WO1990004459A1 - Grenzflächenaktive fettsäureester- und/oder fettsäurederivate als sammler bei der flotation von nichtsulfidischen erzen - Google Patents

Grenzflächenaktive fettsäureester- und/oder fettsäurederivate als sammler bei der flotation von nichtsulfidischen erzen Download PDF

Info

Publication number
WO1990004459A1
WO1990004459A1 PCT/EP1989/001256 EP8901256W WO9004459A1 WO 1990004459 A1 WO1990004459 A1 WO 1990004459A1 EP 8901256 W EP8901256 W EP 8901256W WO 9004459 A1 WO9004459 A1 WO 9004459A1
Authority
WO
WIPO (PCT)
Prior art keywords
fatty acid
flotation
ester
collectors
acid derivatives
Prior art date
Application number
PCT/EP1989/001256
Other languages
German (de)
English (en)
French (fr)
Inventor
Ansgar Behler
Rita Köster
Wolfgang Von Rybinski
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to BR898907743A priority Critical patent/BR8907743A/pt
Publication of WO1990004459A1 publication Critical patent/WO1990004459A1/de
Priority to FI912023A priority patent/FI912023A0/fi

Links

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

  • Surfactant fatty acid ester and / or fatty acid derivatives as collectors in the flotation of non-sulfidic ores.
  • 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, Scheel it, 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 ground and dry, but preferably ground wet, 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 fans (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 brings to reaction and optionally saponified the ester bond, as a collector in the flotation of non-sulfidic ores.
  • the substances proposed here as collectors are from the
  • 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. 62 (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 C 1 -C 4 -alkyl esters of monounsaturated fatty acids with 16 to 22 carbon atoms or such Fatty acid mixtures, which consist 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.
  • Epoxy fatty acid esters with a content of 3 to 5% by weight of epoxy oxygen in particular epoxidized oleic acid methyl testers or epoxidized methyl esters of fatty acid fractions which contain more than 50% by weight of oleic acid, are preferred.
  • R 1 in the case of the C 1 to C 4 alkyl esters is an alkyl group having 1 to 4 C atoms.
  • the sum (x + y) is a number from 9 to 17.
  • the sulfonation on the double bond proceeds in the sense of the known sulfonation of olefins and leads to sulfoalkenecarboxylic esters with -SO 3 H groups in the alpha position to the double bond, and to 2- and 3-hydroxyalkanesulfonates.
  • reaction products of the first stage of the process according to the invention are distinguished 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 e.g. Hydroxides, alcoholates, phenates 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:
  • R 2 can be a hydrogen atom, a C 1 -C 4 alkyl, phenyl, benzyl or C 1 -C 4 acyl group and R 3 , R 4 and R 5 can each be a hydrogen atom or a C 1 -C Can represent 4 alkyl group.
  • the fatty acid ester derivatives accessible in this way have surface-active properties due to the water-solubilizing sulfate ester groups -OSO 3 (-) and optionally sulfonate groups -SO 3 (-).
  • reaction product (A) Preference is given to the further reaction of the reaction product (A) with metal hydroxides, in particular alkali metal hydroxides, as a nucleophilic reagent with hydrolytic splitting of the glycol sulfate group to give beta-hydroxyethanesulfate groups.
  • 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 approximately 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 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 fatty acid ester derivatives described above 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 work-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 the separation of 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 resulting foam is separated off together with the mineral contained therein , where one uses fatty acid ester and / or fatty acid derivatives as collectors, 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 for the reaction brings and optionally saponified the ester bond.
  • the collectors In order to achieve economically viable 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 doped and on their content of valuable minerals. As a result, the fluctuations in the required amounts vary widely.
  • the collectors according to the invention are used in amounts 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 prior art methods. 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.
  • Anionic surfactant (DGF methods * H-III-10): 19.0% by weight
  • Anionic surfactant (DGF method H-III-100): 15.9% by weight
  • 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 refers 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.
  • Table I The results of the flotation tests with the substance to be used according to the invention are summarized in Table I and compared with the values obtained with sodium oleate as the reference substance.
  • the substances to be used according to the invention lead to higher values for the W03 output when the dosage is low.
  • the WO 3 content in the flotation concentrate is not significantly lower. 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.
  • Example 2
  • 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 tests were carried out in a laboratory flotation machine (type D 2 from Denver Equipment with a 1 1 flotation cell). Water with a Ca 2+ 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 in 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) was used in a dosage of 700 g / t as a comparison collector.
  • the flotation tests 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 became 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 significantly higher value mineral yield with a considerably reduced dosage.
  • the very high P 2 O 5 output also explains the somewhat lower mineral value in the concentrate.
  • the products to be used according to the invention offer considerable advantages over the conventional apatite collector sodium oleate.

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Epoxy Compounds (AREA)
  • Fats And Perfumes (AREA)
  • Manufacture And Refinement Of Metals (AREA)
PCT/EP1989/001256 1988-10-29 1989-10-20 Grenzflächenaktive fettsäureester- und/oder fettsäurederivate als sammler bei der flotation von nichtsulfidischen erzen WO1990004459A1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
BR898907743A BR8907743A (pt) 1988-10-29 1989-10-20 Derivados de acido graxo e/ou de ester de acido graxo tensoativos como coletores na flotacao de minerios nao sulfidicos
FI912023A FI912023A0 (fi) 1988-10-29 1991-04-26 Ytaktiva fettsyraester- och/eller fettsyraderivat som samlare foer flotation av ej-sulfidmalmer.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3836891A DE3836891A1 (de) 1988-10-29 1988-10-29 Grenzflaechenaktive fettsaeureester- und/oder fettsaeurederivate als sammler bei der flotation von nichtsulfidischen erzen
DEP3836891.9 1988-10-29

Publications (1)

Publication Number Publication Date
WO1990004459A1 true WO1990004459A1 (de) 1990-05-03

Family

ID=6366156

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1989/001256 WO1990004459A1 (de) 1988-10-29 1989-10-20 Grenzflächenaktive fettsäureester- und/oder fettsäurederivate als sammler bei der flotation von nichtsulfidischen erzen

Country Status (10)

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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Families Citing this family (3)

* 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

Citations (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

Patent Citations (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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
EP0368061A1 (de) 1990-05-16
EP0440746A1 (de) 1991-08-14
DE58903805D1 (de) 1993-04-22
ZA898203B (en) 1990-07-25
PT92128A (pt) 1990-04-30
PT92128B (pt) 1995-07-03
DE3836891A1 (de) 1990-05-03
TR24025A (tr) 1991-02-04
EP0368061B1 (de) 1993-03-17
CA2001736A1 (en) 1990-04-29
BR8907743A (pt) 1991-08-20
ES2041939T3 (es) 1993-12-01
AU627805B2 (en) 1992-09-03
AU4631389A (en) 1990-05-14

Similar Documents

Publication Publication Date Title
EP0201815B2 (de) Verwendung von Tensidgemischen als Hilfsmittel für die Flotation von nichtsulfidischen Erzen
EP0270933B1 (de) Tensidmischungen als Sammler für die Flotation nichtsulfidischer Erze
EP0585277B1 (de) Verfahren zur gewinnung von mineralien aus nichtsulfidischen erzen durch flotation
EP0609257B1 (de) Verfahren zur herstellung von eisenerzkonzentraten durch flotation
EP0219057B1 (de) Verwendung von Gemischen enthaltend nichtionische Tenside als Hilfsmittel für die Flotation von nichtsulfidischen Erzen
EP0108914B1 (de) Flotationshilfsmittel und Verfahren zur Flotation nichtsulfidischer Minerale
EP0368061B1 (de) Grenzflächenaktive Fettsäureester- und/oder Fettsäurederivate als Sammler bei der Flotation von nichtsulfidischen Erzen
EP0270986B1 (de) Alkylsulfosuccinate auf der Basis von propoxylierten sowie propoxylierten und ethoxylierten Fettalkoholen als Sammler für die Flotation nichtsulfidischer Erze
CA1320769C (en) N-alkyl and n-alkenyl aspartic acids as co-collectors for the flotation of non-sulfidic ores
EP0344553B1 (de) Tensidmischungen als Sammler für die Flotation nichtsulfidischer Erze
WO1991018674A1 (de) Verfahren zur gewinnung von mineralien aus nichtsulfidischen erzen durch flotation
DE4325017A1 (de) Verfahren zur Flotation von Kupfer- und Kobalterzen
DE4010279A1 (de) Verfahren zur gewinnung von mineralien aus nichtsulfidischen erzen durch flotation
WO1993011100A1 (de) Verfahren zur gewinnung von mineralien aus nichtsulfidischen erzen durch flotation
WO1992004981A1 (de) Verfahren zur gewinnung von mineralien aus nichtsulfidischen erzen durch flotation
EP0241839A2 (de) Verfahren zur Herstellung von grenzflächenaktiven Fettsäureester-Derivaten
DE2263988C2 (de) Flotationsschäumer

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR FI US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LU NL SE

WWE Wipo information: entry into national phase

Ref document number: 1989913082

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 912023

Country of ref document: FI

WWP Wipo information: published in national office

Ref document number: 1989913082

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1989913082

Country of ref document: EP