EP0368061B1 - Dérivés tensio-actifs d'acides gras et/ou d'esters d'acides gras comme collecteurs pour la flottation de minerais non sulfurés - Google Patents

Dérivés tensio-actifs d'acides gras et/ou d'esters d'acides gras comme collecteurs pour la flottation de minerais non sulfurés Download PDF

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Publication number
EP0368061B1
EP0368061B1 EP89119493A EP89119493A EP0368061B1 EP 0368061 B1 EP0368061 B1 EP 0368061B1 EP 89119493 A EP89119493 A EP 89119493A EP 89119493 A EP89119493 A EP 89119493A EP 0368061 B1 EP0368061 B1 EP 0368061B1
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EP
European Patent Office
Prior art keywords
fatty acid
flotation
collectors
esters
ore
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP89119493A
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German (de)
English (en)
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EP0368061A1 (fr
Inventor
Ansgar Dr. Behler
Rita Köster
Wolfgang Dr. Von Rybinski
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • 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
    • 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

Definitions

  • the invention relates to the use of surface-active fatty acid ester and / or fatty acid derivatives, which can be obtained via the reaction of epoxidized fatty acid esters with sulfur trioxide, subsequent reaction with nucleophilic reagents and optionally saponification of the ester bond, as a collector in the flotation of non-sulfidic ores.
  • Non-sulfidic minerals in the sense of the present invention are, for example, apatite, fluorite, scheelite, barite, iron oxides and other metal oxides, e.g. B. the oxides of titanium and zirconium, as well as certain silicates and aluminosilicates.
  • the ore is first crushed and dry, but preferably wet-ground and suspended in water.
  • collectors are usually added, often in connection with foaming agents and possibly other auxiliary reagents such as regulators, pushers (deactivators) and / or stimulants (activators), which support the separation of the valuable minerals from the gangue minerals of the ore during the subsequent flotation.
  • these reagents are usually allowed to act on the finely ground ore for a certain time (conditioning).
  • the collector ensures that the surface of the minerals is rendered hydrophobic, so that these minerals adhere to the gas bubbles formed during the aeration.
  • the mineral components are made hydrophobic selectively in such a way that the undesirable components of the ore do not adhere to the gas bubbles.
  • the mineral-containing foam is stripped off and processed.
  • the aim of flotation is to extract the mineral of value from the ores in the highest possible yield and at the same time to obtain the best possible enrichment of the mineral.
  • anionic surfactants as collectors in the flotation of non-sulfidic ores is in itself state of the art.
  • Known anionic collectors are, for example, saturated and unsaturated fatty acids, alkyl sulfates, alkyl ether sulfates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl benzene sulfonates, alkyl sulfonates, petroleum sulfonates, acylatylates, alkyl phosphates and alkyl ether phosphates.
  • the invention therefore relates to the use of surface-active fatty acid ester and / or fatty acid derivatives which can be obtained by reacting epoxidized fatty acid esters with 1 to 3 moles of sulfur trioxide per mole of epoxy oxygen at 20 to 100 ° C, the reaction product (A) with nucleophilic reagents , selected from the group consisting of hydroxides, alcoholates, phenolates, carboxylates, ammonia, primary, secondary and tertiary amines, reacting and optionally saponifying the ester bond, in quantities of 50 to 2000 g per metric ton of crude ore as collector the flotation of non-sulfidic ores.
  • nucleophilic reagents selected from the group consisting of hydroxides, alcoholates, phenolates, carboxylates, ammonia, primary, secondary and tertiary amines
  • the substances proposed here as collectors are known from DE-A-36 12 481.
  • the epoxy fatty acid esters used as starting material in their production can in turn be obtained by epoxidation of esters of unsaturated fatty acids, for example according to the method described in J. Am. Chem. Soc. 67 (1945), pp. 412-414 can be obtained by reacting unsaturated fatty acid esters with peracetic acid.
  • Suitable fatty acid esters are those of unsaturated fatty acids with 14 to 22 carbon atoms and mono- or polyhydric alcohols with 1 to 6 carbon atoms, for example methyl esters, ethyl esters, isopropyl esters, ethylene glycol esters, triglycerides, trimethylol propane esters, pentaerythritol esters and sorbitan esters.
  • Preferred epoxy fatty acid esters are epoxidized C1-C4 alkyl esters of monounsaturated fatty acids with 16 to 22 carbon atoms or such Fatty acid mixtures consisting predominantly of monounsaturated fatty acids with 16 to 22 carbon atoms are used.
  • the epoxidized esters of technical fatty acid fractions which contain up to about 20% by weight of saturated fatty acids with 14 to 22 carbon atoms and / or up to about 50% by weight of polyunsaturated fatty acids, for example linoleic acid, are also suitable.
  • Portions of non-epoxidized, unsaturated fatty acid esters are also sulfonated on the double bond.
  • the sulfonation on the double bond proceeds in the sense of the known sulfonation of olefins and leads to sulfoalkenecarboxylic esters with -SO3H groups in the alpha position to the double bond, and to 2- and 3-hydroxyalkanesulfonates.
  • the reaction products of the first stage process are characterized in that they now have a glycol sulfate group instead of the epoxy groups.
  • This is reactive and can be implemented in the second stage with numerous nucleophilic reagents with the formation of new fatty acid ester derivatives.
  • Suitable nucleophilic reagents are hydroxides, alcoholates, phenolates or carboxylates, ammonia, primary, secondary and tertiary amines.
  • the glycol sulfate ring opens with the formation of beta-substituted ethyl sulfate groups according to the following formula: or where, for example, R2 can be a hydrogen atom, a C1-C4 alkyl, phenyl, benzyl or C1-C4 acyl group and R3, R4 and R5 can each represent a hydrogen atom or a C1-C4 alkyl group.
  • the fatty acid ester derivatives accessible in this way have surface-active properties due to the water-solubilizing sulfate ester groups -OSO3 (-) and optionally sulfonate groups -SO3 (-) .
  • metal hydroxides in particular alkali metal hydroxides
  • Sodium or potassium hydroxide is preferably used as the alkali metal hydroxide.
  • the hydrolytic breakdown of the glycol sulfate groups is about 50% by weight when used Alkali metal hydroxide solution at 90 ° C completed after a maximum of 15 to 20 hours. The hydrolysis can be accelerated by using a higher temperature and applying pressure.
  • the anionic surfactant content in the aqueous surfactant solutions obtained can be determined by determining the content of sulfonate groups and sulfate groups by the so-called two-phase titration method (DGF unit method H-111-10). The breakdown of the glycol sulfate groups is complete when the anionic surfactant content no longer increases.
  • sulfonate and sulfate groups can be made by two-phase titration after acid hydrolysis.
  • the sulfate groups can be split off by acid hydrolysis, so that only the content of sulfonate groups is then determined.
  • the surface-active derivatives of free fatty acids also contemplated for use in the context of the invention are obtained from the above-described fatty acid ester derivatives by saponification of the ester bond with at least stoichiometric amounts of alkali metal hydroxide, preferably sodium hydroxide.
  • alkali metal hydroxide preferably sodium hydroxide.
  • reaction product (A) In cases where the reaction product (A) is reacted with alkali metal hydroxide as a nucleophilic reagent, the reaction product (A) can be converted into the desired di-salt in one step if it is reacted with an amount of alkali metal hydroxide which both sufficient for the hydrolytic breakdown of the glycol sulfate groups and for the hydrolysis of the ester bonds.
  • Mixtures can be selected by suitable selection of the working-up conditions for the reaction product (A) be prepared from surface-active fatty acid ester derivatives and fatty acid derivatives.
  • surface-active fatty acid ester and / or fatty acid derivatives are used, which are obtainable by contacting the reaction product (A) in aqueous solution with 1 to 2 moles of alkali metal hydroxide per mole of sulfur trioxide added and until the glycol sulfate groups are split up or heated to the hydrolysis of the ester groups.
  • the invention further relates to a process for separating non-sulfidic minerals from an ore by flotation, in which ground ore is mixed with water to form a suspension, air is passed into the suspension in the presence of a collector and the foam formed is separated off together with the mineral contained therein ,
  • Bie one uses as a collector in amounts of 50 to 2000 g per metric ton of raw ore fatty acid ester and / or fatty acid derivatives, which are obtainable by reacting epoxidized fatty acid esters with 1 to 3 moles of sulfur trioxide per mole of epoxy oxygen at 20 to 100 ° C , the reaction product (A) with nucleophilic reagents, selected from the group formed by hydroxides, alcoholates, phenates, carboxylates, ammonia, primary, secondary and tertiary amines, and optionally saponifies the ester bond.
  • nucleophilic reagents selected from the group formed by hydroxides, alcoholates, phenates, carboxylates
  • the collectors In order to achieve economically useful results in the flotation of non-sulfidic ores, the collectors must be used in a certain minimum amount. However, a maximum amount of collectors must not be exceeded, since otherwise the foam formation becomes too strong and the selectivity towards the valuable minerals decreases.
  • the amounts in which the collectors to be used according to the invention are used depend in each case on the type of ores to be floated and on their content of valuable minerals. As a result, the the necessary quantities vary within wide limits. In general, the collectors are used in quantities of 50 to 2000, preferably 100 to 1500, g per metric ton of crude ore.
  • Anionic collectors suitable for combination with the substances to be used according to the invention are, for example, fatty acids, alkyl sulfates, alkyl ether sulfates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl benzene sulfonates, petroleum sulfonates, acyl lactates, alkyl phosphates, alkyl ether phosphates and styrene phosphonic acid.
  • Suitable cationic collectors are e.g.
  • ampholytic collectors are, for example, sarcosides, taurides, N-substituted aminopropionic acids and N- (1,2-dicarboxyethyl) -N-alkylsulfosuccinamates.
  • nonionic collectors examples include adducts of ethylene oxide with alkylphenols or fatty alcohols, adducts of ethylene oxide and propylene oxide with fatty alcohols, fatty alcohol / ethylene oxide adducts end-capped with short-chain alkyl radicals and alkylglucosides.
  • the surface-active fatty acid ester and / or fatty acid derivatives to be used according to the invention are used in the known flotation processes for non-sulfidic ores instead of known collectors used. Accordingly, in addition to the collectors described, the customary reagents such as foaming agents, regulators, activators, deactivators, etc. are also added to the aqueous sponges of the ground ores.
  • the flotation is carried out under the conditions of the methods of the prior art. In this context, reference is made to the following references on the technological background of ore processing: H. Schubert, Processing of Solid Mineral Substances, Leipzig 1967; B.
  • a preferred area of use for the collector mixtures to be used according to the invention is the processing of ores such as Scheelite, Barite or Apatite.
  • the grain size of the flotation task was less than 200 ⁇ m.
  • the products C, D, E and F described in the production examples were used as collectors.
  • Products C and E were added to the flotation slurries in a dosage of 300 g / t and products D and F in a dosage of 200 g / t.
  • Sodium oleate (product X) in a dosage of 500 g / t was used as a reference collector. (All information on the collector concentration relates to active substance).
  • the flotation experiments were carried out in a modified Hallimond tube (microflotation cell) according to B. Dobias, Colloid & Polymer Science, 259 (1981) pages 775-776, each with 2 g of ore at 23 ° C. and the naturally occurring pH value. Distilled water was used to prepare the flotation slurry. The conditioning time was 15 minutes each. During the flotation, an air stream was passed through the slurry at a flow rate of 4 ml / min. The flotation lasted 2 minutes in all experiments.
  • the substances to be used according to the invention Compared to sodium oleate, the substances to be used according to the invention, at low doses, lead to higher values for the WO3 output.
  • the WO3 content in the flotation concentrate is not significantly lower despite the higher output. Since the highest possible yield must be achieved for an economical processing of ores in the first flotation stage with sufficient selectivity with a low collector dosage, the products to be used according to the invention offer clear advantages.
  • a baryter ore from Mexico was used as the flotation task, which had the following chemical composition with regard to the main components:
  • the flotation task had the following grain size distribution:
  • Products A and B described in the examples were used as collectors in doses of 230 and 170 g / t, respectively.
  • Sodium dodecylbenzenesulfonate (product Y) in a dosage of 500 g / t, was used as a reference collector.
  • the flotation experiments were carried out in a laboratory flotation machine (type D 2 from Denver Equipment with a 1 l flotation cell). Water with a Ca2+ ion content of 144 mg / l was used to produce the flotation turbidity. The cloud density was 500 g / l. Soda water glass with a dosage of 1000 g / t was used as the pusher in all experiments. The flotation took place at pH 9.5. The pusher, like the collector used, was conditioned at 1100 rpm for 5 minutes. The preconcentrate was cleaned twice in the 1 l cell without further reagent addition. For the The preconcentrate and the cleaning stages were each floated at 1000 rpm for 6 minutes.
  • the flotation task had the following grain size distribution:
  • Products A and B described in the examples were used as collectors in a dosage of 200 g / t.
  • Sodium oleate (product X) in a dosage of 700 g / t was used as the comparison collector.
  • the flotation experiments were carried out in the laboratory flotation machine type D 2 mentioned in Example 2.
  • the preflotation took place in 2 l cells, the cleaning flotation in 1 l cells.
  • the cloud density was 36% by weight of solids in water with a total hardness of 27 ° dH.
  • Sodium water glass with a dosage of 400 g / t was used as the pusher.
  • Flotation was carried out at a pH of approx. 8, as established by the addition of water glass.
  • Pushers and collectors were conditioned at 1400 rpm for 5 minutes each.
  • the flotation was carried out at 1200 rpm for 6 minutes.
  • the substances to be used according to the invention result in a substantially higher value mineral yield with a considerably reduced dosage.
  • the very high P2O5 output also explains the somewhat lower mineral value in the concentrate. Because for an economical processing of ores, the extraction of valuable mineral and the required collector dosage in the foreground stand, the products to be used according to the invention offer considerable advantages over the conventional apatite collector sodium oleate.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Epoxy Compounds (AREA)
  • Fats And Perfumes (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Claims (8)

  1. Utilisation de dérivés tensioactifs d'esters d'acide gras et/ou de d'acides gras, qu'on peut obtenir en faisant réagir des esters d'acide gras non saturés époxydés ayant 14 à 22 atomes de carbone et un ou des alcools à plusieurs valences ayant 1 à 6 atomes de carbone avec 1 à 3 moles de trioxyde de soufre par mole d'oxygène époxyde, entre 20 et 100°C, on fait réagir le produit de réaction (A) avec des réactifs nucléophiles, choisis dans le groupe formé par des hydroxydes, alcoolats, phénolates, carboxylates, ammoniac, amines primaires, secondaires et tertiaires, et le cas échéant on saponifie la liaison ester, l'utilisation se fait à raison de 50 à 2000 g par tonne métrique de minerai brut comme collecteur pour la flottation de minerais non sulfurés.
  2. Utilisation selon la revendication 1, caractérisée en ce qu'on utilise comme C₁₋₄ alkyl esters époxydés d'acides gras monoinsaturés avec 16 à 22 atomes de carbone, ou de mélanges d'acides gras qui sont essentiellement constitués de tels acides gras.
  3. Utilisation selon la revendication 2, caractérisée en ce qu'on utilise comme ester d'acide gras époxydé de l'oléate de méthyle technique époxydé.
  4. Utilisation selon au moins une des revendications 1 à 3, caractérisée en ce qu'on met en contact le produit de réaction (A) en solution aqueuse avec 1 à 2 moles d'hydroxyde de métal alcalin par mole de trioxyde de soufre additionné et qu'on chauffe jusqu'à l'ouverture des groupes sulfate de glycol ou jusqu'à l'hydrolyse des groupes esters.
  5. Procédé de fractionnement de minéraux non sulfurés à partir d'un minerai par flottation, procédé dans lequel on mélange du minerai broyé avec de l'eau à une suspension, on introduit de l'air dans la suspension en présence d'un collecteur et on sépare la mousse formée avec le minéral qui y est contenu, caractérisé en que qu'on utilise comme collecteur à des doses de 50 à 2000 g par tonne métrique de minerai brut des dérivés d' esters d'acide gras et/ou des dérivés d'acides gras, qu'on peut obtenir, en faisant réagir des esters d'acide gras insaturés avec 14 à 22 atomes de carbone, époxydés avec 1 à 3 moles de trioxyde de soufre par mole d'oxygène époxyde, entre 20 et 100°C, on fait réagir le produit de réaction (A) avec des réactifs nucléophiles, choisis dans le groupe formé par des hydroxydes, alcoolats, phénolates, carboxylates, ammoniac, amines primaires, secondaires et tertiaires, et le cas échéant on saponifie la liaison ester.
  6. Procédé selon la revendication 5, caractérisé en ce qu'on met en oeuvre des esters d'acides gras et/ou des dérivés d'acides gras tensioactifs à des doses de 100 à 1500 g par tonne métrique.
  7. Procédé selon au moins une des revendications 5 et 6, caractérisé en ce qu'on met en oeuvre les esters d'acide gras et/ou les dérivés d'acides gras tensioactifs avec les collecteurs connus.
  8. Procédé selon au moins l'une des revendications 5 à 7, caractérisé en ce que le minerai est constitué de scheelite, baryte ou apatite.
EP89119493A 1988-10-29 1989-10-20 Dérivés tensio-actifs d'acides gras et/ou d'esters d'acides gras comme collecteurs pour la flottation de minerais non sulfurés Expired - Lifetime EP0368061B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3836891 1988-10-29
DE3836891A DE3836891A1 (de) 1988-10-29 1988-10-29 Grenzflaechenaktive fettsaeureester- und/oder fettsaeurederivate als sammler bei der flotation von nichtsulfidischen erzen

Publications (2)

Publication Number Publication Date
EP0368061A1 EP0368061A1 (fr) 1990-05-16
EP0368061B1 true EP0368061B1 (fr) 1993-03-17

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP89913082A Pending EP0440746A1 (fr) 1988-10-29 1989-10-20 Derives tensio-actifs d'ester d'acide gras et/ou d'acide gras servant de collecteurs lors de la flottation de minerais non sulfures
EP89119493A Expired - Lifetime EP0368061B1 (fr) 1988-10-29 1989-10-20 Dérivés tensio-actifs d'acides gras et/ou d'esters d'acides gras comme collecteurs pour la flottation de minerais non sulfurés

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP89913082A Pending EP0440746A1 (fr) 1988-10-29 1989-10-20 Derives tensio-actifs d'ester d'acide gras et/ou d'acide gras servant de collecteurs lors de la flottation de minerais non sulfures

Country Status (10)

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EP (2) EP0440746A1 (fr)
AU (1) AU627805B2 (fr)
BR (1) BR8907743A (fr)
CA (1) CA2001736A1 (fr)
DE (2) DE3836891A1 (fr)
ES (1) ES2041939T3 (fr)
PT (1) PT92128B (fr)
TR (1) TR24025A (fr)
WO (1) WO1990004459A1 (fr)
ZA (1) ZA898203B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4025371A1 (de) * 1990-08-10 1992-02-13 Kali & Salz Ag Verfahren zur reinigung von elektrostatisch gewonnenem steinsalz
CN107442294A (zh) * 2017-09-04 2017-12-08 江西理工大学 一种在常温下浮选获得合格白钨精矿的方法
CN108543631A (zh) * 2018-05-10 2018-09-18 江西理工大学 一种矽卡岩型白钨矿的选矿方法
CN111804442A (zh) * 2019-04-10 2020-10-23 杨立 一种基于低温皂化反应的反浮选方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE670048C (de) * 1935-11-07 1939-01-10 Erz & Kohleflotation Gmbh Verfahren zur Schwimmaufbereitung nichtsulfidischer Mineralien unter Zusatz eines Salzes einer sulfurierten Fettsaeure
GB589800A (en) * 1939-07-03 1947-07-01 Thorbjorn Heilmann Improvements relating to the separation of calcium carbonate by froth flotation
DE3612481A1 (de) * 1986-04-14 1987-10-15 Henkel Kgaa Verfahren zur herstellung von grenzflaechenaktiven fettsaeureester-derivaten

Also Published As

Publication number Publication date
PT92128B (pt) 1995-07-03
PT92128A (pt) 1990-04-30
ES2041939T3 (es) 1993-12-01
TR24025A (tr) 1991-02-04
CA2001736A1 (fr) 1990-04-29
EP0368061A1 (fr) 1990-05-16
DE58903805D1 (de) 1993-04-22
AU627805B2 (en) 1992-09-03
WO1990004459A1 (fr) 1990-05-03
DE3836891A1 (de) 1990-05-03
BR8907743A (pt) 1991-08-20
EP0440746A1 (fr) 1991-08-14
ZA898203B (en) 1990-07-25
AU4631389A (en) 1990-05-14

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