EP2885081A1 - Sammelvorrichtungen für die erzanreicherung - Google Patents

Sammelvorrichtungen für die erzanreicherung

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Publication number
EP2885081A1
EP2885081A1 EP13756649.3A EP13756649A EP2885081A1 EP 2885081 A1 EP2885081 A1 EP 2885081A1 EP 13756649 A EP13756649 A EP 13756649A EP 2885081 A1 EP2885081 A1 EP 2885081A1
Authority
EP
European Patent Office
Prior art keywords
collector
formula
compound
carbon atoms
ppm
Prior art date
Legal status (The legal status 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 status listed.)
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Application number
EP13756649.3A
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English (en)
French (fr)
Inventor
Isabelle Birken
Mathieu SPINNHIRNY
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Carbonisation et Charbons Actifs CECA SA
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Carbonisation et Charbons Actifs CECA SA
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Publication of EP2885081A1 publication Critical patent/EP2885081A1/de
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Classifications

    • 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
    • B03D1/0043—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
    • B03D1/02—Froth-flotation processes
    • 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

Definitions

  • the present invention relates to the use of cationic collectors in flotation processes for the beneficiation of ores, more particularly in reverse flotation processes for the enrichment of ores, especially ores containing silicates.
  • Flotation is the extraction of minerals from a suspension, usually an aqueous suspension, an ore, making more hydrophobic (less wettable by water) particles to float, using specific reagents, generally called "collectors" by the skilled person.
  • the direct flotation process refers to the case where the floated particles are valuable ores, whereas the reverse flotation process refers to the case where the floated particles are the impurities to extract valuable ores.
  • the flotation process generally takes place in a cell containing an aqueous suspension of the ore to be treated and an air bubble generator. At least one manifold is added and the collector (s) adsorb to the surface of the particles of minerals or impurities to be removed, increasing the attachment of the particles with the air bubbles during the collision. The combined air / particle bubbles, less dense than the pulp, rise to the surface, leading to the formation of a foam, which can be collected by skimming or overflow.
  • the flotation of minerals is generally performed using cationic collectors.
  • Cationic collectors are molecules that are at least partially positively charged when added in an aqueous environment at an appropriate pH.
  • cationic collectors is included herein as organic collecting compounds containing at least one amino group.
  • Such cationic collectors are already known and widely used, and include, for example, fatty amines and their salts, fatty propylene polyamines and their salts, alkyl ether amines and alkyl ether diamines and their salts, quaternary ammonium salts, imidazoline derivatives, alkoxylated amines and the like.
  • U.S. Patent 5,261,539 proposed alkoxylated alkylguanidines in Cs C2 4 containing 1 to 10 alkoxy groups, alkoxylated fatty alkyl amines in Cs-C2 4 containing 1 to 6 alkoxy groups and mixtures thereof, as cationic collectors to remove quartz, micaceous minerals, chlorite, pyrite and other mineral impurities from finely ground calcium carbonate.
  • This patent discloses higher calcium carbonate recoveries compared to Alkazene ® , an imidazoline type collector.
  • US Pat. No. 4,995,965 claims a mixture containing at least one compound from the group comprising a hydroxypropylated quaternary ammonium compound, dialkyldimethyl quaternary ammonium compounds. asymmetric and dialkylhexahydropyrimidine.
  • US Patent 5,540,337 claims a etheramine-based flotation material free of acrylonitrile.
  • WO 2007/122148 describes the combination of at least two collectors, belonging to the fatty quaternary ammonium salts or the quaternary ammonium compounds of bis-imidazoline, and more preferably a combination of two quaternary ammonium salts for the inverse foam flotation of a calcite ore.
  • WO2008 / 084391 specifically claims a calcium carbonate purification process using as collector at least one compound which is a quaternary imidazolium methosulfate, more particularly the aminoethylimidazolium methylsulfate of 1-methyl- 2-norologyyl-3-oleic acid.
  • US patent application 2009/0152174 claims a mixture of alkyletheramine, alkyletherdiamine, alkylamine or a quaternary ammonium salt with a fatty triamine corresponding to the formula RN- [A]. -NH 2 ] 2, for use as an improved collector for the flotation of silicates. Examples are given for reverse flotation of silicates in calcite. The most effective mixture indicated in the examples is a mixture of 29% fatty triamine with 71% of the standard quaternary ammonium salt (dicocoalkyldimethylammonium chloride).
  • a common feature of all known enrichment processes is that the collectors, which are inherently attached to the floated particles, remain in the residues. It is known that most amines and amine derivatives exhibit aquatic and environmental toxicity. In order to reduce the environmental impact, studies have been carried out to improve the performance of the flotation reagents, thus leading to a reduced dosage of the flotation reagents used. From the prior art, it is clearly taught to those skilled in the art that effective collectors for the flotation of silicates, especially in calcium carbonate ores, have been developed in recent years, these efficient collectors being mainly mixtures of cationic reagents containing at least one cationic molecule permanently charged (at least one quaternary nitrogen atom in the molecule).
  • the effectiveness of the flotation step is evaluated by measuring the yield of the product, which must be as high as possible (low losses of calcite in the foam), and the amount of Insoluble materials in the acids in the products (remaining silicates), which should be as low as possible.
  • a first object of the present invention is to provide an effective reagent for mineral mineral foam flotation, which is environmentally friendly, i.e. less toxic and / or more biodegradable than collectors already known in the state of the art.
  • Another object of the present invention is to provide an effective reagent (or collector) for the flotation of mineral ore foam, which is respectful of the environment, i.e. less toxic and / or more biodegradable than collectors already known in the state of the art, and which allows to obtain satisfactory enrichment yields.
  • an effective reagent or collector for the flotation of mineral ore foam, which is respectful of the environment, i.e. less toxic and / or more biodegradable than collectors already known in the state of the art, and which allows to obtain satisfactory enrichment yields.
  • the collector comprises at least one of the following compounds of formula (1).
  • the present invention relates to a collector for the flotation enrichment of an aqueous suspension of minerals, said collector comprising at least one compound of formula (1):
  • R21 represents a hydrocarbon group containing from 6 to 30 carbon atoms
  • R22 and R23 which are identical or different, each independently represent a hydrocarbon group containing from 1 to 6 carbon atoms,
  • R2 4 represents hydrogen or a hydrocarbon group containing from 1 to 6 carbon atoms
  • a 2 represents an alkylene group containing from 1 to 6 carbon atoms
  • R 2 i is a linear hydrocarbon group, cyclic or branched, saturated or unsaturated, preferably a linear or branched unsaturated hydrocarbon group, containing from 6 to 30, preferably from 8 to 26 more preferably from 12 to 22 carbon atoms, said group optionally containing one or more rings.
  • the compounds of formula (1) may also be used in the form of their addition salts with one or more acids, said acid or acids being chosen from inorganic and organic acids, including, without being limited to, hydrochloric acid, acetic acid, phosphoric acid, sulfuric acid, alkane (eg, methane) sulfonic acid, toluene sulfonic acid and the like.
  • Preferred compounds of formula (1) are those having one or more of the following characteristics:
  • R 22 and R 2 which are identical or different, each independently represent a hydrocarbon group containing 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and are preferably selected from methyl, ethyl, propyl and butyl,
  • R 24 represents hydrogen
  • a 2 represents an alkylene group containing 1, 2, 3 or 4 carbon atoms, A 2 is preferably ethylene or propylene, A 2 is more preferably propylene, and
  • Q is 1 or 2, q being preferably 1.
  • the compounds of formula (1) are available commercially or may be prepared by known preparation techniques.
  • the compounds of formula (1) can easily be obtained by condensation of an unsaturated fatty acid (rapeseed oil, tall oil) with an amine compound of formula (1 '):
  • R 22, R 2 3, R 24, A 2 and q are as defined above.
  • the condensation products of dimethylaminopropylamine with an unsaturated fatty acid Ci Ci 6- 8, such as rapeseed oil (CAS No. 85408-42-0) or tall oil (CAS No. 68650-79- 3) are particularly interesting because they are liquid at room temperature (easy to handle), easily dispersible in water, i.e. do not need to be totally or partially salified, at the dosage level used in the flotation process (typically from 10 ppm to 1000 ppm), and have the additional advantage of being biodegradable.
  • compounds of formula (1) are the condensation products of dimethylaminopropylamine with a coconut, palm, tallow and / or oleic fatty acid, and / or with a C 12 fatty acid (p eg, lauric), and / or with a C 18 fatty acid (eg ricinoleic), and / or with a C 20 -C 22 fatty acid, and / or the like.
  • compounds of formula (1) are those having the following CAS numbers: 68188-30-7, 69278-64-4, 691400-76-7, 165586-99-2, 226994-25-8, 97552 -95-9, which are respectively the condensation products of dimethylaminopropylamine with soybean oil, castor oil, peanut oil, almond oil, avocado, fish oil.
  • the collector of the present invention for the enrichment by flotation of aqueous suspensions of ores, may consist of one or more compounds of formula (1) as defined above, alone.
  • one or more of the compounds of formula (1) may advantageously be formulated with any one or more conventional additives known in the field of flotation.
  • Nonlimiting examples of such additives are pH adjusting agents, such as sodium or potassium carbonate and sodium or potassium hydroxide; solvents (water, organic solvents and mixtures thereof); depressants, such as starch, quebracho, tannin, dextrin and guar gum, and polyelectrolytes, such as polyphosphates and waterglass, which have a dispersing effect, often combined with a depressing effect.
  • pH adjusting agents such as sodium or potassium carbonate and sodium or potassium hydroxide
  • solvents water, organic solvents and mixtures thereof
  • depressants such as starch, quebracho, tannin, dextrin and guar gum
  • polyelectrolytes such as polyphosphates and waterglass
  • foaming agents such as methylisobutylcarbinol, triethoxybutane, pine oil, terpineol and polypropylene oxide and its alkyl ethers, among which is methyl isobutylcarbinol, triethoxybutane, Pine oil, terpineol are favorite foams.
  • foaming agents such as methylisobutylcarbinol, triethoxybutane, pine oil, terpineol and polypropylene oxide and its alkyl ethers, among which is methyl isobutylcarbinol, triethoxybutane, Pine oil, terpineol are favorite foams.
  • foaming agents such as methylisobutylcarbinol, triethoxybutane, pine oil, terpineol and polypropylene oxide and its alkyl ethers, among which is methyl isobutylcarbinol, triethoxybutane, Pine oil, terpin
  • the compound or compounds of formula (1) may also advantageously be formulated with one or more other conventional collector compounds known in the field of flotation, more preferably cationic collectors, " cationic collectors "having the meaning given above.
  • Such preferred conventional cationic collectors are those containing no sulfur atoms, and those most preferred are those containing only carbon, nitrogen and hydrogen atoms, and optionally oxygen atoms.
  • Said conventional cationic collectors, in the form of their addition salts with acids may, however, contain one or more sulfur atoms when the salifying acid itself comprises one or more sulfur atoms, e.g. ex. sulfuric acid, sulfonic acid or alkanesulfonic acid.
  • collectors of formula (1) examples include, but are not limited to:
  • fatty poly (alkyleneamines) and their salts e.g. ex. poly (ethyleneamines), poly (propyleneamines) and their salts, as well as their alkoxylated derivatives,
  • N-fatty alkylaminocarboxylic acids and their salts e.g. ex. N-fatty alkylaminopropionic acids and their salts
  • quaternary ammonium compounds • quaternary ammonium compounds, p. ex. fatty quaternary ammonium compounds, mono (fatty alkyl) quaternary ammonium compounds, di (fatty alkyl) quaternary ammonium compounds, such as those described in WO 2007/122148,
  • polyamine refers to a compound comprising two or more amine groups, the amino groups being optionally substituted, i.e. that the two or more amino groups may be the same or different and may be primary, secondary or tertiary amine groups.
  • N, N ', N'-tri-hydroxyethyl-N-tallowpropylenediamine (CAS RN 61790-85-0), N, N', N ' -tri-hydroxyethyl-N-oleylpropylenediamine (CAS No. 103625-43-0), N, N ', N'-tri-hydroxyethyl-N-laurylpropylenediamine (CAS No. 25725-44-4), fatty alkylimidazoline obtained by condensation of diethylenetriamine and an oleic fatty acid (CAS No. 162774-14-3), N, N ', N'-tri-hydroxyethyl-N-behenylpropylenediamine (CAS No.
  • isodecyloxypropyl-1,3-diaminopropane (CAS No. 72162 -46-0), N, N-di (tallow carboxyethyl) -N-hydroxyethyl-N-methylammonium methylsulfate (CAS No. 91995-81-2), N-cocoaminopropionic acid (CAS No. 84812-94-2), N-laurylaminopropionic acid (CAS No. 1462-54-0), N-myristylaminopropionic acid (CAS No. 14960-08-8), their addition with one or more acids, the sodium salt of N-lauryl-aminopropionic acid (CAS No.
  • the collector of the present invention comprises from 1% by weight to 100% by weight of at least one compound of formula (1), more preferably from 10% by weight to 100% by weight, typically from 20% by weight to 100% by weight, of at least one compound of formula (1), advantageously from 1% by weight to 99% by weight of at least one compound of formula (1) ), more preferably from 10% by weight to 99% by weight, typically from 20% by weight to 99% by weight of at least one compound of formula (1), relative to the total amount of the compound (s) of formula (1) and other cationic compounds.
  • the collector according to the present invention comprises, and preferably consists of, at least one compound of formula (1) as described above, and at least one compound of formula 2):
  • Ri represents a hydrocarbon group containing from 6 to 30 carbon atoms
  • Al represents an alkylene group containing from 1 to 6 carbon atoms
  • E 1 , E 2 and E 3 which are identical or different from one another, are chosen independently from alkylene oxide groups containing from 2 to 6 carbon atoms,
  • N, n 2 and n 3 which are identical or different from each other, and independently of each other, each represent an integer whose value is from 1 to 20, and
  • the compounds of formula (2) may also be used in the form of their addition salts with one or more acids, said acid or acids being chosen from inorganic and organic acids, including, without being limited to, hydrochloric acid, acetic acid, phosphoric acid, sulfuric acid, alkane (eg, methane) sulfonic acid, toluene sulfonic acid and the like.
  • the collector of the present invention comprises at least one compound of formula (1) as defined above, optionally with at least one compound of formula (2) above, and is essentially free, more preferably is free of any quaternary ammonium-containing compound.
  • the mixtures of compounds of formula (2) containing various radicals R1 are included in the present invention, for example mixtures of compounds of formula (2) in which the various radicals Ri contain from 16 to 18 carbon atoms.
  • R 1 is a linear hydrocarbon group, cyclic or branched, saturated or unsaturated, containing from 6 to 30, preferably from 8 to 26, more preferably preferred from 12 to 22 carbon atoms, said group optionally containing one or more rings.
  • preferred compounds of formula (2) are those in which A 1 represents an alkylene group containing from 1 to 6 carbon atoms, preferably from 2 to 6 carbon atoms, more preferably 2, 3 or 4 carbon atoms.
  • Preferred compounds of formula (2) are those wherein A 1 is propylene.
  • E 1 , E 2 and E 3 are chosen from methylene oxide - (CH 2 -O) -, ethylene oxide - (CH 2 -CH 2 -O) ) -, propylene oxide (CH 2 -CH (CH 3 ) -O) - and / or - (CH (CH 3 ) -CH 2 -O) -, and butylene oxide - (CH (CH 2) 2 -CH 3 ) -CH 2 -O) - and / or - (CH 2 -CH (CH 2 -CH 3 ) -O) -, E 1 , E 2 and E 3 being connected to the respective nitrogen atom by their sp 2 carbon atom.
  • Ei, E 2 and E 3 are selected from ethylene oxide - (CH 2 -CH 2 -O) -, and propylene oxide (CH 2 - CH (CH 3) -O) - and / or - (CH (CH 3 ) -CH 2 -O) -. More preferably, from 70 mole% to 100 mole% of all the alkylene oxide groups present in the compound of formula (1) are ethylene oxide groups, and 0 mole% to 30 mole%. moles are propylene oxide groups. Even more preferably, E 1 , E 2 and E 3 are identical radicals and are selected from ethylene oxide and propylene oxide. Even more preferably, E 1 , E 2 and E 3 are all identical radicals and are ethylene oxide groups. It should also be understood that E 1 , E 2 and E 3 can each comprise two or more different alkylene oxide groups, which can be arranged in a sequenced or random distribution.
  • the compounds of formula (2) are those in which ni, n 2 and n 3 , which are identical or different, represent independently an integer whose value is from 3 to 20, preferably from 3 to 10. Preference is also given to compounds of formula (2) in which the sum ni + n 2 + n3 is from 10 to 40, preferably from 10 to 30.
  • the compounds of formula (2) are those in which ni, n 2 and n 3 , which are identical or different, independently represent an integer whose value is from 1 to 10, more preferably from 1 to 5, even more preferably from 1 to 3. Preference is also given to compounds of formula (2) in which the sum ni + n 2 + n 3 is strictly less than 10.
  • p is preferably 1 or 2. More preferably, p is 1.
  • the compound of formula (2) above has one or more of the following characteristics:
  • R 1 represents a linear or branched hydrocarbon group containing from 6 to 30 carbon atoms, preferably from 8 to 26, more preferably from 12 to 22 carbon atoms, optionally containing one or more unsaturations, in the form of a or more than one double and / or three
  • a 1 represents a linear or branched alkylene group containing from 1 to 6 carbon atoms, preferably from 2 to 6 carbon atoms, particularly preferably 2, 3 or 4 carbon atoms,
  • E 1 , E 2 and E 3 are independently selected from the group ethylene oxide (EO), the propylene oxide group (OP) and the butylene oxide group (OB), preferably from the EO group and the OP group, more preferably, E i, E 2 and E 3 each represent an EO group,
  • N, n 2 and n 3 which are identical or different, independently represent an integer whose value is from 1 to 20, preferably from 1 to 10, and the sum ni + n 2 + n 3 ranges from 3 to 40 preferably from 3 to 30,
  • the compound of formula (2) above has one or more of the following characteristics:
  • R 1 represents a linear alkyl group containing from 8 to 26, more preferably from 12 to 22 carbon atoms
  • Al represents a linear alkylene group containing from 2 to 4 carbon atoms, for example a - (CH 2 ) 3 (propylene) group,
  • E 1 , E 2 and E 3 are independently selected from the group E E and the group OP, more preferably E 1 , E 2 and E 3 each represent an EO group,
  • N, n 2 and n 3 which are identical or different, independently represent an integer whose value is from 1 to 5, preferably from 1 to 3, and the sum ni + n 2 + n 3 ranges from 3 to 9 , for example the sum ni + n 2 + n 3 is 3,
  • P is 1 or 2, and preferably 1.
  • the compound of formula (2) above has one or more of the following characteristics:
  • R 1 represents a linear alkyl group containing from 8 to 26, more preferably from 12 to 22 carbon atoms
  • Al represents a linear alkylene group containing from 2 to 4 carbon atoms, for example a - (CH 2 ) 3 (propylene) group,
  • E 1 , E 2 and E 3 are independently selected from the group E E and the group OP, more preferably E 1 , E 2 and E 3 each represent an EO group,
  • N, n 2 and n 3 which are identical or different, independently represent an integer whose value is from 3 to 20, preferably from 3 to 10.
  • P is 1 or 2, and preferably 1.
  • the compounds of formula (2) are chosen from alkoxylated fatty C 6 -C 3 o -polyamine alkyls, and even more advantageously from ethoxylated or propoxylated fatty C 6 -C 3 o-diamino diamines.
  • the compounds of formula (2) are commercially available or may be prepared by known preparation techniques.
  • the compounds of formula (2) can easily be obtained by condensation of a fatty polyamine with an alkylene oxide.
  • a typical example of a compound of formula (2) is an ethoxylated tallow diamine, for example a tallow diamine reacted with one or more ethylene oxide molecules, typically N ', N', N '. tris-hydroxyethyl-N-tallow-propylenediamine (tallow diamine with 3 moles of ethylene oxide) having a CAS number 61790-85-0.
  • This compound is particularly interesting because it is liquid at room temperature, easy to handle, easily dispersible in water, i.e. does not need to be totally or partially salified, at the dosage level used in the flotation process (typically from 10 ppm to 1000 ppm). In addition, this product is biodegradable.
  • the collector according to the present invention thus preferably comprises, and more preferably consists of:
  • At least one other conventional collector preferably a conventional cationic collector
  • one or more additives conventionally used in the state of the art, and for example chosen from pH adjusting agents, depressants, polyelectrolytes, foaming agents and the like.
  • the collector according to the present invention preferably comprises, and more preferably consists of:
  • At least one compound of formula (1) as defined above At least one compound of formula (2) as defined above;
  • At least one other conventional collector preferably a conventional cationic collector
  • one or more additives conventionally used in the state of the art, and for example chosen from pH adjusting agents, depressants, polyelectrolytes, foaming agents and the like.
  • the collector according to the present invention preferably comprises, and more preferably consists of:
  • At least one other conventional collector preferably a conventional cationic collector
  • one or more additives conventionally used in the state of the art, and for example chosen from pH adjusting agents, solvents, depressants, polyelectrolytes, foaming agents and the like.
  • the collector according to the present invention preferably comprises, and more preferably consists of:
  • At least one other conventional collector preferably a conventional cationic collector
  • one or more additives conventionally used in the state of the art, and for example chosen from pH adjusting agents, depressants, polyelectrolytes, foaming agents and the like.
  • the collector according to the present invention comprises, and preferably consists of:
  • the ratio by weight between the compound (s) of formula (1) and the compound (s) of formula (2) in the collector of the present invention may vary in large proportions, without any specific limitation. According to a preferred embodiment, this weight ratio is from 1: 99 to 99: 1, more preferably preferred from 20:80 to 80:20, even more preferably from 40:60 to 60:40. Particularly satisfactory results are obtained with a mixture of a weight ratio of 50:50 of at least one compound of formula (1) and at least one compound of formula (2), and typically with a mixture of a weight ratio of 50:50 of one or more compounds of formula (1) and one or more compounds of formula (2).
  • the present invention relates to the use of at least one collector, and preferably a collector, as defined above, for the direct or reverse flotation enrichment, of reverse preference, an aqueous suspension of ores containing minerals.
  • the collector of the present invention is effective either in direct flotation processes or in reverse flotation processes.
  • the collector of the present invention is particularly suitable for enriching aqueous suspensions of ores using the reverse flotation process.
  • the use of the present invention is particularly effective for the enrichment of all types of ores containing impurities, and more specifically for the enrichment of carbonates (calcium and / or magnesium carbonates), phosphates and phosphates. iron ores, enrichment of calcium carbonates being particularly preferred.
  • the use of the present invention is particularly suitable for the enrichment of all types of calcium carbonates (natural or crushed), such as limestone, chalk, marble, calcite, carbonate-containing materials.
  • calcium (minimum CaCO3 content 70%) calcium carbonates containing alkaline earth metals (eg calcium carbonate calcium or gaylussite), magnesium carbonates (eg calcium carbonates containing magnesium carbonate, such as dolomite), beryllium carbonates, strontium carbonates, barium carbonates, radium carbonates, and mixtures thereof.
  • Natural calcium carbonate in the sense of the present invention is a calcium carbonate (calcite) obtained from natural sources, such as marble, limestone or chalk.
  • crushed calcium carbonate GCC within the meaning of the present invention is a natural calcium carbonate which is machined by a wet and / or dry treatment such as grinding, sieving and / or fractionation, for example by a cyclone or classifier.
  • the aluminum oxides containing other elements such as sodium (eg diaoyudaoite), and other oxides, sulphates and sulphides, such as zinc oxides, zirconium dioxides, tin dioxide , lead carbonate, barium sulphate and zinc sulphide, including mixtures of two or more of the foregoing in all proportions.
  • elements such as sodium (eg diaoyudaoite), and other oxides, sulphates and sulphides, such as zinc oxides, zirconium dioxides, tin dioxide , lead carbonate, barium sulphate and zinc sulphide, including mixtures of two or more of the foregoing in all proportions.
  • a white pigment is a pigment which has a white color.
  • the white color of the white pigments is mainly based on the relatively low absorption of light in combination with non-selective light scattering of visible light on the pigments.
  • the white pigments in the present invention are inorganic white pigments that can be obtained naturally or synthetically.
  • Non-white pigments include, but are not limited to, minerals selected from phosphates, potassium chloride, ores containing a metal, "metal” meaning p. ex. iron, platinum, aluminum, nickel, copper and the like.
  • the minerals which are effectively removed, or at least whose content in ores is significantly reduced by flotation may be of any type known to those skilled in the art, preferably provided that they are negatively charged to pH. which flotation is carried out.
  • said impurities include, but are not limited to, insoluble graphite, iron sulphides (eg, pyrite, marcasite, magnetopyrite, pyrrhotite, mackinawite), iron oxides (eg, wustite, magnetite), iron hydroxides, and iron oxyhydroxides (eg, bernalite, goethite, lepidocrocite, feroxyhyte, ferrihydrite, schwertmannite, akaganéite), silica, silicates (neosilicates, sorosilicates, cyclosilicates, inosilicates, phyllosilicates, tectosilicates and / or amorph
  • the minerals that are effectively removed, or at least the ore content of which is significantly reduced, by direct or inverse, preferably inverse, foam flotation of ores include silicates, preferably quartz minerals, such as quartz, tridymite and / or cristobalite, more preferably quartz, as well as mixtures of quartz and one or more additional silicates, even more preferably quartz alone.
  • silicates preferably quartz minerals, such as quartz, tridymite and / or cristobalite, more preferably quartz, as well as mixtures of quartz and one or more additional silicates, even more preferably quartz alone.
  • the use of the present invention is particularly well suited for the enrichment of calcium carbonate, and the minerals (impurities) that are effectively removed typically include silicates, preferably quartz.
  • one or more compounds of formula (1) When one or more compounds of formula (1) are used with one or more other compounds as defined above, for example those of formula (2), they may be added separately, but are preferably added together under the form of an individual flotation reagent (collector).
  • the collector according to the invention for use in the process of enrichment by flotation of an aqueous suspension of ores according to the present invention may vary within wide limits depending on the nature of the ores to be purified and the nature and the amount of impurities contained in them.
  • the total amount of collector is from 10 ppm to 5000 ppm by weight, preferably from 50 ppm to 1000 ppm, for example from 200 ppm to 500 ppm, based on the amount of ore (s) to be enriched.
  • Flotation experiments in the laboratory are performed using an Outotec flotation cell, filled with 2 L of water. 800 g of calcium carbonate are added in order to obtain a suspension at 30% by weight.
  • the calcium carbonate sample used for the experiment contains between 2.5% by weight and 3% by weight of impurities.
  • the flotation experiment takes place at neutral pH.
  • the flotation reagent (collector) is weighed and added directly into the flotation cell.
  • the quantity introduced is expressed in ppm by weight relative to the initial amount of CaCO3 introduced into the suspension.
  • the suspension is stirred for 5 minutes (conditioning time) at 1200 rpm without air bubbles, followed by 20 to 30 minutes flotation maximum. Air is finally bubbled into the suspension, the air flow being set at 3 L-min "1 .
  • the purified carbonate sample is filtered, weighed after drying and analyzed: an attack of hydrochloric acid (HCl) is followed by a second drying and a weighed to measure the amount of acid-insoluble compounds (remaining silicates).
  • the attack of HCI aims to obtain complete dissolution of the calcium carbonate by appropriate dissolution with a concentrated solution of hydrochloric acid (typically 10%).
  • the remaining minerals that are not digested correspond to the silicates (impurities).
  • the foam is also rinsed and filtered. It is then dried, weighed, attacked with HCl, dried and weighed again to deduce the amount of impurities and losses of calcium carbonate.
  • Collector A (comparative) dicoco chloride, dimethylammonium, CAS No. 61789-77-3, 75% by weight in isopropanol (15% by weight) and water (10% by weight);
  • B-collector (comparative) coconut chloride, dimethylbenzylammonium CAS No. 61789-71 -7, 50% by weight in water;
  • Collector D N, N ', N'-tri-hydroxyethyl-N-tallowpropylenediamine, CAS No. 61790-85-0;
  • Collector F N, N ', N'-tri-hydroxyethyl-N-oleylpropylenediamine, CAS No. 103625-43-0;
  • Collector G N, N ', N'-tri-hydroxyethyl-N-cocopropylenediamine, CAS No. 25725-44-4;
  • H-collector N-tallow alkyl, ethoxylated trimethylenediamine (CAS No. 61790-85-0), obtained by ethoxylation of N-tallow-1,3-propylenediamine with 7 moles of ethylene per mole of diamine;
  • J collector (comparative) N-tallow-alkyl, ethoxylated propylenediamine, (CAS RN 61790-85-0), obtained by ethoxylation of N-tallow-1,3-propylenediamine with 12 moles of ethylene oxide per mole diamine;
  • L collector fish oil, N- (3- (dimethylamino) propyl)) amide, (CAS No. 97552-95-9);
  • N-collector (comparative) isodecyloxypropyl-1,3-diaminopropane, (CAS No. 72162-46-0);
  • O collector (comparative) mixture of 10% by weight of propan-2-ol and 90% by weight of N, N-di (tallow carboxyethyl) -N-hydroxyethyl-N-methylammonium methylsulfate;
  • a collector which is a mixture of 75% by weight of hydrogenated tallow dimethylbenzylammonium chloride (CAS No. 61789-75-1) in 15% by weight of propan-2-ol and 10% by weight of water weight;
  • Collectors D and E do not require any partial salification before use, unlike the commercial etheramine and ether-diamine collectors.
  • the results obtained with the collector E at 500 ppm, in terms of loss of calcite in the foam, are better than a formulation of the standard collector C which is a mixture of a quaternary ammonium salt, diacetate of diamine and a highly ethoxylated fatty monoamine.
  • the collector E is biodegradable, while the formulation C contains a product which has a poor biodegradability.
  • collector of the present invention (mixture of 50% by weight D + 50% by weight E) can advantageously be formulated with well-known conventional additives, such as a well-known foaming agent, terpineol in this example.
  • the formulation containing terpineol makes it possible to collect more impurities than the collector D + E without terpineol, while maintaining calcite losses at a correct level ( ⁇ 3% by weight). ).
  • Table 5 lists the results obtained with various collectors of general formula (1).
  • collector D + collector E provides better results than another type of biodegradable collector.
  • the collector O is also not very foaming, leading to a crust above the foam, which could lead to problems on an industrial scale during skimming.

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  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Paper (AREA)
  • Manufacture And Refinement Of Metals (AREA)
EP13756649.3A 2012-08-20 2013-08-01 Sammelvorrichtungen für die erzanreicherung Withdrawn EP2885081A1 (de)

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FR1257882A FR2994534B1 (fr) 2012-08-20 2012-08-20 Collecteurs pour enrichissement de minerais
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