Sulfur composition for ore froth flotation

Abstract

A composition for mineral flotation separation in ore is provided. The composition is thiol-based and comprises a) at least one thiol having the structure i) or ii), R1R2-CH-SH i) or R3-CH2-SH ii) or a combination thereof; b) one or more aromatic, aliphatic or polyalkylene oxide compounds. Another composition for mineral flotation separation in ore is also provided. The flotation composition is trithiocarbonate based and comprises d) at least one trithiocarbonate having the structure R1R2-CH-S-C (= S)-SH or a salt thereof; or a trithiocarbonate having the structure R3-CH2-S-C (= S)-SH, or a salt thereof; or a combination thereof; and b) one or more aromatic, aliphatic or polyalkylene oxide compounds. Methods of flotation separation of minerals in ore using these flotation compositions are also provided.

Description

Technical Field

[0001] The present invention relates to compositions and methods for the froth flotation separation of minerals in ores. Background Art

[0002] Froth flotation, or flotation, is a process for extracting metals from low-grade ores through a concentration stage that is carried out prior to subsequent processing, which includes heat treatment (also known as smelting) or leaching and refining. Especially in the case of oxide and / or sulfide ores of lead, zinc, copper, silver, gold, molybdenum, nickel, cobalt, iron, and platinum group metals, the platinum group metals include: platinum, palladium, rhodium, ruthenium, iridium, and osmium.

[0003] Flotation is a method of concentrating and separating valuable components in ores from unwanted components ("gangue") to produce mineral concentrates for pyrometallurgical or hydrometallurgical operations. The froth flotation process first crushes the ore into fine particles to provide separated particles of the desired ore and unwanted gangue components, and then the ore particles are foamed or "pulped" with water. Prior to the foaming process, the aqueous ore particles are combined with a flotation composition (also known as a flotation agent or collector or collecting agent), which contains appropriate additives. Based on their respective compositions, these flotation agents selectively render the surfaces of different types of particles hydrophobic and / or hydrophilic. The foaming process is achieved by introducing an air stream or inert gas bubbles into the aqueous composition of the ore and flotation agent (sometimes called a "slurry") in a flotation cell, and these bubbles attach to the already hydrophobic particles and suspend them. These suspended particles attach to the bubbles and then aggregate in a foam layer that flows over the weir of the flotation cell. Unwanted gangue may be unaffected by the flotation agent or become hydrophilic and sink to the bottom of the flotation cell.

[0004] As described above, froth flotation separates minerals by exploiting the hydrophobicity differences between minerals and gangue. By using surfactants and wetting agents, the hydrophobicity differences between valuable minerals and waste gangue are increased because surfactants and wetting agents have different effects on the various compounds in the crushed ore. The action of one or more flotation agents used promotes the adhesion of bubbles to the crystals. Then, the metal compound crystals rise to the surface and are recovered in the form of foam, also known as the flotation concentrate. Gangue particles are recovered at the lower part of the flotation cell.

[0005] Therefore, the flotation concentrate flowing over the weir at the top of the flotation cell contains a much higher content of the desired metal than the initial ore. This content depends on the initial content in the ore and the selectivity of the flotation agent composition.

[0006] After the filtration and drying stages, the flotation concentrate is fed into the heat treatment (or smelting) stage. This stage is typically a furnace where the temperature can exceed 1500 °C. At this stage, the desired metal is separated in the molten state from other substances, especially from the vein impurities originating from the ore, which must be removed in the form of slag.

[0007] US 4,211,644 discloses a collector composition for concentrating metal ores by froth flotation, which comprises a mixture of a mercaptan and an emulsifier or wetting agent adapted to improve the dispersion of the mercaptan in the slurry, and a method for concentrating metal ores by froth flotation, in which the above collector composition is used as a collector.

[0008] US 4,554,137 discloses a method for enriching minerals by flotation using a collector comprising a thio compound which is a straight-chain or branched dialkyl or dienyl polysulfide.

[0009] US 4,556,500 discloses a composition and method for recovering valuable zinc, molybdenum, copper, lead, iron (pyrite), and iron containing small amounts of gold or uranium (or both) from ores containing these mineral sulfides. The aqueous composition is an impure form of an alkali metal alkyl trithiocarbonate compound. The method comprises using the aqueous composition as a collector for the above minerals during ore recovery.

[0010] US 4,594,151 discloses a method for mineral flotation which consists of introducing a flotation collector in the form of a microemulsion composition into the mineral slurry to be treated. Generally, the collector is a sulfur-containing organic compound, especially a mercaptan, a thioether or a polysulfide, which are generally slightly soluble in water.

[0011] US 7,014,048 discloses a composition for ore flotation, which comprises a combination (A) of n-dodecyl mercaptan (or NDM) and tert-dodecyl mercaptan (or TDM), the weight ratio of NDM / TDM being from 0.5 to 1.5, and a product (B) consisting of one or more aromatic or aliphatic compounds containing from 4 to 100 carbon atoms and having one or two -OH groups.

[0012] US 9,527,090 discloses a method for recovering metals from ores using a collector composition. The method comprises contacting the ore with the collector composition. The collector composition comprises specific sulfur-containing compounds.

[0013] Therefore, it is very important to use a flotation agent which provides a flotation concentrate with a suitably high content of the desired metal to facilitate the subsequent treatment of the concentrate and the final separation of the metal. SUMMARY OF THE INVENTION

[0014] The inventors have discovered two compositions that can be used for the flotation separation of minerals in ores. These compositions are based on specific thiols (mercaptans) and / or trithiocarbonates. Thiols and trithiocarbonates, either alone or in combination with one or more aromatic, aliphatic or polyalkylene oxide compounds, exhibit desirable activity as flotation aids.

[0015] A composition for the flotation separation of minerals in ores is provided. The composition is thiol-based and comprises:

[0016] a) at least one thiol having structure i), or ii), or a combination thereof

[0017]

[0018] wherein R 1 and R 2 are each independently selected from branched or straight-chain C1-C23 alkyl groups, preferably C1-C18, more preferably C1-C15, most preferably C1-C10; and wherein R 3 is C6-C24, preferably C6-C20, more preferably C6-C16, most preferably C6-C14 branched alkyl; wherein the average number of carbon groups in the thiol of a) is from 6 to 24, preferably 6-19, more preferably 6-16, most preferably 6-14, and preferably a) is 2-butyl-1-octanethiol, 2-dodecanethiol and / or 2-ethyl-1-decanethiol; and

[0019] b) one or more aromatic, aliphatic or polyalkylene oxide compounds containing from 4 to 100 carbon atoms and having one or two -OH groups, preferably polypropylene glycol, pine oil, cresylic acid and / or methyl isobutyl carbinol.

[0020] Another composition for the flotation separation of minerals in ores is also provided. The flotation composition is trithiocarbonate-based and comprises:

[0021] d) at least one trithiocarbonate or its salt having the following structure

[0022] or a combination thereof,

[0023] wherein R 1 and R 2 are each independently selected from branched or straight-chain C1-C23 alkyl groups, preferably C1-C18, more preferably C1-C15, most preferably C1-C10, wherein the average number of carbon groups in the thiol of a) is from 6 to 24, preferably 6-19, more preferably 6-16, most preferably 6-14; and wherein R 3 is C6-C24, preferably C6-C20, more preferably C6-C16, most preferably C6-C14 branched alkyl; and

[0024] b) one or more aromatic, aliphatic or polyalkylene oxide compounds containing 4 to 100 carbon atoms and having one or two -OH groups.

[0025] Also provided is a method for flotation separation of minerals in ores. The method includes: introducing an effective amount of any of the above flotation compositions and the ore to be separated into a flotation cell; and flotation separating part or all of the ore into multiple minerals. Description of the Drawings

[0026] Figure 1 Shows the relationship between Cu recovery and flotation time obtained using Examples 1 - 3 in a Denver flotation machine;

[0027] Figure 2 Shows the relationship between molybdenum recovery and flotation time obtained using Examples 1 - 3 in a Denver flotation machine;

[0028] Figure 3 Shows the relationship between Fe recovery and flotation time obtained using Examples 1 - 3 in a Denver flotation machine;

[0029] Figure 4 Shows the relationship between Fe recovery and Fe grade for all examples; and

[0030] Figure 5 Shows the relationship between chalcopyrite recovery and pH in a Hallimond tube for Examples 4 and 6, and compares with experiments without using a collector. Detailed Description

[0031] It is well known that high molecular weight liquid thiols, such as N-dodecyl mercaptan (NDM) and tertiary dodecyl mercaptan (TDM), are used as collectors in the froth flotation of sulfide ores and have better recovery and selectivity for copper and molybdenum than iron and other gangue minerals. It is also recognized in the industry that due to molecular differences affecting the interaction with mineral particles and the fluidity in the flotation pulp, NDM and TDM exhibit different performances in flotation kinetics, total recovery and selectivity.

[0032] The present invention discloses collector formulations that include certain thiols and / or trithiocarbonates, which, either alone or in combination with one or more aromatic, aliphatic, or polyalkylene oxide compounds, significantly improve the recovery kinetics of copper and molybdenum relative to commercially available branched thiol TDM. Another benefit of these specific thiols and / or trithiocarbonates relative to TDM is the improved odor profile due to lower volatility. Additionally, blends of these specific thiols and / or trithiocarbonates with additional additives can provide different properties according to the requirements of different mineral compositions in mines worldwide. The blend can include other sulfur-containing collectors (such as xanthates, xanthates esters, dithiophosphates / esters, dithiophosphonites / esters, etc.), frothers (alcohols, diols, polyethylene glycols, etc.), and / or hydrocarbon blends (alkanes, alkenes, diesel, kerosene, etc.) used as diluents in the flotation separation process.

[0033] Specifically relevant to the present invention is the discovery that dioctyl sulfide or DOS (which can be di-N-octyl sulfide or N-octyl, sec-octyl sulfide) can be mixed with specific thiols and / or trithiocarbonates over a wide range of compositions to form a stable liquid product that retains the differential properties of the specific thiols and / or trithiocarbonates compared to NDM and TDM.

[0034] As briefly discussed above, two compositions for the flotation separation of ore minerals are disclosed herein. One composition is thiol-based and the other is trithiocarbonate-based. The thiol-based composition can include trithiocarbonates present in the trithiocarbonate composition. These two flotation compositions are related because the trithiocarbonate composition can be conveniently prepared by reacting the thiol-based composition with CS2 to form trithiocarbonates. According to certain embodiments, some or all of the thiols can be converted to similar trithiocarbonates. Thus, if all of the thiols in the thiol-based flotation composition are converted to similar trithiocarbonates, a trithiocarbonate flotation composition is produced. Of course, it is not necessary to directly prepare the trithiocarbonate-based flotation composition from the thiol-based composition - the trithiocarbonate-based composition can be prepared directly by combining suitable components.

[0035] Mercapto group flotation composition

[0036] A thiol-based composition for the flotation separation of minerals in ore is provided. The thiol-based composition includes:

[0037] a) at least one thiol having structure i) or ii), or a combination thereof

[0038]

[0039] wherein R 1 and R 2independently selected from branched or linear C1-C23 alkyl groups, preferably C1-C18, more preferably C1-C15, and most preferably C1-C10; and wherein R 3 is a C6-C24, preferably C6-C20, more preferably C6-C16, and most preferably C6-C14 branched alkyl group; wherein a) the average number of carbon groups in the mercaptan is 6 to 24, preferably 6-19, more preferably 6-16, and most preferably 6-14, and preferably a) is 2-butyl-1-octanethiol, 2-dodecanethiol, and / or 2-ethyl-1-decanethiol; and

[0040] b) one or more aromatic, aliphatic, or polyalkylene oxide compounds containing 4 to 100 carbon atoms and having one or two -OH groups, preferably polypropylene glycol, terpineol, cresylic acid, and / or methyl isobutyl carbinol.

[0041] According to one embodiment, the mercaptan-based flotation composition comprises 30-99, preferably 30-90, more preferably 30-70% by weight of a) at least one mercaptan having structure i) based on the total weight of the mercaptans in the composition.

[0042] According to one embodiment, the mercaptan-based flotation composition comprises 5-95, preferably 5-75, more preferably 40-75% by weight of a) at least one mercaptan having structure ii) based on the total weight of the mercaptans in the composition.

[0043] According to another embodiment, the mercaptan-based flotation composition comprises 1-35% by weight, preferably 10 to 30, more preferably 15 to 25 of b) one or more aromatic or aliphatic compounds containing 4 to 100 carbon atoms and having one or two -OH groups based on the total weight of the composition.

[0044] According to one embodiment, the mercaptan-based flotation composition further comprises c) at least one sulfide having the structure R 4 -S-R 5 wherein R

[0045] wherein R 4 and R 5 are independently selected from C1-C16, preferably C1-C14, more preferably C1-C12, and most preferably C1-C10 linear and branched alkyl groups, and wherein c) the average number of carbons in the sulfide is 10-24, preferably 12-22, more preferably 12-20, and most preferably 14-18.

[0046] According to one embodiment, the mercaptan-based flotation composition comprises 1-99% by weight, preferably 25 to 75, more preferably 40 to 60 of c) at least one sulfide, the total weight not including the weight of b) one or more aromatic or aliphatic compounds containing 4 to 100 carbon atoms and having one or two -OH groups.

[0047] According to one embodiment, the mercapto-based flotation composition further comprises d) at least one trithiocarbonate having the following structure or a salt thereof

[0048] or a combination thereof. If present in the mercapto-based flotation composition, the trithiocarbonate comprises 1-99% by weight, preferably 5-85% by weight, more preferably 5 to 50% by weight, and most preferably 5-25% by weight of d) at least one trithiocarbonate or a salt thereof, based on the total weight of the mercapto-based flotation composition, the total weight excluding the weight of b) one or more aromatic or aliphatic compounds having from 4 to 100 carbon atoms and having one or two -OH groups.

[0049] According to one embodiment, the mercapto-based composition further comprises e) at least one C6-C12 branched or straight-chain alkane and / or at least one C6-C14 branched or straight-chain alkene, preferably dodecane, dodecene and / or tetradecene.

[0050] Trithiocarbonate group flotation composition:

[0051] There is also provided another composition for the flotation separation of minerals in ores. The flotation composition is trithiocarbonate-based and comprises: d) at least one trithiocarbonate having the following structure or a salt thereof

[0052] or a combination thereof,

[0053] wherein R 1 and R 2 are each independently selected from branched or straight-chain C1-C23 alkyl groups, preferably C1-C18, more preferably C1-C15, most preferably C1-C10, wherein a) the average number of carbon groups in the mercaptan is from 6 to 24, preferably 6-19, more preferably 6-16, most preferably 6-14; and wherein R 3 is a C6-C24, preferably C6-C20, more preferably C6-C16, most preferably C6-C14 branched alkyl group; and

[0054] b) one or more aromatic, aliphatic or polyalkylene oxide compounds having from 4 to 100 carbon atoms and having one or two -OH groups.

[0055] According to one embodiment, the trithiocarbonate-based flotation composition may comprise 1-99% by weight, preferably 5-95, more preferably 10-90, most preferably 20-80 of d) at least one trithiocarbonate or a salt thereof, based on the total weight of the composition, the total weight excluding the weight of b) one or more aromatic or aliphatic compounds having from 4 to 100 carbon atoms and having one or two -OH groups.

[0056] According to another embodiment, the trithiocarbonate-based flotation composition may comprise b) one or more aromatic or aliphatic compounds containing from 4 to 100 carbon atoms and having one or two -OH groups, in an amount of 1-45% by weight, preferably 5-35% by weight, more preferably 10-30% by weight, and most preferably 15-25% by weight of the total weight of the composition.

[0057] According to one embodiment, the trithiocarbonate-based flotation composition may further comprise a) at least one mercaptan having structure i), or ii), or a combination thereof

[0058]

[0059] wherein R 1 and R 2 are each independently selected from branched or straight-chain C1-C23 alkyl groups, preferably C1-C18, more preferably C1-C15, and most preferably C1-C10, wherein the average number of carbon groups in a) the mercaptan is 6 to 24, preferably 6-19, more preferably 6-16, and most preferably 6-14, preferably 2-butyl-1-octanethiol, 2-dodecanethiol, and / or 2-ethyl-decanethiol; and wherein R 3 is a C6-C24, preferably C6-C20, more preferably C6-C16, and most preferably C6-C14 branched alkyl group. According to one embodiment, the trithiocarbonate-based flotation composition may comprise a) at least one mercaptan having structure i) in an amount of 30-99, preferably 30-90, more preferably 30-70% by weight of the total weight of the mercaptan in the composition. According to one embodiment, the trithiocarbonate-based flotation composition comprises a) at least one mercaptan having structure ii) in an amount of 5-95, preferably 5-75, more preferably 40-75% by weight of the total weight of the mercaptan in the composition.

[0060] According to one embodiment, the trithiocarbonate-based flotation composition may further comprise c) at least one sulfide having the structure R 4 -S-R 5 wherein R 4 and R 5 are each independently selected from C1-C16, preferably C1-C14, more preferably C1-C12, and most preferably C1-C10 straight-chain and branched alkyl groups, wherein the average number of carbon atoms in c) the sulfide is 10-25, preferably 12-23, more preferably 12-21, and most preferably 14-19. According to one embodiment, the trithiocarbonate-based flotation composition may comprise 1-99% by weight of the total weight of the composition

[0061] %, preferably 20 - 80, more preferably 30 - 70, most preferably 40 - 60 of c) at least one sulfide, the total weight not including the weight of b) one or more aromatic or aliphatic compounds having from 4 to 100 carbon atoms and having one or two -OH groups.

[0062] According to one embodiment, the trithiocarbonate may further comprise: f) at least one C6 - C12 branched or straight-chain alkane and / or at least one C6 - C14 branched or straight-chain alkene, preferably dodecane, dodecene and / or tetradecene.

[0063] a) Mercaptans:

[0064] The mercaptans that can be used in the flotation composition of the present disclosure have the following structures:

[0065] i) or ii), or a combination thereof

[0066] wherein R 1 and R 2 are each independently selected from branched or straight-chain C1 - C23 alkyl groups, preferably C1 - C18, more preferably C1 - C15, most preferably C1 - C10, wherein the average number of carbon groups in a) the mercaptan is from 6 to 24, preferably 6 - 19, more preferably 6 - 16, most preferably 6 - 14, preferably 2-butyl-1-octanethiol, 2-dodecanethiol and / or 2-ethyl-1-decanethiol; and wherein R 3 is C6 - C24, preferably C6 - C20, more preferably C6 - C16, most preferably C6 - C14 branched alkyl.

[0067] For example, R 1 can be methyl or ethyl, or can be a straight-chain or branched C3, C4, C5, C6, C7, C8, C8, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22 or C23 alkyl. R 2 can be methyl or ethyl, or can be a straight-chain or branched C3, C4, C5, C6, C7, C8, C8, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22 or C23 alkyl. R 3It may be a straight-chain or branched C6, C7, C8, C8, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22 or C23 alkyl group. a) The average number of carbons in the mercaptan may be at least 6, 7, 8, 9, 10, 11, 12, 13, 14 or at least 16. a) The average number of carbons in the mercaptan is at most 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12 or 11. According to one embodiment, the mercaptan a) preferably comprises at least one of 2-butyl-1-octanethiol, 2-dodecanethiol, 2-ethyl-1-decanethiol, or a combination thereof. According to one embodiment, the mercaptan may further include 3-dodecanethiol, 4-dodecanethiol, 5-dodecanethiol and / or 6-dodecanethiol.

[0068] According to some embodiments, the mercaptan a) does not include NDM (n-dodecyl mercaptan) or TDM (tert-dodecyl mercaptan), although the mercaptan-based flotation composition or the trithiocarbonate-based flotation composition may optionally contain one or both of NDM and TDM in addition to the mercaptan a).

[0069] b) Aromatic, aliphatic or polyalkylene oxide compounds

[0070] The aromatic, aliphatic or polyalkylene oxide compound may comprise at least one phenol, cresol, naphthol, xylenol, indanol or a mixture of these compounds optionally substituted by one or more C1-C4 alkyl groups. Also suitable are polypropylene glycols (weight average molecular weight from 100 to 1,000 g / mol), diols, alcohols, which compounds may contain one or two -OH groups. The polyalkylene oxide compound may comprise one or more propylene oxide oligomers having a weight average molecular weight of 50 to 2,000, preferably 100 to 800; and / or 2-methyl-4-pentanol (also known as methyl isobutyl carbinol or MIBC), having the formula: CH3-CH(OH)-CH2-CH(CH3)-CH3 or may comprise polypropylene glycol.

[0071] c) Sulfide

[0072] c) The structure of the sulfide compound is R 4 -S-R 5 where R 4 and R 5 are each independently selected from C1-C16, preferably C1-C14, more preferably C1-C12, most preferably C1-C10 straight-chain and branched alkyl groups, where the average number of carbons in the sulfide c) is 10-24, preferably 12-22, more preferably 12-20, most preferably 14-18. For example, R 1 and / or R 2It can be methyl, ethyl, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15 or C16 branched or linear alkyl groups. c) The average number of carbons in the sulfide can be at least 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbons. c) The average number of carbons in the sulfide can be at most 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13 or 12 carbons. c) The sulfide can be dioctyl sulfide, dinonyl sulfide or didecyl sulfide.

[0073] d) Trithiocarbonate

[0074] d) The structure of trithiocarbonate is:

[0075] or its salt, or or its salt; or a combination thereof,

[0076] wherein R 1 and R 2 are each independently selected from branched or linear C1-C23 alkyl groups, preferably C1-C18, more preferably C1-C15, most preferably C1-C10, wherein d) the average number of carbon groups in the trithiocarbonate is from 6 to 24, preferably 6-19, more preferably 6-16, most preferably 6-14; and wherein R 3 is C6-C24, preferably C6-C20, more preferably C6-C16, most preferably C6-C14 branched alkyl. For example, R 1 can be methyl or ethyl, or can be linear or branched C3, C4, C5, C6, C7, C8, C8, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22 or C23 alkyl. R 2 can be methyl or ethyl, or can be linear or branched C3, C4, C5, C6, C7, C8, C8, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22 or C23 alkyl. R 3It may be a linear or branched C6, C7, C8, C8, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22 or C23 alkyl group. d) The average number of carbons in the trithiocarbonate may be at least 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or at least 17. d) The average number of carbons in the trithiocarbonate is at most 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12 or 11. The d) trithiocarbonate may be in the form of a salt. If the d) trithiocarbonate is in the form of a salt, non-limiting examples of suitable counterions include Na + , Li + , K + , Rb + , Mg 2+ , Ca 2+ , Ba 2+ , guanidine CN3H6 + , tetramethylammonium C4NH 12 + or ammonium ion NH4 + . Preferably Na + and K + .

[0077] e) Branched or linear alkanes or alkenes

[0078] The e) branched or linear alkane or alkene may contain at least one C6-C12 branched or linear alkane and / or at least one C6-C14 branched or linear alkene, preferably dodecane, dodecene and / or tetradecane. For example, the branched or linear alkane may be a C6, C7, C8, C9, C10, C11 or C12 alkane. For example, the branched or linear alkene may be a C6, C7, C8, C9, C10, C11 or C12 alkene. The branched or linear alkene may contain at least one or more degrees of unsaturation. The branched or linear alkane or alkene may contain dodecene (1-10 wt%), dodecane (1-10 wt%) and / or tetradecene (1-10 wt%).

[0079] Additional collector:

[0080] According to some embodiments, the mercapto-based flotation composition or the trithiocarbonate-based flotation composition may further comprise one or more additional collectors. Optional additional collectors may include, for example, one or more of xanthates, xanthates esters, formate / xanthate esters, dithiophosphates / esters, monothiophosphates / esters, dithiophosphinates / esters, dithiocarbamates / esters, mercaptobenzothiazole, polysulfides, or thiocarbamates / esters. Non-limiting examples of specific compounds are ethyl xanthate, butyl xanthate, sodium isobutyl xanthate, sodium diethyldithiophosphate, potassium diisobutyldithiophosphate, potassium di-sec-butyldithiophosphate, diisobutyl monothiophosphate, sodium diisobutyldithiophosphinate, potassium n-decyldithiocarbamate, and O-isopropyl thiocarbamate.

[0081] According to some embodiments, optional additional collectors may include mercaptans different from mercaptan a), such as NDM (n-dodecyl mercaptan) or TDM (tert-dodecyl mercaptan).

[0082] Method :

[0083] A method for the flotation separation of minerals in an ore is provided. The method includes: introducing an effective amount of a mercapto-based flotation composition and the ore to be separated into a flotation cell; and flotation separating some or all of the ore into multiple minerals.

[0084] Another method for the flotation separation of minerals in an ore is also provided. The method includes: introducing an effective amount of a trithiocarbonate-based flotation composition and the ore to be separated into a flotation cell; and flotation separating some or all of the ore into multiple minerals.

[0085] Non-limiting examples of minerals that can be separated using the mercapto-based or trithiocarbonate-based compositions disclosed herein are to recover as much Cu and Mo as possible while selectively separating Fe (and other non-metallic minerals such as carbonates, silicates, etc.). Mo is usually different from other minerals. In addition, Au or Cu-Au and Ag-Au minerals can be recovered separately while selectively separating Fe and other very valuable minerals. When Mo and Au are present together with Cu or Ag, the main targets are Mo and Au. The flotation compositions disclosed herein can be used to separate Cu-Mo and / or Cu-Au and / or Au-Mo and / or Ag-Au ores. Non-limiting examples of ores that can be separated using the flotation composition are chalcopyrite, chalcocite, bornite, and molybdenite.

[0086] Certain non-limiting aspects of the present invention can be summarized as follows.

[0087] Aspect 1: A composition for the flotation separation of minerals in an ore, comprising:

[0088] a) At least one thiol having structure i), or ii), or a combination thereof

[0089]

[0090] wherein R 1 and R 2 are each independently selected from branched or linear C1-C23 alkyl groups, preferably C1-C18, more preferably C1-C15, and most preferably C1-C10; and wherein R 3 is a C6-C24, preferably C6-C20, more preferably C6-C16, and most preferably C6-C14 branched alkyl group; wherein the average number of carbon groups in the thiol of a) is from 6 to 24, preferably 6-19, more preferably 6-16, and most preferably 6-14, and preferably a) is 2-butyl-1-octanethiol, 2-dodecanethiol, and / or 2-ethyl-1-decanethiol;

[0091] b) One or more aromatic, aliphatic, or polyalkylene oxide compounds containing from 4 to 100 carbon atoms and having one or two -OH groups, preferably polypropylene glycol, terpineol, cresylic acid, and / or methyl isobutyl carbinol; and

[0092] Optionally, one or more additional collectors different from at least one thiol of a), which include at least one of xanthates, xanthates esters, formate / xanthate esters, dithiophosphates / esters, monothiophosphates / esters, dithiophosphinates / esters, dithiocarbamates / esters, mercaptobenzothiazole, polysulfides, thiocarbamates / esters, NDM (n-dodecyl mercaptan), or TDM (tert-dodecyl mercaptan).

[0093] Aspect 2: The composition according to aspect 1, further comprising:

[0094] c) at least one sulfide having the structure R 4 -S-R 5 wherein R

[0095] and R 4 and R 5 are each independently selected from C1-C16, preferably C1-C14, more preferably C1-C12, and most preferably C1-C10 linear and branched alkyl groups, and wherein the average number of carbon atoms in the sulfide of c) is 10-24, preferably 12-22, more preferably 12-20, and most preferably 14-18.

[0096] Aspect 3: The composition according to aspect 1 or aspect 2, further comprising:

[0097] d) at least one trithiocarbonate or its salt having the following structure

[0098] or a combination thereof.

[0099] Aspect 4: The composition according to any one of aspects 1-3, further comprising e) at least one C6-C12 branched or straight-chain alkane and / or at least one C6-C14 branched or straight-chain alkene, preferably dodecane, dodecene, and / or tetradecene.

[0100] Aspect 5: The composition according to any one of aspects 1-4, comprising 30-99, preferably 30-90, more preferably 30-70% by weight of a) at least one mercaptan having structure i) based on the total weight of the mercaptans in the composition.

[0101] Aspect 6: The composition according to any one of aspects 1-5, comprising 1-25% by weight of b) one or more aromatic or aliphatic compounds containing 4 to 100 carbon atoms and having one or two -OH groups based on the total weight of the composition.

[0102] Aspect 7: The composition according to any one of aspects 2-6, comprising 1-99% by weight of c) at least one sulfide, the total weight not including the weight of b) one or more aromatic or aliphatic compounds containing 4 to 100 carbon atoms and having one or two -OH groups.

[0103] Aspect 8: The composition according to any one of aspects 3-7, comprising 1-99% by weight of d) at least one trithiocarbonate or its salt, the total weight not including the weight of b) one or more aromatic or aliphatic compounds containing 4 to 100 carbon atoms and having one or two -OH groups.

[0104] Aspect 9: The composition according to any one of aspects 4-8, comprising 5-95, preferably 5-75, more preferably 40-75% by weight of a) at least one mercaptan having structure ii) based on the total weight of the mercaptans in the composition.

[0105] Aspect 10: A method for the flotation separation of minerals in an ore, comprising:

[0106] introducing an effective amount of the composition according to any one of aspects 1-9 and the ore to be separated into a flotation cell; and

[0107] flotation-separating some or all of the ore into multiple minerals.

[0108] Aspect 11: A composition for the flotation separation of minerals in an ore, comprising:

[0109] d) at least one trithiocarbonate or its salt having the following structure

[0110] or a combination thereof.

[0111] wherein R 1 and R 2 are each independently selected from branched or linear C1-C23 alkyl groups, preferably C1-C18, more preferably C1-C15, most preferably C1-C10, wherein a) the average number of carbon groups in the thiol is from 6 to 25, preferably 6-20, more preferably 6-17, most preferably 6-15; and wherein R 3 is C6-C24, preferably C6-C20, more preferably C6-C16, most preferably C6-C14 branched alkyl;

[0112] b) one or more aromatic, aliphatic or polyalkylene oxide compounds having from 4 to 100 carbon atoms and having one or two -OH groups; and

[0113] optionally, one or more additional collectors comprising at least one of xanthates, xanthates esters, formate / xanthate esters, dithiophosphates / esters, monothiophosphates / esters, dithiophosphinates / esters, dithiocarbamates / esters, mercaptobenzothiazole, polysulfides, thiocarbamates / esters, NDM (n-dodecyl mercaptan) or TDM (tert-dodecyl mercaptan).

[0114] Aspect 12: The composition according to aspect 11, further comprising:

[0115] c) at least one sulfide having the structure R 4 -S-R 5 wherein R

[0116] and R 4 and R 5 are each independently selected from C1-C16, preferably C1-C14, more preferably C1-C12, most preferably C1-C10 linear and branched alkyl groups, wherein c) the average number of carbon atoms in the sulfide is from 10 to 24, preferably 12 to 22, more preferably 12 to 20, most preferably 14 to 18.

[0117] Aspect 13: The composition according to aspect 11 or aspect 12, further comprising:

[0118] a) at least one thiol having the structure i), or ii), or a combination thereof

[0119]

[0120] wherein R 1 and R 2Selected independently from branched or linear C1-C23 alkyl groups, preferably C1-C18, more preferably C1-C15, most preferably C1-C10, wherein a) the average number of carbon groups in the mercaptan is from 6 to 24, preferably 6-19, more preferably 6-16, most preferably 6-14, preferably 2-butyl-1-octanethiol, 2-dodecanethiol and / or 2-ethyl-1-decanethiol; and wherein R 3 is a C6-C24, preferably C6-C20, more preferably C6-C16, most preferably C6-C14 branched alkyl group.

[0121] Aspect 14: A composition according to any one of aspects 11-13, further comprising e) at least one C6-C12 branched or linear alkane and / or at least one C6-C14 branched or linear alkene, preferably dodecane, dodecene and / or tetradecene.

[0122] Aspect 15: A composition according to any one of aspects 11-14, comprising b) one or more aromatic or aliphatic compounds having from 4 to 100 carbon atoms and one or two -OH groups, in an amount of 1-25% by weight of the total weight of the composition.

[0123] Aspect 16: A composition according to any one of aspects 12-15, comprising c) at least one sulfide in an amount of 1-99% by weight of the total weight of the composition, the total weight not including the weight of b) one or more aromatic or aliphatic compounds having from 4 to 100 carbon atoms and one or two -OH groups.

[0124] Aspect 17: A composition according to any one of aspects 11-16, comprising d) at least one trithiocarbonate or a salt thereof in an amount of 1-99% by weight of the total weight of the composition, the total weight not including the weight of b) one or more aromatic or aliphatic compounds having from 4 to 100 carbon atoms and one or two -OH groups.

[0125] Aspect 18: A composition according to any one of aspects 13-17, comprising a) at least one mercaptan having structure i) in an amount of 30-99, preferably 30-90, more preferably 30-70% by weight of the total weight of the mercaptans in the composition.

[0126] Aspect 19: A composition according to any one of aspects 13-18, comprising a) a mercaptan having structure ii) in an amount of 5-95, preferably 5-75, more preferably 40-75% by weight of the total weight of the mercaptans in the composition.

[0127] Aspect 20: A method for the flotation separation of minerals in ores, comprising:

[0128] Introduce an effective amount of the composition as described in any one of aspects 11 - 19 and the ore to be separated into a flotation cell; and

[0129] Float at least a portion of the ore to separate it into multiple minerals.

[0130] In this specification, the embodiments have been described in a manner that enables a clear and concise description. However, it is intended and should be understood that the embodiments can be combined or separated in various ways without departing from the present disclosure. For example, it should be understood that all the preferred features described herein apply to all aspects of the invention described herein.

[0131] In some embodiments, the invention herein can be construed as not including any element or process step that does not materially affect the basic and novel characteristics of the composition, the method of manufacturing the composition, the method of using the composition, and the article prepared from the composition. Additionally, in some embodiments, the invention can be construed as not including any element or method not specified herein.

[0132] Although the present invention has been shown and described with reference to specific embodiments, the present invention is not intended to be limited to the details shown. Instead, various modifications can be made in the details within the scope of equivalents of the claims without departing from the present invention.

[0133] Examples

[0134] The following experiments were conducted in a 2.5 L Denver - type flotation cell. These experiments were carried out with different formulations to evaluate the effect of mixtures of thiols (2 - butyl - 1 - octanethiol, 2 - dodecanethiol, and 2 - ethyl - 1 - decanethiol), hydrocarbons (branched or straight - chain alkanes or alkenes containing 8 to 14 carbon atoms), and monosulfides (containing 16 to 28 carbon atoms) according to the present invention on the recovery performance of minerals rich in copper (Cu), molybdenum (Mo), and iron (Fe). As shown in Table 1, two comparative examples (Examples 1 and 2) and three examples of the present invention (Examples 3 - 5) were tested. Examples 1 and 2 used commercially available thiol products NDM (n - dodecyl mercaptan) and TDM (tert - dodecyl mercaptan) well - known in the art. Example 3 contained a higher amount of a mixture of 2 - butyl - 1 - octanethiol, 2 - dodecanethiol, and 2 - ethyl - 1 - decanethiol, a lower amount of hydrocarbon, and an appropriate amount of monosulfide. Example 4 contained a mixture of 2 - butyl - 1 - octanethiol, 2 - dodecanethiol, and 2 - ethyl - 1 - decanethiol and had the highest hydrocarbon content, and Example 5 contained a mixture of 2 - butyl - 1 - octanethiol, 2 - dodecanethiol, and 2 - ethyl - 1 - decanethiol and had the highest monosulfide content. Table 2 shows the amounts of each thiol component in Examples 3 - 5. The hydrocarbon component in the examples was dodecane and dodecene.

[0135] Table 1: Composition of Examples 1 - 5

[0136]

[0137] Table 2: Mixture of mercaptans in Examples 3 - 5

[0138]

[0139]

[0140] During the flotation process, in the presence of kerosene and lime (to maintain a pH of 11.2), 700 g of ore in 460 ml of water was ground in a rod mill for 30 minutes. Then the slurry was transferred from the mill to a 2.5 L flotation cell for testing. The examples of the present invention were added to the flotation cell in a formulation containing 20% polypropylene glycol (PPG), and the weight - average molecular weight of the PPG was 425 g / mol. After 3 minutes of conditioning, additional PPG was added as a foaming agent before starting to collect the experiment, and it was collected for 12 minutes. The total amount of reagents used in the flotation experiment is shown in Table 3.

[0141] Table 3: Froth flotation reagents used in flotation machine experiments

[0142]

[0143] The results are as Figures 1 - 3 shown, which shows the relationship curves of metal recovery vs. flotation time for commercially available NDM (Example 1), commercially available TDM (Example 2), and blended mercaptans (Example 3). It can be seen from these figures that although the recoveries of Cu and Mo for all mercaptans are similar, the selectivity for Fe follows an obvious trend: the total recovery and kinetics of the TDM product are the highest, while the NDM product is the lowest. Interestingly, the blended mercaptan product of the present invention has differentiated performance between the two commercial products. Figure 4 The relationship between Fe recovery and Fe grade for all examples is shown, and it can be clearly seen that the formulations containing the blended mercaptans of the present invention all fall on the same line, and their performance is between NDM and TDM.

[0144] Finally, a formulation containing more than 50% monosulfide (Example 6) was tested as a collector for chalcopyrite (CuFeS2) using a Hallimond tube flotation device. This example was compared with Example 4 to test how a large amount of monosulfide would affect the performance. As Figure 5 shown, the performance of Example 6 is comparable to that of Example 4 and is better than the experiment without a collector.

[0145] Table 4: Composition of Example 6

[0146] Example 6 (wt%) Hydrocarbon 3.67 Mixed mercaptans (Table 2) 37.75 NDM 3.75 Other mercaptans 3.09 Di-n-octyl sulfide 50.0 Other monosulfides 1.67 Disulfide 0.10

Claims

1. A composition for the flotation separation of minerals in ores, comprising: a) at least one mercaptan having structure i), or ii), or a combination thereof R 1 R 2 -CH-SH i) or R 3 -CH2-SH ii) wherein R 1 and R 2 are each independently selected from branched or straight-chain C1-C23 alkyl groups, preferably C1-C18, more preferably C1-C15, most preferably C1-C10; and wherein R 3 is a C6-C24, preferably C6-C20, more preferably C6-C16, most preferably C6-C14 branched alkyl group; wherein a) the average number of carbon groups in the mercaptan is from 6 to 24, preferably 6-19, more preferably 6-16, most preferably 6-14, and preferably a) is 2-butyl-1-octanethiol, 2-dodecanethiol and / or 2-ethyl-1-decanethiol; b) one or more aromatic, aliphatic or polyalkylene oxide compounds containing 4 to 100 carbon atoms and having one or two -OH groups, preferably polypropylene glycol, pine oil, cresylic acid and / or methyl isobutyl carbinol; and Optionally, one or more additional collectors different from at least one mercaptan a), including at least one of xanthates, xanthates, formate / xanthates, dithiophosphates / esters, monothiophosphates / esters, dithiophosphinates / esters, dithiocarbamates / esters, mercaptobenzothiazole, polysulfides, thiocarbamates / esters, NDM (n-dodecyl mercaptan) or TDM (tert-dodecyl mercaptan).

2. The composition according to claim 1, further comprising: c) at least one sulfide having the structure R 4 -S-R 5 and wherein R 4 and R 5 are each independently selected from C1-C16, preferably C1-C14, more preferably C1-C12, and most preferably C1-C10 straight-chain and branched alkyl groups, where c) the average number of carbon atoms in the sulfide is from 10 to 24, preferably from 12 to 22, more preferably from 12 to 20, and most preferably from 14 to 18.

3. The composition according to claim 1 or claim 2, further comprising: d) at least one trithiocarbonate having the following structure or a salt thereof or a combination thereof.

4. The composition according to any one of claims 1-3, further comprising e) at least one C6-C12 branched or straight-chain alkane and / or at least one C6-C14 branched or straight-chain alkene, preferably dodecane, dodecene and / or tetradecene.

5. The composition according to any one of claims 1-4, comprising a) at least one mercaptan having structure i) in an amount of 30-99, preferably 30-90, more preferably 30-70% by weight of the total weight of mercaptans in the composition.

6. The composition according to any one of claims 1-5, comprising b) one or more aromatic or aliphatic compounds containing 4 to 100 carbon atoms and having one or two -OH groups in an amount of 1-25% by weight of the total weight of the composition.

7. The composition according to any one of claims 2-6, comprising c) at least one sulfide in an amount of 1-99% by weight of the total weight of the composition, the total weight not including the weight of b) one or more aromatic or aliphatic compounds containing 4 to 100 carbon atoms and having one or two -OH groups.

8. The composition according to any one of claims 3-7, comprising d) at least one trithiocarbonate or a salt thereof in an amount of 1-99% by weight of the total weight of the composition, the total weight not including the weight of b) one or more aromatic or aliphatic compounds containing 4 to 100 carbon atoms and having one or two -OH groups.

9. The composition according to any one of claims 4-8, comprising a) at least one mercaptan having structure ii) in an amount of 5-95, preferably 5-75, more preferably 40-75% by weight of the total weight of mercaptans in the composition.

10. A method for the flotation separation of minerals in ores, comprising: introducing an effective amount of the composition according to any one of claims 1-9 and the ore to be separated into a flotation cell; and flotation separating part or all of the ore into various minerals.

11. A composition for the flotation separation of minerals in ores, comprising: d) at least one trithiocarbonate having the following structure or a salt thereof or a combination thereof. wherein R 1 and R 2 are each independently selected from branched or straight-chain C1-C23 alkyl groups, preferably C1-C18, more preferably C1-C15, most preferably C1-C10, wherein a) the average number of carbon groups in the thiol is from 6 to 25, preferably 6-20, more preferably 6-17, most preferably 6-15; and wherein R 3 is a C6-C24, preferably C6-C20, more preferably C6-C16, most preferably C6-C14 branched alkyl group; b) one or more aromatic, aliphatic or polyalkylene oxide compounds containing 4 to 100 carbon atoms and having one or two -OH groups; and Optionally, one or more additional collectors, including at least one of xanthate, xanthate ester, formate / xanthate ester, dithiophosphate / ester, monothiophosphate / ester, dithiophosphinate / ester, dithiocarbamate / ester, mercaptobenzothiazole, polysulfide, thiocarbamate / ester, NDM (n-dodecyl mercaptan) or TDM (tert-dodecyl mercaptan).

12. The composition according to claim 11, further comprising: c) at least one sulfide having the structure R 4 -S-R 5 ​ wherein R 4 and R 5 are each independently selected from C1-C16, preferably C1-C14, more preferably C1-C12, and most preferably C1-C10 straight-chain and branched alkyl groups, wherein c) the average number of carbon atoms in the sulfide is from 10 to 24, preferably from 12 to 22, more preferably from 12 to 20, and most preferably from 14 to 18.

13. The composition according to claim 11 or claim 12, further comprising: a) at least one thiol having structure i), or ii), or a combination thereof Wherein R 1 and R 2 are each independently selected from branched or straight-chain C1-C23 alkyl groups, preferably C1-C18, more preferably C1-C15, most preferably C1-C10, wherein a) the average number of carbon groups in the mercaptan is from 6 to 24, preferably 6-19, more preferably 6-16, most preferably 6-14, and preferably 2-butyl-1-octanethiol, 2-dodecanethiol, and / or 2-ethyl-1-decanethiol; and wherein R 3 is a C6-C24, preferably C6-C20, more preferably C6-C16, most preferably C6-C14 branched alkyl group.

14. The composition according to any one of claims 11-13, further comprising e) at least one C6-C12 branched or straight-chain alkane and / or at least one C6-C14 branched or straight-chain alkene, preferably dodecane, dodecene and / or tetradecene.

15. The composition according to any one of claims 11-14, comprising b) one or more aromatic or aliphatic compounds containing 4 to 100 carbon atoms and having one or two -OH groups, accounting for 1-25% by weight of the total weight of the composition.

16. The composition according to any one of claims 12-15, comprising c) at least one sulfide, accounting for 1-99% by weight of the total weight of the composition, the total weight not including the weight of b) one or more aromatic or aliphatic compounds containing 4 to 100 carbon atoms and having one or two -OH groups.

17. The composition according to any one of claims 11-16, comprising d) at least one trithiocarbonate or its salt, accounting for 1-99% by weight of the total weight of the composition, the total weight not including the weight of b) one or more aromatic or aliphatic compounds containing 4 to 100 carbon atoms and having one or two -OH groups.

18. The composition according to any one of claims 13-17, comprising a) at least one thiol having structure i), accounting for 30-99, preferably 30-90, more preferably 30-70% by weight of the total weight of thiols in the composition.

19. The composition according to any one of claims 13-18, comprising a) a thiol having structure ii), accounting for 5-95, preferably 5-75, more preferably 40-75% by weight of the total weight of thiols in the composition.

20. A method for the flotation separation of minerals in ores, comprising: introducing an effective amount of the composition according to any one of claims 11-19 and the ore to be separated into a flotation cell; and flotation-separating part or all of the ore into various minerals.

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