US20150361522A1
2015-12-17
14/763,759
2014-01-24
We propose a method of removing iron from leach solutions, obtained by leaching of metal bearing materials with acids, in the form of hydroxide and/or oxide by precipitation. The advantages with the method according to the invention include that the method can be performed at atmospheric pressure and at temperatures from ambient to boiling temperatures and that no gases are emitted. Another important advantage is, by prevention of gel formation of the iron precipitate, that solid/liquid separation becomes much easier and loss of valuable metals is minimized.
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C22B23/0461 » CPC further
Obtaining nickel or cobalt by wet processes; Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
C22B3/44 » CPC main
Extraction of metal compounds from ores or concentrates by wet processes; Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
C22B3/00 IPC
Extraction of metal compounds from ores or concentrates by wet processes
The present invention relates to the precipitation of iron with lime and/or limestone from leach solutions.
Leaching of metal bearing materials with acids is widely applied in the industry. Iron removal from leach solutions is important for the recovery of metals and for process economics. Iron is normally removed from the solution as jarosite, goethite or hematite but can also be precipitated out of the leach solution as hydroxide by precipitation with a suitable pH adjuster such as lime, limestone, magnesium hydroxide, caustic or ammonia etc. Main problems with this method ariose from the fact that iron hydroxide precipitated in this way presents difficulties in filtering so that an unacceptable amount of metallic values is lost in the filter cake.
The object of the invention is to provide a method for efficient removal of iron as iron hydroxide/oxide from leach solutions containing other metals resulting from leaching of metal bearing materials with acids.
This object is achieved by means of the method according to claim 1. Advantageous further embodiments of the invention are defined in the dependent claims.
During the work leading to the present invention it was found possible to precipitate iron under atmospheric conditions from a sulphate leach solution comprising, inter alia and without limitation, nickel and cobalt sulphates.
The advantages with the method according to the invention include that the method can be performed at atmospheric pressure and at temperatures from ambient to boiling temperatures and that no gases are emitted. Another important advantage is, by prevention of gel formation of the iron precipitate, that solid/liquid separation becomes much easier and loss of valuable metals is minimized.
Thus, the present invention relates to a process for efficent precipitaion of iron from leach solutions.
The characterizing features of the invention will be evident from the following description and the appended claims.
The term ‘metal’ used herein and in the appended claims encompasses nickel, cobalt and any other metals that are normally soluble in acids.
Method step a) through l) described hereinafter may be combined in suitable fashion to yield a method as defined in the appended claims or advantageous further developments thereof.
Practically, the method is preferably performed in vessels made from stainless steel or mild steel or concrete tanks which could be lined with proper protective lining.
The invention will now be further explained in the following example. This example is only intended to illustrate the invention and should in no way be considered to limit the scope of the invention.
1. A leach solution obtained from leaching of a nickel laterite ore was used. The pH of the process leach solution (PLS) was 0.2 and contained 82.000 ppm Fe, 4500 ppm Ni.
2. 400 grams of limestone was placed in a beaker and the volume was made up to 1 liter with water. The emulsion was stirred for four hours and the pH of this emulsion reached over 10. The a mount of limestone was adjusted in such a way that for 1 gm of iron in the PLS, between 2-4 gm of CaCO3 was used.
3. In order to avoid gel formation of iron oxide/hydroxite, the leach solution from laterite leaching was then added into this limestone emulsion prepared as above until a pH of 2.8-3.0 was reached, while stirring at atmospheric conditions. Normally, no additional pressure is required. Then this mixture emulsion was stirred for up to four hours. This ‘shock pH adjustment’ eliminates gel formation opportunity.
4. At this pH, iron was converted to oxide/hydroxide and was separated as precipitate by solid/liquid separation from the solution. Fe concentration in thickener overflow dropped to 600 ppm indicating more than 95% removal of iron from the leach solution. The thickener overflow contained 2200 ppm Ni indicating over 95% recovery of nickel into the filtrate.
5. To this thickener overflow solution, initially limestone emulsion was added to bring the pH to around 4.5 and then the pH was lowered down to a constant value between 3.25-3.5 with dilute hydrogen peroxide, and the solution was stirred. Again with a fresh addition of limestone emulsion, the pH of this solution was increased back to around 4.5. With this procedure, all of any remaining dissolved iron and aluminium precipitated out of the solution.
6. Following solid/liquid separation, the solution contained less than 1 ppm iron and aluminium.
7. The thickener underflow was also filtered easily and precipitate was washed with water to remove any metallic values. This iron oxide/hydroxite/gypsum cake was found to contain less than 0.02% confirming a nickel loss, in the iron precipitate, of less than 5%.
1. A method of removing iron from a metal bearing material, the method comprising:
leaching the metal bearing material with an acid, wherein the iron is removed in the form of a hydroxide, an oxide or a combination thereof, thereby forming an iron bearing leach solution;
precipitating the iron from the iron bearing leach solution by adding the iron bearing leach solution with a first acidic pH to an emulsion of lime, limestone or a combination thereof with a pH of over 10, wherein adding the iron bearing leach solution to the emulsion raises the first acidic pH to a second acidic pH.
2. The method according to the claim 1, wherein the first acidic pH of the iron bearing leach solution is ≧0.1.
3. (canceled)
4. The method according to claim 1, wherein iron and aluminum remaining in the iron bearing leach solution with the second acidic pH are completely precipitated out of the iron bearing leach solution by initially increasing the iron bearing leach solution pH to around 4.5 with lime, limestone or a combination thereof, then lowering the iron bearing leach solution pH to between 3.25-3.5 with dilute hydrogen peroxide, and then increasing the iron bearing leach solution pH back to around 4.5 with lime, limestone or a combination thereof.
5. The method according to claim 1, performed at essentially atmospheric pressure.
6. The method according to claim 1, wherein a temperature is anywhere between an ambient temperature and a boiling temperature.
7. The method according to claim 1, wherein the iron bearing leach solution is a ferric leach solution which comprises dissolved metals such as nickel, cobalt, zinc, copper, similar other similar metals that are normally soluble in a relevant acid or a combination thereof.
8. The method according to claim 1, wherein the method is used in continuous mode, in a batch mode or a combination thereof.
9. The method according to claim 1, wherein a shock pH increase of the iron bearing leach solution is achieved with alkalines selected from the group consisting of soda ash, magnesium oxide, magnesium hydroxide, magnesium carbonate, caustic and ammonia to prevent formation of a gel of the iron oxide/iron hydroxide precipitate thus enabling easy filtration and minimizing loss of any other metallic values.
10. The method according to claim 1, wherein the first acidic pH is preferably essentially as low as 0.1.
11. The method according to claim 1, wherein the first acidic pH is more preferably 0.1.
12. The method according to claim 1, wherein the second acidic pH is between 2.8 and 3.0.
13. The method according to claim 1, wherein the emulsion is preferably prepared separately.
14. The method of claim 9, wherein the shock pH increase is performed instead of or in addition to raising the first acidic pH of the iron bearing leach solution to the second acidic pH.
15. A method of removing iron from an iron bearing leach solution, the method comprising:
precipitating iron, which is present in the form of iron oxide, iron hydroxide or a combination thereof, from the iron bearing leach solution by adding the iron bearing leach solution with a first acidic pH to an emulsion of lime, limestone or a combination thereof with a pH of over 10, wherein adding the iron bearing leach solution to the emulsion raises the first acidic pH to a second acidic pH.
16. The method according to claim 15, wherein the first acidic pH is about 0.1 and the second acidic pH is between 2.8 and 3.0.
17. The method according to claim 15, wherein iron and aluminum remaining in the iron bearing leach solution with the second acidic pH are completely precipitated out of the iron bearing leach solution by initially increasing the iron bearing leach solution pH to around 4.5 with lime, limestone or a combination thereof, then lowering the iron bearing leach solution pH to between 3.25-3.5 with dilute hydrogen peroxide, and then increasing the iron bearing leach solution pH back to around 4.5 with lime, limestone or a combination thereof.
18. The method according to claim 15, wherein the iron bearing leach solution is a ferric leach solution which comprises dissolved metals such as nickel, cobalt, zinc, copper, other similar metals that are normally soluble in a relevant acid or a combination thereof.
19. The method according to claim 15, wherein a shock pH increase of the iron bearing leach solution is achieved with alkalines selected from the group consisting of soda ash, magnesium oxide, magnesium hydroxide, magnesium carbonate, caustic and ammonia to prevent formation of a gel of the iron oxide/iron hydroxide precipitate thus enabling easy filtration and minimizing loss of any other metallic values, and wherein the shock pH increase is performed instead of or in addition to raising the first acidic pH of the iron bearing leach solution to the second acidic pH.