CA1212789A - 1,3-oxatholane-2-thione as sulfide mineral collectors in froth flotation - Google Patents
1,3-oxatholane-2-thione as sulfide mineral collectors in froth flotationInfo
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- CA1212789A CA1212789A CA000462843A CA462843A CA1212789A CA 1212789 A CA1212789 A CA 1212789A CA 000462843 A CA000462843 A CA 000462843A CA 462843 A CA462843 A CA 462843A CA 1212789 A CA1212789 A CA 1212789A
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- thione
- oxathiolane
- sulfide
- hexyl
- butyl
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Abstract
ABSTRACT OF THE DISCLOSURE
The invention is a process of concentrating sulfide ores, which comprises subjecting a sulfide ore, in the form of a pulp, to a flotation process in the presence of a flotation collector for the sulfides com-prising a 1,3-oxathiolane-2-thione.
The invention is a process of concentrating sulfide ores, which comprises subjecting a sulfide ore, in the form of a pulp, to a flotation process in the presence of a flotation collector for the sulfides com-prising a 1,3-oxathiolane-2-thione.
Description
1, 3--OXATEIIOLANE--2-TElIONES USED
AS A SIJLFIDE MINERAL COLLECTOR
IN FRQI'H FLOTATION
This i~vention relates to the concentration of sulfide mineral ores by froth flotation using 1,3-oxathiolane-2-thiones as collertors.
Flotation is a process of treating a mixture of finely divided mineral solids, e.g., a pulverulent ore, suspended in a liguid whereby a portion of such solids are 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 ln situ) in the liguid to produce a frothy mass containing certain of the solids on the top of the liguid, and leaving suspended (unfrothed) other solid components of the ore. Flotation is based on the principle that introducing a gas into a liquid containi~g solid particles of different materials uspended therein cauces adherence of some gas to certain suspended solids and not to others and makes the particles having the gas t~us adhered thereto lighter than the liquid.
Accordingly, these particles rise to the top of the liguid to form a fxoth.
31,453-F
Various flotation agen~s have been a~mixed with the suspension to improve the frothing process. Such added agents are classed according to the function to be performed- collector6, for sulfide minerals including xanthates, ~hionocaxbamates and the like; frothers which impart the property of forming a stable froth, e.g., natural oils such as pine oil and eucalyptus oil, modi fiers such as activators to induce flotation in the presence of a collector, e.g., copper sulfate; depres-sants, e.g., sodium cyanide, which tend to prevent acollector from functioning as such on a mineral which it is desired to retain in the liquid, and thereby dis-courage a substance from being carried up and forming a part of the froth; p~ regulators to produce optimum metallurgical results, e.g., lime, soda ash and the like.
USP 3,464,551 discloses using dialkyl dithiocarbamates Rl_N - C_s_~2 20 as flotation collectors; USP 3,590,995 describes flo-tation of sulfide ores using certain thionocarbamates.
It is of importance to bear in mind that addi-tives of the above type are selected for use according to the na~re of the ore, the mineral sought to be recovered, and the other additaments which are to be used in combina-tion therewith.
An understanding of the phenomena which makes flotation a particularly valuable industrial operation is not essential to the practice of the present invention.
They appear, however, to be largely ~ssociated with 31,453-F - -2 f ~ 7~
. -3-selective affinity of the surface of particulated solids, suspended in a liguid containing entrapped gas, for the liquid on ~he one hand, the gas on the other.
The flotation principle is applied in a num-ber of mineral separation processes among which is theselective separation of such minerals as sulfide copper minerals, sulfide zinc minerals, sulfide molybdenum minerals and others from sulfide iron minerals.
Among commonly used collectors are the xan-thates and the dithiophosphates. These collectors mustbe dried after preparation or shipped in solution which creates handling problems. Such collectors are rela-tively inexpensive but their activity as collectors is not as good as some other collectors.
1i5 Another class of commonly used collectors is the thionocarbamates. The preparation of these compounds normally reguires a three-step synthesis, wherein salts and mercaptans are by-products. Such compounds are relatively expensive to prepare but have good activity.
What is needed is a collector for sulfide ores which can be prepared in a simple synthesis scheme without the preparation of salt or mercaptan by-products.
Further needed is a collector which does not necessitate drying or shipping in solution. What is further needed is a collector which is relatively inexpensive to prepare with good collector activity;
The invention is a process of concentrating sulfide ores, which comprises subjecting a metal sulfide ore, in the form of a pulp, to a flotation process in 31,453-F -3-th~ presence of a flotation col].ecko.r for the sulfides wherein the flota~ion collector comprises a 1,3 oxa-thiolane-2-thione, and recovering the desired metal sulfide oxe.
The 1,3~oxathiolane-2-thione collector can be prepared relatively inexpensi~ely by a simple s~nthesis ~cheme which does not prepare sal~ or mercaptan by-products. Further, the compound does not need to be dried or shipped in water. Surprisingly, the compound shows much better activity than the ~anthates or dithiophosphakes.
Detailed Descri~tion of the Invention The 1,3-oxathiolane-2-thiones (hereinafter referred to as a cyclic thione) of this i~vention include those which correspond to the formulas /C \
l R~4 ¦
wherein R , R , R and R4 are separately in each occur rence hydrogen, an unsubstituted hydrocarbyl group or a hydrocarbyl group substituted with a halo, carbonyl-alkoxy, alkoxy, thioalkyl, thiol, cyano, hydroxyl or nitro group.
~ ydrocarbyl means herein an organic radical containing betwe~n one and twenty carbon atoms to which 31,453-F -4-r ~
~5~
are bonded hydrogen atoms. Inc:luded are the following groups: alkyl, alkenyl, alkynyl, cycloalkyl, cyclo-alkenyl, aryl, alkaryl ox aralk~yl.
The term aryl refers herein to biaryl, phenyl, naphthyl, phenanthranyl an~ anthranyl. Alkaryl refers herPin to an alkyl-, alkenyl~ or alkynyl substituted aryl substituent wherein aryl is as defined herein-before. ~.ralkyl means herein an alkyl, alXenyl or Plkynyl substituent substituted with an aryl group, wherein aryl is as de*ine~ hereinbefore. Alkyl includes straight and branched chain methyl, ethyl, propyl, butyl, p~ntyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups. Alkenyl includes straight and branched chain ethenyl, propenyl, butenyl, pentenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, no~adecenyl and eicosenyl groups. Alkynyl groups include straight and branched chai~ ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nony~yl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecy~yl, heptadecynyl, octadecynyl, nonadecynyl and eicosynyl groups.
Cycloalkyl refers to an alkyl group con-taining one, two, three or more cyclic rings, including cyclopropyl, cyclobutyl, cyclopen~yl, cycloh~xyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, cyclo-te~radecyl, cyclopentadecyl, cyclohexadecyl, cyclo-hep~adecyl, cyclooctade~yl, cyclononadecyl, cyclo-eicosyl, bicyclopropyl, bicyclobutyl, bicyclopentyl, 31,453-~ -5-bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclodecyl, tricyclopropyl, tricyclobutyl, tricyclo-pentyl, tricyclohexyl groups ancl group~ containing two or more of the cycloalkyl groups named hereinbefore.
Cycloalkenyl refers to mono , di- and polycyclic groups containin~ one or more double bonds including cyclopro-penyl, cyclobu-tenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cycloundecenyl, cyclododecenyl, cyclotridecenyl, cyclo-tetradecenyl, cyclopentadecenyl, cyclohexadecenyl,cycloheptadecenyl, cyclooctaZecenyl, cyclononadecenyl, cycloeicosenyl, bicyclopropenyl, bicyclobutenyl, bicyclopentenyl, bicy d oheptenyl, bicyclooctenyl, bicyclononenyl, bicyclopentenyl, tricyclopropenyl, tricyclobutenyl, tricyclopentenyl, tricyclohexenyl groups. Cycloalkenyl also refers to the above-named cycloalkenyl groups wherein two or more double bonds are present, for examplP, cyclobutadienyl, cyclopenta-dienyl and cyclohexadienyl groups.
In the above formula Rl is preferably Cl 20 hydrocarbyl. R1 is more preferably Cl 20 alkyl or C 20 aryl, even more preferably C2_~0 alkyl, and m preferably C4 6 alkyl. ~ , R and R are preferably Cl 20 hydrocarbyl or hydrogen, and more preferably hydrogen.
Among the compound~ within the scope of the 1,3-oxathiolane-2-thione, collector are S-methyl-1,3-oxathiolane-2-thione, 5-ethyl-1,3-oxathiolane-
AS A SIJLFIDE MINERAL COLLECTOR
IN FRQI'H FLOTATION
This i~vention relates to the concentration of sulfide mineral ores by froth flotation using 1,3-oxathiolane-2-thiones as collertors.
Flotation is a process of treating a mixture of finely divided mineral solids, e.g., a pulverulent ore, suspended in a liguid whereby a portion of such solids are 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 ln situ) in the liguid to produce a frothy mass containing certain of the solids on the top of the liguid, and leaving suspended (unfrothed) other solid components of the ore. Flotation is based on the principle that introducing a gas into a liquid containi~g solid particles of different materials uspended therein cauces adherence of some gas to certain suspended solids and not to others and makes the particles having the gas t~us adhered thereto lighter than the liquid.
Accordingly, these particles rise to the top of the liguid to form a fxoth.
31,453-F
Various flotation agen~s have been a~mixed with the suspension to improve the frothing process. Such added agents are classed according to the function to be performed- collector6, for sulfide minerals including xanthates, ~hionocaxbamates and the like; frothers which impart the property of forming a stable froth, e.g., natural oils such as pine oil and eucalyptus oil, modi fiers such as activators to induce flotation in the presence of a collector, e.g., copper sulfate; depres-sants, e.g., sodium cyanide, which tend to prevent acollector from functioning as such on a mineral which it is desired to retain in the liquid, and thereby dis-courage a substance from being carried up and forming a part of the froth; p~ regulators to produce optimum metallurgical results, e.g., lime, soda ash and the like.
USP 3,464,551 discloses using dialkyl dithiocarbamates Rl_N - C_s_~2 20 as flotation collectors; USP 3,590,995 describes flo-tation of sulfide ores using certain thionocarbamates.
It is of importance to bear in mind that addi-tives of the above type are selected for use according to the na~re of the ore, the mineral sought to be recovered, and the other additaments which are to be used in combina-tion therewith.
An understanding of the phenomena which makes flotation a particularly valuable industrial operation is not essential to the practice of the present invention.
They appear, however, to be largely ~ssociated with 31,453-F - -2 f ~ 7~
. -3-selective affinity of the surface of particulated solids, suspended in a liguid containing entrapped gas, for the liquid on ~he one hand, the gas on the other.
The flotation principle is applied in a num-ber of mineral separation processes among which is theselective separation of such minerals as sulfide copper minerals, sulfide zinc minerals, sulfide molybdenum minerals and others from sulfide iron minerals.
Among commonly used collectors are the xan-thates and the dithiophosphates. These collectors mustbe dried after preparation or shipped in solution which creates handling problems. Such collectors are rela-tively inexpensive but their activity as collectors is not as good as some other collectors.
1i5 Another class of commonly used collectors is the thionocarbamates. The preparation of these compounds normally reguires a three-step synthesis, wherein salts and mercaptans are by-products. Such compounds are relatively expensive to prepare but have good activity.
What is needed is a collector for sulfide ores which can be prepared in a simple synthesis scheme without the preparation of salt or mercaptan by-products.
Further needed is a collector which does not necessitate drying or shipping in solution. What is further needed is a collector which is relatively inexpensive to prepare with good collector activity;
The invention is a process of concentrating sulfide ores, which comprises subjecting a metal sulfide ore, in the form of a pulp, to a flotation process in 31,453-F -3-th~ presence of a flotation col].ecko.r for the sulfides wherein the flota~ion collector comprises a 1,3 oxa-thiolane-2-thione, and recovering the desired metal sulfide oxe.
The 1,3~oxathiolane-2-thione collector can be prepared relatively inexpensi~ely by a simple s~nthesis ~cheme which does not prepare sal~ or mercaptan by-products. Further, the compound does not need to be dried or shipped in water. Surprisingly, the compound shows much better activity than the ~anthates or dithiophosphakes.
Detailed Descri~tion of the Invention The 1,3-oxathiolane-2-thiones (hereinafter referred to as a cyclic thione) of this i~vention include those which correspond to the formulas /C \
l R~4 ¦
wherein R , R , R and R4 are separately in each occur rence hydrogen, an unsubstituted hydrocarbyl group or a hydrocarbyl group substituted with a halo, carbonyl-alkoxy, alkoxy, thioalkyl, thiol, cyano, hydroxyl or nitro group.
~ ydrocarbyl means herein an organic radical containing betwe~n one and twenty carbon atoms to which 31,453-F -4-r ~
~5~
are bonded hydrogen atoms. Inc:luded are the following groups: alkyl, alkenyl, alkynyl, cycloalkyl, cyclo-alkenyl, aryl, alkaryl ox aralk~yl.
The term aryl refers herein to biaryl, phenyl, naphthyl, phenanthranyl an~ anthranyl. Alkaryl refers herPin to an alkyl-, alkenyl~ or alkynyl substituted aryl substituent wherein aryl is as defined herein-before. ~.ralkyl means herein an alkyl, alXenyl or Plkynyl substituent substituted with an aryl group, wherein aryl is as de*ine~ hereinbefore. Alkyl includes straight and branched chain methyl, ethyl, propyl, butyl, p~ntyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups. Alkenyl includes straight and branched chain ethenyl, propenyl, butenyl, pentenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, no~adecenyl and eicosenyl groups. Alkynyl groups include straight and branched chai~ ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nony~yl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecy~yl, heptadecynyl, octadecynyl, nonadecynyl and eicosynyl groups.
Cycloalkyl refers to an alkyl group con-taining one, two, three or more cyclic rings, including cyclopropyl, cyclobutyl, cyclopen~yl, cycloh~xyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, cyclo-te~radecyl, cyclopentadecyl, cyclohexadecyl, cyclo-hep~adecyl, cyclooctade~yl, cyclononadecyl, cyclo-eicosyl, bicyclopropyl, bicyclobutyl, bicyclopentyl, 31,453-~ -5-bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclodecyl, tricyclopropyl, tricyclobutyl, tricyclo-pentyl, tricyclohexyl groups ancl group~ containing two or more of the cycloalkyl groups named hereinbefore.
Cycloalkenyl refers to mono , di- and polycyclic groups containin~ one or more double bonds including cyclopro-penyl, cyclobu-tenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cycloundecenyl, cyclododecenyl, cyclotridecenyl, cyclo-tetradecenyl, cyclopentadecenyl, cyclohexadecenyl,cycloheptadecenyl, cyclooctaZecenyl, cyclononadecenyl, cycloeicosenyl, bicyclopropenyl, bicyclobutenyl, bicyclopentenyl, bicy d oheptenyl, bicyclooctenyl, bicyclononenyl, bicyclopentenyl, tricyclopropenyl, tricyclobutenyl, tricyclopentenyl, tricyclohexenyl groups. Cycloalkenyl also refers to the above-named cycloalkenyl groups wherein two or more double bonds are present, for examplP, cyclobutadienyl, cyclopenta-dienyl and cyclohexadienyl groups.
In the above formula Rl is preferably Cl 20 hydrocarbyl. R1 is more preferably Cl 20 alkyl or C 20 aryl, even more preferably C2_~0 alkyl, and m preferably C4 6 alkyl. ~ , R and R are preferably Cl 20 hydrocarbyl or hydrogen, and more preferably hydrogen.
Among the compound~ within the scope of the 1,3-oxathiolane-2-thione, collector are S-methyl-1,3-oxathiolane-2-thione, 5-ethyl-1,3-oxathiolane-
-2-thione, 5-propyl-1,3-oxathiolane~2-thione, 5-butyl-30 -1,3-oxathiolane-2-thione, 5-pentyl-1,3 oxathiolane-2 thi-one, 5-hexyl-1,3-oxathiolane-2-thione, 5-heptyl-1,3~oxa-thiolane-2-thione, 5-octyl-1,3-oxathiolane-2-thione, 31,453-F -6-5 nonyl-1,3-oxathiolane-2 thione, 5 decyl~l,3-oxathiolane--2-thione, 5,5-dimethyl-1,3-oxathiolane-2-thione, 5,5-diethyl-1,3-oxathiolane-2-thione, 5,5-dipropyl--1,3-oxathiolane-2-thione, 5,5-di~utyl 1,3-oxathio].ane-S ~2-thione, 5,5-dipentyl-1,3-oxathiolane-2-thione, 5,5-dihexyl~1,3-oxathiolane-2-thione, 5,5 diAeptyl--1,3-oxathiolane-2-thione,~5,5-dioctyl 1,3-oxathlolane--2 thione, 5,5-dinonyl 1,3-oxathiolane-2-thione, 5,5-didecyl-1,3-oxathiolane-2~thione, 5-methyl-5-ethyl-10 -1,3-oxa~hiolane-2-thione, 5 methyl-5-propyl-1,3--oxathiolane-2-thione, 5~methyl-5-butyl-1,3-oxathio-lane-2-thione, 5-methyl-5 pentyl-1,3-oxathiolane-2-thione, 5-methyl 5-hexyl-1,3-o~athiolane-2-thione, 5-ethyl-5-pro-pyl-1,3-oxathiolane-2-thione, 5-ethyl-5-butyl-1,3-oxathio-15 lane-2-thio~e, 5~ethyl-5-pentyl-1,3-oxa~hiolane-2-thione, 5-ethyl-5-hexyl-1,3-oxathiolane-2-thione, 5-propyl-5-butyl~
-1,3-oxathiolane-2-thione, 5-propyl-5-pentyl-1,3-oxathio-lane-2~thione, 5-pro~yl-5-hexyl-1,3-oxathiolane-2 thione, 5-butyl-5-pentyl-1,3-oxathiolane-2-thion~, 5-butyl-5 hexyl 20 -1,3-oxathiolane-2-thione, 5-pentyl-5~hexyl-1,3-oxathio-lane 2-thione or 5-phenyl-1,3-oxathiolane-2-thione.
Preferred 1,3~oxathiolane-2-thiones i~clude 5~butyl--1,3-oxathislane-2-thione, 5-pentyl-1,3-oxathiolane--2-thione and 5-hexyl-1,3-oxathiolane-2~thione.
The cyclic ~hiones of this invention demonstrate good recovery and rates of recovery as sulfide mineral collectors in froth flotation processes. Any one of the cyclic thiones within the scope of this invention can be used as collectors. Further, a mixture of two or more of the cyrlic thiones could be used.
Examples of sulfide minerals for which these collectors are useful include copper sulfide, zinc 31,453~F . -7-__ sulfide, molybdenum sulfide, cobalt sulfide, nickel sulfide, lead sulfide, arsenic sulfide, antimony sul~ide, silver sulfide, chromium sulfide, gold sulfide, platinum sulfide and uranillm sul~ide. The most preferred sulfide mineral i5 copper sulfide.
Examples of sulfide ores from which metal sulfides may be concentrated by froth flotation using the cyclic thiones as collectors include copper-bearing ores: covallite (CuS), chalcocite (Cu2S), chalcopyrite (CuFeS2), bornite (Cu5FeS4), cubanite SCu2SFe4S5), valerite (Cu2Fe4S7 or Cu3Fe4S7) enargite (Cu3~As,Sb)S4), tetrahedrite (Cu3SbS2), tennanite (Cul2As4S13), famatinite (Cu3(Sb,~s~S4), bournonite (pbrusbs3); lead-bearing ores: galena (PbS); antimony-bearing ores: stilnite (Sb2S4); æinc-bearing ores: sphalerite (ZnS); silver--bearing ores: argentite (Ag2S), stephanite (Ag5SbS4~;
chromium-bearing ores: daubreelite (FeSCrS3); platinum--bearing ores: cooperite (Pt~AsS)2).
The amount of the cyclic thione collectors used is dependent upon the particular collector used,-the mineral being concentrated, the size of the ore particles and other conditions. Generally the amount of collector which concentrates the sulfide mineral in the froth is suitable. Preferably between about 0.005 to 0.25 pounds of cyclic thione per ton of ore is used, most preferably between 0.015 and 0.08 pounds of cyclic thione per ton of ore is use~.
The use of cyclic thiones as collectors results in a higher rate of recovery and a higher recovery than many of the known collectors for sulfide ores. Preferably the recovery or the mineral sulfide - 31,453-F -8 is greater than or egual to 0.80, more preferably 0.90.
Preferably, the rate of recovery for the minexal sulfide is greater ~han or equal ~o 5O5~ more pr~ferably 7.0, and most preferably 8O0. RecovF~ry and rate of recovery are defined hereinafter.
The froth flotation processes in which the cyclic thione~ of this invention are used, are those which are well-known in the art. In most of these pro-cesses, the use of frothing agents is required.
The cyclic thiones can be used in a mixture with any known collectors. Numerous collectors are known in flotation practice or have been proposed in the technical and patent literature. Generic examples include ~anthates,- thiocarbamates, dithiophosphates, thiocarbanilide, xanthogen formates, alkylamines, ~uaternary ammonium compounds, sulfonates and the like.
Any collector which is known in the art is suitable for the beneficiation by flotation of a sulfide mineral ore can be used in this invention. Further blends of known collectors can also be used in this invention Suitable frothers include some compounds which are also commonly used as collectors such as fatty acids, soaps, and alkyl aryl sulfonates, but the best frothers are those which have a minimum of collecting properties. They are polar-nonpolar molecules of the type C5HllOH, amyl alcohol or CloH170H, the active constituent of the well-known fro~her pine oil. The aliphatic alcohols used as frothers preferably have chain lengths of 5 to 8 carbon atoms, provided there is sufficient branching in the chain. Alcohol~ in the 10 to 12 carbon atom range are 31,453-F -9-good frothers. Other examples include polyalkylene glycols, polyalkylene glycol ethers, polyoxyalkylene paraffins and cresylic acids. ~ilends of frothers may also be used. All frothers which are suitable for beneficiation of mineral ores by froth flotation can be used in this invention.
The cyclic thiones of this invention can be prepared by the processes described in USP 3,44~,120 and USP 3,40~,635.
Specific Embodiments The following examples are included for illustration and do not limit the scope of the invention or claims. Unless otherwise indicated, all parts and percentages are by weight.
In the following examples, the performance of the frothing processes described is shown by giving the rate constant of flotation and the amount of recovery at infinite time. These numbers are calculated by using the formula ~ = R~ [1- 1 kt ]
wherein: ~ is the amount of mineral recovered at time t, k is the rate constant for the rate of recovery and R~ is the calculated amount of the mineral which should be recovered at infinite time.
The amount recovered at various times is determined experimentally and the series of values are substituted into the equation to obtain the R~ and k. The above formula is explained in ~l~iLrr ~
"Selection of Chemical Reagents for Flotation" by R. R.
Kimpel, Ch. 45, Mineral Processinq Plant Design, 2nd Ed., pp. 907-934 ~1980), Mul~r and Bhappud ~ditor~, The Society of Minlng Engineers, NY.
Experimental Procedure - Examples 1 to 7 Several of the 1,3-oxathiolane-2-thiones and prior art collectors are used for the flotation of copper sulfide. The procedure for such flotation is described hereinafter. The results are compiled in Table Io Procedure:
The flotation cell used is a 6.5 x 6.5 x 8-inch plexiglass container which holds approximately 2.8 liters of deionized water, ore, collector and frother. A rotating paddle is provided for skimming the frother from the top of the cell into a collection tray. ~n air inlet is placed in th~ bottom of the cell.
A copper sulfide ore from the Inspiration Consolidated Copper Company is preground to -10 mesh.
Immediately before floating the ore is ground in a rod mill for an additional period of time to obtain the desired mesh size. The process for this grinding is as follows. Eight rods of one inch each are put in a rod mill along with 1000 g of ore, 0.6 g of lime (to bring the pH to 10.6), 600 g of deionized water, 0.05 lb of collector per ton of ore (0.025 g), and the mixture is ground at 60 rpm for about 25 minutes, until approxi-mately 80 percent of the particles had a size of less than 200 mesh.
31,453-F -11-Z7~
Thereafter/ the slurry~ is transferred to the float cell as described hereinbe!fore. The frot~er, ~owfroth~ 101~ (a polypropylene glycol ether available from The Dow Chemical Co~pany, Midland, Michigan) is added to the cell, 0.08 lb per ton of ore (0O04 g).
Deionized water is added to bring the water up to the desired level in the float cell. The mixture in the float cell is stirred at 900 rpm for 2 minutes to conditlon the ore. After 2 minutes of stirring, the air flow of 9 liters/minute is started, with continued stirring, and a paddle rotation of 10 rpm is started.
Further water is added to maintain the water level.
The froth from the cell is skimmed by the paddle into a collection tray. The froth skimmed off is collected at 15 i~tervals of 0.5, 1.5, 3.0, 5.0 and 8.0 minutes. Each sample is dried oveEnight in a forced air oven at 95C.
The samples are weighed and analyzed for cop-per content by plasma emission spectroscopy.
The procedure for the analysis by plasma emission spectroscopy is as follows. Into a 100-cc flask is placed 0.2 to 0.25 g of ore sample (approxi-mately 2.0 g i~ it is a tailings sample, the ore left in the cell after flotation~. To this is added 3.5 cc of concentrated hydrochloric acid and 5.0 cc of concen-trated nitric acid. The mixture is heated to boilingand boiled for 25 minutes, and then allowed to cool.
To this is added 25 cc of deionized water. The mixture is heated to boiling then allowed to cool. The mi~ture is filled to the volumetric line. A plasma emission spectrometer (Spectrospan IV) is used to determine the copper level in the solutions prepared. The copper emission line at 2135O98 nm is found to give a linear 31,453-F -12- -response with copper concentration. The instrument is standardized by the use of copper solution standards.
When ~he sample solution is asp:irated into the plasma, the concentration in ppm of Cu is shown by the in~trument by digital display. This ppm of Cu is ~onverted into percent Cu in ~he original sample by the following equation:
% Cu in original sample = ~ppm Cu~(10 )~ d-) x 100%
The percent recovery and rate are calculated by substituting the weight of the copper in each sample and the time each sample was taken into the equation desrribed hereinbefore.
The r~sults are compiled in Table I.
TABLE I
op~er R Gan~ue Example Collector R K 8 minl R K
1 Z_2002 0.65 7.7 0.63 0.14 ~,2 2 Z-113 0.55 4.3 0.54 0.03 3.7
-1,3-oxathiolane-2-thione, 5-propyl-5-pentyl-1,3-oxathio-lane-2~thione, 5-pro~yl-5-hexyl-1,3-oxathiolane-2 thione, 5-butyl-5-pentyl-1,3-oxathiolane-2-thion~, 5-butyl-5 hexyl 20 -1,3-oxathiolane-2-thione, 5-pentyl-5~hexyl-1,3-oxathio-lane 2-thione or 5-phenyl-1,3-oxathiolane-2-thione.
Preferred 1,3~oxathiolane-2-thiones i~clude 5~butyl--1,3-oxathislane-2-thione, 5-pentyl-1,3-oxathiolane--2-thione and 5-hexyl-1,3-oxathiolane-2~thione.
The cyclic ~hiones of this invention demonstrate good recovery and rates of recovery as sulfide mineral collectors in froth flotation processes. Any one of the cyclic thiones within the scope of this invention can be used as collectors. Further, a mixture of two or more of the cyrlic thiones could be used.
Examples of sulfide minerals for which these collectors are useful include copper sulfide, zinc 31,453~F . -7-__ sulfide, molybdenum sulfide, cobalt sulfide, nickel sulfide, lead sulfide, arsenic sulfide, antimony sul~ide, silver sulfide, chromium sulfide, gold sulfide, platinum sulfide and uranillm sul~ide. The most preferred sulfide mineral i5 copper sulfide.
Examples of sulfide ores from which metal sulfides may be concentrated by froth flotation using the cyclic thiones as collectors include copper-bearing ores: covallite (CuS), chalcocite (Cu2S), chalcopyrite (CuFeS2), bornite (Cu5FeS4), cubanite SCu2SFe4S5), valerite (Cu2Fe4S7 or Cu3Fe4S7) enargite (Cu3~As,Sb)S4), tetrahedrite (Cu3SbS2), tennanite (Cul2As4S13), famatinite (Cu3(Sb,~s~S4), bournonite (pbrusbs3); lead-bearing ores: galena (PbS); antimony-bearing ores: stilnite (Sb2S4); æinc-bearing ores: sphalerite (ZnS); silver--bearing ores: argentite (Ag2S), stephanite (Ag5SbS4~;
chromium-bearing ores: daubreelite (FeSCrS3); platinum--bearing ores: cooperite (Pt~AsS)2).
The amount of the cyclic thione collectors used is dependent upon the particular collector used,-the mineral being concentrated, the size of the ore particles and other conditions. Generally the amount of collector which concentrates the sulfide mineral in the froth is suitable. Preferably between about 0.005 to 0.25 pounds of cyclic thione per ton of ore is used, most preferably between 0.015 and 0.08 pounds of cyclic thione per ton of ore is use~.
The use of cyclic thiones as collectors results in a higher rate of recovery and a higher recovery than many of the known collectors for sulfide ores. Preferably the recovery or the mineral sulfide - 31,453-F -8 is greater than or egual to 0.80, more preferably 0.90.
Preferably, the rate of recovery for the minexal sulfide is greater ~han or equal ~o 5O5~ more pr~ferably 7.0, and most preferably 8O0. RecovF~ry and rate of recovery are defined hereinafter.
The froth flotation processes in which the cyclic thione~ of this invention are used, are those which are well-known in the art. In most of these pro-cesses, the use of frothing agents is required.
The cyclic thiones can be used in a mixture with any known collectors. Numerous collectors are known in flotation practice or have been proposed in the technical and patent literature. Generic examples include ~anthates,- thiocarbamates, dithiophosphates, thiocarbanilide, xanthogen formates, alkylamines, ~uaternary ammonium compounds, sulfonates and the like.
Any collector which is known in the art is suitable for the beneficiation by flotation of a sulfide mineral ore can be used in this invention. Further blends of known collectors can also be used in this invention Suitable frothers include some compounds which are also commonly used as collectors such as fatty acids, soaps, and alkyl aryl sulfonates, but the best frothers are those which have a minimum of collecting properties. They are polar-nonpolar molecules of the type C5HllOH, amyl alcohol or CloH170H, the active constituent of the well-known fro~her pine oil. The aliphatic alcohols used as frothers preferably have chain lengths of 5 to 8 carbon atoms, provided there is sufficient branching in the chain. Alcohol~ in the 10 to 12 carbon atom range are 31,453-F -9-good frothers. Other examples include polyalkylene glycols, polyalkylene glycol ethers, polyoxyalkylene paraffins and cresylic acids. ~ilends of frothers may also be used. All frothers which are suitable for beneficiation of mineral ores by froth flotation can be used in this invention.
The cyclic thiones of this invention can be prepared by the processes described in USP 3,44~,120 and USP 3,40~,635.
Specific Embodiments The following examples are included for illustration and do not limit the scope of the invention or claims. Unless otherwise indicated, all parts and percentages are by weight.
In the following examples, the performance of the frothing processes described is shown by giving the rate constant of flotation and the amount of recovery at infinite time. These numbers are calculated by using the formula ~ = R~ [1- 1 kt ]
wherein: ~ is the amount of mineral recovered at time t, k is the rate constant for the rate of recovery and R~ is the calculated amount of the mineral which should be recovered at infinite time.
The amount recovered at various times is determined experimentally and the series of values are substituted into the equation to obtain the R~ and k. The above formula is explained in ~l~iLrr ~
"Selection of Chemical Reagents for Flotation" by R. R.
Kimpel, Ch. 45, Mineral Processinq Plant Design, 2nd Ed., pp. 907-934 ~1980), Mul~r and Bhappud ~ditor~, The Society of Minlng Engineers, NY.
Experimental Procedure - Examples 1 to 7 Several of the 1,3-oxathiolane-2-thiones and prior art collectors are used for the flotation of copper sulfide. The procedure for such flotation is described hereinafter. The results are compiled in Table Io Procedure:
The flotation cell used is a 6.5 x 6.5 x 8-inch plexiglass container which holds approximately 2.8 liters of deionized water, ore, collector and frother. A rotating paddle is provided for skimming the frother from the top of the cell into a collection tray. ~n air inlet is placed in th~ bottom of the cell.
A copper sulfide ore from the Inspiration Consolidated Copper Company is preground to -10 mesh.
Immediately before floating the ore is ground in a rod mill for an additional period of time to obtain the desired mesh size. The process for this grinding is as follows. Eight rods of one inch each are put in a rod mill along with 1000 g of ore, 0.6 g of lime (to bring the pH to 10.6), 600 g of deionized water, 0.05 lb of collector per ton of ore (0.025 g), and the mixture is ground at 60 rpm for about 25 minutes, until approxi-mately 80 percent of the particles had a size of less than 200 mesh.
31,453-F -11-Z7~
Thereafter/ the slurry~ is transferred to the float cell as described hereinbe!fore. The frot~er, ~owfroth~ 101~ (a polypropylene glycol ether available from The Dow Chemical Co~pany, Midland, Michigan) is added to the cell, 0.08 lb per ton of ore (0O04 g).
Deionized water is added to bring the water up to the desired level in the float cell. The mixture in the float cell is stirred at 900 rpm for 2 minutes to conditlon the ore. After 2 minutes of stirring, the air flow of 9 liters/minute is started, with continued stirring, and a paddle rotation of 10 rpm is started.
Further water is added to maintain the water level.
The froth from the cell is skimmed by the paddle into a collection tray. The froth skimmed off is collected at 15 i~tervals of 0.5, 1.5, 3.0, 5.0 and 8.0 minutes. Each sample is dried oveEnight in a forced air oven at 95C.
The samples are weighed and analyzed for cop-per content by plasma emission spectroscopy.
The procedure for the analysis by plasma emission spectroscopy is as follows. Into a 100-cc flask is placed 0.2 to 0.25 g of ore sample (approxi-mately 2.0 g i~ it is a tailings sample, the ore left in the cell after flotation~. To this is added 3.5 cc of concentrated hydrochloric acid and 5.0 cc of concen-trated nitric acid. The mixture is heated to boilingand boiled for 25 minutes, and then allowed to cool.
To this is added 25 cc of deionized water. The mixture is heated to boiling then allowed to cool. The mi~ture is filled to the volumetric line. A plasma emission spectrometer (Spectrospan IV) is used to determine the copper level in the solutions prepared. The copper emission line at 2135O98 nm is found to give a linear 31,453-F -12- -response with copper concentration. The instrument is standardized by the use of copper solution standards.
When ~he sample solution is asp:irated into the plasma, the concentration in ppm of Cu is shown by the in~trument by digital display. This ppm of Cu is ~onverted into percent Cu in ~he original sample by the following equation:
% Cu in original sample = ~ppm Cu~(10 )~ d-) x 100%
The percent recovery and rate are calculated by substituting the weight of the copper in each sample and the time each sample was taken into the equation desrribed hereinbefore.
The r~sults are compiled in Table I.
TABLE I
op~er R Gan~ue Example Collector R K 8 minl R K
1 Z_2002 0.65 7.7 0.63 0.14 ~,2 2 Z-113 0.55 4.3 0.54 0.03 3.7
3 Sodium Aerofloat~4 0.55 4.6 0.54 0.03 4.1
4 5-methyl-1,3-oxa 0.18 - 0.18 0.06 3.4 ~hiolane-2-thione
5 ethyl-1,3-oxa- 0.65 5.9 0.59 0.14 3.0 thiolane-2-thione
6 S-butyl-1,3-oxa- 0.68 8.3 0.67 0.23 4.3 thiolane-2-thione
7 5-hexyl-1,3-oxa- 0.69 8.2 0.68 0.17 4.1 thiolane-2 thione 31,453-F 13-~14-The recovery of mineral aftex 8 minutes.
S
2Z-200 is (CH332CHOCNHcH2 3 S
( 332 ~Sodium Aerofloat is tC2HSO)2PSNa and is avail~ble from American Cyanamid.
Examples l to 3 demonstrate the activity of known collector~ and are not e~bodime~ts of this inven tion.
Table I demonstrates that the 1,3-*xathiolane~
-2 thion~s generally give rates that are comparable wi~h the xanthates, dithiophosphates, and the thiono-carbamates which are generally considered some of the better sulfide ore collectors.
Examples 8-15 Kennecott ore from the Arthur Mill in Utah was subjected to froth flotation conditions using the procedure de~cribed hereinafter. Several known collec-tors were tested along with the novel cyclic thione collectors of this invention. The results are compiled in Table II.
Experimental Procedure - Examples 8 to 15 The flotation cell used is a containsr which holds approximately 107 liters of deionized water, ore, collec-tor and fro~her. A rotating double-paddle is 31,453-F -14-7.;~
provided for skimming the frother from the top of the cell into a collection tray. An air inlet is placed in the bottom of the cell.
.
Kennecott ore containing copper sulfide from 5 the Arthur Mill in Utah i5 preground to -10 mesh.
I~mediately before floating ~he ore is ground in a rod mill for an additional period of time to obtain the desired mesh size. The process for this grinding i5 as follows. Eight rods of one inch each are put in a rod mill along with 500 g of ore and 1 g of NaC03, lime is added to adjust the pH to between 10.0 and 10.2, 333 g of deionized water, the collector is added, and the mixture is ground at 60 rpm for about 5 minutes, until approximately 52 percent of the particles had a size of less than 200 mesh.
Thereafter, the slurry is transferred to the f.loat cell as described hereinbefore. The frother, methyl isobutyl, carbinol 50 ~l is added to the cell.
Deionized water is added to bring the water up to the desired level in the float cell. The mixture in the float cell is stirred at 1050 rpm for 2 minutes to con-dition the ore. After 2 minutes of stirring, the aIr flow of 19 cubic feet/hour is started, with continued stirring, and a paddle rotation of 12 rpm is started.
Further water is added to maintain the water level.
The froth from the cell is skimmed by the paddle into a collection tray. The froth skimmed off is collected ak intervals of 0.5, 1.0, 2.0, 4.0 and 8.0 minutes. Each sample is dried overnight in a forced air oven at about 30 100C.
31~453-F . -15-.
The samples are weighed and analyzed for cop-per content by pl~sma emission spectroscopy.
The procedure for the analysis by plasma emissicn spectroscopy is as fol:Lows. Into a 100-cc flask is placed 0.2 to 0.25 g of ore sample (approxi-mately 2.0 g if it is a tailings sample, the ore left in the cell after flotation). To this is added 3.5 cc of concentrated hydrochloric acid and 5.0 cc of concen-trated nitric acid. The mixture is heated to boiling and boiled for 25 minutes, and then allowed to cool.
To this is added 25 cc of deionized water. The mi~ture is heated to boiling then allowed to cool. The mixture is filled to the volumetric line. A plasma emission spectrometer (Spectrospan IV~ is u6ed to determine the copper level in the solutions prepared. The copper emission line at 2135.98 nm is found to give a linear response with copper concentration. The instrument is standardized by the use o~ ~opper solution stardards.
When the sample solution is aspirated into the plasma, the concentration in ppm of Cu is shown by the ins~rument by digital display. This ppm of Cu i5 converted into percent Cu in the original sample by ~he following eguation:
25 % Cu in original sample = ((g~rPamsCU)(lamp~(lOO)d) x 100%
The percent recovery and rate are calculated by substituting the weight of the copper in each sample and the time each sample was taken into ~he eguation de~cribed hereinbefore.
31,453-F -16-,b~
0~ D O C0 CO N
~D ~ ~ ~ aD ~ O
u~ ~ o ~1 0 0 ~ ~1 0 0 O O O O O O O O
,~ rl O ~J) O ~
O O O O O O O O
a~
~ 1 . d~ 0 I
a~
~ 1 0 ~ ~ D O
I ~: O~ ~ ~
OOOO~oOo ~1 11~
O O O O O O O O
1 O O O O O O C~ O' hi O O 0 ~1 N N (N r~ ilO
a~ E
~ ~ ~ 0 o ,1 ,1 ,1 s~
o o o . . . ~ $ o X ~ 1 X ~ ~
O o o ~ ~ V
Z ~ ~n Z
U ~ u~ I P4 N
.~1 0 0 ,~ ~ ~ O rl ~`1 0 ~1 N ~1 ~ O C~
O N 1!~ ~ N N U) ~ V
O ~_ O P~
o~
~1 ~ ~1 0 C4 0~ O rl Nt~ 1 ~1~1 0 ~ ,~ I i I I
X ~I N X ~C N
~1 ~ c~
31, 453-F . -17--18~
Examples 8 to 15 demonstrate that the 1,3-oxa-thiolane-2-thiones demonstrate a recovery of greater than 85 percent, and that such recovery is comparable to the recoveries demonstrated by present co~mercial collectors.
31,453-~ -18-
S
2Z-200 is (CH332CHOCNHcH2 3 S
( 332 ~Sodium Aerofloat is tC2HSO)2PSNa and is avail~ble from American Cyanamid.
Examples l to 3 demonstrate the activity of known collector~ and are not e~bodime~ts of this inven tion.
Table I demonstrates that the 1,3-*xathiolane~
-2 thion~s generally give rates that are comparable wi~h the xanthates, dithiophosphates, and the thiono-carbamates which are generally considered some of the better sulfide ore collectors.
Examples 8-15 Kennecott ore from the Arthur Mill in Utah was subjected to froth flotation conditions using the procedure de~cribed hereinafter. Several known collec-tors were tested along with the novel cyclic thione collectors of this invention. The results are compiled in Table II.
Experimental Procedure - Examples 8 to 15 The flotation cell used is a containsr which holds approximately 107 liters of deionized water, ore, collec-tor and fro~her. A rotating double-paddle is 31,453-F -14-7.;~
provided for skimming the frother from the top of the cell into a collection tray. An air inlet is placed in the bottom of the cell.
.
Kennecott ore containing copper sulfide from 5 the Arthur Mill in Utah i5 preground to -10 mesh.
I~mediately before floating ~he ore is ground in a rod mill for an additional period of time to obtain the desired mesh size. The process for this grinding i5 as follows. Eight rods of one inch each are put in a rod mill along with 500 g of ore and 1 g of NaC03, lime is added to adjust the pH to between 10.0 and 10.2, 333 g of deionized water, the collector is added, and the mixture is ground at 60 rpm for about 5 minutes, until approximately 52 percent of the particles had a size of less than 200 mesh.
Thereafter, the slurry is transferred to the f.loat cell as described hereinbefore. The frother, methyl isobutyl, carbinol 50 ~l is added to the cell.
Deionized water is added to bring the water up to the desired level in the float cell. The mixture in the float cell is stirred at 1050 rpm for 2 minutes to con-dition the ore. After 2 minutes of stirring, the aIr flow of 19 cubic feet/hour is started, with continued stirring, and a paddle rotation of 12 rpm is started.
Further water is added to maintain the water level.
The froth from the cell is skimmed by the paddle into a collection tray. The froth skimmed off is collected ak intervals of 0.5, 1.0, 2.0, 4.0 and 8.0 minutes. Each sample is dried overnight in a forced air oven at about 30 100C.
31~453-F . -15-.
The samples are weighed and analyzed for cop-per content by pl~sma emission spectroscopy.
The procedure for the analysis by plasma emissicn spectroscopy is as fol:Lows. Into a 100-cc flask is placed 0.2 to 0.25 g of ore sample (approxi-mately 2.0 g if it is a tailings sample, the ore left in the cell after flotation). To this is added 3.5 cc of concentrated hydrochloric acid and 5.0 cc of concen-trated nitric acid. The mixture is heated to boiling and boiled for 25 minutes, and then allowed to cool.
To this is added 25 cc of deionized water. The mi~ture is heated to boiling then allowed to cool. The mixture is filled to the volumetric line. A plasma emission spectrometer (Spectrospan IV~ is u6ed to determine the copper level in the solutions prepared. The copper emission line at 2135.98 nm is found to give a linear response with copper concentration. The instrument is standardized by the use o~ ~opper solution stardards.
When the sample solution is aspirated into the plasma, the concentration in ppm of Cu is shown by the ins~rument by digital display. This ppm of Cu i5 converted into percent Cu in the original sample by ~he following eguation:
25 % Cu in original sample = ((g~rPamsCU)(lamp~(lOO)d) x 100%
The percent recovery and rate are calculated by substituting the weight of the copper in each sample and the time each sample was taken into ~he eguation de~cribed hereinbefore.
31,453-F -16-,b~
0~ D O C0 CO N
~D ~ ~ ~ aD ~ O
u~ ~ o ~1 0 0 ~ ~1 0 0 O O O O O O O O
,~ rl O ~J) O ~
O O O O O O O O
a~
~ 1 . d~ 0 I
a~
~ 1 0 ~ ~ D O
I ~: O~ ~ ~
OOOO~oOo ~1 11~
O O O O O O O O
1 O O O O O O C~ O' hi O O 0 ~1 N N (N r~ ilO
a~ E
~ ~ ~ 0 o ,1 ,1 ,1 s~
o o o . . . ~ $ o X ~ 1 X ~ ~
O o o ~ ~ V
Z ~ ~n Z
U ~ u~ I P4 N
.~1 0 0 ,~ ~ ~ O rl ~`1 0 ~1 N ~1 ~ O C~
O N 1!~ ~ N N U) ~ V
O ~_ O P~
o~
~1 ~ ~1 0 C4 0~ O rl Nt~ 1 ~1~1 0 ~ ,~ I i I I
X ~I N X ~C N
~1 ~ c~
31, 453-F . -17--18~
Examples 8 to 15 demonstrate that the 1,3-oxa-thiolane-2-thiones demonstrate a recovery of greater than 85 percent, and that such recovery is comparable to the recoveries demonstrated by present co~mercial collectors.
31,453-~ -18-
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process of concentrating sulfide ores, which comprises subjecting a metal sulfide ore, in the form of a pulp, to a flo-tation process in the presence of a flotating amount of a flo-tation collector for the sulfides wherein the collector comprises a 1,3-oxathiolane-2-thione and recovering the desired metal sul-fide in the froth.
2. The process of claim 1 wherein the amount of the 1,3-oxathiolane-2-thione is between about 0.005 and 0.25 pound per ton of ore.
3. The process of claim 1 which further includes the use of a frother.
4. The process of claim 1 wherein the collector further comprises a xanthate, thiocarbamate, dithiophosphate, thiocar-banilide, xanthogen formate, alkylamine, quaternary ammonium compound, a sulfonate or a mixture thereof.
5. The process of claim 1 wherein the collector comprises 1,3-oxathiolane-2-thione, 5-methyl-1,3-oxathiolane-2-thione, 5-ethyl-1,3-oxathiolane-2-thione, 5-propyl-1,3-oxathiolane-2-thione, 5-butyl-1,3-oxathiolane-2-thione, 5-pentyl-1,3-oxathiolane-2-thione, 5-hexyl-1,3-oxathiolane-2-thione, 5-heptyl-1,3-oxathiolane-2-thione, 5-oxtyl-1,3-oxathiolane-2-thione, 5-nonyl-1,3-oxathio-lane-2-thione, 5-decyl-1,3-oxathiolane-2-thione, 5,5-dimethyl--1,3-oxathiolane-2-thione, 5,5-diethyl-1,3-oxathiolane-2-thione, 5,5-dipropyl-1,3-oxathiolane-2-thione, 5,5-dibutyl-1,3-oxathio-lane-2-thione, 5,5-dipentyl-1,3-oxathiolane-2-thione, 5,5-dihexyl-1,3-oxathiolane-2-thione, 5,5-diheptyl-1,3-oxathiolane-2-thione, 5,5-dioctyl-1,3-oxathiolane-2-thione, 5,5-c1illonyl-1,3-oxathio-lane-2-thione, 5,5-didecyl-1,3-oxathiolane-2-thione, 5-methyl-5-ethyl-1,3-oxathiolane-2-thione, 5-methyl-5-propyl-1,3-oxathio-lane-2-thione, 5-methyl-5-butyl-1,3-oxathiolane-2-thione, 5-methyl-5-pentyl-1,3-oxathiolane-2-thione, 5-methyl-5-hexyl-1,3-oxathiolane-2-thione, 5-ethyl-5-propyl-1,3-oxathiolane-2-thione, 5-ethyl-5-butyl-1,3-oxathiolane-2-thione, 5-ethyl-5-pentyl-1,3-oxathiolane-2-thione, 5-ethyl-5-hexyl-1,3-oxathiolane-2-thione, 5-propyl-5-butyl-1,3-oxathiolane-2-thione, 5-propyl-5-pentyl-1,3-oxathiolane-2-thione, 5-propyl-5-hexyl-1,3-oxathiolane-2-thione, 5-butyl-5-pentyl-1,3-oxathiolane-2-thione, 5-butyl-5-hexyl-1,3-oxathiolane-2-thione, 5-pentyl-5-hexyl-1,3-oxathiolane-2-thione or 5-phenyl-1,3-oxathiolane-2-thione or mixtures thereof.
6. The process of claim 1 wherein the collector comprises 5-butyl-1,3-oxathiolane-2-thione, 5-pentyl-1,3-oxathiolane-2-thione or 5-hexyl-1,3-oxathiolane-2-thione or mixtures thereof.
7. The process of claim 1 wherein the sulfide ore is a copper sulfide.
8. The process of claim 1 wherein the 1,3-oxathiolane-2-thione corresponds to the formula wherein R1, R2, R3, and R4 are separately in each occurrence hydrogen, a hydrocarbyl group or a hydrocarbyl group substituted with a halo, carbonylalkoxy, alkoxy, sulfide, mercapto, cyano, hydroxyl or nitro group.
9. The process of claim 8 wherein R1, R2, R3 and R4 are separately in each occurrence C1-20 hydrocarbyl or hydrogen.
10. The process of claim 9 wherein R1 is C1-20 alkyl or C1-20 aryl, and R2, R3 and R4 is hydrogen.
11. The process of claim 10 wherein R1 is C2-10 alkyl.
12. The process of claim 11 wherein R1 is C4-6 alkyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000462843A CA1212789A (en) | 1984-09-11 | 1984-09-11 | 1,3-oxatholane-2-thione as sulfide mineral collectors in froth flotation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000462843A CA1212789A (en) | 1984-09-11 | 1984-09-11 | 1,3-oxatholane-2-thione as sulfide mineral collectors in froth flotation |
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| Publication Number | Publication Date |
|---|---|
| CA1212789A true CA1212789A (en) | 1986-10-14 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114100863A (en) * | 2021-11-24 | 2022-03-01 | 中南大学 | Application of alpha-enol ketone in lead sulfide mineral flotation |
-
1984
- 1984-09-11 CA CA000462843A patent/CA1212789A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114100863A (en) * | 2021-11-24 | 2022-03-01 | 中南大学 | Application of alpha-enol ketone in lead sulfide mineral flotation |
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