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WO2018191179A1 - Nouveaux réactifs collecteurs d'exploitation minière - Google Patents

Nouveaux réactifs collecteurs d'exploitation minière Download PDF

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WO2018191179A1
WO2018191179A1 PCT/US2018/026738 US2018026738W WO2018191179A1 WO 2018191179 A1 WO2018191179 A1 WO 2018191179A1 US 2018026738 W US2018026738 W US 2018026738W WO 2018191179 A1 WO2018191179 A1 WO 2018191179A1
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asphalt emulsifier
amines
cooh
synthesis
collectors
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Thomas P. Daly
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
    • C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/0046—Organic compounds containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/01—Organic compounds containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/01—Organic compounds containing nitrogen
    • B03D1/011—Quaternary ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/012—Organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/42—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having etherified hydroxy groups and at least two amino groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/50—Ethers of hydroxy amines of undetermined structure, e.g. obtained by reactions of epoxides with hydroxy amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
    • C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
    • C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/02—Monothiocarbamic acids; Derivatives thereof
    • C07C333/04—Monothiocarbamic acids; Derivatives thereof having nitrogen atoms of thiocarbamic groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/06—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • C07F9/3817—Acids containing the structure (RX)2P(=X)-alk-N...P (X = O, S, Se)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/14—Flotation machines
    • B03D1/1431—Dissolved air flotation machines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors

Definitions

  • the present invention relates to the field of amine mining collectors and more particularly to a class of ether amines.
  • the present invention relates to the field of amine mining collectors that improve the yield of ore concentration.
  • the use of amines with sufficient water solubility, that form strong water insoluble complexes with the desired mineral, and not with competing minerals results in a higher yield of the desired minerals.
  • the family of amine, xanthate and dithiocarbamate collectors of the present invention does just that.
  • Fig. 1 shows the synthesis of novel ether amine cationic mineral collectors.
  • Fig. 2 shows the synthesis of novel anionic mineral collectors.
  • Fig. 3 shows the synthesis of derivatives of the cationic collectors.
  • Fig. 4 shows the synthesis of tertiary amine derivatives.
  • Fig. 5 shows the synthesis of polyprimary amines.
  • Fig. 6 shows the synthesis of secondary amines and derivatives.
  • Fig. 7 shows the synthesis of highly branched primary ether amines.
  • Fig. 8 - 9 show the synthesis of betaines and polybetaines.
  • Fig. 10 shows the synthesis of various sulfur derivatives.
  • Fig. 11 shows the synthesis of amides and imidazoline analogs.
  • Figs. 12-13 show the synthesis of a mineral collectors with higher hydrophobicity.
  • Fig. 14 shows the synthesis of amines via direct amination.
  • Fig. 15 shows the synthesis of the analogous betaines and polybetaines of
  • the non target components of the dirt / ore mixture are left to settle to the bottom of the floatation ponds, thus concentrating the desired minerals to an extent that they can then enter the next processing steps, be it reduction, purification or other processing steps.
  • the present invention utilizes alkoxylates as the backbone of the collector.
  • alkoxylates as the backbone of the collector.
  • side chains on the collector and the chain length either though increasing the number of repeating units, or by utilizing different chain length or conformations of alcohols to initiate the alkoxylation adjustments to the water solubility frothing potential and density of the mineral- collector complex can be made. These adjustments allow for the optimization of the collector, by increasing the yield of the target mineral and reducing the collection of non-target minerals, such as silicates.
  • Figure 1 shows the synthesis of primary amine and diamine collectors.
  • the diamines may continue to be sequentially, cyanoethylated to make higher polyamines, such as triamines, tetramines and higher.
  • Water is typical used to make polyalkoxylates.
  • the resulting polyalkoxylates have 2 terminal hydroxyls and can react with 2 moles of acrylonitrile to form the di-primary amine.
  • diols and polyols such as resorcinol, glycerin, neopentyl glycol, and pentaerythritol produce multiple hydroxyls and the analogous products can be formed.
  • a monohydric alcohol such as methanol, ethanol, propanol or butanol results in a polyalkoxylate with just one terminal hydroxyl to react the acrylonitrile with, resulting in a primary amine collector.
  • Utilizing higher carbon number alcohols reduces the water solubility of both the collector and the collector-mineral complex.
  • Non-linear alcohols like phenol, cylcohexanol, isopropanol, or t-butanol reduces the pour point for easier handling in cold climates.
  • a diamine can also be formed by reacting the previously formed primary amine with an additional mole of acrylonitrile, which is then reduced to form the diamine. This same addition can be done with the primary diamines to yield di-(diamines).
  • the Michael Addition of acrylonitrile to the alcohol and the amine is well known, as is the reduction of the nitrile to the amine with sponge nickel or other sponge metals, either promoted or not, with hydrogen. The reduction typically takes place at a pressure between 400 to 800 psi at less than 40 C over 4 to 12 hours.
  • the Michael Addition is typically done by adding acrylonitrile to the alcohol or amine at ambient temperature with cooling at such a rate as to maintain temperature.
  • Figure 2 shows the synthesis of the anionic analogs of the collectors in Figure 1 .
  • the xanthates and dithiocarbamates may be made from the diamines.
  • the anionic collectors are typically used in sulfide ores. The same solubility trends apply to the anionics as to the cationic collectors of Figure 1 .
  • the xanthates are synthesized by reacting carbon disulfide (CS2) with the alcohol group under basic conditions.
  • CS2 carbon disulfide
  • dithiocarbamates are made similarly, but reacting an amino group instead of an alcohol group.
  • the result is a salt of the xanthate or dithiocarbamate.
  • the salt shown in Figure 2 is always a sodium salt, but any cationic salt is possible and part of the invention.
  • the xanthates and dithiocarbamates can be made as the salts of amines, as well as of mineral bases.
  • the collectors of the present invention have additional uses as well.
  • the cationic collectors have utility in personal care as surfactants, cleaners, emollients, rheology modifiers, and to buffer the products.
  • the primary amines and diamines also have utility in asphalt as antistrips and as asphalt emulsifiers.
  • Figure 3 shows several derivatives. Amides with fatty acids of the cationic collectors are made simply by combining the cationic collector with the desired fatty acid, typically stearic acid or coconut fatty acid and heating to remove a mole of water for each amide group formed.
  • the amides are versatile rheology modifiers.
  • Amphoterics of the cationic collectors can be made through the reaction of sodium
  • monochloroacetic acid (reflux 1 : 1 molar equivalents of SMCA for approximately 8 hours), or for a salt free form, acrylic acid or methacrylic acid may be reacted by adding the acid at ambient temperature or below to the cationic collector with sufficient cooling to keep the temperature below 30 C.
  • the esters can be made by reacting the esters of the acids. A diaddition can be made to the amino group by continuing the reactions.
  • Sulfonates can be made by reacting sodium vinyl sulfonate, propane sultone or butane sultone, or higher sultones can be reacted similarly to create the sulfonates with a longer carbon chain between the nitrogen and the sulfur.
  • Phosphonates can be made by reacting phosphonic acid and formaldehyde.
  • the salted products derivatives of the cationic collectors in Figure 3 can be in their free form through ion exchange or be salted with any other cation.
  • Figure 4 shows that tertiary amines can be made by reacting 2 moles of formaldehyde, or other aldehydes, followed by a reduction with sponge nickel under similar conditions to the nitrile reductions in Figure 1 . If different aldehydes are used, an asymmetric tertiary amine results. The tertiary amines can then be made into quaternaries or amine oxides.
  • the starting material may be an alcohol, an amine, a polyamine such as Tallow Diamine, common trade name Akzo Duomeen T, or polyether amine, such as Air Products DA-14, ethoxylated amines, such as Akzo Ethomeen T12, or ethoxylated ether amines, such as Air Products E-17-5.
  • a second equivalent of the allylic polyacrylonitrile can be added, versus the secondary amines that can only accept one equivalent. Any alcohol or amine functional starting material may be reacted with the allylic polyacrylonitrile and then reduced to form the polyamine is part of this invention.
  • Figure 6 shows the synthesis of the secondary amines.
  • the reactants are 2 moles of the same ether nitrile, but this need not be the case.
  • R and R 1 may be different and even a wade range of blends may be used which will give a mixture of symmetric and asymmetric secondary amines.
  • the ether nitriles of the invention may also be reacted alkyl nitriles, such as tallow nitrile, or more conventional ether nitriles, such as the ether nitrile formed by the synthesis of fatty alcohols such as Exxal 10 and acrylonitrile to form
  • the dimethyl quaternary shown in row 3 of Figure 6 is particularly well suited to treated drilling clays to form hydrophobic clays for use in oilfield drilling muds, as well as biodegradeable fabric softeners.
  • These dimethyl quats me be formed as either the sulfate or chloride salt depending on the methylating agent, typically DMS or methyl chloride.
  • the benzyl chloride quats are useful for antimicrobials and corrosion inhibitors.
  • the ethylbenzyl and naphtha quats are anti-fungal as well.
  • the symmetric tertiary amine of the first row of Figure 6 is obtained with slightly different conditions.
  • An 85% yield of tertiary amine is obtainable by running the reaction at a lower pressure, ⁇ 100 psi, for 4-6 hrs.
  • the corresponding asymmetric tertiary amines can be made by varying the nitriles used as starting materials in the reaction vessel.
  • the derivatives, such as amine oxides, and quaternaries analogous to the those shown with the methyl tertiary amine are similarly obtained.
  • the tertiary polyalkoxylate quaternaries are particularly useful as hair conditioners, particularly when a silyl nitrile is used as a starting material.
  • Figure 7 shows the synthesis of highly branched primary ether amines.
  • the starting materials in Figure 7 are Pentaerythritol and glycerin, other short chain polyols, such as, but not limited to, neopentyl glycol, ethylene glycol and propylene glycol can be used to obtain the similar analogs.
  • the ether nitriles can be distilled into discreet fractions and then alkoxylated and reduced to obtain more or less discreet products. The range comes from the distribution of alkoxylation then only, not the position of the acrylonitrile addition.
  • Figures 8 and 9 show the synthesis of polyamine derivatives, such as polyquaternaries or polybetaines.
  • the polyquaternaries are shown in the figure to be made with methyl chloride, giving the methyl quats with CI " anions. Similar to in figure 3, other quating agents can be used, including, but not limited to methyl chloride, diethylsulfate, dimethylsulfate, ethyl benzyl chloride, and benzyl chloride.
  • the anions that are generated vary based on the quaternarizing agent, but can also be exchanged through ion exchange to give a wide array of counterions, such as carbonate, borate, phosphate and almost any other anion.
  • Figure 10 shows the synthesis of various sulfur derivatives, including the salt free betaines based on sultones. While propane sultone is shown, reacting butane sultone and higher sultones are included as part of this invention, with the resulting betaines having a longer carbon chain between the amine group and the sulfonate group, depending on the sultone. Also shown are the synthesis of novel thionocarbamates. The thionocarbamates are useful as ore collectors for such minerals as gold, copper, zinc, nickel and others minerals.
  • Figure 11 shows the synthesis of amides and imidazoline analogs.
  • the Figure shows the synthesis from the diamine, but higher polyamines may also be used, leaving the additional propylamine blocks between the ring and the alcohol that was used to make the polyamine.
  • the imidazoline analogs can also be alkoxylated or quaternized, as described in Figure 4 or Figure 6 to alter the water solubility and HLB as desired or to impart cationicity. These products are typically used as corrosion inhibitors, but can be used as lubricity aids and to impart other properties to formulated products. These analogs are part of this invention.
  • Figure 12 shows the synthesis of amines based on nitroalcohols. These amines have advantages in the manufacturing and offer a more hydrophobic amine.
  • the alkoxylation must take place with an acid catalyst, or the position of the hydrogen bound to the carbon adjacent to the nitro group will be alkoxylated as in Figure 13. While the figure shows R 1 as a discreet species, it is understood that a mixture of alkoxylating agents could be used to form copolymeric chains among the options for R 1 . For example, some moles of ethylene oxide could be reacted, followed by some moles of propylene oxide, which would give mixed alkoxylation polymeric chains.
  • the alkoxylation could also take place in one step with various alkoxylating agents added at the same time.
  • the amines present can be reacted with acrylonitrile to make polyamines.
  • the amines in Figure 12 all have terminal hydroxyls that react with acrylonitrile the same way as the alcohol groups in Figure 1 , either as single cyanoethylation, or sequentially to add polyamines. If the primary amine
  • the amines of Figures 12 and 13 all have terminal hydroxyls. These can be capped with methyl chloride, or other alkyl halide, prior to reduction from nitro to amine, eliminating the hydroxyl group.
  • the amines of Figure 12 are preferred to those of Figure 13 due to the process for manufacturing being safer and the use of formaldehyde to form the nitro alcohol does not add substantial cost.
  • the amines in Figure 5, Figure 6, Figure 7, Figure 12, and Figure 13 can be derivatized into tertiary amines, amine oxides, quaternaries, sulfonates, sulfates, betaines, betaine esters, phosphonates and alkoxylates.
  • the amine products taught in this invention are used in mineral floatation, either alone or in combination with other known collectors, and or with non-ionic surfactants or other frothing aids, asphalt emulsifiers.
  • Figure 14 shows the synthesis of amines via the direct amination route that is most commonly used to make alkyl dimethyl amines (ADMAs).
  • the same route when properly controlled forms primary, dialkyl or trialkyl amines.
  • the primary amines can similarly be derivatized into polyamines via cyanoethylation as shown in Figure 1 , and sequential cyanoethylation produces the higher polyamines, such as triamines, tetramines, pentamines, and so on.
  • the primary amines and polyamines can also be derivatized into dithiocarbamates, analogous to those in Figure 2 and amphoterics as shown in Figure 3.
  • the primary amines and polyamines of Figure 14 can be alkoxylated with typical alkoxylating agents such as ethylene oxide, propylene oxide and butylene oxide to make particularly useful adjuvants for agriculture or fuel additives that act as detergents.
  • the ethoxylated primary and diamines are particularly well suited as adjuvants in agriculture. This is also the case for the analogous amines and polyamines of Figure 1 .
  • the primary amines and polyamines of Figure 14 can also be used as starting materials for amphoterics by the reaction with MCA, acrylic acid, methacrylic acid, sodium vinyl sulfonate, sultanes and formaldehyde with phosphorous acid analogous to those shown in Figures 3, 8, and 9.
  • the teriary amines and polyamines of Figure 14 can be converted to quaternary ammonium compounds and amine oxides that are analogous to those in Figures 4 and 6.
  • Figure 15 shows the tertiary amines and tertiary polyamines can be used as starting materials to produce the analogous betaines of those shown in Figure 10.
  • variable J is not present, but as an anion of the terminal oxygen. This is the case in Figure 10 as well.
  • betaines and polybetaines of Figure 10 and Figure 15 are well suited to emulsifying difficult to emulsify asphalt.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Une famille de réactifs collecteurs à base d'amine pour l'exploitation minière qui utilise des alcoxylates permet d'effectuer l'ajustement aisé de la solubilité et du poids moléculaire utiles étant donné que les réactifs anioniques et cationiques pour l'exploitation minière nécessitent de tels degrés variables de solubilité et de poids moléculaire. La famille de la présente invention permet d'optimiser les deux paramètres et d'augmenter l'efficacité du réactif collecteur.
PCT/US2018/026738 2017-04-11 2018-04-09 Nouveaux réactifs collecteurs d'exploitation minière Ceased WO2018191179A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US201762484041P 2017-04-11 2017-04-11
US62/484,041 2017-04-11
US201762511297P 2017-05-25 2017-05-25
US62/511,297 2017-05-25
US201862636058P 2018-02-27 2018-02-27
US62/636,058 2018-02-27
US201862647600P 2018-03-23 2018-03-23
US62/647,600 2018-03-23

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WO2018191179A1 true WO2018191179A1 (fr) 2018-10-18

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0812983A (ja) * 1994-06-29 1996-01-16 Kao Corp ガソリン組成物
US20160214933A1 (en) * 2015-01-26 2016-07-28 Thomas P. Daly Amine Mining Collectors
FR3040994A1 (fr) * 2015-09-10 2017-03-17 Ceca Sa Composes etheramines et son utilisation en tant que collecteur de flottation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0812983A (ja) * 1994-06-29 1996-01-16 Kao Corp ガソリン組成物
US20160214933A1 (en) * 2015-01-26 2016-07-28 Thomas P. Daly Amine Mining Collectors
US20170101371A1 (en) * 2015-01-26 2017-04-13 Thomas P. Daly Amine Mining Collectors
FR3040994A1 (fr) * 2015-09-10 2017-03-17 Ceca Sa Composes etheramines et son utilisation en tant que collecteur de flottation

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