AU627805B2 - Surface-active fatty acid ester and/or fatty acid derivatives as collectors in the flotation of non-sulphidic ores - Google Patents

Description

-7 OPI DATE 14/05/90 AOJP DATE 21/06/90 APPLN. I D 46313 89 PCT NUMBER PCI/EP89/01256

PCI

I NTERNATIG, 1..1.JU± i at_.iiI l.i I.V 2 INTERNATIONALE ZUSAMMENARBEIT AUF DEM GEBIET DES PATENTXESENS (PCT) (51) Internationale Patentklassilikation 5 (11) Internationale Ver6ffentlichungsnummer: WAO 90/04459 B03D 1/012 Al (43) Internationales Ver~ffentlichungsdatuin: 3. Mai I990 (01,05.90) (21) Internationales Aktenzeichen: PCT/EP89/0l256 Bestirnmungsstaaten: AT (europ~iische'. Patent). AU. BE (europtiisches Patent). BR. CH (europtiisches Patent).

(22) Interuationales Anmreldedaturn: 20. Oktober 1989 (20.10.89) DE (europ~iisches Patent). Fl. FR (europtiisches Patent).

GB (europiiisches Patent), IT (europ~iisches Patent). LU: (europttisches Patent), NL (europ~isches Patent). SE (eti- Prioritiitsdaten: roptiisches Patent), US.

P 38 36 891.9 29. Oktober 1988 (29.10.88) DE V'erbiffentlicht (71) Anmelder (fdr allk Bestirmmungsstaaten ausser US): H EN- Mit internatiolal'm Reclterchenherichi.

KEL KOM MAN DITGESELLSC HAFT AUF AKTIEN Vor Ablauf derflir 4nde~ningen derk.4npriche':gllS [DE IDE]; Henkelstrage 67, D-4000 Dusseldorf- Hoith au- pica Frist. Verliffenlichunig vwI-ird wiederholifiaIl; ,4nderu-111 sen geti eintreffn.

(72) Erfinder; und Erfinder/Anmelder (nurfiir LIS) BEH LER. Ansgar [DE' DE]; Siegfriedstrage 80. D-4250 Bottrop KG- STER. Rita [DE"DE]; Taubenstra~e 7, D-4000 Dtisseldorf VON RYBINSKI, Wolfgang [DE Leinenweberweg 12. D-4000 Dasseldorf (DE).

(54)Title: SURFACE-ACTIVE FATTY ACID ESTER AND/OR FATTY ACID DERIVATIVES AS COLLECTORS IN THE FLOTATION OF NON-SULPHIDIC ORES (54) Bezeiclinung: GRENZFLACHENAKTIVE FETTSAUREESTER- UND 'ODER FETTSAUREDERIVATE ALS SANINI- LER BEI DER FLOTATION VON NICHTSULFIDISCHEN ERZEN (57) Abstract Surface-active fatty acid ester and /or fatty acid derivatives obtained by reacting epoxidized fatt\ acid esters with I to 3 mol of sulphur trioxide per mol of epoxide oxygen at 20 to 100: C, reacting the reaction product with nucleophil ic reagents and, if necessary. saponifying the ester bond are used as collectors in the flotation of non-sulphidic ores, (57) Zusanimenfassung Grenzfltichenaktive Fettsiiureester- und/oder Fettstiurederivate, dadurch erh~ltlich, dali man epoxidierte Fettstiureester mit I bis 3 Mol Schwefeltrioxid pro Mol Epoxidsauerstoff bei 20 bis 100'C umsetzt. dlas Umsetzungsprodukt mit nucleophilen Reagenzien zur Reaktion bringt und gegebenenfalls die Esterbindung verseift. werden als Sammler bei der Flotation Non nichtsulfidischen Erzen verwendet.

:2 WO 90/04459 1 PCT/EP89/01256 Surface-active fatty acid ester derivatives and/or fatty acid derivatives as collecting agents in the flotation of non-sulfide ores.

The invention relates to the use of surfaceactive fatty acid ester derivatives and/or fatty acid derivatives which can be obtained by the reaction of epoxidized fatty acid esters with sulfur trioxide, subsequent reaction with nucleophilic reagents and, if desired, saponification of the ester bond, as collecting agents in the flotation of non-sulfide ores.

The separation of valuable minerals from the gangue by flotation is a generally applied sorting method for the processing of mineral ores. Examples of nonsulfide minerals within the meaning of the present invention are apatite, fluorite, scheelite, barytes, iron oxides and other metal oxides, for example the oxides of titanium and zirconium, as well as certain silicates and aluminosilicates. In flotation processing methods, the ore is usually first crushed and ground dry, or preferably wet, and suspended in water. Normally, collecting agents are then added, frequently in conjunction with frothing agents and, if necessary, further auxiliary reagents such as regulators, deactivators and/or activators, which assist the separation of the valuable minerals from the gangue minerals of the ore during the subsequent flotation. Before air is blown into the suspension (flotation), in order to generate froth at its surface, these reagents are usually allowed to act for a certain time on the finely ground ore (conditioning). The collecting agent ensures that the surface of the minerals is rendered hydrophobic, so that adhesion of these minerals to the gas bubbles formed during the aeration is effected. The mineral constituents are selectively rendered hydrophobic, such that the undesired constituents of the ore do not remain adhering to the gas bubbles. The mineral-containing froth is stripped off and REPLACEMENT PAGE

JAI

WO 90/04459 2 PCT/EP89/01256 processed further. The object of the flotation is to recover the valuable mineral of the ores in the highest possible recovery and, at the same time, tc obtain the highest possible beneficiation of the valuable mineral.

The use of anionic surfactants as collecting agents in the flotation of non-sulfide ores is per se state of the art. Examples of known anionic collecting agents are saturated and unsaturated fatty acids, alkylsulfates, alkylether-sulfates, alkylsulfosuccinates, alkylsulfosuccinamates, alkylbenzenesulfonates, alkylsulfonates, petroleumsulfonates, acyllactates, alkylphosphates and alkylether-phosphates.

In the processing of non-sulfide ores by flotation, a large number of separation problems must be overcome because of the wide fluctuation in the composition of the raw material which is to be separated, depending on the provenance of the latter. The minerals to be separated are frequently very finely intergrown and, in addition, also have a close chemical similarity. Consequently, for successful operation of such flotation processes, there is a large demand for reagents of selective activity, in particular for collecting agents of selective activity.

It has been found that surface-active fatty acid ester derivatives and/or fatty acid derivatives, such as can be obtained by the reaction of epoxidized esters of unsaturated fatty acids with sulfur trioxide and subsequent reaction with nucleophilic reagents and in the case of the fatty acid derivatives (di-salts) saponification of the ester bond, show advantages over known anionic standard flotation collecting agents with respect to selectivity when used as collecting agents for the flotation of non-sulfide ores.

The invention therefore relates to the use of surface-active fatty acid ester derivatives and/or fatty acid derivatives, which are obtainable by reacting epoxidized fatty acid esters with 1 to 3 moles of sulfur REPLACEMENT PAGE WO 90/04459 3 PCT/EP89/01256 trioxide per mole of epoxide oxygen at 20 to 100'C, reacting the reaction product with nucleophilic reagents and, if desired, saponifying the ester bond, as collecting agents in the flotation of non-sulfide ores.

The substances here suggested as collecting agents are known from DE-A-3,612,481. The epoxy-fatty acid esters employed as the starting material in the preparation thereof can in turn be obtained by epoxidation of esters of unsaturated fatty acids, for example according to the process described in J. Am. Chem. Soc.

67 (1945), pages 412-414, by reacting unsaturated fatty acid esters with peracetic acid. Suitable fatty acid esters are those obtained from unsaturated fatty acids having 14 to 22 carbon atoms and monohydric or polyhydric alcohols having 1 to 6 carbon atoms, for example methyl esters, ethyl esters, isopropyl esters, ethylene glycol esters, triglycerides, trimethylolpropane esters, pentaerythritol esters and sorbitan esters. The epoxy-fatty acid esters preferably used are epoxidized C 1

-C

4 -alkyl esters of the mono-unsaturated fatty acids having 16 to 22 carbon atoms or of such fatty acid mixtures which consist predominantly of mono-unsaturated fatty acids having 16 to 22 carbon atoms. However, the epoxidized esters of technical grade fatty acid fractions, which contain up to about 20% by weight of saturated fatty acids having 14 to 22 carbon atoms and/or up to about by weight of polyunsaturated fatty acids, for example linoleic acid, are also suitable. Epoxy-fatty acid esters having a content of from 3 to 5% by weight of epoxide oxygen, in particular epoxidized methyl oleate or epoxidized methyl esters of fatty acid fractions containing more than 50% by weight of oleic acid are preferred.

In the reaction of the epoxy-fatty acid esters with sulfur trioxide, a simultaneous sulfonation in the alpha-position relative to the carboxyl group takes place as a side reaction. The reaction proceeds in accordance with the following equation REPLACEMENT PAGE IzMVS

I

ii

I

-f i i WO 90/04459 4 PCT/EP89/01256

CH

3 (CH2)x CH CH (CH 2 )y CH 2 C OR 1 03- 0'

CH

3 (CH2)x CH CH (CH2)y CH 2

OR

1 0 0 S02 where R 1 in the case of the Cj- to C 4 -alkyl esters represents an alkyl group having 1 to 4 C atoms. The sum (x+y) is a number from 9 to 17. In the case of epoxidized methyl oleate, R 1 is -CH 3 and 13. Because of the alpha-sulfonation of the fatty acid esters, which takes place under the same reaction conditions, fractions of non-epoxidized, saturated fatty acid esters are converted into alpha-sulfofatty acid esters under the reaction conditions. Fractions of non-epoxidized unsaturated fatty acid esters are additionally sulfta-rnxbed at the double bond. The same applies to only partially epoxidized polyunsaturated fatty acid esters. The sulfonation at the double bond proceeds in the same way as the known sulfonation of olefins and leads to sulfoalkenecarboxylic acid esters with -SO 3 H groups in the alpha-position relative to the double bond, and to 2- and 3-hydroxyalkanesulfonates.

The reaction products of the first stage of the process according to the invention are distinguished by the fact that, in place of the epoxy groups, they now REPLACEMENT PAGE i M Ivfr

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WO 90/04459 5 PCT/EP89/01256 contain a glycol sulfate group. The latter is reactive and can, in the second stage, be reacted with numerous nucleophilic reagents to form new fatty acid ester derivatives. Examples of suitable nucleophilic reagents are hydroxides, alcoholates, phenolates or carboxylates, ammonia and primary, secondary and tertiary amines.

During the reaction with the nucleophilic reagents, the glycol sulfate ring is opened to form beta-substituted ethyl sulfate groupings in accordance with the following equation: CH CH R20(-) H CH I I I 0 0 OR 2 S03() S02 or CH CH NR 3

R

4

R

5 CH CH 0 0 ()NR 3

R

4

R

5 0S03 502 where, for example, R 2 can be a hydrogen atom, a C -C 4 alkyl group, phenyl group, benzyl group or CI-C 4 -acyl group, and R 3

R

4 and R 5 can each represent a hydrogen atom or a C 1

-C

4 -alkyl group.

The fatty acid ester derivatives accessible in this way possess surface-active properties due to the water-solubilizing sulfate ester groups -OSO,' and, if appropriate, sulfonate groups -S0 The further conversion of the reaction product with metal hydroxides, in particular alkali metal hydroxides, as the nucleophilic reagent with hydrolytic cleavage of the glycol sulfate group to give betahydroxyethanesulfate groups if preferred. This can easily be accomplished by contacting the reaction product (A) with an aqueous solution of 1 to 1.3 moles of alkali REPLACEMENT PAGE 1 M^ L1 1 -i Ii WO 90/04459 6 PCT/EP89/01256 metal hydroxide per mole of added sulfur trioxide and heating until the glycol sulfate groups have been cleaved to give groupings of the formulae j CH CH CH CH CH OH OS0 3 OS0 3 and Sodium hydroxide or potassium hydroxide is preferably used as the alkali metal hydroxide. When an about 50% by weight alkali metal hydroxide solution is used, the hydrolytic cleavage of the glycol sulfate groups is complete after at most 15 to 20 hours at 90C. The hydrolysis can be accelerated by a higher temperature and the application of pressure.

The content of anionic surfactant in the resulting aqueous surfactant solutions can be established by determining the content of sulfonate groups and sulfate groups by the so-called two-phase titration method (DGF Standard Method H-ill-10). The cleavage of the glycol sulfate groups is complete when the content of anionic surfactant no longer rises.

A distinction between sulfonate groups and sulfate groups can be made by two-phase titration after acid hydrolysis. The sulfate groups can be eliminated by acid hydrolysis, so that afterwards only the content of sulfonate groups is still detected.

The surface-active derivatives of free fatty acids (di-salts), also considered for the use within the meaning of the invention, are obtained from the fatty acid ester derivatives described above by saponification of the ester bond by means of at least stoichiometric REPLACEMENT PAGE A Ifle> a M v t--

I

I

B

ri I c u~ai WO 90/04459 7 PCT/EP89/01256 quantities of an alkali metal hydroxide, preferably sodium hydroxide. Here again, the reaction can be accelerated by-an elevated temperature and the application of pressure. In the cases where the reaction product is reacted with an alkali metal hydroxide as the nucleophilic reagent, the reaction product can be converted into the desired di-salt in one step, if it is reacted with a quantity of alkali metal hydroxide which is sufficient for both the hydrolytic cleavage of the glycol sulfate groups and for the hydrolysis of the ester bonds.

Mixtures of surface-active fatty acid ester derivatives and fatty acid derivatives can be prepared by suitable selection of the working-up conditions for the reaction product In a preferred embodiment of the invention, surface-active fatty acid ester derivatives and/or fatty acid derivatives are used which are obtainable by contacting the reaction product in aqueous solution, with 1 to 2 moles of alkali metal hydroxide per mole of added sulfur trioxide and heating until the glycol sulfate groups are cleaved and/or until the ester groups are hydrolysed.

The invention also relates to a process for the separation of non-sulfide minerals from an ore by flotation, in which ground ore is mixed with water to give a suspension, air is passed into the suspension in the presence of collecting agent and the resulting froth together with the mineral contained therein is separated off, which comprises using, as the collecting agent, fatty acid ester derivatives and/or fatty acid derivatives which are obtainable by reacting epoxidized fatty acid esters with 1 to 3 moles of sulfur trioxide per mole of epoxide oxygen at 20 to 100 0 C, reacting the reaction product with nucleophilic reagents and, if desired, saponifying the ester bond.

In order to achieve economically useful results in the flotation of non-sulfide ores, the collecting REPLACEMENT PAGE T 01 WO 90/04459 8 PCT/EP89/01256 agents must be employed in a certain minimum quantity.

However, a maximum quantity of collecting agent also must not be exceeded, since otherwise the froth formation becomes too extensive and the selectivity towards the valuable minerals decreases. The quantities in which the collecting agents to be used according to the invention are employed depend in each case on the nature of the ores which are to be floated and on their content of valuable minerals. Consequently, the necessary quantities to be employed can fluctuate within wide limits. In general, the collecting agents according to the invention are employed in quantities from 50 to 2,000 g, preferably 100 to 1,500 g, per metric ton of crude ore.

In practice, it can prove advantageous to employ the surface-active fatty acid ester derivatives and/or fatty acid derivatives, which are to be used according to the invention, together with known anionic, cationic, ampholytic or nonionic collecting agents in order to achieve special effects, in particular to increase the selectivity. Examples of anionic collectng agents suitable for combination with the substances to be used according to the invention are fatty acids, alkylsulfates, alkylether-sulfates, alkylsulfosuccinates, alkylsulfosuccinamates, alkylbenzenesulfonates, petroleumsulfonates, acyllactates, alkyl-phosphates, alkylether-phosphates and styrenephosphonic acid. Examples of suitable cationic collecting agents are primary allphatic amines, alkylenediamines substituted by alpha-branched alkyl radicals, hydroxyalkyl-substituted alkylenediamines and water-soluble acid addition salts of these amines.

Examples of suitable ampholytic collecting agents are sarcosides, taurides, N-substituted aminopropionic acids and N-(1,2-dicarboxyethyl)-N-alkylsulfosuccinamates.

Examples of known nonionic collecting agents are the products of addition of ethylene oxide to alkyl-phenols or fatty alcohols, the prod7cts of addition of ethylene oxide and propylene oxide atty alcohols, fatty REPLACE~ PAGE 1 1 1 WO 90/04459 9 PCT/E 89/01256 alcohol/ethylene oxide addition products, the end groups of which are capped with short-chain alkyl radicals, and alkyl glucosides.

The surface-active fatty acid ester derivatives and/or fatty acid derivatives, to be used according to the invention, are employed in the known flotation processes for non-sulfide ores in place of known collecting agents. Accordingly, in addition to the collecting agents described, the reagents usual in each case, such as frothing agents, regulators, activators, deactivators and the like, are here also added to the aqueous slurries of the ground ores. The flotation is carried out under the conditions of the processes of the state of the art.

In this connection, reference is made to the following literature references with regard to the technological background of ore dressing: H. Schubert, Aufbereitung fester mineralischer Stoffe [Processing of Solid Mineral Substances], Leipzig 1967; B. Wills, Mineral Processing Technology Plant Design, New York, 1978; D. B. Purchas (editor), Solid/Liquid Separation Equipment Scale-up, Croydon 1977; E. S. Perry, C. J. van Oss, E. Grushka (editors) Separation and Purification Methods, New York, 1973-1978.

A preferred field of application for the collecting agent mixtures to be used according to the invention is the processing of ores such as scheelite, Sbarytes or apatite.

Preparation Example A g (0.5 mole) of gaseous sulfur trioxide were passed via a dip tube into 148 g (0.5 mole) of an epcxidized technical grade methyl oleate (epoxide oxygen content 3.5% by weight) in an upright laboratory reactor in the course of 50 minutes. The reaction temperature was 140 g (0.37 mole) of the resulting crude sulfation product (degree of sulfation 65.9%) were neutralized i REPLACEMENT PAGE i~rv g* r-- WO 90/04459 10 PCT/EP89/01256 with 15 g (0.38 mole) of sodium hydroxide in 330 ml of water. For hydrolysis, the neutralized mixture was heated for 4 hours at 90°C. The pH shift occurring during this time was compensated by continuous addition of 3.1 g (0.08 mole) in total of sodium hydroxide. After the hydrolysis, the aqueous solution (product A) showed the following characteristic data: Anionic surfactant (DGF methods* H-III-10): 19.0% by weight Unsulfated (DGF methods* G-III-6 7.3% by weight Di-Na salt, relative to anionic surfactant: 41.6 mol% German Standard Methods for the examination of fats, fat products and related substances, issued by Deutsche Gesellschaft fUr Fettwissenschaft [German Fat Science Society], Stuttgart 1950-1981.

Preparation Example B g (0.5 mole) of gaseous sulfur trioxide were passed via a dip tube into 148 g (0.5 mole) of an epoxidized technical grade methyl oleate (epoxide oxygen content 3.5% by weight) in an upright laboratory reactor in the course of 50 minutes. The reaction temperature was 0

C.

29.8 g (0.75 mole) of sodium hydroxide in 660 ml of water were added to 140 g (0.37 mole) of the crude sulfation product obtained (degree of sulfation: 62.6%).

For hydrolysis, the alkaline mixture was heated for 4 hours *at 90°C. After this, the product B, as a clear solution in water, showed the following characteristic data: Anionic surfactant (DGF method H-III-100): Unsulfated (DGF method G-III-6 b): REPLACEMENT PAGE 15.9% by weight 7.1% by weight y ;.n1C% Pn~ y i i I-~ 7 WO 90/04459 11 PCT/EP89/01256 Di-Na salt, relative to anionic surfactant: 100 mol%.

Preparation Examples C to F Analogously to Preparation Examples A and B, sulfur trioxide was reacted with the epoxidized methyl oleate, described therein, in molar ratios from 0.8 to 1.2 at 60 to 80 0 C in the course of 50 minutes.

Products C to F were obtained in the form of their aqueous solutions by subsequent neutralization and hydrolysis with aqueous sodium hydroxide solution at 90 0

C.

The reaction conditions of the sulfation reaction, the degree of sulfation achieved in each case, the quantity of sulfated epoxide employed for working-up and, the total quantity of the sodium hydroxide used in Preparation Examples C to F are shown in the following Table I together with the analytical data of the corresponding products C to F. Table I also contains the corresponding data for the Preparation Examples A and B and the products A and B.

REPLACEMENT PAGE

C,

jMfvlS "o 4 J Table I Preparation Examples A to F Preparation Example/Product A B C D E F S03 Epoxide 1 :1 1 :1 1.2 :1 1.2 :1 0.8 :1 1:1 Sulfation temperature 0 C] 30 30 70 80 60 Degree of sulfation []65.9 62.6 70.7 39 61.7 72.5 Mole of sulfated epoxide 0.37 0.37 0.27 0.25 0.16 0.33 Mole of sodium hydroxide 0.46 0.75 0.38 0.5 0.22 0.68 Anionic surfactant by weight] 19 15.9 19 11 27 18.4 Unsulfated by weight] 7.3 7.1 6 13 12 5.2 Di-Na salt by weight] 41.6 100 80 about 100 85 64 1, 1 WO 90/04459 13 PCT/EP89/01256 Example 1 A scheelite ore from Austria which, in respect of its main_ constituents, had the following chemical composition: 0.33 by weight of W03 8.8 by weight of CaO 55.8 by weight of SiO 2 was used as flotation feed.

The particle size of the flotation feed was less than 200 Am.

As the collecting agents, the products C, D, E and F described in the preparation examples were used.

The products C and E were added to the flotation pulps in a quantity of 300 g/t, and the products D and F in a quantity of 200 g/t. As a comparative collecting agent sodium oleate (product X) was used in a quantity of 500 g/t. (All the data on the collecting agent concentration relate to active substance).

The flotation tests were carried out in a modified Hallimond tube (microflotation cell) according to B. Dobias, Colloid Polymer Science, 259 (1981) pages 775-776, with 2 g of ore in each case at 23 0 C and at the naturally established pH value. Distilled water was used for preparing the flotation pulp. The conditioning time was 15 minutes in each case. During the flotation, a stream of air was passed through the pulp at a flow velocity of 4 ml/minute. In all tests, the flotation took 2 minutes.

The results of the flotation tests with the substances to be used according to the invention are summarized in Table I (sic) and compared with the values obtained with sodium oleate as a comparative substance.

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i'" I o o-

_C

-I I WO 90/04459 14 PCT/EP89/01256 Table II Flotation of scheelite Collecting Quantity Recovery W0 3 content of agent Overall W0 3 the concentrate Product C 300 9.1 55 Product D 200 9.7 57 1.9 Product E 300 9.8 53 1.8 Product F 200 6.7 43 2.1 Product X 500 4.0 34 2.7 In comparison with sodium oleate, the substances to be used according to the invention give higher values of the W0 3 recovery, in a low quantity. In spite of the higher recovery, the WO 3 content in the flotation concentrate is not significantly lower. Since, for economical processing of ores, the highest possible recovery must be achieved in the first flotation stage with adequate selectivity at a low collecting agent quantity, the products to be used according to the invention have marked advantages.

Example 2 The flotation feed used was a barytes ore from Mexico which, in respect of the main constituents, had the following chemical composition: 69 by weight of BaSO 4 24 by weight of SiOz 3 by weight of AlO, The flotation feed had the following particle size distribution: 39 by weight 25 ym 45 by weight 25 100 ;,m REPLACEMENT PAGE t '1i m i- WO 90/04459 15 PCT/EP89/01256 16 by weight 100 jm Products A and B described in the examples were used as the collecting agents in quantities of 230 and 170 g/t respectively. As a comparative collecting agent, sodium dodecylbenzenesulfonate (product Y) was used in a quantity of 500 g/t.

The flotation tests were carried out in a laboratory flotation machine (type D 2 made by Denver Equipd ment, with a 1 1 flotation cell). Water having a Ca 2 ion content of 144 mg/1 was used for preparing the flotation pulps. The pulp density was 500 g/l. The deactivator used in all the tests was sodium water-glass in a quantity of 1000 g/t. The flotation was carried out at p'H 9.5. Like the collecting agent used in each case, the deactivator was conditioned for -5 minutes at 1100 rpm. The preconcentrate was repurified twice in the 1 1 cell without further addition of reagent. For the preconcentrate and in the purification stages, flotation was carried out each time for 6 minutes at 1000 rpm.

The results of the flotation tests with the substances to be used according to the invention are summarized in Table III and compared with the values obtained with sodium dodecylbenzenesulfonate as a comparative substance.

Table III Flotation of barvtes 4/ 7k? -altAA ItV

S.'

Collecting Quantity Concentrate agent BaSO 4 content BaSO 4 recovery Product A 230 95.0 93 Product B 170 96.1 94 Product Y 500 98.8 93 REPLACEMENT PAGE

I

WO 90/04459 16 PCT/EP89/01256 As compared with sodium dodecylbenzenesulfonate, a comparable result with respect to concentrate content and BaSO 4 recovery can be obtained with one third of the quantity when product B is used. Product A floats a corresponding concentrate at a quantity which is reduced to half as compared with product Y.

Example 3 1 The flotation feed used was an apatite ore from Sweden which, in respect of its main constituents, had the following chemical composition: 11 by weight of P 2 0 by weight of SiO 2 7 by weight of Fe 2 0 3 21 by weight of CaO distribution: 42.9 by weight 25 Am 48.7 by weight 25 200 Am 8.4 by weight 200 Am The products A and B described in the examples were used as the collecting agents in a quantity of 200 g/t. Sodium oleate (product X) in a quantity of 700 g/t was used as a comparative collecting agent.

The flotation tests were carried out in the type D 2 laboratory flotation machine mentioned in Example 2.

The preflotation took place in 2 litre cells, and the purification flotation in 1 litre cells. The pulp density was 36% by weight of solids in water of a total hardness of 27° German hardness. The deactivator used was in each case sodium water-glass in a quantity of 400 g/t. The flotation was carried out at a pH value of about 8, such as was established by the addition of water-glass. The deactivator and the collecting agent were each conditioned for 5 minutes at 1400 rpm. The flotation was carried out in each case for 6 minutes at 1200 rpm.

The results of the flotation tests with the REPLACEMENT

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t/^.MY 4 1 ic v WO 90/04459 17 PCT/EP89/01256 substances A and B to be used according to the invention are given in Table IV and compared with the values obtained with sodium oleate as a comparative substance.

Table IV Flotation of apatite Collecting Quantity Concentrate after 2 agent purifications

P

2 O, content P 2 zO recovery Product A 200 27.3 91 Product D 200 22.0 98 Product X 700 31.4 58 In comparison with sodium oleate, the substances to be used according to the invention lead to a substantially higher recovery of valuable mineral at a considerably reduced quantity. The very high P 2 zO recovery also explains the somewhat lower content of valuable mineral in the concentrate. Since the recovery of valuable mineral and the collecting agent quantity required therefore are the most important factors for economical processing of ores, the products to be used according to the invention have considerable advantages over sodium oleate, the conventional collecting agent for apatite.

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N,!TO7

Claims (10)

1. The use of surface-active fatty acid ester derivatives and/or fatty acid derivatives, obtainable by reacting epoxidized fatty acid esters with 1 to 3 moles of sulfur trioxide per mole of epoxide oxygen at 20 to 100 0 C, reacting the reaction product with nucleophilic reagents and, if desired, saponifying the ester bond, as collecting agents in the flotation of non-sulfide ores.

2. The use as claimed in claim i, wherein epoxidized C 1 4 -alkyl esters of mono-unsaturated fatty acids having 16 to 22 carbon atoms, or of fatty acid mixtures which predominantly consist of such acids, are employed as the epoxy-fatty acid esters.

3. The use as claimed in claim 2, wherein epoxidized technical grade methyl oleate is employed as the epoxy- fatty acid ester.

4. The use as claimed in at least one of claims 1 to 3, wherein hydroxides, alcoholates, phenolates or car- boxylates, ammonia and primary, secondary or tertiary amines are employed as the nucleophilic reagents. The use as claimed in claim 4, wherein hydroxides are used as the nucleophilic reagents.

6. The use as claimed in at least one of claims 1 to wherein the reaction product is contacted in aqueous solution with 1 to 2 moles of alkali metal hydroxide per mole of added sulfur trioxide and heated until the glycol sulfate groups are cleaved and/or until the ester groups are hydrolysed.

7. A process for the separation of non-sulfide minerals from an ore by flotation, in which ground ore is mixed with water to give a suspension, air is passed into the suspension in the presence of a collecting agent and the resulting froth together with the mineral contained therein is separated off, which comprises using, as the collecting agent, fatty acid ester derivatives and/or fatty acid derivatives which are obtainable by reacting epoxidized fatty acid esters with 1 to 3 moles of sulfur Ri REPLACEMENT PAGE WO 90/0445 9 19 PCT/EP89/01256 i trioxide per mole of epoxide oxygen at 20 to 100°C, reacting the reaction product with nucleophilic reagents and, if desired, saponifying the ester bond.

8. The process as claimed in claim 7, wherein the surface-active fatty acid ester derivatives and/or fatty acid derivatives are employed in quantities of from 50 to 2000 g per metric ton of crude ore.

9. The process as claimed in claim 8, wherein the surface-active fatty acid ester derivatives and/or fatty acid derivatives are employed in quantities of from 100 to 1500 g per metric ton of crude ore. The process as claimed in at least one of claims 7 and 8, wherein the surface-active fatty acid ester derivatives and/or fatty acid derivatives are employed together with known collecting agents.

11. The process as claimed in at least one of claims 7 to 10, wherein the ore consists of scheelite, barytes or apatite. REPLACEMENT PAGE ~2~6 I 2 in INTERNATIONAL SEARCH REPORT linemvartonal ARD11cation N $o PCT/EP89/01256 1. CLASSIFICATION OF SUBJECT MATTER meveral I ifgcatIon symols apply, Indlicate all) iAceoleing to Iteitafiaonal Patent Cialfiemualon (IIPCI or to both National Ciasaffication and IPC B03D 1/012 If. P1ELOS SEARCHED MInimum Documeton11110 Searched I C.12maficaiion bstle Classification SymIOciA B03D DOCUMentation fearched other than Minimum Documentaion IS th@ lZAen that Such Documents are includedj tn the Fields Searched III, DOCUMENTS CONSIDERED TO E1 RILEVANTs Category Citation ot Docurii. 1i with indication, where appornia, 0t tie# vasevant DBSBOgesI I Rtelevant to Claim No Is A DE, A, 3612481 (HENKEL) 15 October 1987 1-7 see claims 1-6 (cited in the application) A GB, A, 589800 HEILMANN) 1 JUly 1947 1,7 see page 5, lines 68-83 A DE, C, 670048 (ERZ- UND KOHLEFLOTATION) 1r January 1939 Cspecimi caiegories of cie uen ta'Spe he T" later doacument pubtished athar the International fiino Sate Document defining the general e116te Ot thel 8M1 which as not of Priority aoia anda 6oi in conflict with the aficailon cui consieoooia teatcid owa cited to unfdraland the Principle of theory Unoorlying tha to b fi earicuar rlevnceinvention *9 earlier OocWRMn but OW6llahoafon or alter the tinterimttonai document ot Particular ielevance: tile claimned invention filing Sate cannot be coaalera novel or ten,ot be consioarec to document which may throw doubts an ariori claim(*) or lInvoiva an inventive stop wnich ao ct to astaiuiah tna Dublication daute at another document Ot om11iC-lile felevanca: the Claimed Invantion citation or Other, *social qeaaan fee moecifiad) cannot am coneiaereo to Involve an inventive oleo whon the document relevryt~i to an orai disctlsure, use, exhibition ar ificuMunt a Caomainaed with one, or marie Diner such aCci- Othe? iMeana Montm. sucn combination bwein obvious to a Dorson atiiu ,P Document eubliehea prior to the rnter~ationsi filing data butl in the amt titer than in* priority flute ciaimed coCUMent Member 0t the Same, foetigt famtily IV. CERT IFICATION Data at the Actual Coempletion w, the itternhatiansi search Date of Maling fit tite international bearch Report 22 January 1990 (22.01,90) 21 February 1990 (21.02.90) Intierinli So rCning Autnority European Patent Office form PCT11SAi'210 isecono Shootl ldemeiy III$) Signature at Autnarlied Officer ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. PCT/EP 89/01256 SA 32368 Thk artrex lte patent family mernbers relating to thle patent document'; cited if) thle ahlove-rnlentioned international searchn report. The meinhers ire contained iii fihe Furopean Patent Office Ft)P File ott The IFiropeaim Patent Office iq in no nay liable for the.se particutlar,; %hiclt are merely given for the purpose of information, 09/02/90 Patent docunment Publication Patent famil Publication cited in ~ren report date membher(.s) date DE-A-3612481 1.5-10-87 EP-A- 0241839 21-10-87 ~JP-A- 62270554 24-11-87 GB-A- 589800 None DE-C-670048 None F or more detaik about tli,, anntex sc Official Journal of the Etiropean Platent Office, No. 1 2/8: li, [ER NATIONALER RECHERCIIENBERICH-T Internationalos Akicozeichen PCT/EP 89/01256 1. KLASSIFIKATnON DES ANNMIJ.UNGSGEGI.NS'rANIS (bol mebreren K1aSnifikationssrntholon sind 211C ancugobenl 1 Nach der Internationalen I'ateniklaslf i kat inn IC) odor riach der nationalon Kiassifikaion und der II'C Int.K1. 5 B03D1/012 11. Rtx(:IIERCIII'R'FE SACIIGEICI: Recherchicrter Mindeslprllfstoffl Klassifilizationnss~r Kiaoif ikationnss rn bole Int 5 B030 Rechorchiorle nicht 7um Mindestprllfstoff Rchorende X'ertfntlichrrnpon, sonocii diese unter die recherchierton Sachzohiclo fallcen Ill. FINSCIILAGIGF, VEROFFENTLICHIIN(EN9 A rIP Kenucich nung der \'orbffentlichung noroit erfordorlich unter An~ahe dor mallooblichon M e 1 Belt. Anspruch Nr A 0EA3612481 (HENKEL) 15 Oktober 1987 1-7 s jehe AnsprUche 1-6 (in der Anmeldung erw~hnt) AGB,A,589800 HEILMANN) 01 Juli 1947 1, 7 siehe Seite 5, Zeilen 68 -83 IA DE,C,670048 (ERZ- UND K0HLEFL0TATION) Januar 1939 oRonondere Katcgonien von an~cgehenon Verilffenflichunpcmnin Verijffentlichung. die den a1Il~meinen Stand der Technik T Sp11lre V or bffonllichung, die noch dom intornatinnalon An. dofiniort, 2hor nCIch als bonondors bedoutoni anzuohon it nomedaun odor dn Prinritbtdatun, %1,ffenlichl roordon tlieres Dokumoot, dan jodoch erst am oder nach dor Interna- 01t und mi? der AnnoldunR nicht kollidiori, nondorn our zurn tionalon Annieldedatun; verbffcnlliclit noordon ist Vernlbodnins dos der Frfindung zugrundoltegenden I'rinelpg odor dot 1hr 7ugrundelioefonden I hCooie 2ngevoben ist 'U Verijffenflichung, die eigner ist, omnen Prinritbtsanspruch 'X Vorhffcotlichung von hesonderer lledeutunr, die bosospruch- zonoifeihaft erscheinen Zn 1anoen. odor dutch die don VerdP-toEfnngknnih innodrafefneichrIi- fontlichungsdatUn) oino andoron in, Rochorchenhoricht Rc* t brund botrocht ls noe d orenefnershrTtg nannton Vertiffentlichung boloun '.ordon soil odor die aus oenr etbrhnbmcit"r 2 ndoc benonderen Grund angoehon in, (-Ail ausnouhril 'N Verilffontlichung von bosonderer Iledculun-, die beosprucn. .0 'bfetihndie sich aUf Oine rolndliche Offonbarung, to Frfindung kann nicht a1S aol erfiodorischor Tb~iglmoil be- O~ Vrhfentichngruhond I)Cirachtetoioredon, Aionn die N oroffoollichunR mit eino Ilenutcung. eine Ausorolluno odor ndoro N16alohnion elnor odor monreron andoron N orifentlichungon dioser Kate- bozcht gorie in Vorbindung Robracht twird nd dro';e Verhlndunp, flur Verbffentlichumo die vor demn internationslen Anmoldeds- eimen roebmaon nahelio~ood Siq turn, abet nach demn hoanopruchion I'rinrilsdatlim vertiffent- W~ V'rliffetlcung. die Nillillod doerolben Patentfamilic 101 IN'. BESCHLI'N;U NG Datsr des Abhhussen det infunaoalsln Recherche Ahoendednlnor dom mlnl tiolO en Rochcrchoohotichis

22.JANUAR 1990 2 1.02 f Intornationalo Rochorchenbohordo Ljnterschriftdshi,,l EUROVA ISCIJES PA'rF.NTAN-T T.KI. v~ tomthiall PC.l IISAI21O (111Wl 2)1 I1anuar 19001 L I ANI-ANG ZUM INTERNATIONALEN RECHERCHENBERICHT OBER DIE INTERNATIONALE PATENTANMELDtJNG NR. PCT/EP 89/01256 SA 32368 In dieserm Anhauig sind die Nlitglieder der Platentfaunillen der im ohengcruarintcn internationalc'n IRccherchieruericht arigefuihrteri I'alcntdocumoole angcgcbcn. DIe Angahon Obecr die Farnilienmitglicder cntsprechvi demn Stand der I)atei de,. 1Iuropaischen flitcntamntq an IDie~ze Angnhcen dicnen flUr 7ur (interrichtung tind erfolgen ohne ;Cvih~r. 09/02/90 Im IPechcrcherubericht Iturn der Nlitglied(cr) de'r Datum der angerfihrte,; Patentdnkumnt e ntlichung I'atentfamilic Vc'r~ientlichung DE-A-3612481 15-10-87 EP-A- 0241839 21-10-87 JP-A- 62270554 24-1 1-87 GBA-589800 Keine DE-C-670048 Keine Ffir nivr rin7eihciten 711 diemcn Anhatig qice Arntshlatt deq E-uropfiiqchen l'atentamt.,. Nr.12/82