US3313412A - Recovery of molybdenite from copper sulfide concentrates by froth flotation - Google Patents
Recovery of molybdenite from copper sulfide concentrates by froth flotation Download PDFInfo
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- US3313412A US3313412A US387813A US38781364A US3313412A US 3313412 A US3313412 A US 3313412A US 387813 A US387813 A US 387813A US 38781364 A US38781364 A US 38781364A US 3313412 A US3313412 A US 3313412A
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- Prior art keywords
- molybdenite
- flotation
- copper sulfide
- copper
- concentrate
- Prior art date
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- 229910052961 molybdenite Inorganic materials 0.000 title claims description 29
- 239000012141 concentrate Substances 0.000 title claims description 26
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims description 24
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims description 11
- 238000011084 recovery Methods 0.000 title claims description 10
- 238000009291 froth flotation Methods 0.000 title description 5
- 238000000034 method Methods 0.000 claims description 24
- 238000005188 flotation Methods 0.000 claims description 21
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 18
- 230000000881 depressing effect Effects 0.000 claims description 3
- 230000000994 depressogenic effect Effects 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 17
- 239000010949 copper Substances 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 239000003350 kerosene Substances 0.000 description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 229910001779 copper mineral Inorganic materials 0.000 description 4
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical class [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- 239000002516 radical scavenger Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NAVJNPDLSKEXSP-UHFFFAOYSA-N Fe(CN)2 Chemical class N#C[Fe]C#N NAVJNPDLSKEXSP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052569 sulfide mineral Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical class [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940103272 aluminum potassium sulfate Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052948 bornite Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052947 chalcocite Inorganic materials 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052955 covellite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- PANJMBIFGCKWBY-UHFFFAOYSA-N iron tricyanide Chemical compound N#C[Fe](C#N)C#N PANJMBIFGCKWBY-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- NKCCODPFBDGPRJ-UHFFFAOYSA-N nitridocarbon(1+) Chemical compound N#[C+] NKCCODPFBDGPRJ-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- GJPYYNMJTJNYTO-UHFFFAOYSA-J sodium aluminium sulfate Chemical compound [Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJPYYNMJTJNYTO-UHFFFAOYSA-J 0.000 description 1
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 description 1
- 239000000264 sodium ferrocyanide Substances 0.000 description 1
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/002—Inorganic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/006—Hydrocarbons
-
- 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
- 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
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/06—Depressants
Definitions
- This invention relates to recovery of molybdenite from molybdenite-bearing copper sulfide ores or concentrates.
- U.S. Patent No. 1,649,685 discloses the use of alkaline cyanides or carbonates with aluminum sulfate to separate zinc and iron sulfides.
- US. Patent No. 2,205,194 discloses the combination of an aluminum salt and a sulfite to form sulfur dioxide which depresses zinc sulfide.
- US. Patent No. 2,620,068 discloses a combination of cyanide radical, ammonia in the form of a free base and a metal from the group of magnesium, zinc or aluminum for depressing copper minerals.
- the general method employed in the invention is a conventional froth flotation procedure in which the ore is first ground to fine particle size, water is then added to the pulp as required and the pulp is passed to a flotation cell where air is introduced for flotation. Reagents are added to the pulp at the grinding stage, the preflotation conditioning stage, or the flotation stage as required.
- the starting material may be a concentrate from a previous flotation of copper sulfide ore.
- the process is ordinarily carried out at room temperature and pressure using any 3,3 lBJilZ Patented Apr. ll, 1967 kind of water available, although distilled or otherwise treated water may be beneficial in some cases.
- the raw material employed is a copper sulfide-molybdenite ore or concentrate, the exact composition of which will vary according to the deposit from which the ore is obtained and the nature of the beneficiation to which the ore may have been subjected.
- Copper sulfide-molybdenite concentrates used as starting materials in the process of the invention, are usually thickened to about 40 percent solids before conditionirn with reagents and subsequent flotation. Such concentrates will typically contain 25 to 30 percent copper and 0.6 to 0.9 percent M05 These percentages will, of course, vary with the type of ore and the flotation process employed in concentrating the copper sulfidemolybdenite minerals.
- the raw material is conditioned with aluminum salt for a period of about 1 minute to about 15 minutes at a pulp density of about 25 percent to about 40 percent solids.
- the aluminum salt may be added as solid or in solution.
- Pulp density of the mixture in the subsequent rougher flotation is usually about 15 percent to about 30 percent solids, with about 25 percent solids usually being optimum.
- aluminum salts examples include aluminum sulfate, aluminum potassium sulfate, aluminum sodium sulfate, aluminum chloride, and aluminum nitrate. Amounts of the aluminum salt will usually vary from about 1 pound per ton of ore or concentrate to about 30 pounds per ton of ore or concentrate. These variables, as well as those discussed in the preceding paragraph m-ay all vary considerably depending on the type and amount of ore or concentrate, particularly aluminum salt employed, nature of collector, if any, etc.
- Addition of the aluminum salt will usually lower the pH, sometimes as low as about 4.0 to 4.5; however, the value of pH is not critical in the process of the invention. This lack of cn'ticality is, in fact, one of the ad vantages of the invention.
- Kerosine in an amount of from about 0.1 pound to about 4.0 pounds per ton of feed has been found to be particularly effective as a collector; however, other collectors such as fuel oil, motor oil, mineral oil, and similar petroleum products, as well as orthodichlorobenzeue, nitrobenzene, and similar benzene products, may also be used.
- Compounds such as pine oil, nitrobenzene, methyl isobutyl carbinol, isopropyl alcohol, n-octyl alcohol, n-decyl alcohol, and other multicarbon alcohols and their derivatives may also improve efiiciency of the process with some ores when used as frothers or froth modifiers.
- the process of the invention may, in some instances, be further improved by the use of an alkali iron cyanide such as sodium ferrocyanide to depress copper sulfides in the final cleaning steps while employing the aluminum salts of the invention in the roughing and early cleaning steps according to the process of the instant invention.
- an alkali iron cyanide such as sodium ferrocyanide
- This obviates the need for using large quanities of expensive reagents, such as alkali iron cyanides, since the amount of copper sulfide left in the pulp in the final cleaning steps is relatively small compared to that in the original bulk concentrate.
- Use of cyanides and alkali iron cyanides in flotation recovery of molybdenite is disclosed in US. Patent No. 2,664,199.
- Example 1 About a 70-liter sample of bulk copper sulfidemolybdenite concentrate thickened to about 40 percent solids was obtained from a large soiled copper concentrator located in the vicinity of Arlington, Arizona. The sample contained 0.64 percent M and 29.83 percent Cu. The copper minerals were predominantly chalcopyrite with minor amounts of chalcocite, covellite, bornite, and metallic copper. The bulk sample was split into smaller portions containing about 540 grams. Tests were then made using no reagents, aluminum salts, and sulfuric acid. The sample of pulp was conditioned with reagents in a 600-gram laboratory float cell for a period of 5 minutes 'followed by a 12-minute flotation period to insure that most of the molbdenite floated.
- AMSOO A 5.0 0. 83 31. 60 94. 7 79. 8 t1. 6 20. 0 1. 98 32. 55 91. 4 32. 7 3. 6 5. O 0.97 31. 28 94. 9 73. 1 6. 7 20. 0 2. 30 33. 65 92. 9 32. 1 5. 2 5.0 2.05 32.84 85.9 30. 6 3. 9 20. 0 2. 57 33. 04 91. 6 27. 9 3. 6 5. 0 0. 97 31. 90 89. 7 64. 7 6. 2 20. 0 2. 37 31. 44 41. 5 12. 0 3. 8 l5. 0 1. 38 31.03 94. 9 41. 8 4. 8 10.0 0.83 30.98 95. 5 58. 3 3. 8 0. 69 30. 86 97. 0 77. 6 7. 4 0.64 29. 83 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
- Example 2 Although it may be possible to eflect a good separation of molybdenite and copper sulfides by the use of aluminum salts alone, testing has revealed that better results are obtained when a molybdenite collector such as kerosine also is used. A sample similar to the one previously described was obtained and split in appropriately sized portions. The tests were made in the same type of cell and in approximately the same manner as the prior tests except a 1-minute conditioning period was used after the addition of the reagents. The first five tests of Table 2 summarize the results obtained in this series when using kerosine in addition to an aluminum salt. Good concentration of molybdenite at even higher recoveries often were obtained as illustrated in the last two tests of Table 2.
- Reagent amounts were, in pounds per ton, 16.0 Al (SO to the conditioner, 2.6 kerosine to the conditioner, and 0.83 Al (SO to all four cleaners.
- a small amount of froth modifier, n-decyl alcohol was used to help control the froth.
- the middlings were circulated countercurrent to the cleaner froths and finally, together with the scavenger froth, back to the conditioner. The results of this test are summarized in Table 4.
- a froth flotation process for the recovery of moly-bdenite from a molybdenite-copper sulfide concentrate wherein said concentrate is present in a flotation cell as an aqueous pulp, the improvement consisting of depressing the copper sulfide by adding to said aqueous pulp a depressant consisting solely of an aluminum salt and then froth floating the molybdenite.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
United States Patent 3,313,412 RECOVERY OF MOLYBDENI'I'E FROM C0?- PER SULFIDE CONCENTRATES BY FROTH FLOTATIGN Philip A. Bloom and Stuart J. Hussey, Tucson, Ariz., as-
signors to the United States of America as represented by the Secretary of the Interior No Drawing. Filed Aug. 5, 1964, Ser. No. 387,813 6 Claims. (Cl. 209167) The invention herein described and claimed may be manufactured and used 'by or for the Government of the United States of America for governmental purposes without the payment of royalties thereon or therefor.
This invention relates to recovery of molybdenite from molybdenite-bearing copper sulfide ores or concentrates.
Large porphyry copper sulfide deposits containing very small amounts of molybdenite have recently become a significant source of molybdenite. Reagents used for flotation of copper minerals from these deposits also float the molybdenite in a bulk copper sulfide-molybdenite concentrate containing from 0.2 to 1.2 percent M08 To mills producing about 300 tons of copper concentrates a day this MoS represents an important source of added revenue. 1
Similar flotation characteristics of copper sulfides and molybdenite minerals and the small particle size of the copper sulfide concentrate make it difficult to separate the molybdenite and copper sulfide minerals by froth flotation. At the present time, the more popular ways used to separate these minerals are to depress the copper by drying or steaming the bulk concentrate, or using strong oxidizing agents that presumably attack the copper flotation reagents or the copper minerals, or both. These methods, however, have the disadvantage of being expensive or corrosive to equipment and in some cases in volve the use of toxic gases with an ever present hazard to employees.
It is accordingly an object of the present invention to provide a simple and eflicient method for recovery of molybdenite from molybdenite-copper sulfide ores or concentrates without excessive corrosion of equipment or hazard to employees.
It has now been found that these objectives may be accomplished by means of a flotation process in which aluminum salts are used for depression of copper sulfides without inhibiting the flotation of molybdenite.
Aluminum salts have previously been used in flotation processes; however, none of the prior art processes are analogous to applicants process and do not provide the advantages of applicants process. U.S. Patent No. 1,649,685 discloses the use of alkaline cyanides or carbonates with aluminum sulfate to separate zinc and iron sulfides. US. Patent No. 2,205,194 discloses the combination of an aluminum salt and a sulfite to form sulfur dioxide which depresses zinc sulfide. US. Patent No. 2,620,068 discloses a combination of cyanide radical, ammonia in the form of a free base and a metal from the group of magnesium, zinc or aluminum for depressing copper minerals.
The general method employed in the invention is a conventional froth flotation procedure in which the ore is first ground to fine particle size, water is then added to the pulp as required and the pulp is passed to a flotation cell where air is introduced for flotation. Reagents are added to the pulp at the grinding stage, the preflotation conditioning stage, or the flotation stage as required. In the process of the invention, the starting material may be a concentrate from a previous flotation of copper sulfide ore. The process is ordinarily carried out at room temperature and pressure using any 3,3 lBJilZ Patented Apr. ll, 1967 kind of water available, although distilled or otherwise treated water may be beneficial in some cases. The raw material employed is a copper sulfide-molybdenite ore or concentrate, the exact composition of which will vary according to the deposit from which the ore is obtained and the nature of the beneficiation to which the ore may have been subjected. Copper sulfide-molybdenite concentrates, used as starting materials in the process of the invention, are usually thickened to about 40 percent solids before conditionirn with reagents and subsequent flotation. Such concentrates will typically contain 25 to 30 percent copper and 0.6 to 0.9 percent M05 These percentages will, of course, vary with the type of ore and the flotation process employed in concentrating the copper sulfidemolybdenite minerals.
The raw material is conditioned with aluminum salt for a period of about 1 minute to about 15 minutes at a pulp density of about 25 percent to about 40 percent solids. The aluminum salt may be added as solid or in solution. Pulp density of the mixture in the subsequent rougher flotation is usually about 15 percent to about 30 percent solids, with about 25 percent solids usually being optimum.
Examples of aluminum salts that may be used are aluminum sulfate, aluminum potassium sulfate, aluminum sodium sulfate, aluminum chloride, and aluminum nitrate. Amounts of the aluminum salt will usually vary from about 1 pound per ton of ore or concentrate to about 30 pounds per ton of ore or concentrate. These variables, as well as those discussed in the preceding paragraph m-ay all vary considerably depending on the type and amount of ore or concentrate, particularly aluminum salt employed, nature of collector, if any, etc.
Addition of the aluminum salt will usually lower the pH, sometimes as low as about 4.0 to 4.5; however, the value of pH is not critical in the process of the invention. This lack of cn'ticality is, in fact, one of the ad vantages of the invention.
Although a collector is not essential in the process of the invention, separation may be enhanced by the use of a collector in conjunction with the aluminum salt. Kerosine, in an amount of from about 0.1 pound to about 4.0 pounds per ton of feed has been found to be particularly effective as a collector; however, other collectors such as fuel oil, motor oil, mineral oil, and similar petroleum products, as well as orthodichlorobenzeue, nitrobenzene, and similar benzene products, may also be used. Compounds such as pine oil, nitrobenzene, methyl isobutyl carbinol, isopropyl alcohol, n-octyl alcohol, n-decyl alcohol, and other multicarbon alcohols and their derivatives may also improve efiiciency of the process with some ores when used as frothers or froth modifiers.
It has also been found that the process of the invention may, in some instances, be further improved by the use of an alkali iron cyanide such as sodium ferrocyanide to depress copper sulfides in the final cleaning steps while employing the aluminum salts of the invention in the roughing and early cleaning steps according to the process of the instant invention. This obviates the need for using large quanities of expensive reagents, such as alkali iron cyanides, since the amount of copper sulfide left in the pulp in the final cleaning steps is relatively small compared to that in the original bulk concentrate. Use of cyanides and alkali iron cyanides in flotation recovery of molybdenite is disclosed in US. Patent No. 2,664,199.
The invention will be more specifically illustrated by the following examples.
Example 1 About a 70-liter sample of bulk copper sulfidemolybdenite concentrate thickened to about 40 percent solids was obtained from a large southwestern copper concentrator located in the vicinity of Tucson, Arizona. The sample contained 0.64 percent M and 29.83 percent Cu. The copper minerals were predominantly chalcopyrite with minor amounts of chalcocite, covellite, bornite, and metallic copper. The bulk sample was split into smaller portions containing about 540 grams. Tests were then made using no reagents, aluminum salts, and sulfuric acid. The sample of pulp was conditioned with reagents in a 600-gram laboratory float cell for a period of 5 minutes 'followed by a 12-minute flotation period to insure that most of the molbdenite floated. In the case where no reagents were added, there was no conditioning period prior to the molybdenite flotation. The residual reagents left in the bulk copper concentrate were relied on to promote the molybdenite to flotation. Table 1 gives a comparison of the results obtained using the conditions described above.
conditioner. Reagent consumption was about pounds of Al (SO and 2 pounds of kerosine per ton of feed. The results obtained are summarized in Table 3.
1 Contents are expressed as ounces per ton instead of percent.
FLOTATION OF MOS:
Concentrate ConsumppH of Reagent tion, lbs. rougher per ton Analysis, Pet. Recovery, Pct. float M08; Cu MOS; Cu
AMSOO: A 5.0 0. 83 31. 60 94. 7 79. 8 t1. 6 20. 0 1. 98 32. 55 91. 4 32. 7 3. 6 5. O 0.97 31. 28 94. 9 73. 1 6. 7 20. 0 2. 30 33. 65 92. 9 32. 1 5. 2 5.0 2.05 32.84 85.9 30. 6 3. 9 20. 0 2. 57 33. 04 91. 6 27. 9 3. 6 5. 0 0. 97 31. 90 89. 7 64. 7 6. 2 20. 0 2. 37 31. 44 41. 5 12. 0 3. 8 l5. 0 1. 38 31.03 94. 9 41. 8 4. 8 10.0 0.83 30.98 95. 5 58. 3 3. 8 0. 69 30. 86 97. 0 77. 6 7. 4 0.64 29. 83 100.0 100.0
Example 2 Example 4 Although it may be possible to eflect a good separation of molybdenite and copper sulfides by the use of aluminum salts alone, testing has revealed that better results are obtained when a molybdenite collector such as kerosine also is used. A sample similar to the one previously described was obtained and split in appropriately sized portions. The tests were made in the same type of cell and in approximately the same manner as the prior tests except a 1-minute conditioning period was used after the addition of the reagents. The first five tests of Table 2 summarize the results obtained in this series when using kerosine in addition to an aluminum salt. Good concentration of molybdenite at even higher recoveries often were obtained as illustrated in the last two tests of Table 2.
TABLE 2.-EFFECT OF KEROSINE AND ALUMINUM SULFATE ON THE COPPER SULFIDE-MOLYBDENITE About 100 gallons of a bulk copper sulfide-molybdenite concentrate similar to that used in the two prior examples was obtained for use in a small scale continuous operation. The fiowsheet was restricted to a conditioner, a rougher cell, a cleaner cell, and two scavenger cells. The middlings and scavenger froth were returned to the Using a sample similar to the one cited in Example 3 another continuous test was made differing from the previous one in that four cleaning steps were used. Reagent amounts were, in pounds per ton, 16.0 Al (SO to the conditioner, 2.6 kerosine to the conditioner, and 0.83 Al (SO to all four cleaners. In addition to these reagents a small amount of froth modifier, n-decyl alcohol, was used to help control the froth. The middlings were circulated countercurrent to the cleaner froths and finally, together with the scavenger froth, back to the conditioner. The results of this test are summarized in Table 4.
TABLE 4.RESULTS OF PILOT PLANT TEST USING FOUR CLEANING STEPS Analysis, Recovery, pct. MOS; pct. IVIOS] Example 5 to the cleaner froth and then together with the scavenger froth to the conditioner. Table 5 lists the reagent requirements and addition points. The results obtained are summarized in Table 6.
TABLE 5.REAGENT DATA Reagent, pounds per ton of feed Addition point Alg(SO4)a Kerosine K4Fe(CN) Conditioner 18. 6 2. 9 Cleaner No. 1 0.9 Cleaner No. 2 9 Cleaner No. 3 9 .2 CleanerNoul .9 .2 Cleaner No. 5 .9 2 Cleaner No. 6 .9 2
1 Small amount of n-deeyl alcohol was added to the first cleaner to reduce the volume of the froth.
2 Small amount of nitrobenzene was added to increase the froth and flotation of the molybdenite.
TABLE 6.RESULTS OF PILOT PLANT TESTING USING ALUMINUM SULFATE AND POTASSIUM FERROCYANIDE TO DEPRESS COPPER SULFIDE MINERALS Analysis Distribution Product M052 Cu M082 Cu Cleaner eoncentrate 76. 34 3. 59 81.9 10. 3 0. 15 29. 62 18. 1 89. 7
What is claimed is:
1. In a froth flotation process for the recovery of moly-bdenite from a molybdenite-copper sulfide concentrate wherein said concentrate is present in a flotation cell as an aqueous pulp, the improvement consisting of depressing the copper sulfide by adding to said aqueous pulp a depressant consisting solely of an aluminum salt and then froth floating the molybdenite.
2. The process of claim 1 in which the aluminum salt is aluminum sulfate.
3. The process of claim 1 in which kerosine is also added to the pulp as a collector for the molybdenite.
4. The process of claim 1 in which the floated molybdenite is subject to further froth flotation to obtain a cleaner concentrate.
5. The process of claim 4 in which an alkali ferrocyanide is employed as depressant for copper sulfide in obtaining the cleaner concentrate.
6. The process of claim 1 in which the amount of aluminum salt is from about 1 to about 30 pounds per ton of molybdenite containing material.
References Cited by the Examiner UNITED STATES PATENTS 1,203,372 10/1916 Lyster 209167 1,569,266 9/1924 Spearman 209167 X 2,492,936 12/1949 Nokes 209-467 2,620,068 12/ 1952 Allen 209167 2,664,199 12/1953 Barker 209167 FOREIGN PATENTS 77,571 3/1947 Russia.
HARRY B. THORNTON, Primary Examiner.
R. HALPER, Assistant Examiner.
Claims (1)
1. IN A FROTH PROCESS FOR THE RECOVERY OF MOLYBDENITE FROM A MOLYBDENITY-COPPER SULFIDE CONCENTRATE WHEREIN SAID CONCENTRATE IS PRESENT IN A FLOTATION CELL AS AN AQUEOUS PULP, THE IMPROVEMENT CONSISTNG OF DEPRESSING THE COPPER SULFIDE BY ADDING TO SAID AQUEOUS PULP A DEPRESSANT CONSISTING SOLELY OF AN ALUMINUM SALT AND THEN FROTH FLOATING THE MOLYBDENITE.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US387813A US3313412A (en) | 1964-08-05 | 1964-08-05 | Recovery of molybdenite from copper sulfide concentrates by froth flotation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US387813A US3313412A (en) | 1964-08-05 | 1964-08-05 | Recovery of molybdenite from copper sulfide concentrates by froth flotation |
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US3313412A true US3313412A (en) | 1967-04-11 |
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Application Number | Title | Priority Date | Filing Date |
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US387813A Expired - Lifetime US3313412A (en) | 1964-08-05 | 1964-08-05 | Recovery of molybdenite from copper sulfide concentrates by froth flotation |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3811569A (en) * | 1971-06-07 | 1974-05-21 | Fmc Corp | Flotation recovery of molybdenite |
US3837489A (en) * | 1972-11-24 | 1974-09-24 | Nalco Chemical Co | Molybdenum disulfide flotation antifoam |
US3921810A (en) * | 1972-01-10 | 1975-11-25 | Pima Mining Co | Talc-molybdenite separation |
US4317543A (en) * | 1979-11-29 | 1982-03-02 | Olivares Juan P | Process for separating copper and iron minerals from molybdenite |
US4606817A (en) * | 1985-01-31 | 1986-08-19 | Amax Inc. | Recovery of molybdenite |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1203372A (en) * | 1913-05-08 | 1916-10-31 | Minerals Separation American Syndicate 1913 Ltd | Separation of metallic sulfid ores. |
US1509266A (en) * | 1919-08-16 | 1924-09-23 | Spearman Charles | Process of ore separation |
US2492936A (en) * | 1948-10-16 | 1949-12-27 | Charles M Nokes | Differential froth flotation of sulfide ores |
US2620068A (en) * | 1951-08-16 | 1952-12-02 | American Cyanamid Co | Depression of copper minerals from ores and concentrates |
US2664199A (en) * | 1952-08-27 | 1953-12-29 | Phelps Dodge Corp | Flotation recovery of molybdenite |
-
1964
- 1964-08-05 US US387813A patent/US3313412A/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1203372A (en) * | 1913-05-08 | 1916-10-31 | Minerals Separation American Syndicate 1913 Ltd | Separation of metallic sulfid ores. |
US1509266A (en) * | 1919-08-16 | 1924-09-23 | Spearman Charles | Process of ore separation |
US2492936A (en) * | 1948-10-16 | 1949-12-27 | Charles M Nokes | Differential froth flotation of sulfide ores |
US2620068A (en) * | 1951-08-16 | 1952-12-02 | American Cyanamid Co | Depression of copper minerals from ores and concentrates |
US2664199A (en) * | 1952-08-27 | 1953-12-29 | Phelps Dodge Corp | Flotation recovery of molybdenite |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3811569A (en) * | 1971-06-07 | 1974-05-21 | Fmc Corp | Flotation recovery of molybdenite |
US3921810A (en) * | 1972-01-10 | 1975-11-25 | Pima Mining Co | Talc-molybdenite separation |
US3837489A (en) * | 1972-11-24 | 1974-09-24 | Nalco Chemical Co | Molybdenum disulfide flotation antifoam |
US4317543A (en) * | 1979-11-29 | 1982-03-02 | Olivares Juan P | Process for separating copper and iron minerals from molybdenite |
US4606817A (en) * | 1985-01-31 | 1986-08-19 | Amax Inc. | Recovery of molybdenite |
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