Patent Grant
10722904
This application is a national stage filing under 35 U.S.C. § 371 of PCT/EP2017/066709, filed Jul. 5, 2017, which claims priority to European Patent Application No. 16178726.2 filed Jul. 8, 2016, the contents of which are each incorporated herein by reference in their entireties.
The present invention relates to a collector composition containing alkylethermonoamine and a process to treat ores, like magnetite ores, with such collector composition.
US 2012/0325725 discloses a flotation reagent for iron ores that contains a composition containing a diamine alkoxylate ester A and an amine B. The amine B may be an etheramine (II) or etherdiamine (III) and many examples of both the etheramines and diamines are mentioned. The use of only or mainly an ethermonoamine is discouraged as it is shown that using a C10ethermonoamine is less effective than using the same compound in combination with a diamine alkoxylate ester compound.
US2014/0021104 discloses a branched C10ethermonoamine for use in a process for enriching an iron mineral from a silicate containing iron ore. The C10ethermonoamine may be used in an admixture with a C13-C15ethermonoamine. This second component has a degree of branching of 0.3 to 0.7. The compounds are used in hematite ores flotation.
US2014/0144290 discloses mixed collector compositions containing an amidoamine and etheramine or etherdiamine. One example of the etheramine is isotridecyloxypropylamine. The mixtures are said to be useful for many separations such as for magnetite. In the Examples it is shown that using only an etheramine gives less favorable results than when mixing with the amidoamine in an undefined type of iron ore, using a branched C10 alkyl-enriched alkylethermonoamine as the etheramine.
WO 2008/077849 discloses amine formulations for reverse froth flotation of silicates from iron ores which are a mixture of an etherdiamine with a second compound that may an ethermonoamine. The ethermonoamine in an explicit embodiment is isotridecoxypropylamine mixed 50/50 with the corresponding diamine. In general the ore is said to be a hematite or magnetite ore, the one used in the Example seems to be undefined.
U.S. Pat. No. 3,363,758 discloses the use of etheramines in froth flotation such as to separate siliceous materials from iron ore such as magnetite. The etheramine can preferably be a C7-13etheramine, and explicit examples include an unbranched n-tridecoxypropylamine.
WO 93/06935 discloses the flotation of iron ores by using a collector containing an etheramine and another anionic or nonionic collector. The etheramine is a C6-C22 ether mono-, di-, tri- or tetraamine. The ores can in general be hematite or magnetite. One collector is a C8-C12etherpropylamine for use in hematite ore treatment. The results suggest that the ethermonoamine is beaten by the etherdiamine for magnetite treatment, as for magnetite only diamines are explicitly disclosed.
US2014/0048455 discloses the use of ether mono- and diamines in flotation for enriching an iron mineral from silicate-containing iron ore. The preferred etheramine is a branched C13alkyletherpropylamine, wherein the alkyl group is—as it is based on Tridecanol N ex BASF—around 99% C13 alkyl. The results presented in the document suggest that the ethermonoamine is beaten by the corresponding etherdiamine in performance in hematite. The document suggests that the formulations disclosed therein will also work for other iron ores, especially iron ores with high silica content, although no results are presented as evidence of this.
There is a continued need for collector compositions that provide a higher efficiency, in particular in terms of a better selectivity in separation of desired components and impurities, and hence an improved and higher recovery of magnetic iron oxide ores.
The present invention provides a collector composition suitable for treating iron ores that contains 80 to 100 wt % of alkylethermonoamine, less than 20 wt % alkyletherdiamine, all wt % based on total weight of all amine components, and wherein the alkylethermonoamine contains between 60 and 93% isotridecyl(C13)etherpropylamine, 5 and 30% of isododecyl(C12)-etherpropylamine, 0 and 10% of isoundecyl(C11)etherpropylamine, 0 and 10% of isodecyl(C10)etherpropylamine, 2 and 10% tetradecyl(C14)-etherpropylamine, all % being based on total weight of alkylethermonoamine, and a process to treat magnetite ore using the above collector composition, the process containing a step of (froth) flotating the ore in the presence of a collector composition.
The advantages of the present disclosure will be readily appreciated as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings.
We have found that collector compositions containing specific monoamine mixtures are much more efficient than diamines or other monoamine-containing compositions in treating iron ores, such as magnetite ores, in a (reverse) flotation process. It has been established that the use of a collector composition containing as amines predominantly alkylethermonoamines of the claimed composition provides for unexpected good results in a flotation process to remove silica from magnetite ore, said results being 30% better than for corresponding alkyletherdiamines and also significantly better than for compositions that contain mainly or only isotridecanol(C13) based monoamines. Besides, diamines are less desirable from a health, safety and environmental perspective as they are associated with higher toxicity compared to monoamines.
Magnetite ores are magnetic iron oxide ores that contain magnetite, i.e. Fe3O4. Such ores are typically called magnetite ores, but also other ores can contain magnetite, which in some cases are referred to as magnetic ores, like magnetic taconite ores. Magnetite ores can be distinguished from hematite ores which contain hematite, i.e. Fe2O3.
By “the degree of branching” (DB) as used herein is meant the total number of (terminal) alkyl—such as methyl—groups present on the alkyl chain minus one. It should be noted that degree of branching is an average value for the (alkyl group in the) alkylethermonoamine and hence does not have to be an integer.
The alkylethermonoamine contains between 60 and 93% isotridecyl(C13)-etherpropylamine, 5 and 30% of isododecyl(C12)etherpropylamine, 0 and 10% of isoundecyl(C11)etherpropylamine, 0 and 10% of isodecyl(C10)-etherpropylamine, 2 and 10% tetradecyl(C14)etherpropylamine, all % being based on total weight of alkylethermonoamine.
Preferably, the alkylethermonoamine contains between 60 and 80 wt % isotridecyl(C13)etherpropylamine, 10 and 30% of isododecyl(C12)-etherpropylamine, 0 and 10% of isoundecyl(C11)etherpropylamine, 0 and 5% of isodecyl(C10)etherpropylamine, 2 and 10% tetradecyl(C14)-etherpropylamine, all % being based on total weight of alkylethermonoamine.
Most preferably, the alkylethermonoamine contains between 65 and 75 wt % isotridecyl(C13)etherpropylamine, 15 and 25% of isododecyl(C12)-etherpropylamine, 0.5 and 5% of isoundecyl(C11)etherpropylamine, 0.1 and 3% of isodecyl(C10)etherpropylamine, 4 and 9% tetradecyl(C14)-etherpropylamine, all % being based on total weight of alkylethermonoamine.
In a preferred embodiment the degree of branching of the alkylethermonoamine, and the optionally present alkyletherdiamine in the composition, is between 1.5 and 3.5, more preferred it is from 2.0 to 3.0.
In another preferred embodiment the collector composition contains less than 10 wt %, even more preferably less than 5 wt % of alkyletherdiamine on total amine components.
The invention in an embodiment also relates to a process to treat iron ore to enrich iron from silica, wherein the iron ores are preferably magnetite ores.
The alkyletherpropylamine compound may be made by reaction of an alkyl alcohol (fatty alcohol) with acrylonitrile, whereafter the obtained intermediate containing a nitrile group is hydrogenated to make primary amine, and the obtained product optionally is partially neutralized.
The collector composition in an embodiment may contain further components that are known to the skilled person to be of benefit in a process to treat iron ores, such as but not limited to (iron) depressants, frothers/froth modifiers/froth regulators/defoamers, secondary collectors, neutralizing agents, pH regulators, cationic surfactants.
It has been found that the efficiency of the flotation process can be improved when the amine is at least partially neutralized by an acid. The amine may be fully or partially neutralized. Preferably, the amine may be neutralized with a 30 to 70% on molar basis amount of acid, preferably between 40 and 60 molar %. The neutralizing agent can be an inorganic acid, such as hydrochloric acid, or preferably a carboxylic acid, more preferably a C1-C5 carboxylic acid, such as formic acid, acetic acid and propionic acid. In one most preferred embodiment, the amine is neutralized with acetic acid.
The collector composition may in an embodiment additionally contain a secondary collector to improve performance. The secondary collector is preferably selected from the group of nonionics, like unbranched and branched fatty alcohols, alkoxylated fatty alcohols, fatty amines, alkylamidoamines, preferably fatty alcohols, or alkoxylated fatty alcohols. Examples of secondary collectors in a more preferred embodiment are branched 011-017 fatty alcohols, such as iso 013 fatty alcohols, and their ethoxylates and propoxylates.
The weight ratio between the primary collector and the secondary collector is preferably from 15:85, more preferably 20:80, most preferably 25:75 to 99:1, preferably 98:2, most preferably 97:3. All weight ratios herein refer to the ratio of active materials, unless stated otherwise.
The flotation process of the invention is preferably a reversed flotation process. Reversed flotation means that the desired ore is not concentrated in the froth, but in the residue of the flotation process. The process of the invention is preferably a reversed flotation process for magnetite ores, more preferably for ores that contain more than 80 wt % of Fe3O4 on total iron oxide content, even more preferably more than 90 wt %, most preferably 95 to 100 wt %. In another preferred embodiment the ores contain less than 15 wt % of silica, even more preferably less than 12 wt %, most preferably less than 10 wt %, on total solids weight in the ore. In a reversed flotation process for concentrating magnetite iron ores, the pH during flotation in a preferred embodiment is suitably in the range of 5-10, preferably in the range of 7 to 9.
The reversed froth flotation process of the invention in an embodiment comprises the steps of
The collector composition of the present invention is very beneficially used in a reversed froth flotation process as claimed, especially in a reversed froth flotation process of magnetite ores to enrich iron.
The composition is preferably liquid at ambient temperature, i.e., at least in the range of 15 to 25° C.
The process of the invention may involve other additives and auxiliary materials that can be typically present in a froth flotation process, which additives and auxiliary materials can be added at the same time or preferably separately during the process. Further additives that may be present in the flotation process are (iron) depressants, frothers/froth regulators/froth modifiers/defoamers, cationic surfactants (such as alkylamines, quaternized amines, alkoxylates), and pH-regulators. Depressants include polysaccharides, e.g. dextrin, starch, such as maize starch activated by treatment with alkali, or synthetic polymers such as polyarylamides. Other examples of (hydrophilic) polysaccharides are cellulose esters, such as carboxymethylcellulose and sulphomethylcellulose; cellulose ethers, such as methyl cellulose, hydroxyethylcellulose and ethyl hydroxyethylcellulose; hydrophilic gums, such as gum arabic, gum karaya, gum tragacanth and gum ghatti, alginates; and starch derivatives, such as carboxymethyl starch and phosphate starch. The depressant is normally added in an amount of about 10 to about 1,000 g per ton of ore. After conditioning of the ore, the ether monoamine can be added, preferably partially neutralized, and the mixture is further conditioned for a while before the froth flotation is carried out. If desired, froth regulators can be added before the froth flotation. Examples of suitable froth regulators are methylisobutyl carbinol and alcohols having 6-12 carbon atoms which optionally are alkoxylated with ethylene oxide and/or propylene oxide, especially branched and unbranched octanols and hexanols. After completion of the flotation, a silicate-enriched flotate and a bottom fraction rich in iron and poor in silicate can be withdrawn.
In another aspect, the present invention relates to a pulp comprising crushed and ground iron, preferably magnetite, ore, the collector composition as defined herein, and optionally further flotation aids. These flotation aids may be the same as the above other additives and auxiliary materials which can be typically present in a froth flotation process.
The amount of the collector used in the process of reversed flotation of the present invention will depend on the amount of impurities present in the ore and on the desired separation effect, but in some embodiments will be in the range of from 1-500 g/ton dry ore, preferably in the range of from 10-200 g/ton dry ore, more preferably 20-120 g/ton dry ore.
Materials and Method
Ore in Flotation Tests:
Magnetite ore: Fe3O4—87% (Fe—63.0%), SiO2—9.7%, −44 μm—96%
Flotation Chemicals
Collector composition 1 (comparative) containing about 10 wt % acetic acid and about 90 wt % alkyletherpropylaminepropylamine (i.e. a diamine) wherein the alkyl has a degree of branching of about 3.0 and about 70% of the alkyl group is C13, about 20% C12 and the remainder C11 or lower or C14 or higher alkyl. Collector composition 2 containing about 10 wt % acetic acid and about 90 wt % alkyletherpropylmonoamine wherein the alkyl has a degree of branching of about 3.0 and about 70% of the alkyl group is C13, about 20% C12 and the remainder C11 or lower or C14 or higher alkyl.
Synthetic Process Water
Synthetic process water was used in the flotation tests. It was prepared by adding appropriate amounts of commercial salts to deionized water, following the composition described by chemical analysis of process water from plant, Table 1.
Flotation Procedure
The study was done as a stepwise rougher flotation with a Denver laboratory flotation machine. The machine was modified and equipped with an automatic froth scraping device and a double lip cell. For apparatus parameters see Table 2.
The ore sample was added to the flotation cell and the cell filled with synthetic process water (37% solids). Water temperature of 19-22° C. was used as standard. The rotor speed was constant during the test, 900 rpm.
The material from the different flotation steps was then dried, weighed out and analyzed for iron and silica content with XRF method.
Preparation of Chemicals
The collectors were dispersed in water and added as a 1%-solution.
Frothing Procedure
Results
The results of the flotation process are given in below Table 3
Flotation
As one can see from Table 3 and
However, the efficiency of these two surfactants is different: in order to obtain 74% Fe recovery around 110-115 g/t of comparative collector composition 1 is needed and 75-80 g/t of collector composition 2 (
Frothing
In order to show the frothing properties of the collector compositions two frothing experiments were conducted with ore. Dosages of the surfactants needed to obtain 74% Fe recovery were used (
As one can see from the results, collector composition 2 in accordance with the present invention creates more froth than comparative collector composition 1, but the created froth is breaking fast (see
Conclusions
It was found that the efficiency of collector composition 2 is at least 30% higher at the same grade/recovery target than the one provided by comparative collector composition 1. Alkylethermonoamine gives an improved performance in treating low silica magnetite ores when compared to alkyletherdiamine.
Materials and Method
Example 2 was performed using the ore and the process as described for Example 1 above unless indicated differently below.
Collector composition 2 containing about 10 wt % acetic acid and about 90 wt % alkyletherpropylmonoamine wherein the alkyl has a degree of branching of about 3.0 and about 70% of the alkyl group is C13, about 20% C12 and the remainder C11 or lower or C14 or higher alkyl was now compared with a Comparative Collector composition 3 in which more than 99% of the alklyletherpropylmonoamine is based on isotridecanol C13 alkyl with a DB of 2.2.
Results
The results of the flotation process are given in Table 4 below.
Conclusions
The key to a successful flotation collector is to have high recovery of the value mineral and high reduction of gangue minerals at the lowest possible dosage of flotation chemicals including the collector. Comparing the results in a grade-recovery plot it is obvious that collector composition 2 of the invention is more efficient than comparative collector compositions 1 and 3 without losing any selectivity.
| Number | Date | Country | Kind |
|---|---|---|---|
| 16178726 | Jul 2016 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2017/066709 | 7/5/2017 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2018/007419 | 1/11/2018 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 3363758 | Cronberg et al. | Jan 1968 | A |
| 4168227 | Polgaire et al. | Sep 1979 | A |
| 4319987 | Shaw et al. | Mar 1982 | A |
| 6076682 | Gustafsson et al. | Jun 2000 | A |
| 20120325725 | Pedain et al. | Dec 2012 | A1 |
| 20130277280 | Gustafsson et al. | Oct 2013 | A1 |
| 20140021104 | Bittner et al. | Jan 2014 | A1 |
| 20140048455 | Bittner et al. | Feb 2014 | A1 |
| 20140144290 | Martins | May 2014 | A1 |
| Number | Date | Country |
|---|---|---|
| 1100239 | Apr 1981 | CA |
| 101795776 | Aug 2010 | CN |
| 103260765 | Aug 2013 | CN |
| 103476506 | Dec 2013 | CN |
| 103501915 | Jan 2014 | CN |
| 104919062 | Sep 2015 | CN |
| 201391473 | Apr 2014 | EA |
| 2 017 009 | Jan 2009 | EP |
| 2 489 714 | Mar 1982 | FR |
| 2 529 475 | Jan 1984 | FR |
| 2469794 | Dec 2012 | RU |
| 2599113 | Oct 2016 | RU |
| 9306935 | Apr 1993 | WO |
| 2008077849 | Jul 2008 | WO |
| 2009077015 | Jun 2009 | WO |
| 2018007418 | Jan 2018 | WO |
| Entry |
|---|
| Guo Fang, et al.; “Improving the Grade of a Siliceous-Calcareouse Phospate Ore with Fine Size by Reverse Flotation Method”; College of Chemical Engineering, 2010; 1 pg. |
| Howard James Haselhuhn III; “The Dispersion and Selective Flocculation of Hematite Ore”; Michigan Technical University, 2015. |
| Mark Ma; “Froth Flotation of Iron Ores”; International Journal of Mining Engineering and Mineral Processing; 2012; 1(2); pp. 56-61; Scientific & Academic Publishing. |
| Notification of Transmittal of the International Search Report and the Written Opinion of the International Searching Authority, or the Declaration from the International Bureau of WIPO for International Application No. PCT/EP2017/066709 dated Oct. 16, 2017. |
| European Search Report issued in the counterpart European Application No. 16178726.2-1370 dated Jan. 5, 2017. |
| Russian Patent Office, Search Report issued in the Notice of Allowance for Russian Patent Application No. 2019102712, dated Jul. 2, 2019. |
| Number | Date | Country | |
|---|---|---|---|
| 20190240677 A1 | Aug 2019 | US |
