WO2017075003A1 - Réactifs collecteurs à base d'amine pour l'exploitation minière - Google Patents

Réactifs collecteurs à base d'amine pour l'exploitation minière Download PDF

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Publication number
WO2017075003A1
WO2017075003A1 PCT/US2016/058789 US2016058789W WO2017075003A1 WO 2017075003 A1 WO2017075003 A1 WO 2017075003A1 US 2016058789 W US2016058789 W US 2016058789W WO 2017075003 A1 WO2017075003 A1 WO 2017075003A1
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WO
WIPO (PCT)
Prior art keywords
amine
collector
collectors
mining
amines
Prior art date
Application number
PCT/US2016/058789
Other languages
English (en)
Inventor
Thomas P. Daly
Original Assignee
Daly Thomas P
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US15/005,162 external-priority patent/US9481634B2/en
Application filed by Daly Thomas P filed Critical Daly Thomas P
Priority to BR112018008468-9A priority Critical patent/BR112018008468B1/pt
Priority to CA3003268A priority patent/CA3003268A1/fr
Priority to CN201680063037.6A priority patent/CN108349854A/zh
Priority to AU2016344360A priority patent/AU2016344360B2/en
Publication of WO2017075003A1 publication Critical patent/WO2017075003A1/fr
Priority to ZA2018/02746A priority patent/ZA201802746B/en
Priority to AU2021221877A priority patent/AU2021221877B2/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • C07C329/12—Dithiocarbonic acids; Derivatives thereof
    • C07C329/14—Esters of dithiocarbonic acids
    • 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
    • B03D1/0043—Organic compounds modified so as to contain a polyether group
    • 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
    • B03D1/012—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
    • C07C217/06—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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; specified applications
    • B03D2203/02—Ores
    • B03D2203/04—Non-sulfide ores

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.
  • 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.
  • 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. Elevated temperatures lead to polymerization of the acrylonitrile.
  • a catalytic amount of caustic may be used to accelerate the Michael Addition with alcohols.
  • the yields are typically in excess of 96% and no further purification is necessary for a commercial product.
  • These collectors are useful where cationic collectors are required, such as iron ore and potash.
  • Figure 2 shows the synthesis of the anionic analogs of the collectors in Figure 1 .
  • the di-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.
  • the 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.
  • 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.
  • FIG 4 shows that tertiary amines can be made by reacting 2 moles of formaldehyde, followed by a reduction with sponge nickel under similar conditions to the nitrile reductions in Figure 1 .
  • the tertiary amines can then be made into quaternaries or amine oxides.
  • the quaternaries of methyl chloride, diethylsulfate, ethyl benzyl chloride, and benzyl chloride are all facile reactions at ambient temperature that yield the analogous quaternaries.
  • Figure 5 shows the synthesis of novel collectors based on allylic polynitriles that are then reduced to the polyamines.
  • 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 Ethomeet 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 asymmetric secondary amines and even the nitriles formed from acrylonitrile and hydroxyl terminated siloxanes or silyl alcohols.
  • the use of differing nitriles allows the chemist to produce secondary amines with a range of hydrophobicities and surfactancies. Conditions for the synthesis are more severe than the synthesis of the primary amines.
  • the reaction generally takes 2 hrs at 220 C, but only about 300 psi pressure of hydrogen.
  • Typical sponge nickel may be used, but beta branched products to appear in larger quantities.
  • a nickel carbonate catalyst will reduce this byproduct formation.
  • Figure 6 only shows the synthesis of symmetric secondary amines, the asymmetric secondary amines and their derivatives are part of this invention.
  • 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 bezyl 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 alower 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.
  • the amines in Figure 5 and Figure 6 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

Une famille de réactifs collecteurs à base d'amine pour l'exploitation minière qui utilise des alcoxylates d'amine permet d'effectuer l'ajustement aisé de la solubilité et du poids 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/US2016/058789 2015-10-27 2016-10-26 Réactifs collecteurs à base d'amine pour l'exploitation minière WO2017075003A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BR112018008468-9A BR112018008468B1 (pt) 2015-10-27 2016-10-26 Coletores de minério de amina
CA3003268A CA3003268A1 (fr) 2015-10-27 2016-10-26 Reactifs collecteurs a base d'amine pour l'exploitation miniere
CN201680063037.6A CN108349854A (zh) 2015-10-27 2016-10-26 胺类选矿捕收剂
AU2016344360A AU2016344360B2 (en) 2015-10-27 2016-10-26 Amine mining collectors
ZA2018/02746A ZA201802746B (en) 2015-10-27 2018-04-25 Amine mining collectors
AU2021221877A AU2021221877B2 (en) 2015-10-27 2021-08-26 Amine Mining Collectors

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201562247029P 2015-10-27 2015-10-27
US62/247,029 2015-10-27
US15/005,162 US9481634B2 (en) 2015-01-26 2016-01-25 Amine mining collectors
US15/005,162 2016-01-25

Publications (1)

Publication Number Publication Date
WO2017075003A1 true WO2017075003A1 (fr) 2017-05-04

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PCT/US2016/058789 WO2017075003A1 (fr) 2015-10-27 2016-10-26 Réactifs collecteurs à base d'amine pour l'exploitation minière

Country Status (8)

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CN (1) CN108349854A (fr)
AU (2) AU2016344360B2 (fr)
BR (1) BR112018008468B1 (fr)
CA (1) CA3003268A1 (fr)
CL (2) CL2018001091A1 (fr)
PE (1) PE20181315A1 (fr)
WO (1) WO2017075003A1 (fr)
ZA (1) ZA201802746B (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110064523B (zh) * 2019-05-15 2020-03-24 中南大学 一种含铁硫化矿的抑制剂、浮选药剂及其应用
CN113695085B (zh) * 2021-06-29 2023-03-21 郑州大学 一种磷石膏脱硅除碳组合捕收剂及其溶液制备方法、应用

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US4186254A (en) * 1978-12-11 1980-01-29 Texaco Development Corporation Amine derivatives and use as polyurethane catalyst
SU1489838A1 (ru) * 1987-11-04 1989-06-30 Красноярский институт цветных металлов им.М.И.Калинина Способ селективной флотации апатит-карбонатных руд
WO2008152029A1 (fr) * 2007-06-12 2008-12-18 Akzo Nobel N.V. Collecteur pour la flottation de matières minérales argileuses dans des minerais de potasse
WO2009077015A1 (fr) * 2007-07-20 2009-06-25 Clariant (Brazil) S.A. Flottation inverse du minerai de fer au moyen de collecteurs dans une nanoémulsion aqueuse
WO2010060477A1 (fr) * 2008-11-26 2010-06-03 Akzo Nobel N.V. Mélange de collecteurs pour la flottation de minéraux argileux à partir de minerais de potasse

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DE1163850B (de) * 1960-07-14 1964-02-27 Henkel & Cie Gmbh Verfahren zur Herstellung neuer, nichtionischer, hautfreundlicher Abkoemmlinge von kapillaraktiven tertiaeren Aminen
US3398189A (en) * 1965-05-10 1968-08-20 Rohm & Haas Phosphorimidic triamide salts
US5068324A (en) * 1989-09-05 1991-11-26 Lce Partnership Novel amphoteric polymers
FR2681312A1 (fr) * 1991-09-16 1993-03-19 Francais Prod Ind Cfpi Solution lubrifiante et desinfectante pour chaine transporteuse de recipients dans l'industrie agro-alimentaire et procede pour sa mise en óoeuvre.
US6260561B1 (en) * 1998-08-13 2001-07-17 The Dow Chemical Company Method for using aliphatic amines as cleaners for swimming pools
US6114585A (en) * 1999-12-13 2000-09-05 Nova Molecular Technologies Inc Ether amines from 2-pentenenitrile
CN101088623A (zh) * 2007-06-28 2007-12-19 武汉理工大学 一种矿物浮选捕收剂及其制备方法
CN102009001B (zh) * 2010-10-18 2013-09-04 中蓝连海设计研究院 含原生矿泥胶磷矿的选择性絮凝反浮选脱硅工艺
CN102441498B (zh) * 2011-10-31 2013-07-24 中蓝连海设计研究院 一种磷矿双反浮选工艺
FR3040994B1 (fr) * 2015-09-10 2019-07-26 Arkema France Composes etheramines et son utilisation en tant que collecteur de flottation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4186254A (en) * 1978-12-11 1980-01-29 Texaco Development Corporation Amine derivatives and use as polyurethane catalyst
SU1489838A1 (ru) * 1987-11-04 1989-06-30 Красноярский институт цветных металлов им.М.И.Калинина Способ селективной флотации апатит-карбонатных руд
WO2008152029A1 (fr) * 2007-06-12 2008-12-18 Akzo Nobel N.V. Collecteur pour la flottation de matières minérales argileuses dans des minerais de potasse
WO2009077015A1 (fr) * 2007-07-20 2009-06-25 Clariant (Brazil) S.A. Flottation inverse du minerai de fer au moyen de collecteurs dans une nanoémulsion aqueuse
WO2010060477A1 (fr) * 2008-11-26 2010-06-03 Akzo Nobel N.V. Mélange de collecteurs pour la flottation de minéraux argileux à partir de minerais de potasse

Also Published As

Publication number Publication date
BR112018008468A2 (pt) 2018-11-06
CN108349854A (zh) 2018-07-31
AU2021221877A1 (en) 2021-09-23
BR112018008468B1 (pt) 2021-03-30
CL2019003065A1 (es) 2020-03-27
AU2016344360B2 (en) 2021-05-27
CA3003268A1 (fr) 2017-05-04
ZA201802746B (en) 2019-02-27
CL2018001091A1 (es) 2018-08-17
AU2016344360A1 (en) 2018-05-24
PE20181315A1 (es) 2018-08-14
AU2021221877B2 (en) 2023-09-07

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