EP0174866A2 - Collecteurs pour la flottation à mousse de minérais enrichis - Google Patents

Collecteurs pour la flottation à mousse de minérais enrichis Download PDF

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Publication number
EP0174866A2
EP0174866A2 EP85306521A EP85306521A EP0174866A2 EP 0174866 A2 EP0174866 A2 EP 0174866A2 EP 85306521 A EP85306521 A EP 85306521A EP 85306521 A EP85306521 A EP 85306521A EP 0174866 A2 EP0174866 A2 EP 0174866A2
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Prior art keywords
collector
hydrocarbyl
integer
metal
omega
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German (de)
English (en)
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EP0174866B1 (fr
EP0174866A3 (en
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Richard R. Klimpel
Robert D. Hansen
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Dow Chemical Co
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Dow Chemical Co
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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00Flotation
    • B03D1/02Froth-flotation processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00Flotation
    • B03D1/001Flotation agents
    • B03D1/004Organic compounds
    • B03D1/014Organic compounds containing phosphorus
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00Flotation
    • B03D1/001Flotation agents
    • B03D1/004Organic compounds
    • B03D1/008Organic compounds containing oxygen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00Flotation
    • B03D1/001Flotation agents
    • B03D1/004Organic compounds
    • B03D1/01Organic compounds containing nitrogen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00Flotation
    • B03D1/001Flotation agents
    • B03D1/004Organic compounds
    • B03D1/012Organic compounds containing sulfur
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00Specified effects produced by the flotation agents
    • B03D2201/02Collectors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00Specified materials treated by the flotation agents; specified applications
    • B03D2203/02Ores

Definitions

  • This invention relates to novel collectors for the recovery of mineral values from mineral ores by froth flotation.
  • Flotation is a process of treating a mixture of finely divided mineral solids, e.g., a pulverulent ore, suspended in a liquid whereby a portion of such solids is separated from other finely divided mineral solids, e.g., clays and other like materials present in the ore, by introducing a gas (or providing a gas in situ) in the liquid to produce a frothy mass containing certain of the solids on the top of the liquid, and leaving suspended (unfrothed) other solid components of the ore.
  • a gas or providing a gas in situ
  • Flotation is based on the principle that introducing a gas into a liquid containing solid particles of different materials suspended therein causes the selective adherence of some gas to certain suspended solids and not to others and makes the particles having the gas thus adhered thereto lighter than the liquid. Accordingly, these particles rise to the top of the liquid to form a froth.
  • agents have been admixed with the suspension to improve the frothing and collection process.
  • Such added agents are classed according to the function to be performed and include, for example; collectors, for sulfide minerals including xanthates, thionocarbamates and the like; frothers which impart the property of forming a stable froth, e.g., natural oils such as pine oil and eucalyptus oil, and the like; modifiers such as activators to induce flotation in the presence of a collector, such as copper sulfate; depressants, such as sodium cyanide, which tend to prevent a collector from functioning as such on a mineral which it is desired to retain in the liquid, and thereby discourage a substance from being carried up and forming a part of the froth; pH regulators to produce optimum metallurgical results, such as lime, soda ash, and the like.
  • additives of the hereinbefore described types are selected for use according to the nature of the ore, the mineral sought to be recovered, and the other additaments which are to be used in combination therewith.
  • the flotation principle is applied in a number of mineral separation processes among which is the selective separation of such minerals as sulfide copper minerals, sulfide zinc minerals, sulfide molybdenum minerals and others from iron sulfide minerals, e.g., pyrite.
  • collectors commonly used for the recovery of sulfide-containing metal values are xanthates, dithiophosphates, and thionocarbamates.
  • Collectors for the recovery of sulfide-containing metal values are common and used widely.
  • the difficulty is in the recovery of oxide-containing mineral values, as collectors suitable for the recovery of such mineral values are generally not of a commercially acceptable quality.
  • collectors which are useful for the recovery of a broad range of metal values from metal ores, including the recovery of sulfide--containing mineral values and oxide-containing mineral values. Furthermore, what is needed are collectors which give high rates of recovery of the mineral values along with good selectivities towards the mineral values over the gangue, that is, the undesired portions of the mineral ore.
  • the invention particularly resides in a collector for recovering metal values from a metal ore in which the metal ore, in the form of an aqueous pulp, is subjected to froth flotation, wherein the collector is a compound corresponding to the formula where R is -C H 2 - ' or a combination thereof and n is an integer from 1 to 6 or ( ⁇ R) ⁇ n is ( ⁇ CH 2 ) ⁇ m C ⁇ where m is an integer from 0 to 6; R 1 and each R 2 are independently C 1-22 hydrocarbyl or a C 1-22 hydrocarbyl substituted with one or more hydroxy, amino, phosphonyl, alkoxy, imino, carbamyl, carbonyl, thiocarbonyl, cyano, carboxyl, hydrocarbylthio, hydrocarbyloxy, hydrocarbylamino or hydrocarbylimino groups, with the proviso that R 2 can be a divalent radical with both valencies bonded directly to the N atom or
  • the invention also resides in a method for recovering metal values from a metal ore which comprises subjecting the metal ore, in the form of an aqueous pulp, to a froth flotation process in the presence of a flotation collector under conditions such that the metal values are recovered in the froth, wherein the collector comprises a compound corresponding to the formula wherein: R is -CH 2 -, or mixtures thereof and n is an integer from 1 to 6 or ( ⁇ R) ⁇ n is ( ⁇ CH 2 ) ⁇ m C ⁇ wherein m is an integer from 0 to 6; R 1 and each R 2 are independently C 1-22 hydrocarbyl or a C 1-22 hydrocarbyl substituted with one or more hydroxy, amino, phosphonyl, -alkoxy, imino, carbamyl, carbonyl, thiocarbonyl, cyano, carboxyl, hydrocarbylthio, hydrocarbyloxy, hydrocarbylamino, or hydrocarbylimino groups;
  • the collector comprises a compound corresponding to the formula wherein:
  • the preferred novel collectors of this invention include omega-(hydrocarbylthio)alkylamines; S-(omega--aminoalkyl)hydrocarbon thioates; N-(hydrocarbyl)-alpha, -omega-alkanediamines; (omega-aminoalkyl) hydrocarbon amides; omega-(hydrocarbyloxy-)alkylamines; omega-aminoalkyl hydrocarbonoates; or mixtures thereof.
  • More preferred collectors include omega-(hydrocarbylthio)-alkylamines; N-(hydrocarbyl)-alpha,omega-alkanediamines; and omega-(hydrocarbyloxy-)alkylamines; or mixtures thereof.
  • Most preferred collectors include omega--(hydrocarbylthio)alkylamines; N-(hydrocarbyl)-alpha,omega--alkanediamines; or mixtures thereof.
  • the most preferred class of collectors are the omega-(hydrocarbylthio)-alkylamines.
  • R 1 is preferably C 2-14 hydrocarbyl, and more preferably C 4-11 hydrocarbyl.
  • R 2 is preferably C 1-6 alkyl or C 1-6 alkylcarbonyl, more preferably C 1-4 alkyl or C 1-4 alkylcarbonyl, and most preferably C 1-2 alkyl or C 1-2 alkylcarbonyl.
  • R 3 is preferably hydrogen or C 2-14 hydrocarbyl, more preferably hydrogen or C4-11 hydrocarbyl, and most preferably hydrogen.
  • a is the integer 0 or 1.
  • b is the integer 1 or 2.
  • n is an integer from 1 to 4, and most preferably the integer 2 or 3.
  • X is preferably -S-, -N-R , or -O-.
  • X is more preferably -S- or -N-R 3 .
  • X is most preferably -S-.
  • Preferred S-(omega-aminoalkyl) hydrocarbon thioates correspond to the formula
  • N-(hydrocarbyl)-alpha,omega-alkanediamines correspond to the formula wherein R 1 , R 2 , R 3 , a, b and n are as hereinbefore defined.
  • N-(omega-aminoalkyl) hydrocarbon amides correspond to the formula
  • Preferred omega-(hydrocarbyloxy-)alkylamines correspond to the formula wherein R 1 , R 2 , a, b and n are as hereinbefore defined.
  • Preferred omega-aminoalkyl hydrocarbonoates correspond to the formula wherein R 1 , R 2 , a, b and n are as hereinbefore defined. In those embodiments wherein X is or
  • Hydrocarbon means herein an organic compound containing carbon and hydrogen atoms.
  • hydrocarbon includes the following organic compounds: alkanes, alkenes, alkynes, cycloalkanes, cycloalkenes, cycloalkynes, aromatics, aliphatic and cycloaliphatic aralkanes and alkyl-substituted aromatics.
  • Aliphatic refers herein to straight- and branched-chain, and saturated and unsaturated, hydrocarbon compounds, that is, alkanes, alkenes or alkynes.
  • Cycloaliphatic refers herein to saturated and unsaturated cyclic hydrocarbons, that is, cycloalkenes and cycloalkanes.
  • aromatic includes biaryl, benzene, naphthene, phenanthracene, anthracene and two aryl groups bridged by an alkylene group.
  • Cycloalkane refers to an alkane containing one, two, three or more cyclic rings. Cycloalkene refers to mono-, di- and polycyclic groups containing one or more double bonds.
  • Hydrocarbyl means herein an organic radical containing carbon and hydrogen atoms.
  • hydrocarbyl includes the following organic radicals: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, aliphatic and cycloaliphatic aralkyl and alkaryl.
  • Aliphatic refers herein to straight- and branched-, and saturated and unsaturated, hydrocarbon radicals, that is, alkyl, alkenyl or alkynyl.
  • Cycloaliphatic refers herein to saturated and unsaturated cyclic hydrocarbon radicals, that is, cycloalkenyl and cycloalkyl.
  • aryl includes radicals of biaryl, biphenylyl, phenyl, naphthyl, phenanthrenyl, anthracenyl and two aryl groups bridged by an alkylene group.
  • Alkaryl refers herein to an alkyl-, alkenyl- or alkynyl-substituted aryl substituent wherein aryl is as defined hereinbefore.
  • Aralkyl means herein an alkyl, alkenyl or alkynyl group substituted with an aryl group, wherein aryl is as defined hereinbefore.
  • Alkenearyl refers herein to a radical which contains at least one alkene portion and one aromatic portion, and includes those radicals in which more than one alkene radical alternates with more than one aryl radical.
  • C 1-20 alkyl includes straight- and branched-chain methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl., hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups.
  • Cl-5 alkyl includes methyl, ethyl, propyl, butyl and pentyl.
  • Cycloalkyl refers to alkyl groups containing one, two, three or more cyclic rings. Cycloalkenyl refers to mono-, di- and polycyclic groups containing one or more double bonds. Cycloalkenyl also refers to cycloalkenyl groups wherein two or more double bonds are present.
  • a metal ore includes the metal as it is taken out of the ground and comprises the metal values in admixture with the gangue.
  • Gangue refers herein to those materials which are of no value and need to be separated from the metal values. This process can be used to recover metal oxides, metal sulfides and other metal values.
  • Sulfide ores for which these compounds maybe used include copper sulfide-, zinc sulfide-, molybdenum sulfide-, cobalt sulfide-, nickel sulfide-, lead sulfide-, arsenic sulfide-, silver sulfide-, chromium sulfide-, gold sulfide-, platinum sulfide- and uranium sulfide--containing ores.
  • Examples of sulfide ores from which metal sulfides may be concentrated by froth flotation using the process of this invention include copper-bearing ores such as, for example, covellite (CuS), chalcocite (Cu 2 S), chalcopyrite (CuFeS 2 ), vallierite (Cu 2 Fe 4 S 7 or Cu 3 Fe 4 S 7 ), bornite (Cu 5 FeS 4 ), cubanite (Cu 2 SFe 4 S 5 ), enargite (Cu 3 (AS 1 Sb)S 4 ), tetrahedrite (Cu 3 SbS 2 ), tennantite (Cu 12 As 4 S 13 ), brochantite (Cu 4 (OH) 6 SO 4 ), antlerite (Cu 3 SO 4 (OH) 4 ), famatinite (Cu 3 (SbAs)S 4 ), and bournonite (PbCuSbS 3 ); lead-bearing ores such as, for example, galena (PbS
  • Oxide ores for which this process may be used include copper oxide-, aluminum oxide-, iron oxide-, iron titanium oxide-, magnesium aluminum oxide-, iron chromium oxide-, titanium oxide-, manganese oxide-, tin oxide-, and uranium oxide-containing ores.
  • oxide ore from which metal oxides may be concentrated by froth flotation using the process of this invention include copper-bearingores, for example cuprite (Cu 2 O), tenorite ( C uO), malachite (Cu 2 OH) 2 CO 3 ), azurite (Cu 3 (OH) 2 (CO 3 ) 2 ), atac a mite (Cu 2 Cl(OH) 3 ), chrysocolla (CuSiO 3 ); aluminum--bearing ores, for example corundum; zinc-containing ores, such as zincite (znO), and smithsonite (ZnC03); iron--containing ores, for example hematite and magnetite; chromium-containing ores, for example chromite (FeOCr 2 O 3 ) ; iron- and titanium-containing ores, for example ilmenite; magnesium- and aluminum-containing ores, for example spinel; iron-chromium-containing ores, for example chromite ; titanium-
  • gold-bearing ores for example sylvanite (AuAgTe 2 ) and calaverite (AuTe); platinum- and palladium--bearing ores, for example sperrylite (PtAs 2 ); and silver-bearing ores, such as hessite (AgTe 2 ), for example.
  • AuAgTe 2 sylvanite
  • AuTe calaverite
  • platinum- and palladium--bearing ores for example sperrylite
  • silver-bearing ores such as hessite (AgTe 2 ), for example.
  • oxide- or sulfide-containing values are recovered.
  • copper sulfide, nickel sulfide, lead sulfide, zinc sulfide or molybdenum sulfide values are recovered.
  • copper sulfide values are recovered.
  • the collectors of this invention can be used in any concentration which gives the desired recovery of the desired metal values.
  • concentration used is dependent upon the particular metal value to be recovered, the grade of the ore to be subjected to the froth flotation process, the desired quality of the metal value to be recovered, and the particular mineral value which is being recovered.
  • the collectors of this invention are used in concentrations of from 5 g to 250 g per metric ton of ore, more preferably from 10 g to 100 g of collector per metric ton of ore to be subjected to froth flotation.
  • Froth flotation of this invention usually requires the use of frothers. Any frother well-known in the art, which results in the recovery of the desired metal value is suitable. Further, in the process of this invention it-is contemplated that collectors of this invention can be used in mixtures with other collectors,eg. well-known in the art.
  • Collectors known in the art, which may be used in admixture with the collectors of this invention are those which will give the desired recovery of the desired mineral value.
  • Examples of collectors useful in this invention include alkyl monothiocarbonates, alkyl dithio- carbonates, alkyl trithiocarbonates, dialkyl dithiocarbamates, alkyl thionocarbamates, dialkyl thioureas, monoalkyl dithiophosphates, dialkyl and diaryl dithiophosphates, dialkyl monothiophosphates, thiophosphonyl chlorides, dialkyl and diaryl dithiophosphonates, alkyl mercaptans, xanthogen formates, xanthate esters, mercapto benzothiazoles, fatty acids and salts of fatty acids, alkyl sulfuric acids and salts thereof, alkyl and alkaryl sulfonic acids and salts thereof, alkyl phosphoric acids and salts thereof, alkyl and
  • Frothers useful in this invention include any frothers known in the art which give the recovery of the desired mineral value.
  • frothers include C S-8 alcohols, pine oils, cresols, C l-4 alkyl ethers of polypropylene glycols, dihydroxylates of polypropylene glycols, glycols, fatty acids, soaps, alkylaryl sulfonates, and the like.
  • blends of such frothers may also be used. All frothers which are suitable for beneficiation of mineral ores by froth flotation can be used in this invention.
  • the omega-(hydrocarbylthio)alkylamines can be prepared by the processes disclosed in Berazosky et al., U.S. Patent 4,086,273; French Patent 1,519,829; or Beilstein, 4, 4 Ed., 4th Supp., 1655 (1979).
  • the (omega-aminoalkyl) hydrocarbon amides can be prepared by the processes described in Fazio, U.S. Patent 4,326,067; Acta Polon Pharm, 19, 277 (1962); or Beilstein, 4, 4th Ed., 3rd Supp., 587 (1962).
  • the omega-(hydrocarbyloxy-)alkylamines can be prepared by the processes described in British Patent 869,409; or Hobbs, U.S.
  • the S-(omega--aminoalkyl) hydrocarbon thioates can be prepared by the processes described in Faye et al., U.S. Patent 3,328,442; or Beilstein, 4, 4th Ed., 4th Supp., 1657 (1979).
  • the omega-aminoalkyl hydrocarbonoates can be prepared by the process described in J. Am. Chem. Soc., 83, 4835 (1961); Beilstein, 4, 4th Ed., 4th Supp., 1413 (1979); or Beilstein, 4, 4th Ed., 4th Supp., 1785 (1979).
  • the N-(hydrocarbyl)--alpha,omega-alkanediamines can be prepared by the process well-known in the art, one example is the process described in East German Patent 98,510.
  • r is the amount of mineral recovered at time t
  • K is the rate constant for the rate of recovery
  • R is the calculated amount of the mineral which would be recovered at infinite time. The amount recovered at various times is determined experimentally and the series of values are substituted into the equation to obtain the R and K values. The above formula is explained in "Selection of Chemical Reagents for Flotation", Chapter 45, pp. 907-934, Mineral Processing Plant Design, 2nd Ed., 1980, by R. Klimpel AIME (Denver).
  • a 500-g quantity of Chilean copper ore, chalcopyrite copper sulfide ore, previously packaged is placed in a rod mill with 257 g of deionized water.
  • the copper ore comprises 80.2 percent with a particle size of about 75 micrometers of less.
  • a quantity of lime is also added to the rod mill, based on the desired pH for the subsequent flotation.
  • the rod mill is then rotated at 60 rpm for a total of 360 revolutions.
  • the ground slurry is transferred to a 1500 ml cell of an Agitair® Flotation machine.
  • the float cell is agitated at 1150 rpm and the pH is adjusted to 10.5 by the addition of further lime, if necessary.
  • the collector is added to the float cell (at a rate of 50 g/metric ton), followed by a conditioning time of one minute, at which time the frother, DOWFROTH® 250 (Trademark of The Dow Chemical Company) is added (at a rate of 40 g/metric ton).
  • DOWFROTH® 250 Trademark of The Dow Chemical Company
  • the air to the float cell is turned on at a rate of 4.5 liters per minute and the automatic froth removal paddle is started.
  • the froth samples were taken off at 0.5, 1.5, 3, 5 and 8 minutes.
  • the froth samples are dried overnight in an oven, along with the flotation tailings.
  • the dried samples are weighed, divided into suitable samples for analysis, pulverized to insure suitable fineness, and dissolved in acid for analysis.
  • the samples are analyzed using a DC Plasma Spectrograph.
  • collectors that were tested for flotation of copper sulfide values of a Chilean copper ore are compiled in Table I and demonstrate that a wide variety of compounds within the scope of the invention are effective in the recovery of copper sulfide values.
  • a base case example which employed no collector is included in Table I for comparison. It should be noted that the collectors of the invention in Table I were not selected for optimum performance, but represent arbitrary selection of compounds that show a significant response in the recovery and selectivity of mineral values.
  • a Central African copper oxide ore (Cu 2 0) is subjected to the froth flotation process described in Example 1 using 40 grams per metric ton of the frother, DOWFROTH® 250 (Trademark of The Dow Chemical Company). The results are compiled in Table II with Collectors A and B being chosen from Table I.
  • a Central Canadian sulfide ore containing copper sulfide, nickel sulfide, platinum, palladium and gold metal values is subjected to a series of froth flotations as described in Example 1 using the collectors of this invention and several collectors known in the art.
  • the frother used is DOWFROTH 6 1263 (Trademark of The Dow Chemical Company) at a concentration of 0.00625 lb/ton (3.12 g/metric ton)
  • the collectors are used at a concentration of 0.0625 lb/ton (31.2 g/metric ton).
  • the froths produced are recovered at 0.5, 1.0, 2.0, 4.0, 7.0, 11.0 and 16.0 minutes.
  • Table III The results are compiled in Table III with collectors chosen from Table I.
  • Table III illustrates the use of two novel compounds of this invention, i.e. OHTEA and NOPA as compared to three optimized industrial collector standards.
  • the ore was complex containing various metal values.
  • the collectors are comparable in performance in the recovery of copper values.
  • the OHTEA collector was clearly superior in the recovery of nickel, platinum, palladium and gold.
  • the R-16 value of OHTEA when compared to Z-211 showed a slight increase but a very surprising and significant decline in the recovery of pyrrhotite, i.e. 15.5 percent.
  • a substantial improvement was also realized in the reduction of the tailings for platinum and palladium - the values were about equal for gold.
  • the collector NOPA showed a good recovery for copper and nickel when compared against the best known collectors employed in the field. It showed a superior performance in the reduction of R-16 pyrrhotite values- when compared against the standards.
  • the ratio of nickel recovery to pyrrhotite recovery is clearly superior when compared to known collectors, i.e., a 30 percent increase in the ratio.
  • the selectivity of NOPA is significant if it is desired to lower the demand on smelters since much of the flotation product is undesired sulfur containing material.
  • a quantity of lime is also added to the rod mill, based on the desired pH for the subsequent flotation.
  • the ground slurry is transferred to a 1500 ml cell of an Agitair Flotation machine.
  • the float cell is agitated at 1150 rpm and the pH is adjusted to 8.5 by the addition of further lime.
  • the collector is added to the float cell at the rate of 8 g/metric ton, followed by a conditioning time of 1 minute, at which time the frother, DOWFROTH® (Trademark of The Dow Chemical Company) is added at the rate of 18 g/metric ton.
  • DOWFROTH® Trademark of The Dow Chemical Company
  • the air to the float cell is turned on at a rate of 4.5 liters per minute and the automatic froth removal paddle is started.
  • the froth samples were taken off at 0.5, 1.5, 3, 5 and 8 minutes.
  • the froth samples are dried overnight in an oven, along with the flotation tailings.
  • the dried samples are weighed, divided into suitable samples for analysis, pulverized to insure suitable fineness, and dissolved in acid for analysis.
  • the samples are analyzed using a DC Plasma Spectrograph. The results are compiled in Table IV.
  • the compounds that were used in Examples 1 through 31 in Table IV are separately tabulated herein below:
  • Example 4 is similar to Example 1 except that various different compounds within the scope of the invention were tested on a different copper sulfide ore. No optimization of the collectors was attempted but all of the compounds were found to be clearly superior when compared against "no collector" in.the recovery of copper values.
  • the collectors of this invention will show superior recovery and selectivity when compared to the standard known collectors and when optimized with regard to a particular ore under consideration.
  • Bags of homogeneous ore are prepared with each bag containing 1200 grams.
  • the rougher flotation procedure is to grind a 1200 gram charge with 800 cc of tap water for 14 minutes in a ball mill having a mixed ball charge (to produce appoximately a 13 percent plus 100 mesh grind).
  • This pulp is transferred to an Agitair 500 flotation cell outfitted with an automated paddle removal system.
  • the slurry pH is adjusted to 10.2 using lime. No further pH adjustments are made during the test.
  • the standard frother is methyl isobutyl carbinol (MIBC). A four-stage rougher flotation scheme is then followed.
  • Table V illustrates that a substantially higher grade was achieved for copper and molybdenum as compared to the Standard Collector A.
  • the minimum increase was over 10 percent and the maximum increase was 77 percent.
  • the minimum increase in grade was about 30 percent and the maximum optimized increase was about 122 percent.
  • the grade for iron with any of the Collectors B of the invention again show a substantial reduction of about 50 percent as compared to the Standard Collector A, indicating that substantially less of the undesirable pyrite is collected.
  • This surprising selectivity in the collection of metal sulfide values over iron sulfide values is highly advantageous in the downstream operation of a mining operation as it reduces sulfur emissions.
  • a series of 750 gram charges of a nickel/cobalt ore are prepared in slurry form (30 percent solids).
  • the flotation cell is an Agitair® LA-500 outfitted with an automatic peddle for froth removal operating at 60 rpm's.
  • a standard run is to first add 0.2 kg/metric ton of CuS0 4 , condition for 7 minutes, add 0.1 kg/ton collector, condition for 3 minutes, add 0.14 kg/ton guar depressant for talc, and 0.16 kg/metric ton collector, add a frother (e.g., triethoxybutane) to form a reasonable froth bed.
  • Concentrate collection is initiated for 5 minutes (denoted as rougher concentrate).
  • the data in Table VI represents a full scale simulation of a continuous industrial flotation process.
  • the data in the column entitled "Flotation Tail” is the most significant data since it shows actual metal loss, i.e. the lower the value in the Flotation Tail column, the lower the metal loss.
  • the superiority of the experimental collectors of the invention over the industrial standard in this category is apparent.
  • the Flotation Tail for nickel recovery showed an 8 percent drop
  • the flotation tail drop showed a surprising 81 percent drop.
  • Similar improvements were realized except for Collector 3.
  • Uniform 1000 gram samples of ore are prepared. For each flotation run, a sample is added to a rod mill along with 500 cc of tap water and 7.5 ml of S0 2 solution. 6-1/2 minutes of mill time are used to prepare a feed in which 90 percent of the particles have a size of less than 200 mesh (75 microns). After grinding, the contents are transferred to a cell fitted with an automated paddle for froth removal. The cell is attached to a standard Denver flotation mechanism.
  • a two-stage flotation procedure is then performed.
  • Stage I a copper/lead/silver rougher
  • Stage II a zinc rougher.
  • 1.5 g/kg Na 2 co 3 is added and the pH adjusted to 8.5, followed by the addition of the collector(s).
  • the pulp is then conditioned for 5 minutes with air and agitation. This is followed by a 2-minute condition period with agitation only.
  • MIBC frother is then added (standard dose of 0 .015 ml/kg). Concentrate is collected for 5 minutes of flotation and labeled as copper/lead rougher concentrate.
  • the Stage II flotation consists of adding 0.3 kg/metric ton of CuSO to the cell remains of Stage I.
  • the pH is then adjusted to 9.5 with lime addition. This is followed by a condition period of 5 minutes with agitation only.
  • the pH is. then rechecked and adjusted back to 9.5 with lime.
  • the collector(s) is added, followed by a 5-minute condition period with agitation only.
  • MIBC frother is then added (standard dose of 0.020 ml/kg).
  • the concentrate is collected for 5 minutes and labeled as zinc rougher concentrate.
  • Concentrate samples are dried, weighed, and appropriate samples prepared for assay using X-ray techniques. Using the assay data, recoveries and grades are calculated using standard mass balance formulae.
  • Table VII illustrates the performance of optimized industrial standard collectors when compared to the collector of the invention in the recovery of metal values.
  • Stage I of test 1 employed a combination of standard collectors A and B, while Stage II employed a combination.of standard collectors A and C.
  • Stage I of test 2 employed a mixture of a standard collector B and collector D of the invention in approximate equal amounts.
  • Stage II of test 2 employed collector D of the invention.

Landscapes

  • Manufacture And Refinement Of Metals (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Physical Water Treatments (AREA)
EP85306521A 1984-09-13 1985-09-13 Collecteurs pour la flottation à mousse de minérais enrichis Expired - Lifetime EP0174866B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
MYPI87001262A MY101975A (en) 1984-09-13 1987-08-10 Collector compositions for the froth flotation of mineral values

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US64989084A 1984-09-13 1984-09-13
US649890 1984-09-13

Publications (3)

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EP0174866A2 true EP0174866A2 (fr) 1986-03-19
EP0174866A3 EP0174866A3 (en) 1989-09-06
EP0174866B1 EP0174866B1 (fr) 1993-03-10

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JP (2) JPS6186960A (fr)
KR (1) KR900002702B1 (fr)
CN (3) CN85107378A (fr)
AR (1) AR242135A1 (fr)
AU (1) AU562083B2 (fr)
BR (1) BR8504419A (fr)
CA (1) CA1265877A (fr)
DE (1) DE3587166D1 (fr)
ES (1) ES8700699A1 (fr)
FI (1) FI79951C (fr)
MX (1) MX169955B (fr)
MY (1) MY101975A (fr)
NO (1) NO166846C (fr)
PH (1) PH21358A (fr)
PL (1) PL146943B1 (fr)
RO (1) RO95694B (fr)
SU (1) SU1419507A3 (fr)
TR (1) TR25780A (fr)
YU (1) YU45741B (fr)
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3716012A1 (de) * 1987-05-11 1988-11-24 Gerhard Dr Rer Nat Heinrich Verfahren zur anreicherung von bleiverbindungen
EP0320783A2 (fr) * 1987-12-16 1989-06-21 The Dow Chemical Company Procédé pour la préparation de sels des alcoylthioéthylamines
US5061459A (en) * 1989-10-27 1991-10-29 The British Petroleum Company P.L.C. Prevention of copper dissolution during cyanidation of gold ores
AU2006317498B2 (en) * 2005-11-22 2010-10-14 Barry Graham Lumsden Improving mineral recovery from ore
US9630937B2 (en) 2013-11-08 2017-04-25 Promentis Pharmaceuticals, Inc. Substituted N-acetyl-L-cysteine derivatives and related compounds
US10522883B2 (en) 2010-05-10 2019-12-31 Rsr Technologies, Inc. Recycling electrochemical cells and batteries
CN113245064A (zh) * 2021-04-30 2021-08-13 瓮福(集团)有限责任公司 一种复杂难选胶磷矿中倍半氧化物的脱除方法
WO2022034047A1 (fr) 2020-08-11 2022-02-17 Basf Se Procédé de flottation d'un minerai de fer contenant du silicate

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PH24537A (en) * 1985-11-29 1990-08-03 Dow Chemical Co Collector composition for the froth flotation of mineral values
ZA918140B (en) * 1991-10-11 1992-07-29 American Cyanamid Co Recovery of platinum group metals and gold by synergistic reaction between allylalkylthionocarbamates and dithiophosphates
US5700369A (en) * 1997-01-14 1997-12-23 Guangzhou Institute Of Geochemistry Chinese Academy Of Sciences Process for adsorboaggregational flotation of Carlin type natural gold ore dressing
US6833460B2 (en) 1999-06-18 2004-12-21 E. I. Du Pont De Nemours And Company Preparation and use of gamma-butyrolactones as cross-linking agents
CN101321588A (zh) * 2005-11-22 2008-12-10 巴里·格雷厄姆·拉姆斯登 提高矿石中矿物的回收率
CN104028387B (zh) * 2014-06-17 2017-01-25 扬州大学 一种新型煤炭浮选剂的合成
CN104874488B (zh) * 2015-06-05 2017-05-24 昆明冶金研究院 一种捕收剂及其制备方法与应用
CN106669959B (zh) * 2016-06-20 2019-02-22 中国矿业大学 一种细粒中煤的浮选药剂及其应用
CN107138289B (zh) * 2017-06-26 2019-07-12 乌拉特前旗西沙德盖钼业有限责任公司 一种阳离子型选矿用起泡剂
CN109174463B (zh) * 2018-08-21 2020-02-28 中国矿业大学 用于氧化煤煤泥浮选的捕收剂以及制备方法、浮选方法
JP7344504B2 (ja) * 2018-09-14 2023-09-14 国立大学法人九州大学 選鉱方法
CN109365138B (zh) * 2018-11-30 2021-03-05 河南城建学院 一种用于硫化铜镍矿浮选的新型复合浮选剂
CN109530094B (zh) * 2019-01-17 2021-05-28 湖南中医药大学 酰胺基羟基羧酸/羟肟酸类化合物及其在矿物浮选中的应用
CN110015727B (zh) * 2019-05-09 2021-07-09 安徽工业大学 一种电解气浮除去水体中微塑料的方法
CN112058502B (zh) * 2020-09-07 2021-08-27 中南大学 一种硫化锌的高效浮选捕收剂及其应用

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GB547292A (en) * 1940-03-30 1942-08-21 American Cyanamid Co Concentration process for separating acidic minerals from ore materials
GB554814A (en) * 1941-09-06 1943-07-20 American Cyanamid Co Concentration of acidic minerals
US2364272A (en) * 1941-09-04 1944-12-05 American Cyanamid Co Mineral concentration
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GB578695A (en) * 1943-04-20 1946-07-09 American Cyanamid Co Improvements in or relating to methods of concentrating ores
FR1136073A (fr) * 1955-11-09 1957-05-09 Penarroya Miniere Metall Perfectionnements au procédé de flottation des minerais de zinc oxydés
US3772345A (en) * 1970-09-08 1973-11-13 Dow Chemical Co Process for preparing n-alkylthioalkyl-o-alkylthiocarbamates and n-alkyl-thioalkyl-o-alkylcarbamates
FR2171281A1 (fr) * 1972-02-08 1973-09-21 Dow Chemical Co
US3985645A (en) * 1973-10-11 1976-10-12 Canadian Patents And Development Limited Scheelite flotation
US4422928A (en) * 1981-03-09 1983-12-27 Exxon Research & Engineering Co. Silica flotation collectors derived from isononyl alcohol
EP0070534A1 (fr) * 1981-07-21 1983-01-26 Hoechst Aktiengesellschaft Acides 3-alcoxypropyleneimino-bis(méthylènephosphoniques) et leurs sels, leur procédé de préparation et leur utilisation

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3716012A1 (de) * 1987-05-11 1988-11-24 Gerhard Dr Rer Nat Heinrich Verfahren zur anreicherung von bleiverbindungen
EP0320783A2 (fr) * 1987-12-16 1989-06-21 The Dow Chemical Company Procédé pour la préparation de sels des alcoylthioéthylamines
EP0320783A3 (en) * 1987-12-16 1990-12-05 The Dow Chemical Company Process for preparing alkylthioethylamine salts
US5061459A (en) * 1989-10-27 1991-10-29 The British Petroleum Company P.L.C. Prevention of copper dissolution during cyanidation of gold ores
AU2006317498B2 (en) * 2005-11-22 2010-10-14 Barry Graham Lumsden Improving mineral recovery from ore
US10522883B2 (en) 2010-05-10 2019-12-31 Rsr Technologies, Inc. Recycling electrochemical cells and batteries
US9630937B2 (en) 2013-11-08 2017-04-25 Promentis Pharmaceuticals, Inc. Substituted N-acetyl-L-cysteine derivatives and related compounds
US10112897B2 (en) 2013-11-08 2018-10-30 Promentis Pharmaceuticals, Inc. Substituted N-acetyl-L-cysteine derivatives and related compounds
US10358414B2 (en) 2013-11-08 2019-07-23 Promentis Pharmaceuticals, Inc. Substituted N-acetyl-L-cysteine derivatives and related compounds
US10961187B2 (en) 2013-11-08 2021-03-30 Promentis Pharmaceuticals, Inc. Substituted N-acetyl-L-cysteine derivatives and related compounds
WO2022034047A1 (fr) 2020-08-11 2022-02-17 Basf Se Procédé de flottation d'un minerai de fer contenant du silicate
CN113245064A (zh) * 2021-04-30 2021-08-13 瓮福(集团)有限责任公司 一种复杂难选胶磷矿中倍半氧化物的脱除方法

Also Published As

Publication number Publication date
MY101975A (en) 1992-02-29
MX169955B (es) 1993-08-02
KR900002702B1 (ko) 1990-04-23
RO95694B (ro) 1989-01-31
PH21358A (en) 1987-10-15
JPH0152063B2 (fr) 1989-11-07
EP0174866B1 (fr) 1993-03-10
CN85107378A (zh) 1987-03-18
PL255363A1 (en) 1987-10-19
FI853490A0 (fi) 1985-09-12
NO853580L (no) 1986-03-14
AU562083B2 (en) 1987-05-28
AR242135A1 (es) 1993-03-31
YU144085A (en) 1987-12-31
SU1419507A3 (ru) 1988-08-23
ZM6585A1 (en) 1987-04-30
KR860002300A (ko) 1986-04-24
BR8504419A (pt) 1986-07-15
ZW15285A1 (en) 1987-04-08
FI79951B (fi) 1989-12-29
ES546919A0 (es) 1986-10-16
ES8700699A1 (es) 1986-10-16
CN85109643A (zh) 1987-04-15
DE3587166D1 (de) 1993-04-15
TR25780A (tr) 1993-07-28
JPS63107761A (ja) 1988-05-12
RO95694A (fr) 1989-01-30
PL146943B1 (en) 1989-04-29
ZA856955B (en) 1987-05-27
CN1006689B (zh) 1990-02-07
NO166846B (no) 1991-06-03
CN1020551C (zh) 1993-05-12
CN85106476A (zh) 1987-03-25
FI853490L (fi) 1986-03-14
EP0174866A3 (en) 1989-09-06
AU4739785A (en) 1986-03-20
FI79951C (fi) 1990-04-10
CA1265877A (fr) 1990-02-13
YU45741B (sh) 1992-07-20
JPS6186960A (ja) 1986-05-02
NO166846C (no) 1991-09-11

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