US3822014A - Process of flotation of minterals and ores - Google Patents

Process of flotation of minterals and ores Download PDF

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Publication number
US3822014A
US3822014A US00114613A US11461371A US3822014A US 3822014 A US3822014 A US 3822014A US 00114613 A US00114613 A US 00114613A US 11461371 A US11461371 A US 11461371A US 3822014 A US3822014 A US 3822014A
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coor
formula
agents
sulfonates
so3m
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A Verheyden
J Hartmann
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UCB SA
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Citrex SA
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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
    • 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
    • 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

  • ABSTRACT Process of froth flotation of oxide minerals which comprises using at least one of the following collector agents 1. mixed salts of ammonium and amines of the formula:
  • mineral is generally understood any natural inorganic substance that possesses a determined chemical composition and that has specific physical properties, whereas by ore is rather understood an inorganic substance extracted from the soil in order to isolate certain constituents, mostoften metallic substances, contained therein.
  • oreand mineral will be considered as equivalent and will therefore be used indiscriminately.
  • flotation agents comprise collectors, frothers, and various modifying agents, such as depressants, activators, pH regulators and the like.
  • Collectors are the main flotation agents because it is with the use thereof that a hydrophobic, film is formed on the particles of ore, thereby enabling them to be entrained by air bubbles, whereas the .gangue, on to which the collector is not fixed, retains its hydrophilic properties and, consequently remains within the aqueous suspension in which finally it forms a sediment.
  • collectors are already known for oxide minerals, for example, fatty acids, fatty acid salts, amines and quarternary long carbon chain ammonium compounds containing 8 to 18 carbon atoms.
  • oxide minerals for example, fatty acids, fatty acid salts, amines and quarternary long carbon chain ammonium compounds containing 8 to 18 carbon atoms.
  • these collectors do not give very good results.
  • Certain minerals, such as cassiterite, are, in fact, not readily amenable to flotation and the recuperation rate of this mineral leaves much to be desired. It would, therefore, be very advantageous to extend the range of collectors utilisable for oxide minerals and to discover collectors which would be for oxide minerals what the xanthates are for of controlled pyrolysis of alkaline earth metal citrates,
  • alkaline earth metal salts preferably calcium salts of an unsaturated polycarboxylic acid of unknown chemical structure. It is known, however, that this acid contains a hydrocarbon chain carrying four carboxyl groups and a carbon-carbon double bond.
  • X represents the hydrocarbon radical of the acid obtained by controlled pyrolysis of calcium citrate and acidification of the obtained pyrolysate;
  • R is a C C alkyl radical;
  • R, [R'', RR" and R which may be the same or different, are hydrogen atoms or C -C alkyl radicals or cycloalkyl, aralkyl, alkaryl or aryl radicals, at least one of R, R", R'R" and R"" being other than hydrogen; and
  • M is sodium, potassium or ammonium.
  • the second column indicates the number of frequently happens, however, that these oxide ores the general formula of each reagent.
  • these oxide ores the general formula of each reagent.
  • the meanings of the symbol 10 trons simultaneously as for example in the case of ru- R, R, R", R', R"" and M used in the general f rmutile, which is used not only as an ore from which metallae (I) to (IV) mentioned above.
  • n-dodecyl radical derived from commercial n-dodecylamine ARMEEN k2 D sold by ARMOUR Co.
  • the alkyl is the residue of a C,,-C technical alcohol. 0.
  • the alkyl is the residue of a C C technical alcohol.
  • the alkyl is the residue of a (I -C technical alcohol.
  • hentiafiafme compounds used according to the present invention are particularly suitable for the flotation of oxide minerals, in other words minerals which are not in the form of native elements, of sulfides, arsenides, antimonides or the like but are in Oxide minerals of:
  • oxide ores will be used hereinbelow to designate all these natural mineral substances.
  • minerals such as fluorspar or cryolite will also be considered as oxide minerals, although they do not contain oxygen.
  • minerals such as barytine, i.e., borium sulfate, which contains sulfur in the form of sulfate (and not in the form of sulfide) will also be considered as oxide minerals.
  • oxide ores and minerals which may be treated by flotation by using, as collectors, the compounds of general formulae (I) to (IV) according to the present invention.
  • fergu sonite formanite, euxenite, polycrase, tapiolite, mossite, dysanalyte, betafite, yttrotantalite;
  • the collectors used according to the present invention can be used in all flotation equipment normally employed. For the experiments described in the Examples given below, use was made of Fagergren type cells but it is obvious that any other cell enabling froth flotation to be carried out could be suitable (see, for exam ple, Kirk-Othmer, Encyclopaedia of Chemical Technology, 2nd edition, volume 9, (l966),p.392).
  • the collectors of the present invention are used at ambient temperature but, nevertheless, operation at an elevated temperature for particular separation operations may be contemplated.
  • An advantage of the compounds used according to the present invention is that most of them possess frothing properties so that the use of frothing agents can frequently be dispensed with. Nevertheless, it may happen that an additional frothing agent will be necessary and, in this case, pine oil, camphor oil, cresylic acid, higher alcohols, higher ether-alcohols, non-ionic surfactants, amines or the like may be used as frothing agents.
  • the compoundsused according to the present invention may be used together with conventional reagents used in flotation, particularly ordinary collectors for oxide minerals, for example, fatty acids, fatty acid salts, alkylsulfates, alkylarylsulfonates, phosphonic and arsenic homologues, amines or quaternary long chain. ammonium compounds containing eight to 18 carbon atoms.
  • auxiliary flotation agents which may be used are depressants, activators, precipitation agents, dispersing agents, organic colloidal materials and the like.
  • the crushed ore or mineral 400 microns to 5 microns
  • the resulting slurry contains about 10 to 40 percent of said ore or mineral.
  • the pH of the slurry is then adjusted by suitable addition of acid or alkali and the collector or collectors according to the present invention and optionally the auxiliary flotation agents mentioned above is or are introduced. Not more than about 3 minutes are needed for the slurry to be conditioned and then air is injected into the slurry in order to produce a froth which, by flotation becomes charged with concentrated ore. This is then collected.
  • the discontinuous flotation operation lasts, on average, less than 15 minutes.
  • the process of the present invention permits the flotation of cassiterite under far better conditions, both as regards the content of the concentrate or concentrates and the rate of recuperation and as regards convenience of performance (no preliminary treatment is required).
  • the collectors used according to the present invention are inexpensive products which are obtained from an acid produced by pyrolysis of calcium citrate, which is a readily available commercial product, and also from esterification alcohols and from amines or salt-producing bases, which are commercially freely available.
  • the chemical composition of the collectors may be varied infinitely by modifying the nature and proportion of the salt forming and/or ester forming agents, which makes it possible to obtain a sulficiently wide range of collectors to meet the most difficult flotation requirements.
  • the following Examples are given for the purpose of illustrating the present invention.
  • the flotation is carried out in a Fagergren cell.
  • the solids content of the slurry is about percent by weight and the conditioning time is 2 to 3 minutes: the pH is first adjusted and then the collector is added.
  • the flotation time is the time required for the exhaustion of the mineralised froth; on average, it is less than 15 minutes.
  • the ores and minerals used in the tests are, in some cases, purerarelogical species and sometimes run of mine ores.
  • a pegmatite-greisen originating from Katanga is subjected to flotation. This ore is rich in cassiterite; the gangue is composed mainly of quartz and muscovite but it also contains feldspar and tourmaline.
  • the SnO recovery rate is 97.5 percent; the concentrate obtained titrates at 55.6 percent SnO whereas the original titration of the ore was 8.9 percent SnO
  • the recovery rate reaches 100 percent and the concentrate obtained titrates at 28 percent SnO Example 2.
  • reagent N6 at the rate of 1,000 g. per ton (pH 8.9) for the flotation of a vein-bearing fluorspar with partially silicified calcareous gangue, having an initial CaF content of 37.0 percent, a concentrate is obtained with a CaF content of 80.4 percent at a recovery rate of 99.7 percent.
  • reagent N3 500 g. per ton, pH 6.7
  • the portion rich in barium sulfate of a quartz and barytine vein, worked in France, is subjected to flotation.
  • the concentrate obtained titrates at 93.9 percent BaSO whereas theuntreated ore titrated at 77.8 percent.
  • the recovery rate is 96.2 percent.
  • a batch of barytine from the same deposit but of poorer quality (BaSO 39.0 percent) is subjected to flotation.
  • the collector is the same reagent N 3, likewise used at the rate of 500 g. per ton (pH 5.6).
  • Reagent N 3 is used at the rate of 1,000 g. per ton (pH 6.3) to treat the same fluorspar as in Example 3. A concentrate containing 78.5 percent of CaF is obtained with a recovery rate of 98.0 percent.
  • Reagent N 10 is used (500 g. per ton, pH 7.6) to treat a Belgian vein-bearing barytine with quartz gangue, containing significant quantities of calcite, pyrites, blende and galena. Despite the complexity of the ore treated, it was possible to obtain a concentrate titrating at 63.7 percent BaSO, with a recovery rate of 75.2 percent, whereas the original BaSO, content was 45.0 percent.
  • a l/l mixture of reagents N 2 and N 8 is used at the rate of 2,000 g. per ton for the flotation of a North African carbonated zinc-lead ore (smithsonite-cerusite).
  • the pH is adjusted to 7.4.
  • the lead content which is 10.3 percent in the initial ore, reaches 33.6 percent in the concentrate, whereas the zinc content falls from 20.4 percent to 11.2 percent.
  • the lead recovery rate is 69.2 percent.
  • this reagent when used at a rate of 1,000 g. per ton and with a pH close to 7, gives a cassiterite recovery rate of 99.4 percent, whereas with the same pH this rate for quartz is 0 percent and for muscovite is 26.0 percent. This explains the excellentflotation results indicated in Example 1 in connection with a pegmatite-greisen from Katanga, the main constituents of which are cassiterite, quartz and mica.
  • FIG. 2 there is indicated the behaviour of reagent N 2 in dependence upon the pH for the two minerals fluorspar and calcite.
  • the recovery rate for fluorspar is 88.3 percent, whereas that for calcite under the same conditions is practically nil.
  • Results comparable with those given in Example 3, where reagent N"6 was used, are thus obtained here.
  • the two reagents N2 and N6 are, therefore, excellent collectors for the recuperation of fluorspar from calcareous gangue fluorspars.
  • FIG. 3 there is indicated the behaviour of reagent N3 in dependence upon the pH for the two minerals barytine and quartz.
  • the recovery rate for barytine is practically quantitative, whereas that for quartz under the same conditions is practically nil. This explains the possibility of excellent separation of barytine, as shown in Example 4.
  • FIG. 4 there is illustrated an example of inverse flotation in which the desired ore (beryl) sinks, while the gangue (quartz) floats.
  • Example 10 A copper ore from Katanga (malachite with a dolornitie gangue), titrating 5.7 percent Cu, is subjected to flotation.
  • Reagent Nll cited in Table I is used at the rate of 500 g/ton (pH 5.6).
  • the copper recovery rate is 66 percent and the concentrate obtained titrates at 27 percent Cu.
  • Example 11 An itabirite containing percent Fe, mainly in the form of haematite with a siliceous gangue is subjected Reagent N 12 mentioned in Table l is used at the rate of 500 g/ton (pH 5.6).
  • the iron recovery rate is 68 percent and the concentrate obtained titrates at 63 percent Fe.
  • collector agents which comprises using as collector agents at least one member selected from the group consisting of:
  • X respresents the hydrocarbon radical of the acid obtained by controlled pyrolysis of calcium citrate at a temperature within the range of 230C to 400C and acidification of the obtained pyrolysate;
  • R is a C,-C alkyl radical;
  • R, R", R and R"" is a member selected from the group consisting of hydrogen atoms and C,-C alkyl, cycloalkyl, aralkyl, alkaryl and aryl radicals, at least one of R, R", R and R being other than hydrogen and wherein M is a member selected from the group consisting of sodium, potassium and ammonium.
  • collector agents are used together with products selected from the group consisting of ordinary collector agents not according to the invention, frothing agents, depressants, activators, precipitation agents, and dispersing agents.

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  • Manufacture And Refinement Of Metals (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00114613A 1970-02-12 1971-02-11 Process of flotation of minterals and ores Expired - Lifetime US3822014A (en)

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AU (1) AU2533471A (enExample)
BE (1) BE762727A (enExample)
BR (1) BR7100949D0 (enExample)
DE (1) DE2106417A1 (enExample)
ES (1) ES388134A1 (enExample)
FR (1) FR2079374B1 (enExample)
GB (1) GB1259738A (enExample)
MY (1) MY7300255A (enExample)
NL (1) NL7101632A (enExample)
SU (1) SU394962A3 (enExample)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4098686A (en) * 1976-03-19 1978-07-04 Vojislav Petrovich Froth flotation method for recovering of minerals
US4482454A (en) * 1981-11-09 1984-11-13 Ceca S.A. Process for treating cassiterite ore
US20100200510A1 (en) * 2007-07-17 2010-08-12 Basf Se Process for the beneficiation of ores by means of hydrophobic surfaces
US20130068666A1 (en) * 2010-01-08 2013-03-21 Universite De Lorraine Flotation process for recovering feldspar from a feldspar ore
CN113731626A (zh) * 2021-08-25 2021-12-03 湖南有色黄沙坪矿业有限公司 低品位钨钼多金属矿选矿方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2497467A1 (fr) * 1981-01-05 1982-07-09 Ceca Sa Procede d'enrichissement par flottation de minerais a gangues carbonatees et/ou silicatees par des collecteurs amphoteres

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2278107A (en) * 1940-03-30 1942-03-31 American Cyanamid Co Process for concentrating ore materials
US2278060A (en) * 1940-03-30 1942-03-31 American Cyanamid Co Mineral concentration
US2285773A (en) * 1940-08-07 1942-06-09 Colgate Palmolive Peet Co Chemical substance
US2337118A (en) * 1940-10-07 1943-12-21 Du Pont Beneficiation of ores
US2356821A (en) * 1940-09-04 1944-08-29 American Cyanamid Co Froth flotation of acidic minerals
US2477402A (en) * 1947-09-26 1949-07-26 American Cyanamid Co Beneficiation of garnet ores by froth flotation
US2657800A (en) * 1950-07-05 1953-11-03 Distillers Co Yeast Ltd Frothing agents for the flotation of ores
US2689046A (en) * 1950-12-02 1954-09-14 Minerec Corp Concentration of minerals
US3586715A (en) * 1965-07-19 1971-06-22 Citrique Belge Nv Unsaturated carboxylic salt materials and derivatives thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2278107A (en) * 1940-03-30 1942-03-31 American Cyanamid Co Process for concentrating ore materials
US2278060A (en) * 1940-03-30 1942-03-31 American Cyanamid Co Mineral concentration
US2285773A (en) * 1940-08-07 1942-06-09 Colgate Palmolive Peet Co Chemical substance
US2356821A (en) * 1940-09-04 1944-08-29 American Cyanamid Co Froth flotation of acidic minerals
US2337118A (en) * 1940-10-07 1943-12-21 Du Pont Beneficiation of ores
US2477402A (en) * 1947-09-26 1949-07-26 American Cyanamid Co Beneficiation of garnet ores by froth flotation
US2657800A (en) * 1950-07-05 1953-11-03 Distillers Co Yeast Ltd Frothing agents for the flotation of ores
US2689046A (en) * 1950-12-02 1954-09-14 Minerec Corp Concentration of minerals
US3586715A (en) * 1965-07-19 1971-06-22 Citrique Belge Nv Unsaturated carboxylic salt materials and derivatives thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Chem. Abst., Vol. 66, 1967, 21197 X. *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4098686A (en) * 1976-03-19 1978-07-04 Vojislav Petrovich Froth flotation method for recovering of minerals
US4482454A (en) * 1981-11-09 1984-11-13 Ceca S.A. Process for treating cassiterite ore
US20100200510A1 (en) * 2007-07-17 2010-08-12 Basf Se Process for the beneficiation of ores by means of hydrophobic surfaces
US8408395B2 (en) * 2007-07-17 2013-04-02 Basf Se Process for the beneficiation of ores by means of hydrophobic surfaces
US20130068666A1 (en) * 2010-01-08 2013-03-21 Universite De Lorraine Flotation process for recovering feldspar from a feldspar ore
US9675980B2 (en) * 2010-01-08 2017-06-13 Imerys Ceramics France Flotation process for recovering feldspar from a feldspar ore
CN113731626A (zh) * 2021-08-25 2021-12-03 湖南有色黄沙坪矿业有限公司 低品位钨钼多金属矿选矿方法

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ES388134A1 (es) 1973-05-01
ZA71876B (en) 1971-10-27
MY7300255A (en) 1973-12-31
NL7101632A (enExample) 1971-08-16
FR2079374B1 (enExample) 1974-08-19
GB1259738A (en) 1972-01-12
BE762727A (fr) 1971-08-10
BR7100949D0 (pt) 1973-04-19
SU394962A3 (enExample) 1973-08-22
DE2106417A1 (de) 1971-08-19
ZM971A1 (en) 1971-11-22
FR2079374A1 (enExample) 1971-11-12
AU2533471A (en) 1972-08-17

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