Patent Grant
9027757
The present invention relates to the use of compositions of alkylammonium salts and amine alkoxylate esters in the refining by flotation of minerals and ores containing silicate.
In reverse flotation, impurities are floated out of the mineral of value. In particular, iron ore, calcium carbonate, phosphate and feldspar are frequently refined in this manner. In many cases, minerals containing silicates are the main component of these impurities, which cause reductions in quality of the end product. In addition to quartz, mica and feldspar, these also include muscovite and biotite. For example, a high silicate content reduces the quality of iron ore concentrate and so this concentrate is purified by flotation, for example in Brazil, by using alkyl ether amines and alkyl ether diamines, in order to be able to produce high-value steels from the low-silicate concentrate.
Calcium carbonate is purified from silicate-containing and coloring minerals using quaternary ammonium salts based on fatty acids or fatty alkyl imidazoline compounds. Since calcium carbonate, in addition to kaolin, rutile and talc is used as a white pigment in papermaking and plastics production, a degree of whiteness as high as possible or a low concentration of coloring minerals is desirable. Owing to the hardness of silicate, in papermaking, this would also lead to increased wear on the calenders of the papermaking machines. Therefore, calcium carbonate, in addition to dry refining, is purified by the flotation process.
In general, attempts are made by means of reverse flotation to reduce the silicate content, which in the case of calcium carbonate is frequently characterized as acid-insoluble component, below 1.0% by weight. The silicate content in the feed can vary and can sometimes be 10 to 20% by weight.
As silicate collectors, for example fatty amines, alkyl ether amines, alkyl ether diamines or quaternary ammonium salt compounds are used. These are also known under the trade name Flotigam®.
In WO-A-00/62937, the use of quaternary ammonium salts for the flotation of iron ore is disclosed.
EP-A-0 876 222 describes the use of biodegradable esterquats as collector for the flotation of non-sulfidic ores.
U.S. Pat. No. 4,995,965 discloses the use of hydroxypropylated quaternary ammonium salts, unsymmetrically substituted dimethyldialkylammonium salts and dialkylhexahydropyrimidine compounds as collectors in the reverse flotation of calcium carbonate.
CA-A-1 187 212 discloses quaternary ammonium salts and bisimidazolines as collectors in silicate flotation.
U.S. Pat. No. 5,720,873 discloses a collector for silicate flotation, which collector, in addition to a quaternary ammonium compound, comprises an amine alkoxylate.
The collectors for silicate flotation that are described in the prior art, however, exhibit inadequate results with respect to selectivity and yield. The object of the present invention was therefore to provide an improved collector for silicate flotation, which improved collector can be used, in particular in reverse flotation, but also in direct flotation.
Surprisingly, it has been found that a collector combination of an alkylammonium salt and an amine alkoxylate ester delivers less calcite fine grain than the previously described collectors and collector combinations and the yield of valuable material is thereby significantly improved without the content of silicates in the concentrate thereby being increased.
The invention relates to the use of a composition of
A) at least one quaternary ammonium compound which contains at least one organic radical having 8 to 36 carbon atoms that is bound to the ammonium nitrogen atom and possibly contains heteroatoms, and
B) at least one amine alkoxylate ester of the formula (1) or a salt thereof
where
The invention further relates to a process for the flotation of silicate-containing mineral, by bringing a composition of A) and B) into contact with the silicate-containing mineral.
The invention further relates to a composition containing 1 to 99% by weight of the component A) and 1 to 99% by weight of the component B).
The composition of A) and B) is hereinafter also termed the collector according to the invention.
Preferably, the quaternary ammonium compound which makes up the component A) is a tetraalkylammonium salt of the formula (2)
where
R6, R7 independently of one another are C1 to C6 alkyl groups or benzyl groups,
R8, R9 independently of one another are C8 to C36 alkyl groups or C8 to C36 alkenyl groups
and
X is an anion.
Esterquats corresponding to the formula (3) are further preferred embodiments of the quaternary ammonium compound according to component A),
where
R10, R11, R12 independently of one another are H or C8 to C24 acyl groups,
R5 is a C1 to C6 alkyl group or a benzyl group,
k, l, m are integers from 0 to 5, and
X is an anion, preferably C1 or CH3SC4.
R1, R8 and R9, independently of one another, are a linear or branched alkyl or alkenyl group. Preferably, the radicals comprise 8 to 18 carbon atoms. Particular preference is given to 2-ethylhexyl, isononyl, isodecyl and isotridecyl and also dodecyl radicals.
R2, R3, R4, R10, R11 and R12 are acyl radicals having 8 to 24 carbon atoms. The acyl radicals preferably comprise 10 to 18 carbon atoms. They can be linear or branched. The acyl radicals can be saturated or unsaturated. Preferred acyl radicals are stearoyl and oleoyl radicals.
Component A) of the collector according to the invention contains at least one organic radical having 8 to 36 carbon atoms that is bound to the ammonium nitrogen atom and possibly contains heteroatoms. The radical can preferably be an alkyl, alkenyl or acyl radical which is further preferably such as is disclosed for R1 or R2.
A in particular is either an ethylene (—C2H4—), a propylene (—C3H6—) or a butylene group (—C4H8—). Preferably, A is an ethylene group.
B is in particular either an ethylene (—C2H4—), a propylene (—C3H6—) or a butylene group (—C4H8—). Preferably, B is an isopropylene group.
k, l and m are preferably independently of one another 2, 3 or 4, in particular 3.
The sum of x, y and z preferably gives an integer from 15 to 30, in particular 20 to 25.
In a preferred embodiment, the aminoethoxylate ester which makes up the component B) is in the form of monoammonium or diammonium salts thereof which are obtained by neutralization not only with organic but also mineral acids.
The components A) and B) of the collector according to the invention can be used together with other collectors of the prior art which are different from A) and B). Examples of such further collectors which are different from A) and B) are
R14—O—R13—NH2 (II)
where R14 is a hydrocarbon group having 1 to 40, preferably 8 to 32, carbon atoms and R13 is an aliphatic hydrocarbon group having 2 to 4 carbon atoms;
R17—O—R15—NH—R16—NH2 (III)
where R17 is a hydrocarbon group having 1 to 40, preferably 8 to 32, carbon atoms, R15 and R16 are one or several aliphatic hydrocarbon groups having 2 to 4 carbon atoms;
(R21R18NR19R20)+Y− (IV)
where R21, R18, R19 and R20 are one or several hydrocarbon groups having 1 to 22 carbon atoms and Y− is a suitable anion;
R22—NH2 (V)
where R22 is a hydrocarbon group having 1 to 40, preferably 8 to 32, carbon atoms;
R23—N—[D-NH2]2 (VI)
where R23 is a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms and D is a C2 to C4 alkylene group.
The use of the collector according to the invention can also proceed in combination with frothers and depressants, such as are known from the prior art. In order to avoid, in the silicate flotation from iron ore, this iron ore being co-discharged, preferably hydrophilic polysaccharides such as, for example, modified starch, carboxymethylcellulose, or gum Arabic, are added as depressants in doses of 10 to 1000 g/metric ton.
The silicate flotation is preferably carried out at a pH of 6 to 12, in particular 8 to 11, which is set, for example, using sodium hydroxide.
The use according to the invention can proceed either in direct or else reverse silicate flotation. The use according to the invention is also suitable for freeing silicate sand from impurities by separating the silicate sand from the impurities by flotation using the compound of the composition of A) and B).
The preferred amount of the collector according to the invention added is 100 to 1500 g/metric ton of ore, in particular 500 to 600 g/metric ton of ore.
The preferred weight ratio for the composition according to the invention and use according to the invention is A:B=99:1 to 1:99, in particular 20:80 to 80:20.
The laboratory flotation experiments were carried out using a Denver flotation machine type D 12 in a 2.5 l glass cell, wherein the pulp level was kept at a constant height by constant addition of drinking water. The pulp contained 130 g of solids per liter.
Ground calcite, 100%<250 μm, which contained approximately 12% by weight of silicate minerals such as quartz, mica, and also graphite, was transferred to a 2.5 l glass cell. The flotation pulp was then adjusted with drinking water to a content of 130 g of solids per liter of pulp. The flotation pulp was conditioned and the subsequent flotation performed using a DENVER flotation machine, type D-12.
For flotation of the graphite, the flotation pulp was first conditioned using 20 g/t of a pine oil. The pine oil was added to the pulp undiluted and conditioned for 1 min.
The graphite was floated out in the froth phase (graphite flotation tailings). The flotation period was ended after 3 min.
The chamber product was then subjected to a silicate flotation, wherein the silicates were floated out in the froth phase (silicate flotation tailings). The purified calcite (concentration) remained in the flotation cell. The silicate collectors were added undiluted to the flotation pulp and conditioned for 1 min. The subsequent silicate flotation was ended after 4 min.
The flotation fractions (graphite flotation tailings, silicate flotation tailings and concentrate) were dewatered, dried, weighed and dissolved for determining the acid-insoluble proportion in 25% strength HCl solution. The acid-insoluble component (AIR) of the concentrate is a quality feature. The AIR content is calculated: % AIR=dried residue from the HCl solution/initial weight into the HCl solution×100%.
A further quality feature of the flotation concentrate is the degree of whiteness thereof, which was measured using a photometer against barite.
The collectors used and the flotation results achieved therewith are shown in the tables hereinafter.
The standard collectors used were dicocoalkyl dimethylammonium chloride (standard collector 1), dioleoyloxyethylhydroxyethylmethylammonium methosulfate (standard collector 2) and tallow fat propylenediamine containing 40 mol of EO (standard collector 3).
As an example of the collector according to the invention (collector 4), a mixture of dicocoalkyldimethylammonium chloride (standard collector 1, component A)) and ethoxylated cocoalkylpropylenediamine, esterified with oleic acid (A=ethylene, R1=coconut fatty alkyl, R2,R3,R4=oleic acid, x,y,z total 50, component B)) was used in various weight ratios according to table 3.
The results show that the standard collector gives a much lower calcite recovery compared with the collector according to the invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2008 056 338 | Nov 2008 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2009/007147 | 10/6/2009 | WO | 00 | 4/27/2011 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2010/051895 | 5/14/2010 | WO | A |
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| 6211139 | Keys et al. | Apr 2001 | B1 |
| Number | Date | Country |
|---|---|---|
| 1187212 | Apr 1982 | CA |
| 293955 | Dec 1988 | EP |
| 643038 | Mar 1995 | EP |
| 739976 | Apr 1996 | EP |
| 1949964 | Jul 2008 | EP |
| WO 8909204 | Oct 1989 | WO |
| WO 9218685 | Oct 1992 | WO |
| WO 9726995 | Jul 1997 | WO |
| WO 0062937 | Oct 2000 | WO |
| WO 0177434 | Oct 2001 | WO |
| Entry |
|---|
| International Search Report for PCT/EP2009/0007147, dated Feb. 12, 2010. |
| Translation of the International Preliminary Report on Patentability for PCT/EP2009/007147, dated May 19, 2011. |
| Papini, R.M. et al, “Cationic flotation of iron ores: amine characterization and performance”, Minerals and Metallurgical Processing, Co, vol. 18, No. 1, Jan. 1, 2001, pp. 5-9. |
| English abstract for CA 1187212, Apr. 23, 1982. |
| Number | Date | Country | |
|---|---|---|---|
| 20110203975 A1 | Aug 2011 | US |
