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United States Patent (19) 11 Patent Number: 4,514,290 Swiatkowski Et Al

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United States Patent (19) 11 Patent Number: 4,514,290 Swiatkowski Et Al United States Patent (19) 11 Patent Number: 4,514,290 Swiatkowski et al. 45 Date of Patent: Apr. 30, 1985 54 FLOTATION COLLECTOR COMPOSITION 4,206,045 6/1980 Wang et al.......................... 209/166 AND ITS USE 4,358,368 1/1982 Helsten et al........................ 252/61 4,425,229 1/1984 Baronet al. .......................... 252/61 (75) Inventors: Piotr Swiatkowski, Huddinge; Thomas Wiklund, Nacka, both of FOREIGN PATENT DOCUMENTS Sweden 1 155072 10/1963 Fed. Rep. of Germany ...... 209/167 73) Assignee: KenoGard AB, Stockholm, Sweden Primary Examiner-Bernard Nozick 21 Appl. No.: 471,006 Attorney, Agent, or Firm-Fred Philpitt 22 Filed: Mar. 1, 1983 57 ABSTRACT 30 Foreign Application Priority Data A flotation collector composition comprises a combina tion of fatty acids, amidocarboxylic acids or amidosul Mar. 5, 1982 SE Sweden ................................ 8201363 fonic acids and partial esters of phosphoric acid and 51 Int. Cl. ............................................... BO3D 1/14 alkoxylated alcohols. The collector composition is used 52 U.S. C. ....................................... 209/166; 252/61 for upgrading nonsulfide minerals containing alkaline 58) Field of Search ................... 252/61; 209/166, 167 earth metals by froth flotation. Minerals such as apatite, calcite, scheelite, fluorspar, magnesite and baryte can be 56) References Cited separated from the gangues using the collector compo U.S. PATENT DOCUMENTS sition. 2,297,664 9/1942 Tartaron ............................. 209/167 4,139,481 2/1979 Wang et al. ........................... 252A61 13 Claims, No Drawings 4,514,290 1. 2 The amidocarboxylic acids and the amidosulfonic FLOTATION COLLECTOR COMPOSITION AND acids which are used in the present collector combina ITS USE tions can be characterized by the general formula The present invention relates to a flotation collector R-X-(CH2)n-A, wherein x is the group composition comprising fatty acids, amido carboxylic acids or amidosulfonic acids and certain phosphate es R ters. The invention also relates to the use of such con positions in froth flotation for enriching nonsulfide min erals containing alkaline earth metals, such as calcium, 10 barium and magnesium. Minerals containing alkaline earth metals, such as and A is the carboxylic acid group or the sulfonic acid apatite, scheelite, magnesite and baryte, are in the ores group. R is the organic hydrophobic group which suit usually associated with silicates, silica, different iron ably has 7 to 30 carbon atoms. R1 is hydrogen or an minerals, e.g. hematite and magnetite, etc. and they are 15 alkyl group having 1 to 4 carbon atoms and n is an generally separated from these gangues by flotation integer between 1 and 8. methods. The hydrophobic group in the amidoacids can be a It is very well-known to use fatty acids in the flota straight or branched, saturated or unsaturated aliphatic tion of different minerals and fatty acids are usually group. Non-interfering, inert substituents can be present used in all flotation of apatite. However, fatty acids as 20 in the group and hereby should be understood substitu the sole collector reagent often give unsatisfactory met ents which do not have any essential effect on the hy allurgical results, particularly when the minerals are drophobic character of the group or on the affinity of finely divided. When fatty acids are used it is often the compounds to the minerals which shall be flotated, necessary to have long periods of conditioning or alter the substituents can for example be ether or ester brid natively to charge the acids in the form of highly di 25 ges. The hydrophobic aliphatic group suitably contains luted solutions. It is also well-known to use amidocar 7 to 30 carbon atoms and preferably 11 to 22 carbon boxylic and amidosulfonic acids for flotation of differ atoms. As has been mentioned, R1 is hydrogen or an ent minerals. In most cases amidocarboxylic and amido alkyl group having 1 to 4 carbon atoms and n is an sulfonic acids give better metallurgical results than the integer between 1 and 8, suitably between 1 and 6. In fatty acids. The amido acids are, however, compara 30 the above given formula X is preferably the group tively expensive and they often give rise to an undesir ably high degree of foam formation and the foam has a high stability. Use of combinations of fatty acids and amidocarboxylic acids or amidosulfonic acids for flota tion of minerals such as wolframite and scheelite has 35 O been suggested in the German Auslegeschrift No. 1 155 072. Fatty acid soaps control the foam formation and wherein R1 has the above given meaning. A is prefera also lead to some improvement in the purity of the bly a carboxylic acid group. The preferred amido acids obtained products. can thus be termed condensation products of fatty acids According to the present invention it has been found and aminocarboxylic acids. that a composition of fatty acid, amidocarboxylic acid or amidosulfonic acid and certain phosphate esters is As for the fatty acids, the amidocarboxylic and ami particularly useful as collector reagent in froth flotation dosulfonic acids can of course be used in the form of and especially for upgrading nonsulfide minerals con salts instead of as free acids. Alkali metal salts or ammo taining alkaline earth metals. The phosphate esters are 45 nium salts of the acids can for example be used. Sodium esters of (ortho)phosphoric acid and alkoxylated alco salts are preferred. hols. The combinations of the invention give a consider As examples of some suitable amidocarboxylic acids able improvement of the metallurgical results, in the and amidosulfonic acids can be mentioned form of higher yields and/or more pure concentrates. dodecylamido propionic acid, dodecylamido acetic The combinations are very easy to handle and can for 50 acid, oktadecylamido propionic acid, octadecylamido example be added to the mineral pulp in the form of acetic acid, octadecenylamido propionic acid, oc undiluted product and this without requirements on tadecenyl-N-methyl-amido acetic acid, dodecylamido longer conditioning times. ethanesulfonic acid, octadecylamido propanesulfonic The present invention thus relates to a flotation col acid, octadecenyl-N-methyl-amido ethanesulfonic acid lector reagent which comprises (a) a fatty acid or a salt 55 etc. thereof, (b) an amidocarboxylic acid or an amidosul According to the present invention the above men fonic acid containing an organic hydrophobic group, or tioned previously known collector reagents are com a salt thereof, and (c) a partial ester of phosphoric acid bined with a further substance of quite a different chem and at least one alkoxylated alcohol. ical type, namely partial esters of phosphoric acid and The term fatty acid is used herein for monocarboxylic 60 alkoxylated alcohols. By partial ester should be under acids containing a straight or branched, saturated or stood that this component essentially is a partial ester of unsaturated hydrocarbon group having 14 to 22 carbon phosphoric acid, i.e. an ester wherein not more than atoms. As examples of suitable fatty acids can be men two of the original acid groups have been esterified. tioned lauric, palmitic, stearic and oleic acid. In a con However, many commercial products of this kind con ventional manner the fatty acids can be used in the form 65 tain small amounts of completely esterified phosphoric of salts instead of as free acids, alkali metal salts or acid, obtained as byproduct at the production, and such ammonium salts can for example be used. Sodium salts products can of course also be used. The phosphoric are preferred. acid ester here is thus essentially a mono- or diester, or 4,514,290 3 4. a mixture of mono- and diesters, of phosphoric acid and from the gangues by froth flotation under neutral or alkoxylated alcohols, preferably ethoxylated alcohols. alkaline conditions whereby the mineral containing The phosphoric acid mono- and diesters can be char alkaline earth metal is obtained as foam product. acterized by the general formulae According to the invention the combination of fatty acid, amido acid and phosphate ester is used for separa OR OR tion of minerals containing alkaline earth metals, prefer / / OeP-OH and O-P-OR ably minerals containing calcium, barium and/or mag N N nesium, from their gangues. As examples of representa OH OH tive minerals which can be upgraded can be mentioned 10 apatite, calcite, fluorspar, scheelite, magnesite and bar wherein R is the rest of the alkoxylated alcohol. The yte. These minerals occur naturally in ores with silica, alcohol rest contains 1 to 10, preferably 2 to 5, alkylene silicates and different iron minerals and can be separated oxide groups which can be ethylene oxide, propylene from these gangues with very good results. In other oxide or isopropylene oxide groups, or mixtures of aspects the flotation is carried out in a conventional these. The alkylene oxide groups are suitably ethylene 15 manner, i.e. a pulp of the raw minerals is prepared and, oxide groups. The original alcohol should be hydropho after optional conditioning, subjected to treatment with bic and contain at least 6 carbon atoms. It can be ali gas or air in the presence of the collector combination. phatic or be an alkylaryl alcohol, e.g. nonylphenol. The minerals containing alkaline earth metals will Aliphatic, cyclic or acyclic alcohols having 6 to 20, hereby be hydrophobed and obtained as froth product suitably 12 to 18, carbon atoms are preferred. The alco 20 hols can be straight or branched, saturated or unsatu while the gangues will be removed as tailings. The rated. R' can be an alcohol rest as above, i.e. have the flotation is carried out under neutral or alkaline condi same meaning as R, or be a rest of such an alcohol tions at a pH above 6.
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