EP0107561B1 - Perfectionnement à la flottation de minerais - Google Patents

Perfectionnement à la flottation de minerais Download PDF

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Publication number
EP0107561B1
EP0107561B1 EP83401956A EP83401956A EP0107561B1 EP 0107561 B1 EP0107561 B1 EP 0107561B1 EP 83401956 A EP83401956 A EP 83401956A EP 83401956 A EP83401956 A EP 83401956A EP 0107561 B1 EP0107561 B1 EP 0107561B1
Authority
EP
European Patent Office
Prior art keywords
surfactant
collector
flotation
composition according
composition
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
Application number
EP83401956A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0107561A1 (fr
Inventor
Raymond Delourme
Jean-Louis Detienne
Jacques Komornicki
Jacques Tellier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Societe Nationale Elf Aquitaine Production SA
Original Assignee
Societe Nationale Elf Aquitaine Production SA
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 Societe Nationale Elf Aquitaine Production SA filed Critical Societe Nationale Elf Aquitaine Production SA
Publication of EP0107561A1 publication Critical patent/EP0107561A1/fr
Application granted granted Critical
Publication of EP0107561B1 publication Critical patent/EP0107561B1/fr
Expired legal-status Critical Current

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
    • B03D1/00—Flotation
    • 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
    • B03D1/01—Organic compounds containing nitrogen
    • B03D1/011—Quaternary ammonium compounds
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents

Definitions

  • the present invention relates to an improvement in the flotation of ores, in particular ores based on oxides and sulphides. It relates more specifically to the use, for flotation, of organic collectors with little or no water solubility; such collectors are found in particular among thio-organic compounds.
  • the invention relates to a flotation process using collectors which are poorly or not water-soluble; it includes new collectors of this type, as well as a composition containing flotation collectors.
  • the present invention provides a substantial improvement in this matter: it makes possible the use of certain collectors which are very insufficiently soluble or practically insoluble in water, to give excellent results all the same, in terms of both yield and which concerns selectivity.
  • the ore flotation process according to the invention is characterized in that the flotation collector is used in the form of a composition which, added to the ore pulp to be treated, gives a microemulsion.
  • the collector is an organic thiocompound and it is mixed with a surfactant compound, added with a co-surfactant.
  • the invention comprises the application of this process to the enrichment of ores with sulphides or / and metal oxides, in particular of Cu, Pb, Zn and Mo. It also comprises a composition of ore flotation collector, characterized in what it consists of is a mixture of a compound serving as a collector, with a surfactant compound, and a co-surfactant, the whole being dilutable with water with the formation of a microemulsion.
  • microemulsions according to the invention are with external water, the co-surfactant being able to not be soluble in water, unlike the adjuvants of the polyglycol type recommended in the prior art, mentioned above.
  • microemulsions are systems very different from emulsions: their definition is known in the art, so it is no longer necessary to recall it here (P. A. Winsor Trans. Faraday Soc. 1948-44-376).
  • Two collecting agents are generally organic compounds containing sulfur, in particular mercaptans, thioethers, polysulphides, etc.
  • the invention makes it possible to very significantly improve the collecting effect of mercaptans with more than 8 carbon atoms and more especially in C 12 to C is , that is to say mercaptans very poorly soluble in water.
  • collectors giving excellent results, according to the present invention, are polysulfides RS x -R 'where R and R' have the same meaning as above, while x takes mean values of the order of 2 to 8 and, most often, from 3 to 5; these polysulphides are new flotation agents, the interest of which comes out especially when they are put in the form of microemulsion.
  • Dihexyl or dioctyl sulfides Dihexyl or dioctyl sulfides.
  • the sulfides C 10 H 21 SCH 3 , C 12 H 25 SCH 3 and C 14 H 29 SCH 3 give excellent results with chalcopyrite, galena, blende and pyrite in the conventional method, and their counterparts with alkyls heavier instead of CH 3 are suitable for microemulsion.
  • the conventional manner is still very well suited for methyl and ethyl esters, while for esters of higher alcohols, in particular C 4 to C 12 , it is preferable to use the collector in microemulsion.
  • the polysulfides RS x -R or RS x- R ' they give good results, without it being necessary to put them in microemulsion, as long as their molar mass and the sulfur content do not exceed a certain limit.
  • di-hexyl trisulfide C 6 H 13 SSSC 6 H 13 are good collectors of chalcopyrite and galena, but the results are better when they are used in microemulsion; for polysulphides of higher molar masses, the improvement, due to the microemulsion, becomes very significant.
  • compositions of the collectors for flotation resides in that the liquid phase, associated with the collector itself, consists of a liquid surfactant or at least dissolved in a small amount of suitable solvent.
  • preferred surfactants are nonionic compounds which can be selected from the many classes known per se; these are, for example, polyxyalkylene which can carry different groups, corresponding to the general formula wherein R may be an alkyl to C 30, preferably C 6 -C 18; an aryl or substituted aryl preferably bearing a linear C 1 -C 18 or better C 6 -C 12 alkyl; a heterocyclic group or a cycloalkyl or optionally a hydrogen atom; R 'denotes an alkylene, generally linear, most often C, to C 6 ; n is an integer from 1 to 12 and, most often, from 2 to 6.
  • the industrially most common compounds, corresponding to formula (1) are polyoxyethylenes and alkyl phenyl polyoxyethylenes, known
  • Polyoxyethylenes can also be used in the form of their adducts with sorbitan esters, known under the name of "TWEEN •.
  • Other useful surfactant compounds are polyoxyalkylene esters or ethers of formula (1), such as laurates, stearates, oleate or ricinoleate of a polyoxyethylene, optionally carrying an alkylphenol group.
  • surfactants of the alkyl glucoside type are also suitable.
  • liquid surfactant compounds listed above are non-ionic compounds which appear to be most suitable. However, it is also possible to use anionic or cationic surfactants, when the desired pH for the pulp treated by flotation allows it. Thus, can the invention be achieved by the use of compositions of collectors mixed in advance, in the form of liquid, with surfactants constituted by petroleum sulfonates, sulfates of fatty alcohols, which are anionic or alkylolamides, fatty amines or quaternary ammoniums, cationic.
  • the surfactant When the surfactant is solid or viscous, it is always possible to create a liquid medium by the addition of a little water or a third solvent, for example a mono- or polyol; moreover, the co-surfactant may be sufficient to make the medium liquid.
  • a third solvent for example a mono- or polyol
  • the composition according to the invention comprises a third constituent, namely a co-surfactant.
  • a co-surfactant The nature and role of this agent are known in the art: it is sufficient, to carry out the invention, to choose one or more co-surfactants from those which have been described in the prior art.
  • the agents in question are organic molecules having a lipophilic part and at least one polar group; these are, for example, alcohols, generally C 3 or more, alkylene glycols, in particular ethylene-, propylene-, butylene- or hexylene glycols; these compounds can be linear or branched.
  • co-agents are alkyl ethers and glycol esters, ketones, fatty acid esters, that is to say more than C 4 and especially C 6 to C 18 , primary and secondary amines. and tertiary, preferably with more than 4 carbon atoms, urea and its derivatives, etc.
  • alkyl ethers and glycol esters ketones, fatty acid esters, that is to say more than C 4 and especially C 6 to C 18 , primary and secondary amines. and tertiary, preferably with more than 4 carbon atoms, urea and its derivatives, etc.
  • it is different alcohols, and more particularly C 3 to C 8 alcohols, which are the most used.
  • the water-solubility of the co-surfactant is not necessary in the case of the present invention.
  • the proportions of the constituents must be such that the microemulsion can be formed.
  • the nature and proportions of the collector, of the compounds surfactants and co-surfactant are chosen so that the mixture obtained is stable, optically isotropic, homogeneous and dilutable with water.
  • a microemulsion or swollen micellar solution of the collector is formed in water, which corresponds to an extremely fine dispersion of this collector; thus, even with substances insoluble in water, used as a collector, it can be dispersed very finely in the pulp at the time of use.
  • compositions according to the invention can be completely anhydrous, but it is possible to add a certain amount of water to them to facilitate their handling.
  • aqueous composition for example:
  • compositions according to the invention may optionally contain other substances, such as, for example, foaming products. They are suitable for different flotation modes, in particular primary, secondary flotation, etc.
  • a first series of flotation tests is carried out on copper sulphide ore from the South African mine at Palabora, with a copper content of 0.45 to 0.48%.
  • 600 g of this ore are ground to a fineness such that 76% of the powder passes through a 148 micron mesh screen.
  • the product is subjected to flotation for 20 minutes at pH 7.5 in a 2.5-liter laboratory cell of the MINEMET M 130 type, in the presence of methyl-isobutyl carbinol (MIBC) as a foaming agent, added at a rate of 25 g per tonne of ore.
  • MIBC methyl-isobutyl carbinol
  • the experienced collector is n.dodecyl mercaptan, the introduction of which into the pulp is carried out in 4 different ways, as indicated below.
  • composition comprises by weight:
  • Example 2 The operations are the same as in Example 1, except that the n.dodecyl mercaptan is replaced by tert.dodecyl mercaptan as a collector.
  • the latter has been used in three different forms.
  • Example 3 The tests of Example 3 are repeated with di-tert.dodecyl trisulfide in place of pentasulfide.
  • the proportions of the two alcohols have been modified: iso-propanol 6.25%, 2-ethylhexanol 3.35%.
  • Example 4ME The flotation test of Example 4ME at 0.173 mole of collector per ton is repeated with di-tert.nonyl trisulfide instead of di-tert.dodecyl.
  • the xanthate allows a greater recovery of Cu, it on the other hand provides concentrates with a copper content much lower than that which one arrives with microemulsified polysulphides.
  • the process according to the invention is likely to increase by about 50% the concentration of desired metal in the flotation product, which constitutes a considerable improvement.
  • the flotation tests were carried out in a manner similar to that of the previous tests, but on a lead-zinc sulphide ore coming from the Pyrenean mine of NERBIOU. This ore contains 4.8% lead and 12.1% zinc.
  • the cell used was the same as in the previous tests.
  • the sample was added beforehand with 30 g of foaming agent per ton.
  • the collector used is n.dodecyl mercaptan. It is taken, in a first test, in the form of a microemulsion ME1, identical to that of Example 1.

Landscapes

  • Paper (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Colloid Chemistry (AREA)
EP83401956A 1982-10-13 1983-10-07 Perfectionnement à la flottation de minerais Expired EP0107561B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8217127A FR2534492A1 (fr) 1982-10-13 1982-10-13 Perfectionnement a la flottation de minerais
FR8217127 1982-10-13

Publications (2)

Publication Number Publication Date
EP0107561A1 EP0107561A1 (fr) 1984-05-02
EP0107561B1 true EP0107561B1 (fr) 1986-07-30

Family

ID=9278232

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83401956A Expired EP0107561B1 (fr) 1982-10-13 1983-10-07 Perfectionnement à la flottation de minerais

Country Status (10)

Country Link
US (2) US4526696A (es)
EP (1) EP0107561B1 (es)
AU (1) AU562922B2 (es)
CA (1) CA1222379A (es)
DE (2) DE3364986D1 (es)
ES (1) ES526760A0 (es)
FI (1) FI74891C (es)
FR (1) FR2534492A1 (es)
SU (1) SU1304737A3 (es)
ZA (1) ZA837619B (es)

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US4789392A (en) * 1984-09-13 1988-12-06 The Dow Chemical Company Froth flotation method
US4684459A (en) * 1985-11-29 1987-08-04 The Dow Chemical Company Collector compositions for the froth flotation of mineral values
DE3517154A1 (de) * 1985-05-11 1986-11-13 Henkel KGaA, 4000 Düsseldorf Verwendung von tensidgemischen als hilfsmittel fuer die flotation von nichtsulfidischen erzen
US4735711A (en) * 1985-05-31 1988-04-05 The Dow Chemical Company Novel collectors for the selective froth flotation of mineral sulfides
ES8800077A1 (es) * 1985-05-31 1987-10-16 Dow Chemical Co Un procedimiento para recuperar minerales de sulfuro, que contienen metales, o minerales de oxido sulfurados, que contienen metales, a partir de una mena
DE3536975A1 (de) * 1985-10-17 1987-04-23 Henkel Kgaa Verwendung von nichtionischen tensiden als hilfsmittel fuer die flotation von nichtsulfidischen erzen
US4676890A (en) * 1985-11-29 1987-06-30 The Dow Chemical Company Collector compositions for the froth flotation of mineral values
FI73899C (fi) * 1986-04-01 1987-12-10 Kemira Oy Foerfarande foer flotation av ett fosfatmineral och ett medel avsett att anvaendas daeri.
DE3641447A1 (de) * 1986-12-04 1988-06-09 Henkel Kgaa Tensidmischungen als sammler fuer die flotation nichtsulfidischer erze
DE3818482A1 (de) * 1988-05-31 1989-12-07 Henkel Kgaa Tensidmischungen als sammler fuer die flotation nichtsulfidischer erze
US4883585A (en) * 1988-10-27 1989-11-28 Phillips Petroleum Company Ore flotation and sulfenyl dithiocarbamates as agents for use therein
US5132008A (en) * 1991-09-30 1992-07-21 Phillips Petroleum Company Preparation of bis(alkylthio) alkanes or bis(arylthio) alkanes and use thereof
GB9600525D0 (en) * 1996-01-11 1996-03-13 Allied Colloids Ltd Process for recovering minerals and compositions for use in this
WO1999014285A1 (en) 1997-09-15 1999-03-25 Sofitech N.V. Electrically conductive non-aqueous wellbore fluids
US6405809B2 (en) 1998-01-08 2002-06-18 M-I Llc Conductive medium for openhold logging and logging while drilling
US6793025B2 (en) * 1998-01-08 2004-09-21 M-I L. L. C. Double emulsion based drilling fluids
FR2855987B1 (fr) * 2003-06-16 2005-11-04 Atofina Composition de mercaptans utilisable dans un procede de flottation de minerais
FR2857278B1 (fr) * 2003-06-16 2005-08-26 Atofina Compositions de mercaptans utilisables dans un procede de flottation de minerais
CN101081378B (zh) * 2007-05-23 2012-04-18 华锡集团车河选矿厂 粗选高浓度开路高效浮选新工艺
EP2017009B1 (en) * 2007-07-20 2013-07-03 Clariant (Brazil) S.A. Reverse iron ore flotation by collectors in aqueous nanoemulsion
US8950090B2 (en) * 2011-02-22 2015-02-10 Nike, Inc. Article of footwear with adjustable cleats
US9266120B2 (en) * 2013-10-01 2016-02-23 Ecolab Usa Inc Collectors for mineral flotation
US9440242B2 (en) * 2013-10-01 2016-09-13 Ecolab Usa Inc. Frothers for mineral flotation
CN104148163B (zh) * 2014-07-29 2016-08-31 广西金山铟锗冶金化工有限公司 一种处理低品位锡铅锌多金属氧化矿的选矿方法
FR3041272B1 (fr) * 2015-09-17 2019-06-14 Arkema France Agent de flottation de structure thiol ether
US9447481B1 (en) * 2015-10-07 2016-09-20 Chevron Phillips Chemical Company Lp Dipentene dimercaptan compositions and use thereof as a mining chemical collector
US10040758B2 (en) 2015-12-28 2018-08-07 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and methods of making same
US10011564B2 (en) 2015-12-28 2018-07-03 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and methods of making same
US10294200B2 (en) 2015-12-28 2019-05-21 Chevron Phillips Chemical Company, Lp Mixed branched eicosyl polysulfide compositions and methods of making same
US9512248B1 (en) 2015-12-28 2016-12-06 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and use thereof as chain transfer agents
US9512071B1 (en) 2015-12-28 2016-12-06 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and methods of making same
US9505011B1 (en) * 2015-12-28 2016-11-29 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and use thereof as mining chemical collectors
CN105903552B (zh) * 2016-04-26 2021-03-12 中南大学 一种高效回收微细粒钼矿的选矿方法

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FR2429617A1 (fr) * 1978-06-27 1980-01-25 Elf Aquitaine Nouveaux collecteurs pour la flottation des minerais
SE436000B (sv) * 1978-06-27 1984-11-05 Elf Aquitaine Forfarande for flotation av mineral
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Also Published As

Publication number Publication date
FI74891C (fi) 1988-04-11
US4594151A (en) 1986-06-10
FR2534492A1 (fr) 1984-04-20
CA1222379A (fr) 1987-06-02
DE107561T1 (de) 1984-09-13
SU1304737A3 (ru) 1987-04-15
US4526696A (en) 1985-07-02
DE3364986D1 (en) 1986-09-04
ZA837619B (en) 1985-02-27
EP0107561A1 (fr) 1984-05-02
ES8501252A1 (es) 1984-12-16
FI833715A (fi) 1984-04-14
FI833715A0 (fi) 1983-10-12
AU2015383A (en) 1984-04-19
ES526760A0 (es) 1984-12-16
FI74891B (fi) 1987-12-31
FR2534492B1 (es) 1984-12-28
AU562922B2 (en) 1987-06-25

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