WO2024094486A1 - Procédé de valorisation de minéraux ou de minerais non sulfurés - Google Patents

Procédé de valorisation de minéraux ou de minerais non sulfurés Download PDF

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WO2024094486A1
WO2024094486A1 PCT/EP2023/079600 EP2023079600W WO2024094486A1 WO 2024094486 A1 WO2024094486 A1 WO 2024094486A1 EP 2023079600 W EP2023079600 W EP 2023079600W WO 2024094486 A1 WO2024094486 A1 WO 2024094486A1
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formula
alkyl
moiety
ores
phosphate
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Mikhail GOLETS
Natalija Smolko Schwarzmayr
Henrik NORDBERG
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Nouryon Chemicals International B.V.
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    • 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
    • B03D1/008—Organic compounds containing oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • 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
    • 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
    • B03D1/014—Organic compounds containing phosphorus
    • 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
    • B03D2203/06—Phosphate ores

Definitions

  • the present disclosure relates to a beneficiation process for non-sulfidic minerals or ores, and to a collector composition for use in said process.
  • Froth flotation is a physico-chemical process used to separate mineral particles considered economically valuable from those considered waste. It is based on the ability of air bubbles to selectively attach to those particles that were previously rendered hydrophobic. The particlebubble combinations then rise to the froth phase from where the flotation cell is discharged, whilst the hydrophilic particles remain in the flotation cell. Particle hydrophobicity is, in turn, induced by special chemicals called collectors. In direct flotation systems, it is the economically valuable minerals which are rendered hydrophobic by the action of the collector. Similarly, in reverse flotation systems, the collector renders hydrophobicity to those mineral particles considered waste. The efficiency of the separation process is quantified in terms of recovery and grade. Recovery refers to the percentage of valuable product contained in the ore that is removed into the concentrate stream after flotation. Grade refers to the percentage of the economically valuable product in the concentrate after flotation. A higher value of recovery or grade indicates a more efficient flotation system.
  • phosphate concentrate with P 2 O 5 grade higher than 30% and recovery of >85-90%.
  • the flotation of phosphate allows to reduce to minimal values the content of following gangue minerals: quartz, clay, feldspar, calcite, magnetite, dolomite etc.
  • the applicable flotation method is affected by the nature of the phosphate ore.
  • the direct flotation is commonly applied for the igneous/magmatic apatite phosphate ores with generally low P 2 O 5 feed grade (5-10%) and the valuable apatite phosphate concentrate is separated with the froth. Meanwhile, the reversed flotation is used for the sedimentary phosphate ores with generally higher P 2 O 5 feed grade. In the latter case the impurities are separated from the phosphate concentrate with the froth whereas the valuable phosphate concentrate is resided in the cell tailings product. In some cases, the direct flotation can be also used to float phosphorous-containing minerals from sedimentary phosphates.
  • Anionic collectors can be used in both mentioned cases: for the direct flotation of apatite/phosphate from igneous or sedimentary phosphate ores and for flotation of calcite, dolomite, and other carbonaceous impurities from sedimentary phosphate ores, respectively.
  • the process of phosphate flotation generally includes following stages: ore classification, ore grinding, pulp conditioning with reagents and further flotation.
  • the flotation of slime impurities is commonly applied in the beneficiation processes of potash. Both anionic and nonionic collectors can be used in slime flotation, which is commonly performed prior to the flotation of potash. Further the direct flotation of KCI and NaCI is performed for sylvite and halite ores, respectively. Slimes are undesirable in KCI or NaCI flotation stages since they cause elevated consumption of potash collectors and decrease the purity of concentrate. Commonly, slimes contain 2/3 of clay minerals (dolomite, anhydrite, hematite, silica) and 1/3 clay (chlorite, Illite). The content of slimes in the flotation feed commonly varies between 1 and 6%.
  • the process of potash slime flotation generally includes following stages: ore classification, ore grinding, pulp conditioning with reagents and further the flotation desliming.
  • WO 2019/007712 A1 and WO2019/007714 A1 disclose a process to treat carbonatitic or siliceous non-sulfidic ores with a collector composition that comprises a phosphate compound of the formula: wherein R is linear or branched, saturated or unsaturated hydrocarbon group containing 1 to 24 carbon atoms, A is an alkylene oxide unit; Y is H, Na, K or an ammonium or alkylated ammonium, n is 1 - 3, p is 0 - 25, X is chosen from the same groups as R-Ap or Y. These processes have been shown to provide the required grade of separation of the desired product from the ore and an improvement in recovery and selectivity.
  • RU2717862C1 An alternative process for recovering phosphates from phosphate ores is described in RU2717862C1 .
  • a collector containing ethoxylated derivatives of cashew nutshell liquid (CNSL) having a degree of ethoxylation from 1 to 100 is used.
  • RU2744327C1 discloses flotation desliming of potash ores using a collector containing propoxylated Cardanol (part of CNSL) having a degree of propoxylation from 10 to 70, or a mixture of propoxylated Cardanol and ethoxylated Cardanol having a degree of ethoxylation and propoxylation from 10 to 70.
  • collector compositions comprising anionic, cationic, and/or amphoteric (i.e., charge-containing) derivatives of CNSL meet this need. Accordingly, the present disclosure relates to a beneficiation process for non-sulfidic minerals or ores, the process comprising contacting said non-sulfidic minerals or ores with a collector composition comprising:
  • Ri is a saturated or unsaturated, linear C15 alkyl
  • R2 is selected from H, -C(O)OH, -C(O)-Ap-OH, or -C(O)-Ap-O-Z, preferably H,
  • Rs is selected from -OH, -O-Z, -Ap-OH, or -Ap-O-Z,
  • R4 is selected from H or -CH3,
  • Rs is selected from H, -OH, -O-Z, -Ap-OH, or -Ap-O-Z,
  • A is an alkylene oxide unit, preferably an ethylene oxide and/or propylene oxide unit, more preferably an ethylene oxide unit, p is 1 - 30, preferably 2-15, more preferably 3-12, and
  • Z is an anionic moiety, a cationic moiety, or an amphoteric moiety, with the proviso that the compound of formula (I) comprises at least one Z group;
  • a “beneficiation process” is a process that improves (benefits) the economic value of the mineral or ore by removing undesired impurities/valueless material (more commonly referred to as “gangue”). That results in a higher-grade product (concentrate), usually with high levels of product recovery, and produces a waste stream (tailings). This is a well-established term of the mining industry, the meaning of which would be well understood by a person skilled in this technical field.
  • the compounds of formula (I) are preferably derived from four components of cashew nutshell liquid (CNSL): anacardic acid [A], cardol [B], cardanol [C] and/or methylcardol [D]:
  • the R’ group is typically a mixture of saturated, monoene, diene and triene linear C15 alkyls, such as (but not necessarily limited to):
  • CNSL is a common by-product produced by the cashew industry and is therefore a renewable and sustainable alternative to petrochemically derived alkylaromatic compounds.
  • Natural cold extracted CNSL (C-CNSL) contains 60-75% anacardic acid, 15-25% cardol, 3-5% Cardanol and 1 -2% methylcardol, respectively.
  • technical CNSL (T-CNSL) can be obtained by a heat extraction process where anacardic acid is converted to Cardanol. After removal of undesirable polymeric materials, T-CNSL generally contains >75% Cardanol and ⁇ 4-8% cardol. The production of T-CNSL has been practiced for decades.
  • the one or more compounds of formula (I) prefferably be anionic, cationic, or amphoteric derivatives of anacardic acid, cardol, cardanol and/or methylcardol, wherein the anacardic acid, cardol, cardanol and/or methylcardol are preferably obtained from CNSL.
  • the one or more compounds of formula (I) are anionic, cationic, or amphoteric derivatives of cardanol, cardol and/or methylcardol, wherein the cardanol, cardol and/or methylcardol are preferably obtained from T-CNSL.
  • the collector composition comprises one or more compounds of formula (la): wherein:
  • Ri is a saturated or unsaturated, linear C15 alkyl, Rs is selected from OH, O-Z, Ap-OH, or Ap-O-Z,
  • R4 is H or CH 3 ,
  • Rs is selected from H, OH, O-Z, Ap-OH, or Ap-O-Z,
  • A is an alkylene oxide unit, preferably an ethylene oxide and/or propylene oxide unit, more preferably an ethylene oxide unit, p is 1 - 30, preferably 2-15, more preferably 3-12, and
  • Z is an anionic moiety, a cationic moiety, or an amphoteric moiety, with the proviso that the compound of formula (la) comprises at least one Z group.
  • the collector composition comprises at least one compound of formula (lb): wherein:
  • R1 is a saturated or unsaturated, linear C15 alkyl
  • R3 is selected from O-Z or Ap-O-Z, preferably Ap-O-Z,
  • A is an alkylene oxide unit, preferably an ethylene oxide and/or propylene oxide unit, more preferably an ethylene oxide unit, p is 1 - 30, preferably 2-15, more preferably 3-12, and
  • Z is an anionic moiety, a cationic moiety, or an amphoteric moiety.
  • the compounds of formulae (I), (la) and/or (lb) are anionic, cationic or amphoteric derivatives of anacardic acid, cardol, cardanol and methylcardol, wherein the anacardic acid, cardol, cardanol and methylcardol are obtained from CNSL and then derivatized to produce compounds of formulae (I), (la) and/or (lb).
  • the compounds of formulae (I), (la) and/or (lb) are anionic, cationic or amphoteric derivatives of cardanol, cardol and/or methylcardol, wherein the cardanol, cardol and/or methylcardol are obtained from T-CNSL and then derivatized to produce compounds of formulae (I), (la) and/or (lb).
  • the anacardic acid, cardol, cardanol and/or methylcardol obtained from CNSL or T-CNSL may be directly derivatized as a mixture, or each component may be purified and derivatized separately.
  • the compounds of formulae (I), (la) and/or (lb) are anionic or amphoteric derivatives of anacardic acid, cardol, cardanol and methylcardol, wherein the anacardic acid, cardol, cardanol and methylcardol are obtained from CNSL and then derivatized to produce compounds of formulae (I), (la) and/or (lb).
  • the compounds of formulae (I), (la) and/or (lb) are anionic or amphoteric derivatives of cardanol, cardol and/or methylcardol, wherein the cardanol, cardol and/or methylcardol are obtained from T-CNSL and then derivatized to produce compounds of formulae (I), (la) and/or (lb).
  • the anacardic acid, cardol, cardanol and/or methylcardol obtained from CNSL or T-CNSL may be directly derivatized as a mixture, or each component may be purified and derivatized separately.
  • the compounds of formulae (I), (la) and/or (lb) are anionic derivatives of anacardic acid, cardol, cardanol and methylcardol, wherein the anacardic acid, cardol, cardanol and methylcardol are obtained from CNSL and then derivatized to produce compounds of formulae (I), (la) and/or (lb).
  • the compounds of formulae (I), (la) and/or (lb) are anionic derivatives of cardanol, cardol and/or methylcardol, wherein the cardanol, cardol and/or methylcardol are obtained from T-CNSL and then derivatized to produce compounds of formulae (I), (la) and/or (lb).
  • the anacardic acid, cardol, cardanol and/or methylcardol obtained from CNSL or T-CNSL may be directly derivatized as a mixture, or each component may be purified and derivatized separately.
  • the anionic, cationic, or amphoteric moiety Z of formulae (I), (la) and/or (lb) preferably comprise or consist of a phosphate, a pyrophosphate, a polyphosphate, a phosphonate, a phosphinate, a sulfate, a sulfonate, a carboxylic acid, a sulfosuccinate, a sarcosinate, a polysulfate, a polysulfonate, a betaine, a sulfobetaine, an aminocarboxylate, an aminosulfonate, (alkyl)amines, (alkyl)diamines, etheramines, etherdiamines, esteramines, esterdiamines, and quaternary ammonium moieties.
  • the cationic moieties Z comprise or consist of:
  • esteramines of the formula esterdiamines of the formula: wherein k is a value of 1 to 3, m is an integer of 0 to 25, f is an integer of at least 3 and at most 8, and wherein X is an anion derivable from deprotonating a Bronsted-Lowry acid
  • the cationic moiety Z may also comprise or consist of polyester polyamines (PEPA) and/or polyester polyquats (PEPQ). These are polymeric components containing multiple amine or quaternary ammonium centres, respectively. Commonly, PEPA and PEPQ are obtained from reaction of an amine, a dicarboxylic acid and a hydrophobic precursor (for example, fatty acid or fatty alcohol). In a preferred embodiment, the cationic moiety Z comprises or consists of a PEPA or PEPQ of the formula: wherein:
  • R is a linear or branched, saturated or unsaturated, C2-C20 alkyl
  • R2 is either a link point to a compound of formulae (I), (la), or (lb) (i.e., R2-O-Z), or is a linear or branched, saturated or unsaturated, C1 -C20 alkyl;
  • D is a halogen counterion (preferably Cl’, I’, Br or F ) or an organic counterion (preferably sulfate, sulfonate, phosphate, phosphonate, carboxylate with C1 -C10 alkyl); p is 0 or 1 ; n is 1 to 10;
  • R3 and R4 are each independently:
  • PEPA H or a linear or branched, saturated or unsaturated, substituted or unsubstituted C1 -C20 alkyl (preferably CH 3 or CH2CH2OH),
  • a linear or branched, saturated or unsaturated, substituted or unsubstituted C1 -C20 alkyl preferably CH 3 or CH2CH2OH
  • at least one R2 is a link point to a compound of formulae (I), (la), or (lb) (i.e., R2-O-Z, which corresponds to an ester of a compound of formulae (I), (la) or (lb) (R2-O) with the PEPA/PEPQ moiety (Z)).
  • Z of formulae (I), (la) and/or (lb) comprises or consists of an anionic moiety or an amphoteric moiety, more preferably an anionic moiety.
  • Preferred amphoteric moieties Z comprise or consist of a betaine, a sulfobetaine, an aminocarboxylate, and/or an aminosulfonate.
  • Preferred anionic moieties Z comprise of consist of phosphates (cf. formula [E], below), sulfosuccinates (cf. formula [F], below), sarcosinates (cf. formula [G], below), maleates (cf. formula [H], below), amidocarboxylates (cf. formula [I], below), glycinates (cf. formula [J], below), taurates (cf. formula [K], below), hydroxamates (cf. formula [L], below), and/or sulfonates (cf. formula [N], below).
  • the anionic moiety Z of formulae (I), (la) and/or (lb) comprises or consists of a phosphate of formula (II): wherein: n is 0 - 3, and each X is independently selected from H, a cationic counterion (preferably an alkali(ne) metal cation, ammonium, or an alkyl ammonium), or Y; or when n is 2 or 3, the terminal O-X and a second O-X jointly may be a -O- bridge to give a cyclic phosphate, wherein Y is a compound of formula (III), wherein:
  • Re is a saturated or unsaturated, linear C15 alkyl, R? is selected from H, -C(O)OH, or C(O)-Ap-OH,
  • Rs is selected from OH or Ap-OH
  • R9 is selected from H or CH 3 ,
  • R10 is selected from H, OH, or Ap-OH
  • A is an alkylene oxide unit, preferably an ethylene oxide and/or propylene oxide unit, more preferably an ethylene oxide unit, p is 1 - 30, preferably 2-15, more preferably 3-12, wherein at least of one of R 7 , Rs or Rw contains an OH group that forms a phosphate ester link with the anionic moiety Z of formula (II), with the proviso that at least one X of Formula (II) must be selected from H or a cationic counterion.
  • Y is a compound of formula (Illa): wherein:
  • Re is a saturated or unsaturated, linear C15 alkyl
  • Rs is selected from OH or Ap-OH
  • R9 is selected from H or CH 3 ,
  • R10 is selected from H, OH, or Ap-OH
  • A is an alkylene oxide unit, preferably an ethylene oxide and/or propylene oxide unit, more preferably an ethylene oxide unit, p is 1 - 30, preferably 2-15, more preferably 3-12, wherein at least of one of Rs or R10 contains an OH group that forms a phosphate ester link with the anionic moiety Z of formula (II).
  • the collector composition comprises a mixture of two or more compounds of formulae [IA1], [IA2], [IA3] and/or [IA4]:
  • Ri is a saturated or unsaturated, linear C15 alkyl
  • R2 is selected from C(O)OH, C(O)-Ap-OH, or C(O)-Ap-O-Z, preferably C(O)OH or
  • Rs is selected from OH, O-Z, Ap-OH, or Ap-O-Z,
  • Rs is selected from OH, O-Z, Ap-OH, or Ap-O-Z,
  • A is an alkylene oxide unit, preferably an ethylene oxide and/or propylene oxide unit, more preferably an ethylene oxide unit, p is 1 - 30, preferably 2-15, more preferably 3-12, and
  • Z is an anionic moiety, a cationic moiety, or an amphoteric moiety, with the proviso that each compound of formulae [IA1], [IA2], [IA3] and [IA4] must each comprise at least one Z group.
  • the collector composition comprises a mixture of compounds of formulae [IA2], [IA3] and [IA4], wherein the weight ratio of [IA3] to the sum of [IA2] and [IA4] (i.e., [I A3]: ([I A2]+[l A4])) is from about 75:25 to >99:1 .
  • the collector composition comprises at least one compound of the formula [IA3]. In a most preferred embodiment, the collector composition comprises at least one compound of formula [IB]: wherein:
  • R’ is a saturated or unsaturated, linear C15 alkyl
  • A is an alkylene oxide unit, preferably an ethylene oxide unit, p is 0 - 30, preferably 2-15, more preferably 3-12 n is 0 - 3, and each X is independently selected from H, a cationic counterion (preferably an alkali(ne) metal cation, ammonium, or an alkyl ammonium), or Y; or when n is 2 or 3, the terminal O-X and a second O-X jointly may be a -O- bridge to give a cyclic phosphate, wherein Y is a compound of formula (Illa), wherein:
  • Re is a saturated or unsaturated, linear C15 alkyl
  • Rs is selected from OH or Ap-OH
  • Rg is selected from H or CH 3 ,
  • Rio is selected from H, OH, or Ap-OH,
  • A is an alkylene oxide unit, preferably an ethylene oxide and/or propylene oxide unit, more preferably an ethylene oxide unit, p is 1 - 30, preferably 2-15, more preferably 3-12, wherein at least of one of Rs or Rw contains an OH group that forms a phosphate ester link with phosphate group of formula [IB], with the proviso that at least one X must be selected from H or a cationic counterion.
  • the cationic counterion X may be any suitable cationic counterion that forms a stable phosphate salt.
  • Preferred cationic counterions in that respect include, but are not limited to, Na, K, Ca, Mg, and ammonium cations of the formula NR a RbR c Rd, wherein R a , Rb, Rc and Rd are each independently selected from H or C1 -C12 alkyl.
  • the cationic counterion is Na, K or NR a R b RcRd-
  • the A unit as used herein is an alkylene oxide ether.
  • alkoxylated products may be produced by procedures well-known in the art by reacting a free OH group with one or more alkylene oxides (e.g., ethylene oxide) in the presence of a suitable catalyst, e.g. a conventional basic catalyst, such as KOH, or a so-called narrow range catalyst (see e.g. Nonionic Surfactants: Organic Chemistry in Surfactant Science Series volume 72, 1998, pp 1 -37 and 87-107, edited by Nico M. van Os; Marcel Dekker, Inc):
  • p in the “Ap” group corresponds to the number of moles of alkylene oxide that was added per mole of alcohol in the alkoxylation reaction. This is the commonly accepted and well understood meaning of this term, because the alkoxylation reaction normally produces a distribution of alkoxylated products (this can be observed, e.g., in WO 2021/140166).
  • p is defined as the molar equivalents of alkylene oxide added per mole of alcohol in the alkoxylation reaction (this is also referred to as the “degree of alkoxylation”). For example, in the below worked example, 10 molar equivalents of ethylene oxide was reacted with the alcohol, hence in the below worked example “p” is 10 (i.e., the cardanol has a degree of ethoxylation of 10).
  • the collector compositions of the present invention may comprise one or more surfactants. It should be understood, however, that the compounds described above may be successfully used in flotation methods without necessarily requiring an additional surfactant. For the avoidance of any doubt, it should be understood that the optional component (ii) of the collector composition disclosed herein is different to that of component (i), and most preferably not a compound of formula (I).
  • the optional surfactant(s) (ii) is not particularly limited, and may be cationic, anionic, non-ionic, amphoteric, or a mixture of two or more of these. Below some examples are given, but these should only be considered as suitable for the invention and are not to be regarded as limiting.
  • Suitable amphoteric surfactants include, but are not limited to, those of the formula [C]: wherein Ri is a hydrocarbyl group with 8-22, preferably 12-18, carbon atoms; A is an alkyleneoxy group having 2-4, preferably 2, carbon atoms; p is a number 0 or 1 ; q is a number from 0 to 5, preferably 0; R2 is a hydrocarbyl group having 1 -4 carbon atoms, preferably 1 , or R2 is the group wherein R1, A, p and q have the same meaning as above; Y- is selected from the group consisting of COO" and SOs", preferably COO-; n is a number 1 or 2, preferably 1 ; M is a cation, which may be monovalent or divalent, and inorganic or organic, and r is a number 1 or 2.
  • the amphoteric surfactant of formula [C] may also be used in its acid form, where the nitrogen is protonated and no external cation is needed.
  • the compounds according to formula [C] can easily be produced in high yield from commercially available starting materials using known procedures.
  • US 4,358,368 discloses some ways to produce the compounds where R1 is a hydrocarbyl group with 8-22 carbon atoms (col 6, line 9 - col 7, line 52), and in US 4,828,687 (col 2, line 2 - col 2, line 31 ) compounds where R2 is attached to the compound of formula [C] via the methylene group, are described.
  • amphoteric surfactants have the formula [D]: wherein R 2 is a hydrocarbyl group with 8-22, preferably 12-18, carbon atoms, D is - CH 2 - or - CH 2 CH 2 -, k is 0-4, preferably 0-3, and most preferably 0-2, and M is hydrogen or a cation, such as sodium or potassium.
  • R 2 is a hydrocarbyl group with 8-22, preferably 12-18, carbon atoms
  • D is - CH 2 - or - CH 2 CH 2 -
  • k is 0-4, preferably 0-3, and most preferably 0-2
  • M is hydrogen or a cation, such as sodium or potassium.
  • the products where D is -CH 2 - are prepared by the reaction between a fatty amine and chloroacetic acid or its salts, and the products where D is -CH 2 CH 2 - are prepared by the reaction between a fatty amine and acrylic acid or esters thereof, in the latter case the reaction is followed by hydrolysis.
  • Suitable anionic surfactants include, but are not limited to, fatty acids (such as those with an
  • alkylphosphates such as those of formula [E]
  • alkylsulfosuccinates such as those of formula [F]
  • alkylsarcosinates such as those of formula [G]
  • alkylmaleates such as those of formula [H]
  • alkylamidocarboxylates such as those of formula [I]
  • alkylglycinates such as those of formula [J]
  • alkyltaurates such as those of formula [K]
  • alkylhydroxamates such as those of formula [L] wherein for each of formulae [K]
  • R is linear or branched, saturated or unsaturated hydrocarbon group containing 1 to 24 carbon atoms
  • A is an alkylene oxide unit
  • X is chosen from the same groups as R-Ap or Y; m is 0-7;
  • B is -H, -CH 3 , - CH(CH 3 ) 2 , -CH 2 CH(CH 3 ) 2 , -CH(CH 3 )CH 2 CH 3 ;
  • Z is -H, -CH 3 or -CH 2 CH 3 ;
  • D is an alkaline metal counterion, preferably Na + , K + , Ca 2+ , or Mg 2+ .
  • esters of the above alkylamidocarboxylates are also contemplated (preferably following the formula [I] of the alkylamidocarboxylates compounds, wherein Y is an alcohol derived hydrocarbon group, such as also described in US20160129456)
  • suitable anionic surfactants include sulphonated fatty acids, alkylbenzensulphonates, such as those of formula [M], and alkylsulfonates, such as those of formula [N], wherein in formulae [M] and [N]:
  • R is linear or branched, saturated or unsaturated hydrocarbon group containing 1 to 24 carbon atoms
  • Y is H, Na, K or an ammonium or alkylated ammonium.
  • Suitable nonionic surfactants include alkoxylates (such as alkoxylated fatty alcohols RO(A)H, alkoxylated fatty acids RC(O)O(A)H), or alkyl glycosides (e.g., R ⁇ OeHn ), or alkylethanolamides, such as those of the formulae [O] or [P],
  • R is linear or branched, saturated or unsaturated hydrocarbon group containing 1 to 24 carbon atoms;
  • A is an alkylene oxide unit;
  • Y is H, Na, K or an ammonium or alkylated ammonium;
  • Z is -H, -CH3 or -CH2CH3;
  • f is 1 -25, preferably f is 1 -15, and most preferable 1 -10 and each f is independently 1 to 25;
  • k is 1 or more, preferably about 1 -5.
  • nonionic surfactants include ethoxylated and/or propoxylated derivatives of anacardic acid [A], cardol [B], cardanol [C] and/or methylcardol [D], preferably ethoxylated and/or propoxylated derivatives of cardol [B], cardanol [C] and/or methylcardol [D],
  • Suitable cationic surfactants include, but are not limited to, fatty amines (preferably C8-C22, linear or branched alkyamines), fatty diamines (preferably C8-C22, linear or branched), alkyl etheramines (preferably C8-C22, linear or branched alky etheramines), alkyl etherdiamines (preferably C8-C22, linear or branched alkyl etherdiamines), alkyl esteramines (preferably C8- C22, linear or branched alkyl esteramines), quaternary ammonium surfactants, polyester polyamines (PEPA), and polyester polyquats (PEPQ).
  • fatty amines preferably C8-C22, linear or branched alkyamines
  • fatty diamines preferably C8-C22, linear or branched
  • alkyl etheramines preferably C8-C22, linear or branched alky etheramines
  • PEPA or PEPQ are related to polymeric components containing multiple amine or quaternary ammonium centres, respectively. Commonly, PEPA and PEPQ are obtained from reaction of an amine, dicarboxylic acid and hydrophobic precursor (for example, fatty acid or fatty alcohol).
  • Preferred PEPA and PEPQ cationic surfactants include, but are not limited to: wherein:
  • R is a linear or branched, saturated or unsaturated, C2-C20 alkyl
  • R2 is a linear or branched, saturated or unsaturated, C1 -C20 alkyl
  • D is a halogen counterion (preferably Cl’, I’, Br or F ) or an organic counterion (preferably sulfate, sulfonate, phosphate, phosphonate, carboxylate with C1 -C10 alkyl);
  • p is 0 or 1 ;
  • n is 1 to 10;
  • R3 and R4 are each independently:
  • PEPA H or a linear or branched, saturated or unsaturated, substituted or unsubstituted C1 -C20 alkyl (preferably CH 3 or CH 2 CH 2 OH),
  • a linear or branched, saturated or unsaturated, substituted or unsubstituted C1 -C20 alkyl preferably CH 3 or CH 2 CH 2 OH.
  • PEPQ cationic surfactants include: wherein:
  • R is a linear or branched, saturated or unsaturated, C1 -C20 alkyl
  • R’ is H or C(O)R
  • R is -CH 2 CH 2 N(CH 3 ) 2 CH 2 CH 2 -; n is 1 to 10; m is 0 to 2; and k is 1 to 6.
  • the collector composition disclosed herein may comprise a mixture of two or more anionic and/or nonionic surfactants.
  • the weight ratio of component (ii) to component (i) in the collector composition is preferably from about 15:85 to 99:1 , preferably about 20:80 to 98:2, preferably about 25:75 to 97:3.
  • the collector composition of the present disclosure comprises component (i) and optional component (ii) in a total amount of about 15 wt.% to about 100 wt.% (relative to the total weight of the collector composition), preferably in the above weight ratio (ii) to (i).
  • the collector compositions described above may further comprise a solvent.
  • Preferred solvents include, but are not limited to, water, isopropyl alcohol, propylene glycol, polyethylene glycol, diethylene glycol, hydrocarbon oils, C6-C18 alcohols, and mixtures thereof. If a solvent is used, then the collector composition preferably comprises at least 50 wt.%, more preferably at least 60 wt.%, more preferably at least 70wt.%, and most preferably at least 75 wt.% of the solvent (relative to the total weight of the collector composition).
  • the beneficiation process disclosed herein is a flotation method, preferably a froth flotation method.
  • Non-sulfidic minerals and ores that may benefit from the presently disclosed process include, but are not necessarily limited to, phosphate-containing minerals and ores (including dephosphorization of iron ore), minerals and ores comprising silicate minerals (such as, but not limited to, lithium and/or magnesium silicate minerals, siliceous phosphate ores, siliceous iron ores), and/or minerals and ores comprising carbonates (such as, but not limited to, calcite, carbonatitic phosphate ores).
  • silicate minerals such as, but not limited to, lithium and/or magnesium silicate minerals, siliceous phosphate ores, siliceous iron ores
  • carbonates such as, but not limited to, calcite, carbonatitic phosphate ores.
  • Non-limiting examples of such minerals and ores include potash, phosphate ores (apatite ores, sedimentary phosphate rock, phosphorite), calcites, iron ores (magnetite, hematite, itabirite, goethite), magnesite, spodumene, wollastonite, fluorite, chromite, dolomite, ilmenite, forsterite, nepheline, pyrochlore, rutile, zircon, olivine, scheelite.
  • potash phosphate ores (apatite ores, sedimentary phosphate rock, phosphorite), calcites, iron ores (magnetite, hematite, itabirite, goethite), magnesite, spodumene, wollastonite, fluorite, chromite, dolomite, ilmenite, forsterite, nepheline, pyrochlore, rutile, zi
  • the process of the present disclosure is particularly suitable for treating (1 ) apatite ores (direct flotation of apatite), (2) sedimentary phosphate ores (direct flotation of sedimentary phosphate rock or direct flotation of carbonate impurities - i.e., in the latter case, reversed flotation of sedimentary phosphate rock) and (3) potash ores (i.e., slime flotation from potash ores).
  • the process is also particularly suitable for the dephosphorization of iron ore, silicates flotation from iron ore, and silicates flotation from sedimentary phosphate ore.
  • a collector composition comprising component (i) improved the P2O5 recovery and grade in the three abovementioned processes (1 ) direct flotation of apatite and (2) direct flotation of sedimentary phosphate rock and (3) reversed flotation of sedimentary phosphate rock (i.e. direct flotation of carbonate impurities from sedimentary phosphate).
  • the use of a collector composition comprising component (i) improved the slime flotation from potash.
  • CNSL components are not estrogenic materials and have better environmental profile comparing to the common nonylphenol ethoxylates if used in these applications.
  • CNSL components are based on the renewable raw material source. Overall, the collector composition of the present disclosure provides numerous technical and environmental advantages over the previously known collector compositions.
  • the collector composition may comprise component (i) only, or may comprise component (i) in combination with one or more surfactant (ii) (most common for this particular application would be a fatty acid).
  • surfactant most common for this particular application would be a fatty acid.
  • the simultaneous presence of compounds (i) and (ii) or so to say the balance between the two compounds allows to reach the optimal recovery and grade of P2O5.
  • “p” is between 0 and 30, more preferably 5 and 15, yet even more preferably between 8 and 12.
  • the collector composition may comprise component (i) only, or may comprise component (i) in combination with one or more surfactants (ii) (most common for this particular application would be alkyl etheramines) and the balance between the two compounds allows to reach the optimal recovery and grade of P2O5 in the bottom concentrate product.
  • surfactants most common for this particular application would be alkyl etheramines
  • p is between 0 and 30, more preferably 2 and 10, yet even more preferably between 3 and 8.
  • the collector composition may comprise component (i) only, or may comprise component (i) in combination with one or more surfactants (ii) (most common for this particular application would be alcohol ethoxylate phosphate ester, ethoxylated or propoxylated fatty alcohol, ethoxylated fatty amine, all C8-C22 linear or branched).
  • surfactants most common for this particular application would be alcohol ethoxylate phosphate ester, ethoxylated or propoxylated fatty alcohol, ethoxylated fatty amine, all C8-C22 linear or branched.
  • the amount of collector composition added to the ore will in general be in the range of from about 10 to about 1000 g/ton dry ore, preferably in the range of from about 20 to about 500 g/ton dry ore, more preferably from about 100 to about 400 g/ton dry ore.
  • reagents can be added either at the same time or, preferably, separately during the process and can include depressants, such as a polysaccharide, alkalized starch or dextrin, extender oils, frothers/froth regulators, such as pine oil, MIBC (methylisobutyl carbinol) and alcohols such as hexanol and alcohol ethoxylates/propoxylates, inorganic dispersants, such as silicate of sodium (water glass) and soda ash, and pH-regulators.
  • depressants such as a polysaccharide, alkalized starch or dextrin
  • extender oils frothers/froth regulators
  • frothers/froth regulators such as pine oil, MIBC (methylisobutyl carbinol) and alcohols such as hexanol and alcohol ethoxylates/propoxylates
  • inorganic dispersants such as silicate of sodium (water glass) and soda ash, and pH-regul
  • the process to treat ores according to the present disclosure preferably comprises the steps of:
  • T-CNSL T-CNSL
  • Cardanol 96. 2 wt- %)
  • Methyl Cardol 0.7 wt-%
  • the reactor was heated at 120 e C for 1 ,5h under N2 sparge to reduce water content to 0.04 wt. %.
  • the reactor was then heated to 130 e C and 622 g (14.12 moles) of ethylene oxide were fed gradually to not exceed the reactor pressure of 55 psig.
  • the post-reaction was carried out for 1 .5 hours at 130 e C until the pressure in the reactor stabilized. Then the reaction mixture was cooled to 80 e C and material was discharged.
  • 500 g of an igneous phosphate ore containing 42% apatite, 38% nepheline, 5% aegirine, 3% feldspar and 2% sphene was ground in a rod mill with 500 g of synthetic process water and 6.2 kg of stainless-steel rods (grinding to 70% -160pm - i.e. a granulometry of 70% through a 160 micron mesh).
  • the ore/water slurry was transferred to a 1.3L cell of a flotation machine and conditioned with 200 g/t of sodium silicate solution (2 min) and 100 g/t of the collector blend (containing 40 wt% of tested component and 60 wt% of tall oil fatty acid) (1 min).
  • the conditioning was performed at a rotor speed of 1000 min 1 .
  • the Rougher - Cleaner 1 - Cleaner 2 flotation set was performed during 4, 3 and 2 min, respectively (at a rotor speed 1000 min 1 and an air flow of 3.0 L/min). Fractions coming from flotation were dried in the oven, weighed, and analyzed by means of XRF analysis. Recovery and Grade values were received.
  • Example 1 substantially outperformed the nonionic equivalent (cf. RU2717862C1 ) - P2O5 recovery was improved by 9.5% and the grade of P2O5 was 0.2% higher.
  • Example 3 Flotation tests - direct flotation of carbonates from sedimentary phosphate
  • the sedimentary phosphate ore containing 19.0% P2O5 and 8.0% SiO2 was used for flotation.
  • the ore contained 37% of particles ⁇ 74pm and 75% ⁇ 215pm.
  • the ore was transferred to a 1 .3L cell of a flotation machine and filled up to the mark with water.
  • the water used in flotation was a synthetic made process water that contain 600 ppm Ca 2+ and 1600 ppm SO 4 2 '.
  • the ore slurry was conditioned with 7000 g/t H3PO4 (30 sec) and 1000 g/t of carbonate collector (2 min). After that the carbonate flotation was performed during 2 min. Further, the pH of the pulp was adjusted to 7 using 10% Na2COs.
  • Example 4 Flotation tests - Direct flotation of spodumene
  • collector composition disclosed herein is effective in the beneficiation of non-sulfidic ores in general (i.e., show that the improvement is not limited only to the beneficiation of phosphate ore) a further flotation was performed on a non-sulfidic siliceous lithium ore.
  • siliceous lithium ore containing spodumene as the main Li-bearing mineral with a Li2O grade in the feed of 2.107% was used for flotation.
  • the gangue minerals in this feed were mica, quartz, albite, muscovite, microcline, kaolinite.
  • the ore contained 80% of particles ⁇ 150 pm.
  • the ore was transferred to a 0.5L cell of a flotation machine and filled up to the mark with water. Tap water was used for flotation.
  • the ore slurry was conditioned with 200 g/t of sodium carbonate and 500 g/t of the collector composition (2 and 6 min, respectively). Further, the spodumene rougher flotation was performed during 2 min. Fractions coming from flotation were dried in the oven, weighed, and analyzed by means of peroxide fusion with an AAS finish.

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Abstract

La présente invention concerne des compositions de collecteur dérivées de l'huile de coque de noix de cajou destinées à être utilisées dans la valorisation de minéraux non sulfurés ou de minerais non sulfurés.
PCT/EP2023/079600 2022-11-04 2023-10-24 Procédé de valorisation de minéraux ou de minerais non sulfurés WO2024094486A1 (fr)

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