Patent Grant
7104404
The present invention relates to the use of alkylamidothiophosphoric acid dialkyl esters in the dressing of sulfide ores by flotation, and to a process for preparation thereof.
In the production of sulfide ores and copper/molybdenum ores by flotation, use is made commercially of various collector types, such as dithiophosphates, xanthates, xanthogen formates and thionocarbamates (Schubert: Aufbereitung fester mineralischer Rohstoffe [Dressing of solid mineral raw materials], volume II, 1977, pp. 296 ff.) and mixtures thereof in combination with frothers. The flotation process separates the copper and molybdenum sulfides from gangue minerals.
Collectors cause wetting of the surface of the mineral of value which leads to the particles being rendered hydrophobic. By injecting air into the aqueous flotation pulp, air bubbles are produced, to which the ore particles which have been rendered hydrophobic have a high affinity and are discharged by the air bubbles to the surface of the flotation pulp, while gangue minerals remain in the pulp. Commercially conventional frothers include, for example, alcohols, propylene glycols and also their ethers and MIBC (methyl isobutyl carbinol).
U.S. Pat. No. 4,699,711 discloses a process for the flotation of sulfide minerals using preferably short-chain alkyl-substituted thionocarbamates.
WO 02/38277 discloses the use of mixtures of thionocarbamates and mercaptobenzothiazoles as collectors for the flotation of sulfide ores, in particular copper ore which is associated with molybdenum and gold.
Klee, F. C., Kirch, E. R., J. Pharm. Sci., 51, 1962, 423–427 discloses a process for preparing alkylamidothiophosphoric acid dialkyl esters by reacting PCl2SN(C2H4) with NaOiBu in absolute diethyl ether with the addition of sodium or potassium metal.
It was an object of the present invention to find an improved collector type for sulfidic copper and copper/molybdenum ores which has better flotation results than collectors of the prior art.
It has been found that alkylamidothiophosphoric acid dialkyl esters, in particular ethylamidothiophosphoric acid diisobutyl ester, give a markedly higher recovery for the same copper/molybdenum content. The object of the present invention was in addition to find an improved process for preparing alkylamidothiophosphoric acid dialkyl esters. It should start in particular from more readily accessible starting materials and succeed without absolute solvent and without alkali metals.
The invention thus relates to a composition for the flotation of sulfide ores comprising at least one compound of the formula
where
The invention further relates to a process for preparing compounds of the formula
where
The invention further relates to the use of the inventive flotation reagent for the flotation of sulfide ores. The sulfide ores are preferably copper ores.
The invention further relates to a process for the flotation of sulfide ores by bringing the inventive flotation reagent into contact with the sulfide ores.
With the inventive flotation reagent, improved results for selectivity and yield can be achieved compared with standard collectors in the flotation of nonferrous metal sulfides.
Preferably, R1, R2, R3 and R4 independently of one another are alkyl or alkenyl groups having 1 to 10 carbon atoms. For example, R1, R2 and R3 independently of one another are C2–C4-alkyl groups. Particularly preferably, R1 and R2 are a butyl group, in particular an isobutyl group. R3 is in particular an ethyl group. R4 is in particular hydrogen.
Me is preferably an alkali metal, alkaline earth metal, ammonium ion or hydrogen ion, in particular Na or K.
As oxidizing agent, use can be made of any able to oxidize dithiophosphate, for example a chlorite, for instance sodium chlorite, hypochlorite or chlorate.
As acid, use can be made of any compound which releases hydrogen ions in aqueous solution. Preferably, this relates to mineral acids, for example sulfuric acid, nitric acid, phosphoric acid or hydrochloric acid. If appropriate, the acid can be an oxidizing acid which simultaneously acts as oxidizing agent.
Preferred dithiophosphates are diisobutyl dithiophosphate, diethyl dithiophosphate, diisopropyl dithiophosphate, di-sec-butyl dithiophosphate and diamyl dithiophosphate.
Flotation can be applied to all metal sulfides (apart from Fe), with Cu, Mo, Pb, Zn, and Ni being particularly preferred. Particularly good results are to be observed in the dressing of Cu and Mo. The inventive flotation reagent can be used in a broad pH range (2 to 12) and is added to the aqueous pulp at a concentration between, preferably, 0.001 and 1.0 kg/tonne of crude ore.
The inventive flotation reagent achieves significant improvement of recovery and selectivity compared with the xanthogen formates and thionocarbamates of the prior art. Examples 1, 3 and 5 clearly show that the recovery of copper and molybdenum is higher than with the corresponding standard reagent. Example 3 is to be emphasized, in which, with 77.3% copper recovery and 69.5% molybdenum recovery, values significantly higher by 4.8 and 7.1% are achieved than with the corresponding amount of ethyl isopropyl thionocarbamate {example 4(V)}, where the copper or molybdenum content remains at the same level.
A) Preparation of ethylamidothiophosphoric acid diisobutyl ester:
Stage 1 (Oxidation):
4(RO)2PS2Na+NaClO2+2H2SO4→2(RO)2PSS—SSP(OR)2+NaCl+H2O+2Na2SO4
R=C4H9-isobutyl
Stage 2 Amidation:
(RO)2PS—S—S—SP(OR)2+2H2NCH2CH3→2(RO)2PSNHR(aq)+H2S2(liq aq) 2a)
H2S2+H2NR→(RNH3)HS2(liq aq) 2b)
To prepare ethylamidothiophosphoric acid diisobutyl ester, 1670 g (3.17 mol) of a 50% strength solution of sodium diisobutyldithiophosphate were homogenized with 725 g of a 22% strength sodium chlorite solution (1.76 mol) for 5 min. 346 g of a 50% strength sulfuric acid were added slowly over 2–3 h with constant stirring, the temperature of the reaction mixture being kept between 40 and 50° C. The mixture was stirred for a further 30 min and the reaction mixture was then cooled to 30–40° C. After separation of the phases, the organic phase (approximately 778 g) was decanted and reacted with 250 g of a 70% strength ethylamine solution which had been added slowly over approximately 2–3 h. The temperature was kept at 40–60° C. by cooling (exothermic reaction). The reaction mixture was then heated under reflux at 70–80° C. for approximately 3 h.
The reaction mixture was cooled to 40–50° C. with stirring, and 441 g of diethylene glycol were added. After a further 30 min, the mixture was cooled to 20–25° C. The concentration of the reaction product was set at the desired active ingredient content using 95 g of water.
After filtration 1551 g of a transparent reddish-oily solution of the product were obtained.
B) Action as Collector
The following collector/frother combinations were used:
Oxo residues here have roughly the following composition:
| Number | Date | Country | Kind |
|---|---|---|---|
| 102 35 574 | Aug 2002 | DE | national |
| 102 52 451 | Nov 2002 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP03/07966 | 7/22/2003 | WO | 00 | 2/3/2005 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2004/014562 | 2/19/2004 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 1783206 | Wigton | Dec 1930 | A |
| 1783207 | Wigton | Dec 1930 | A |
| 1902839 | Cunningham | Mar 1933 | A |
| 1974885 | Wigton | Sep 1934 | A |
| 2134706 | Derby et al. | Nov 1938 | A |
| 2621789 | Booth et al. | Dec 1952 | A |
| 4699711 | Bergmann | Oct 1987 | A |
| 4699712 | Unger | Oct 1987 | A |
| 4822483 | Klimpel | Apr 1989 | A |
| 20040099836 | Hesse | May 2004 | A1 |
| Number | Date | Country |
|---|---|---|
| 36 29 269 | Mar 1988 | DE |
| 4040475 | Jul 1991 | DE |
| 2 267 851 | Dec 1993 | GB |
| WO 0238277 | Mar 2002 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20050263442 A1 | Dec 2005 | US |
