US3837489A - Molybdenum disulfide flotation antifoam - Google Patents
Molybdenum disulfide flotation antifoam Download PDFInfo
- Publication number
- US3837489A US3837489A US00309013A US30901372A US3837489A US 3837489 A US3837489 A US 3837489A US 00309013 A US00309013 A US 00309013A US 30901372 A US30901372 A US 30901372A US 3837489 A US3837489 A US 3837489A
- Authority
- US
- United States
- Prior art keywords
- antifoam
- dioleate
- copper
- flotation
- ppm
- 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
Links
- 239000002518 antifoaming agent Substances 0.000 title claims abstract description 27
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title description 17
- 238000005188 flotation Methods 0.000 title description 7
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title description 4
- -1 polyoxyethylene Polymers 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 18
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003350 kerosene Substances 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 229940049964 oleate Drugs 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 26
- 229910052802 copper Inorganic materials 0.000 abstract description 26
- 239000010949 copper Substances 0.000 abstract description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 10
- 239000011733 molybdenum Substances 0.000 abstract description 10
- 241001279686 Allium moly Species 0.000 abstract description 7
- 238000004140 cleaning Methods 0.000 abstract description 7
- 125000006353 oxyethylene group Chemical group 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 4
- 229930195729 fatty acid Natural products 0.000 abstract description 4
- 239000000194 fatty acid Substances 0.000 abstract description 4
- 150000004665 fatty acids Chemical class 0.000 abstract description 4
- 238000004900 laundering Methods 0.000 abstract description 4
- 229940068918 polyethylene glycol 400 Drugs 0.000 abstract description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052961 molybdenite Inorganic materials 0.000 description 11
- 238000011084 recovery Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 239000000061 acid fraction Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 230000000881 depressing effect Effects 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000012991 xanthate Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241001137901 Centropomus undecimalis Species 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 241000512668 Eunectes Species 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000007630 basic procedure Methods 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910001779 copper mineral Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009291 froth flotation Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052569 sulfide mineral Inorganic materials 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- B03D1/02—Froth-flotation processes
- B03D1/06—Froth-flotation processes differential
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
-
- 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
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
Definitions
- ABSTRACT An antifoam and process for the separation of molybdenum values associated with predominantly copper ores of the sulfide type.
- the antifoam which is primarily directed to laundering or cleaning stages in the moly cycle, consists of a utilization of 1-60 ppm of a polyoxyethylene glycol ester in a hydrocarbon diluent per ton of ore.
- the oxyethylene fraction has a value of about 1002,000 and an optimum value of 400, and the fatty acid fraction is selected from C, C, acids.
- a preferred antifoam is polyethylene glycol 400 dioleate (P.E.G. 400 dioleate) in kerosene or isoparaffin oil as the diluent.
- HLB values for the PEG. antifoam range from 5-12 with a preferred value of 5-10 for the dioleate.
- the present invention relates to an antifoam and process specifically utilized in the separation of molybdenite or molybdenum disulfide from predominantly copper ores of the sulfide type.
- the separation of molybdenum quantities from copper in mixtures offers commercial advantages where originally the production was directed to the recovery only of copper values.
- this process in the molybdenite cycle there occurs one or more cleaner or launderer steps which are set out by example graphically in the figures of U.S. Pat. No. 2,664,199 Barker et al.
- the recovery of the molybdenite involves the depression of copper which is usually achieved by the use of a ferricyanide reagent or utilization of the inorganics exemplified by the Nokes reagent of P, As, or Sb, divalent S and an inorganic cation and commonly using P S NaOI-l; see'U.S. Pat. No. 2,492,936 Nokes et al.
- Modified Nokes reagents have been utilized as for example U.S. Pat. No. 2,957,576 Henderson (Anaconda); U.S. Pat. No. 3,375,924 Corbett et al. (Miami Copper), the latter raises the pH of the usual Nokes to at least 11.4; and U.S. Pat. No.
- this invention adds 1-60 ppm per ton of ore or a preferred amount of 40-50 ppm of a polyethylene glycol monoor di-ester wherein the oxyethylene or ethoxy repeating unit has a value of from about 100 to 2,000.
- the acid fraction may be selected from fatty acids containing 14-22 carbon atoms, such as oleic acid, stearic acid, palmitic acid, ricinoleic acid, lauric acid, myristic acid, cerotic acid, and linoleic acid.
- a most preferred ester is the dioleate of polyethylene glycol having a molecular weight of about 400 (RFC. 400).
- Operable P.E.G. esters have been found to have an HLB value (Hydrophilel- Lypophile Balance) of 5-12. From a consideration of the fact that the l-ILB scale is from 1-20 with the values over indicating greater hydrophilic attraction, the specificity of the invention is noted.
- HLB value Hydrophilic Balance
- the P.E.G. ester when used in this specification and claims is defined as a 'monoor di-ester containing C -C and may be a blend of esters wherein such blend has a composite HLB value within the limits stated as, for example, a 50/50 blend of polyethylene glycol 400 dioleate and polyethylene glycol 400 dilaurate.
- P.E.G. esters containing defoamers for other purposes are known; for example, U.S. Pat. No. 2,715,614 Snook (Nopco) utilizes such esters generally but disclosed for papermaking.
- Jursich (Nalco) utilizes P. E.G. 400 dilaurate as an emulsifying agent in sugar recovery.
- the P.E.G. 400 dioleate is used as an emulsifier for an antifoam composition in the paper industry.
- a most preferred reagent is the polyoxyethylene glycol 400 dioleate and the oxyethylene portion may vary from about l00-2,000.
- This compound and others noted previously when utilized in the process in a laundering step, serve as a spreading agent and form a thin layer on the water which then is dissipated throughout the body of the pulp, modifying the bubbles in the interface.
- the action of the antifoam has a relatively short life so that the moly collector following the launderer is not disturbed.
- the operation of the present preferred antifoams endows to the circuit in the launderer or launderers the capacity to reduce the froth level but also has a short duration of only about 2 seconds. Additionally, the antifoam serves to minimize any reduced oil buildup so as to prevent the copper particles from becoming oil smeared and thus renders the copper particles hydrophobic as well as stabilizing the froth. Finally, the present antifoams display the quality of decreasing froth stability slightly or making the froth slightly unstable so that the trapped copper particles within the froth drop out back into the slurry and thus from bank to bank or stage to stage minimize the copper carryover to the next flotation step.
- an oil carrier such as an isoparaffin, kerosene, mineral seal oil, deoderized kerosene, and paraffin oil may be utilized.
- a typical operational molybdenum circuit or cycle consists of one rougher bank, two scavenger banks, and six cleaner banks or stages, and molybdenum is recovered from the last or No. 6 cleaner bank.
- Typical reagents utilized in the moly circuit are:
- the tailings from each step are recirculated upstream in the previous step of the circuit for maximum moly recovery except in the case of the rougher and second scavenger tailings which go to a final copper concentrate thickener.
- the feed entering the moly circuit is approximately percent solids.
- EXAMPLE I In a molybdenum flotation process utilizing in the molybdenum cycle two stages of launderer, an antifoam composition consisting of 20 parts by weight P.E.G. 400 dioleate and 80 parts by weight of deoderized kerosene in a concentration of 250 ppm was introduced into each launderer stage. Visual inspection at EXAMPLE II In a moly sulfide cycle or circuit following the flotation of the copper values, a circuit was utilized consisting of one rougher bank, two scavenger banks, and six cleaner banks. The final product molybdenum is the froth from No. 6 cleaner.
- step of adding an antifoam consisting of about 40-50 ppm of polyoxyethylene glycol 400 dioleate and isoparaffin oil as a hydrocarbon diluent.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Detergent Compositions (AREA)
Abstract
An antifoam and process for the separation of molybdenum values associated with predominantly copper ores of the sulfide type. The antifoam, which is primarily directed to laundering or cleaning stages in the moly cycle, consists of a utilization of 1-60 ppm of a polyoxyethylene glycol ester in a hydrocarbon diluent per ton of ore. The oxyethylene fraction has a value of about 100-2,000 and an optimum value of 400, and the fatty acid fraction is selected from C14 - C22 acids. A preferred antifoam is polyethylene glycol 400 dioleate (P.E.G. 400 dioleate) in kerosene or isoparaffin oil as the diluent. HLB values for the P.E.G. antifoam range from 5-12 with a preferred value of 5-10 for the dioleate.
Description
United States Patent 1 1 Michalski et al.
[451 Sept. 24, 1974 MOLYBDENUM DISULFIDE FLOTATION ANTIFOAM [75] Inventors: Raymond J. Michalski, Riverdale;
John T. Cantwell, Oak Lawn, both of I11.
[73] Assignee: Nalco Chemical Company, Chicago,
Ill.
22 Filed: Nov. 24, '1972 [21] Appl. N0.: 309,013
[52] US. Cl. 209/167, 209/3 [51] Int. Cl B03d 1/06 [58] Field of Search 209/166, 167; 252/61, 321, 252/319 [56] References Cited UNITED STATES PATENTS 2,259,420 10/1941 Mills 209/166 2,302,338 11/1942 Moeller 2,312,466 3/1943 Erickson 2,362,432 11/1944 Cuhn 2,664,199 12/1953 Barker 2,668,150 2/1954 Luvisi 3,313,412 4/1967 Bloom 3,539,002 11/1970 Last 209/167 X Primary Examiner-Robert Halper Attorney, Agent, or Firm-John G. Premo; John S. Roberts, Jr.; James F. Lambe [5 7] ABSTRACT An antifoam and process for the separation of molybdenum values associated with predominantly copper ores of the sulfide type. The antifoam, which is primarily directed to laundering or cleaning stages in the moly cycle, consists of a utilization of 1-60 ppm of a polyoxyethylene glycol ester in a hydrocarbon diluent per ton of ore. The oxyethylene fraction has a value of about 1002,000 and an optimum value of 400, and the fatty acid fraction is selected from C, C, acids. A preferred antifoam is polyethylene glycol 400 dioleate (P.E.G. 400 dioleate) in kerosene or isoparaffin oil as the diluent. HLB values for the PEG. antifoam range from 5-12 with a preferred value of 5-10 for the dioleate.
5 Claims, N0 Drawings MOLYBDENUM DISULFIDE FLOTAT'ION ANTIFOAM The present invention relates to an antifoam and process specifically utilized in the separation of molybdenite or molybdenum disulfide from predominantly copper ores of the sulfide type. The separation of molybdenum quantities from copper in mixtures offers commercial advantages where originally the production was directed to the recovery only of copper values. In this process in the molybdenite cycle, there occurs one or more cleaner or launderer steps which are set out by example graphically in the figures of U.S. Pat. No. 2,664,199 Barker et al.
The recovery of the molybdenite involves the depression of copper which is usually achieved by the use of a ferricyanide reagent or utilization of the inorganics exemplified by the Nokes reagent of P, As, or Sb, divalent S and an inorganic cation and commonly using P S NaOI-l; see'U.S. Pat. No. 2,492,936 Nokes et al. Modified Nokes reagents have been utilized as for example U.S. Pat. No. 2,957,576 Henderson (Anaconda); U.S. Pat. No. 3,375,924 Corbett et al. (Miami Copper), the latter raises the pH of the usual Nokes to at least 11.4; and U.S. Pat. No. 3,435,952 Corbett (Miami Copper). Examples of additional methods of floating the molybdenite by depressing the copper are set out in U.S. Pat. No. 3,351,193 Martinez (American Cyanamid) and other copper depressants are described post.
In the so-called cleaning or launderer steps of the process for recovering molybdenite, it has been found that an abnormal or unusual amount of foam occurs which vitiates some of the commercial advantages of the process and to obviate this foam this invention adds 1-60 ppm per ton of ore or a preferred amount of 40-50 ppm of a polyethylene glycol monoor di-ester wherein the oxyethylene or ethoxy repeating unit has a value of from about 100 to 2,000. The acid fraction may be selected from fatty acids containing 14-22 carbon atoms, such as oleic acid, stearic acid, palmitic acid, ricinoleic acid, lauric acid, myristic acid, cerotic acid, and linoleic acid. A most preferred ester is the dioleate of polyethylene glycol having a molecular weight of about 400 (RFC. 400). Operable P.E.G. esters have been found to have an HLB value (Hydrophilel- Lypophile Balance) of 5-12. From a consideration of the fact that the l-ILB scale is from 1-20 with the values over indicating greater hydrophilic attraction, the specificity of the invention is noted. A summary of values of surfactants as in emulsions is given in the Encyclopedia of Chemical Technology 11, Volume 8, pages 128-130. The following values are noted at page 129 of ECT and also from McCutcheons Detergents and Emulsifiers, 1972 Annual:
I-ILB 400 monooleate 400 monostearate 100 monoricinoleate 200 dilaurate 400 dioleate I00 monolaurate 1500 dioleate 600 dioleate The P.E.G. ester when used in this specification and claims is defined as a 'monoor di-ester containing C -C and may be a blend of esters wherein such blend has a composite HLB value within the limits stated as, for example, a 50/50 blend of polyethylene glycol 400 dioleate and polyethylene glycol 400 dilaurate.
P.E.G. esters containing defoamers for other purposes are known; for example, U.S. Pat. No. 2,715,614 Snook (Nopco) utilizes such esters generally but disclosed for papermaking. U.S. Pat. No. 2,727,009 Jursich (Nalco) utilizes P. E.G. 400 dilaurate as an emulsifying agent in sugar recovery. In U.S. Pat. No. 3,198,744 Lamont (Nalco), the P.E.G. 400 dioleate is used as an emulsifier for an antifoam composition in the paper industry.
The problems of the above prior art differ from separation of the molybdenite by depressing the associated copper sulfide values.
The general process is discussed in:
A.M. Gaudin, Flotation, 2d edition, McGraw-Hill,
1957, pages 449-457;
American Institute of Metallurgical Engineering, Froth Flotation, 50th Anniversary Volume, 1962, AIME, Chapter 16, pages 363-426.
As stated above, a most preferred reagent is the polyoxyethylene glycol 400 dioleate and the oxyethylene portion may vary from about l00-2,000. This compound and others noted previously, when utilized in the process in a laundering step, serve as a spreading agent and form a thin layer on the water which then is dissipated throughout the body of the pulp, modifying the bubbles in the interface. The action of the antifoam has a relatively short life so that the moly collector following the launderer is not disturbed.
The operation of the present preferred antifoams endows to the circuit in the launderer or launderers the capacity to reduce the froth level but also has a short duration of only about 2 seconds. Additionally, the antifoam serves to minimize any reduced oil buildup so as to prevent the copper particles from becoming oil smeared and thus renders the copper particles hydrophobic as well as stabilizing the froth. Finally, the present antifoams display the quality of decreasing froth stability slightly or making the froth slightly unstable so that the trapped copper particles within the froth drop out back into the slurry and thus from bank to bank or stage to stage minimize the copper carryover to the next flotation step.
The basic procedures which depress the copper sulfide minerals and float the molybdenite all include the use of a diluent liquid hydrocarbon which functions as a smearing collector for the molybdenite. In the present process an oil carrier such as an isoparaffin, kerosene, mineral seal oil, deoderized kerosene, and paraffin oil may be utilized. Of particular interest and effectiveness is the combination of RES. 400 dioleate diluted 20/80 with deoderized kerosene.
In the usual case of the predominantly copper mineral, the copper is floated first and subsequently the remaining pulp containing the copper collector is laundered or washed in one or more steps prior to the molybdenite flotation procedure. A typical operational molybdenum circuit or cycle consists of one rougher bank, two scavenger banks, and six cleaner banks or stages, and molybdenum is recovered from the last or No. 6 cleaner bank. Typical reagents utilized in the moly circuit are:
a. sodium hypochlorite to render the xanthate ion inactive b. sulfuric acid pH control 0. potassium ferricyanide to depress the copper d. antifoam In the utilization of this, the tailings from each step are recirculated upstream in the previous step of the circuit for maximum moly recovery except in the case of the rougher and second scavenger tailings which go to a final copper concentrate thickener. The feed entering the moly circuit is approximately percent solids.
It is in the laundering or cleaning banks where the present polyoxyethylene glycol esters are utilized to suppress foam. In the subsequent molybdenum flotation steps sufficient copper depressants may be utilized such as alkali sulfides, cyanides, cuprocyanides, ferrocyanides, or ferricyanides. It has been found that the utilization of the present antifoams in the cleaning stages assists in reducing the amount of copper passing through to the final recovery of molybdenum sulfide, and it is for this reason that multiple cleaning or launderer stages are utilized.
EXAMPLE I In a molybdenum flotation process utilizing in the molybdenum cycle two stages of launderer, an antifoam composition consisting of 20 parts by weight P.E.G. 400 dioleate and 80 parts by weight of deoderized kerosene in a concentration of 250 ppm was introduced into each launderer stage. Visual inspection at EXAMPLE II In a moly sulfide cycle or circuit following the flotation of the copper values, a circuit was utilized consisting of one rougher bank, two scavenger banks, and six cleaner banks. The final product molybdenum is the froth from No. 6 cleaner. In the process, sodium hypochlorite was utilized to render the xanthate ion inactive which had been previously utilized for copper recovery and potassium ferricyanide was utilized to depress the copper in this moly cycle. Additionally, sulfuric acid was utilized for pH control and 50 ppm of polyoxyethylene 400 dilaurate was added as an antifoam in the circuit. The result was a decrease in the amount of copper recovered in the latter stages evidenced by the visual appearance of a gray color substituted for a previous greenish color in the cleaning or launderer stage of a surfeit of foam.
The embodiments of this invention in which an exclusive property or privilege is claimed are defined as follows:
1. In the recovery process of molybdenite from associated copper values froth flotation where the copper values are depressed, the step of adding to the launderer stage of the molybdenum recovery cycle an antifoam consisting of about 1-60 ppm per ton of ore of a polyoxyethylene glycol ester wherein the oxyethylene repeating unit has a molecular weight of from about 2,000 and the acid fraction is selected from fatty acids containing 14-22 carbon atoms and a hydrocarbon diluent and subsequently floating off the molybdenite.
2. Inthe process according to claim 1, the step of adding an antifoam consisting of about 40-50 ppm of polyoxyethylene glycol 400 dioleate and kerosene as a hydrocarbon diluent.-
3. In the process according to claim 1, the step of adding an antifoam consisting of about 40-50 ppm of polyoxyethylene glycol 400 dioleate and isoparaffin oil as a hydrocarbon diluent.
4. In the process according to claim 1, the step of adding an antifoam consisting of a polyoxyethylene ester having an HLB range of from 5-12.
5. In the process according to claim 1, the step of adding an antifoam consisting of about 40-50 ppm of a polyoxyethylene oleate ester having an HLB value of from 5-10.
Claims (4)
- 2. In the process according to claim 1, the step of adding an antifoam consisting of about 40-50 Ppm of polyoxyethylene glycol 400 dioleate and kerosene as a hydrocarbon diluent.
- 3. In the process according to claim 1, the step of adding an antifoam consisting of about 40-50 ppm of polyoxyethylene glycol 400 dioleate and isoparaffin oil as a hydrocarbon diluent.
- 4. In the process according to claim 1, the step of adding an antifoam consisting of a polyoxyethylene ester having an HLB range of from 5-12.
- 5. In the process according to claim 1, the step of adding an antifoam consisting of about 40-50 ppm of a polyoxyethylene oleate ester having an HLB value of from 5-10.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00309013A US3837489A (en) | 1972-11-24 | 1972-11-24 | Molybdenum disulfide flotation antifoam |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00309013A US3837489A (en) | 1972-11-24 | 1972-11-24 | Molybdenum disulfide flotation antifoam |
Publications (1)
Publication Number | Publication Date |
---|---|
US3837489A true US3837489A (en) | 1974-09-24 |
Family
ID=23196290
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00309013A Expired - Lifetime US3837489A (en) | 1972-11-24 | 1972-11-24 | Molybdenum disulfide flotation antifoam |
Country Status (1)
Country | Link |
---|---|
US (1) | US3837489A (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1980000422A1 (en) * | 1978-08-15 | 1980-03-20 | Pennwalt Corp | Froth flotation process |
US4317543A (en) * | 1979-11-29 | 1982-03-02 | Olivares Juan P | Process for separating copper and iron minerals from molybdenite |
US5182039A (en) * | 1991-03-29 | 1993-01-26 | Exxon Chemical Patents, Inc. | Synergistic fluorinated ore flotation aids |
US5545351A (en) * | 1995-09-19 | 1996-08-13 | Baker Hughes Incorporated | Use of stearic acid esters of polypropylene glycol to control foam |
EP0779330A1 (en) * | 1995-12-15 | 1997-06-18 | Bridgestone Corporation | Sulfur curable mix compositions including silica and an antistatic agent, particularly for manufacturing tires; tire tread produced from such mixes; and tire comprising such a tread |
US6409799B1 (en) * | 1998-11-19 | 2002-06-25 | Betzdearborn Inc. & Corporacion Nacional Del Cobre De Chile | Copper leach process aids |
CN100348332C (en) * | 2005-11-28 | 2007-11-14 | 中国铝业股份有限公司 | Bauxite positive flotation headings three-phase foam removing method |
CN100551544C (en) * | 2007-02-13 | 2009-10-21 | 金堆城钼业股份有限公司 | The molybdenite foaming agent for ore dressing |
CN101264467B (en) * | 2007-03-13 | 2011-04-13 | 金堆城钼业股份有限公司 | Molybdenite flotation foaming agent |
US10344353B2 (en) * | 2015-04-08 | 2019-07-09 | Ecolab Usa Inc. | Leach aid for metal recovery |
CN112958285A (en) * | 2021-02-01 | 2021-06-15 | 核工业北京化工冶金研究院 | Compound auxiliary collecting agent for beta stone flotation and application thereof |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2259420A (en) * | 1939-02-01 | 1941-10-14 | Freeport Sulphur Co | Flotation process for oxidized manganese ore |
US2302338A (en) * | 1938-05-18 | 1942-11-17 | Moeller August | Froth flotation |
US2312466A (en) * | 1940-02-08 | 1943-03-02 | American Cyanamid Co | Oxygen-bearing ore flotation |
US2362432A (en) * | 1941-07-03 | 1944-11-07 | Emulsol Corp | Flotation of ores |
US2664199A (en) * | 1952-08-27 | 1953-12-29 | Phelps Dodge Corp | Flotation recovery of molybdenite |
US2668150A (en) * | 1951-03-26 | 1954-02-02 | Nat Aluminate Corp | Antifoam compositions and method of foam inhibition |
SU137072A1 (en) * | 1960-10-03 | 1960-11-30 | В.Р. Гантимуров | Method of flotation concentration of oxidized sulfide molybdenum ores |
US3313412A (en) * | 1964-08-05 | 1967-04-11 | Philip A Bloom | Recovery of molybdenite from copper sulfide concentrates by froth flotation |
FR1482821A (en) * | 1965-06-10 | 1967-06-02 | Ind Chimiques De Voreppe | Improved process for making pure grape seed almond oil |
US3539002A (en) * | 1967-12-11 | 1970-11-10 | Kennecott Copper Corp | Process for separating molybdenite from copper sulfide concentrates |
US3595390A (en) * | 1968-06-18 | 1971-07-27 | American Cyanamid Co | Ore flotation process with poly(ethylene-propylene)glycol frothers |
-
1972
- 1972-11-24 US US00309013A patent/US3837489A/en not_active Expired - Lifetime
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2302338A (en) * | 1938-05-18 | 1942-11-17 | Moeller August | Froth flotation |
US2259420A (en) * | 1939-02-01 | 1941-10-14 | Freeport Sulphur Co | Flotation process for oxidized manganese ore |
US2312466A (en) * | 1940-02-08 | 1943-03-02 | American Cyanamid Co | Oxygen-bearing ore flotation |
US2362432A (en) * | 1941-07-03 | 1944-11-07 | Emulsol Corp | Flotation of ores |
US2668150A (en) * | 1951-03-26 | 1954-02-02 | Nat Aluminate Corp | Antifoam compositions and method of foam inhibition |
US2664199A (en) * | 1952-08-27 | 1953-12-29 | Phelps Dodge Corp | Flotation recovery of molybdenite |
SU137072A1 (en) * | 1960-10-03 | 1960-11-30 | В.Р. Гантимуров | Method of flotation concentration of oxidized sulfide molybdenum ores |
US3313412A (en) * | 1964-08-05 | 1967-04-11 | Philip A Bloom | Recovery of molybdenite from copper sulfide concentrates by froth flotation |
FR1482821A (en) * | 1965-06-10 | 1967-06-02 | Ind Chimiques De Voreppe | Improved process for making pure grape seed almond oil |
US3539002A (en) * | 1967-12-11 | 1970-11-10 | Kennecott Copper Corp | Process for separating molybdenite from copper sulfide concentrates |
US3595390A (en) * | 1968-06-18 | 1971-07-27 | American Cyanamid Co | Ore flotation process with poly(ethylene-propylene)glycol frothers |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1980000422A1 (en) * | 1978-08-15 | 1980-03-20 | Pennwalt Corp | Froth flotation process |
US4317543A (en) * | 1979-11-29 | 1982-03-02 | Olivares Juan P | Process for separating copper and iron minerals from molybdenite |
US5182039A (en) * | 1991-03-29 | 1993-01-26 | Exxon Chemical Patents, Inc. | Synergistic fluorinated ore flotation aids |
AU700014B2 (en) * | 1995-09-19 | 1998-12-17 | Baker Petrolite Corporation | Use of stearic acid esters of polypropylene glycol to control foam |
WO1997010889A1 (en) * | 1995-09-19 | 1997-03-27 | Baker Hughes Incorporated | Use of stearic acid esters of polypropylene glycol to control foam |
US5545351A (en) * | 1995-09-19 | 1996-08-13 | Baker Hughes Incorporated | Use of stearic acid esters of polypropylene glycol to control foam |
EP0779330A1 (en) * | 1995-12-15 | 1997-06-18 | Bridgestone Corporation | Sulfur curable mix compositions including silica and an antistatic agent, particularly for manufacturing tires; tire tread produced from such mixes; and tire comprising such a tread |
US6409799B1 (en) * | 1998-11-19 | 2002-06-25 | Betzdearborn Inc. & Corporacion Nacional Del Cobre De Chile | Copper leach process aids |
CN100348332C (en) * | 2005-11-28 | 2007-11-14 | 中国铝业股份有限公司 | Bauxite positive flotation headings three-phase foam removing method |
CN100551544C (en) * | 2007-02-13 | 2009-10-21 | 金堆城钼业股份有限公司 | The molybdenite foaming agent for ore dressing |
CN101264467B (en) * | 2007-03-13 | 2011-04-13 | 金堆城钼业股份有限公司 | Molybdenite flotation foaming agent |
US10344353B2 (en) * | 2015-04-08 | 2019-07-09 | Ecolab Usa Inc. | Leach aid for metal recovery |
CN112958285A (en) * | 2021-02-01 | 2021-06-15 | 核工业北京化工冶金研究院 | Compound auxiliary collecting agent for beta stone flotation and application thereof |
CN112958285B (en) * | 2021-02-01 | 2022-08-05 | 核工业北京化工冶金研究院 | Compound auxiliary collecting agent for beta stone flotation and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0662865B1 (en) | Coal flotation process | |
US3837489A (en) | Molybdenum disulfide flotation antifoam | |
US4309282A (en) | Process of phosphate ore beneficiation in the presence of residual organic polymeric flocculants | |
US4929344A (en) | Metals recovery by flotation | |
US4192737A (en) | Froth flotation of insoluble slimes from sylvinite ores | |
US2267307A (en) | Concentrating ores | |
CA1320769C (en) | N-alkyl and n-alkenyl aspartic acids as co-collectors for the flotation of non-sulfidic ores | |
US3910836A (en) | Pyrochlore flotation | |
US4883586A (en) | Process for beneficiating ores containing fine particles | |
US2410376A (en) | Beneficiation of iron ores | |
US4054442A (en) | Method for recovering scheelite from tungsten ores by flotation | |
US1585756A (en) | Treatment of minerals | |
US3331505A (en) | Flotation process for reagent removal | |
US1102873A (en) | Ore concentration. | |
US2483890A (en) | Cationic froth flotation of iron ore | |
US3037627A (en) | Method of beneficiating sulfide and oxide ores of copper, manganese, lead and zinc | |
US1208171A (en) | Concentration of sulfid ores. | |
US1914695A (en) | Concentration of phosphate-bearing material | |
US4556545A (en) | Method for conditioning phosphate ores | |
US3151062A (en) | Method for the froth flotation of slimed minerals and ores | |
US2724499A (en) | Concentration of potash ores containing sylvite | |
US4642181A (en) | Increased reduction of magnesium content by use of inorganic promoters during beneficiation of phosphate ores by flotation | |
US2300827A (en) | Flotation of nonmetallic minerals | |
US4732666A (en) | Froth flotation | |
US1236934A (en) | Concentration of ores. |