order to enable that the ore particles can attach to air bubbles during flotation. The collector may comprise for example at least one or two or three different collectors. A collector composition may comprise collector components which are named for example primary, secondary, ternary collector and can influence the collector composition properties. A collector composition comprises in particular mixtures of fatty acids and surfactants. The collectors can in particular be surface active, can have emulsification properties, can act as wetting agent, can be a solubility enhancer and/or a foam or froth regulator.

As used herein, the term hydrophilic-lipophilic balance (HLB) refers to the degree to which a substance, in particular a surfactant is hydrophilic or lipophilic. The HLB value is determined by calculating values for the different regions of the molecule, as for example described by Davies.

As used herein, the term "grade" relates to the content of the desired mineral or valuable or targeted material in the obtained concentrate after the enrichment via flotation. In particular, grade is the concentration of P2O5 obtained by the phosphate flotation process. The grade in particular refers to the P2O5 concentration and describes the content of P2O5 in the concentrate (w/w), particularly in the froth product at direct phosphate flotation and the content of P2O5 in the cell product in reverse phosphate flotation.

As used herein, the term "recovery" refers to the percentage of valuable material recovered af- ter the enrichment via flotation. The relationship of grade (concentration) vs. recovery (amount) is a measure for the selectivity of froth flotation. The selectivity increases with increasing values for grade and/or recovery. With the selectivity the effectiveness / performance of the froth flotation can be described. As used herein, the term "degree of branching" refers to the degree of branching of an alcohol which arises from the branches of the carbon backbone. For each alcohol molecule, it is defined as the number of carbon atoms which are bound to three further carbon atoms, plus two times the number of carbon atoms which are bonded to four further carbon atoms. The average degree of branching of an alcohol mixture arises from the sum of all degrees of branching of the individual molecules divided by the number of individual molecules. The degree of branching is determined, for example by means of NMR methods. This can be carried out through analysis of the carbon backbone with suitable coupling methods (COSY, DEPT, INADEQUATE), followed by a quantification via ¹³C NMR with relaxation reagents. However, other NMR methods or GC-MS methods are also possible.

Preferably, the component A comprises fatty acids or derivatives thereof, for example saturated or unsaturated fatty acids with at least 12 carbon atoms. Preferably the fatty acids or derivatives thereof comprise 12 to 22 carbon atoms, more preferably 14 to 20 carbon atoms and most preferably 16 to 18 carbon atoms. Also preferred is a component A which comprises a fatty acid blend of 12 to 22 carbon atoms with more than 50 % C12 fatty acids. Further preferred is that component A comprises a fatty acid blend with 90% or more C16 to C18 fatty acids and with an average unsaturation degree of 0.5 to 3. The meaning of for example "fatty acids with 12 to 22 carbon atoms" is similar to the meaning of for example "C12 to C22 fatty acids". It is preferred, that the component A is a natural product from plant or vegetable source or from animal source. The main source of component A besides palm oil and vegetable oils are tallow (animal) and tall oil (wood pulp side product). In particular, component A is a blend or mixture of fatty acids. The component A for example can contain different side products. Such side products may have an influence on the performance of the component A as collector in froth-flotation of non-sulfidic ores in particular during direct and/or reverse flotation of phosphates from phosphate containing ores. Oleic acid or a blend comprising oleic acid is a preferred substance for component A. Particularly preferred are also tall oil fatty acids (TOFA). Tall oil can be obtained as wood pulp side product. Tall oil comprises for example a fatty acid blend of oleic acid, linoleic acid, conjugated linoleic acid, stearic acid and for example other fatty acids and/or other components. Compo- nent A, in particular TOFA, can comprises resins in addition to the fatty acids or the fatty acid blend. Component A can also comprise fatty acid ester or fatty acid peptides. Component A can influence the hydrophobicity of foams in froth flotation for beneficiation of phosphates from phosphate containing ores. Component A in particular acts as primary collector in froth flotation processes.

Further preferred as component A are fatty acid blends derived from, for example, soybean oil or rapeseed oil as vegetable oils. In particular, component A with an amount of about 70% or more of C22 fatty acids is preferred, which for example may derive from rapeseed oil. It is preferred, that the component B in particular comprises non-ionic surfactants. It is preferred that component B is a branched alkoxylated alcohol. Ethoxylated isotridecanol grades are preferred as component B. In particular, the component B can be used as secondary collector in froth flotation of non-sulfidic ores, in particular phosphoric ores. It is preferred, that the component C is in particular a non-ionic surfactant or an anionic surfactant or a mixture thereof. It is further preferred that component C is a blend of non-ionic surfactants or of anionic surfactants or a mixture thereof. In particular, the component C can act as secondary and/or ternary collector in froth flotation of non-sulfidic ores, in particular phosphoric ore. Preferably, component C comprises sulfonated fatty acids, dialkyl sulfosuccinates, di- or tetraalkyl sulfosuccinamates, sodium dodecyl sulfate, alkyl ether sulfates, alkyl benzenesul- fonates. Dioctyl sulfosuccinate is a preferred component C. Also preferred as component C are for example sulfonates or sulfates like dodecylbenzene sulfonic acid or salts thereof, sodium lauryl sulfate, sodium laureth sulfate, sodium coco sulfate, alkyl sulfates, alkyl sulfonates, petroleum sulfonates. It is further preferred that component C is a branched alkoxylated alcohol. Eth- oxylated isotridecanol grades are preferred as component C, wherein the ethoxylated isotridecanol grade of component C is in particular different to the ethoxylated isotridecanol grade of component B. In particular, the collector composition of the present invention comprises at least two different ethoxylated isotridecanol grades. Preferably the difference between component B and component C is in the degree of ethoxylation. Further preferred is that component B and component C have different HLB values. The average number of alkoxy groups arises from the sum of all alkoxy groups of the individual molecules divided by the number of individual molecules. In particular, "degree of alkoxylation" means the average molar ratio between the molecule which gets alkoxylated (reaction with oxiran or alkyloxirans), and the selected respective (alkyl)oxirans. Preferably, the collector composition according to the present invention comprises a component B which comprises the alkoxylation product of branched alcohols, where the alcohols have 9 to 18, preferably 10 to 17, more preferably 1 1 to 15 and most preferably 12 to 14 carbon atoms. It is in particular preferred that the alkoxylated alcohols have 13 carbon atoms. The component B of the collector composition can comprise only one of such alcohols, but in particular comprises a mixture of such alcohols.

Preferably, the collector composition according to the present invention comprises a component C which comprises the alkoxylation product of branched alcohols, where the alcohols have 6 to 20, preferably 8 to 18, more preferably 10 to 16 and most preferably 12 to 14 carbon atoms. It is in particular preferred that the alkoxylated alcohols have 13 carbon atoms. The component C of the collector composition can comprise only one of such alcohols, but in particular comprises a mixture of such alcohols. Preferably, the degree of alkoxylation of the alcohols for the component B in the collector composition according to the present invention assumes, on average, values in the range from 0.1 to 15, preferably from 1 to 12, more preferably from 1 to 10, even more preferred from 2 to 7 and most preferably from 3 to 5. As degree of alkoxylation of the alcohols for the component B any value between these values or ranges thereof are also preferred. It is in particular preferred that the degree of alkoxylation of the alcohols for the component B is about 3, 4, 5, 6, 7, 8, 9 or 10.

Preferably, the degree of alkoxylation of the alcohols for the component C in the collector composition according to the present invention assumes, on average, values in the range from 1 to 30, preferably from 2 to 25, more preferably from 4 to 20 and most preferably from 6 to 15. It is in particular preferred that the degree of alkoxylation of the alcohols for the component C is about 7, 8, 9, 10, 1 1 , 12, 13, 14 or any value between these values or ranges thereof.

It is further preferred that the difference in degree of alkoxylation between component B and C in the collector composition according to the present invention assumes, on average, values in the range from 1 to 20, preferably from 1 to 16, more preferably from 2 to 14 and most preferably from 3 to 12. It is in particular preferred that the difference in degree of alkoxylation between component B and C is in the range from 4 to 10. Preferably, the alkoxy groups are C2-Cio-alkoxy groups, for example ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy and decoxy groups. However, preference is given to ethoxy, propoxy, butoxy, and pentoxy. Ethoxy, propoxy and butoxy groups are more preferred. More preferred still are ethoxy and propoxy groups. Particular preference is given to ethoxy groups. It is possible for the alkoxylation to take place in random distribution or blockwise, meaning that the aforementioned alkoxy groups - whether these are different - occur blockwise.

It is preferred if the alcohol mixture of component B has an average degree of branching from 1 to 5, preferably from 1 .5 to 4.5, more preferably from 2 to 4 and most preferably from 2.5 to 3.5. It is in particular preferred that the degree of branching is about 3. It is preferred if the alcohol mixture of component C has an average degree of branching from 1 to 5, preferably from 1 .5 to 4.5, more preferably from 2 to 4 and most preferably from 2.5 to 3.5. It is in particular preferred that the degree of branching is about 3. Preferably the HLB value of component B is in the range of 5 to 15, preferably in the range from 6 to 14, more preferably in the range from 7 to 13 and most preferably in the range from 7.5 to 12.5. It is in particular preferred that the HLB value of the component B is in the range of 8 to 12. Further preferred HLB value of the component B are about 8.1 , 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1 , 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1 , 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 1 1.0, 1 1 .1 , 1 1.2, 1 1.3, 1 1 .4, 1 1.5, 1 1.6, 1 1 .7, 1 1.8, 1 1.9 or any value between these values or ranges thereof.

Preferably the HLB value of component C is in the range of 8 to 18, preferably in the range from 8 to 17, more preferably in the range from 8 to 16 and most preferably in the range from 8.5 to 15.5. It is in particular preferred that the H LB value of the component C is in the range of 9 to 15. Further preferred HLB value of the component C are about 9.1 , 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1 , 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 1 1 .0, 1 1.1 , 1 1.2, 1 1 .3, 1 1 .4, 1 1.5, 1 1 .6, 1 1 .7, 1 1.8, 1 1.9, 12.0, 12.1 , 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1 , 13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, 14.0, 14.1 , 14.2, 14.3, 14.4, 14.5, 14.6, 14.7, 14.8, 14.9 or any value between these values or ranges thereof.

The hydrophilic lipophilic balance (HLB) characterizing the components of the present collector composition has a massive impact on both the collector adsorption selectivity and on froth properties, ultimately affecting the flotation kinetics. It was unexpected that a combination of collec- tor components with different HLB value can effectively enhance the performance of the collector system using an environmentally friendly APEO-free additive system. By that surprisingly the collector composition of the present invention in particular leads to improved flotation plant performance in both igneous and/or sedimentary phosphate ores, combining enhanced metallurgical characteristics with a reduction in reagent cost.

It is preferred that compound B is an ethoxylated isotridecanol grade (branched C13 alcohol) with a degree of ethoxylation of about 3 or of about 10 and with a HLB value of about 9 or of about 13. Preferably compound C is an ethoxylated isotridecanol grade (branched C13 alcohol) with a degree of ethoxylation of about 10 and with a HLB value of about 13 to 14.

Furthermore, the collector composition can have alkoxylation products, in which case alcohols do not have the number of carbon atoms stated above from these products. These are in particular alcohols having 1 to 7 carbon atoms, and also alcohols with more than 12 carbon atoms. However, it is preferred if this group of compounds has a weight fraction of at most 10% by weight, preferably of less than 5% by weight, based on the total weight of the collector composition.

If two or more alcohols are used for the component B and/or component C, in the event that the alcohol has 10 carbon atoms, it is preferred that this mixture is a C10 Guerbet alcohol mixture. Here, the main components are 2-propylheptanol and 5 methyl-2-propylhexanol. Preferably, the component B and/or component C consists to at least 90%, preferably 95%, of such mixture.

Further preferred is that during the flotation process a modifier is added in addition to the collec- tor composition of the present invention. Such modifier can be for example a pH-modifier. PH- modifier comprise for example lime, soda ash, caustic soda, sulfuric acid, hydrochloric acid, phosphoric acid. It is further preferred that for example depressants, activators and/or frothers are used during the flotation process for conditioning the ores as far as necessary. Preferably, the amount of component A in weight-% (wt%) in relation to the total collector composition is in the range from 50 wt% to 99.9 wt%, preferably in the range from 55 wt% to 85 wt%, more preferably in the range from 60 wt% to 80 wt% and most preferably in the range from 65 wt% to 75 wt%. It is in particular preferred that the amount of component A in weight-% in relation to the total collector composition is about 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt% or any value between these values or ranges thereof.

Preferably, the amount of component B in weight-% (wt%) in relation to the total collector composition is in the range from 0.1 wt% to 50 wt%, preferably in the range from 1 wt% to 40 wt%, more preferably in the range from 5 wt% to 35 wt% and most preferably in the range from 10 wt% to 30 wt%. It is in particular preferred that the amount of component B in weight-% in relation to the total collector composition is about 1 1 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt% or any value between these values or ranges thereof. Preferably, the amount of component C in weight-% (wt%) in relation to the total collector composition is in the range from 0.1 wt% to 40 wt%, preferably in the range from 0.5 wt% to 35 wt%, more preferably in the range from 1 wt% to 30 wt% and most preferably in the range from 1 .5 wt% to 25 wt%. It is in particular preferred that the amount of component C in weight-% in relation to the total collector composition is about 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt% , 9 wt% , 10 wt% , 1 1 wt% , 12 wt% , 13 wt% , 14 wt% , 15 wt% , 16 wt% , 17 wt% , 18 wt% , 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt% or any value between these values or ranges thereof.

Preferably, the amount of further additives and/or modifier is in the range from 0% to 10%, pref- erably in the range from 0.2% to 8%, more preferably in the range from 0.4% to 6% and most preferably in the range from 0.5% to 5%.

The collector composition of the present invention comprises in particular the components B and/or C, which in each case may comprise at least one alkoxylation product of alcohols. The collector composition according to the invention can also further comprise unreacted alcohols, which are not ethoxylated. However, it is preferred if their fraction has below 15% by weight, particularly preferably below 10% by weight of the total weight of the collector composition comprising components B and/or C. Further preferred it that the alkoxylated branched alcohols, in particular ethoxylated isotridecanols, have a purity of at least 95%, preferably of at least 97% purity, more preferably of at least 98% purity and most preferably of at least 99% purity.

A further aspect is the use of a collector composition for beneficiation of phosphates from phos- phate containing ores wherein the collector composition comprises

i. a component A, and

ii. at least one component B,

wherein the component A comprises saturated or unsaturated fatty acids or derivatives thereof having 12 to 22 carbon atoms, and wherein the component B is a non-ionic surfactant compris- ing alkoxylated branched alcohols.

It is preferred to use the collector composition for beneficiation of phosphates from phosphate containing ores, wherein the collector composition comprises

i. a component A,

ii. at least one component B, and

iii. at least one component C,

wherein the component A comprises saturated or unsaturated fatty acids or derivatives thereof having 12 to 22 carbon atoms, wherein the component B is a non-ionic surfactant comprising alkoxylated branched alcohols, wherein the component C is a non-ionic or anionic surfactant comprising alkoxylated branched alcohols or sulfur-containing surfactants, and wherein the component C is different to component B.

It is in particular preferred that the collector composition of the present invention is used in form of a "ready to use" composition, which means that a mixture of the component A, component B and optionally component C can be prepared and optionally stored, before the collector composition is used in a flotation process. Such mixture can be named "pre-mixture" and can act for example as self-emulsifying composition when the collector composition (pre-mixture) is added to an ore-slurry before start of the flotation. Further preferred is also that the individual components A, B and optionally C are added separately to an ore-slurry before flotation starts.

Preferably the collector composition is used for direct flotation of phosphates by collecting phosphate in the froth. It is further preferred, that the collector composition is used for reverse flotation of phosphates by collection of impurities from phosphate containing ores in the froth. Also preferred is that the collector composition is used for flotation of phosphates from sedimentary phosphate containing ores and/or from igneous phosphate containing ores. Concentrates produced by flotation from sedimentary ores for examples comprise <1 % MgO, >30% P2O5, <4% S1O2. Concentrates produced by flotation from igneous ores for example comprise <1 % MgO, >35% P2O5, <2% S1O2. Preferably, sedimentary phosphate containing ores are processed by direct flotation or by reverse flotation using for example the collector composition of the present invention. It is preferred, that igneous phosphate containing ores are for example processed by direct flotation using in particular the collector composition of the present invention.

Preferably the collector composition of this invention is used in the mining industry for mineral processing by in particular froth flotation processes for separating desired minerals from gangue and impurities. It is an advantage that by using the collector composition according to the present invention differences in hydrophobicity between desired (valuable) mineral, in particular phosphates, and impurities (waste, gangue), in particular carbonates, are increased. When using the collector composition of the present invention, a selective separation of in particular the minerals phosphates and carbonates is possible. The present collector composition makes complex ore mixtures comprising for example phosphates, silicates, carbonates and optionally other impurities accessible for beneficiation of phosphate. By using the collector composition of the present invention, processing of complex ores, which contain impurities or undesired ores, for example carbonates in phosphate ores, becomes economically feasible. It is possible to use the collector composition in flotation processes for the separation of large ranges of carbonates and silicates prior to further refinement. The collector composition can in particular be used to upgrade (purify) phosphates by flotation technology, in particular by froth flotation processes. With the use of the present collector composition, complex processes can be avoided and the enrichment of phosphate for subsequent use in fertilizers is possible. The collector composition can in particular be used for phosphate containing ores which were up to now not suitable for the beneficiation of phosphates.

In a further aspect the invention relates to a flotation process for beneficiation of phosphate from phosphate containing ores comprising the collector composition of the present invention. As pretreatment of the ores before direct flotation and/or reverse flotation the ores may be crushed or ground to finer particles. For the froth flotation then the targeted mineral, in particular phosphates in case of direct flotation and in particular carbonates and/or silicates or other impurities in case of reverse flotation, is rendered hydrophobic by addition of the collector composition. The targeted minerals can either be collected in the froth (direct flotation) or remain in the slurry as cell product (reverse flotation). Flotation can be undertaken in several stages / cycles to maximize the recovery of the desired mineral and to maximize the concentration of the desired mineral. Surprisingly, by addition of the collector composition of the present invention the number of stages / cycles can be reduce while achieving the same grade as with more stages / cycles. A preferred embodiment of the present invention is the flotation process for beneficiation of phosphates from phosphate containing ores with a collector composition comprising

i. a component A, and

ii. at least one component B,

A preferred embodiment of the present invention is the flotation process for beneficiation of phosphates from phosphate containing ores with a collector composition comprising

i. a component A,

ii. at least one component B, and

iii. at least one component C,

wherein the component A comprises saturated or unsaturated fatty acids or derivatives thereof having 12 to 22 carbon atoms, wherein the component B is a non-ionic surfactant comprising alkoxylated branched alcohols, wherein the component C is a non-ionic or anionic surfactant comprising alkoxylated branched alcohols or sulfur-containing surfactants, and wherein the component C is different to component B. Preferably, the flotation process of the present invention for beneficiation of phosphates from phosphate containing ores is a direct flotation process. Further preferred is that the flotation process of the present invention for beneficiation of phosphates from phosphate containing ores is a reverse flotation process. Preferably, for the direct flotation process of the present invention for beneficiation of phosphates from phosphate containing ores the collector composition comprises in weight-% in relation to the total collector composition an amount of 55% to 80% of component A and an amount of 5% to 40% of component B and an amount of 5% to 40% of component C. More preferably, for the direct flotation process the collector composition comprises in weight-% in relation to the total collector composition an amount of 60% to 75% of component A and an amount of 5% to 35% of component B and an amount of 5% to 20% of component C. Most preferably, for the direct flotation process the collector composition comprises in weight-% in relation to the total collector composition an amount of 65% to 70% of component A and an amount of 10% to 30% of component B and an amount of 5% to 20% of component C.

Preferably, for the reverse flotation process of the present invention for beneficiation of phosphates from phosphate containing ores the collector composition comprises in weight-% in relation to the total collector composition an amount of 55% to 80% of component A and an amount of 20% to 45% of component B. More preferably, for the reverse flotation process the collector composition comprises in weight-% in relation to the total collector composition an amount of 60% to 75% of component A and an amount of 25% to 40% of component B. Most preferably, for the reverse flotation process the collector composition comprises in weight-% in relation to the total collector composition an amount of 70% of component A and an amount of 30% of component B.

Further preferred is that for the reverse flotation process of the present invention for beneficiation of phosphates from phosphate containing ores the collector composition comprises in weight-% in relation to the total collector composition an amount of 55% to 80% of component A and an amount of 5% to 40% of component B and an amount of 5% to 40% of component C. More preferably, for the reverse flotation process the collector composition comprises in weight- % in relation to the total collector composition an amount of 60% to 75% of component A and an amount of 5% to 35% of component B and an amount of 5% to 20% of component C. Most preferably, for the reverse flotation process the collector composition comprises in weight-% in relation to the total collector composition an amount of 70% of component A and an amount of 10% to 25% of component B and an amount of 5% to 20% of component C.

It must be noted that as used herein, the singular forms "a", "an", and "the", include plural references unless the context clearly indicates otherwise. Thus, for example, reference to "a reagent" includes one or more of such different reagents and reference to "the method" includes reference to equivalent steps and methods know to those of ordinary skill in the art that could be modified or substituted for the methods described herein.

Unless otherwise indicated, the term "at least" preceding a series of elements is to be under- stood to refer to every element in the series. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the present invention. The term "and/or" wherever used herein includes the meaning of "and", "or" and "all or any other combination of the elements connected by said term".

The term "about" or "approximately" as used herein means within 20%, preferable within 10%, and more preferably within 5% of a given value or range. The term "about" or "approximately" as used herein also includes the exact respective values or ranges.

Throughout the specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integer or step. When used herein the term "comprising" can be substituted with the term "containing" or "including" or sometimes when used herein with the term "having".

When used herein "consisting of" excludes any element, step, or ingredient not specified in the claim element. When used herein, "consisting essentially of" does not exclude material or steps that do not materially affect the basic and novel characteristics of the claim.

Although the invention has been described with respect to specific embodiments and examples, it should be appreciated that other embodiments utilizing the concept of the present invention are possible without departing from the scope of the invention. The present invention is defined by the claimed elements, and any and all modifications, variations, or equivalents that fall within the true spirit and scope of the underlying principles.

EXAMPLES

The invention is further described by the following examples. The examples relate to practical and in some cases preferred embodiments of the invention that do not limit the scope of the in- vention.

Example 1

Reverse flotation (collection of carbonate impurities in the froth)

Methodology

240 g dry sedimentary calcareous phosphate ore ground and sized to Pio: 50 μηη, Pgo: 500 μηη is diluted to 1 .2 L water. The slurry is conditioned with 3.6ml of 10% H3PO4 for 0.5 min, then the pH is adjusted with 20% H2SO4 to 4.9-5.1 . After that the collector is added, followed by 1 min conditioning at 900 rpm. Then the flotation process is started (Denver D12 Flotation Machine) and during the flotation with an airflow rate of 5L/min the pH was maintained at 4.9 - 5.2. Flota- tion was usually completed after 2 - 2.5 min; if not completed, broken off at 2.5 min. Both fractions (froth product and cell product) were filtered off, dried, weighed and analyzed for phosphate content (P2O5 content). The %-values for the amounts of components A, B and C in table 1 are weight-%.

Table 1

From table 1 it becomes obvious that with the collector composition which comprises the described components A, B and C the grade of P2O5 can be increased to values above 31 wt%. This is unexpected in comparison to the collector composition which either comprises the com- ponents A and B or the components A and C. Consequently, the ternary collector composition and in particular the components B and C offer a synergistic effect with regard to P2O5 grade, which is desirous for subsequent processing to e.g. fertilizer. The oleic acid (CAS-No. 1 12-80-1 ) as component A is for example from vegetable source. The component B is an ethoxylated isotridecanol grade / mixture (CAS-No. 6901 1 -36-5) with a degree of ethoxylation of about 3 and an HLB-value of about 9. The Dioctyl sulfosuccinate (CAS-No. 577-1 1 -7) as component C has an HLB value of about 10.9. Example 2

Reverse flotation (collection of carbonate impurities in the froth)

Methodology

240 g dry sedimentary calcareous phosphate ore ground and sized to Pio: 50 μηη, Pgo: 500 μηη is diluted to 1 .2 L water. The slurry is conditioned with 3.6ml of 10% H3PO4 for 0.5 min, then the pH is adjusted with 20% H2SO4 to 4.9-5.1 . After that the collector is added, followed by 1 min conditioning at 900 rpm. Then the flotation process is started (Denver D12 Flotation Machine) and during the flotation with an airflow rate of 5L/min the pH was maintained at 4.9 - 5.2. Flotation was usually completed after 2 - 2.5 min; if not completed, broken off at 2.5 min. Both frac- tions (froth product and cell product) were filtered off, dried, weighed and analyzed for phosphate content (P2O5 content). The %-values for the amounts of components A, B and C in table 2 are weight-%.

Table 2

From the results in table 2 it can be seen that the ternary mixtures of the collector composition improve the flotation performance with regard to grade values of P2O5. In particular, the combination of two different alkoxylated branched alcohols (an ethoxylated isotridecanol with a degree of ethoxylation of about 3 and an HLB-value of about 9, and an ethoxylated isotridecanol with a degree of ethoxylation of about 10 and an HLB-value of about 13.5) offers an unexpected advantage with regard to grade values of P2O5. With the ternary collector composition surprisingly phosphate containing ores which so far where not accessible for phosphate beneficiation / phosphate enrichments can now be processed using for example collector compositions of the present invention for froth flotation. The component B is an ethoxylated isotridecanol grade / mixture (CAS-No. 6901 1 -36-5) with a degree of ethoxylation of about 3 and an HLB-value of about 9. The ethoxylated isotridecanol grade / mixture of component C (CAS-No. 6901 1 -36-5) has a degree of ethoxylation of about 10 and an HLB-value of about 13.5. The oleic acid (CAS- No. 1 12-80-1 ) as component A is for example from vegetable source. Furthermore, it was unexpected that a binary mixture comprising component A and component B, wherein component A is for example oleic acid and component B is for example an ethoxylated isotridecanol grade / mixture (CAS-No. 6901 1 -36-5) with a degree of ethoxylation of about 3 and an HLB-value of about 9, can be used for reverse flotation for beneficiation of phosphates from phosphate con- taining ores. Unexpectedly, in reverse flotation by collecting carbonate in the froth and phosphate as cell product, P2O5 values about 29 to 30 % can be obtained by using a binary mixture of component A and component B. With that, surprisingly, for example the binary collector composition (oleic acid and ethoxylated isotridecanol with 3 mol EO) of the present invention can be used for reverse flotation processes and make phosphate containing ores accessible for benefi- ciation by reverse flotation.

Example 3

Direct flotation (collection of phosphate in the froth)

Methodology

An igneous phosphate ore feed after magnetite removal, containing 9,6% P2O5 and 10,7% CO2 has been used for the experiments. Sample preparation included grinding, single stage desliming (in a 2 L cylinder, 130 mm decantation height, 5 min waiting time). The resulting flotation feed has ~ 42% -0,071 mm. Flotation experiments were performed in flotation in an open cycle with 2 concentrate cleaning stages (Denver D12 Flotation Machine). The ore sample was conditioned subsequently with 400 g/t Na2C03, 200 g/t sodium silicate and finally with 200 g/t collector blend containing 65% primary collector (tall oil fatty acid (TOFA) from pine wood, CAS-No. 61790-12- 3) and 35% secondary respectively secondary/ternary collector. The results are presented in Table 3. The %-values for the amounts of components A, B and C in table 3 are weight-%.

Table 3

In Table 3 it can be seen that for direct flotation the results with a collector composition which is ternary and comprises the component A, component B and component C leads to higher recov- ery values [% P2O5] in comparison to binary collector compositions with component B as secondary collector. Surprisingly it was further observed that with the collector composition of the present invention comprising for example two different ethoxylated isotridecanol grades with different HLB values (an ethoxylated isotridecanol (CAS-No. 6901 1 -36-5) with a degree of ethoxy- lation of about 3 and an HLB-value of about 9, and an ethoxylated isotridecanol (CAS-No.

6901 1 -36-5) with a degree of ethoxylation of about 10 and an HLB-value of about 13.5), phosphate containing ores are accessible for direct flotation of phosphates. It was unexpected that for example a similar binary mixture of secondary/ternary collectors (two different ethoxylated isotridecanol grades) can be used for direct flotation and for reverse flotation of phosphates. This becomes obvious when comparing the results from table 2 and table 3, in which in both cases the similar component B and component C in a ternary collector composition is used. A further surprise was that even with just a binary mixture of component A and component B, wherein component B is ethoxylated isotridecanol grade with an ethoxylation degree of about 3 (3 mol EO) or wherein component B is ethoxylated isotridecanol grade with an ethoxylation de- gree of about 10 (10 mol EO) (see table 3) in direct flotation processes with collection of phosphate in the froth, recovery values larger than 60% P2O5 can be obtained.

Example 4

Direct flotation (collection of phosphate in the froth)

Methodology

A partly weathered igneous phosphate ore feed after magnetite removal, containing 9,6% P2O5 and 10,7% CO2 has been used for the experiments. Sample preparation included grinding, single stage desliming (in a 2 L cylinder, 130 mm decantation height, 5 min waiting time). The resulting flotation feed has ~ 42% -0,071 mm.

Flotation experiments were performed in flotation in an open cycle with 2 concentrate cleaning stages (Denver D12 Flotation Machine). The ore sample was conditioned subsequently with 400 g/t Na2C03, 300 g/t sodium silicate and finally with 500 g/t collector blend containing 70% primary collector (soybean fatty acid, CAS-No. 68308-53-2) and 30% secondary respectively secondary/ternary collector. The results are presented in Table 4. The %-values for the amounts of com- ponents A, B and C in table 4 are weight-%.

Table 4

From table 4 it can be seen that for a direct flotation process with recovering phosphate in the froth a ternary mixture of component A, B and C in comparison to a binary mixture with just component A and B shows better results for grade values [wt% P2O5]. In particular, two different ethoxylated isotridecanol grades, one with a degree of ethoxylation of 3 and one with a degree of ethoxylation of 10, results in an increase in grade values, which was unexpected. When comparing the two binary mixtures, on the one hand side soybean fatty acids and ethoxylated isotridecanols (3EO) and on the other hand soybean fatty acids and ethoxylated isotridecanols (10EO) it becomes obvious that the degree of ethoxylation influences the flotation performance. With ethoxylated isotridecanols (10EO) a stable froth was obtained, which is undesirable, because a stable froth prevents further processing of the phosphates which are collected in the froth. For further processing of the collected ores (phosphates), the froth must collapse after flotation so that the ores are accessible for subsequent process steps. Furthermore, when comparing the results of table 3 and table 4 it become obvious that there is a dependency between the collector component A and the collector component B (either ethoxylated isotridecanol with 3EO or ethoxylated isotridecanol with 10EO). When just using a binary mixture of components A and B the type of fatty acid component A has a significant influence on the flotation performance. Such influence of fatty acid component A can be compensated by using two different types of ethoxylated isotridecanols, for example one with 3EO and one with 10EO. With such a combination the flotation process becomes much more robust, which was unexpected.

Claims

CLAIMS:

1 . Collector composition for beneficiation of phosphates from phosphate containing ores comprising

i. a component A,

ii. at least one component B, and

iii. at least one component C,

wherein the component A comprises saturated or unsaturated fatty acids or derivatives thereof having 12 to 22 carbon atoms, wherein the component B comprises non-ionic sur- factants comprising alkoxylated branched alcohols, wherein the component C comprises non-ionic surfactants or anionic surfactants comprising alkoxylated branched alcohols or sulfur-containing surfactants, and wherein the component C is different to component B.

2. Collector composition according to claim 1 , wherein the component A is selected from the group consisting of a saturated or unsaturated fatty acid having 12 to 22 carbon atoms or mixtures thereof, a fatty acid blend with > 90% Ci6 to Cie fatty acids with an unsaturation degree of 0.5 to 3, oleic acid, tall oil, resins, fatty acid peptides of the formula C_n-i H2n-iCO- NH-R with R being a residue of natural or artificial amino acids comprising glycine, sarco- sine or taurine.

3. Collector composition according to claim 1 or 2, wherein the alkoxylated branched alcohols of component B comprise alcohols having 9 to 18 carbon atoms.

4. Collector composition according to anyone of claims 1 to 3, wherein the component C is selected from the group consisting of sulfonated fatty acids, dialkyl sulfosuccinates, di- or tetraalkyl sulfosuccinamates, sodium dodecyl sulfate, dioctyl sulfosuccinate, alkyl ether sulfates, alkyl benzenesulfonates, alkoxylated branched alcohols with alcohols having 6 to 20 carbon atoms, alkyl sulfates of the formula C_nH2n+iOS03^" with n=12 to 22.

5. Collector composition according to anyone of the preceding claims, wherein the degree of alkoxylation of component B is in the range of 0.1 to 15.

6. Collector composition according to anyone of the preceding claims, wherein the degree of alkoxylation of the branched alkoxylated alcohol of component C is in the range of 1 to 30.

7. Collector composition according to anyone of the preceding claims, wherein the degree of branching of the alkoxylated branched alcohols of component B and/or component C is in average in the range of 1 to 5.

8. Collector composition according to anyone of the preceding claims, wherein the HLB

value of component B is in average in the range of 5 to 15.

9. Collector composition according to anyone of the preceding claims, wherein the HLB

value of component C is in average in the range of 8 to 18.

10. Collector composition according to anyone of the preceding claims, wherein the amount of component A in weight-% (wt%) in relation to the total collector composition is in the range from 50 wt% to 99.9 wt%.

Collector composition according to anyone of the preceding claims, wherein the amount of component B in weight-% (wt%) in relation to the total collector composition is in the range from 0.1 wt% to 50 wt%.

Collector composition according to anyone of the preceding claims, wherein the amount of component C in weight-% (wt%) in relation to the total collector composition is in the range from 0.1 wt% to 40 wt%.

13. Use of collector composition for beneficiation of phosphates from phosphate containing ores wherein the collector composition comprises

i. a component A, and

ii. at least one component B,

14. Use of collector composition according to claim 13, wherein the collector composition comprises

a component A,

at least one component B, and

at least one component C,

wherein the component A comprises saturated or unsaturated fatty acids or derivatives thereof having 12 to 22 carbon atoms, wherein the component B comprises non-ionic surfactants comprising alkoxylated branched alcohols, wherein the component C comprises non-ionic surfactants or anionic surfactants comprising alkoxylated branched alcohols or sulfur-containing surfactants, and wherein the component C is different to component B.

15. Use of collector composition according to claim 13 or 14 for direct flotation of phosphates by collecting phosphate in the froth.

16. Use of collector composition according to claim 13 or 14 for reverse flotation of phosphates by collection of impurities from phosphate containing ores in the froth.

17. Use of collector composition according to anyone of claims 13 to 16 for beneficiation of phosphates by flotation from sedimentary phosphate containing ores and/or from igneous phosphate containing ores.

18. Use of collector composition according to anyone of claims 13 to 17, wherein the component A is selected from the group consisting of a saturated or unsaturated fatty acid having 12 to 22 carbon atoms or mixtures thereof, a fatty acid blend with > 90% Ci6 to Cis fatty acids with an unsaturation degree of 0.5 to 3, oleic acid, tall oil, resins, fatty acid peptides of the formula C_n-i H2n-iCO-NH-R with R being a residue of natural or artificial amino acids comprising glycine, sarcosine or taurine.

19. Use of collector composition according to anyone of claims 13 to 18, wherein the alkoxylated branched alcohols of component B comprise alcohols having 9 to 18 carbon atoms.

20. Use of collector composition according to anyone of claims 13 to 19, wherein the component C is selected from the group consisting of sulfonated fatty acids, dialkyl sulfosuccin- ates, di- or tetraalkyl sulfosuccinamates, sodium dodecyl sulfate, dioctyl sulfosuccinate, alkyl ether sulfates, alkyl benzenesulfonates, alkoxylated branched alcohols with alcohols having 6 to 20 carbon atoms, alkyl sulfates of the formula C_nH2n+iOS03^" with n=12 to 22.

21 . Use of collector composition according to anyone of claims 13 to 20, wherein the degree of alkoxylation of component B is in the range of 0.1 to 15.

22. Use of collector composition according to anyone of claims 13 to 21 , wherein the degree of alkoxylation of the branched alkoxylated alcohol of component C is in the range of 1 to 30.

23. Use of collector composition according to anyone of claims 13 to 22, wherein the degree of branching of the alkoxylated branched alcohols of component B and/or component C is in average in the range of 1 to 5.

24. Use of collector composition according to anyone of claims 13 to 23, wherein the HLB value of component B is in average in the range of 5 to 15.

25. Use of collector composition according to anyone of claims 13 to 24, wherein the HLB value of component C is in average in the range of 8 to 18.

26. Use of collector composition according to anyone of claims 13 to 25, wherein the amount of component A in weight-% (wt%) in relation to the total collector composition is in the range from 50 wt% to 99.9 wt%.

27. Use of collector composition according to anyone of claims 13 to 26, wherein the amount of component B in weight-% (wt%) in relation to the total collector composition is in the range from 0.1 wt% to 50 wt%.

28. Use of collector composition according to anyone of claims 13 to 27, wherein the amount of component C in weight-% (wt%) in relation to the total collector composition is in the range from 0.1 wt% to 40 wt%.

29. Flotation process for beneficiation of phosphates from phosphate containing ores comprising the collector composition according to anyone of claims 1 to 12.

30. Flotation process according to claim 29 for direct flotation of phosphates, comprising the steps

Comminution of ores,

Optionally, conditioning of ores with depressants and/or activators,

pH adjustment,

Collector addition,

Flotation,

Collection of phosphate in the froth.

31 . Flotation process according to claim 29 for reverse flotation of phosphates by collection of impurities from phosphate containing ores in the froth, comprising the steps

Comminution of ores,

Optionally, conditioning of ores with depressants and/or activators,

pH adjustment,

Collector addition,

Flotation,

Collection of carbonate and/or other impurities in the froth,

Recovering of phosphates from the cell product.

32. Flotation process according to anyone of claims 29 to 31 , wherein the phosphate containing ores are pretreated to remove silicates.

33. Flotation process according to anyone of claims 29 to 32, wherein one or more modifiers and/or one or more frothers and/or one or more depressants are used.

34. Flotation process according to anyone of claims 29 to 33, wherein the collector composition comprises

i. a component A,

ii. at least one component B, and

iii. at least one component C,

35. Flotation process according to anyone of claims 29 to 34, wherein the component A is selected from the group consisting of a saturated or unsaturated fatty acid having 12 to 22 carbon atoms or mixtures thereof, a fatty acid blend with > 90% Ci6 to Cie fatty acids with an unsaturation degree of 0.5 to 3, oleic acid, tall oil, resins, fatty acid peptides of the formula Cn-i H2n-iCO-NH-R with R being a residue of natural or artificial amino acids comprising glycine, sarcosine or taurine.

Flotation process according to anyone of claims 29 to 35, wherein the alkoxylated branched alcohols of component B comprise alcohols having 9 to 18 carbon atoms.

Flotation process according to anyone of claims 29 to 36, wherein the component C is selected from the group consisting of sulfonated fatty acids, dialkyl sulfosuccinates, di- or tetraalkyl sulfosuccinamates, sodium dodecyl sulfate, dioctyl sulfosuccinate, alkyl ether sulfates, alkyl benzenesulfonates, alkoxylated branched alcohols with alcohols having 6 to 20 carbon atoms, alkyl sulfates of the formula C_nH2n+iOS03^" with n=12 to 22.

Flotation process according to anyone of claims 29 to 37, wherein the degree of alkoxyla- tion of component B is in the range of 0.1 to 15.

39. Flotation process according to anyone of claims 29 to 38, wherein the degree of alkoxyla- tion of the branched alkoxylated alcohol of component C is in the range of 1 to 30.

40. Flotation process according to anyone of claims 29 to 39, wherein the degree of branching of the alkoxylated branched alcohols of component B and/or component C is in average in the range of 1 to 5.

41 . Flotation process according to anyone of claims 29 to 40, wherein the HLB value of component B is in average in the range of 5 to 15.

42. Flotation process according to anyone of claims 29 to 41 , wherein the HLB value of component C is in average in the range of 8 to 18.

43. Flotation process according to anyone of claims 29 to 42, wherein the amount of component A in weight-% (wt%) in relation to the total collector composition is in the range from 50 wt% to 99.9 wt%.

Flotation process according to anyone of claims 29 to 43, wherein the amount of component B in weight-% (wt%) in relation to the total collector composition is in the range from 0.1 wt% to 50 wt%.

Flotation process according to anyone of claims 29 to 44, wherein the amount of component C in weight-% (wt%) in relation to the total collector composition is in the range from 0.1 wt% to 40 wt%.

Flotation process according to anyone of claims 29 to 45 for direct flotation for beneficia- tion of phosphates from phosphate containing ores, wherein the collector composition comprises in weight-% (wt%) in relation to the total collector composition an amount of 60 wt% to 75 wt% of component A and an amount of 5 wt% to 35 wt% of component B and an amount of 5 wt% to 20 wt% of component C. Flotation process according to anyone of claims 29 to 46 for reverse flotation for beneficia- tion of phosphates from phosphate containing ores, wherein the collector composition comprises in weight-% (wt%) in relation to the total collector composition an amount of 60 wt% to 75 wt% of component A and an amount of 5 wt% to 35 wt% of component B and an amount of 5 wt% to 20 wt% of component C.