EP0609257B1 - Method of producing iron-ore concentrates by froth flotation - Google Patents

Method of producing iron-ore concentrates by froth flotation Download PDF

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Publication number
EP0609257B1
EP0609257B1 EP19920920650 EP92920650A EP0609257B1 EP 0609257 B1 EP0609257 B1 EP 0609257B1 EP 19920920650 EP19920920650 EP 19920920650 EP 92920650 A EP92920650 A EP 92920650A EP 0609257 B1 EP0609257 B1 EP 0609257B1
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alkyl
collector
flotation
phosphates
carbon atoms
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German (de)
French (fr)
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EP0609257A1 (en
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Berthold Schreck
Rita Köster
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/0043—Organic compounds modified so as to contain a polyether group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/008—Organic compounds containing oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/01—Organic compounds containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/012—Organic compounds containing sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/014—Organic compounds containing phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; Specified applications
    • B03D2203/02—Ores
    • B03D2203/04—Non-sulfide ores

Definitions

  • the invention relates to a process for the production of iron ore concentrates by flotation of iron ores, in which mixtures of special ether amines with anionic collectors are used as collectors.
  • Iron ores are found in nature preferably in the form of oxides, among which magnetite, hematite, martite, limonite and goethite are the best known.
  • the main contaminants are silicates, especially quartz, as well as phosphorus and sulfur compounds.
  • the iron ore is usually first crushed and dry, but preferably ground wet and in water suspended.
  • a collector is then added, often in conjunction with other reagents, which include foaming agents, regulators, pushers (deactivators) and / or stimulants (activators), which supports the separation of the valuable minerals from the gangue minerals in the ore during the subsequent flotation.
  • these reagents are usually allowed to act on the finely ground ore for a certain time (conditioning).
  • the collector causes the surface of the impurities contained in the iron ore to become hydrophobic, so that these minerals adhere to the gas bubbles formed during the aeration.
  • the hydrophobicization of the mineral components takes place selectively in such a way that the gait is floated out and the concentrate remains as a residue (indirect flotation).
  • Aminic compounds are preferably used as collectors in the flotative processing of iron ores. These have the task of adsorbing as selectively as possible on the surface of the contaminants in order to ensure a high depletion of these undesirable constituents in the flotation concentrate. In addition, the collectors should develop a stable, but not too stable, flotation foam.
  • anionic surfactants as collectors or co-collectors in the flotation of non-sulfidic ores.
  • examples include alkyl phosphates and alkyl ether phosphates [ Erzmetall 30 , 505 (1977) ], ether carboxylic acids [ DE 22 37 359 A1 ], sulfosuccinamides and succinamates [ US-A-4,206,045; US-A-4,309,282 and US-A-4,139,481 ] as well as alkyl aspartic acids [ EP 0 270 018 A1 ].
  • US-A-4,472,270 describes iron ore flotation using ether amines and a non-polar hydrocarbon as a nonionic collector.
  • the object of the invention was therefore to develop an improved flotation process for the production of iron ore concentrates which is free from the disadvantages described.
  • the collector mixtures to be used according to the invention can selectively remove phosphorus impurities from iron ores and do not negatively influence the cationic flotation of the silicates.
  • the invention includes the knowledge that phosphorus and Silicate flotation can be carried out both separately and in one step.
  • the concentrates obtainable by the process according to the invention have phosphorus contents of less than 0.015% by weight, based on the concentrate.
  • Etheramines of the formula (I) are known compounds which are obtainable by the relevant preparative organic chemistry processes. Their preparation is usually based on fatty alcohol sulfates which are reacted with alkanolamines or aminoalkylalkanolamines in the presence of alkali metal hydroxides at temperatures of about 180 ° C., alkali metal sulfate being formed as a by-product [ DE 35 04 242 A1 ].
  • Suitable starting materials for the ether amines to be used according to the invention are fatty alcohol sulfates based on saturated or unsaturated fatty alcohols and primary amines or diamines. Typical examples are reaction products of octyl sulphate, decyl sulphate, lauryl sulphate, myristyl sulphate, cetyl sulphate, stearyl sulphate, oleyl sulphate, elaidyl sulphate, petroselinyl sulphate, linolyl sulphate, linolenyl sulphanol, arachyl sulphate, eraducylyl sulphate, badenoleyl sulphate amine, gadoleyl sulphanol amine, gadoleyl sulphanol amine , Aminopropylethanolamine and aminopropylpropanolamine.
  • sulfates based on technical fatty alcohol cuts can also be reacted with the amines mentioned.
  • anionic collectors are to be understood as anionic surfactants of the fatty acid type, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl phosphates, alkyl ether phosphates, alkyl aspartic acids and ether carboxylic acids. All of these anionic surfactants are known compounds, the preparation of which - unless stated otherwise - for example in J. Falbe, U. Hasserodt (ed.), "Catalysts, Surfactants and Mineral Oil Additives, Thieme Verlag, Stuttgart, 1978 or J. Falbe (ed.) "Surfactants in Consumer Products", Springer Verlag, Berlin, 1986 .
  • Suitable fatty acids here are in particular the straight-chain fatty acids of the formula (II) obtained from vegetable or animal fats and oils, for example by splitting and optionally fractionating and / or separating by the crosslinking process.
  • R2 is an aliphatic hydrocarbon radical having 12 to 18 carbon atoms and 0, 1, 2 or 3 double bonds and Y is an alkali metal, alkaline earth metal or an ammonium radical.
  • the sodium and potassium salts of oleic and tall oil fatty acids are of particular importance.
  • Suitable alkylsulfosuccinates are sulfosuccinic acid monoesters of fatty alcohols of the formula (V) in which R6 represents a linear or branched alkyl radical having 8 to 22, preferably 12 to 18 carbon atoms and Z has the meaning given above.
  • Suitable alkylsulfosuccinamates are sulfosuccinic acid monoamides of fatty amines of the formula (VI) , in which R7 represents a linear or branched alkyl radical having 8 to 22, preferably 12 to 18 carbon atoms and Z has the meaning given above.
  • Suitable alkyl phosphates and alkyl ether phosphates are substances of the formulas (XI) and (XII) in which R12 and R13 independently of one another are an alkyl or alkenyl radical having 8 to 22 carbon atoms and p and q in the case of the alkyl phosphates are 0, in the case of the alkyl ether phosphates are numbers from 1 to 15 and Z has the meaning given above.
  • the phosphates can be present as mono- or diphosphates. In this case, preference is given to using mixtures of mono- and dialkylphosphates of the type obtained in the industrial production of such compounds.
  • Alkyl aspartic acids are to be understood as meaning compounds of the formula (XIII) in which R14 represents an alkyl or alkenyl radical having 8 to 22 carbon atoms and Z has the meaning given above.
  • Suitable ether carboxylic acids are compounds of the formula (XIV) in which R15 represents an alkyl or alkenyl radical having 8 to 22 carbon atoms and n represents 0 or numbers from 1 to 10 and Z has the meaning given above.
  • nonionic co-collectors selected from the group of fatty alcohol polyglycol ethers, are also used.
  • nonionic surfactants are known compounds, the preparation of which - unless stated otherwise - for example in J. Falbe, U. Hasserodt (ed.), "Catalysts, Surfactants and Mineral Oil Additives, Thieme Verlag, Stuttgart, 1978 or J. Falbe (ed.) "Surfactants in Consumer Products", Springer Verlag, Berlin, 1986 .
  • Suitable fatty alcohol polyglycol ethers are addition products of an average of n moles of ethylene and / or propylene oxide onto fatty alcohols, which follow the formula (XV) in which R16 represents a linear or branched alkyl radical having 8 to 22, preferably 12 to 18 carbon atoms, R5 represents hydrogen or a methyl group and n represents numbers from 1 to 30, preferably 2 to 15.
  • the mixtures of the ether amines with the anionic and / if appropriate nonionic collectors can have a content of 5 to 95% by weight, preferably 10 to 60% by weight of the ether amines. Particularly advantageous results are achieved with mixtures which, in addition to ether amines, contain fatty acids, alkyl aspartic acids and / or ether carboxylic acids or alkyl sulfosuccinamates, alkyl phosphates and / or alkyl ether phosphates.
  • the collector mixture In order to achieve economically viable results in the flotation of iron ore, the collector mixture must be used in a certain minimum amount. However, a maximum amount must also not be exceeded, since otherwise the foam formation becomes too strong and the selectivity towards the contaminants to be flotated out decreases.
  • the amounts in which the collector mixtures to be used according to the invention can be used are usually 20 to 2000, preferably 50 to 1000 g per ton of raw ore.
  • the method according to the invention includes the use of reagents customary for flotation, such as foaming agents, regulators, activators, deactivators, etc.
  • the flotation is carried out under the conditions of the methods of the prior art.
  • the ground ore had the following grain size distribution: > 31 ⁇ m: 7.7% by weight 11 to 31 ⁇ m: 45.3% by weight ⁇ 11 ⁇ m: 47.0% by weight
  • the finely ground ore was then transferred to the desludging stage, diluted to about 8 l (solids content: 7% by weight), mixed with 3 ml of heat-treated corn starch (2.25% by weight) and the supernatant sludge was separated off after 2 minutes.
  • the desludged flotation task (volume: approx. 1 l) was transferred to a 2 l Denver agitator cell (type D1). Then 67 ml of sodium hydroxide and 12 ml of corn starch (2.25% by weight) were added, the cell was filled with flotation water and the slurry was conditioned with stirring for 2 minutes. The amine collector and the anionic and / or nonionic collector were then metered in. The Rougher flotation was then carried out at a stirring speed of 1200 rpm, at which a foam product and a concentrate were obtained in the cell. After metering the collector again, the flotation was carried out a second time and another foam product and the desired iron ore concentrate were obtained.
  • a magnetite ore of the chemical composition specified under II was used, which had a grain size of 89% by weight less than 43 ⁇ m.
  • Flotation was again carried out in a 2 l Denver cell (type D1) with a turbidity density of approx. 220 g / l in water with a calcium ion content of 4 mg / l.
  • the pH of the slurry was adjusted to 8.5 by adding sodium hydroxide; the stirring speed was 1200 rpm.
  • air was introduced and floated at a flow rate of 130 to 150 l / h.
  • the foam was removed over a period of 2 min in the general silicate flotation, with an additional phosphate flotation the flotation time was extended in accordance with the information in Table 7.
  • the amine collector was dosed as a 0.25% by weight aqueous solution, and the anionic collector mixtures were added as 5% by weight aqueous solutions.
  • a commercial foamer based on aldehydes, alcohols and esters with a dosage of 30 g / t was used in all flotation experiments and metered into the slurry undiluted.
  • Tab.7a Magnetite collector systems and dosing E.g.

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  • Manufacture And Refinement Of Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Described is a method of producing iron-ore concentrates by the flotation washing of iron ore using as the collector mixtures containing (a) at least one ether amine of the formula (I): R1O-[CnH2n]y-NH-[CmH2m-NH]xH, in which R1 is a straight-chain or branched-chain aliphatic hydrocarbon group with 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds; n and m, independently of each other, are the numbers 1, 2 or 3; x is 0 or the number 1, 2 or 3; and y is 2 or 3; and (b) at least one other anionic and/or non-ionic collector.

Description

Gebiet der ErfindungField of the Invention

Die Erfindung betrifft ein verfahren zur Herstellung von Eisenerzkonzentraten durch Flotation von Eisenerzen, bei dem man als Sammler Gemische von speziellen Etheraminen mit anionischen Sammlern einsetzt.The invention relates to a process for the production of iron ore concentrates by flotation of iron ores, in which mixtures of special ether amines with anionic collectors are used as collectors.

Stand der TechnikState of the art

Eisenerze finden sich in der Natur vorzugsweise in Form von Oxiden, unter denen Magnetit, Hämatit, Martit, Limonit und Goethit die bekanntesten sind. Als Verunreinigungen enthalten diese hauptsächlich Silicate, insbesondere Quarz sowie Anteile an Phosphor- und Schwefelverbindungen. Für die Herstellung von qualitativ hochwertigem Stahl ist es erforderlich, die genannten Verunreinigungen möglichst weitgehend aus den Eisenerzen zu entfernen, wobei man sich in der Regel der Flotation bedient.Iron ores are found in nature preferably in the form of oxides, among which magnetite, hematite, martite, limonite and goethite are the best known. The main contaminants are silicates, especially quartz, as well as phosphorus and sulfur compounds. For the production of high quality steel, it is necessary to remove the above-mentioned impurities as much as possible from the iron ores, usually using flotation.

Üblicherweise wird hierzu das Eisenerz zunächst zerkleinert und trocken, vorzugsweise aber naß vermahlen und in Wasser suspendiert. Im Anschluß wird ein Sammler, häufig in Verbindung mit weiteren Reagenzien, zu denen Schäumer, Regler, Drücker (Desaktivatoren) und/oder Beleber (Aktivatoren) gehören, zugegeben, der die Abtrennung der Wertminerale von den Gangartmineralien des Erzes bei der anschließenden Flotation unterstützt. Bevor in die Suspension Luft eingeblasen wird, um an ihrer Oberfläche Schaum zu erzeugen und die Flotation in Gang zu setzen, läßt man diese Reagenzien üblicherweise eine gewisse Zeit auf das feingemahlene Erz einwirken (Konditionieren). Der Sammler bewirkt eine Hydrophobierung der Oberfläche der im Eisenerz enthaltenen Verunreinigungen, so daß ein Anhaften dieser Minerale an den während der Belüftung gebildeten Gasblasen stattfindet. Die Hydrophobierung der Mineralbestandteile erfolgt hierbei selektiv in der Weise, daß die Gangart ausflotiert wird und das Konzentrat als Rückstand verbleibt (indirekte Flotation).For this purpose, the iron ore is usually first crushed and dry, but preferably ground wet and in water suspended. A collector is then added, often in conjunction with other reagents, which include foaming agents, regulators, pushers (deactivators) and / or stimulants (activators), which supports the separation of the valuable minerals from the gangue minerals in the ore during the subsequent flotation. Before air is blown into the suspension in order to generate foam on its surface and to start the flotation, these reagents are usually allowed to act on the finely ground ore for a certain time (conditioning). The collector causes the surface of the impurities contained in the iron ore to become hydrophobic, so that these minerals adhere to the gas bubbles formed during the aeration. The hydrophobicization of the mineral components takes place selectively in such a way that the gait is floated out and the concentrate remains as a residue (indirect flotation).

Bei der flotativen Aufbereitung von Eisenerzen werden als Sammler bevorzugt aminische Verbindungen eingesetzt. Diesen kommt die Aufgabe zu, an der Oberfläche der Verunreinigungen möglichst selektiv zu adsorbieren, um eine hohe Abreicherung dieser unerwünschten Bestandteile im Flotationskonzentrat sicherzustellen. Außerdem sollen die Sammler einen tragfähigen, aber nicht zu stabilen Flotationsschaum entwickeln.Aminic compounds are preferably used as collectors in the flotative processing of iron ores. These have the task of adsorbing as selectively as possible on the surface of the contaminants in order to ensure a high depletion of these undesirable constituents in the flotation concentrate. In addition, the collectors should develop a stable, but not too stable, flotation foam.

Aus der US-A-4,168,227 ist ein Verfahren zur Entfernung von Silicatverunreinigungen aus Eisenerzen bekannt, bei dem als Sammler Alkylamine, Alkylendiamine und Etheramine eingesetzt werden.From US-A-4,168,227 a process for removing silicate impurities from iron ores is known, in which alkyl amines, alkylenediamines and ether amines are used as collectors.

In der AU-A-86/53 766 wird vorgeschlagen, die flotative Abtrennung von Silicaten und Phosphaten aus Eisenerzen mit Hilfe von Sammlergemischen enthaltend Etheramine und Ethercarbonsäureamide vorzunehmen.In AU-A-86/53 766 it is proposed to carry out the flotative separation of silicates and phosphates from iron ores with the aid of collector mixtures containing ether amines and ether carboxamides.

Die Verwendung von anionischen Tensiden als Sammler oder Co-Sammler in der Flotation von nichtsulfidischen Erzen ist aus einer Vielzahl von Veröffentlichungen bekannt. Beispiele hierzu sind Alkylphosphate und Alkyletherphosphate [Erzmetall 30, 505 (1977)], Ethercarbonsäuren [DE 22 37 359 A1], Sulfosuccinamide und Succinamate [US-A-4,206,045; US-A-4,309,282 und US-A-4,139,481] sowie Alkylasparaginsäuren [EP 0 270 018 A1].The use of anionic surfactants as collectors or co-collectors in the flotation of non-sulfidic ores is known from a large number of publications. Examples include alkyl phosphates and alkyl ether phosphates [ Erzmetall 30 , 505 (1977) ], ether carboxylic acids [ DE 22 37 359 A1 ], sulfosuccinamides and succinamates [ US-A-4,206,045; US-A-4,309,282 and US-A-4,139,481 ] as well as alkyl aspartic acids [ EP 0 270 018 A1 ].

Die Verwendung einer Mischung aus Etheraminen und stickstoffhaltigen, anionischen Tensiden als Sammler ist aus der US-A-4,732,667 bekannt.The use of a mixture of ether amines and nitrogen-containing anionic surfactants as collectors is known from US-A-4,732,667 .

Die US-A-4,472,270 beschreibt die Eisenerzflotation unter Einsatz von Etheraminen und einem unpolaren Kohlenwasserstoff als nichtionischem Sammler. US-A-4,472,270 describes iron ore flotation using ether amines and a non-polar hydrocarbon as a nonionic collector.

In Ullmann, Encyklopädie der technischen Chemie, 4. Aufl., Bd. 2, S.117, Ziff. 1.3.4 werden Kohlenwasserstoffe (Petroleum und andere Öle) als unpolare, nichtionenaktive Sammler genannt.In Ullmann, Encyclopedia of Technical Chemistry , 4th ed., Vol. 2, p.117, no. 1.3.4 hydrocarbons (petroleum and other oils) are named as non-polar, non-ionic collectors.

Die flotative Reinigung von Eisenerzen zu Konzentraten, die den steigenden Qualitätsansprüchen der Industrie genügen, stellt jedoch nach wie vor ein technisches Problem dar. Insbesondere mangelt es an Sammlersystemen, mit deren Hilfe sich Eisenerzkonzentrate herstellen lassen, die Phosphorgehalte von weniger als 0,015 Gew.-% aufweisen.However, the flotative cleaning of iron ores into concentrates that meet the increasing quality demands of industry continues to be a technical problem. In particular, there is a shortage of collector systems with whose help Have iron ore concentrates produced that have phosphorus contents of less than 0.015% by weight.

Die Aufgabe der Erfindung bestand somit darin, ein verbessertes Flotationsverfahren zur Herstellung von Eisenerzkonzentraten zu entwickeln, das frei von den geschilderten Nachteilen ist.The object of the invention was therefore to develop an improved flotation process for the production of iron ore concentrates which is free from the disadvantages described.

Beschreibung der ErfindungDescription of the invention

Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Eisenerzkonzentraten durch Flotation, bei dem man gemahlenes Eisenerz mit Wasser zu einer Suspension mischt, in die Suspension in Gegenwart eines Reagenziensystems Luft einleitet und den entstandenen Schaum zusammen mit den darin flotierten Feststoffen abtrennt, das sich dadurch auszeichnet, daß man als Sammler Gemische enthaltend

  • a) mindestens ein Etheramin der Formel (I),
    Figure imgb0001
     in der R¹ für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 6 bis 22 Kohlenstoffatomen und 0, 1, 2 oder 3 Doppelbindungen, n und m unabhängig voneinander für die Zahlen 1, 2 oder 3, x für 0 oder die Zahlen 1, 2 oder 3 und y für 2 oder 3 steht, und
  • b) mindestens einen weiteren anionischen Sammler aus der Gruppe der Aniontenside, umfassend
    Fettsäuren,
    Alkylsulfosuccinate,
    Alkylsulfosuccinamate,
    Alkylphosphate und Alkyletherphosphate der Formeln
    Figure imgb0002
     in der R¹² und R¹³ unabhängig voneinander für einen Alkyl- oder Alkenylrest mit 8 bis 22 Kohlenstoffatomen und p und q im Falle der Alkylphosphate für 0, im Falle der Alkyletherphosphate für Zahlen von 1 bis 15 stehen und Z ein Alkalimetall oder ein Ammoniumion darstellt,
    Alkylasparaginsäuren und
    Ethercarbonsäuren der Formel (XIV)
    Figure imgb0003
     in der R¹⁵ für einen Alkyl- oder Alkenylrest mit 8 bis 22 Kohlenstoffatomen und n für 0 oder Zahlen von 1 bis 10 steht und Z ein Alkalimetall- oder Ammonium-Ion darstellt,
einsetzt.The invention relates to a process for the production of iron ore concentrates by flotation, in which ground iron ore is mixed with water to form a suspension, air is introduced into the suspension in the presence of a reagent system and the resulting foam is separated off, together with the solids floated therein, which is distinguished by this that as a collector containing mixtures
  • a) at least one etheramine of the formula (I) ,
    Figure imgb0001
     in which R¹ is a linear or branched aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, n and m independently of one another for the numbers 1, 2 or 3, x for 0 or the numbers 1, 2 or 3 and y represents 2 or 3, and
  • b) comprising at least one further anionic collector from the group of anionic surfactants
    Fatty acids,
    Alkyl sulfosuccinates,
    Alkyl sulfosuccinamates,
    Alkyl phosphates and alkyl ether phosphates of the formulas
    Figure imgb0002
     in which R 12 and R 13 independently of one another represent an alkyl or alkenyl radical having 8 to 22 carbon atoms and p and q in the case of the alkyl phosphates are 0, in the case of the alkyl ether phosphates they are numbers from 1 to 15 and Z represents an alkali metal or an ammonium ion,
    Alkyl aspartic acids and
    Ether carboxylic acids of the formula (XIV)
    Figure imgb0003
     in which R¹⁵ represents an alkyl or alkenyl radical having 8 to 22 carbon atoms and n represents 0 or numbers from 1 to 10 and Z represents an alkali metal or ammonium ion,
starts.

Überraschenderweise wurde gefunden, daß die erfindungsgemäß einzusetzenden Sammlergemische selektiv Phosphorverunreinigungen aus Eisenerzen entfernen können und dabei die kationische Flotation der Silicate nicht negativ beeinflussen. Die Erfindung schließt dabei die Erkenntnis ein, daß Phosphor- und Silicatflotation sowohl separat als auch in einem Schritt durchgeführt werden können. Insbesondere wurde gefunden, daß die nach dem erfindungsgemäßen Verfahren erhältlichen Konzentrate Phosphorgehalte von weniger als 0,015 Gew.-% - bezogen auf das Konzentrat - aufweisen.Surprisingly, it was found that the collector mixtures to be used according to the invention can selectively remove phosphorus impurities from iron ores and do not negatively influence the cationic flotation of the silicates. The invention includes the knowledge that phosphorus and Silicate flotation can be carried out both separately and in one step. In particular, it has been found that the concentrates obtainable by the process according to the invention have phosphorus contents of less than 0.015% by weight, based on the concentrate.

Etheramine der Formel (I) stellen bekannte Verbindungen dar, die nach den einschlägigen Verfahren der präparativen organischen Chemie zugänglich sind. Üblicherweise geht man zu ihrer Herstellung von Fettalkoholsulfaten aus, die in Gegenwart von Alkalihydroxiden bei Temperaturen von ca. 180°C mit Alkanolaminen oder Aminoalkylalkanolaminen umgesetzt werden, wobei als Nebenprodukt Alkalisulfat gebildet wird [DE 35 04 242 A1]. Etheramines of the formula (I) are known compounds which are obtainable by the relevant preparative organic chemistry processes. Their preparation is usually based on fatty alcohol sulfates which are reacted with alkanolamines or aminoalkylalkanolamines in the presence of alkali metal hydroxides at temperatures of about 180 ° C., alkali metal sulfate being formed as a by-product [ DE 35 04 242 A1 ].

Als Ausgangsstoffe für die erfindungsgemäß zu verwendenden Etheramine kommen Fettalkoholsulfate auf Basis von gesättigten oder ungesättigten Fettalkoholen sowie primäre Amine bzw. Diamine in Betracht. Typische Beispiele sind Umsetzungsprodukte von Octylsulfat, Decylsulfat, Laurylsulfat, Myristylsulfat, Cetylsulfat, Stearylsulfat, Oleylsulfat, Elaidylsulfat, Petroselinylsulfat, Linolylsulfat, Linolenylsulfat, Arachylsulfat, Gadoleylsulfat, Behenylsulfat und Erucylsulfat mit Methanolamin, Ethanolamin, n-Propanolamin, i-Propanolamin, Aminoethylethanolamin, Aminoethylpropanolamin, Aminopropylethanolamin und Aminopropylpropanolamin. Wie in der Fettchemie üblich, können auch Sulfate auf Basis technischer Fettalkoholschnitte mit den genannten Aminen zur Reaktion gebracht werden. Bevorzugt sind Etheramine der Formel (I), in der R¹ für einen Alkylrest mit 6 bis 18, insbesondere 8 bis 12 Kohlenstoffatomen steht.Suitable starting materials for the ether amines to be used according to the invention are fatty alcohol sulfates based on saturated or unsaturated fatty alcohols and primary amines or diamines. Typical examples are reaction products of octyl sulphate, decyl sulphate, lauryl sulphate, myristyl sulphate, cetyl sulphate, stearyl sulphate, oleyl sulphate, elaidyl sulphate, petroselinyl sulphate, linolyl sulphate, linolenyl sulphanol, arachyl sulphate, eraducylyl sulphate, badenoleyl sulphate amine, gadoleyl sulphanol amine, gadoleyl sulphanol amine , Aminopropylethanolamine and aminopropylpropanolamine. As is common in fat chemistry, sulfates based on technical fatty alcohol cuts can also be reacted with the amines mentioned. Preference is given to ether amines of the formula (I) in which R 1 represents an alkyl radical having 6 to 18, in particular 8 to 12, carbon atoms.

Unter anionischen Sammlern sind im Sinne der Erfindung Aniontenside vom Typ der Fettsäuren, Alkylsulfosuccinate, Alkylsulfosuccinamate, Alkylphosphate, Alkyletherphosphate, Alkylasparaginsäuren und Ethercarbonsäuren zu verstehen. Bei allen diesen anionischen Tensiden handelt es sich um bekannte Verbindungen, deren Herstellung - sofern nicht anders angegeben - z.B. in J.Falbe, U.Hasserodt (ed.), "Katalysatoren, Tenside und Mineralöladditive, Thieme Verlag, Stuttgart, 1978 oder J.Falbe (ed.) "Surfactants in Consumer Products", Springer Verlag, Berlin, 1986 beschrieben ist.For the purposes of the invention, anionic collectors are to be understood as anionic surfactants of the fatty acid type, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl phosphates, alkyl ether phosphates, alkyl aspartic acids and ether carboxylic acids. All of these anionic surfactants are known compounds, the preparation of which - unless stated otherwise - for example in J. Falbe, U. Hasserodt (ed.), "Catalysts, Surfactants and Mineral Oil Additives, Thieme Verlag, Stuttgart, 1978 or J. Falbe (ed.) "Surfactants in Consumer Products", Springer Verlag, Berlin, 1986 .

Als Fettsäuren kommen hier vor allem die aus pflanzlichen oder tierischen Fetten und Ölen, beispielsweise durch Fettspaltung und gegebenenfalls Fraktionierung und/oder Trennung nach dem Umnetzverfahren, gewonnenen geradkettigen Fettsäuren der Formel (II) in Betracht,

Figure imgb0004

in der R² für einen aliphatischen Kohlenwasserstoffrest mit 12 bis 18 Kohlenstoffatomen und 0, 1, 2 oder 3 Doppelbindungen und Y für ein Alkali-, Erdalkalimetall oder einen Ammoniumrest steht. Eine besondere Bedeutung kommt hierbei den Natrium- und Kaliumsalzen der Öl- und der Tallölfettsäure zu.Suitable fatty acids here are in particular the straight-chain fatty acids of the formula (II) obtained from vegetable or animal fats and oils, for example by splitting and optionally fractionating and / or separating by the crosslinking process.
Figure imgb0004
in which R² is an aliphatic hydrocarbon radical having 12 to 18 carbon atoms and 0, 1, 2 or 3 double bonds and Y is an alkali metal, alkaline earth metal or an ammonium radical. The sodium and potassium salts of oleic and tall oil fatty acids are of particular importance.

Als Alkylsulfosuccinate eignen sich Sulfobernsteinsäuremonoester von Fettalkoholen der Formel (V),

Figure imgb0005

in der R⁶ für einen linearen oder verzweigten Alkylrest mit 8 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen steht und Z die oben angegebene Bedeutung besitzt.Suitable alkylsulfosuccinates are sulfosuccinic acid monoesters of fatty alcohols of the formula (V)
Figure imgb0005
in which R⁶ represents a linear or branched alkyl radical having 8 to 22, preferably 12 to 18 carbon atoms and Z has the meaning given above.

Als Alkylsulfosuccinamate eignen sich Sulfobernsteinsäuremonoamide von Fettaminen der Formel (VI),

Figure imgb0006

in der R⁷ für einen linearen oder verzweigten Alkylrest mit 8 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen steht und Z die oben angegebene Bedeutung besitzt.Suitable alkylsulfosuccinamates are sulfosuccinic acid monoamides of fatty amines of the formula (VI) ,
Figure imgb0006
in which R⁷ represents a linear or branched alkyl radical having 8 to 22, preferably 12 to 18 carbon atoms and Z has the meaning given above.

Als Alkylphosphate und Alkyletherphosphate eignen sich Substanzen der Formeln (XI) und (XII),

Figure imgb0007

in der R¹² und R¹³ unabhängig voneinander für einen Alkyl- oder Alkenylrest mit 8 bis 22 Kohlenstoffatomen und p und q im Falle der Alkylphosphate für 0, im Falle der Alkyletherphosphate für Zahlen von 1 bis 15 stehen und Z die oben angegebene Bedeutung besitzt.Suitable alkyl phosphates and alkyl ether phosphates are substances of the formulas (XI) and (XII)
Figure imgb0007
in which R¹² and R¹³ independently of one another are an alkyl or alkenyl radical having 8 to 22 carbon atoms and p and q in the case of the alkyl phosphates are 0, in the case of the alkyl ether phosphates are numbers from 1 to 15 and Z has the meaning given above.

Werden die Etheramine im Sinne der Erfindung im Gemisch mit Alkylphosphaten oder Alkyletherphosphaten eingesetzt, können die Phosphate als Mono- oder Diphosphate vorliegen. Vorzugsweise werden in diesem Fall Gemische aus Mono- und Dialkylphosphaten eingesetzt, wie sie bei der technischen Herstellung solcher Verbindungen anfallen.If the ether amines are used in the sense of the invention in a mixture with alkyl phosphates or alkyl ether phosphates, the phosphates can be present as mono- or diphosphates. In this case, preference is given to using mixtures of mono- and dialkylphosphates of the type obtained in the industrial production of such compounds.

Unter Alkylasparaginsäuren sind Verbindungen der Formel (XIII) zu verstehen,

Figure imgb0008

in der R¹⁴ für einen Alkyl- oder Alkenylrest mit 8 bis 22 Kohlenstoffatomen steht und Z die oben angegebene Bedeutung besitzt. Alkyl aspartic acids are to be understood as meaning compounds of the formula (XIII)
Figure imgb0008
in which R¹⁴ represents an alkyl or alkenyl radical having 8 to 22 carbon atoms and Z has the meaning given above.

Als Ethercarbonsäuren kommen schließlich Verbindungen der Formel (XIV) in Betracht,

Figure imgb0009

in der R¹⁵ für einen Alkyl- oder Alkenylrest mit 8 bis 22 Kohlenstoffatomen und n für 0 oder Zahlen von 1 bis 10 steht und Z die oben angegebene Bedeutung besitzt. Bei einer speziellen Ausführungsform der Erfindung werden neben den Sammler-Gemischen aus Etheraminen und anionischen Tensiden zusätzlich nichtionische Co-Sammler, ausgewählt aus der Gruppe der Fettalkoholpolyglykolether, eingesetzt. Finally , suitable ether carboxylic acids are compounds of the formula (XIV)
Figure imgb0009
in which R¹⁵ represents an alkyl or alkenyl radical having 8 to 22 carbon atoms and n represents 0 or numbers from 1 to 10 and Z has the meaning given above. In a special embodiment of the invention, in addition to the collector mixtures of ether amines and anionic surfactants, nonionic co-collectors, selected from the group of fatty alcohol polyglycol ethers, are also used.

Bei diesen nichtionischen Tensiden handelt es sich um bekannte Verbindungen, deren Herstellung - sofern nicht anders angegeben - z.B. in J.Falbe, U.Hasserodt (ed.), "Katalysatoren, Tenside und Mineralöladditive, Thieme Verlag, Stuttgart, 1978 oder J.Falbe (ed.) "Surfactants in Consumer Products", Springer Verlag, Berlin, 1986 beschrieben ist.These nonionic surfactants are known compounds, the preparation of which - unless stated otherwise - for example in J. Falbe, U. Hasserodt (ed.), "Catalysts, Surfactants and Mineral Oil Additives, Thieme Verlag, Stuttgart, 1978 or J. Falbe (ed.) "Surfactants in Consumer Products", Springer Verlag, Berlin, 1986 .

Als Fettalkoholpolyglycolether eignen sich Anlagerungsprodukte von durchschnittlich n Mol Ethylen- und/oder Propylenoxid an Fettalkohole, die der Formel (XV) folgen,

Figure imgb0010

in der R¹⁶ für einen linearen oder verzweigten Alkylrest mit 8 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen, R⁵ für Wasserstoff oder eine Methylgruppe und n für Zahlen von 1 bis 30, vorzugsweise 2 bis 15 steht.Suitable fatty alcohol polyglycol ethers are addition products of an average of n moles of ethylene and / or propylene oxide onto fatty alcohols, which follow the formula (XV)
Figure imgb0010
in which R¹⁶ represents a linear or branched alkyl radical having 8 to 22, preferably 12 to 18 carbon atoms, R⁵ represents hydrogen or a methyl group and n represents numbers from 1 to 30, preferably 2 to 15.

Die Gemische der Etheramine mit den anionischen und/gegebenenfall nichtionischen Sammlern können einen Gehalt von 5 bis 95 Gew.-%, vorzugsweise 10 bis 60 Gew.-% der Etheramine aufweisen. Besonders vorteilhafte Ergebnisse werden mit Gemischen erzielt, die neben Etheraminen Fettsäuren, Alkylasparaginsäuren und/oder Ethercarbonsäuren beziehungsweise Alkylsulfosuccinamate, Alkylphosphate und/oder Alkyletherphosphate enthalten.The mixtures of the ether amines with the anionic and / if appropriate nonionic collectors can have a content of 5 to 95% by weight, preferably 10 to 60% by weight of the ether amines. Particularly advantageous results are achieved with mixtures which, in addition to ether amines, contain fatty acids, alkyl aspartic acids and / or ether carboxylic acids or alkyl sulfosuccinamates, alkyl phosphates and / or alkyl ether phosphates.

Zur Erzielung wirtschaftlich brauchbarer Ergebnisse bei der Flotation von Eisenerz muß das Sammlergemisch in einer gewissen Mindestmenge eingesetzt werden. Es darf aber auch eine Höchstmenge nicht überschritten werden, da sonst die Schaumbildung zu stark wird und die Selektivität gegenüber den auszuflotierenden Verunreinigungen abnimmt. Die Mengen, in denen die erfindungsgemäß zu verwendenden Sammlergemische eingesetzt werden können, betragen üblicherweise 20 bis 2000, vorzugsweise 50 bis 1000 g pro Tonne Roherz.In order to achieve economically viable results in the flotation of iron ore, the collector mixture must be used in a certain minimum amount. However, a maximum amount must also not be exceeded, since otherwise the foam formation becomes too strong and the selectivity towards the contaminants to be flotated out decreases. The amounts in which the collector mixtures to be used according to the invention can be used, are usually 20 to 2000, preferably 50 to 1000 g per ton of raw ore.

Das erfindungsgemäße Verfahren schließt die Mitverwendung von für die Flotation üblichen Reagenzien wie beispielsweise Schäumern, Reglern, Aktivatoren, Desaktivatoren usw. ein. Die Durchführung der Flotation erfolgt unter den Bedingungen der Verfahren des Standes der Technik. In diesem Zusammenhang sei auf die folgenden Literaturstellen zum technologischen Hintergrund der Erzaufbereitung verwiesen : H.Schubert, "Aufbereitung fester mineralischer Stoffe", Leipzig, 1967; D.B. Puchas (Ed.), "Solid/liquid separation equipment scale-up", Croydon, 1977; E.S.Perry, C.J.VanOss, E.Grushka (Ed.), "Separation and Purification Methods", New York, 1973 - 1978. The method according to the invention includes the use of reagents customary for flotation, such as foaming agents, regulators, activators, deactivators, etc. The flotation is carried out under the conditions of the methods of the prior art. In this context, reference is made to the following references on the technological background of ore processing : H. Schubert, "Processing solid mineral substances", Leipzig, 1967; DB Puchas (Ed.), "Solid / liquid separation equipment scale-up", Croydon, 1977; ESPerry, CJVanOss, E. Grushka (Ed.), Separation and Purification Methods, New York, 1973-1978.

Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken.The following examples are intended to explain the subject matter of the invention in more detail without restricting it.

BeispieleExamples I. Eingesetzte Sammler und SammlerI. Collectors and collectors employed

Tab.1Tab. 1 SammlerCollector Aminische SammlerAmine collectors A1)A1) Etheramin auf BasisEtheramine based n-Propanolamin und C₈₋₁₀-Fettalkoholsulfatn-propanolamine and C₈₋₁₀ fatty alcohol sulfate (C₈₋₁₀H₁₇₋₂₁)-O-(CH₂)₃-NH₂(C₈₋₁₀H₁₇₋₂₁) -O- (CH₂) ₃-NH₂ A2)A2) Etheramin auf BasisEtheramine based n-Propanolamin und C₈₋₁₂-Fettalkoholsulfatn-propanolamine and C₈₋₁₂ fatty alcohol sulfate (C₈₋₁₂H₁₇₋₂₅)-O-(CH₂)₃-NH₂(C₈₋₁₂H₁₇₋₂₅) -O- (CH₂) ₃-NH₂ A3)A3) Etheramin auf BasisEtheramine based Aminopropylpropanolamin und DecylsulfatAminopropylpropanolamine and decyl sulfate C₁₀H₂₁-O-(CH₂)₃-NH-(CH₂)₃-NH₂C₁₀H₂₁-O- (CH₂) ₃-NH- (CH₂) ₃-NH₂

Figure imgb0011
Figure imgb0011
Figure imgb0012
Figure imgb0012

II. Verwendete ErzeII. Ores used

Für die Untersuchungen wurden zwei nordamerikanische Hämatit-Proben sowie ein Magnetiterz eingesetzt. Neben Eisenoxid enthielt das Hämatiterz etwa 44 Gew.-% Silicate (vorwiegend Quarz) und 0,1 bis 0,2 Gew.-% Apatit. Die genaue chemische Analyse der verwendeten Erzproben ist Tab.3 zu entnehmen: Tab.3 Analyse der Erzproben (Durchschnittswerte) Erz-Typ Fe Gew.-% P Gew.-% SiO₂ Gew.-% Hämatit-Probe I 35,9 0,038 43,9 Hämatit-Probe II 38,4 0,025 44,8 Magnetit 65,0 0,015 7,0 Two North American hematite samples and a magnetite ore were used for the investigations. In addition to iron oxide, the hematite ore contained about 44% by weight of silicates (predominantly quartz) and 0.1 to 0.2% by weight of apatite. The exact chemical analysis of the ore samples used can be found in Table 3: Tab. 3 Analysis of the ore samples (average values) Ore type Fe % by weight P % by weight SiO₂ wt .-% Hematite sample I 35.9 0.038 43.9 Hematite sample II 38.4 0.025 44.8 Magnetite 65.0 0.015 7.0

III. Flotationsbeispiele HämatiterzIII. Flotation examples hematite ore

Die Aufbereitung beinhaltete die folgenden Teilschritte:

  • Mahlung,
  • Selektive Entschlämmung und
  • Rougher-Flotation
Der aminische Sammler und die anionischen und/oder nichtionischen Sammler wurden in der Rougher-Flotationsstufe eingesetzt.The preparation comprised the following sub-steps:
  • Grinding,
  • Selective desludging and
  • Rougher flotation
The amine collector and the anionic and / or nonionic collector were used in the Rougher flotation stage.

600 g des zuvor grob zerkleinerten Erzes wurden unter Zugabe von 13,4 mg Natriummetasilicat, 40,2 mg Natriumhydroxid und etwa 400 ml Flotationswasser (Härte : 14,7 mg/l CaCl₂ x 2H₂O und 4,9 mg/l MgSO₄ x 7H₂O)) 45 min in einer Stangenmühle gemahlen. Das gemahlene Erz wies folgende Korngrößenverteilung auf:
   > 31 µm : 7,7 Gew.-%
11 bis 31 µm : 45,3 Gew.-%
   < 11 µm : 47,0 Gew.-%
Anschließend wurde das feingemahlene Erz in die Entschlämmungsstufe überführt, auf etwa 8 l verdünnt (Feststoffgehalt : 7 Gew.-%), mit 3 ml wärmebehandelter Maisstärke (2,25 gew.-%ig) versetzt und nach 2 min der überstehende Schlamm abgetrennt.600 g of the previously roughly crushed ore were added with the addition of 13.4 mg sodium metasilicate, 40.2 mg sodium hydroxide and about 400 ml flotation water (hardness: 14.7 mg / l CaCl₂ x 2H₂O and 4.9 mg / l MgSO₄ x 7H₂O) ) Ground in a bar mill for 45 min. The ground ore had the following grain size distribution:
> 31 µm: 7.7% by weight
11 to 31 µm: 45.3% by weight
<11 µm: 47.0% by weight
The finely ground ore was then transferred to the desludging stage, diluted to about 8 l (solids content: 7% by weight), mixed with 3 ml of heat-treated corn starch (2.25% by weight) and the supernatant sludge was separated off after 2 minutes.

Die entschlämmte Flotationsaufgabe (Volumen: ca. 1 l) wurde in einer 2-l-Denver-Rührwerkszelle (Typ D1) überführt. Anschließend wurden 67 ml Natriumhydroxid und 12 ml Maisstärke (2,25 gew.-%ig) zugefügt, die Zelle mit Flotationswasser aufgefüllt und die Trübe unter Rühren 2 min konditioniert. Danach wurden der aminische Sammler sowie die anionischen und/oder nichtionischen Sammler zudosiert. Im Anschluß wurde die Rougher-Flotation bei einer Rührgeschwindigkeit von 1200 UpM durchgeführt, bei der ein Schaumprodukt und ein Konzentrat in der Zelle erhalten wurde. Nach erneuter Dosierung des Sammlers wurde ein zweitesmal flotiert und ein weiteres Schaumprodukt sowie das gewünschte Eisenerzkonzentrat erhalten. Einzelheiten zu den Flotationsversuchen sind den Tabellen 4, 5 und 6 zu entnehmen. Tab.4a Hämatit, Probe I:
Sammlersysteme und Dosierung Bsp. Sammler A Einsatzmenge Sammler B Einsatzmenge g/t FS I g/t FS II g/t 1 A1 48 48 B1 90 2 A1 48 48 B1 180 3 A1 48 96 B1 180 4 A2 48 48 B2 126 5 A1 48 48 B3 60 6 A1 48 48 B1/B3 60/60 7 A1 32 32 B1/B3 80/ 9 8 A1 32 32 B1/B3 80/ 9 9 A1 48 48 B1/B3 39/39 10 A1 36 48 B1/B3 45/45 11 A1 36 48 B1/B3 60/60 V1 A1 48 48 - - Legende:
FS I : Flotationsstufe I
FS II : Flotationsstufe II Tab.4b Hämatit, Probe II:
Sammlersysteme und Dosierung Bsp. Sammler A Einsatzmenge Sammler B Einsatzmenge g/t FS I g/t FS II g/t 12 A1 48 48 B1/B3 60/60 13 A1 48 48 B1/B3 84/36 14 A1 48 48 B1/B3 96/24 15 A1 48 48 B1/B3 108/12 16 A1 48 48 B1/B3 48/72 17 A1 48 48 B4/B5/B6 24/40/ 80 18 A1 48 48 B4/B5/B6 10/34/100 19 A1 48 48 B4/B5/B6 28/21/ 95 20 A1 48 48 B4/B5/B6 20/57/ 67 V2 A1 48 48 - - Tab.5a Hämatit, Probe I:
Ergebnisse Entschlämmung Prozentangaben als Gew.-% Bsp. Schlamm Aufgabe P % Menge % Fe % P % SiO₂ % 1 30,2 12,8 0,051 75,8 0,038 2 29,9 12,6 0,055 76,1 0,039 3 29,9 12,6 0,055 76,1 0,039 4 29,6 12,8 0,049 73,1 0,036 5 26,9 13,3 0,052 76,4 0,034 6 26,9 13,9 0,053 77,8 0,035 7 28,1 12,1 0,058 75,2 0,038 8 27,1 12,6 0,055 75,0 0,037 9 27,2 13,9 0,055 77,9 0,037 10 29,8 11,4 0,057 76,8 0,039 11 31,5 11,1 0,053 74,3 0,039 V1 29,2 13,7 0,057 74,8 0,038 Tab.5b Hämatit, Probe II:
Ergebnisse Entschlämmung Prozentangaben als Gew.-% Bsp. Schlamm Aufgabe P % Menge % Fe % P % SiO₂ % 12 27,3 8,5 0,054 88,8 0,026 13 28,6 9,9 0,052 86,1 0,027 14 31,9 10,1 0,046 78,1 0,025 15 28,3 8,6 0,050 82,4 0,025 16 30,9 10,1 0,047 83,4 0,026 17 29,6 10,3 0,050 81,9 0,026 18 30,7 9,9 0,045 79,7 0,024 19 30,6 9,9 0,046 82,4 0,025 20 30,2 9,5 0,048 85,7 0,025 V2 26,0 8,6 0,053 85,8 0,025 Tab.6a Hämatit, Probe I:
Konzentrationen auf Mühlenaufgabe bezogen Prozentangaben als Gew.-% Bsp. GK min Eisenkonzentrat Ausbringen Fe % Menge % Fe % SiO₂ % P % 1 2 39,8 67,8 5,5 0,035 72,5 2 2 41,5 66,5 6,2 0,032 75,3 3 2 38,0 68,1 3,9 0,031 70,6 4 0 30,2 67,9 6,0 0,032 55,0 5 0 36,9 67,2 5,6 0,029 65,9 6 4 38,1 68,4 5,9 0,028 68,4 7 0 38,9 65,4 4,9 0,029 70,7 8 0 31,5 66,1 3,6 0,025 58,0 9 2 37,9 70,1 3,8 0,034 69,5 10 0 34,9 65,5 4,1 0,030 64,0 11 0 33,8 66,6 4,1 0,029 63,1 V1 0 33,9 66,8 5,0 0,044 60,6 Tab.6b Hämatit, Probe II:
Konzentrationen auf Mühlenaufgabe bezogen Prozentangaben als Gew.-% Bsp. GK min Eisenkonzentrat Ausbringen Fe % Menge % Fe % SiO₂ % P % 12 0 32,8 69,8 3,1 0,012 57,4 13 0 31,8 68,8 2,7 0,013 56,1 14 0 33,4 68,5 2,3 0,012 60,2 15 0 33,5 68,4 2,4 0,012 60,1 16 0 31,7 67,7 3,2 0,013 56,5 17 0 31,5 68,2 3,1 0,011 55,2 18 0 30,9 68,1 3,4 0,010 55,1 19 0 31,0 67,5 3,5 0,010 55,3 20 0 31,9 68,2 3,5 0,014 57,3 V2 0 32,4 70,2 2,5 0,021 57,5 The desludged flotation task (volume: approx. 1 l) was transferred to a 2 l Denver agitator cell (type D1). Then 67 ml of sodium hydroxide and 12 ml of corn starch (2.25% by weight) were added, the cell was filled with flotation water and the slurry was conditioned with stirring for 2 minutes. The amine collector and the anionic and / or nonionic collector were then metered in. The Rougher flotation was then carried out at a stirring speed of 1200 rpm, at which a foam product and a concentrate were obtained in the cell. After metering the collector again, the flotation was carried out a second time and another foam product and the desired iron ore concentrate were obtained. Details of the flotation tests can be found in Tables 4, 5 and 6. Tab.4a Hematite, sample I:
Collector systems and dosing E.g. Collector A Amount used Collector B Amount used g / t FS I g / t FS II g / t 1 A1 48 48 B1 90 2nd A1 48 48 B1 180 3rd A1 48 96 B1 180 4th A2 48 48 B2 126 5 A1 48 48 B3 60 6 A1 48 48 B1 / B3 60/60 7 A1 32 32 B1 / B3 80/9 8th A1 32 32 B1 / B3 80/9 9 A1 48 48 B1 / B3 39/39 10th A1 36 48 B1 / B3 45/45 11 A1 36 48 B1 / B3 60/60 V1 A1 48 48 - - Legend:
FS I: Flotation level I
FS II: Flotation level II Hematite, sample II:
Collector systems and dosing E.g. Collector A Amount used Collector B Amount used g / t FS I g / t FS II g / t 12th A1 48 48 B1 / B3 60/60 13 A1 48 48 B1 / B3 84/36 14 A1 48 48 B1 / B3 96/24 15 A1 48 48 B1 / B3 108/12 16 A1 48 48 B1 / B3 48/72 17th A1 48 48 B4 / B5 / B6 24/40/80 18th A1 48 48 B4 / B5 / B6 10/34/100 19th A1 48 48 B4 / B5 / B6 28/21/95 20th A1 48 48 B4 / B5 / B6 20/57/67 V2 A1 48 48 - - Hematite, sample I:
Results of desludging percentages as% by weight E.g. mud Task P % Quantity % Fe % P % SiO₂ % 1 30.2 12.8 0.051 75.8 0.038 2nd 29.9 12.6 0.055 76.1 0.039 3rd 29.9 12.6 0.055 76.1 0.039 4th 29.6 12.8 0.049 73.1 0.036 5 26.9 13.3 0.052 76.4 0.034 6 26.9 13.9 0.053 77.8 0.035 7 28.1 12.1 0.058 75.2 0.038 8th 27.1 12.6 0.055 75.0 0.037 9 27.2 13.9 0.055 77.9 0.037 10th 29.8 11.4 0.057 76.8 0.039 11 31.5 11.1 0.053 74.3 0.039 V1 29.2 13.7 0.057 74.8 0.038 Hematite, sample II:
Results of desludging percentages as% by weight E.g. mud Task P % Quantity % Fe % P % SiO₂ % 12th 27.3 8.5 0.054 88.8 0.026 13 28.6 9.9 0.052 86.1 0.027 14 31.9 10.1 0.046 78.1 0.025 15 28.3 8.6 0.050 82.4 0.025 16 30.9 10.1 0.047 83.4 0.026 17th 29.6 10.3 0.050 81.9 0.026 18th 30.7 9.9 0.045 79.7 0.024 19th 30.6 9.9 0.046 82.4 0.025 20th 30.2 9.5 0.048 85.7 0.025 V2 26.0 8.6 0.053 85.8 0.025 Hematite, sample I:
Concentrations related to the mill task Percentages as% by weight E.g. GK min Iron concentrate Spread Fe % Quantity % Fe % SiO₂ % P % 1 2nd 39.8 67.8 5.5 0.035 72.5 2nd 2nd 41.5 66.5 6.2 0.032 75.3 3rd 2nd 38.0 68.1 3.9 0.031 70.6 4th 0 30.2 67.9 6.0 0.032 55.0 5 0 36.9 67.2 5.6 0.029 65.9 6 4th 38.1 68.4 5.9 0.028 68.4 7 0 38.9 65.4 4.9 0.029 70.7 8th 0 31.5 66.1 3.6 0.025 58.0 9 2nd 37.9 70.1 3.8 0.034 69.5 10th 0 34.9 65.5 4.1 0.030 64.0 11 0 33.8 66.6 4.1 0.029 63.1 V1 0 33.9 66.8 5.0 0.044 60.6 Hematite, sample II:
Concentrations related to the mill task Percentages as% by weight E.g. GK min Iron concentrate Spread Fe % Quantity % Fe % SiO₂ % P % 12th 0 32.8 69.8 3.1 0.012 57.4 13 0 31.8 68.8 2.7 0.013 56.1 14 0 33.4 68.5 2.3 0.012 60.2 15 0 33.5 68.4 2.4 0.012 60.1 16 0 31.7 67.7 3.2 0.013 56.5 17th 0 31.5 68.2 3.1 0.011 55.2 18th 0 30.9 68.1 3.4 0.010 55.1 19th 0 31.0 67.5 3.5 0.010 55.3 20th 0 31.9 68.2 3.5 0.014 57.3 V2 0 32.4 70.2 2.5 0.021 57.5

Reihenfolge der Sammlerzugabe [Beispiele]:Sequence of collectors' allowances [examples]:

  • a)
    Rougher 1
    : Sammler A, Sammler B [1-5,7,10,11,V1]
    a)
    Rougher 1
    : Collector A, collector B [1-5,7,10,11, V1]
  • b)
    Rougher 1
    : Sammler A und Sammler B1 und B3 [6]
    b)
    Rougher 1
    : Collector A and collector B1 and B3 [6]
  • c)
    Vorflotation
    : Sammler B [8]
    Rougher 1, 2
    : Sammler A
    c)
    Pre-flotation
    : Collector B [8]
    Rougher 1, 2
    : Collector A
  • d)
    Rougher 1
    : Sammler A, Sammler B (30/30 g/t)
    Rougher 2
    : Sammler A, Sammler B ( 9/ 9 g/t) [9]
    d)
    Rougher 1
    : Collector A, collector B (30/30 g / t)
    Rougher 2
    : Collector A, collector B (9/9 g / t) [9]
  • e)
    Rougher 1
    : Sammler A, Sammler B, keine Konditionierung [12-20, V2]
    e)
    Rougher 1
    : Collector A, collector B, no conditioning [12-20, V2]
GKGK
: Gesamtkonditionierungszeit: Total conditioning time
IV. Flotationsbeispiele MagnetiterzIV. Examples of flotation magnetite ore

Es wurde ein Magnetiterz der unter II) angegebenen chemischen Zusammensetzung verwendet, das eine Korngröße von 89 Gew.-% kleiner als 43 µm aufwies. Flotiert wurde wiederum in einer 2-l-Denverzelle (Typ D1) mit einer Trübedichte von ca. 220 g/l in Wasser mit einem Calciumionengehalt von 4 mg/l. Der pH-Wert der Trübe wurde durch Zugabe von Natriumhydroxid auf 8,5 eingestellt; die Rührgeschwindigkeit betrug 1200 UpM. Nach der Zugabe von Sammler und Schäumer wurde Luft mit einer Strömungsgeschwindigkeit von 130 bis 150 l/h eingeleitet und flotiert. Der Schaum wurde über einen Zeitraum von 2 min bei der allgemeinen Silicatflotation abgenommen, bei einer zusätzlichen Phosphatflotation wurde die Flotationszeit entsprechend den Angaben in Tab.7 verlängert.A magnetite ore of the chemical composition specified under II) was used, which had a grain size of 89% by weight less than 43 μm. Flotation was again carried out in a 2 l Denver cell (type D1) with a turbidity density of approx. 220 g / l in water with a calcium ion content of 4 mg / l. The pH of the slurry was adjusted to 8.5 by adding sodium hydroxide; the stirring speed was 1200 rpm. After the addition of the collector and foamer, air was introduced and floated at a flow rate of 130 to 150 l / h. The foam was removed over a period of 2 min in the general silicate flotation, with an additional phosphate flotation the flotation time was extended in accordance with the information in Table 7.

Der aminische Sammler wurde als 0,25 gew.-%ige wäßrige Lösung dosiert, die anionischen Sammlergemische als 5 gew.-%ige wäßrige Lösungen zugegeben. In allen Flotationsversuchen wurde ein handelsüblicher Schäumer auf Basis von Aldehyden, Alkoholen und Estern mit einer Dosierung von 30 g/t eingesetzt und unverdünnt in die Trübe dosiert. Tab.7a Magnetit: Sammlersysteme und Dosierung Bsp. Sammler A Einsatzmenge g/t Sammler B Einsatzmenge g/t 21 A3 65 B6 95 22 A3 65 B7 100 23 A3 65 B1/B3 60/ 7 24 A3 65 B1/B3 60/ 7 25 A3 65 B4/B5/B6 9/14/28 26 A3 65 B4/B5/B6 9/14/28 27 A3 65 B1/B3 60/ 7 28 A3 65 B4/B5/B6 9/14/28 V3 A3 65 - - Tab.7b Magnetit: Prozentangaben als Gew.-% Bsp. Eisenkonzentrat Ausbringen Fe % Menge % Fe % SiO₂ % P % 21 87,7 67,6 4,6 0,011 91,3 22 91,4 68,1 4,2 0,012 95,1 23 86,2 68,6 3,8 0,011 89,7 24 92,2 67,7 4,9 0,012 94,5 25 88,7 68,5 4,2 0,010 91,9 26 89,2 68,0 4,5 0,010 92,0 27 91,7 67,4 4,9 0,011 94,0 28 91,3 66,9 4,7 0,011 93,7 V3 92,1 68,3 3,9 0,015 95,3 The amine collector was dosed as a 0.25% by weight aqueous solution, and the anionic collector mixtures were added as 5% by weight aqueous solutions. A commercial foamer based on aldehydes, alcohols and esters with a dosage of 30 g / t was used in all flotation experiments and metered into the slurry undiluted. Tab.7a Magnetite: collector systems and dosing E.g. Collector A Amount used g / t Collector B Amount used g / t 21 A3 65 B6 95 22 A3 65 B7 100 23 A3 65 B1 / B3 60/7 24th A3 65 B1 / B3 60/7 25th A3 65 B4 / B5 / B6 9/14/28 26 A3 65 B4 / B5 / B6 9/14/28 27 A3 65 B1 / B3 60/7 28 A3 65 B4 / B5 / B6 9/14/28 V3 A3 65 - - Magnetite: percentages as% by weight E.g. Iron concentrate Spread Fe % Quantity % Fe % SiO₂ % P % 21 87.7 67.6 4.6 0.011 91.3 22 91.4 68.1 4.2 0.012 95.1 23 86.2 68.6 3.8 0.011 89.7 24th 92.2 67.7 4.9 0.012 94.5 25th 88.7 68.5 4.2 0.010 91.9 26 89.2 68.0 4.5 0.010 92.0 27 91.7 67.4 4.9 0.011 94.0 28 91.3 66.9 4.7 0.011 93.7 V3 92.1 68.3 3.9 0.015 95.3

Reihenfolge und Flotationszeiten [Beispiele]:Sequence and flotation times [examples]:

  • a) Silicatflotation 2 min, Apatitflotation 1 min [21-23,25,V3]a) Silicate flotation 2 min, apatite flotation 1 min [21-23.25, V3]
  • b) Apatitflotation 0,5 min, Silicatflotation 2,5 min [24]b) Apatite flotation 0.5 min, silicate flotation 2.5 min [24]
  • c) Apatit- und Silicatflotation gleichzeitig 2,5 min [27,28]c) Apatite and silicate flotation at the same time 2.5 min [27.28]

Claims (5)

  1. A process for the production of iron ore concentrates by flotation, in which crushed iron ore is mixed with water to form a suspension, air is introduced into the suspension in the presence of a reagent system and the foam formed is removed together with the solids floated therein, characterized in that mixtures containing
    a) at least one ether amine corresponding to formula (I):
    Figure imgb0016
     in which R¹ is a linear or branched aliphatic hydrocarbon radical containing 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, n and m independently of one another represent the number 1, 2 or 3, x = 0 or the number 1, 2 or 3 and y = 2 or 3, and
    b) at least one other anionic collector from the group of anionic surfactants comprising
    fatty acids,
    alkyl sulfosuccinates,
    alkyl sulfosuccinamates,
    alkyl phosphates and alkylether phosphates corresponding to formulae (XI) and (XII):
    Figure imgb0017
     in which R¹² and R¹³ independently of one another represent an alkyl or alkenyl radical containing 8 to 22 carbon atoms and p and q have a value of 0 in the case of the alkyl phosphates and a value of 1 to 15 in the case of the alkylether phosphates and Z is an alkali metal ion or an ammonium ion,
    alkyl aspartic acids and
    ether carboxylic acids corresponding to formula (XIV):
    Figure imgb0018
     in which R¹⁵ is an alkyl or alkenyl radical containing 8 to 22 carbon atoms and n is 0 or a number of 1 to 10 and Z is an alkali metal ion or an ammonium ion,
    are used as collectors.
  2. A process as claimed in claim 1, characterized in that ether amines of formula (I), in which R¹ is a C₆₋₁₈ alkyl radical, are used.
  3. A process as claimed in at least one of claims 1 to 2, characterized in that nonionic co-collectors selected from the group of fatty alcohol polyglycol ethers are additionally used.
  4. A process as claimed in at least one of claims 1 to 3, characterized in that mixtures containing 5 to 95% by weight of ether amines (I) are used.
  5. A process as claimed in at least one of claims 1 to 4, characterized in that the collector mixtures are used in quantities of 20 to 2,000 g/t crude iron ore.
EP19920920650 1991-10-04 1992-09-25 Method of producing iron-ore concentrates by froth flotation Expired - Lifetime EP0609257B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4133063 1991-10-04
DE4133063A DE4133063A1 (en) 1991-10-04 1991-10-04 PROCESS FOR PRODUCING IRON ORE CONCENTRATES BY FLOTATION
PCT/EP1992/002224 WO1993006935A1 (en) 1991-10-04 1992-09-25 Method of producing iron-ore concentrates by froth flotation

Publications (2)

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EP0609257B1 true EP0609257B1 (en) 1996-06-12

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CA (1) CA2120742A1 (en)
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WO (1) WO1993006935A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102259060A (en) * 2010-12-07 2011-11-30 鞍钢集团矿业公司 Low-grade iron mineral flotation collecting agent

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5540337A (en) * 1994-04-04 1996-07-30 Baker Hughes Incorporated Alkyloxyalkaneamines useful as cationic froth flotation collectors
US5724986A (en) * 1995-11-06 1998-03-10 Jones Medical Instrument Co. Casing and spirometer for metered dose inhaler
SE521949C2 (en) * 1997-11-27 2003-12-23 Akzo Nobel Nv Process for foam flotation of silicate-containing iron ore
US7480848B2 (en) * 2006-02-10 2009-01-20 The Directv Group, Inc. Methods and apparatus to select tornado error correction parameters
DE102006010939A1 (en) * 2006-03-09 2007-09-13 Clariant International Limited Flotation reagent for silicates
DE102006019561A1 (en) 2006-04-27 2007-10-31 Clariant International Limited 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
AU2007338062B2 (en) * 2006-12-22 2012-01-12 Akzo Nobel Chemicals International B.V. Amine formulations for reverse froth flotation of silicates from iron ore
EP2017009B1 (en) 2007-07-20 2013-07-03 Clariant (Brazil) S.A. Reverse iron ore flotation by collectors in aqueous nanoemulsion
BRPI0705593B1 (en) * 2007-11-22 2016-04-12 Univ Minas Gerais method of quantifying amines in iron ore flotation waste
CN101234367B (en) * 2008-03-04 2011-04-06 昆明晶石矿冶有限公司 Siderite floatation collector and preparation thereof
DE102010004893A1 (en) * 2010-01-19 2011-07-21 Clariant International Limited Flotation reagent for magnetite- and / or hematite-containing iron ores
CA2914544A1 (en) 2013-07-05 2015-01-08 Akzo Nobel Chemicals International B.V. The synthesis of new anionic surfactants and their use as collectors in froth flotation of non-sulphidic ores
US10376901B2 (en) * 2014-09-18 2019-08-13 Akzo Nobel Chemicals International B.V. Use of branched alcohols and alkoxylates thereof as secondary collectors
US10786819B2 (en) * 2016-01-21 2020-09-29 Regents Of The University Of Minnesota Cationic flotation of silica and apatite from oxidized iron ores at natural pH
AU2017293089B2 (en) 2016-07-08 2019-04-18 Akzo Nobel Chemicals International B.V. Process to treat magnetite ore and collector composition
WO2019007714A1 (en) 2017-07-04 2019-01-10 Akzo Nobel Chemicals International B.V. Process to treat siliceous non-sulfidic ores and collector composition therefor
BR112019027874B1 (en) 2017-07-04 2023-05-09 Nouryon Chemicals International B.V PROCESS FOR TREATMENT OF NON-SULPHIDI CARBONATE ORE WITH A COLLECTOR COMPOSITION, COLLECTOR COMPOSITION FOR PROCESS USE AND PULP
MX2020013179A (en) * 2018-06-19 2021-02-26 Clariant Int Ltd Use of polyols for improving a process for reverse froth flotation of iron ore.
SE2450839A1 (en) 2022-03-25 2024-08-15 Clariant Int Ltd Novel Cationic Collectors for Improving a Process for Froth Flotation of Silicates
CN117585653B (en) * 2023-11-13 2024-08-09 湖北三峡实验室 Method for preparing low-cost battery-grade ferric phosphate by multiple precipitation method

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3363758A (en) * 1966-12-08 1968-01-16 Ashland Oil Inc Use of primary aliphatic ether amine acid salts in froth flotation process
AT317807B (en) * 1971-07-30 1974-09-10 Chem Y Flotation process
FR2367820A1 (en) * 1976-10-18 1978-05-12 Ceca Sa OXIDIZED ORE FLOTATION PROCESS
CA1100239A (en) * 1976-10-18 1981-04-28 Robert E. Lawlor Emulsified ether amines and process for using same in froth flotation
US4139481A (en) * 1977-12-21 1979-02-13 American Cyanamid Company Combinations of alkylamidoalkyl monoesters of sulfosuccinic acid and fatty acids as collectors for non-sulfide ores
US4206045A (en) * 1978-12-07 1980-06-03 American Cyanamid Company Process for froth flotation of phosphate using combination collector
US4309282A (en) * 1980-04-14 1982-01-05 American Cyanamid Company Process of phosphate ore beneficiation in the presence of residual organic polymeric flocculants
US4319987A (en) * 1980-09-09 1982-03-16 Exxon Research & Engineering Co. Branched alkyl ether amines as iron ore flotation aids
DE3238060A1 (en) * 1982-10-14 1984-04-19 Henkel KGaA, 4000 Düsseldorf FLOTATION AGENTS AND METHOD FOR FLOTATION OF NON-SULFIDIC MINERALS
US4472270A (en) * 1983-05-18 1984-09-18 Mobil Oil Corporation Beneficiation of ores
DE3504242A1 (en) * 1985-02-08 1986-08-14 Henkel KGaA, 4000 Düsseldorf METHOD FOR PRODUCING TERTIAL ETHERAMINES
US4732667A (en) * 1985-02-20 1988-03-22 Berol Kemi Ab Process and composition for the froth flotation beneficiation of iron minerals from iron ores
DE3536975A1 (en) * 1985-10-17 1987-04-23 Henkel Kgaa USE OF NON-ionic surfactants as aids for the flotation of non-sulphide ores
DE3641579A1 (en) * 1986-12-05 1988-06-16 Henkel Kgaa N-ALKYL- AND N-ALKENYLASPARAGINIC ACIDS AS CO-COLLECTORS FOR THE FLOTATION OF NON-SULFIDIC ORES
DE3723323C2 (en) * 1987-07-15 1998-03-12 Henkel Kgaa Hydroxy mixed ethers, processes for their preparation and their use
DE3723826A1 (en) * 1987-07-18 1989-01-26 Henkel Kgaa METHOD FOR PRODUCING ALKYL GLYCOSIDES

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102259060A (en) * 2010-12-07 2011-11-30 鞍钢集团矿业公司 Low-grade iron mineral flotation collecting agent
CN102259060B (en) * 2010-12-07 2012-11-28 鞍钢集团矿业公司 Low-grade iron mineral flotation collecting agent

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AU658226B2 (en) 1995-04-06
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