EP2012929B1 - Flotation reagent for minerals containing silicate - Google Patents

Flotation reagent for minerals containing silicate Download PDF

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Publication number
EP2012929B1
EP2012929B1 EP07724263.4A EP07724263A EP2012929B1 EP 2012929 B1 EP2012929 B1 EP 2012929B1 EP 07724263 A EP07724263 A EP 07724263A EP 2012929 B1 EP2012929 B1 EP 2012929B1
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Prior art keywords
flotation
silicate
collector
group
carbon atoms
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German (de)
French (fr)
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EP2012929A1 (en
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Klaus-Ulrich Pedain
Tobias Rau
Michael Patzke
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Clariant Finance BVI Ltd
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Clariant Finance BVI Ltd
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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
    • B03D1/01—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
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; specified applications
    • B03D2203/02—Ores
    • B03D2203/04—Non-sulfide ores

Definitions

  • the present invention relates to the use of alkyltriarnines in the flotation of siliceous minerals and ores.
  • Calcium carbonate is purified from silicate-containing and color-providing minerals with the aid of quaternary ammonium salts based on fatty acids or fatty alkylimidazoline compounds. Since calcium carbonate is used in addition to kaolin, rutile and talc as a white pigment in paper and plastic production, the highest possible whiteness or a low concentration of coloring minerals is desired. Due to the hardness of silicate, this would also lead to increased wear on the calenders of paper machines in papermaking. Therefore, calcium carbonate is purified in addition to dry processing via the flotation process.
  • the aim is to reduce the silicate content, which in the case of calcium carbonate is often characterized as an acid-insoluble constituent, by less than 1.0% by weight due to the reverse flotation.
  • the content of silicate in the task can vary and in some cases be from 10 to 20% by weight.
  • fatty amines alkyl ether amines, alkyl ether diamines or quaternary ammonium salt compounds are used as silicate collectors. These are also known under the trade name Flotigam ®.
  • Alkyl ether amines and alkyl ether diamines are mostly used in their partially neutralized forms as partial acetates, as in U.S. 4,319,987 described. The reason for this is the better solubility of the partially neutralized amine functions.
  • U.S. 4,995,965 describes the use of methyl bis (2-hydroxypropyl) cocosammonium methyl sulfate as a flotation reagent to float silicate-containing impurities out of calcite.
  • the silicate flotation, including iron ore, with the help of Alkyloxyalkanaminen is in U.S. 5,540,337 described.
  • U.S. 5,720,873 describes the combination of quaternary ammonium salts with fattyoxyalkylene compounds for the purification of calcium carbonate. This combination achieved an improvement over the quaternary ammonium salts in separating acid-insoluble components.
  • the object of the present invention was therefore to provide an improved collector for the silicate flotation, which can be used in particular in the reverse flotation but also in the direct flotation.
  • the collectors used today for the flotation of silicate-containing minerals have relatively high specific amounts used, which can lead to environmental problems with regard to the residual content of amine in the concentrate or in the mountains. It is known that amines and amine derivatives have high aqua and environmental toxicity. Therefore, one strives to minimize their specific amounts. Furthermore, their residual concentration in the final product should be kept as low as possible.
  • alkyl dipropylene triamines leads to a marked improvement in the flotation of silicate-containing minerals compared to the known flotation reagents, it being possible to significantly reduce the specific amounts used.
  • the invention thus relates to the use of a compound of formula 1 RN- [A-NH 2 ] 2 (1) wherein R is a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms and A is a propylene group (-C 3 H 6 -), as a collector in the silicate flotation.
  • Another object of the invention is a method for flotation of silicate mineral by bringing a compound of formula 1 with the silicate-containing mineral in contact.
  • Another object of the invention is a composition containing 1 to 99 wt .-% of a collector for silicate flotation, which is an alkyl ether, alkyletherdiamine, alkylamine or quaternary ammonium salt, and 1 to 99 wt .-% of a compound of formula 1.
  • a collector for silicate flotation which is an alkyl ether, alkyletherdiamine, alkylamine or quaternary ammonium salt, and 1 to 99 wt .-% of a compound of formula 1.
  • the compound of formula 1 is also referred to below as a collector according to the invention.
  • the collector according to the invention can be used alone or in combination with other nitrogen-containing compounds for the flotation of silicate, in particular iron ore, phosphate or calcium carbonate.
  • Preferred nitrogen-containing compounds are alkyl ether amines, alkyl ether diamines, alkyl amines or quaternary ammonium salts.
  • the ratio of alkyletheramine, alkyletherdiamine, alkylamine or quaternary ammonium salt to compound of the formula is preferably between 95: 5 and 50:50 by weight.
  • R is a linear or branched hydrocarbon group. It is further preferred that R comprises 8 to 18 carbon atoms. Particularly preferred are 2-ethylhexyl, isononane, isodecane and Isotridekan- and dodecane radicals.
  • the silicate flotation collectors which are an alkyl ether amine, alkyl ether diamine, alkyl amine or quaternary ammonium salt, and which may be used together with a compound of formula 1, are preferably one or more of the compounds of formulas (II) to (V) ).
  • the use of the flotation reagent according to the invention can also be carried out in combination with foaming agents and pushers, as known from the prior art.
  • hydrophilic polysaccharides such as, for example, modified starch, carboxymethylcellulose or gum arabic in dosages of from 10 to 1000 g / t as a pusher.
  • the silicate flotation is preferably carried out at a pH of 7 to 12, in particular 8 to 11, which is set, for example, with sodium hydroxide.
  • the use according to the invention can be carried out both in direct and in reverse silicate flotation.
  • the use according to the invention is also suitable for liberating silicate sand from impurities by flotatively separating the silicate sand from the impurities using the compound of formula 1.
  • Table 1 presents the flotative results of the collector B according to the invention in comparison to the standard reagent A.
  • the flotation experiments were carried out on a silicate-containing calcium carbonate, the acid-insoluble constituents in the task accounting for 14.9%.
  • the reagent according to the invention in Example 6 already at a low dosage of only 121 g / t shows a much lower proportion of acid-insoluble constituents in the purified concentrate, which the standard reagent only reaches above 400 g / t.
  • the reagent according to the invention behaves analogously with regard to the degree of whiteness. This is already at the low dosage 92.0, which is achieved with the standard reagent only with three to four times the amount used.
  • Table 2 Effectiveness of a mixture of the collector B according to the invention and the standard collector A.
  • Examples 7 to 10 represent mixtures containing 10% of the collector B according to the invention and 90% of the standard collector A.
  • Examples 11 to 16 show mixtures containing about 29% of the collector B according to the invention and about 71% of the standard collector A, represents.
  • the flotation reagent according to the invention can be used in a wide pH range, for example 6 to 12, preferably 6 to 8, and is added to the aqueous slurry in a concentration of preferably between 0.001 and 1.0 kg / ton of crude mineral.

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  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Detergent Compositions (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The invention relates to the use of a compound of formula R—N-[A-NH2]2  (1) wherein R represents a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms while A represents a C2 to C4 alkylene group, as collector in silicate flotation.

Description

Die vorliegende Erfindung betrifft die Verwendung von Alkyltriarninen in der flotativen Aufbereitung von silikathaltigen Mineralen und Erzen.The present invention relates to the use of alkyltriarnines in the flotation of siliceous minerals and ores.

In der umgekehrten Flotation werden Verunreinigungen aus dem Wertmineral ausflotiert. Insbesondere Eisenerz, Calciumcarbonat, Phosphat und Feldspat werden häufig auf diese Weise aufbereitet. In vielen Fällen sind silikathaltige Mineralien die Hauptbestandteile dieser Verunreinigungen, die im Endprodukt Qualitätsminderungen hervorrufen. Hierzu gehören neben Quarz, Glimmer und Feldspat, auch Muskovit und Biotit. Zum Beispiel senkt ein hoher Silikatgehalt die Qualität von Eisenerzkonzentrat, so dass dieses zum Beispiel in Brasilien durch die Verwendung von Alkyletheraminen und Alkyletherdiaminen flotativ gereinigt wird, um aus dem silikatarmen Konzentrat hochwertige Stähle herstellen zu können.In reverse flotation impurities are floated out of the value mineral. In particular, iron ore, calcium carbonate, phosphate and feldspar are often processed in this way. In many cases, siliceous minerals are the main constituents of these contaminants, causing quality degradation in the final product. These include quartz, mica and feldspar, as well as muscovite and biotite. For example, a high silicate content lowers the quality of iron ore concentrate, so that it is flotatively purified in Brazil, for example, by the use of alkyletheramines and alkylether diamines in order to be able to produce high-quality steels from the low-silicate concentrate.

Calciumcarbonat wird mit Hilfe von quaternären Ammoniumsalzen, basierend auf Fettsäuren oder Fettalkylimidazolinverbindungen, von silikathaltigen und farbgebenden Mineralien gereinigt. Da Calciumcarbonat neben Kaolin, Rutil und Talk als Weißpigment in der Papier- und Kunststoffherstellung verwendet wird, ist ein möglichst hoher Weißgrad beziehungsweise eine geringe Konzentration an farbgebenden Mineralien erwünscht. Aufgrund der Härte von Silikat würde dieses bei der Papierherstellung auch zu einer erhöhten Abnutzung an den Kalandern der Papiermaschinen führen. Daher wird Calciumcarbonat neben der Trockenaufbereitung über den flotativen Prozess gereinigt.Calcium carbonate is purified from silicate-containing and color-providing minerals with the aid of quaternary ammonium salts based on fatty acids or fatty alkylimidazoline compounds. Since calcium carbonate is used in addition to kaolin, rutile and talc as a white pigment in paper and plastic production, the highest possible whiteness or a low concentration of coloring minerals is desired. Due to the hardness of silicate, this would also lead to increased wear on the calenders of paper machines in papermaking. Therefore, calcium carbonate is purified in addition to dry processing via the flotation process.

Allgemein strebt man an, durch die umgekehrte Flotation den Silikatgehalt, der im Falle des Calciumcarbonates oft als säureunlöslicher Bestandteil charakterisiert wird, unter 1,0 Gew.-% zu reduzieren. Der Gehalt an Silikat in der Aufgabe kann variieren und teilweise 10 bis 20 Gew.-% betragen.In general, the aim is to reduce the silicate content, which in the case of calcium carbonate is often characterized as an acid-insoluble constituent, by less than 1.0% by weight due to the reverse flotation. The content of silicate in the task can vary and in some cases be from 10 to 20% by weight.

Als Silikatsammler werden beispielsweise Fettamine, Alkyletheramine, Alkyletherdiamine oder quaternäre Ammoniumsalzverbindungen eingesetzt. Diese sind auch unter dem Handelsnamen Flotigam® bekannt.For example, fatty amines, alkyl ether amines, alkyl ether diamines or quaternary ammonium salt compounds are used as silicate collectors. These are also known under the trade name Flotigam ®.

Alkyletheramine und Alkyletherdiamine werden zumeist in deren teilneutralisierten Formen als Teilacetate eingesetzt, wie in US-4 319 987 beschrieben. Grund hierfür ist die bessere Löslichkeit der teilneutralisierten Aminfunktionen.Alkyl ether amines and alkyl ether diamines are mostly used in their partially neutralized forms as partial acetates, as in U.S. 4,319,987 described. The reason for this is the better solubility of the partially neutralized amine functions.

Die Kombination eines primären Amins mit einer stickstoffhaltigen Verbindung, enthaltend eine anionische Gruppe, wird durch US-4 830 739 offenbart.The combination of a primary amine with a nitrogen-containing compound containing an anionic group is performed by U.S. 4,830,739 disclosed.

US-4 995 965 beschreibt die Verwendung von Methyl-bis(2-hydroxypropyl)-cocosammonium methyl sulfat als Flotationsreagenz, um silikathaltige Verunreinigungen aus Calcit heraus zu flotieren. U.S. 4,995,965 describes the use of methyl bis (2-hydroxypropyl) cocosammonium methyl sulfate as a flotation reagent to float silicate-containing impurities out of calcite.

In US-5 261 539 wird die Verwendung von alkoxylierten Alkylguanidinen und alkoxylierten Aminen zur umgekehrten Flotation von Calcit beschrieben.In U.S. 5,261,539 describes the use of alkoxylated alkylguanidines and alkoxylated amines for the reverse flotation of calcite.

In US-5 540 336 wird die synergistische Wirkung von Etheraminen und anionischen Sammlern zur Eisenerzflotation dargestellt.In U.S. 5,540,336 shows the synergistic effect of ether amines and anionic collectors for iron ore floatation.

Die Silikatflotation, u.a. aus Eisenerz, unter Zuhilfenahme von Alkyloxyalkanaminen wird in US-5 540 337 beschrieben.The silicate flotation, including iron ore, with the help of Alkyloxyalkanaminen is in U.S. 5,540,337 described.

US-5 720 873 beschreibt die Kombination von quaternären Ammoniumsalzen mit Fettoxyalkylenverbindungen zur Reinigung von Calciumcarbonat. Durch diese Kombination wurde eine Verbesserung gegenüber den quaternären Ammoniumsalzen hinsichtlich der Abtrennung säureunlöslicher Bestandteile erzielt. U.S. 5,720,873 describes the combination of quaternary ammonium salts with fattyoxyalkylene compounds for the purification of calcium carbonate. This combination achieved an improvement over the quaternary ammonium salts in separating acid-insoluble components.

US-6 076 682 beschreibt die kombinierte Verwendung von Alkylethermonoamin mit Alkyletherdiamin zur Silikatflotation aus Eisenerz. US Pat. No. 6,076,682 describes the combined use of alkylethermonoamine with alkyletherdiamine for silicate flotation from iron ore.

In WO-A-00/62937 wird die Verwendung quaternärer Amine zur Flotation von Eisenerz offenbart.In WO-A-00/62937 discloses the use of quaternary amines for flotation of iron ore.

Die im Stand der Technik beschriebenen Sammler für die Silikatflotation zeigen jedoch unzureichende Ergebnisse hinsichtlich Selektivität und Ausbeute. Aufgabe vorliegender Erfindung war es daher, einen verbesserten Sammler für die Silikatflotation bereitzustellen, der insbesondere in der umgekehrten Flotation aber auch in der direkten Flotation verwendet werden kann.However, the silicate flotation collectors described in the prior art show insufficient results in terms of selectivity and yield. The object of the present invention was therefore to provide an improved collector for the silicate flotation, which can be used in particular in the reverse flotation but also in the direct flotation.

Die heutzutage verwendeten Sammler für die Flotation silikathaltiger Mineralien weisen relativ hohe spezifische Einsatzmengen auf, was hinsichtlich des Restgehaltes von Amin im Konzentrat oder in den Bergen zu Umweltproblemen führen kann. Es ist bekannt, dass Amine und Aminderivate eine hohe Aqua- und Umwelttoxizität aufweisen. Deshalb ist man bestrebt, deren spezifischen Einsatzmengen zu minimieren. Weiterhin soll ihre Restkonzentration im Endprodukt so gering wie möglich gehalten werden.The collectors used today for the flotation of silicate-containing minerals have relatively high specific amounts used, which can lead to environmental problems with regard to the residual content of amine in the concentrate or in the mountains. It is known that amines and amine derivatives have high aqua and environmental toxicity. Therefore, one strives to minimize their specific amounts. Furthermore, their residual concentration in the final product should be kept as low as possible.

Überraschenderweise wurde gefunden, dass die Verwendung von Alkyldipropylentriaminen zu einer deutlichen Verbesserung der Flotation silikathaltiger Mineralien gegenüber den bekannten Flotationsreagenzien führt, wobei die spezifischen Einsatzmengen deutlich reduziert werden können.Surprisingly, it has been found that the use of alkyl dipropylene triamines leads to a marked improvement in the flotation of silicate-containing minerals compared to the known flotation reagents, it being possible to significantly reduce the specific amounts used.

Gegenstand der Erfindung ist somit die Verwendung einer Verbindung der Formel 1

        R-N-[A-NH2]2     (1)

worin R eine lineare oder verzweigte Alkylgruppe oder Alkenylgruppe mit 6 bis 20 Kohlenstoffatomen und A eine Propylengruppe (-C3H6-) bedeuten, als Sammler in der Silikatflotation.The invention thus relates to the use of a compound of formula 1

RN- [A-NH 2 ] 2 (1)

wherein R is a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms and A is a propylene group (-C 3 H 6 -), as a collector in the silicate flotation.

Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Flotation von silikathaltigem Mineral, indem man eine Verbindung der Formel 1 mit dem silikathaltigen Mineral in Kontakt bringt.Another object of the invention is a method for flotation of silicate mineral by bringing a compound of formula 1 with the silicate-containing mineral in contact.

Ein weiterer Gegenstand der Erfindung ist eine Zusammensetzung, enthaltend 1 bis 99 Gew.-% eines Sammlers für die Silikatflotation, welcher ein Alkyletheramin, Alkyletherdiamin, Alkylamin oder quaternäres Ammoniumsalz ist, sowie 1 bis 99 Gew.-% einer Verbindung der Formel 1.Another object of the invention is a composition containing 1 to 99 wt .-% of a collector for silicate flotation, which is an alkyl ether, alkyletherdiamine, alkylamine or quaternary ammonium salt, and 1 to 99 wt .-% of a compound of formula 1.

Die Verbindung der Formel 1 wird im Folgenden auch als erfindungsgemäßer Sammler bezeichnet.The compound of formula 1 is also referred to below as a collector according to the invention.

Der erfindungsgemäße Sammler kann alleine oder in Kombination mit anderen stickstoffhaltigen Verbindungen für die Flotation von Silikat, insbesondere aus Eisenerz, Phosphaterz oder Calciumcarbonat verwendet werden. Bevorzugte stickstoffhaltige Verbindungen sind Alkyletheramine, Alkyletherdiamine, Alkylamine oder quaternäre Ammoniumsalze.The collector according to the invention can be used alone or in combination with other nitrogen-containing compounds for the flotation of silicate, in particular iron ore, phosphate or calcium carbonate. Preferred nitrogen-containing compounds are alkyl ether amines, alkyl ether diamines, alkyl amines or quaternary ammonium salts.

Das Verhältnis von Alkyletheramin, Alkyletherdiamin, Alkylamin oder quaternärem Ammoniumsalz zur Verbindung der Formel liegt vorzugsweise zwischen 95:5 und 50:50 nach Gewicht.The ratio of alkyletheramine, alkyletherdiamine, alkylamine or quaternary ammonium salt to compound of the formula is preferably between 95: 5 and 50:50 by weight.

R steht für eine lineare oder verzweigte Kohlenwasserstoffgruppe. Weiterhin bevorzugt ist, dass R 8 bis 18 Kohlenstoffatome umfasst. Besonders bevorzugt sind 2-Ethylhexyl-, isononan-, isodekan- und Isotridekan- sowie Dodekanreste.R is a linear or branched hydrocarbon group. It is further preferred that R comprises 8 to 18 carbon atoms. Particularly preferred are 2-ethylhexyl, isononane, isodecane and Isotridekan- and dodecane radicals.

Bei den Sammlern für die Silikatflotation, welche ein Alkyletheramin, Alkyletherdiamin, Alkylamin oder quaternäres Ammoniumsalz sind, und die mit einer Verbindung der Formel 1 zusammen verwendet werden können, handelt es sich vorzugsweise um eine oder mehrere der Verbindungen der Formeln (II) bis (V).The silicate flotation collectors, which are an alkyl ether amine, alkyl ether diamine, alkyl amine or quaternary ammonium salt, and which may be used together with a compound of formula 1, are preferably one or more of the compounds of formulas (II) to (V) ).

Diese Verbindungen sind

        R2-O-R3-NH2     (II)

worin R2 einer Kohlenwasserstoffgruppe mit 1 bis 40, vorzugsweise 8 bis 32 Kohlenstoffatomen und R3 einer aliphatischen Kohlenwasserstoffgruppe mit 2 bis 4 Kohlenstoffatomen entsprechen;

        R4-O-R5-NH-R6-NH2     (III)

worin R4 einer Kohlenwasserstoffgruppe mit 1 bis 40, vorzugsweise 8 bis 32 Kohlenstoffatomen, R5 und R6 einer oder verschiedenen aliphatischen Kohlenwasserstoffgruppe mit 2 - 4 Kohlenstoffatomen entsprechen;

        (R7R8NR9R10)+ B-     (IV)

worin R7, R8, R9 und R10 einer oder verschiedenen Kohlenwasserstoffgruppen mit 1 bis 22 Kohlenstoffatomen und B- einem geeigneten Anion entsprechen;

        R11-NH2     (V)

worin R11 einer Kohlenwasserstoffgruppe mit 1 bis 40, vorzugsweise 8 bis 32 Kohlenstoffatomen entspricht.These connections are

R 2 -OR 3 -NH 2 (II)

wherein R 2 is a hydrocarbon group of 1 to 40, preferably 8 to 32 carbon atoms and R 3 is an aliphatic hydrocarbon group of 2 to 4 carbon atoms;

R 4 -OR 5 -NH-R 6 -NH 2 (III)

wherein R 4 is a hydrocarbon group having 1 to 40, preferably 8 to 32 carbon atoms, R 5 and R 6 are one or more aliphatic hydrocarbon group having 2 to 4 carbon atoms;

(R 7 R 8 NR 9 R 10 ) + B - (IV)

wherein R 7 , R 8 , R 9 and R 10 correspond to one or more hydrocarbon groups of 1 to 22 carbon atoms and B - a suitable anion;

R 11 -NH 2 (V)

wherein R 11 corresponds to a hydrocarbon group having 1 to 40, preferably 8 to 32 carbon atoms.

Die Verwendung des erfindungsgemäßen Flotationsreagenzes kann auch in Kombination mit Schäumern und Drückern, wie sie aus dem Stand der Technik bekannt sind, erfolgen. Um zu vermeiden, dass bei der Silikatflotation aus Eisenerz dieses mit ausgetragen wird, werden vorzugsweise hydrophile Polysaccharide, wie beispielsweise modifizierte Stärke, Carboxymethylcellulose, oder Gummi Arabicum in Dosierungen von 10 bis 1000 g/t als Drücker zugegeben.The use of the flotation reagent according to the invention can also be carried out in combination with foaming agents and pushers, as known from the prior art. In order to avoid that in the case of silicate flotation from iron ore this is carried along, it is preferable to add hydrophilic polysaccharides, such as, for example, modified starch, carboxymethylcellulose or gum arabic in dosages of from 10 to 1000 g / t as a pusher.

Die Silikatflotation wird vorzugsweise bei einem pH von 7 bis 12, insbesondere 8 bis 11 durchgeführt, welcher beispielsweise mit Natriumhydroxid eingestellt wird.The silicate flotation is preferably carried out at a pH of 7 to 12, in particular 8 to 11, which is set, for example, with sodium hydroxide.

Die erfindungsgemäße Verwendung kann sowohl in der direkten als auch in der umgekehrten Silikatflotation erfolgen. Die erfindungsgemäße Verwendung ist auch dazu geeignet, Silikatsand von Verunreinigungen zu befreien, indem man den Silikatsand von den Verunreinigungen unter Verwendung der Verbindung der Formel 1 flotativ trennt.The use according to the invention can be carried out both in direct and in reverse silicate flotation. The use according to the invention is also suitable for liberating silicate sand from impurities by flotatively separating the silicate sand from the impurities using the compound of formula 1.

BeispieleExamples

Laborflotationsversuche wurden mit Hilfe einer Denver Flotationszelle durchgeführt.Laboratory flotation experiments were performed using a Denver flotation cell.

Tabelle 1 stellt die flotativen Ergebnisse des erfindungsgemäßen Sammlers B im Vergleich zum Standardreagenz A dar. Die Flotationsversuche wurden an einem silikathaltigen Calciumcarbonat durchgeführt, wobei die säureunlöslichen Bestandteile in der Aufgabe 14,9 % ausmachen.Table 1 presents the flotative results of the collector B according to the invention in comparison to the standard reagent A. The flotation experiments were carried out on a silicate-containing calcium carbonate, the acid-insoluble constituents in the task accounting for 14.9%.

Als Standardreagenz A wurde ein Dicocosalkyldimethylammoniumchlorid verwendet. Tabelle 1: Wirksamkeit des erfindungsgemäßen Sammlers B im Vergleich zum Standardsammler A = Dicocosalkyldimethylammoniumchlorid Beispiel Sammler Dosierung in g/t Säureunlösliche Bestandteile im Calcit in % Weißgrad in % 1 A 305 6,4 90,4 2 A 355 4,2 91,2 3 A 404 3,1 91,4 4 A 488 2,3 92,3 5 A 728 1,1 92,0 6 B 121 2,8 92,0 As standard reagent A, a dicocoalkyl dimethyl ammonium chloride was used. Table 1: Effectiveness of the collector B according to the invention in comparison with the standard collector A = dicocoalkyldimethylammonium chloride example collector Dosage in g / t Acid-insoluble components in calcite in% Whiteness in% 1 A 305 6.4 90.4 2 A 355 4.2 91.2 3 A 404 3.1 91.4 4 A 488 2.3 92.3 5 A 728 1.1 92.0 6 B 121 2.8 92.0

Bemerkenswerterweise zeigt das erfindungsgemäße Reagenz im Beispiel 6 bereits bei einer geringen Dosierung von nur 121 g/t einen wesentlich geringeren Anteil an säureunlöslichen Bestandteilen im gereinigten Konzentrat, welchen das Standardreagenz erst oberhalb von 400 g/t erreicht. Analog verhält sich das erfindungsgemäße Reagenz hinsichtlich des Weißgrades. Dieser beträgt bei der geringen Dosierung bereits 92,0, welcher mit dem Standardreagenz erst mit der drei- bis vierfachen Einsatzmenge erzielt wird. Tabelle 2: Wirksamkeit einer Mischung aus dem erfindungsgemäßen Sammlers B und dem Standardsammler A. Beispiel Sammler A in g/t Sammler B in g/t Säureunlösliche Bestandteile im Calcit in % Weißgrad in % 7 222 25 4,45 92,0 8 261 29 2,98 93,8 9 324 36 1,34 94,0 10 369 41 0,85 94,1 11 176 70 1,86 93,3 12 236 94 0,82 93,3 13 272 109 0,60 93,8 14 286 114 0,40 94,1 15 317 127 0,33 93,7 16 365 146 0,28 93,5 Notably, the reagent according to the invention in Example 6 already at a low dosage of only 121 g / t shows a much lower proportion of acid-insoluble constituents in the purified concentrate, which the standard reagent only reaches above 400 g / t. The reagent according to the invention behaves analogously with regard to the degree of whiteness. This is already at the low dosage 92.0, which is achieved with the standard reagent only with three to four times the amount used. Table 2: Effectiveness of a mixture of the collector B according to the invention and the standard collector A. example Collector A in g / t Collector B in g / t Acid-insoluble components in calcite in% Whiteness in% 7 222 25 4.45 92.0 8th 261 29 2.98 93.8 9 324 36 1.34 94.0 10 369 41 0.85 94.1 11 176 70 1.86 93.3 12 236 94 0.82 93.3 13 272 109 0.60 93.8 14 286 114 0.40 94.1 15 317 127 0.33 93.7 16 365 146 0.28 93.5

Die Beispiele 7 bis 10 stellen Mischungen, enthaltend 10 % des erfindungsgemäßen Sammlers B und 90 % des Standardsammlers A, dar. Die Beispiele 11 bis 16 stellen Mischungen, enthaltend ca. 29 % des erfindungsgemäßen Sammlers B und ca. 71 % des Standardsammlers A, dar.Examples 7 to 10 represent mixtures containing 10% of the collector B according to the invention and 90% of the standard collector A. Examples 11 to 16 show mixtures containing about 29% of the collector B according to the invention and about 71% of the standard collector A, represents.

Die Ergebnisse in den Beispielen 7 bis 10 und 11 bis 16 zeigen ein durchgängig geringeren Anteil an säureunlöslichen Bestandteilen sowie einen höheren Weißgrad im Konzentrat gegenüber dem Standardreagenz in den Beispielen 1 bis 5.The results in Examples 7 to 10 and 11 to 16 show a consistently lower proportion of acid-insoluble constituents and a higher degree of whiteness in the concentrate over the standard reagent in Examples 1 to 5.

Das erfindungsgemäße Flotationsreagenz ist in einem weiten pH Bereich anwendbar beispielsweise 6 bis 12, vorzugsweise 6 bis 8 und wird der wässrigen Trübe in einer Konzentration zwischen vorzugsweise 0,001 und 1,0 kg/Tonne Rohmineral zugesetzt.The flotation reagent according to the invention can be used in a wide pH range, for example 6 to 12, preferably 6 to 8, and is added to the aqueous slurry in a concentration of preferably between 0.001 and 1.0 kg / ton of crude mineral.

Mit dem erfindungsgemäßen Flotationsreagenz wird gegenüber den Sammlern des Standes der Technik eine signifikante Verbesserung von Ausbringen und Selektivität erreicht. Die Tabellen 1 bis 2 zeigen einen wesentlich gesteigerten Weißgrad sowie einen geringeren säureunlöslichen Anteil im Calcit gegenüber dem entsprechenden Standardreagenz.With the flotation reagent according to the invention, a significant improvement in spreading and selectivity is achieved compared to the collectors of the prior art. Tables 1 to 2 show a significantly increased whiteness and a lower acid-insoluble content in calcite compared to the corresponding standard reagent.

Claims (13)

  1. The use of a compound of the formula

            R-N-[A-NH2]2     (1)

    where R is a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms and A is a propylene group (-C3H6-), as collector in silicate flotation.
  2. The use as claimed in claim 1, wherein R is a linear aliphatic hydrocarbon moiety having 8 to 18 carbon atoms.
  3. The use as claimed in claim 1 and/or 2, wherein R is a 2-ethylhexane, isononane, isodecane, decane, dodecane or isotridecane moiety.
  4. The use as claimed in one or more of claims 1 to 3, for reverse flotation of silicaceous minerals from iron ore, phosphate ore or calcium carbonate.
  5. The use as claimed in one or more of claims 1 to 4 for purifying silicate sand.
  6. The use as claimed in one or more of claims 1 to 4 in the flotation of quartz, mica, feldspar or muscovite from iron ore, calcium carbonate or phosphate ore.
  7. The use as claimed in one or more of claims 1 to 6 in the flotation of silicaceous minerals, wherein the ore contains between 0.1 and 50% by weight silicate.
  8. The use as claimed in one or more of claims 1 to 7 in combination with frothers and depressants.
  9. The use as claimed in one or more of claims 1 to 8 in a pH range of 7 to 12.
  10. The use as claimed in one or more of claims 1 to 9 in amounts of 0.001 to 1.0 kg per tonne of crude ore.
  11. The use as claimed in one or more of claims 1 to 10, wherein, in addition to the compound of formula 1, at least one further nitrogenous silicate collector selected from the group of alkyl ether amines, alkyl ether diamines, alkylamines and quaternary ammonium salts is present.
  12. A composition containing 1 to 99% by weight of a collector for silicate flotation, which collector is an alkyl ether amine, alkyl ether diamine, alkylamine or quaternary ammonium salt, and also 1 to 99% by weight of a compound of the formula 1

            R-N-[A-NH2]2     (1)

    where R is a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms and A is a propylene group (-C3H6-).
  13. A process for the flotation of silicaceous mineral, which comprises bringing the silicaceous material into contact with at least one flotation reagent according to formula 1

            R-N-[A-NH2]2     (1)

    where R is a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms and A is a propylene group (-C3H6-).
EP07724263.4A 2006-04-27 2007-04-16 Flotation reagent for minerals containing silicate Expired - Fee Related EP2012929B1 (en)

Applications Claiming Priority (2)

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DE102006019561A DE102006019561A1 (en) 2006-04-27 2006-04-27 Use of an amine compound as collectors in silicate flotations, for the reverse flotation of silicate containing minerals from e.g. iron ore, for the cleaning of silicate sand and in the flotation of quartz, glimmer, feldspar and muscovite
PCT/EP2007/003325 WO2007124853A1 (en) 2006-04-27 2007-04-16 Flotation reagent for minerals containing silicate

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EP2012929B1 true EP2012929B1 (en) 2013-12-25

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DE102006019561A1 (en) 2007-10-31
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US8172089B2 (en) 2012-05-08
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CA2650392C (en) 2014-01-07
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RU2440854C2 (en) 2012-01-27
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