EP0107561A1 - Flotation of ores - Google Patents
Flotation of ores Download PDFInfo
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- EP0107561A1 EP0107561A1 EP83401956A EP83401956A EP0107561A1 EP 0107561 A1 EP0107561 A1 EP 0107561A1 EP 83401956 A EP83401956 A EP 83401956A EP 83401956 A EP83401956 A EP 83401956A EP 0107561 A1 EP0107561 A1 EP 0107561A1
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- Prior art keywords
- surfactant
- collector
- flotation
- composition according
- composition
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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
- B03D1/012—Organic compounds containing sulfur
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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
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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
- B03D1/008—Organic compounds containing oxygen
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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
- B03D1/01—Organic compounds containing nitrogen
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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
- B03D1/01—Organic compounds containing nitrogen
- B03D1/011—Quaternary ammonium compounds
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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
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
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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
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
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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
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
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- 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 new process according to the invention consists in introducing the flotation collector in the form of a micro-emulsifiable composition into the ore pulp to be treated.
- the new composition for flotation is therefore characterized in that it contains the collector, a surfactant compound, a co-surfactant and optionally water, the whole being dilutable with water from the pulp to be treated, 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).
- 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 18 ′, that is to say mercaptans which are very sparingly soluble in water.
- Another type of collectors giving excellent results are polysulphides 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.
- 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. It is the same for the 2-alkyl thio-acetic acids RSCH 2 COOH which give excellent results, in the ordinary way, when R is C 12 to C 16 , and are well suited in microemulsion for heavier and branched R.
- 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, polyoxyalkylene which can carry different groups, corresponding to the general formula where R can be C 1 -C 30 , preferably C 6 -C 18 alkyl; 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 1 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 type alkyl glucoside 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, fatty alcohol sulfates, 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 cosurfactant.
- a cosurfactant 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.
- fatty acid esters i.e. with more than C 4 and on all in C 6 to C 18 ′ of primary, secondary and tertiary amines, 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 the proportions of collector, surfactant compounds 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 the right rate. 25g 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 ways different, as shown below.
- the following table 1 gives the results of these flotation tests.
- the second vertical column of this table indicates the quantities of n.dodecyl mercaptan used: on the one hand in grams per tonne of ore, g / T, and on the other hand, in brackets, in mole per tonne.
- 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-ethylhexa- The results are collated in Table 4.
- 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 capable of increasing the concentration of desired metal in the flotation product by about 50%, 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.
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- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Colloid Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Procédé de flottation de minerais qui consiste à introduire le collecteur de flottation sous la forme d'une composition microémulsionnable dans la pulpe du minerai à traiter. Les agents collecteurs sont en général des composés organiques renfermant du soufre, notamment mercaptans, thioéthers, polysulfures en général très peu solubles dans l'eau. Ce procédé convient particulièrement bien pour les minerais à base d'oxydes et de sulfures.Ore flotation process which consists in introducing the flotation collector in the form of a microemulsifiable composition into the pulp of the ore to be treated. The collecting agents are generally organic compounds containing sulfur, in particular mercaptans, thioethers, polysulphides in general very poorly soluble in water. This process is particularly suitable for ores based on oxides and sulphides.
Description
La présente invention concerne un perfectionnement à la flottation de minerais, notamment minerais à base d'oxydes et de sulfures. Elle se rapporte plus spécialement à l'utilisation, pour la flottation, de collecteurs organiques peu ou pas solubles dans l'eau ; de tels collecteurs se trouvent notamment parmi des composés thio-organiques. Ainsi, l'invention vise-t-elle un procédé de flottation utilisant des collecteurs peu ou non hydrosolubles ; elle comprend des nouveaux collecteurs de ce type, ainsi qu'une composition renfermant des collecteurs de flottation.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. Thus, 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.
La flottation, procédé à présent classique pour la séparation et la concentration de différents minéraux, est bien connue, il n'y a donc pas lieu de l'exposer ici. On rappellera seulement que cette méthode est extrêmement utile pour l'enrichissement de minerais pauvres avant le traitement de ceux-ci par pyrométallurgie ou hydrométallurgie ; c'est par exemple le cas de minerais d'oxydes ou/et sulfures de plomb, de zinc, de cuivre, de molybdène, etc. On connait les différents collecteurs, couramment employés, comme les xanthates alcalins,à chaîne d'alkyle inférieur, en particulier éthyl- ou amyl-xanthate de potassium, des mercaptobenzo thiazols, dithiocarbamates, thiocarbamates et dithio phosphates. Ces composés sont suffisamment solubles dans l'eau, pour qu'ils puissent être ajoutés directement dans la pulpe de minerai à traiter. Il existe cependant des composés qui pourraient être très efficaces comme collecteurs de flottation, mais dont la solubilité dans l' eau est trop faible pour que ces produits puissent conduire à de bons résultats. C'est par exemple le cas des mercaptans, à plus de 8 atomes de carbone dans la chaîne hydrocarbonée, et des xanthates à alkyles à plus de 6 atomes de carbone, qu'il serait intéressant d'utiliser à cause de leur forte sélectivité. On a donc cherché, dans la technique antérieure, à solubiliser de tels composés, pour qu'ils puissent mieux servir de collecteur de flottation. Ainsi le brevet US 4 211 644, qui porte sur l'utilisation, en tant que collecteurs, d'alkyl mercaptans en C12 ou plus, préconise-t-il l'adjonction d'un polyglycol dans le but de mouiller ou/et émulsionner le mercaptan trop peu soluble dans l'eau. Si cette solution amène un certain progrès, celui-ci n'est cependant que partiel. En effet selon ce brevet l'agent solubilisant doit être lui-même soluble dans l'eau, ce qui limite la gamme des produits qui peuvent être utilisés.Flotation, a now classic process for the separation and concentration of different minerals, is well known, so there is no need to expose it here. It will only be recalled that this method is extremely useful for the enrichment of poor ores before the treatment of these by pyrometallurgy or hydrometallurgy; this is the case, for example, with ores of oxides and / or sulfides of lead, zinc, copper, molybdenum, etc. We know the different collectors, commonly used, such as alkaline xanthates, lower alkyl chain, in particular ethyl- or potassium amyl-xanthate, mercaptobenzo thiazols, dithiocarbamates, thiocarbamates and dithio phosphates. These compounds are sufficiently soluble in water, so that they can be added directly to the ore pulp to be treated. There are, however, compounds which could be very effective as flotation collectors, but whose solubility in water is too low for these products to lead to good results. This is for example the case of mercaptans, with more than 8 carbon atoms in the hydrocarbon chain, and xanthates with alkyls with more than 6 carbon atoms, which it would be interesting to use because of their high selectivity. Attempts have therefore been made in the prior art to dissolve such compounds so that they can better serve as a flotation collector. Thus, US Pat. No. 4,211,644, which relates to the use, as collectors, of C 12 or more alkyl mercaptans, recommends the addition of a polyglycol for the purpose of wetting or / and emulsify the mercaptan which is not very soluble in water. If this solution brings some progress, it is however only partial. According to this patent, the solubilizing agent must itself be soluble in water, which limits the range of products which can be used.
La présente invention apporte, en cette matière, un perfectionnement sensible : elle rend possible l'utilisation de certains collecteurs très insuffisamment solubles ou pratiquement insolubles dans l'eau , pour donner tout de même d'excellents résultats, tant en rendement qu'en ce qui concerne la sélectivité.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.
Le nouveau procédé suivant l'invention consiste à introduire le collecteur de flottation à l'état d'une composition micro-émulsionnable dans la pulpe de minerai à traiter.The new process according to the invention consists in introducing the flotation collector in the form of a micro-emulsifiable composition into the ore pulp to be treated.
La nouvelle composition pour flottation, suivant l'invention, est donc caractérisée en ce qu'elle renferme le collecteur, un composé tensio-actif, un co-tensioactif et éventuellement de l'eau, le tout étant diluable à l'eau de la pulpe à traiter, avec formation d'une microémulsion.The new composition for flotation, according to the invention, is therefore characterized in that it contains the collector, a surfactant compound, a co-surfactant and optionally water, the whole being dilutable with water from the pulp to be treated, with the formation of a microemulsion.
Les microémulsions suivant l'invention sont à eau externe, l'agent co-tensio actif pouvant ne pas être soluble dans l'eau, contrairement aux adjuvants du type polyglycol préconisés dans l'art antérieur, mentionnés plus haut.The 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.
Comme bien connu, les microémulsions sont des systèmes très différents des émulsions : leur définition est connue dans l'art, il n'est donc plus nécessaire de la rappeler ici (P.A. Winsor Trans. Faraday Soc. 1948-44-376).As is well known, 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).
Des agents collecteurs, auxquels la présente invention s' applique particulièrement bien, sont en général des composés organiques renfermant du soufre, notamment des mercaptans, des thioéthers, des polysulfures, etc. Ainsi l'invention permet-elle d'améliorer très sensiblement l'effet collecteur des mercaptans à plus de 8 atomes de carbone et plus spécialement en C12 à C18' c'est-à-dire des mercaptans très peu solubles dans l'eau. Une amélioration également est obtenue lorsqu'on utilise des sulfures organiques du type R-S-R', dans lesquels R et R', semblables ou différents, sont des groupes hydrocarbonés en C1à C24; ceux de ces composés dont le R' porte un groupe -OH, -SH, -COOR", -CSOR" ou CSSR", R" étant H, un cation ou un groupe hydrocarbyle en C1 à C18, conviennent par eux-mêmes en tant que bons collecteurs, comme montré dans la demande de brevet français 2 429 617, mais ils donnent des résultats encore meilleurs lorsqu'ils sont utilisés sous forme de microémulsion, conformément à la présente invention. Un autre type de collecteurs donnant d'excellents résultats, suivant la présente invention, sont des polysulfures R-SX-R' où R et R' ont la même signification que plus haut, tandis que x prend des valeurs moyennes de l'ordre de 2 à 8 et, le plus souvent, de 3 à 5 ; ces polysulfures sont des agents de flottation nouveaux dont l'intérêt ressort surtout lorsqu'ils sont mis sous la forme de microémulsion.Collecting agents, to which the present invention applies particularly well, are generally organic compounds containing sulfur, in particular mercaptans, thioethers, polysulphides, etc. Thus, 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 18 ′, that is to say mercaptans which are very sparingly soluble in water. An improvement is also obtained when organic sulfides of the RS-R 'type are used, in which R and R', which are similar or different, are C 1 to C 24 hydrocarbon groups; those of these compounds in which the R ′ carries a group -OH, -SH, -COOR ", -CSOR" or CSSR ", R" being H, a cation or a C 1 to C 18 hydrocarbyl group, are themselves suitable as good collectors, as shown in French patent application 2,429,617, but they give even better results when they are used in the form of a microemulsion, in accordance with the present invention. Another type of collectors giving excellent results, according to the present invention, are polysulphides 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.
Bien que tous les thiocomposés sus-indiqués bénéficient, en tant que collecteurs de flottation, de l'application du procédé en microémulsion suivant l'invention, on cite ci-après, à titre d'exemples non limitatifs, quelques-uns de ces composés utilisables. Mercapto esters d'alkyle HS(CH2)nCOOR où n est 1 ou 2 et R un alkyle en C1 à C12; lorsque R est un heptyle ou un octyle, notamment un éthyl-2-hexyle, ces composés, très solubles dans l'eau, sont d' excellents collecteurs, surtout pour la chalcopyrite. Leurs homologues, de masse molaire plus élevée, moins solubles, deviennent intéressants lorsqu'ils sont employés en microémulsion.Although all of the above-mentioned thiocompounds benefit, as flotation collectors, from the application of the microemulsion process according to the invention, some of the following are cited as non-limiting examples these compounds usable. Mercapto alkyl esters HS ( CH2 ) nCOOR where n is 1 or 2 and R is C 1 -C 12 alkyl; when R is a heptyl or an octyl, in particular an ethyl-2-hexyl, these compounds, very soluble in water, are excellent collectors, especially for chalcopyrite. Their counterparts, of higher molar mass, less soluble, become interesting when they are used in microemulsion.
Les sulfures C10H21SCH3,C12H25 SCH3 et C14H29SCH3 donnent d'excellents résultats avec la chalcopyrite, la galène, la blende et la pyrite dans la méthode classique, et leurs homologues avec des alkyles plus lourds à la place du CH3 conviennent en microémulsion. Il en est de même des acides alkyl thio-2 acétiques RSCH2COOH qui donnent d'excellents résultats, à la manière ordinaire, lorsque R est en C12 à C16, et conviennent bien en microémulsion pour des R plus lourds et ramifiés. Lorsque le groupe acétique de ces sulfures est estérifié, la manière classique convient encore fort bien pour des esters méthyliques et éthyliques, alors que pour des esters d'alcools supérieurs, notamment C4 à C12, il est préférable d'employer le collecteur en microémulsion. En ce qui concerne les polysulfures R-Sx-R ou R-Sx-R', ils donnent de bons résultats, sans qu'il soit nécessaire de les mettre en microémulsion, tant que leur masse molaire et la teneur en soufre ne dépassent pas une certaine limite. Ainsi par exemple, le trisulfure de di-hexyle C6H13SSSC6H13, ainsi que le penta sulfure de dihexyle, sont de bons collecteurs de la chalcopyrite et de la galène, mais les résultats sont meilleurs lorsqu'on les emploie en microémulsion ; pour les polysulfures de masses molaires plus élevées, l'amélioration,du fait de la microémulsion, devient très sensible.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. It is the same for the 2-alkyl thio-acetic acids RSCH 2 COOH which give excellent results, in the ordinary way, when R is C 12 to C 16 , and are well suited in microemulsion for heavier and branched R. When the acetic group of these sulfides is esterified, 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 . As regards 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. So for example, di-hexyl trisulfide C 6 H 13 SSSC 6 H 13 , as well as dihexyl penta sulfide, 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.
La particularité des compositions des collecteurs pour flottation, suivant l'invention, réside en ce que la phase liquide, associée au collecteur lui-même, est constituée par un agent tensio-actif liquide ou du moins dissous dans une petite quantité de solvant approprié. De tels agents tensio actifs préférés sont des composés non ioniques qui peuvent être choisis dans les nombreuses classes connues en soi ; ce sont par exemple des polyoxy-alkylènes pouvant porter différents groupements, correspondant à la formule générale
Des polyoxy éthylènes peuvent également être utilisés sous la forme de leurs produits d'addition avec des esters de sorbitan, connus sous la dénomination de "TWEEN". D'autres composés tensioactifs utiles sont des esters ou éthers de polyoxy alkylène de la formule (1), comme des laurates, stéarates, oléate ou ricinoléate d'un polyoxy éthylène, éventuellement porteur d'un groupe alkyl-phénol. Peuvent être également employés des thio éthers polyoxy alkylènes, c'est-à-dire des corps dans lesquels le premier oxygène dans la formule (1) est remplacé par le soufre ; tel est par exemple le cas du tert-dodécyl monothio éther et dodéca- éthylène glycol. Conviennent aussi des tensioactifs du type alkyl-glucoside.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. Can also be used thio polyoxyalkylene ethers, that is to say bodies in which the first oxygen in formula (1) is replaced by sulfur; this is for example the case of tert-dodecyl monothio ether and dodeca-ethylene glycol. Also suitable are surfactants of the type alkyl glucoside.
Les composés tensioactifs liquides, indiqués ci-dessus, sont des composés non ioniques qui semblent convenir le mieux. Cependant, il est également possible d'employer des tensioactifs anioniques ou cationiques, lorsque le pH voulu pour la pulpe traitée par flottation le permet. Ainsi, l'invention peut-elle être réalisée par l'emploi de compositions des collecteurs mélangées d'avance, sous la forme de liquide, avec des tensio-actifs constitués par des sulfonates de pétrole, des sulfates d'alcools gras, qui sont anioniques ou bien des alkylolamides, des amines grasses ou des ammoniums quaternaires, cationiques.The 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, fatty alcohol sulfates, which are anionic or alkylolamides, fatty amines or quaternary ammoniums, cationic.
Lorsque l'agent tensioactif est solide ou visqueux, il est toujours possible de créer un milieu liquide par l'adjonction d'un peu d'eau ou d'un solvant tiers, par exemple un mono- ou polyol ; d'ailleurs le co-tensioactif peut suffire pour rendre le milieu liquide.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.
Comme indiqué plus haut, dans la définition même de l'invention, la composition, suivant l'invention, comporte un troisième constituant, à savoir un agent cotensioactif. La nature et le rôle de cet agent sont connus dans l'art : il suffit, pour réaliser l'invention, de choisir un ou plusieurs co-tensioactifs parmi ceux qui ont été décrits dans la technique antérieure. On rappellera seulement que les agents en question sont des molécules organiques possédant une partie lipophile et au moins un groupement polaire ; ce sont par exemple des alcools, généralement en C3 ou davantage, des alkylène glycols, en particulier éthylène-, propylène-, butylène- ou hexylène-glycols ; ces composés peuvent être linéaires ou ramifiés. Conviennent également comme co- agents les alkyl éthers et esters de glycol, des cétones, des esters d'acides gras, c'est-à-dire à plus de C4 et surtout en C6 à C18' des amines primaires, secondaires et tertiaires, de préférence à plus de 4 atomes de carbone, l'urée et ses dérivés, etc. Pour des raisons économiques, ce sont différents alcools, et plus spécialement alcools en C3 à C8, qui sont le plus employés. La solubilité dans l'eau du co-tensioactif n'est pas nécessaire dans le cas de la présente invention.As indicated above, in the very definition of the invention, the composition according to the invention comprises a third constituent, namely a cosurfactant. 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. It will only be recalled that 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. Also suitable as co-agents are alkyl ethers and glycol esters, ketones, fatty acid esters, i.e. with more than C 4 and on all in C 6 to C 18 ′ of primary, secondary and tertiary amines, preferably with more than 4 carbon atoms, urea and its derivatives, etc. For economic reasons, 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.
Puisque le principe même de l'invention réside dans la mise en microémulsion du composé devant servir de collecteur de flottation, il va de soi que les proportions des constituants doivent être telles que la microémulsion puisse se former. Autrement dit, la nature et les proportions de collecteur, des composés tensio-actifs et d'agent co-ten sioactif, sont choisies de telle façon que le mélange obtenu soit stable, optiquement isotrope, homogène et diluable à l'eau. Au moment de cette dilution, il se forme une microémulsion ou solution micellaire gonflée du collecteur dans l'eau, ce qui correspond à une dispersion extrêmement fine de ce collecteur ; ainsi, même avec des substances insolubles dans l'eau, employées comme collecteur, on arrive à disperser celui-ci de façon très fine dans la pulpe au moment de l'utilisation.Since the very principle of the invention resides in the microemulsion of the compound intended to serve as a flotation collector, it goes without saying that the proportions of the constituents must be such that the microemulsion can be formed. In other words, the nature and the proportions of collector, surfactant compounds and co-surfactant, are chosen so that the mixture obtained is stable, optically isotropic, homogeneous and dilutable with water. At the time of this dilution, 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.
Les compositions suivant l'invention peuvent être tout à fait anhydres, mais il est possible de leur ajouter une certaine quantité d'eau pour faciliter leur manipulation.The 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.
Bien que les proportions des 3 constituants définis plus haut varient selon la nature de ces constituants, on peut indiquer - à titre d'exemple non limitatif - les proportions approximatives suivantes pour des compositions pratiquement exemptes d'eau :
Dans les cas de composition aqueuse, on a par exemple :
Les compositions suivant l'invention peuvent éventuellement renfermer d'autres substances, comme par exemple des produits moussants. Elles conviennent aux différents modes de flottation, notamment flottation primaire, secondaire, etc.The 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.
L'invention est illustrée par les exemples non limitatifs qui suivent.The invention is illustrated by the following nonlimiting examples.
Une première série d'essais de flottation est effectuée sur un minerai sulfuré de cuivre provenant de la mine Sud Africaine de Palabora, à teneur en cuivre de 0,45 à 0,48%.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 de ce minerai sont broyés à une finesse telle que 76% de la poudre traverse un tamis à mailles de 148 microns.600 g of this ore are ground to a fineness such that 76% of the powder passes through a 148 micron mesh screen.
Le produit est soumis à la flottation pendant 20 minutes à pH 7,5 dans une cellule de laboratoire de 2,5 litres du type MINEMET M 130, en présence de méthyl-isobutyl carbi- nol (MIBC) comme agent moussant, ajouté à raison de 25g par tonne de minerai.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 the right rate. 25g per tonne of ore.
Le collecteur expérimenté est le n.dodécyl mercaptan dont l'introduction dans la pulpe est effectuée de 4 manières différentes, comme indiqué ci-après.The experienced collector is n.dodecyl mercaptan, the introduction of which into the pulp is carried out in 4 ways different, as shown below.
ME Introduction sous la forme d'une composition qui donne lieu à la formation d'une microémulsion, lorsqu' elle est ajoutée à la pulpe du minerai.ME Introduction in the form of a composition which gives rise to the formation of a microemulsion, when it is added to the pulp of the ore.
Cette composition comprend en poids :
- E1 Introduction sous la forme d'une émulsion classique de composition pondérale :Ce qui correspond au même rapport mercaptan/tensioactif que dans le mélange ME précédent.
- E2 Sous la forme d'une émulsion classique :
- E3 Emulsion :
- E1 Introduction in the form of a conventional emulsion of weight composition: This corresponds to the same mercaptan / surfactant ratio as in the previous ME mixture.
- E2 In the form of a classic emulsion:
- E3 Emulsion:
Le tableau 1 suivant donne les résultats de ces essais de flottation. La 2ème colonne verticale de ce tableau indique les quantités de n.dodécyl mercaptan utilisées : d'une part en grammes par tonne de minerai, g/T, et d'autre part, entre parenthèses, en mole par tonne.The following table 1 gives the results of these flotation tests. The second vertical column of this table indicates the quantities of n.dodecyl mercaptan used: on the one hand in grams per tonne of ore, g / T, and on the other hand, in brackets, in mole per tonne.
Voir Tableau 1 à la page suivante.
Comme on peut le voir, la récupération du Cu est considérablement augmentée lorsqu'on applique la méthode ME, c'est-à-dire l'introduction du collecteur sous une forme micro- émulsionnable.As can be seen, the recovery of Cu is considerably increased when the ME method is applied, that is to say the introduction of the collector in a microemulsifiable form.
A quantité de collecteur égale, les procédés en émulsion, E1 et E2, correspondant à l'art antérieur, donnent des résultats beaucoup moins bons que la méthode de microémulsion.For an equal quantity of collector, the emulsion processes, E1 and E2, corresponding to the prior art, give much less good results than the microemulsion method.
Les opérations sont les mêmes que dans l'exemple 1, sauf que le n.dodécyl mercaptan est remplacé par le tert.dodécyl mercaptan comme collecteur. Ce dernier a été utilisé sous trois formes différentes.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.
ME Collecteur microméulsionnable
Le tableau 2, analogue au précédent, réunit les résultats obtenus.
Comme dans l'exemple précédent, on peut constater que le même collecteur donne des résultats bien meilleurs lorsqu' il est introduit sous une forme conduisant à la microémulsion (ME).As in the previous example, it can be seen that the same collector gives much better results when it is introduced in a form leading to the microemulsion (ME).
Des essais de flottation similaires à ceux des exemples précédents sont effectués avec, comme collecteur, du pentasulfure de di.tert.dodécyle.Flotation tests similar to those of the preceding examples are carried out with di.tert.dodecyl pentasulfide as collector.
Les trois modes d'introduction sont les mêmes que dans l' exemple 2.The three modes of introduction are the same as in Example 2.
ME Collecteur microémulsionnable
E1 Emulsion ordinaire :
E2 Emulsion
L'avantage d'opérer l'introduction du collecteur sous une forme micro-émulsionnable se confirme d'après ces résultats.The advantage of operating the collector in a micro-emulsifiable form is confirmed by these results.
Les essais de l'exemple 3 sont répétés avec du trisulfure de di-tert.dodécyle à la place du pentasulfure. Pour le collecteur microémulsionnable, les proportions des deux alcools ont été modifiées : iso-propanol 6,25%, éthyl-2 hexa-Les résultats sont réunis au tableau 4.
Comme pour le pentasulfure, on trouve donc des résultats bien meilleurs lorsque le trisulfure est introduit à l'état d'une composition qui donne une microémulsion dans la pulpe.As with pentasulfide, we therefore find much better results when trisulfide is introduced in the form of a composition which gives a microemulsion in the pulp.
Dans un essai de flottation, similaire à ceux de l'exemple 3, on répète l'opération ME en remplaçant le pentasulfure de di-tert.dodécyle par du pentasulfure dedi-tert.nonyle, toutes les autres conditions étant les mêmes que précédemment.In a flotation test, similar to those of Example 3, the ME operation is repeated, replacing the di-tert.dodecyl pentasulfide with dedi-tert.nonyl pentasulfide, all the other conditions being the same as above.
Avec une quantité de collecteur de 71,6 g/T, soit 0,173 mole par tonne de minerai, on obtient une teneur en cuivre de 15,8% dans le concentré, et une récupération de cuivre de 65,2%. On voit donc que le changement des alkyles dans le pentasulfure modifie peu le % de récupération et ne change pas la teneur en cuivre dans le concentré, cette teneur étant plus élevée que dans les opérations utilisant une émulsion simple (essais E1 et E2).With a collector quantity of 71.6 g / T, or 0.173 mole per tonne of ore, a copper content of 15.8% in the concentrate is obtained, and a copper recovery of 65.2%. It is therefore seen that the change of the alkyls in the pentasulfide modifies the% recovery little and does not change the copper content in the concentrate, this content being higher than in the operations using a simple emulsion (tests E1 and E2).
L'essai de flottation de l'exemple 4ME à 0,173 mole de collecteur par tonne est répété avec du trisulfure de di- tert.nonyle au lieu de di-tert.dodécyle.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.
Le résultat obtenu est encore meilleur qu'au tableau 4 plus haut, puisqu'on trouve une teneur en Cu de 16,4% dans le concentré et un pourcentage de Cu récupéré de 59,9.The result obtained is even better than in Table 4 above, since there is a Cu content of 16.4% in the concentrate and a percentage of Cu recovered of 59.9.
Dans les mêmes conditions qu'aux exemples 3 à 6, sur le même minerai, on effectue des essais de flottation avec, comme collecteur, de l'amyl xanthate de potassium très usuel dans cette technique. Cet agent est introduit dans la pulpe à la manière habituelle, c'est-à-dire sous forme de sa solution aqueuse.Under the same conditions as in Examples 3 to 6, on the same ore, flotation tests are carried out with, as collector, potassium amyl xanthate very usual in this technique. This agent is introduced into the pulp in the usual way, that is to say in the form of its aqueous solution.
On trouve les résultats suivants.
Il en résulte que, si le xanthate permet une récupération plus grande du Cu, il fournit par contre des concentrés à teneur en cuivre bien plus faible que celle à laquelle on arrive avec des polysulfures microémulsionnés. En comparant les 10,3 à 10,4% de teneur en cuivre dans le concentré, obtenus avec du xanthate, avec les 14,6 à 16,4% que donnent les essais ME des exemples 3 à 6, on voit que le procédé suivant l'invention est susceptible d'augmenter d' environ 50% la concentration en métal voulu, dans le produit de la flottation, ce qui constitue un perfectionnement considérable.As a result, if 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. By comparing the 10.3 to 10.4% copper content in the concentrate, obtained with xanthate, with the 14.6 to 16.4% that give the tests ME of examples 3 to 6, it can be seen that the process according to the invention is capable of increasing the concentration of desired metal in the flotation product by about 50%, which constitutes a considerable improvement.
Les essais de flottation furent effectués à la manière analogue à celle des essais précédents,mais sur un minerai sulfuré plomb-zinc provenant de la mine pyrénéenne du NERBIOU. Ce minerai renferme 4,8% de plomb et 12,1% de zinc.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.
500 g en sont broyés jusqu'à ce que 90% traversent un tamis à mailles de 100 microns. La poudre est soumise à la flottation à pH 10 pendant 15 minutes.500 g are crushed until 90% pass through a 100 micron mesh screen. The powder is subjected to flotation at pH 10 for 15 minutes.
La cellule utilisée était la même que dans les essais précédents. L'échantillon fut additionné préalablement de 30g d'agent moussant par tonne.The cell used was the same as in the previous tests. The sample was added beforehand with 30 g of foaming agent per ton.
Le collecteur employé est le n.dodécyl mercaptan. Il est pris, dans un premier essai, sous la forme d'une microémulsion ME1, identique à celle de l'exemple 1.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.
Dans un second essai, la formule de la microméulsion ME2 était :
En outre, un essai fut effectué avec le collecteur pris sous la forme d'une émulsion ordinaire E constituée par :
Les résultats de cette flottation sont donnés dans le tableau 5.
Il en résulte que pour le zinc et le plomb, également la méthode à la microémulsion conduit à une amélioration considérable du rendement de récupération par flottation.It follows that for zinc and lead, also the microemulsion method leads to a considerable improvement in the recovery yield by flotation.
Claims (11)
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FR8217127 | 1982-10-13 | ||
FR8217127A FR2534492A1 (en) | 1982-10-13 | 1982-10-13 | IMPROVEMENT IN MINERAL FLOTATION |
Publications (2)
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EP0107561A1 true EP0107561A1 (en) | 1984-05-02 |
EP0107561B1 EP0107561B1 (en) | 1986-07-30 |
Family
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Application Number | Title | Priority Date | Filing Date |
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EP83401956A Expired EP0107561B1 (en) | 1982-10-13 | 1983-10-07 | Flotation of ores |
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US (2) | US4526696A (en) |
EP (1) | EP0107561B1 (en) |
AU (1) | AU562922B2 (en) |
CA (1) | CA1222379A (en) |
DE (2) | DE107561T1 (en) |
ES (1) | ES8501252A1 (en) |
FI (1) | FI74891C (en) |
FR (1) | FR2534492A1 (en) |
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- 1983-10-07 EP EP83401956A patent/EP0107561B1/en not_active Expired
- 1983-10-07 DE DE8383401956T patent/DE3364986D1/en not_active Expired
- 1983-10-12 SU SU833657073A patent/SU1304737A3/en active
- 1983-10-12 FI FI833715A patent/FI74891C/en not_active IP Right Cessation
- 1983-10-12 CA CA000438866A patent/CA1222379A/en not_active Expired
- 1983-10-13 ZA ZA837619A patent/ZA837619B/en unknown
- 1983-10-13 ES ES526760A patent/ES8501252A1/en not_active Expired
- 1983-10-13 US US06/541,560 patent/US4526696A/en not_active Expired - Lifetime
- 1983-10-13 AU AU20153/83A patent/AU562922B2/en not_active Ceased
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0219057A2 (en) * | 1985-10-17 | 1987-04-22 | Henkel Kommanditgesellschaft auf Aktien | Use of non-ionic surfactants as reagents for the flotation of non-sulphidic minerals |
EP0219057A3 (en) * | 1985-10-17 | 1990-03-21 | Henkel Kommanditgesellschaft Auf Aktien | Use of non-ionic surfactants as reagents for the flotation of non-sulphidic minerals |
US5108585A (en) * | 1985-10-17 | 1992-04-28 | Henkel Kommanditgesellschaft Auf Aktien | Flotation of non-sulfidic ore with a glycosidic collector |
EP0270933A2 (en) * | 1986-12-04 | 1988-06-15 | Henkel Kommanditgesellschaft auf Aktien | Surfactant mixtures as collectors for the flotation of non-sulfidic minerals |
EP0270933A3 (en) * | 1986-12-04 | 1989-10-25 | Henkel Kgaa | Surfactant mixtures as collectors for the flotation of non-sulfidic minerals |
EP0344553A1 (en) * | 1988-05-31 | 1989-12-06 | Henkel Kommanditgesellschaft auf Aktien | Surfactant mixtures as collectors for the flotation of non-sulfidic minerals |
US4995998A (en) * | 1988-05-31 | 1991-02-26 | Henkel Kommanditgesellschaft Auf Aktien | Surfactant mixtures as collectors for the flotation of non-sulfidic ores |
CN105903552A (en) * | 2016-04-26 | 2016-08-31 | 中南大学 | Beneficiation method for effectively recovering extremely-fine-particle molybdenum ore |
CN105903552B (en) * | 2016-04-26 | 2021-03-12 | 中南大学 | Beneficiation method for efficiently recovering micro-fine particle molybdenum ore |
Also Published As
Publication number | Publication date |
---|---|
DE107561T1 (en) | 1984-09-13 |
AU2015383A (en) | 1984-04-19 |
FI74891B (en) | 1987-12-31 |
FI74891C (en) | 1988-04-11 |
FR2534492A1 (en) | 1984-04-20 |
SU1304737A3 (en) | 1987-04-15 |
FI833715A (en) | 1984-04-14 |
CA1222379A (en) | 1987-06-02 |
FI833715A0 (en) | 1983-10-12 |
DE3364986D1 (en) | 1986-09-04 |
ES526760A0 (en) | 1984-12-16 |
US4594151A (en) | 1986-06-10 |
ZA837619B (en) | 1985-02-27 |
US4526696A (en) | 1985-07-02 |
ES8501252A1 (en) | 1984-12-16 |
AU562922B2 (en) | 1987-06-25 |
FR2534492B1 (en) | 1984-12-28 |
EP0107561B1 (en) | 1986-07-30 |
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