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EP3433021B1 - Utilisation d'émulsifiants en composition collectrice - Google Patents

Utilisation d'émulsifiants en composition collectrice Download PDF

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EP3433021B1
EP3433021B1 EP17711222.4A EP17711222A EP3433021B1 EP 3433021 B1 EP3433021 B1 EP 3433021B1 EP 17711222 A EP17711222 A EP 17711222A EP 3433021 B1 EP3433021 B1 EP 3433021B1
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EP3433021A2 (fr
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Henrik NORDBERG
Natalija Smolko-Schvarzmayr
Magnus Svensson
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Nouryon Chemicals International BV
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/0043—Organic compounds modified so as to contain a polyether group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/008—Organic compounds containing oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/01—Organic compounds containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/012—Organic compounds containing sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; Specified applications
    • B03D2203/02—Ores
    • B03D2203/04—Non-sulfide ores
    • B03D2203/06—Phosphate ores

Definitions

  • the present invention relates to the use of emulsifiers in branched alcohol alkoxylate-containing secondary collector compositions and the use of such compositions for the froth flotation of non-sulfidic ores, especially phosphate ores, in combination with a primary collector which is an anionic or an amphoteric surface active-compound.
  • Phosphate rocks contain calcium phosphate minerals largely in the form of apatite, usually together with other minerals, e.g. silicate minerals and carbonate minerals, such as calcite.
  • Apatite is a generic name for a group of calcium phosphate minerals also containing other elements or radicals, such as fluorapatite, chlorapatite, hydroxylapatite, carbonate-rich fluorapatite and carbonate-rich hydroxylapatite.
  • the froth characteristics include both the amount and the stability of the froth. It is important in the flotation process that the froth collapses as soon as possible after it leaves the flotation cell for the next step in the beneficiation process. A too stable froth will cause both entrainment of particles and froth product pumping problems. Entrainment, especially on a large scale, will result in decreased selectivity (grade, recovery). Problems with froth product pumping will make a process of flotation technically impossible.
  • Collector performance may be improved by using collector combinations of a primary (main) collector and a secondary collector (co-collector).
  • collector composition shall be used to describe compositions containing both a primary and a secondary collector.
  • Nonylphenol ethoxylates have been the dominating nonionic surfactant used as a co-collector in a combination with sarcosine-type primary collectors in selective flotation of apatite from calcite-containing ores.
  • US 4,789,466 discloses the flotation of apatite ores with a collector composition that contains two components, wherein one is an ethoxylated and propoxylated fatty alcohol and the other is a cationic, anionic or ampholytic surfactant, preferably a sulfosuccinamate surfactant.
  • the surfactant is the primary collector and the alkoxylated fatty alcohol the secondary collector in the apatite ore flotation process.
  • the degree of branching of the used fatty alcohol is either not disclosed or fatty alcohols are applied which are known to have a degree of branching that is 1 or less.
  • SE 409291 discloses a method for foam flotation of calcium phosphate-containing minerals, using an amphoteric surface-active compound as the primary collector.
  • the primary collector's flotating ability may further be strengthened by the presence of a secondary collector, which is described as a polar, water-insoluble, hydrophobic substance having affinity to the mineral particles that have been coated by the primary collector.
  • the polar components are e.g. water-insoluble soaps, such as calcium soaps, water-insoluble surface-active alkylene oxide adducts, organic phosphate compounds, such as tributyl phosphate, and esters of carbonic acids, such as tributyl ester of nitrilotriacetic acid.
  • nonylphenol that has been reacted with two moles of ethylene oxide was used as the secondary collector.
  • the secondary collector disclosed in SE'291 is still considered a good choice in treating ores, as it provides for an excellent mineral recovery at a P 2 O 5 grade of higher than 30%.
  • an intense search for a replacement of nonylphenol ethoxylates has been ongoing for a long time.
  • EP 0 270 933 A2 discloses mixtures as collectors for flotation of non-sulfidic ores that contain an alkyl or alkenyl polyethylene glycol ether that is end-capped with a hydrophobic group and an anionic tenside.
  • the end-capped alkyl or alkenyl polyethylene glycol ether in some embodiments is based on a fatty alcohol, preferably a C12 to C18 fatty alcohol.
  • non-end-capped fatty alcohols are used together with anionic tensides.
  • Shell "Branching and Carbon Number Type in Detergent Range Alcohols* Branching and Carbon Number Type in Detergent Range Alcohols", of 16 September 2009 discloses the branching of and carbon numbers of Neodol alcohols commercialized by the Shell Group.
  • Shell Typical distributions of NEODOLTM ethoxylate adducts" of 5 November 2009 discloses EO distributions of NEODOL ethoxylates commercialized by the Shell Group.
  • Lutensol ® TO types of 28 February 1997 discloses that the Lutensol TO range products are ethoxylated iso C13 alcohols. The degree of ethoxylation of a number of Lutensol ® TO products is also disclosed.
  • Neodol 45-7 Primary alcohol ethoxylate
  • Shell brochure: "Neodol 45-7, Primary alcohol ethoxylate" of 1 October 2005 discloses the properties of Neodol 45-7 as commercialized by the Shell Group EP0687726 discloses emulsions of a hydrophilic nonionic surfactant and a hydrophobic nonionic surfactant.
  • the compositions are said to be suitable for the bleaching of fabrics.
  • aqueous formulation with a pH of 4 the surfactants
  • Dobanol 45-7 and Lutensol TO 3 are present together with benzoyl peroxide and sodium coconut alkyl sulfate, and this formulation is employed to bleach a cotton fabric.
  • US 4,358,368 discloses a process for the froth flotation of calcium phosphate containing minerals using a collector composition that contains an amphoteric surfactant.
  • the surfactant can be combined with a second compound that is hydrophobic and that can be selected from a group of compounds and that is said to be water insoluble.
  • an emulsifier may be added.
  • Co-pending patent application PCT appl # EP 2015/071003 discloses the use of a secondary collector, suitable for use with a primary collector of the amphoteric or anionic type, for the froth flotation of non-sulfidic ores to recover oxides, carbonates, phosphates and other salt-type minerals, especially calcium phosphate-containing minerals, in which the secondary collector is a branched fatty alcohol-based compound 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.
  • a secondary collector which is used in combination with a primary collector of the amphoteric or anionic type for the froth flotation of non-sulfidic ores to recover oxides, carbonates, phosphates and other salt-type minerals, especially calcium phosphate-containing minerals
  • the secondary collector is a mixture containing at least one compound (i) selected from the group of branched fatty alcohols with 12-16 carbon atoms having a degree of branching of 1-3.5 and their alkoxylates with a degree of ethoxylation (DE) of up to 4, and at least one compound (ii) selected from the group of alkoxylates of nonionic hydrocarbon compounds, such as fatty amines, fatty alcohols, fatty (di)ethanolamides, fatty acids, triglycerides, with a degree of ethoxylation (DE) of higher than 3, leads to similar good efficiency in recovering apatite in the presence of silicate and/or carbonate minerals as when using
  • the invention relates to the use of a mixture as a secondary collector for the froth flotation of non-sulfidic ores, in combination with a primary collector selected from the group of amphoteric and anionic surface active compounds, wherein the mixture contains at least one compound (i) selected from the group of branched fatty alcohols with 12-16 carbon atoms having a degree of branching of 1-3.5 and their alkoxylates with a degree of ethoxylation of up to 4, and at least one compound (ii) selected from alkoxylates of nonionic hydrocarbon compounds with a degree of ethoxylation of more than 3, such as alkoxylates of hydrocarbon compounds of the group of fatty alcohols, fatty amines, fatty ethanolamides, fatty diethanolamides, fatty acids, triglycerides with a degree of ethoxylation of more than 3, wherein when both compounds (i) and (ii) are ethoxylated alcohols, the mixture has a bimodal degree
  • the mixture of compounds (i) and (ii) - in the embodiments wherein both compounds are ethoxylated alcohol compounds - has a bimodal DE distribution (bimodal meaning a statistical distribution with two maxima).
  • the mixture is not an inherent mixture of more than one molecule that is obtained when a single ethoxylation reaction is performed with a hydrocarbon compound and wherein always some lower and higher ethoxylated molecules are formed and wherein the DE distribution would be unimodal (i.e. have a single maximum).
  • the mixture is a mixture obtained by mixing two separately ethoxylated alcohol compounds (i) and (ii).
  • both compounds (i) and (ii) are ethoxylated, preferably the degree of ethoxylation of compound (ii) is higher than that of compound (i).
  • the invention relates to the use of the mixture of the above compounds (i) and (ii) as secondary collectors for the froth flotation of non-sulfidic ores, to recover calcium phosphate-containing minerals, such as apatite, in combination with a primary collector which is an amphoteric or anionic surfactant and to collector compositions containing such primary and secondary collectors.
  • a primary collector which is an amphoteric or anionic surfactant
  • collector compositions containing such primary and secondary collectors examples of other valuable minerals that may be recovered using this combination of primary and secondary collectors include scheelite, fluorspar, calcite and dolomite.
  • the ratio of compound (i) to compound (ii) on a weight basis is from 30:70 to 99:1, more preferably from 40:60 to 98:2, even more preferably from 50:50 to 90:10.
  • the degree of branching (DB) as used herein is meant the total number of methyl groups present on the alkyl or alkenyl chain of the alcohol or alkoxylate thereof, minus one. The mean number of methyl groups in the molecules of a sample can easily be determined by NMR spectroscopy. It should be understood that the degree of branching (DB) in the C12-C16 branched fatty alcohol that delivers the branched alkyl or alkenyl chain for compound (i) is an average degree of branching for the fatty alcohol used. Fatty alcohols are oftentimes available or applied as a mixture of several components and therefore DB does not have to be an integer. Consequently, the degree of branching for compound (i) is an average degree of branching, wherein the average degree of branching is the statistical mean of the degree of branching of the molecules of a sample.
  • the DB in compound (i) is higher than 1, even more preferably it is higher than 1.5, most preferably higher than 2. In another more preferred embodiment the DB is lower than 3.2, most preferred it is 3 or lower.
  • the molecular formula of the secondary collector compounds (i) and (ii) in a preferred embodiment is R-A (I),
  • the mixture may in addition contain further components such as a liquid.
  • a liquid is an aqueous liquid, even more preferably the liquid contains more than 95% of water.
  • compound (ii) acts as an emulsifier for compound (i).
  • the alcohols as such, as well as their alkoxylates may be used in the secondary collector mixtures.
  • the alkoxylated products according to formula (I) may be produced by procedures well-known in the art by reacting the appropriate starting alcohol, acid, amide, amine or triglyceride with ethylene oxide, or propylene oxide and ethylene oxide, in the presence of a suitable catalyst, e.g. a conventional basic catalyst, such as KOH, or a so-called narrow range catalyst (see e.g. Nonionic Surfactants: Organic Chemistry in Surfactant Science Series volume 72, 1998, pp 1-37 and 87-107, edited by Nico M. van Os; Marcel Dekker, Inc ). If both propylene oxide and ethylene oxide are used, the alkoxides may be added as blocks in either order, or may be added randomly. The products obtained from reaction with only ethylene oxide are the most preferred.
  • a suitable catalyst e.g. a conventional basic catalyst, such as KOH, or a so-called narrow range catalyst (see e.g. Nonionic Surfactants: Organic Chemistry in Surfactant Science Series volume 72,
  • Preferred compounds (i) are alcohol alkoxylates with a degree of ethoxylation of up to 3.
  • Preferred compounds (ii) are alcohol alkoxylates with a degree of ethoxylation of higher than 3, even more preferred higher than 4. In an embodiment their degree of ethoxylation is up to 30, preferably up to 20.
  • the primary collectors used in the froth flotation according to the present invention may be either amphoteric or anionic surface-active compounds. Below some examples of formulae for the primary collectors are given, but these should only be considered as suitable for the invention, and are not to be regarded as limiting.
  • the primary collector for the above-mentioned froth flotation procedure has the formula (II)
  • the primary collector has the formula (III) wherein R 2 is a hydrocarbyl group with 8-22, preferably 12-18, carbon atoms, D is -CH 2 - or -CH 2 CH 2 -, k is 0-4, preferably 0-3, and most preferably 0-2, and M is hydrogen or a cation, such as sodium or potassium.
  • the primary collector is selected from anionic surface-active compounds such as fatty acids (with a C8 to C24-acyl group), sulfonates, alkyl phosphates, alkyl sulfates and compounds of formula (IV) where R is a hydrocarbyl group having from 7-23, preferably 11-21, carbon atoms, optionally substituted; R 1 is H or CH 3 , preferably H; R 2 is H or a C1-C4 alkyl group, preferably H; R 3 is H or CH 3 , preferably CH 3 ; n is a number 1-20; p is a number 1-3, preferably 1; X is H + or a cation which is organic or inorganic, and m represents the valency of the cation and is a number 1-2, preferably 1.
  • anionic surface-active compounds such as fatty acids (with a C8 to C24-acyl group), sulfonates, alkyl phosphates, alkyl sul
  • the cation is preferably selected from the group consisting of an alkali metal cation, an alkaline earth metal cation, ammonium, and a substituted ammonium group having one or more C 1 to C 3 alkyl and/or hydroxyalkyl groups.
  • mixtures of the above compounds as a primary collector.
  • the invention relates to a method for froth flotation of non-sulfidic ores, especially phosphate ores, to recover apatite minerals, in which method the collector mixture described above is used.
  • Such froth flotation method for phosphate ores may typically comprise the steps of:
  • the weight ratio between the primary collector and the secondary collector in both the collector compositions and the flotation processes is preferably from 15:85, more preferably 20:80, most preferably 25:75 to 99:1, preferably 98:2, most preferably 97:3. All weight ratios herein refer to the ratio of active materials, unless stated otherwise.
  • the amount of collector composition added to the ore will in general be in the range of from 10 to 1000 g/ton dry ore, preferably in the range of from 20 to 500, more preferably from 100 to 400 g/ton dry ore.
  • flotation aids that may be present in the flotation process are depressants, such as a polysaccharide, alkalized starch or dextrin, extender oils, frothers/froth regulators, such as pine oil, MIBC (methylisobutyl carbinol) and alcohols such as hexanol and alcohol ethoxylates/propoxylates, inorganic dispersants, such as silicate of sodium (water glass) and soda ash, and pH-regulators.
  • depressants such as a polysaccharide, alkalized starch or dextrin
  • extender oils frothers/froth regulators
  • frothers/froth regulators such as pine oil, MIBC (methylisobutyl carbinol) and alcohols such as hexanol and alcohol ethoxylates/propoxylates
  • inorganic dispersants such as silicate of sodium (water glass) and soda ash
  • pH-regulators such as sodium (water glass) and soda
  • the pH during the flotation process will preferably be in the range of 8-11.
  • 500 g of the ore were placed in a 1.4L Denver flotation cell, 500 ml of process water (25mg/l Ca 2+ , 40mg/l Mg 2+ ) were added and the mixing was started. Then 5 minutes conditioning with 1000g/t of a 1%(w/w) aqueous starch solution was performed, the collector (600g/t (or a mixture of primary acylglycide collector and secondary collectors)) was added to the flotation cell as a 1% aqueous solution and conditioning was continued for 2.5 minutes. After the conditioning steps tap water was added so that a total volume of 1.4L was obtained, the pH of the flotation mixture was adjusted to 9.5 with a 10% NaOH aqueous solution and the flotation was started. The experiment was performed at RT (20 ⁇ 1°C).
  • the flotation results can be improved only if use is made of the mixture of two nonionic surfactants as a secondary collector .
  • Figure 1 the distribution of the degree of ethoxylation for the formulation according to the invention and the comparison 2 formulation are graphically represented. The results clearly show that the double peak distribution plays a crucial role in the flotation.
  • the mixture of two ethoxylated alcohols with a degree of ethoxylation equal to 1.5 and 8.5, respectively provides much better recovery than the single ethoxylated alcohol with a degree of ethoxylation equal to 5.
  • the emulsion formation and stability were tested by preparing aqueous 5 w% solutions as follows: five (5) g of the surfactant or surfactant mixture were added to 150 ml beaker, diluted with 95 g of water and vigorously mixed. After 5 min the mixing was stopped. Visual observation of the prepared solutions was done after 1, 2, 3, 4, 5, 10 and 60 min.

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  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (13)

  1. Utilisation d'un mélange en tant que collecteur secondaire pour la flottation par moussage de minerais non sulfurés, en combinaison avec un collecteur primaire sélectionné dans le groupe des composés tensioactifs amphotères et anioniques, dans laquelle le mélange contient au moins un composé (i) sélectionné dans le groupe des alcoxylates d'alcools gras ramifiés comprenant de 12 à 16 atomes de carbone ayant un degré de ramification de 1 à 3,5, avec un degré d'éthoxylation allant jusqu'à 4 et au moins un composé (ii) sélectionné dans le groupe des alcoxylates de composés hydrocarbonés non ioniques avec un degré d'éthoxylation supérieur à 3, dans laquelle si les deux composés (i) et (ii) sont des alcools éthoxylés, le mélange présente un degré bimodal de distribution d'éthoxylation.
  2. Utilisation selon la revendication 1 dans laquelle le composé (ii) est sélectionné dans le groupe des alcoxylates de composés hydrocarbonés non ioniques du groupe des alcools gras, des aminés grasses, des éthanolamides gras, des diéthanolamides gras, des acides gras et des triglycérides avec un degré d'éthoxylation supérieur à 3.
  3. Utilisation selon la revendication 1 ou 2 où la formule moléculaire des composés (i) et (ii) répond à la formule (I)

            R-A     (I)

    dans laquelle pour le composé (i) R est un groupe alkyle ou alcényle comprenant de 12 à 16, de préférence de 12 à 15, atomes de carbone, et où ledit groupe alkyle ou alcényle a un degré de ramification de 1 à 3, et dans laquelle pour le composé (ii) R est n'importe quel groupe alkyle, aryle ou alcényle ramifié ou linéaire comprenant de 8 à 24 atomes de carbone ; A est sélectionné parmi les groupes O-(PO)x(EO)y(PO)zH, pour les composés (i) et (ii)
    (CO)N(CH2CH2O(PO)x(EO)y(PO)zH)2, pour le composé (ii)
    (CO)NH(CH2CH2O(PO)x(EO)y(PO)zH), pour le composé (ii)
    (CO)O((PO)x(EO)y(PO)zH), pour le composé (ii)
    N(PO)x(EO)y(PO)zH)2, pour le composé (ii)
    (CO)O((PO)x(EO)y(PO)zOCH2CH(O(PO)x(EO)y(PO)zO(CO)R)CH2O et
    ((PO)x(EO)y(PO)zO(CO)R), pour le composé (ii),
    dans laquelle PO est un motif propylèneoxy et EO est un motif éthylèneoxy, et pour le composé (i) ; x est un nombre de 0 à 2, de préférence égal à 0, y est un nombre de 0 à 4, de préférence de 0 à 3, plus préférablement de 0 à 2,5, encore plus préférablement de 0 à 2,3 et de manière préférée entre toutes de 0 à 2, et z est un nombre de 0 à 2, de préférence égal à 0, et pour le composé (ii) x est un nombre de 0 à 20, de préférence égal à 0, y est un nombre supérieur à 3 allant jusqu'à 30, de préférence de 4 à 20, plus préférablement de 5 à 15, encore plus préférablement de 7 à 12, et z est un nombre de 0 à 20, de préférence égal à 0.
  4. Utilisation selon l'une quelconque des revendications 1 à 3 dans laquelle le mélange contient en outre un liquide dans laquelle le composé (ii) est un émulsifiant pour le composé (i) dans le liquide.
  5. Utilisation selon l'une quelconque des revendications 1 à 4 dans laquelle ledit collecteur primaire est un composé tensioactif amphotère sélectionné dans le groupe constitué par les composés répondant à la formule (II)
    Figure imgb0022
    dans laquelle R1 est un groupe hydrocarbyle comprenant de 8 à 22, de préférence de 12 à 18, atomes de carbone ; A est un groupe alkylèneoxy comprenant de 2 à 4 atomes de carbone ; p est un nombre égal à 0 ou 1 ; q est un nombre de 0 à 5, de préférence égal à 0, R2 est un groupe hydrocarbyle comprenant de 1 à 4 atomes de carbone, de préférence 1, ou R2 est le groupe
    Figure imgb0023
    dans lequel R1, A, p et q ont la même signification que ci-dessus, Y- est sélectionné dans le groupe constitué par COO- et SO3 -, de préférence COO- ; n est un nombre égal à 1 ou 2, de préférence égal à 1 ; M est un cation qui peut être monovalent ou divalent et inorganique ou organique, et r est un nombre égal à 1 ou 2 ; ou lorsque le composé (II) est sous sa forme protonée acide sans cation externe (Mr+) 1/r ; et les composés répondant à la formule (III)
    Figure imgb0024
    dans laquelle R2 est un groupe hydrocarbyle comprenant de 8 à 22, de préférence de 12 à 18, atomes de carbone, D est -CH2- ou -CH2CH2-, k vaut de 0 à 4, de préférence de 0 à 3, et de manière préférée entre toutes de 0 à 2, et M est un atome d'hydrogène ou un cation, tel que le sodium ou le potassium, et
    un composé tensioactif anionique sélectionné dans le groupe constitué par les acides gras, les sulfonates, les alkylphosphates, les alkylsulfates et les composés de formule (IV)
    Figure imgb0025
    dans laquelle R est un groupe hydrocarbyle comprenant de 7 à 23, de préférence de 11 à 21, atomes de carbone, éventuellement substitué ; R1 est H ou CH3, de préférence H ; R2 est H ou un groupe alkyle en C1 à C4, de préférence H ; R3 est H ou CH3, de préférence CH3 ; n est un nombre de 1 à 20 ; p est un nombre de 1 à 3, de préférence égal à 1 ; X est H+ ou un cation qui est organique ou inorganique, et m représente la valence du cation et est un nombre de 1 à 2, de préférence égal à 1, et des mélanges de ceux-ci.
  6. Utilisation selon l'une quelconque des revendications 1 à 5 précédentes dans laquelle le rapport pondéral entre le collecteur primaire et le collecteur secondaire est compris entre 15:85 et 99:1.
  7. Utilisation selon l'une quelconque des revendications 1 à 6 précédentes dans laquelle le minerai non sulfuré est un minerai contenant du phosphate de calcium.
  8. Procédé pour la flottation par moussage de minerais non sulfurés utilisant une composition collectrice comprenant un collecteur primaire sélectionné dans le groupe des composés tensioactifs amphotères et anioniques, et un collecteur secondaire qui contient un mélange contenant au moins un composé (i) sélectionné dans le groupe des alcoxylates d'alcools gras ramifiés comprenant de 12 à 16 atomes de carbone ayant un degré de ramification de 1 à 3,5, avec un degré d'éthoxylation allant jusqu'à 4, et au moins un composé (ii) sélectionné dans le groupe des alcoxylates de composés hydrocarbonés non ioniques, avec un degré d'éthoxylation supérieur à 3, dans lequel si les deux composés (i) et (ii) sont des alcools éthoxylés, le mélange présente un degré bimodal de distribution d'éthoxylation.
  9. Procédé pour la flottation par moussage de minerais non sulfurés selon la revendication 8 dans lequel le composé (ii) est sélectionné dans le groupe des alcoxylates de composés hydrocarbonés non ioniques du groupe des alcools gras, des aminés grasses, des éthanolamides gras, des diéthanolamides gras, des acides gras et des triglycérides avec un degré d'éthoxylation supérieur à 3.
  10. Procédé selon la revendication 8 ou 9 où la formule moléculaire des composés (i) et (ii) répond à la formule (I)

            R-A     (I)

    dans laquelle pour le composé (i) R est un groupe alkyle ou alcényle comprenant de 12 à 16, de préférence de 12 à 15, atomes de carbone, et où ledit groupe alkyle ou alcényle a un degré de ramification de 1 à 3, et dans laquelle pour le composé (ii) R est n'importe quel groupe alkyle, aryle ou alcényle ramifié ou linéaire comprenant de 8 à 24 atomes de carbone ; A est sélectionné parmi les groupes
    O-(PO)x(EO)y(PO)zH, pour les composés (i) et (ii)
    (CO)N(CH2CH2O(PO)x(EO)y(PO)zH)2, pour le composé (ii)
    (CO)NH(CH2CH2O(PO)x(EO)y(PO)zH), pour le composé (ii)
    (CO)O((PO)x(EO)y(PO)zH), pour le composé (ii)
    N(PO)x(EO)y(PO)zH)2, pour le composé (ii)
    (CO)O((PO)x(EO)y(PO)zOCH2CH(O(PO)x(EO)y(PO)zO(CO)R)CH2O et
    ((PO)x(EO)y(PO)zO(CO)R), pour le composé (ii),
    dans laquelle PO est un motif propylèneoxy et EO est un motif éthylèneoxy, et pour le composé (i) ; x est un nombre de 0 à 2, de préférence égal à 0, y est un nombre de 0 à 4, de préférence de 0 à 3, plus préférablement de 0 à 2,5, encore plus préférablement de 0 à 2,3 et de manière préférée entre toutes de 0 à 2, et z est un nombre de 0 à 2, de préférence égal à 0, et pour le composé (ii) x est un nombre de 0 à 20, de préférence égal à 0, y est un nombre supérieur à 3 allant jusqu'à 30, de préférence de 4 à 20, plus préférablement de 5 à 15, encore plus préférablement de 7 à 12, et z est un nombre de 0 à 20, de préférence égal à 0.
  11. Procédé selon l'une quelconque des revendications 8 à 10 qui comprend les étapes
    i) conditionnement d'un minerai non sulfuré sous forme de pâte, dans lequel le minerai comprend un minéral contenant du phosphate, et des minéraux de la gangue, avec la composition collectrice, et éventuellement d'autres adjuvants de flottation et
    ii) mise en œuvre d'un procédé de flottation par moussage pour récupérer le ou les minéraux contenant du phosphate.
  12. Procédé selon l'une quelconque des revendications 8 à 11 dans lequel ledit collecteur primaire est un composé tensioactif amphotère sélectionné dans le groupe constitué par les composés répondant à la formule (II)
    Figure imgb0026
    dans laquelle R1 est un groupe hydrocarbyle comprenant de 8 à 22, de préférence de 12 à 18, atomes de carbone ; A est un groupe alkylèneoxy comprenant de 2 à 4 atomes de carbone ; p est un nombre égal à 0 ou 1 ; q est un nombre de 0 à 5, de préférence égal à 0 ; R2 est un groupe hydrocarbyle comprenant de 1 à 4 atomes de carbone, de préférence 1, ou R2 est le groupe
    Figure imgb0027
    dans lequel R1, A, p et q ont la même signification que ci-dessus, Y- est sélectionné dans le groupe constitué par COO- et SO3 -, de préférence COO- ; n est un nombre égal à 1 ou 2, de préférence égal à 1 ; M est un cation qui peut être monovalent ou divalent et inorganique ou organique, et r est un nombre égal à 1 ou 2 ; ou lorsque le composé (II) est sous sa forme protonée acide sans cation externe (Mr+) 1/r ; et les composés répondant à la formule (III)
    Figure imgb0028
    dans laquelle R2 est un groupe hydrocarbyle comprenant de 8 à 22, de préférence de 12 à 18, atomes de carbone, D est -CH2- ou -CH2CH2-, k vaut de 0 à 4, de préférence de 0 à 3, et de manière préférée entre toutes de 0 à 2, et M est un atome d'hydrogène ou un cation, tel que le sodium ou le potassium ; ou
    un composé tensioactif anionique sélectionné dans le groupe constitué par les acides gras, les sulfonates, les alkylphosphates, les alkylsulfates et les composés de formule (IV)
    Figure imgb0029
    dans laquelle R est un groupe hydrocarbyle comprenant de 7 à 23, de préférence de 11 à 21, atomes de carbone, éventuellement substitué ; R1 est H ou CH3, de préférence H ; R2 est H ou un groupe alkyle en C1 à C4, de préférence H ; R3 est H ou CH3, de préférence CH3 ; n est un nombre de 1 à 20 ; p est un nombre de 1 à 3, de préférence égal à 1 ; X est H+ ou un cation qui est organique ou inorganique, et m représente la valence du cation et est un nombre de 1 à 2, de préférence égal à 1 ; et des mélanges de ceux-ci.
  13. Procédé selon l'une quelconque des revendications 8 à 12 dans lequel le rapport pondéral entre le collecteur primaire et le collecteur secondaire est compris dans la plage de 15:85 à 99:1.
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EP3194077B1 (fr) 2014-09-18 2020-08-12 Nouryon Chemicals International B.V. Utilisation d'alcools ramifiés et alkoxylates associés comme collecteurs secondaires
MA53497B1 (fr) 2018-08-30 2025-05-30 Basf Se Enrichissement de phosphate à partir de minerais contenant du phosphate par flottation et composition de collector associée
WO2020083793A1 (fr) 2018-10-23 2020-04-30 Basf Se Composition de collecteur et procédé de flottation pour l'enrichissement de phosphate
WO2020212592A1 (fr) * 2019-04-19 2020-10-22 Nouryon Chemicals International B.V. Compositions de collecteur contenant un acide aminé n-acylé et procédé de traitement de minerais non sulfurés
EP4087686A1 (fr) 2020-01-09 2022-11-16 Basf Se Procédé de flottation d'un minerai contenant du phosphate
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