Acid Recovery
Nickel is recovered from a nickeliferous ore, where the ore includes impurities in the form of metals other than nickel and cobalt. The ore is subjected to atmospheric leaching using sulphuric acid to dissolve nickel and cobalt from the ore and produce a leach liquor. The sulphuric acid is regenerated by rapidly heating the leach liquor to a temperature in excess of 120° C. to produce a slurry including sulphuric acid and precipitated oxides of impurities present in the leach liquor, and separating the precipitated oxides from the slurry to produce a clarified acid rich liquor stream for recycle to leaching.
The present invention relates to a process for regeneration of sulphuric acid from leach liquors generated by atmospheric leaching of nickeliferous ore, wherein the ore includes impurities in the form of metals other than nickel and cobalt, and wherein the ore is subjected to atmospheric leaching using sulphuric acid to dissolve nickel and cobalt from the ore and produce a leach liquor.
BACKGROUND TO THE INVENTIONNickel ores can be classified into two major types according to their composition, namely, sulfide and laterite (the latter being also known as “oxidized”). Until recently, the majority of total nickel production came from processing of sulfide ores. In more recent times, laterite ores have started to be treated on a commercial scale as a consequence of higher-grade nickel sulphide deposits being mined out, making the more complex laterite ores economically viable to process. The nickel and cobalt metals present in the laterite ore can be recovered using leaching to take nickel and cobalt into solution for subsequent recovery.
Traditionally, the laterite ores have been treated via an expensive, energy intensive and highly corrosive high pressure sulphuric acid leaching, smelting or the Caron processes. More recently, leaching circuits conducted at atmospheric pressure have been proposed. For example, heap leaching is an operation that involves low investment and circuital costs compared with high pressure leaching, is very well known, and is widely applied mainly for copper, uranium, and gold ores. Heap leaching is conducted at atmospheric pressure and ambient temperature. Dilute acid solution is irrigated over the top of the heap and leaching proceeds for an extended period of time as the nickel and cobalt are dissolve into a pregnant leach liquor which is collected from the base of the heap. Similarly, it is known that laterite ores can be leached in slurry form at atmospheric pressure and elevated temperature, typically above 70° C. In either case, the resultant pregnant leach liquors can be treated to recover the dissolved nickel and cobalt values.
In all cases of such atmospheric acid leaching, excess acid is consumed in dissolving iron, aluminium, chrome, copper, and manganese which are also present in the laterite ores in various concentrations.
Prior art processes have been developed to separate the iron and aluminum impurities from pregnant leach liquors by causing the impurities to precipitate out of the pregnant liquor by adding neutralizing reagents to alter the pH of the pregnant leach liquor (see, for example U.S. Pat. No. 3,720,749; U.S. Pat. No. 3,991,159; U.S. Pat. No. 4,097,575 and U.S. Pat. No. 4,547,348). The most commonly used neutralizing agent are magnesia (MgO) and calcium carbonate rich reagents such as limestone or coral mud, which is typically added to the pregnant liquor in a sufficient quantity to adjust the pH of the liquor within the narrow pH range of about 3.5 to 4.5 at a temperature of about 50 to 100° C. to at atmospheric pressure. Following the precipitation and separation of the aforementioned impurities, the pH of the pregnant or leach liquor is then raised to at least 7 by the further addition of magnesia to cause the nickel and cobalt present in the pregnant leach liquor to precipitate out, allowing the nickel and cobalt-rich precipitates to be separated from the liquor.
It is also known to attempt to minimize consumption of both sulphuric acid and/or the neutralizing agent by separating the nickel bearing ore into high and low magnesium fractions prior to leaching, and subjection only the low magnesium fraction to leaching, whilst using the high magnesium fraction or raw ore itself as some or all of the neutralizing agent (see, for example, U.S. Pat. No. 4,097,575; U.S. Pat. No. 3,804,613; U.S. Pat. No. 3,991,159; and, U.S. Pat. No. 4,044,096).
At the conditions under which these prior art processes are operated, aluminum and iron values precipitate out primarily as gelatinous hydroxides and basic sulfates. These precipitates are not very dense and tend to be voluminous, with the result that particular care must be taken to separate these precipitates from the pregnant leach liquor using solid-liquid separation techniques well known in the hydrometallurgical art. These prior art methods are expensive in terms of the costs associated with the consumption of the neutralising reagents. More importantly, such prior art processes only exacerbate the problems associated with excessive consumption of the acid by the impurities present in the ore.
With atmospheric leaching methods becoming more attractive for processing nickel laterite ores, there remains a need for a process which reduces fresh acid consumption to overcome or at least ameliorate the above-identified problems with the prior art.
SUMMARY OF THE INVENTIONAccording to one aspect of the present invention there is provided a method of recovering nickel from a nickeliferous ore, wherein the ore includes impurities in the form of metals other than nickel and cobalt, and wherein the ore is subjected to atmospheric leaching using sulphuric acid to dissolve nickel and cobalt from the ore and produce a leach liquor, the sulphuric acid is regenerated using a method comprising:
-
- a) rapidly heating the leach liquor to a temperature in excess of 120° C. to produce a slurry comprising sulphuric acid and precipitated oxides of impurities present in the leach liquor; and,
- b) separating the precipitated oxides from the slurry of step a) to produce a clarified acid rich liquor stream for recycle to leaching.
Step a) may be conducted at a temperature in the range of 120 to 220° C. or in the range of 180 to 220° C. to initiate the precipitation of oxides of impurities by hydrolysis.
Advantageously, leach liquors with high iron contents can be treated in that the leach liquor of step a) may have at least 10 g/L or at least 25 g/L of dissolved iron.
Preferably, the precipitated oxides are hematite or alunite.
In one form, the leach liquor of step a) has an initial free acid concentration of at least 10 g/L free acid.
To achieve rapid heating, step a) may be conducted using an autoclave which operates in combination with one or more pre-heating stages arranged to receive steam that is generated from cooling or “flashing” when the slurry discharged from the autoclave is depressurized. The autoclave may include one or more steam injection points arranged received fresh steam to control the temperature within the autoclave in use.
In one form of the present invention, the leach liquor of step a) is a pregnant leach liquor. The pregnant leach liquor may be subjected to a metals recovery process to recover nickel and cobalt from the pregnant leach liquor and form a barren leach liquor. The metals recovery process may be selected from the group consisting of sulphide precipitation with hydrogen sulphide gas, solvent extraction, ion exchange, or a combination thereof. When the metals recovery process is sulphide precipitation, sulphide precipitation may be conducted on a pregnant leach liquor having a level of acidity of less than 10 g/L free acid at a temperature in the range of 80 to 120° C. If required, a neutralizing agent may be added to a bypass stream of the clarified acid-rich liquor stream of step b) to achieve a target free acid content in a neutralized pregnant liquor stream within the range of 1-10 g/L of free acid prior to conducting sulphide precipitation. In this form of the present invention, the neutralized pregnant liquor stream may then be directed to a metals recovery process. In one form, the neutralizing agent is calcium carbonate. The portion of clarified acid-rich leach liquor of step b) which forms the bypass stream may be determined by ensuring that the target amount of nickel recovered using the metals recovery process is equal to the amount of nickel being leached per pass during atmospheric leaching.
Preferably, acid recovery is conducted after metals recovery and the leach liquor of step a) is a barren leach liquor.
In one form of the present invention, atmospheric leaching may be conducted using a heap leaching process.
According to a second aspect of the present invention there is provided a method of regenerating sulphuric acid substantially as herein described with reference to and as illustrated in the accompanying drawings.
In order to facilitate a more detailed understanding of the nature of the invention several embodiments of the present invention will now be described in detail, by way of example only, with reference to the accompanying drawings, in which:
Particular embodiments of the method of regenerating sulphuric acid for re-use in heap leaching to recover nickel and cobalt from a nickeliferous ore. The present invention is equally applicable to the recovery of acid from leach liquors produced using atmospheric leaching operations other than heap leaching. The terminology used herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art to which this invention belongs. In the drawings, it is to be understood that like reference numbers refer to like parts. The abbreviation “° C.” as used throughout this specification refers to “degrees Celsius”.
The term “leaching” as used throughout this specification refers to the selective dissolution of a target metal contained in an insoluble solid phase using a solvent or “leaching solution”. For leaching to occur, an ore to be leached is brought into contact with the solvent, taking the target metal value(s) into solution. Any metals other than the target metal which dissolve in the leach solution are referred to throughout this specification as “impurities”. By way of example, during leaching of laterite ores, the target metals are nickel and (optionally) cobalt, whilst iron, aluminium, chromium, copper and manganese are considered to be impurities.
Leaching results in the formation of “a pregnant leach liquor”, which is a term that is used throughout this specification to refer to a leach liquor which is rich in target metal values. After leaching has been completed, target metals are extracted from the pregnant leach liquor using a “metals recovery process”. Downstream of the metal recovery process, after the target metals have been removed, the leach liquor is referred to throughout this specification as “a barren leach liquor”.
“Atmospheric Leaching” is a process which is conducted at ambient pressure (in contrast to a high pressure leaching process which requires specialist equipment such as pressure vessels or autoclaves). “Heap Leaching” is a process in which the ore is piled up to form a “heap” and the target metals are taken into solution by percolation of the leaching solution through the heap.
One embodiment of a process (10) for regeneration of acid for use in leaching nickel-containing laterite ores is now described with reference to
A suitable leaching solution is any reagent capable of selectively dissolving a target metal from an ore whilst remaining chemically inert to gangue minerals. The leaching solution preferably contains sulphuric acid. When sulphuric acid is used, the leach solution typically contains between 0.1 and 20% sulphuric acid. Optimum recovery of nickel during heap leaching is achieved when about 400 to about 1000 kilograms of sulphuric acid per tonne of dry ore is consumed, without acid regeneration. The acid solution may be applied by spraying it onto a layer of inert bedrock, which acts as liquid distributor on the heap, although any method to adequately and uniformly disperse the acid onto the heap can be used. The acid solution is applied at an irrigation rate or flux in the range of 5 to 30 litres per hour per meter squared, preferably 10 to 25 litres per hour per meter squared.
Pregnant leach liquor (12) is collected using a collection means arranged at the base of each heap. The pregnant leach liquor is either recycled for a second pass through the same heap or another heap in the series, or directed to a metals recovery circuit (16) to recover one or both of the nickel values and the cobalt values present in the pregnant leach liquor. After leaching has been completed, the heap may be rinsed with water (either fresh or salt water), concentrated or dilute acid or a combination of both of these, with an effluent stream being collected from the base of the heap after rinsing. If desired, this effluent stream can be directed to the metals recovery circuit (16) in addition to the pregnant leach liquor to improve overall recovery of nickel and/or cobalt values.
Any suitable metals recovery process known in the art, such as precipitation, solvent extraction or ion exchange, can be used to in the metals recovery circuit (16) to separately recover dissolved target metal values such as nickel and cobalt from the pregnant leach liquor at a satisfactory purity. By way of example, the nickel and cobalt present in the pregnant leach liquor (12) can be removed through the addition of a source of sulphide ions, for example by introducing a hydrogen sulphide gas stream or through the addition of sodium hydrosulphide (NaHS) in slurry form. Other metal recovery methods can equally be used, for example, hydroxide precipitation, solvent extraction or ion exchange. The addition of the sulphide ions under certain conditions causes the nickel and cobalt metal values present in the pregnant leach liquor (12) to precipitate. Precipitation occurs at temperatures in the range of 80 to 120° C. provided that, prior to the introduction of the source of sulphide ions, the acidity of the pregnant leach liquor (12) is maintained at a level of acidity of less than 10 g/L free acid.
Precipitation of the nickel or cobalt occurs according to the following simplified general equation, where “M” is a divalent metal:
MSO4(aq)+H2S→MS(s)+H2SO4 (1)
It is clear from equation (1) above, that the acidity of the leach liquor increases as this precipitation reaction progresses. For a pregnant leach liquor with an initial acidity of 1 g/L, the final acidity after nickel and cobalt precipitation can be as high as 10 g/L. The precipitated solids of nickel and cobalt are removed from the leach liquor after precipitation using any suitable solid/liquid separation equipment (which forms part of the metals recovery circuit (16)) to produce a clarified barren liquor stream (18).
In the embodiment illustrated in
By way of example, sulphuric acid is regenerated when iron and aluminium impurities present in the leach liquor precipitate as oxides according the following simplified reactions:
Fe2(SO4)3(aq)+3H2O→Fe2O3(s)+3H2SO4 (2)
3Al2(SO4)3(aq)+13H2O→3Al2O3.4SO3.8H2O (s)+5H2SO4 (3)
It is clear from equations (2) and (3) above, that when the oxides are caused to form, sulphuric acid is recovered from the leach liquor. By way of example, when the acid level of the leach liquor being treated has an initial free acid concentration of approx 10 g/L free acid, the final free acid concentration after causing rapid precipitation of the impurities from the leach liquor increases to over 50 g/L free acid. The practical outcome of this is that up to half of the acid used to conduct leaching can be recovered and made available for return to the leaching circuit (14).
The precipitated oxides are removed using a solid/liquid separation circuit (22) to produce a clarified acid-rich liquor stream (40) which is available for re-cycle to the leaching circuit (14). The oxides removed from the liquor stream using the solid/liquid separation circuit (22) are disposed of. Solid/liquid separation in the solid/liquid separation circuit (22) can be achieved using any suitable process known in the hydrometallurgical art, for example; thickening, filtering, pressure filtering, centrifugal separation, gravity separation, counter-current decantation, or cyclones. Unlike the hydroxide and basic sulphate precipitates of the prior art, the oxides which precipitate in the acid recovery circuit (20) of the present invention form dense solid particles which settle well and are readily filterable.
Rapid heating in the acid recovery circuit (20) can be achieved in a number of ways. In the embodiments illustrated in
After precipitation of the oxides from the liquor stream, a slurry stream (32) is discharged from the autoclave (26) into one or more stages of pressure let-down using a series of cooling vessels or flash tanks (34). Within each of the flash tanks (34), the hot pressurised slurry stream (32) is caused to pass through a choke valve (not shown) causing rapid acceleration which leads to a drop in pressure. This rapid drop in pressure causes some of the water present in the slurry to flash to steam. The steam that forms within each of the flash vessels (34), apart from the final flash vessel (35), is ducted to the pre-heating stages (24) for heat recovery. Two such flash tank (34)/pre-heating stages (24) are illustrated in each of the embodiments of
The cooled slurry stream (36) downstream of the flash tanks (34), at a nominal temperature in the order of 100° C., is then discharged to the solid/liquid separation circuit (22). The precipitated oxides of the impurities (38) removed from the cooled slurry stream (36) using the solid/liquid separation circuit (22) are discarded. The clarified acid-rich liquor stream (40) which is recovered from the cooled slurry stream (36) using the solid/liquid separation circuit (22) has a high free acid content which makes it suitable for recycle to the leaching circuit (14).
The acid recovery circuit (20) can be located either upstream or downstream of the metals recovery circuit (16). In the flowchart of
In the embodiment illustrated in
With reference to
CaCO3+H2SO4→CaSO4(aq)+CO2+H2O (4)
When the neutralized pregnant liquor stream is saturated with aqueous calcium sulphate, the calcium sulphate precipitates as gypsum in accordance with the following equation:
CaCO3+H2O→CaSO4.H2O (5)
Following separation of the gypsum solids, a neutralized pregnant liquor stream (54) is directed to the metals recovery circuit (16). A suitable metals recovery process, such as sulphide precipitation, is then used in the metals recovery circuit (16) to recover nickel and cobalt values from the neutralized pregnant liquor stream (54). The remaining portion of the clarified acid-rich leach liquor (40) from the solid-liquid separation circuit (22) has a high free acid content, making it suitable for recycle to the leaching circuit (14).
In the embodiment illustrated in
The present invention is particularly suited to the treatment of leach liquors containing at least 10 g/L of dissolved iron and preferably at least 25 g/L of dissolved iron.
The advantages of the various aspects and embodiments of the present invention are further described and illustrated by the following examples and experimental test results. These examples and experimental test results are illustrative of a variety of possible implementations and are not to be construed as limiting the invention in any way. The present invention is also not limited by the particular number nor type of equipment described in the following examples.
EXAMPLESA heap leach column test using sulphuric acid and laterite ore was conducted to produce a leach liquor containing target metal values in the form of nickel and cobalt in solution. The leach liquor also contains dissolved iron, aluminium, chrome, magnesium and manganese impurities.
Approximately 3000 grams of the leach liquor was placed in a titanium Parr autoclave, which was then sealed and heated to 220° C. After achieving this temperature, samples of the solution were taken after 15 minutes. Thereafter, the autoclave was allowed to cool. After cooling the pulp was weighed and filtered to recover precipitated solids. The initial leach liquor from heap leaching, the solids recovered during filtering and the leach liquor after precipitation were analysed to determine the free acid levels and composition of each, with the results being presented below in Table 1.
Now that several embodiments of the invention have been described in detail, it will be apparent to persons skilled in the relevant art that numerous variations and modifications can be made without departing from the basic inventive concepts. For example, a portion of the steam generated by the flash tanks (34) can be directed to one or all of steam injection points (30) of the autoclave (26) if desired. All such modifications and variations are considered to be within the scope of the present invention, the nature of which is to be determined from the foregoing description and the appended claims.
All of the patents cited in this specification, are herein incorporated by reference. It will be clearly understood that, although a number of prior art publications are referred to herein, this reference does not constitute an admission that any of these documents forms part of the common general knowledge in the art, in Australia or in any other country. In the summary of the invention, the description and claims which follow, except where the context requires otherwise due to express language or necessary implication, the word “comprise” or variations such as “comprises” or “comprising” is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.
Claims
1. In a method of recovering nickel from a nickeliferous ore, wherein the ore includes impurities in the form of metals other than nickel and cobalt, and wherein the ore is subjected to atmospheric leaching using sulphuric acid to dissolve nickel and cobalt from the ore and produce a leach liquor, the sulphuric acid is regenerated using a method comprising:
- a) rapidly heating the leach liquor to a temperature in excess of 120° C. to produce a slurry comprising sulphuric acid and precipitated oxides of impurities present in the leach liquor; and,
- b) separating the precipitated oxides from the slurry of step a) to produce a clarified acid rich liquor stream for recycle to leaching.
2. The method of regenerating sulphuric acid of claim 1, wherein step a) is conducted at a temperature in the range of 120° C. to 220° C. to initiate the precipitation of oxides of impurities by hydrolysis.
3. The method of regenerating sulphuric acid of claim 1, wherein step a) is conducted at a temperature in the range of 180° C. to 220° C. to initiate the precipitation of oxides of impurities by hydrolysis.
4. The method of regenerating sulphuric acid of claim 1, wherein the leach liquor of step a) has at least 10 g/L of dissolved iron.
5. The method of regenerating sulphuric acid of claim 1, wherein the leach liquor of step a) has at least 25 g/L of dissolved iron.
6. The method of regenerating sulphuric acid of claim 1, wherein the precipitated oxides are hematite or alunite.
7. The method of regenerating sulphuric acid of claim 1, wherein the leach liquor of step a) has an initial free acid concentration of at least 10 g/L free acid.
8. The method of regenerating sulphuric acid of claim 1, wherein step a) is conducted using an autoclave which operates in combination with one or more pre-heating stages arranged to receive steam that is generated from cooling or “flashing” when the slurry discharged from the autoclave is depressurized.
9. The method of regenerating sulphuric acid of claim 8, wherein the autoclave includes one or more steam injection points arranged received fresh steam to control the temperature within the autoclave in use.
10. The method of regenerating sulphuric acid of claim 1, wherein the leach liquor of step a) is a pregnant leach liquor.
11. The method of regenerating sulphuric acid of claim 10, wherein the pregnant leach liquor is subjected to a metals recovery process to recover nickel and cobalt from the pregnant leach liquor and form a barren leach liquor.
12. The method of regenerating sulphuric acid of claim 11, wherein the metals recovery process is selected from the group consisting of sulphide precipitation with hydrogen sulphide gas, solvent extraction, ion exchange, and combinations thereof.
13. The method of regenerating sulphuric acid of claim 11, wherein the metals recovery process is sulphide precipitation conducted on a pregnant leach liquor having a level of acidity of less than 10 g/L free acid at a temperature in the range of 80° C. to 120° C.
14. The method of regenerating sulphuric acid of claim 10, wherein a neutralizing agent is added to a bypass stream of the clarified acid-rich liquor stream of step b) to achieve a target free acid content in a neutralized pregnant liquor stream within the range of 1 g/L to 10 g/L of free acid.
15. The method of regenerating sulphuric acid of claim 14, wherein the neutralized pregnant liquor stream is directed to a metals recovery process.
16. The method of regenerating sulphuric acid of claim 14, wherein the neutralizing agent is calcium carbonate.
17. The method of regenerating sulphuric acid of claim 14, wherein the portion of clarified acid-rich leach liquor of step b) which forms the bypass stream is determined by ensuring that the target amount of nickel recovered using the metals recovery process is equal to the amount of nickel being leached per pass during atmospheric leaching.
18. The method of regenerating sulphuric acid of claim 1, wherein the leach liquor of step a) is a barren leach liquor.
19. The method of regenerating sulphuric acid of claim 1, wherein atmospheric leaching is conducted using a heap leaching process.
Type: Application
Filed: Jan 18, 2010
Publication Date: Jul 21, 2011
Applicant: GME RESOURCES LTD. (Como)
Inventors: Geoffrey Motteram (Cottesloe), Michael Ryan (Subiaco)
Application Number: 12/688,979
International Classification: C22B 23/00 (20060101);