EP1286780B1 - Agent for dressing of phosphate ore - Google Patents

Agent for dressing of phosphate ore Download PDF

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Publication number
EP1286780B1
EP1286780B1 EP01951475A EP01951475A EP1286780B1 EP 1286780 B1 EP1286780 B1 EP 1286780B1 EP 01951475 A EP01951475 A EP 01951475A EP 01951475 A EP01951475 A EP 01951475A EP 1286780 B1 EP1286780 B1 EP 1286780B1
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EP
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Prior art keywords
weight
flotation
agent
ethylene oxide
flotation agent
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Expired - Lifetime
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EP01951475A
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German (de)
French (fr)
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EP1286780A1 (en
Inventor
Gernot Kremer
Klaus Ulrich Pedain
Juan Balassa
Pablo Lopez
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Clariant Finance BVI Ltd
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Clariant GmbH
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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
    • B03D1/008—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
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/005—Dispersants
    • 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 invention relates to an improved flotation agent for Phosphate ore, which in addition to a fatty acid is a mixture of collectors includes ethoxylated alkylphenols.
  • a dispersant such as, for example, a nonylphenol with 2-5 mol ethylene oxide (EO) and an aliphatic ethoxylated alcohol with the chain length C 11 -C 15 , which contains 2-4 moles of EO, is used.
  • EO nonylphenol with 2-5 mol ethylene oxide
  • a further improvement results if an alcohol with the chain length C 1 -C 15 is dissolved in the dispersant. This alcohol improves the emulsifiability of the dispersant.
  • Another object of the invention is the use of a mixture of alkoxylated alkylphenols as described above as dispersants in the Flotation of phosphate ores.
  • the Use with fatty acids as a collector is the use of a mixture of alkoxylated alkylphenols as described above as dispersants in the Flotation of phosphate ores.
  • the Use with fatty acids as a collector is the use of a mixture of alkoxylated alkylphenols as described above as dispersants in the Flotation of phosphate ores.
  • the dispersant preferably comprises 9 to 15, in particular 10 to 13% by weight of component a).
  • the content of component b) results from the Difference to 100% by weight.
  • the alkyl radicals are preferably linear or branched nonyl residues.
  • ethylene oxide is between 2 and 4, in particular between 2.5 and 3.5 mol.
  • the flotation agent according to the invention contains no alcohols.
  • fatty acid which is the main component of the invention Flotation agent
  • Flotation agent it is preferably a linear or branched monocarboxylic acid with 8 to 26 carbon atoms.
  • Fatty acids known in the art can be used.
  • the flotation agent according to the invention preferably contains between 1 and 30% by weight of the dispersant.
  • the flotation agent according to the invention is preferably in amounts of 100 to 1,000 g / t solids for flotation of Phosphate ores used.
  • the addition amount of the invention Dispersant with separate collector / dispersant metering preferably between 30 and 150 g / t, in particular between 40 and 60 g / t, based on the solids feed.
  • the flotation agent according to the invention can, in addition to the above Ingredients fatty acid and dispersant, pusher or others from the Contain components known in the art. Such ingredients are for example foaming agents and aliphatic polyglycol ethers. You can also different pushers, e.g. Water glass, to be used separately.
  • the flotation agent according to the invention is exemplified below:
  • the reaction can be carried out in such a way that the phenol / nonene mixture is circulated over an acidic fixed bed catalyst.
  • the following mixtures were obtained: Mole of phenol Moles of nons Proportion of dinonylphenol 1 0.9 9% by weight 1 1.0 11% by weight 1 1.1 13% by weight comparison 1 0.6 3% by weight
  • the dosage can reduced from 81 g / t to 40 to 60 g / t compared to the reference product, without the concentrate quality or the yield deteriorating.
  • composition of the raw ore apatite 22% by weight phlogopite 24% by weight calcite 25% by weight dolomite 3% by weight forsterite 7% by weight diopside 8% by weight

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  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Dental Preparations (AREA)
  • Materials For Medical Uses (AREA)
  • Paper (AREA)

Abstract

The invention relates to a flotation agent for phosphate ore, comprising a fatty acid as collector and alkoxylated alkylphenols as dispersing agents, characterized in that the alkylphenols are composed ofa) 8 to 20% by weight of one or more dialkylphenols having alkyl radicals from 8 to 12 carbon atomsb) 80 to 92% by weight of one or more monoalkylphenols having alkyl radicals from 8 to 12 carbon atoms, which have been alkoxylated with 2 to 6 mol of ethylene oxide.

Description

Die vorliegende Erfindung betrifft ein verbessertes Flotationsmittel für Phosphaterz, welches neben einer Fettsäure als Sammler eine Mischung aus ethoxylierten Alkylphenolen umfasst.The present invention relates to an improved flotation agent for Phosphate ore, which in addition to a fatty acid is a mixture of collectors includes ethoxylated alkylphenols.

Es ist in der Flotation von Phosphaterz mit Fettsäuren gemäß ZA-90/9347 Stand der Technik, dass das Flotationsausbringen dadurch verbessert werden kann, dass zusätzlich zum Sammler (Fettsäure) ein Dispergiermittel, wie beispielsweise ein Nonylphenol mit 2 - 5 Mol Ethylenoxid (EO) und ein aliphatischer oxethylierter Alkohol mit der Kettenlänge C11-C15, welcher 2 - 4 Mol EO enthält, eingesetzt wird. Eine weitere Verbesserung ergibt sich, wenn in dem Dispergiermittel ein Alkohol mit der Kettenlänge C1-C15 gelöst wird. Dieser Alkohol verbessert die Emulgierbarkeit des Dispergiermittels.It is the state of the art in the flotation of phosphate ore with fatty acids according to ZA-90/9347 that the flotation yield can be improved in that, in addition to the collector (fatty acid), a dispersant, such as, for example, a nonylphenol with 2-5 mol ethylene oxide (EO) and an aliphatic ethoxylated alcohol with the chain length C 11 -C 15 , which contains 2-4 moles of EO, is used. A further improvement results if an alcohol with the chain length C 1 -C 15 is dissolved in the dispersant. This alcohol improves the emulsifiability of the dispersant.

Überraschenderweise wurde nun gefunden, dass die spezifische Dosierung eines Reaktionsproduktes aus Nonylphenol und 2,75 bis 3,25 Mol Ethylenoxid bei der Flotation von Phosphat aus Phosphaterz bei gleichem Ausbringen und gleicher Qualität signifikant vermindert werden kann, wenn das verwendete Nonylphenol statt der standardmäßigen 2 bis 5 Gew.-% Dinonylphenol 9 bis 13 Gew.-% Dinonylphenol enthält. Ebenso gilt, dass das Phosphatausbringen durch Verwendung des erfindungsgemäßen Dispergiermittels bei gleicher Dosierung sogar verbessert wird, wobei der P2O5-Gehalt im Flotationskonzentrat nicht beeinträchtigt wird.Surprisingly, it has now been found that the specific dosage of a reaction product of nonylphenol and 2.75 to 3.25 mol of ethylene oxide in the flotation of phosphate from phosphate ore can be significantly reduced with the same output and the same quality if the nonylphenol used instead of the standard 2 to 5 wt .-% dinonylphenol contains 9 to 13 wt .-% dinonylphenol. It is also true that the use of the dispersant according to the invention at the same dosage even improves the phosphate yield, the P 2 O 5 content in the flotation concentrate not being impaired.

Gegenstand der Erfindung ist somit ein Flotationsmittel für Phosphaterz, enthaltend eine Fettsäure als Sammler und alkoxylierte Alkylphenole als Dispergiermittel, dadurch gekennzeichnet, dass die Alkylphenole zusammengesetzt sind aus

  • a) 8 bis 20 Gew.-% eines oder mehrerer Dialkylphenole mit Alkylresten von 8 bis 12 C-Atomen
  • b) 80 bis 92 Gew.-% eines oder mehrerer Monoalkylphenole mit Alkylresten von 8 bis 12 C-Atomen,
    • welche mit 2 bis 6 mol Ethylenoxid alkoxyliert sind.The invention thus relates to a flotation agent for phosphate ore, containing a fatty acid as collector and alkoxylated alkylphenols as dispersants, characterized in that the alkylphenols are composed of
  • a) 8 to 20 wt .-% of one or more dialkylphenols with alkyl radicals of 8 to 12 carbon atoms
  • b) 80 to 92% by weight of one or more monoalkylphenols with alkyl radicals of 8 to 12 carbon atoms,
    • which are alkoxylated with 2 to 6 mol of ethylene oxide.

    Ein weiterer Gegenstand der Erfindung ist die Verwendung einer Mischung von alkoxylierten Alkylphenolen wie oben beschrieben als Dispergiermittel in der Flotation von Phosphaterzen. In einer bevorzugten Ausführungsform erfolgt die Verwendung mit Fettsäuren als Sammler.Another object of the invention is the use of a mixture of alkoxylated alkylphenols as described above as dispersants in the Flotation of phosphate ores. In a preferred embodiment, the Use with fatty acids as a collector.

    Das Dispergiermittel umfasst vorzugsweise 9 bis 15, insbesondere 10 bis 13 Gew.-% des Bestandteils a). Der Gehalt an Bestandteil b) ergibt sich durch die Differenz auf 100 Gew.-%. Vorzugsweise handelt es sich bei den Alkylresten um lineare oder verzweigte Nonylreste. Der Gehalt der Bestandteile a) und b) an Ethylenoxid beträgt in einer weiteren bevorzugten Ausführungsform zwischen 2 und 4, insbesondere zwischen 2,5 und 3,5 mol. In einer weiteren bevorzugten Ausführungsform enthält das erfindungsgemäße Flotationsmittel keine Alkohole.The dispersant preferably comprises 9 to 15, in particular 10 to 13% by weight of component a). The content of component b) results from the Difference to 100% by weight. The alkyl radicals are preferably linear or branched nonyl residues. The content of components a) and b) In a further preferred embodiment, ethylene oxide is between 2 and 4, in particular between 2.5 and 3.5 mol. In another preferred In one embodiment, the flotation agent according to the invention contains no alcohols.

    Bei der Fettsäure, die den Hauptbestandteil des erfindungsgemäßen Flotationsmittels ausmacht, handelt es sich vorzugsweise um eine lineare oder verzweigte Monocarbonsäure mit 8 bis 26 C-Atomen. Hierfür können die als Sammler im Stand der Technik bekannten Fettsäuren verwendet werden.For the fatty acid, which is the main component of the invention Flotation agent, it is preferably a linear or branched monocarboxylic acid with 8 to 26 carbon atoms. For this, the as Fatty acids known in the art can be used.

    Das erfindungsgemäße Flotationsmittel enthält vorzugsweise zwischen 1 und 30 Gew.-% des Dispergiermittels. Das erfindungsgemäße Flotationsmittel wird vorzugsweise in Mengen von 100 bis 1.000 g/t Feststoff zur Flotation von Phosphaterzen verwendet. Die Zugabemenge des erfindungsgemäßen Dispergiermittels bei getrennter Sammler/Dispergiermitteldosierung beträgt vorzugsweise zwischen 30 und 150 g/t, insbesondere zwischen 40 und 60g/t, bezogen auf die Feststoffaufgabe. The flotation agent according to the invention preferably contains between 1 and 30% by weight of the dispersant. The flotation agent according to the invention is preferably in amounts of 100 to 1,000 g / t solids for flotation of Phosphate ores used. The addition amount of the invention Dispersant with separate collector / dispersant metering preferably between 30 and 150 g / t, in particular between 40 and 60 g / t, based on the solids feed.

    Das erfindungsgemäße Flotationsmittel kann, neben den genannten Bestandteilen Fettsäure und Dispergiermittel, Drücker oder weitere aus dem Stand der Technik bekannte Bestandteile enthalten. Solche Bestandteile sind beispielsweise Schäumer und aliphatische Polyglykolether. Außerdem können verschiedene Drücker, wie z.B. Wasserglas, separat verwendet werden.The flotation agent according to the invention can, in addition to the above Ingredients fatty acid and dispersant, pusher or others from the Contain components known in the art. Such ingredients are for example foaming agents and aliphatic polyglycol ethers. You can also different pushers, e.g. Water glass, to be used separately.

    Im folgenden wird das erfindungsgemäße Flotationsmittel beispielhaft dargestellt:The flotation agent according to the invention is exemplified below:

    BeispieleExamples Herstellung von Nonyl-/DinonylphenolProduction of nonyl / dinonylphenol

    Die Mischung aus Mono- und Dinonylphenol wird wie folgt hergestellt:

    • Phenol wird vorgelegt
    • Zugabe 0,2 eq konz. Schwefelsäure
    • Unter Rühren Zugabe von Nonen
    • Innentemperatur steigt auf 30 bis 50°C, und es entwickelt sich Chlorwasserstoff
    • Die Reaktion ist beendet, wenn die Chlorwasserstoffentwicklung aufhört
    The mixture of mono- and dinonylphenol is produced as follows:
    • Phenol is presented
    • Add 0.2 eq conc. sulfuric acid
    • With stirring, add nons
    • The internal temperature rises to 30 to 50 ° C, and hydrogen chloride is evolved
    • The reaction is complete when the evolution of hydrogen chloride ceases

    Im technischen Maßstab kann die Reaktion so geführt werden, dass das Phenol-/Nonen-Gemisch im Kreislauf über einen sauren Festbettkatalysator gefahren wird. Es wurden folgende Gemische erhalten: Mol Phenol Mol Nonen Anteil Dinonylphenol 1 0,9 9 Gew.-% 1 1,0 11 Gew.-% 1 1,1 13 Gew.-% Vergleich 1 0,6 3 Gew.-% On an industrial scale, the reaction can be carried out in such a way that the phenol / nonene mixture is circulated over an acidic fixed bed catalyst. The following mixtures were obtained: Mole of phenol Moles of nons Proportion of dinonylphenol 1 0.9 9% by weight 1 1.0 11% by weight 1 1.1 13% by weight comparison 1 0.6 3% by weight

    Herstellung von Nonyl-/DinonylphenolethoxilatProduction of nonyl / dinonylphenol ethoxylate

    Die Ethoxylierung von Nonylphenol erfolgte in folgenden Schritten:

    • Nonylphenol in sauberen Kessel einfüllen.
    • Rührer einschalten.
    • Die angegebene Menge Natronlauge (als Katalysator) zugeben bzw. einsaugen.
    • Kesselinhalt unter Rühren auf 85 - 90°C aufheizen, dann Vakuum anlegen.
    • Vakuum mit Stickstoff aufheben und Kesselinhalt unter Rühren auf 140 - 145°C aufheizen.
    • Bei dieser Temperatur Ethylenoxid zudosieren.
    • Ethylenoxid bis zum Erreichen der berechneten Menge weiter zudosieren.
    • Zur Ethylenoxid-Abreaktion ca. 1 Stunde bei einer Sumpftemperatur von 140 - 150°C nachrühren.
    • Probe ziehen und OH-Zahl oder Trübungspunkt bestimmen und bis zum Gutbefund bei 140 - 150°C weiterrühren.
    • Ist die Ziel-OH-Zahl bzw. Ziel-Trübungspunkt noch nicht erreicht, muss zum Kesselinhalt die berechnete Ethylenoxidmenge nachdosiert werden.
    • Ist die Ziel-OH-Zahl erreicht, wird der Kesselinhalt abgekühlt auf 100 °C und unter Vakuum bei 100°C ausgegast.
    • Es folgt die Neutralisation bei 50 - 70°C mit Essigsäure bis auf einen pH-Bereich von 6,0 - 8,0.
    Nonylphenol was ethoxylated in the following steps:
    • Pour nonylphenol into a clean kettle.
    • Switch on the stirrer.
    • Add or soak in the specified amount of sodium hydroxide solution (as catalyst).
    • Heat the kettle contents to 85 - 90 ° C while stirring, then apply a vacuum.
    • Remove vacuum with nitrogen and heat the kettle contents to 140 - 145 ° C while stirring.
    • Add ethylene oxide at this temperature.
    • Continue metering ethylene oxide until the calculated amount is reached.
    • Stir for approx. 1 hour at a bottom temperature of 140 - 150 ° C for the ethylene oxide reaction.
    • Take a sample and determine the OH number or cloud point and continue stirring at 140 - 150 ° C until good.
    • If the target OH number or target cloud point has not yet been reached, the calculated amount of ethylene oxide must be added to the boiler content.
    • When the target OH number is reached, the contents of the boiler are cooled to 100 ° C and degassed under vacuum at 100 ° C.
    • This is followed by neutralization at 50-70 ° C with acetic acid to a pH range of 6.0-8.0.

    Folgende Ergebnisse wurden erhalten: Ausgangsstoffe Rohstoff Mol Menge Nonyl-/Dinonylphenol 1 231,3/233,9/236,4 kg Ethylenoxid 3 132 kg NaOH (50 %ig) 0,006 0,24 kg Essigsäure (techn. rein) 0,006 0,36 kg erhaltene Substanzen Anteil Dinonylphenol Molverhältnis Nonylphenol/Ethylenoxid Beispiel 1 9 % 1:3       2 11 % 1:3       3 13 % 1:3 Vergleich 3 % 1:4 The following results were obtained: starting materials raw material mol quantity Nonyl / dinonyl 1 231.3 / 233.9 / 236.4 kg ethylene oxide 3 132 kg NaOH (50%) 0,006 0.24 kg Acetic acid (techn. Pure) 0,006 0.36 kg obtained substances Proportion of dinonylphenol Molar ratio of nonylphenol / ethylene oxide example 1 9% 1: 3 2 11% 1: 3 3 13% 1: 3 comparison 3% 1: 4

    Anwendungstechnische UntersuchungenApplication studies

    Reagentien in g/t FeststoffReagents in g / t solids Aufgabe P2O5 in %Exercise P 2 O 5 in% Konzentrat P2O5 in %P 2 O 5 concentrate in% Ausbeuteyield Fettsäurefatty acid Dispergiermitteldispersants Vergleichcomparison 430430 8181 7,27.2 38,138.1 89,889.8 Beispiel 1example 1 430430 6565 6,26.2 38,538.5 87,287.2 Beispiel 2Example 2 430430 5454 6,06.0 38,138.1 89,889.8 Beispiel 3Example 3 430430 4343 5,75.7 37,737.7 92,492.4 Reagentien in g/tReagents in g / t Aufgabe P2O5 in %Exercise P 2 O 5 in% Konzentrat P2O5 in %P 2 O 5 concentrate in% Ausbeuteyield Fettsäurefatty acid Dispergiermitteldispersants Vergleichcomparison 400400 150150 7,37.3 39,939.9 71,371.3 Beispiel 2Example 2 400400 150150 7,87.8 40,140.1 76,276.2 Beispiel 3Example 3 400400 150150 8,18.1 40,340.3 76,476.4

    Auswertungevaluation

    Mit dem neuen Dispergiermittel (Tabelle 4, Beispiele 1 - 3) kann die Dosierung gegenüber dem Vergleichsprodukt von 81 g/t auf 40 bis 60 g/t abgesenkt werden, ohne dass sich die Konzentratqualität oder die Ausbeute verschlechtern.With the new dispersant (Table 4, Examples 1-3) the dosage can reduced from 81 g / t to 40 to 60 g / t compared to the reference product, without the concentrate quality or the yield deteriorating.

    Dosiert man herkömmliches Dispergiermittel (Vergleichsversuch) und erfindungsgemäßes Dispergiermittel (Beispiele 2 und 3) in gleichen Mengen (Tabelle 5), erreicht man bei konstanter Konzentratqualität eine signifikante Verbesserung der Phosphatausbeute.Dosed conventional dispersant (comparative experiment) and Dispersant according to the invention (Examples 2 and 3) in equal amounts (Table 5), one achieves a significant one with constant concentrate quality Improve the phosphate yield.

    Zusammensetzung des Roherzes: Apatit 22 Gew.-% Phlogopit 24 Gew.-% Calcit 25 Gew.-% Dolomit 3 Gew.-% Forsterit 7 Gew.-% Diopsid 8 Gew.-% Composition of the raw ore: apatite 22% by weight phlogopite 24% by weight calcite 25% by weight dolomite 3% by weight forsterite 7% by weight diopside 8% by weight

    Claims (7)

    1. A flotation agent for phosphate ore, comprising a fatty acid as collector and alkoxylated alkylphenols as dispersing agents, characterized in that the alkylphenols are composed of
      a) 8 to 20% by weight of one or more dialkylphenols having alkyl radicals from 8 to 12 carbon atoms
      b) 80 to 92% by weight of one or more monoalkylphenols having alkyl radicals from 8 to 12 carbon atoms,
      which have been alkoxylated with 2 to 6 mol of ethylene oxide.
    2. The flotation agent as claimed in claim 1, comprising nonylphenol ethoxylates as dispersing agents.
    3. The flotation agent as claimed in claim 1 and/or 2, in which 9 to 15% by weight of the dispersing agent consist of one or more dialkylphenol ethoxylates.
    4. The flotation agent as claimed in one or more of claims 1 to 3, in which the ethylene oxide content is between 2 and 4 mol.
    5. The flotation agent as claimed in one or more of claims 1 to 4, in which no alcohol is present.
    6. The use of a flotation agent as claimed in claims 1 to 5 in amounts of from 100 to 1000 g/t for the flotation of phosphate ore.
    7. The use of a dispersing agent as defined in claims 1 to 5 for phosphate flotation.
    EP01951475A 2000-05-18 2001-05-03 Agent for dressing of phosphate ore Expired - Lifetime EP1286780B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE10024667 2000-05-18
    DE10024667A DE10024667C2 (en) 2000-05-18 2000-05-18 Preparations for the treatment of phosphate ore
    PCT/EP2001/004964 WO2001087490A1 (en) 2000-05-18 2001-05-03 Agent for dressing of phosphate ore

    Publications (2)

    Publication Number Publication Date
    EP1286780A1 EP1286780A1 (en) 2003-03-05
    EP1286780B1 true EP1286780B1 (en) 2004-08-04

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    US (1) US6712217B2 (en)
    EP (1) EP1286780B1 (en)
    AT (1) ATE272447T1 (en)
    AU (1) AU7239001A (en)
    BR (1) BR0110820A (en)
    DE (2) DE10024667C2 (en)
    ES (1) ES2225579T3 (en)
    MX (1) MXPA02011316A (en)
    WO (1) WO2001087490A1 (en)
    ZA (1) ZA200208449B (en)

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    DE10024667C2 (en) 2000-05-18 2002-02-28 Clariant Gmbh Preparations for the treatment of phosphate ore
    CA2597176C (en) 2005-02-04 2013-10-22 Mineral And Coal Technologies, Inc. Improving the separation of diamond from gangue minerals
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    CN103920596B (en) * 2014-04-25 2017-02-15 中蓝连海设计研究院 Collophanite combination flotation collector and preparation method and application thereof
    CN104307640B (en) * 2014-11-07 2016-08-17 中蓝连海设计研究院 A kind of collecting agent of phosphate reverse flotation calcite
    CN107511268A (en) * 2017-09-08 2017-12-26 湖北富邦科技股份有限公司 A kind of method for the rock phosphate in powder floating agent for preparing high-strength collecting ability
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    DE4127151C2 (en) * 1991-08-16 1996-08-29 Hoechst Ag Process for the selective flotation of phosphorus minerals
    US5962828A (en) * 1997-10-15 1999-10-05 Custom Chemicals Corporation Enhanced flotation reagents for beneficiation of phosphate ores
    DE10024667C2 (en) 2000-05-18 2002-02-28 Clariant Gmbh Preparations for the treatment of phosphate ore

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    ATE272447T1 (en) 2004-08-15
    US20030146136A1 (en) 2003-08-07
    US6712217B2 (en) 2004-03-30
    MXPA02011316A (en) 2004-09-06
    DE10024667A1 (en) 2001-11-29
    ES2225579T3 (en) 2005-03-16
    AU7239001A (en) 2001-11-26
    EP1286780A1 (en) 2003-03-05
    DE50103125D1 (en) 2004-09-09
    BR0110820A (en) 2003-02-11
    DE10024667C2 (en) 2002-02-28
    ZA200208449B (en) 2003-05-12
    WO2001087490A1 (en) 2001-11-22

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