EP0174866B1 - Novel collectors for the froth flotation of mineral values - Google Patents

Novel collectors for the froth flotation of mineral values Download PDF

Info

Publication number
EP0174866B1
EP0174866B1 EP85306521A EP85306521A EP0174866B1 EP 0174866 B1 EP0174866 B1 EP 0174866B1 EP 85306521 A EP85306521 A EP 85306521A EP 85306521 A EP85306521 A EP 85306521A EP 0174866 B1 EP0174866 B1 EP 0174866B1
Authority
EP
European Patent Office
Prior art keywords
alkyl
collector
metal
flotation
values
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP85306521A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0174866A3 (en
EP0174866A2 (en
Inventor
Richard R. Klimpel
Robert D. Hansen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP0174866A2 publication Critical patent/EP0174866A2/en
Priority to MYPI87001262A priority Critical patent/MY101975A/en
Publication of EP0174866A3 publication Critical patent/EP0174866A3/en
Application granted granted Critical
Publication of EP0174866B1 publication Critical patent/EP0174866B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/02—Froth-flotation processes
    • 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
    • B03D1/014—Organic compounds containing phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/008—Organic compounds containing oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/01—Organic compounds containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/012—Organic compounds containing sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; Specified applications
    • B03D2203/02—Ores

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. Examples of collectors for oxide-containing mineral values can be found in FR-A-1 136 073 and EP-A-0 070 534.
  • 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 also resides in a process for recovering metal values from a metal ore, comprising the steps of subjecting the metal ore, in the form of an aqueous pulp, to a froth flotation process in the presence of a flotation collector as hereinbefore described under conditions such that the metal values are recovered in the froth.
  • the collector comprises an omega-(hydrocarbylthio)alkylamine corresponding to the formula wherein: R1 is C1 ⁇ 22 hydrocarbyl optionally substituted with one or more hydroxy, amino, phosphonyl, or alkoxy moieties; R2 is a C1 ⁇ 6 alkyl,a C1 ⁇ 6 alkylcarbonyl,or a C1 ⁇ 6 alkyl group optionally substituted with an amino, hydroxy or phosphonyl moiety,or a C1 ⁇ 6 alkylcarbonyl group optionally substituted with an amino, hydroxy or phosphonyl moiety; and a, b and n are as defined above.
  • Collectors of this invention surprisingly float a broad range of metal values including sulfide ores, oxide ores and precious metals. Furthermore, such collectors give improved recoveries of the mineral values including mineral oxides, mineral sulfides and precious metals. Not only are surprisingly high recoveries achieved, but the selectivity towards the desired mineral values is surprisingly high.
  • R1 is preferably C2 ⁇ 14 hydrocarbyl and more preferably C4 ⁇ 11 hydrocarbyl.
  • R2 is preferably C1 ⁇ 6 alkyl or C1 ⁇ 6 alkylcarbonyl, more preferably C1 ⁇ 4 alkyl or C1 ⁇ 4 alkylcarbonyl, and most preferably C1 ⁇ 2 alkyl or C1 ⁇ 2 alkylcarbonyl.
  • 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.
  • R1 is preferably C4 ⁇ 10 hydrocarbyl.
  • 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.
  • C1 ⁇ 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.
  • C1 ⁇ 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 may be 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 (Cu2S), chalcopyrite (CuFeS2) vallierite (Cu2Fe4S7 or Cu3Fe4S7), bornite (Cu5FeS4), cubanite (Cu2SFe4S5), enargite (Cu3(As1Sb)S4), tetrahedrite (Cu3SbS2) tennantite (Cu12As4S13), brochantite (Cu4(OH)6SO4), antlerite (Cu3SO4(OH)4), famatinite (Cu3(SbAs)S4), and bournonite (PbCuSbS3); lead-bearing ores such as, for example, galena (Pbs); antimony-bearing ores
  • 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-bearing ores, for example cuprite (Cu2O), tenorite (CuO), malachite (Cu2OH)2CO3), azurite (Cu3(OH)2(CO3)2), atacamite (Cu2Cl(OH)3), chrysocolla (CuSiO3); aluminum-bearing ores, for example corundum; zinc-containing ores, such as zincite (ZnO), and smithsonite (ZnCO3); iron-containing ores, for example hematite and magnetite; chromium-containing ores, for example chromite (FeOCr2O3); iron- and titanium-containing ores, for example ilmenite; magnesium- and aluminum-containing ores, for example spinel; iron-chromium-containing ores, for example chromite; titanium-containing ores, for example rutile; manganese-be
  • AuAgTe2 gold-bearing ores
  • AuTe2 sylvanite
  • AuTe2 calaverite
  • platinum- and palladium-bearing ores for example sperrylite (PtAs2)
  • silver-bearing ores such as hessite (AgTe2), 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 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 dithiocarbonates, 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 aryl
  • Frothers useful in this invention include any frothers known in the art which give the recovery of the desired mineral value.
  • frothers include c5 ⁇ 8 alcohols, pine oils, cresols, C1 ⁇ 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.
  • omega-(hydrocarbylthio)alkylamines can be prepared by the processes disclosed in Berazosky et al., U.S.-A-4,086,273; FR-A-1,519,829; or Beilstein , 4 , 4 Ed., 4th Supp., 1655 (1979).
  • 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 (Cu2O) 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 Collector A being chosen from Table I.
  • TABLE II Collector Conc. g/ton pH Cu K R R-8 A 160 5.1 2.48 0.335 0.308 A 80 9.5 2.55 0.249 0.234 C 160 5.1 4.08 0.135 0.130 A - C6H13-S( ⁇ CH2)2-NH2 C - Sodium isopropyl xanthate, not an embodiment of this invention
  • 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® 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 9/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 novel compound of this invention, i.e. OHTEA 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.
  • 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 27 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.
  • STAGE 1 Collector - 0.0042 kg/ton MIBC - 0.015 kg/ton - condition - 1 minute - float - collect concentrate for 1 minute
  • STAGE 2 Collector - 0.0021 kg/ton MIBC - 0.005 kg/ton - condition - 0.5 minute - float - collect concentrate for 1.5 minutes
  • STAGE 3 Collector - 0.0016 kg/ton MIBC - 0.005 kg/ton - condition - 0.5 minute - float - collect concentrate for 2 minutes
  • STAGE 4 Collector - 0.0033 kg/ton MIBC - 0.005 kg/ton - condition - 0.5 minute - float - collect concentrate for 2.5 minutes
  • 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 paddle for froth removal operating at 60 rpm's.
  • a standard run is to first add 0.2 kg/metric ton of CuSO4, 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 SO2 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 Na2CO3 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 CuSO4 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)
  • Physical Water Treatments (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
EP85306521A 1984-09-13 1985-09-13 Novel collectors for the froth flotation of mineral values Expired - Lifetime EP0174866B1 (en)

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)

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

Family

ID=24606650

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85306521A Expired - Lifetime EP0174866B1 (en) 1984-09-13 1985-09-13 Novel collectors for the froth flotation of mineral values

Country Status (23)

Country Link
EP (1) EP0174866B1 (ro)
JP (2) JPS6186960A (ro)
KR (1) KR900002702B1 (ro)
CN (3) CN85107378A (ro)
AR (1) AR242135A1 (ro)
AU (1) AU562083B2 (ro)
BR (1) BR8504419A (ro)
CA (1) CA1265877A (ro)
DE (1) DE3587166D1 (ro)
ES (1) ES8700699A1 (ro)
FI (1) FI79951C (ro)
MX (1) MX169955B (ro)
MY (1) MY101975A (ro)
NO (1) NO166846C (ro)
PH (1) PH21358A (ro)
PL (1) PL146943B1 (ro)
RO (1) RO95694B (ro)
SU (1) SU1419507A3 (ro)
TR (1) TR25780A (ro)
YU (1) YU45741B (ro)
ZA (1) ZA856955B (ro)
ZM (1) ZM6585A1 (ro)
ZW (1) ZW15285A1 (ro)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2007059559A1 (en) * 2005-11-22 2007-05-31 Barry Graham Lumsden Improving mineral recovery from ore

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PH24537A (en) * 1985-11-29 1990-08-03 Dow Chemical Co Collector composition for the froth flotation of mineral values
DE3716012A1 (de) * 1987-05-11 1988-11-24 Gerhard Dr Rer Nat Heinrich Verfahren zur anreicherung von bleiverbindungen
US5087757A (en) * 1987-12-16 1992-02-11 The Dow Chemical Company Preparation of 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
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
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
EP3674297A1 (en) 2013-11-08 2020-07-01 Promentis Pharmaceuticals, Inc. Substituted n-acetyl-l-cysteine derivatives and related compounds
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
CN116209525A (zh) 2020-08-11 2023-06-02 巴斯夫欧洲公司 含硅酸盐的铁矿石的浮选方法
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
US12036286B2 (en) 2021-03-18 2024-07-16 Seagen Inc. Selective drug release from internalized conjugates of biologically active compounds
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
US20230302464A1 (en) * 2022-03-25 2023-09-28 Clariant International, Ltd. Novel Cationic Collectors for Improving a Process for Froth Flotation of Silicates

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB547292A (en) * 1940-03-30 1942-08-21 American Cyanamid Co Concentration process for separating acidic minerals from ore materials
US2364272A (en) * 1941-09-04 1944-12-05 American Cyanamid Co Mineral concentration
GB554814A (en) * 1941-09-06 1943-07-20 American Cyanamid Co Concentration of acidic minerals
US2365084A (en) * 1942-03-31 1944-12-12 American Cyanamid Co Beneficiation of acidic minerals
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
BE795146A (fr) * 1972-02-08 1973-08-08 Dow Chemical Co Perfectionnements relatifs a la flottation des minerais sulfures
CA1006277A (en) * 1973-10-11 1977-03-01 Harvey L. Noblitt Scheelite flotation
DE2547987C2 (de) * 1975-10-27 1983-05-26 Henkel KGaA, 4000 Düsseldorf Flotationssammler für Sylvin
JPS5599356A (en) * 1979-01-25 1980-07-29 Dow Chemical Co Additive for alkanol amineetolu oil fatty acid coal flotation method
US4422928A (en) * 1981-03-09 1983-12-27 Exxon Research & Engineering Co. Silica flotation collectors derived from isononyl alcohol
DE3128755A1 (de) * 1981-07-21 1983-02-10 Hoechst Ag, 6000 Frankfurt 3-alkoxipropylenimino-bis(methylenphosphonsaeuren) und deren salze, verfahren zu deren herstellung und deren verwendung
JPS58104651A (ja) * 1981-12-15 1983-06-22 ザ・ダウ・ケミカル・カンパニ− 石炭の泡だて浮遊選鉱法の助剤としての脂肪酸とヒドロキシアルキル化ポリアルキレンポリアミンとの縮合物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2007059559A1 (en) * 2005-11-22 2007-05-31 Barry Graham Lumsden Improving mineral recovery from ore

Also Published As

Publication number Publication date
JPH0152063B2 (ro) 1989-11-07
KR900002702B1 (ko) 1990-04-23
AU4739785A (en) 1986-03-20
ZW15285A1 (en) 1987-04-08
AU562083B2 (en) 1987-05-28
JPS63107761A (ja) 1988-05-12
KR860002300A (ko) 1986-04-24
FI853490A0 (fi) 1985-09-12
ZM6585A1 (en) 1987-04-30
ES8700699A1 (es) 1986-10-16
CN1020551C (zh) 1993-05-12
MY101975A (en) 1992-02-29
AR242135A1 (es) 1993-03-31
ZA856955B (en) 1987-05-27
CA1265877A (en) 1990-02-13
FI853490L (fi) 1986-03-14
SU1419507A3 (ru) 1988-08-23
CN1006689B (zh) 1990-02-07
YU144085A (en) 1987-12-31
CN85107378A (zh) 1987-03-18
FI79951B (fi) 1989-12-29
RO95694B (ro) 1989-01-31
DE3587166D1 (de) 1993-04-15
MX169955B (es) 1993-08-02
JPS6186960A (ja) 1986-05-02
CN85106476A (zh) 1987-03-25
RO95694A (ro) 1989-01-30
NO853580L (no) 1986-03-14
FI79951C (fi) 1990-04-10
BR8504419A (pt) 1986-07-15
NO166846C (no) 1991-09-11
PL146943B1 (en) 1989-04-29
NO166846B (no) 1991-06-03
PH21358A (en) 1987-10-15
EP0174866A3 (en) 1989-09-06
TR25780A (tr) 1993-07-28
EP0174866A2 (en) 1986-03-19
ES546919A0 (es) 1986-10-16
YU45741B (sh) 1992-07-20
CN85109643A (zh) 1987-04-15
PL255363A1 (en) 1987-10-19

Similar Documents

Publication Publication Date Title
EP0174866B1 (en) Novel collectors for the froth flotation of mineral values
AU576665B2 (en) Froth flotation of metal-containing sulphide minerals
US4684459A (en) Collector compositions for the froth flotation of mineral values
EP0453677B1 (en) Depression of the flotation of silica or siliceous gangue in mineral flotation
US4797202A (en) Froth flotation method
US5057209A (en) Depression of the flotation of silica or siliceous gangue in mineral flotation
AU586471B2 (en) Collectors for froth flotation
US4582596A (en) Frothers demonstrating enhanced recovery of coarse particles in froth floatation
Aplan et al. Collectors for sulfide mineral flotation
AU588579B2 (en) Collector compositions for the froth flotation of mineral values
US4822483A (en) Collector compositions for the froth flotation of mineral values
CA1267979A (en) Collector composition for froth flotation
US4676890A (en) Collector compositions for the froth flotation of mineral values
US4793852A (en) Process for the recovery of non-ferrous metal sulfides
US4702822A (en) Novel collector composition for froth flotation
US5126038A (en) Process for improved precious metals recovery from ores with the use of alkylhydroxamate collectors
US4735711A (en) Novel collectors for the selective froth flotation of mineral sulfides
US4789392A (en) Froth flotation method
US4511464A (en) 1,3-Oxathiolane-2-thiones as sulfide mineral collectors in froth flotation
US4732668A (en) Novel collectors for the selective froth flotation of mineral sulfides
USRE32778E (en) Frothers demonstrating enhanced recovery of coarse particles in froth floatation
CA1271273A (en) Collectors for froth flotation of minerals
NO168992B (no) Fremgangsmaate for utvinning av metallholdige sulfidmineraler eller sulfifiserte metallholdige oksydmineraler fra enmalm
NO168408B (no) Kollektormaterialer for flotasjon av metallholdige mineraler, samt fremgangsmaate for utvinning av slike mineraler
NO168991B (no) Samlerblanding for skumflotasjon av metallholdige mineraler

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

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

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

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

17P Request for examination filed

Effective date: 19900109

17Q First examination report despatched

Effective date: 19901129

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19930310

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 19930310

Ref country code: FR

Effective date: 19930310

Ref country code: DE

Effective date: 19930310

Ref country code: BE

Effective date: 19930310

REF Corresponds to:

Ref document number: 3587166

Country of ref document: DE

Date of ref document: 19930415

EN Fr: translation not filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19930913

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19930930

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19930913

EAL Se: european patent in force in sweden

Ref document number: 85306521.7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19970602

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980914

EUG Se: european patent has lapsed

Ref document number: 85306521.7