EP0609257A1 - Method of producing iron-ore concentrates by froth flotation. - Google Patents

Method of producing iron-ore concentrates by froth flotation.

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Publication number
EP0609257A1
EP0609257A1 EP92920650A EP92920650A EP0609257A1 EP 0609257 A1 EP0609257 A1 EP 0609257A1 EP 92920650 A EP92920650 A EP 92920650A EP 92920650 A EP92920650 A EP 92920650A EP 0609257 A1 EP0609257 A1 EP 0609257A1
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EP
European Patent Office
Prior art keywords
alkyl
collector
flotation
formula
carbon atoms
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Granted
Application number
EP92920650A
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German (de)
French (fr)
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EP0609257B1 (en
Inventor
Berthold Schreck
Rita Koester
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0609257A1 publication Critical patent/EP0609257A1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/0043—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 and / or nonionic 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 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 Beieber (activators), to help separate 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 mineral components are made hydrophobic 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.
  • a process for removing silicate impurities from iron ores is known from US Pat. No. 4,168,227, in which alkylamines, alkylenediamines and etheramines are used as collectors.
  • the Australian patent AU 86/53 766 proposes 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.
  • 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 Al], sulfosuccinamides and succinamates [US 4,206,045; US 4,309,282 and US 4,139,481] and alkyl aspartic acids [EP 0 270 018 A1].
  • 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 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 mixtures containing a) at least one etheramine of the formula (I),
  • R 1 O- [C n H 2n ] y -NH- [C m H 2m -NH] x H (I) in R 1 for a linear or branched aliphatic hydrocarbon radical with 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, n and m independently of one another represent the numbers 1, 2 or 3, x represents 0 or the numbers 1, 2 or 3 and y represents 2 or 3, and b) uses at least one further anionic and / or nonionic collector.
  • 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 finding 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 anionic surfactants of the fatty acid type, alkyl sulfates, alkyl ether sulfates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl benzene sulfonates, alkane sulfonates, petroleum sulfonates, acyl lactylates, sarcosides, alkyl phosphates, alkyl ether phosphates, and alkyl carboxylic acid 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 ed.
  • Surfactants and Mineral Oil Additives Thieme Verlag, Stuttgart, 1978 or J. Falbe (ed.) "Surfactants in Consumer Products", Springer Verlag, Berlin, 1986.
  • Suitable fatty acids 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,
  • R 2 -COOY (II) in which R 2 represents an aliphatic hydrocarbon radical having 12 to 18 carbon atoms and 0, 1, 2 or 3 double bonds and Y represents an alkali metal, alkaline earth metal or an ammonium radical.
  • R 2 represents an aliphatic hydrocarbon radical having 12 to 18 carbon atoms and 0, 1, 2 or 3 double bonds and Y represents 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 alkyl sulfates are the water-soluble salts of sulfuric acid semi-esters of fatty alcohols of the formula (III)
  • Suitable alkyl ether sulfates are the water-soluble salts of sulfuric acid semiesters of fatty alcohol polyglycol ethers of the formula (IV)
  • R 4 represents a linear or branched alkyl radical having 8 to 22, preferably 12 to 18 carbon atoms
  • R 5 represents hydrogen or a methyl group
  • n represents 1 to 30, preferably 2 to 15 and Z has the meaning given above.
  • Suitable alkylsulfosuccinates are sulfosuccinic acid monoesters of fatty alcohols of the formula (V)
  • R 6 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 R 7 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 alkylbenzene sulfonates are substances of the formula (VII)
  • Suitable alkanesulfonates are substances of the formula (VIII)
  • Suitable petroleum sulfonates are substances which are obtained by reacting lubricating oil fractions with sulfur trioxide or oleum and then neutralizing with sodium hydroxide solution. Products in which the hydrocarbon radicals predominantly have chain lengths of 8 to 22 carbon atoms are particularly suitable here.
  • Suitable acyl lactylates are substances of the formula (IX)
  • R 10 represents an aliphatic, cycloaliphatic or alicyclic, optionally substituted by hydroxyl group hydrocarbon radical having 7 to 23 carbon atoms and 0, 1, 2 or 3 double bonds and Z has the meaning given above.
  • acyl lactylates in flotation is described in German patent application DE 32 38 060 A1.
  • Suitable sarcosides are substances of the formula (X)
  • R 11 represents an aliphatic hydrocarbon radical having 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds.
  • Suitable alkyl phosphates and alkyl ether phosphates are substances of the formulas (XI) and (XII) and
  • R 12 and R 13 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)
  • R 14 represents an alkyl or alkenyl radical having 8 to 22 carbon atoms and Z has the meaning given above.
  • nonionic collectors are to be understood as nonionic surfactants of the fatty alcohol polyglycol ether, alkylphenol polyglycol ether, fatty acid polyglycol ester, fatty acid amide polyglycol ether, fatty amine polyglycol ether, mixed ether, hydroxymethyl ether and alkyl glycoside types. All of 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.
  • 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)
  • R 16 is a linear or branched alkyl radical having 8 to 22, preferably 12 to 18 carbon atoms
  • R 5 is hydrogen or a methyl group
  • n is a number from 1 to 30, preferably 2 to 15.
  • Suitable alkylphenol polyglycol ethers are addition products of an average of n moles of ethylene and / or propylene glycol with alkylphenols, which follow the formula (XVI)
  • R 17 represents an alkyl radical having 4 to 15, preferably 8 to 10 carbon atoms and R 5 and n have the meanings given above.
  • Suitable fatty acid polyglycol esters are adducts of an average of n moles of ethylene and / or propylene oxide with fatty acids which follow the formula (XVII). in which R 18 represents an aliphatic carbon radical having 5 to 21 carbon atoms and 0, 1, 2 or 3 double bonds and R 5 and n have the meanings given above.
  • Suitable fatty acid amide polyglycol ethers are addition products of an average of n moles of ethylene oxide and / or propylene oxide onto fatty acid amides which follow the formula (XVIII)
  • R 19 represents an aliphatic hydrocarbon radical having 5 to 21 carbon atoms and 0, 1, 2 or 3 double bonds and R 5 and n have the meanings given above.
  • Suitable fatty amine polyglycol ethers are addition products of an average of n moles of ethylene and / or propylene oxide with fatty amines, which follow the formula (XIX)
  • Suitable mixed ethers are reaction products of fatty alcohol polyglycol ethers with alkyl chlorides of the formula (XX),
  • R 21 represents an aliphatic carbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds
  • R 22 represents an alkyl radical having 1 to 4 carbon atoms or a benzyl radical and R ⁇ and n have the meanings given above.
  • Suitable hydroxy mixed ethers are substances of the formula (XXI)
  • R 23 represents an alkyl radical having 6 to 16 carbon atoms
  • R 24 represents an alkyl radical having 1 to 4 carbon atoms or a benzyl radical
  • R 5 and n have the meanings given above.
  • the preparation of the hydroxymisethers is described in German patent application DE 37 23 323 A1.
  • Suitable alkyl glycosides are substances of the formula (XXII)
  • G is preferably a glucose unit and x is a number from 1.1 to 1.6.
  • the preparation of the alkyl glycosides is described, for example, in German patent application DE 37 23 826 A1.
  • the mixtures of the ether amines with the anionic and / or 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.
  • hematite ore contained about 44% by weight of silicates (predominantly quartz) and 0.1 to 0.2% by weight of apatite.
  • silicates predominantly quartz
  • apatite 0.1 to 0.2% by weight
  • the preparation comprised the following sub-steps:
  • the amine collector and the anionic and / or nonionic collector were used in the Rougher flotation stage. 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 CaCl 2 ⁇ 2H 2 O and 4.9 mg / l MgSO 4 ⁇ 7H 2 O)) milled in a rod mill for 45 min. The ground ore had the following grain size distribution:
  • 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 1) was transferred to a 2-1 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.
  • Rougher 2 collector A, collector B (9/9 g / t) [9] e) Rougher 1: collector A, collector B, no conditioning
  • a magnetite ore of the chemical composition given under II) was used, which had a grain size of 89% by weight less than 43 ⁇ m.
  • the flotation was again carried out in a 2-1 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.

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

Abstract

Des concentrés de minerais de fer sont obtenus par épuration par flottation de minerais de fer, en utilisant comme collecteurs des mélanges renfermant (a) au moins une étheramine de formule (I): R1O-[CnH2n]y-NH-[CmH2m-NH]xH, dans laquelle R1 désigne un reste d'hydrocarbure aliphatique linéaire ou ramifié de 6 à 22 atomes de carbone et à 0, 1, 2 ou 3 doubles liaisons, n et m désignent, indépendamment l'un de l'autre, un nombre égal à 1, 2 ou 3, x est égal à 0 ou au nombre 1, 2 ou 3, et y est égal à 2 ou 3, et (b) au moins un autre collecteur anionique et/ou non ionique.Concentrates of iron ores are obtained by purification by flotation of iron ores, using as collectors mixtures containing (a) at least one etheramine of formula (I): R1O- [CnH2n] y-NH- [CmH2m-NH ] xH, in which R1 denotes a linear or branched aliphatic hydrocarbon residue of 6 to 22 carbon atoms and with 0, 1, 2 or 3 double bonds, n and m denote, independently of one another, a number equal to 1, 2 or 3, x is equal to 0 or to the number 1, 2 or 3, and y is equal to 2 or 3, and (b) at least one other anionic and / or nonionic collector.

Description

Verfahren zur Herstellung von Eisenerzkonzentraten  Process for the production of iron ore concentrates
durch Flotation  by flotation
Gebiet der Erfindung Field 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 und/oder nichtionischen 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 and / or nonionic collectors are used as collectors.
Stand der Technik State 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 vermählen und in Wasser suspendiert. Im Anschluß wird ein Sammler, häufig in Verbindung mit weiteren Reagenzien, zu denen Schäumer, Regler, Drücker (Desaktivatoren) und/oder Beieber (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). Usually, the iron ore is 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 Beieber (activators), to help separate 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 mineral components are made hydrophobic 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 Flotationsschäum 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 Patentschrift US 4,168,227 ist ein Verfahren zur Entfernung von Silicatverunreinigungen aus Eisenerzen bekannt, bei dem als Sammler Alkylamine, Alkylendiamine und Etheramine eingesetzt werden. In der Australischen Patentschrift AU 86/53 766 wird vorgeschlagen, die flotative Abtrennung von Silicaten und Phosphaten aus Eisenerzen mit Hilfe von Sammlergemischen enthaltend Etheramine und Ethercarbonsäureamide vorzunehmen. A process for removing silicate impurities from iron ores is known from US Pat. No. 4,168,227, in which alkylamines, alkylenediamines and etheramines are used as collectors. The Australian patent AU 86/53 766 proposes 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 Al], Sulfosuccinamide und Succinamate [US 4,206,045; US 4,309,282 und US 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 Al], sulfosuccinamides and succinamates [US 4,206,045; US 4,309,282 and US 4,139,481] and alkyl aspartic acids [EP 0 270 018 A1].
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 purification of iron ores into concentrates that meet the increasing quality demands of industry continues to be a technical problem. In particular, there is a lack of collector systems with the aid of which iron ore concentrates can be produced which have a phosphorus content of less than 0.015% by weight. exhibit.
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 Erfindung Description 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), 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 mixtures containing a) at least one etheramine of the formula (I),
R1O-[CnH2n]y-NH-[CmH2m-NH]xH (I) 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 und/oder nichtionischen Sammler einsetzt. R 1 O- [C n H 2n ] y -NH- [C m H 2m -NH] x H (I) in R 1 for a linear or branched aliphatic hydrocarbon radical with 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, n and m independently of one another represent the numbers 1, 2 or 3, x represents 0 or the numbers 1, 2 or 3 and y represents 2 or 3, and b) uses at least one further anionic and / or nonionic collector.
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 finding 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. Unter anionischen Sammlern sind im Sinne der Erfindung Aniontenside vom Typ der Fettsäuren, Alkylsulfate, Alkylethersulfate, Alkylsulfosuccinate, Alkylsulfosuccinamate, Alkylbenzolsulfonate, Alkansulfonate, Petrolsulfonate, Acyllactylate, Sarcoside, 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. 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. Preferred are 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. For the purposes of the invention, anionic collectors are anionic surfactants of the fatty acid type, alkyl sulfates, alkyl ether sulfates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl benzene sulfonates, alkane sulfonates, petroleum sulfonates, acyl lactylates, sarcosides, alkyl phosphates, alkyl ether phosphates, and alkyl carboxylic acid 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, 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-COOY (II) 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. R 2 -COOY (II) in which R 2 represents an aliphatic hydrocarbon radical having 12 to 18 carbon atoms and 0, 1, 2 or 3 double bonds and Y represents 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 Alkylsulfate eignen sich die wasserlöslichen Salze von Schwefelsäurehalbestern von Fettalkoholen der Formel (III), Suitable alkyl sulfates are the water-soluble salts of sulfuric acid semi-esters of fatty alcohols of the formula (III)
R3-O-SO3Z (III) in der R3 für einen linearen oder verzweigten Alkylrest mit 8 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen und Z für ein Alkalimetall oder einen Ammoniumrest steht. R 3 -O-SO 3 Z (III) in which R 3 represents a linear or branched alkyl radical having 8 to 22, preferably 12 to 18 carbon atoms and Z represents an alkali metal or an ammonium radical.
Als Alkylethersulfate eignen sich die wasserlöslichen Salze von Schwefelsäurehalbestern von Fettalkoholpolyglycolethern der Formel (IV), Suitable alkyl ether sulfates are the water-soluble salts of sulfuric acid semiesters of fatty alcohol polyglycol ethers of the formula (IV)
in der R4 für einen linearen oder verzweigten Alkylrest mit 8 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen, R5 für Wasserstoff oder eine Methylgruppe und n für 1 bis 30, vorzugsweise 2 bis 15 steht und Z die oben angegebene Bedeutung besitzt. in which R 4 represents a linear or branched alkyl radical having 8 to 22, preferably 12 to 18 carbon atoms, R 5 represents hydrogen or a methyl group and n represents 1 to 30, preferably 2 to 15 and Z has the meaning given above.
Als Alkylsulfosuccinate eignen sich Sulfobernsteinsäuremonoester von Fettalkoholen der Formel (V), Suitable alkylsulfosuccinates are sulfosuccinic acid monoesters of fatty alcohols of the formula (V)
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. in which R 6 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), 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), in which R 7 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 Alkylbenzo1sulfonate eignen sich Substanzen der Formel (VII), Suitable alkylbenzene sulfonates are substances of the formula (VII)
R8-C6H4-SO3Z (VII) in der R8 für einen geradkettigen oder verzweigten Alkylrest mit 4 bis 16, vorzugsweise 8 bis 12 Kohlenstoffatomen steht und Z die oben angegebene Bedeutung besitzt. R 8 -C 6 H 4 -SO 3 Z (VII) in which R 8 represents a straight-chain or branched alkyl radical having 4 to 16, preferably 8 to 12 carbon atoms and Z has the meaning given above.
Als Alkansulfonate eignen sich Substanzen der Formel (VIII), Suitable alkanesulfonates are substances of the formula (VIII)
R9-SO3Z (VTII) in der R9 für einen geradkettigen oder verzweigten Alkylrest mit 12 bis 18 Kohlenstoffatomen steht und Z die oben angegebene Bedeutung besitzt. R 9 -SO 3 Z (VTII) in which R 9 represents a straight-chain or branched alkyl radical having 12 to 18 carbon atoms and Z has the meaning given above.
Als Petrolsulfonate eignen sich Substanzen, die man durch Umsetzung von Schmierölfraktionen mit Schwefeltrioxid oder Oleum und anschließende Neutralisation mit Natronlauge erhält. Hier kommen insbesondere solche Produkte in Betracht, in denen die Kohlenwasserstoffreste überwiegend Kettenlängen von 8 bis 22 Kohlenstoffatomen aufweisen. Als Acyllactylate eignen sich Substanzen der Formel (IX), Suitable petroleum sulfonates are substances which are obtained by reacting lubricating oil fractions with sulfur trioxide or oleum and then neutralizing with sodium hydroxide solution. Products in which the hydrocarbon radicals predominantly have chain lengths of 8 to 22 carbon atoms are particularly suitable here. Suitable acyl lactylates are substances of the formula (IX)
in der R10 für einen aliphatischen, cycloaliphatischen oder alicyclischen, gegebenenfalls mit Hydroxylgruppen substituierten Kohlenwasserstoffrest mit 7 bis 23 Kohlenstoffatomen und 0, 1, 2 oder 3 Doppelbindungen steht und Z die oben angegebene Bedeutung besitzt. Die Herstellung und Verwendung der Acyllactylate in der Flotation ist in der Deutschen Patentanmeldung DE 32 38 060 A1 beschrieben. in which R 10 represents an aliphatic, cycloaliphatic or alicyclic, optionally substituted by hydroxyl group hydrocarbon radical having 7 to 23 carbon atoms and 0, 1, 2 or 3 double bonds and Z has the meaning given above. The preparation and use of the acyl lactylates in flotation is described in German patent application DE 32 38 060 A1.
Als Sarcoside eignen sich Substanzen der Formel (X), Suitable sarcosides are substances of the formula (X)
in der R11 für einen aliphatischen Kohlenwasserstoffrest mit 12 bis 22 Kohlenstoffatomen und 0, 1, 2 oder 3 Doppelbindungen steht. in which R 11 represents an aliphatic hydrocarbon radical having 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds.
Als Alkylphosphate und Alkyletherphosphate eignen sich Substanzen der Formeln (XI) und (XII), und Suitable alkyl phosphates and alkyl ether phosphates are substances of the formulas (XI) and (XII) and
in der R12 und R13 unabhängig voneinander für einen Alkyloder 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. in which R 12 and R 13 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. Unter Alkylasparaginsäuren sind Verbindungen der Formel (XIII) zu verstehen, 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. Alkyl aspartic acids are to be understood as meaning compounds of the formula (XIII)
in der R14 für einen Alkyl- oder Alkenylrest mit 8 bis 22 Kohlenstoffatomen steht und Z die oben angegebene Bedeutung besitzt. in which R 14 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, Finally, suitable ether carboxylic acids are compounds of the formula (XIV)
R150-(CH2CH2O)n-CH2-COOZ (XIV) 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. R 15 0- (CH 2 CH 2 O) n -CH 2 -COOZ (XIV) in which R 15 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 the above has the meaning given.
Unter nichtionischen Sammlern sind im Sinne der Erfindung Niotenside vom Typ der Fettalkoholpolyglycolether, Alkylphenolpolyglycolether, Fettsäurepolyglycolester, Fettsäureamidpolyglycolether, Fettaminpolyglycolether, Mischether, Hydroxymisehether und Alkylglykoside zu verstehen. Bei allen 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. Als Fettalkoholpolyglycolether eignen sich Anlagerungsprodukte von durchschnittlich n Mol Ethylen- und/oder Propylenoxid an Fettalkohole, die der Formel (XV) folgen, For the purposes of the invention, nonionic collectors are to be understood as nonionic surfactants of the fatty alcohol polyglycol ether, alkylphenol polyglycol ether, fatty acid polyglycol ester, fatty acid amide polyglycol ether, fatty amine polyglycol ether, mixed ether, hydroxymethyl ether and alkyl glycoside types. All of 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. 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 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. in which R 16 is a linear or branched alkyl radical having 8 to 22, preferably 12 to 18 carbon atoms, R 5 is hydrogen or a methyl group and n is a number from 1 to 30, preferably 2 to 15.
Als Alkylphenolpolyglycolether eignen sich Anlagerungsprodukte von durchschnittlich n Mol Ethylen- und/oder Propylenglycol an Alkylphenole, die der Formel (XVI) folgen, Suitable alkylphenol polyglycol ethers are addition products of an average of n moles of ethylene and / or propylene glycol with alkylphenols, which follow the formula (XVI)
in der R17 für einen Alkylrest mit 4 bis 15, vorzugsweise 8 bis 10 Kohlenstoffatomen steht und R5 und n die oben angegebenen Bedeutungen besitzen. in which R 17 represents an alkyl radical having 4 to 15, preferably 8 to 10 carbon atoms and R 5 and n have the meanings given above.
Als Fettsäurepolyglycolester eignen sich Anlagerungsprodukte von durchschnittlich n Mol Ethylen- und/oder Propylenoxid an Fettsäuren, die der Formel (XVII) folgen. in der R18 für einen aliphatischen Kohlenstoffrest mit 5 bis 21 Kohlenstoffatomen und 0, 1, 2 oder 3 Doppelbindungn steht und R5 und n die oben angegebenen Bedeutungen besitzen. Suitable fatty acid polyglycol esters are adducts of an average of n moles of ethylene and / or propylene oxide with fatty acids which follow the formula (XVII). in which R 18 represents an aliphatic carbon radical having 5 to 21 carbon atoms and 0, 1, 2 or 3 double bonds and R 5 and n have the meanings given above.
Als Fettsäureamidpolyglycolether eignen sich Anlagerungsprodukte von durchschnittlich n Mol Ethylen- und/oder Propylenoxid an Fettsäureamide, die der Formel (XVIII) folgen, Suitable fatty acid amide polyglycol ethers are addition products of an average of n moles of ethylene oxide and / or propylene oxide onto fatty acid amides which follow the formula (XVIII)
in der R19 für einen aliphatischen Kohlenwasserstoffrest mit 5 bis 21 Kohlenstoffatomen und 0, 1, 2 oder 3 Doppelbindungen steht und R5 und n die oben angegebenen Bedeutungen besitzen. in which R 19 represents an aliphatic hydrocarbon radical having 5 to 21 carbon atoms and 0, 1, 2 or 3 double bonds and R 5 and n have the meanings given above.
Als Fettaminpolyglycolether eignen sich Anlagerungsprodukte von durchschnittlich n Mol Ethylen- und/oder Propylenoxid an Fett-amine, die der Formel (XIX) folgen, Suitable fatty amine polyglycol ethers are addition products of an average of n moles of ethylene and / or propylene oxide with fatty amines, which follow the formula (XIX)
in der R20 für einen Alkylrest mit 6 bis 22 Kohlenstoffatomen steht und R5 und n die oben angegebenen Bedeutungen besitzen. Als Mischether eignen sich Umsetzungsprodukte von Fettalkoholpolyglycolethern mit Alkylchloriden der Formel (XX), in which R 20 represents an alkyl radical having 6 to 22 carbon atoms and R 5 and n have the meanings given above. Suitable mixed ethers are reaction products of fatty alcohol polyglycol ethers with alkyl chlorides of the formula (XX),
in der R21 für einen aliphatischen Kohlenstoffrest mit 6 bis 22 Kohlenstoffatomen und 0, 1, 2 oder 3 Doppelbindungen, R22 für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder einen Benzylrest steht und R^ und n die oben angegebenen Bedeutungen besitzen. in which R 21 represents an aliphatic carbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R 22 represents an alkyl radical having 1 to 4 carbon atoms or a benzyl radical and R ^ and n have the meanings given above.
Als Hydroxymischether eignen sich Substanzen der Formel (XXI), Suitable hydroxy mixed ethers are substances of the formula (XXI)
in der R23 für einen Alkylrest mit 6 bis 16 Kohlenstoffatomen, R24 für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder einen Benzylrest steht und R5 und n die oben angegebenen Bedeutungen besitzen. Die Herstellung der Hydroxymisehether ist in der Deutschen Patentanmeldung DE 37 23 323 A1 beschrieben. Als Alkylglykoside eignen sich Substanzen der Formel (XXII), in which R 23 represents an alkyl radical having 6 to 16 carbon atoms, R 24 represents an alkyl radical having 1 to 4 carbon atoms or a benzyl radical and R 5 and n have the meanings given above. The preparation of the hydroxymisethers is described in German patent application DE 37 23 323 A1. Suitable alkyl glycosides are substances of the formula (XXII)
R25-O-(G)x (XXII) in der G ein Symbol für eine Glykose-Einheit darstellt, die sich von einem Zucker mit 5 oder 6 Kohlenstoffatomen ableitet, x für eine Zahl zwischen 1 und 10 und R25 für einen aliphatischen Kohlenwasserstoffrest mit 6 bis 22 Kohlenstoffatomen und 0, 1, 2 oder 3 Doppelbindungen steht. Vorzugsweise steht G für eine Glucoseeinheit und x für Zahlen von 1,1 bis 1,6. Die Herstellung der Alkylglykoside ist beispielsweise in der Deutschen Patentanmeldung DE 37 23 826 A1 beschrieben. R 25 -O- (G) x (XXII) in which G represents a symbol for a glycose unit derived from a sugar with 5 or 6 carbon atoms, x for a number between 1 and 10 and R 25 for an aliphatic Hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds. G is preferably a glucose unit and x is a number from 1.1 to 1.6. The preparation of the alkyl glycosides is described, for example, in German patent application DE 37 23 826 A1.
Die Gemische der Etheramine mit den anionischen und/oder 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 / or 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 Methode", 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; D.B. Puchas (Ed.), "Solid / liquid separation equipment scale-up", Croydon, 1977; E.S.Perry, C.J. VanOss, E. Grushka (Ed.), "Separation and Purification Method", 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.
Beispiele I. Eingesetzte Sammler und Sammler Examples I. Collectors and collectors used
II. Verwendete Erze II. Ores used
Für die Untersuchungen wurden zwei nordamerikanische HämatitProben 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: 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:
III. Flotationsbeispiele Hämatiterz III. Flotation examples hematite ore
Die Aufbereitung beinhaltete die folgenden Teilschritte: The preparation comprised the following sub-steps:
- Mahlung, - grinding,
- Selektive Entschlämmung und  - Selective desludging and
- Rougher-Flotation  - Rougher flotation
Der aminische Sammler und die anionischen und/oder nichtionischen Sammler wurden in der Rougher-Flotationsstufe eingesetzt. 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 × 2H2O und 4,9 mg/l MgSO4 × 7H2O) ) 45 min in einer Stangenmühle gemahlen. Das gemahlene Erz wies folgende Korngrößenverteilung auf: The amine collector and the anionic and / or nonionic collector were used in the Rougher flotation stage. 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 CaCl 2 × 2H 2 O and 4.9 mg / l MgSO 4 × 7H 2 O)) milled in a rod mill for 45 min. The ground ore had the following grain size distribution:
> 31 μm 7,7 Gew.-% > 31 μm 7.7% by weight
11 bis 31 μm 45,3 Gew.-%  11 to 31 μm 45.3% by weight
< 11 μm 47,0 Gew.-%  <11 μm 47.0% by weight
Anschließend wurde das feingemahlene Erz in die Entschlämmungsstufe überführt, auf etwa 8 1 verdünnt (Feststoffgehalt : 7 Gew.-%), mit 3 ml wärmebehandelter Maisstärke (2,25 gew.-%ig) versetzt und nach 2 min der überstehende Schlamm abgetrennt. 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 1) wurde in einer 2-1-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. The desludged flotation task (volume: approx. 1 1) was transferred to a 2-1 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.
Reihenfolge der Sammlerzugäbe [Beispiele]: a) Rougher 1 : Sammler A, Sammler B [1-5,7, 10,11,V1] b) Rougher 1 : Sammler A und Sammler B1 und B3 [6] c) Vorflotation : Sammler B [8] Sequence of collector additions [examples]: a) Rougher 1: collector A, collector B [1-5,7, 10,11, V1] b) Rougher 1: collector A and collector B1 and B3 [6] c) pre-flotation: collector B [8]
Rougher 1, 2 : Sammler A d) Rougher 1 : Sammler A, Sammler B (30/30 g/t)  Rougher 1, 2: collector A d) Rougher 1: collector A, collector B (30/30 g / t)
Rougher 2 : Sammler A, Sammler B ( 9/ 9 g/t) [9] e) Rougher 1 : Sammler A, Sammler B, keine Konditionierung  Rougher 2: collector A, collector B (9/9 g / t) [9] e) Rougher 1: collector A, collector B, no conditioning
[12-20, V2]  [12-20, V2]
GK : Geεamtkonditionierungszeit GK: total conditioning time
IV. Flotationsbeispiele Magnetiterz IV. 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 um aufwies. Flotiert wurde wiederum in einer 2-1-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 1/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 given under II) was used, which had a grain size of 89% by weight less than 43 μm. The flotation was again carried out in a 2-1 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. 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.
Reihenfolge und Flotationszeiten rBeispiele!: a) Silicatflotation 2 min, Apatitflotation 1 min Sequence and flotation times rExamples !: a) Silicate flotation 2 min, apatite flotation 1 min
[21-23,25,V3]  [21-23.25, V3]
b) Apatitflotation 0,5 min, Silicatflotation 2,5 min  b) Apatite flotation 0.5 min, silicate flotation 2.5 min
[24]  [24]
c) Apatit- und Silicatflotation gleichzeitig 2,5 min  c) Apatite and silicate flotation at the same time 2.5 min
[27,28]  [27.28]

Claims

Patentansprüche Claims
1. 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, dadurch gekennzeichnet, daß man als Sammler Gemische enthaltend a) mindestens ein Etheramin der Formel (I), 1. 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, characterized in that a collector Mixtures containing a) at least one etheramine of the formula (I),
R1O-[CnH2n]y-NH-[CmH2m-NH]xH (I) 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 und/oder nichtionischen Sammler einsetzt. R 1 O- [C n H 2n ] y -NH- [C m H 2m -NH] x H (I) in R 1 for a linear or branched aliphatic hydrocarbon radical with 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, n and m independently of one another represent the numbers 1, 2 or 3, x represents 0 or the numbers 1, 2 or 3 and y represents 2 or 3, and b) uses at least one further anionic and / or nonionic collector.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man Etheramine der Formel (I) einsetzt, in der R1 für einen Alkylrest mit 6 bis 18 Kohlenstoffatomen steht. 2. The method according to claim 1, characterized in that ether amines of the formula (I) are used in which R 1 is an alkyl radical having 6 to 18 carbon atoms.
3. Verfahren nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß man als anionische Sammler Aniontenside ausgewählt aus der Gruppe, die von Fettsäuren, Alkylsulfaten, Alkylethersulfaten, Alkylsulfosuccinaten, Alkylsulfosuccinamaten, Alkylbenzolsulfonaten, Alkansulfonaten, Petrolsulfonaten, Acyllactylaten, Sarcosiden, Alkylphosphaten, Alkyletherposphaten, Alkylasparaginsäuren und Ethercarbonsäuren gebildet wird, einsetzt. 3. Process according to claims 1 and 2, characterized in that anionic surfactants selected from the group consisting of fatty acids, alkyl sulfates, alkyl ether sulfates, alkyl sulfosuccinates, alkyl sulfosuccinamates, alkyl benzene sulfonates, alkane sulfonates, petroleum sulfonates, acyl lactylates, sarcosides, alkyl phosphates, alkyl phosphates, Alkyl aspartic acids and ether carboxylic acids is used.
4. Verfahren nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man als nichtionische Co¬4. The method according to at least one of claims 1 to 3, characterized in that one as a non-ionic Co¬
Sammler Niotenside ausgewählt aus der Gruppe, die von Fettalkoholpolyglycolethern, Alkylphenolpolyglycolethern, Fettsäurepolyglycolestern, Fettsäureamidpolyglycolethern, Fettaminpolyglycolethern, Mischethern, Hydroxymisehethern und Alkylglykosiden gebildet wird, einsetzt. Collector nonionic surfactants selected from the group consisting of fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, mixed ethers, hydroxymisethers and alkylglycosides.
5. Verfahren nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man Gemische einsetzt, die einen Anteil an Etheraminen der Formel (I) von 5 bis 95 Gew.-% aufweisen. 5. The method according to at least one of claims 1 to 4, characterized in that mixtures are used which have a proportion of ether amines of the formula (I) from 5 to 95 wt .-%.
6. Verfahren nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die Sammlergemische in Mengen von 20 bis 2000 g/t Roheisenerz einsetzt. 6. The method according to at least one of claims 1 to 5, characterized in that the collector mixtures are used in amounts of 20 to 2000 g / t of pig iron ore.
7. Verfahren nach mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der Restgehalt an Phosphor im Eisenerzkonzentrat nicht mehr als 0,015 Gew.-% - bezogen auf das Konzentrat - beträgt. 7. The method according to at least one of claims 1 to 6, characterized in that the residual phosphorus content in the iron ore concentrate is not more than 0.015 wt .-% - based on the concentrate.
EP19920920650 1991-10-04 1992-09-25 Method of producing iron-ore concentrates by froth flotation Expired - Lifetime EP0609257B1 (en)

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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

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CA2120742A1 (en) 1993-04-15
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WO1993006935A1 (en) 1993-04-15
DE4133063A1 (en) 1993-04-08
DE59206582D1 (en) 1996-07-18

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