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Dokumentenidentifikation EP0699106 17.02.2000
EP-Veröffentlichungsnummer 0699106
Titel VERFAHREN UND REAGENZ ZUR FLOTATION VON KALZIUMKARBONATERZ
Anmelder Berol Nobel AB, Stenungsund, SE
Erfinder KLINGBERG, Anders, S-440 90 Henan, SE;
OLSSON, Lisbeth, S-444 92 Jörlanda, SE
Vertreter Barz, P., Dipl.-Chem. Dr.rer.nat., Pat.-Anw., 80803 München
DE-Aktenzeichen 69422618
Vertragsstaaten AT, DE, DK, ES, FR, GB, GR, IT, PT, SE
Sprache des Dokument EN
EP-Anmeldetag 27.04.1994
EP-Aktenzeichen 949164446
WO-Anmeldetag 27.04.1994
PCT-Aktenzeichen SE9400376
WO-Veröffentlichungsnummer 6419
WO-Veröffentlichungsdatum 24.11.1994
EP-Offenlegungsdatum 06.03.1996
EP date of grant 12.01.2000
Veröffentlichungstag im Patentblatt 17.02.2000
IPC-Hauptklasse B03D 1/01

Beschreibung[en]

The present invention relates to a method of floating calcium carbonate ore containing silicates as impurities. According to the invention, flotation is performed in the presence of a quaternary ammonium compound and an alkylene oxide adduct of an amine compound, the silicate being concentrated in the float.

From US Patent Specification 4,995,965 it is known to separate calcium carbonate from impurities, such as silicate, by the steps of floating the silicate and concentrating the valuable mineral, i.e. the calcium carbonate in the remainder, in the presence of amine-group-containing collectors. From this patent specification appears that a number of cationic compounds, such as methyl-bis (2-hydroxypropyl) -cocoalkyl ammonium methyl sulphate, dimethyl didecyl ammonium chloride, dimethyldi(2-ethylhexyl)-ammonium chloride, dimethyl-(2-ethyl-hexyl)-cocoalkyl ammonium chloride, dicocoalkyl dimethyl ammonium chloride, and n-tallow alkyl-1,3-diamino propane diacetate can be used as collectors in such a flotation procedure. The patent specification also states that quaternary ammonium compounds, as represented by Arquad 2C (dimethyl dicocoalkyl ammonium chloride) and a combination of Duomac T (N-tallow alkyl-1,3-diamino propane diacetate) and Ethomeen 18/16 (long-chain alkylamine + 50 EO) can be used as collectors, although they yield an unacceptably high content of acid-insoluble matter in the valuable mineral.

It has now surprisingly been found that when cleaning calcium carbonate containing silicates as impurity, a very high yield and/or high selectivity (low content of acid-insoluble matter) can be achieved if reverse flotation is performed in the presence of a quaternary ammonium compound in combination with an alkylene oxide adduct of an amine compound. More specifically, the present invention relates to a froth-flotation process perfomed in the presence of a quaternary ammonium compound having the formula

wherein one or two of the groups R1, R2, R3 and R4 are a hydrocarbon group having 8-36 carbon atoms and the remaining groups a hydrocarbon group having 1-7 carbon atoms or a hydroxyalkyl group having 2-7 carbon atoms, and A is an anionic counterion, and an alkylene oxide adduct having the formula
wherein R5 is a hydrocarbon group having 8-22 carbon atoms, A1, A2 and A3 are an alkylene oxide group having 2-4 carbon atoms, R6 is an alkylene group having 2-3 carbon atoms, n1, n2 and n3 are 3-20 and the sum of all n1, n2 and n3 is 10-40, and s is 0-3; the weight ratio of the quaternary ammonium compound to the alkylene oxide adduct being 3:2-11:1, preferably 7:3-9:1, and calcium carbonate being recovered from the remainder while contaminating silicates are removed with the float. By the method of the invention, it has now been found possible to significantly reduce the content of insoluble silicates, such as quartz, feldspar, amphibole and pyroxene.

In formula (I), two of the groups R1, R2, R3 and R4 preferably consist of straight or chained, saturated or unsaturated alkyl groups having 8-22, preferably 10-16 carbon atoms, while the two remaining groups preferably are alkyl groups having 1-3 carbon atoms or hydroxyalkyl groups having 2-3 carbon atoms. A generally is a monovalent ion, such as methyl sulphate or chloride. Specific examples of compounds of formula (I) are dimethyl didecyl ammonium chloride, dimethyl dicocoalkyl ammonium chloride, dimethyl dilauryl ammonium chloride, dimethyl distearyl ammonium chloride, dimethyl ditallow alkyl ammonium chloride and corresponding methyl sulphate salts. Alkylene oxide adducts of formula (II) preferably are such where R5 is a straight or branched, saturated or unsaturated alkyl group having 10-20 carbon atoms and the sum of all n1, n2 and n3 is 12-30. Of all the alkyleneoxy groups in the alkylene oxide adduct, 70-100% preferably are ethyleneoxy groups and 0-30% propyleneoxy groups. For reasons of production technique, such compounds are generally preferred where all alkyleneoxy groups are ethyleneoxy groups. The symbol s preferably is 0 or 1. By suitably varying the number of alkyleneoxy groups, their type and the number of carbon atoms in the hydrophobic moiety R, the compounds of formula (II) can easily be given such properties that they can be mixed with the compounds of formula (I) to form stable mixtures. Moreover, the quaternary ammonium compounds of formula (I) are generally prepared in the presence of an alcoholic solvent, such as isopropanol, in a content of about 10-15% by weight of the ammonium compound. The action of such a solvent usually yields, upon admixture with compounds (I) and (II), a clear, homogeneous and stable liquid phase.

The collectors according to the present invention can be added separately, but are preferably added together as a single flotation reagent. The total content of the two compounds may vary within wide limits but generally amounts to 50-2000, preferably 200-1000 g/tonne of ore to be floated.

In the application of the present invention, it is possible, in addition to the additives mentioned above, to add other additives which are well-known in float flotation. Examples of such additives are pH-adjusting agents, such as sodium carbonate and sodium hydroxide; depressants, such as starch, quebracho, tannin, dextrin and guar gum, and polyelectrolytes, such as polyphosphate and water glass, which have a dispersant effect, often combined with a depressant effect. Other conventional additives are foaming agents, such as methylisobutylcarbinol, triethoxybutane and polypropylene oxide and its alkyl ethers.

The method of the invention is further illustrated by the following Example.

Example 1

Calcite ore containing 1.6% by weight of silicate mineral (quartz, feldspar, amphibole, pyroxene) was ground in an amount of 0.5 kg together with 0.5 kg of water to a particle size of -250 µm. The ground material was transferred to a 1.5-litre flotation cell. After dilution with water to 1.4 l, 56% of the collector reagent used was added in the form of a 0.5% aqueous solution. After conditioning for three minutes, the float was withdrawn during 1.5 min. Another 22% of the reagent was thereafter added to the remainder, which was conditioned for three minutes, whereupon the whole mixture was floated for 1.5 min. To the remainder was charged another 22% of the reaction mixture, and the whole mixture was conditioned for 3 min and thereafter floated. The resulting flotation remainder was dried, weighed and analysed for content acid-insoluble in 25% hydrochloric acid. The collectors used and the results obtained appear from the following tables. Collector Designation Dimethyl dicocoalkyl ammonium chloride I a N-tallow alkyl-1,3-diamine propane diacetate I b Monotallow alkylamine + 15 EO II a Monotallow alkylamine + 50 EO II b Monococoalkylamine + 5 EO III a Monococoalkylamine + 11 EO III b Monococoalkylamine + 17 EO III c Monotallow alkyldiaminopropane + 10 EO IV a Monotallow alkyldiaminopropane + 20 EO IV b Monotallow alkyldiaminopropane + 30 EO IV c Monotallow alkyldiaminopropane + 40 EO IV d
Test Collector 1 Collector 2 Acid insoluble matter % Calcite yield % Type g/tonne Type g/tonne A I a 350 - - 0.32 97.5 B I b 87.5 II b 262.7 0.24 87.8 C I b 175 II b 175 0.18 94.1 D I b 262.7 II b 87.5 0.12 84.2 E - - II b 350 1.34 96.9 F I a 175 II b 175 0.47 97.7 G I a 245 II b 105 0.30 98.0 H I a 280 II b 70 0.20 97.8 I I a 450 - - 0.15 96.8 1 I a 360 II a 90 0.09 98.21) 2 I a 360 III a 90 0.08 97.41) 3 I a 360 III b 90 0.06 97.81) 4 I a 360 III c 90 0.06 97.71) 5 I a 360 IV a 90 0.12 98.01) 6 I a 360 IV b 90 0.08 98.41) 7 I a 360 IV c 90 0.06 98.21) 8 I a 360 IV d 90 0.03 97.61)
1) In tests 1-8, the calcite yield is calculated at 0.20% acid-insoluble matter.

From these results appears that the flotation tests according to the invention, i.e. tests 1-8, gave a considerably lower content of acid-insoluble matter and, at the same content of acid-insoluble matter, a higher calcite yield than the prior-art technique and reference samples.


Anspruch[de]
  1. Verfahren zur Reinigung von Calciumcarbonaterz, das Silicatverunreinigungen enthält, bei dem ein Schaumflotationsverfahren in Gegenwart eines kationischen Sammlers durchgeführt wird, dadurch gekennzeichnet, daß der Sammler eine Kombination aus einer quaternären Ammoniumverbindung mit der Formel
    worin eine oder zwei der Gruppen R1, R2, R3 und R4 eine Kohlenwasserstoffgruppe mit 8 bis 36 Kohlenstoffatomen ist bzw. sind und die restlichen Gruppen eine Kohlenwasserstoffgruppe mit 1 bis 7 Kohlenstoffatomen oder eine Hydroxyalkylgruppe mit 2 bis 7 Kohlenstoffatomen sind und A ein anionisches Gegenion ist, und einem Alkylenoxidaddukt mit der Formel
    worin R5 eine Kohlenwasserstoffgruppe mit 8 bis 22 Kohlenstoffatomen ist, A1, A2 und A3 eine Alkylenoxidgruppe mit 2 bis 4 Kohlenstoffatomen sind, R6 eine Alkylengruppe mit 2 bis 3 Kohlenstoffatomen ist, n1, n2 und n3 3 bis 20 sind und die Summe aller n1, n2 und n3 10 bis 40 ist und s 0 bis 3 ist, ist; wobei das Gewichtsverhältnis von der quaternären Ammoniumverbindung zu dem Alkylenoxidaddukt 3:2 - 11:1 ist und das Calciumcarbonat aus dem Rückstand isoliert wird, während kontaminierende Silicate mit dem Schwimmgut entfernt werden.
  2. Verfahren wie in Anspruch 1 beansprucht, dadurch gekennzeichnet, daß zwei der Gruppen R1, R2, R3 und R4 Kohlenwasserstoffgruppen mit 8 bis 22 Kohlenstoffatomen, bevorzugt 10 bis 16 Kohlenstoffatomen, sind, während die beiden restlichen Gruppen Alkylgruppen mit 1 bis 3 Kohlenstoffatomen oder Hydroxyalkylgruppen mit 2 bis 3 Kohlenstoffatomen sind.
  3. Verfahren wie in Anspruch 2 beansprucht, dadurch gekennzeichnet, daß die quaternäre Ammoniumverbindung ein Dimethyldikokosfettalkylammoniumsalz ist.
  4. Verfahren wie in irgendeinem der Ansprüche 1 bis 3 beansprucht, dadurch gekennzeichnet, daß R5 eine Alkylgruppe mit 10 bis 20 Kohlenstoffatomen ist und die Summe von n1, n2 und n3 12 bis 30 ist.
  5. Verfahren wie in irgendeinem der Ansprüche 1 bis 4 beansprucht, dadurch gekennzeichnet, daß in dem Alkylenoxidaddukt 70 bis 100% aller Alkylenoxygruppen Ethylenoxygruppen sind und 0 bis 30% Propylenoxygruppen sind.
  6. Verfahren wie in den Ansprüchen 1 bis 5 beansprucht, dadurch gekennzeichnet, daß s 0 oder 1 ist.
  7. Flotationsmittel, dadurch gekennzeichnet, daß es eine quaternäre Ammoniumverbindung mit der Formel
    worin eine oder zwei der Gruppen R1, R2, R3 und R4 eine Kohlenwasserstoffgruppe mit 8 bis 36 Kohlenstoffatomen ist bzw. sind und die restlichen Gruppen eine Kohlenwasserstoffgruppe mit 1 bis 7 Kohlenstoffatomen oder eine Hydroxyalkylgruppe mit 2 bis 7 Kohlenstoffatomen sind, und A ein anionisches Gegenion ist, in Kombination mit einem Alkylenoxidaddukt mit der Formel
    worin R5 eine Kohlenwasserstoffgruppe mit 8 bis 22 Kohlenstoffatomen ist, A1, A2 und A3 eine Alkylenoxidgruppe mit 2 bis 4 Kohlenstoffatomen sind, R6 eine Alkylengruppe mit 2 bis 3 Kohlenstoffatomen ist, n1, n2 und n3 3 bis 20 sind und die Summe aller n1, n2 und n3 10 bis 40 ist und s 0 bis 3 ist, enthält; wobei das Gewichtsverhältnis von der quaternären Ammoniumverbindung zu dem Alkylenoxidaddukt 3:2 - 11:1 ist.
  8. Flotationsmittel wie in Anspruch 7 beansprucht, dadurch gekennzeichnet, daß zwei der Gruppen R1, R2, R3 und R4 Kohlenwasserstoffgruppen mit 8 bis 22 Kohlenstoffatomen, bevorzugt 10 bis 16 Kohlenstoffatomen, sind, während die beiden restlichen Gruppen Alkylgruppen mit 1 bis 3 Kohlenstoffatomen oder Hydroxyalkylgruppen mit 2 bis 3 Kohlenstoffatomen sind.
  9. Flotationsmittel wie in Anspruch 7 oder 8 beansprucht, dadurch gekennzeichnet, daß R5 eine Alkylgruppe mit 10 bis 20 Kohlenstoffatomen ist und die Summe von n1, n2 und n3 12 bis 30 ist.
  10. Flotationsmittel wie in irgendeinem der Ansprüche 7 bis 9 beansprucht, dadurch gekennzeichnet, daß in dem Alkylenoxidaddukt 70 bis 100% aller Alkylenoxygruppen Ethylenoxygruppen sind und 0 bis 30% Propylenoxygruppen sind.
Anspruch[en]
  1. A method of cleaning calcium carbonate ore containing silicate impurities, in which a froth-flotation process is performed in the presence of a cationic collector, characterised in that the collector is a combination of a quaternary ammonium compound having the formula
    wherein one or two of the groups R1, R2, R3 and R4 are a hydrocarbon group having 8-36 carbon atoms and the remaining groups a hydrocarbon group having 1-7 carbon atoms or a hydroxyalkyl group having 2-7 carbon atoms and A is an anionic counterion, and an alkylene oxide adduct having the formula
    wherein R5 is a hydrocarbon group having 8-22 carbon atoms, A1, A2 and A3 are an alkylene oxide group having 2-4 carbon atoms, R6 is an alkylene group having 2-3 carbon atoms, n1, n2 and n3 are 3-20 and the sum of all n1, n2 and n3 is 10-40, and s is 0-3, the weight ratio of the quaternary ammonium compound to the alkylene oxide adduct being 3:2-11:1, and that calcium carbonate is recovered from the remainder, while contaminating silicates are removed with the float.
  2. A method as claimed in claim 1, characterised in that two of the groups R1, R2, R3 and R4 are hydrocarbon groups having 8-22 carbon atoms, preferably 10-16 carbon atoms, while the two remaining groups are alkyl groups having 1-3 carbon atoms or hydroxyalkyl groups having 2-3 carbon atoms.
  3. A method as claimed in claim 2, characterised in that the quaternary ammonium compound is a dimethyl dicocoalkyl ammonium salt.
  4. A method as claimed in any one of claims 1-3, characterised in that R5 is an alkyl group having 10-20 carbon atoms and that the sum of n1, n2 and n3 is 12-30.
  5. A method as claimed in any one of claims 1-4, characterised in that 70-100% of all alkyleneoxy groups in the alkylene oxide adduct are ethyleneoxy groups and 0-30% propyleneoxy groups.
  6. A method as claimed in claims 1-5, characterised in that s is 0 or 1.
  7. A flotation reagent, characterised in that it contains a quaternary ammonium compound having the formula
    wherein one or two of the groups R1, R2, R3 and R4 are a hydrocarbon group having 8-36 carbon atoms and the remaining groups a hydrocarbon group having 1-7 carbon atoms or a hydroxyalkyl group having 2-7 carbon atoms and A is an anionic counterion, in combination with an alkylene oxid adduct having the formula
    wherein R5 is a hydrocarbon group having 8-22 carbon atoms, A1, A2 and A3 are an alkylene oxide group having 2-4 carbon atoms, R6 is an alkylene group having 2-3 carbon atoms, n1, n2 and n3 are 3-20, the sum of all n1, n2 and n3 being 10-40, and s being 0-3, the weight ratio of the quaternary ammonium compound to the alkylene oxide adduct being 3:2-11:1,
  8. A flotation reagent as claimed in claim 7, characterised in that two of the groups R1, R2, R3 and R4 are hydrocarbon groups having 8-22 carbon atoms, preferably 10-16 carbon atoms, while the two remaining groups are alkyl groups having 1-3 carbon atoms or hydroxyalkyl groups having 2-3 carbon atoms.
  9. A flotation reagent as claimed in claim 7 or 8, characterised in that R5 is an alkyl group having 10-20 carbon atoms and that sum of n1, n2 and n3 is 12-30.
  10. A flotation reagent as claimed in any one of claims 7-9, characterised in that 70-100% of all alkyleneoxy groups in the alkylene oxide adduct are ethyleneoxy groups and 0-30% propyleneoxy groups.
Anspruch[fr]
  1. Procédé de nettoyage de minerai de carbonate de calcium contenant des impuretés de type silicate, dans lequel une flottation par écumage est effectuée en présence d'un collecteur cationique, caractérisé en ce que le collecteur est une combinaison d'un composé ammonium quaternaire de formule
    dans laquelle un ou deux des groupes R1, R2, R3 et R4 représentent un groupe hydrocarboné ayant 8-36 atomes de carbone et les groupes restant représentent un groupe hydrocarboné ayant 1-7 atomes de carbone ou un groupe hydroxyalkyle ayant 2-7 atomes de carbone et A est un contre-ion anionique, et d'un produit d'addition d'oxyde d'alkylène de formule
    dans laquelle R5 est un groupe hydrocarboné ayant 8-22 atomes de carbone, A1, A2 et A3 représentent un groupe oxyde d'alkylène ayant 2-4 atomes de carbone, R6 est un groupe alkylène ayant 2-3 atomes de carbone, n1, n2 et n3 sont égaux à 3-20 et la somme de n1 + n2+ n3 vaut 10-40, et s est égal à 0-3, le rapport pondéral du composé ainmonium quaternaire au produit d'addition d'oxyde d'alkylène étant de 3:2-11:1, et en ce que le carbonate de calcium est récupéré du reste, tandis que les silicates contaminants sont éliminés avec le flottant.
  2. Procédé selon la revendication 1, caractérisé en ce que deux des groupes R1, R2, R3 et R4 sont des groupes hydrocarbonés ayant 8-22 atomes de carbone, de préférence 10-16 atomes de carbone, tandis que les deux groupes restant sont des groupes alkyle ayant 1-3 atomes de carbone ou des groupes hydroxyalkyle ayant 2-3 atomes de carbone.
  3. Procédé selon la revendication 2, caractérisé en ce que le composé ammonium quaternaire est un sel de diméthyl-di(alkyle de coprah)ammonium.
  4. Procédé selon l'une quelconque des revendications 1-3, caractérisé en ce que R5 est un groupe alkyle ayant 10-20 atomes de carbone et en ce que la somme de n1+n2+n3 vaut 12-30.
  5. Procédé selon l'une quelconque des revendications 1-4, caractérisé en ce que 70-100% de tous les groupes alkylènoxy dans le produit d'addition d'oxyde d'alkylène sont des groupes éthylèneoxy et 0-30% sont des groupes propylèneoxy.
  6. Procédé selon les revendications 1-5, caractérisé en ce que s vaut 0 ou 1.
  7. Réactif de flottation, caractérisé en ce qu'il contient un composé ammonium quaternaire de formule
    dans laquelle un ou deux des groupes R1, R2, R3 et R4 représentent un groupe hydrocarboné ayant 8-36 atomes de carbone et les groupes restant représentent un groupe hydrocarboné ayant 1-7 atomes de carbone ou un groupe hydroxyalkyle ayant 2-7 atomes de carbone et A est un contre-ion anionique, en combinaison avec un produit d'addition d'oxyde d'alkylène de formule
    dans laquelle R5 est un groupe hydrocarboné ayant 8-22 atomes de carbone, A1, A2 et A3 représentent un groupe oxyde d'alkylène ayant 2-4 atomes de carbone, R6 est un groupe alkylène ayant 2-3 atomes de carbone, n1, n2 et n3 sont égaux à 3-20, la somme de n1 + n2 + n3 vaut 10-40, et s est égal à 0-3, le rapport pondéral du composé ammonium quaternaire au produit d'addition d'oxyde d'alkylène étant de 3:2-11:1.
  8. Réactif de flottation selon la revendication 7, caractérisé en ce que deux des groupes R1, R2, R3 et R4 sont des groupes hydrocarbonés ayant 8-22 atomes de carbone, de préférence 10-16 atomes de carbone, tandis que les deux groupes restant sont des groupes alkyle ayant 1-3 atomes de carbone ou des groupes hydroxyalkyle ayant 2-3 atomes de carbone.
  9. Réactif de flottation selon la revendication 7 ou 8, caractérisé en ce que R5 est un groupe alkyle ayant 10-20 atomes de carbone et la somme de n1 + n2 + n3 vaut 12-30.
  10. Réactif de flottation selon l'une quelconque des revendications 7-9, caractérisé en ce que 70-100% des groupes alkylèneoxy dans le produit d'addition d'oxyde d'alkylène sont des groupes éthylèneoxy et 0-30% sont des groupes propylèneoxy.






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