PROCESS FOR RECOVERING METALS FROM SILICATE MATERIALS
RELATED APPLICATIONS
[0001] This application claims the benefit of priority under 35 U.S.C. 1 19(e) to U.S. Provisional Patent Application Serial No. 61/591 ,377 filed on January 27, 2012.
FIELD
[0002] The present disclosure relates to a process for facilitating separation of desirable metals from silicate materials.
BACKGROUND
[0003] Saprolite forms in the lower zones of soil profiles and represents deep weathering of the bedrock surface. Generally, saprolite defines the high nickel content layer of laterite ore. Laterite is mined via open cut mining methods. Nickel is extracted from laterite ore by a variety of processes. There are several hydrometallurgical processes available to concentrate nickel from the laterite ore, including such processes as high pressure acid leach, heap leach, and the Caron process.
SUMMARY
[0004] In one aspect, there is provided a process for treating a silicate material, comprising, contacting operative metal material-comprising silicate material with at least one halide ion-donating agent so as to effect production of a pre-reduction operative metal material-comprising material, wherein the operative metal material-comprising silicate material includes operative metal material to thereby define a silicate material-based operative metal material fraction, and wherein the pre-reduction operative metal material- comprising material includes a pre-reduction material-based operative metal material fraction that includes at least a fraction of the silicate material-based operative metal material fraction, and wherein the operative metal material is defined by at least one operative metallic element, the operative metallic elements being defined by nickel, iron, and cobalt, contacting the pre-reduction operative metal material-comprising material with
at least one reducing agent so as to effect production of a pre-carbonylation operative metal material-comprising material, wherein the pre-carbonylation operative metal material- comprising material includes a pre-carbonylation material-based operative metal material fraction that includes at least a fraction of the pre-reduction material-based operative metal material; and carbonylating at least a fraction of the pre-carbonylation material-based operative metal material fraction.
[0005] In another aspect, there is provided a process for treating metallic material, comprising, carbonylating at least a fraction of a pre-carbonylation material-based operative metal material fraction; wherein production of at least a fraction of the pre- carbonylation material-based operative metal material has been effected by contacting of a pre-reduction operative metal material-comprising material with at least one reducing agent, wherein the pre-carbonylation material-based operative metal material fraction includes at least a fraction of a pre-reduction material-based operative metal material of the pre-reduction operative metal material-comprising material, wherein production of at least a fraction of the pre-reduction operative metal material-comprising material has been effected by contacting of an operative metal material-comprising silicate material with at least one halide ion-donating agent, wherein the operative metal material-comprising silicate material includes operative metal material to thereby define a silicate material- based operative metal material fraction, and wherein the pre-reduction material-based operative metal material fraction includes at least a fraction of the silicate material-based operative metal material fraction; and wherein the operative metal material is defined by at least one operative metallic element, the operative metallic elements being defined by nickel, iron, and cobalt
[0006] In another aspect, there is provided a process for treating a silicate material, comprising, contacting operative metal material-comprising silicate material with a reagent mixture so as to effect production of a pre-carbonylation operative metal material- comprising material, wherein the operative metal material-comprising silicate material includes operative metal material to thereby define a silicate material-based operative metal material fraction, and wherein the pre-carbonylation operative metal material- comprising material includes a pre-carbonylation material-based operative metal material
fraction that includes at least a fraction of the silicate material-based operative metal material; and carbonylating at least a fraction of the pre-carbonylation material-based operative metal material, wherein the operative metal material is defined by at least one operative metallic element, the operative metallic elements being defined by nickel, iron, and cobalt, and wherein the reagent mixture includes at least one halide-ion donating agent and at least one reducing agent.
[0007] In another aspect, there is provide a process for treating metallic material, comprising, carbonylating at least a fraction of a pre-carbonylation material-based operative metal material fraction, wherein production of at least a fraction of the pre- carbonylation material-based operative metal material has been effected by contacting of a operative metal material-comprising silicate material with a reagent mixture, wherein the operative metal material-comprising silicate material includes operative metal material to thereby define a silicate material-based operative metal material fraction, and wherein the pre-carbonylation operative metal material-comprising material includes a pre- carbonylation material-based operative metal material fraction that includes at least a fraction of the silicate material-based operative metal material, and wherein the operative metal material is defined by at least one operative metallic element, the operative metallic elements being selected from nickel, iron, and cobalt, and wherein the reagent mixture includes at least one halide-ion donating agent and at least one reducing agent.
BRIEF DESCRIPTION OF DRAWINGS
[0008] The preferred embodiments of the process will now be described with reference to the following accompanying drawings, in which:
[0009] Figure 1 is a flowsheet illustrating an embodiment of a first aspect of the process;
[0010] Figure 2 is a flowsheet illustrating another embodiment of the first aspect of the process; and
[0011] Figure 3 is a flowsheet illustrating an embodiment of a second aspect of the process; and
[0012] Figure 4 is a graph illustrating the effect of chloride addition on nickel and iron extraction from saprolite.
DETAILED DESCRIPTION
[0013] There is provided a process for treating silicate material 10, or material derived from silicate material, so as to effect production of a material from which recovery of one or more operative metallic elements is facilitated.
[0014] In some embodiments, for example, the silicate material 10 is at least one silicate material type. Examples of silicate material types include nontronite, kaolinite, and serpentine.
[0015] In some embodiments, for example, the silicate material 10 is derived from an ore 12, such as laterite, which includes limonite and saprolite. In some embodiments, for example, the ore is saprolite. In some embodiments, for example, the saprolite includes from 1.8 to 2.3 weight % nickel, based on the total weight of the saprolite material, and also includes from 13 to 18 weight % iron, based on the total weight of the saprolite material. In some embodiments, for example, the limonite includes from 0.8 to 1.7 weight % nickel, based on the total weight of the limonite material, and from 35 to 45 weight % iron, based on the total weight of the limonite material.
[0016] In some embodiments, for example, the ore 12 is dried and subjected to size reduction (for example, by crushing 14, drying 28, milling, and/or grinding 16) prior to being subjected to the treatment of the process.
[0017] In some embodiments, for example, the silicate material is in the form of a solid particulate material.
First aspect
[0018] In one aspect, and referring to Figure 1 , there is provided a process for treating a silicate material 10. The silicate material is a solid material. The process includes contacting an operative metal material-comprising silicate material with at least
one halide ion-donating agent 18 so as to effect production of a pre-reduction operative metal material-comprising material 20.
[0019] An operative metal material is defined by at least one operative metallic element. In some embodiments, for example, the operative metal material is defined by two or more operative metallic elements, such that, in these embodiments, the at least one operative metallic element is two or more operative metallic elements. The operative metallic elements are defined by nickel, iron, and cobalt. In some embodiments, for example, the operative metal material is defined by nickel and iron. In some embodiments, for example, the operative metal material is defined by cobalt and nickel. In some embodiments, for example, the operative metal material is defined by cobalt and iron. In some embodiments, for example, the operative metal material is defined by nickel, cobalt and iron.
[0020] The operative metal material-comprising silicate material 10 includes the operative metal material to thereby define a silicate material-based operative metal material fraction.
[0021] The pre-reduction operative metal material-comprising material 20 includes a pre-reduction material-based operative metal material fraction that includes at least a fraction of the silicate material-based operative metal material fraction. In some embodiments, for example, the pre-reduction operative metal material-comprising material includes a pre-reduction material-based operative metal material fraction that is defined by at least a fraction of the silicate material -based operative metal material fraction.
[0022] The pre-reduction material-based operative metal material fraction includes at least one of the at least one operative metallic element of the operative metal material that defines the silicate material-based operative metal material fraction. In some of these embodiments, the pre-reduction material-based operative metal material fraction is defined by at least one of the at least one operative metallic element of the operative metal material that defines the silicate material-based operative metal material fraction.
[0023] In some embodiments, for example, the pre-reduction material-based operative metal material fraction includes each one of the at least one operative metallic element of the operative metal material that defines the silicate material-based operative metal material fraction. In some embodiments, for example, the pre-reduction material-based operative metal material fraction is defined by the at least one operative metallic element of the operative metal material that defines the silicate material-based operative metal material fraction.
[0024] When the operative metal material of the silicate material-based operative metal material fraction is defined by two or more operative metallic elements, in some embodiments, for example, the pre-reduction material-based operative metal material fraction includes at least two of the operative metallic elements. In some of these embodiments, for example, the pre-reduction material-based operative metal material fraction is defined by at least two of the operative metallic elements.
[0025] In some embodiments, for example, the halide ion is a chloride ion. In some of these embodiments, for example, one of the at least one halide ion donating agent is hydrochloric acid. Other suitable halide donating agents include calcium chloride and other halides of alkali and alkaline earth metals.
[0026] In some embodiments, for example, the contacting of an operative metal material-comprising silicate material 10 with at least one halide ion donating agent 18 is effected within a contacting zone 22, wherein, within the contacting zone, the ratio of [moles of halide ion of the at least one halide ion donating agent] to the [moles of the operative metal material] is between 0.5 and 15.
[0027] In some embodiments, for example, the contacting of an operative metal material-comprising silicate material 10 with at least one halide ion-donating agent 18 effects halidization of at least a fraction of the silicate material-based operative metal material fraction. Where the halide ion is chloride, the effected halidization is chloridization.
[0028] In some embodiments, for example, the at least one halide ion-donating agent is gaseous. In other embodiments, for example, the at least one halide ion-donating agent is disposed in a liquid (for example, aqueous) solution.
[0029] In some embodiments, for example, the contacting of an operative metal material-comprising silicate material 10 with at least one halide ion-donating agent 18 effects liberation of at least a fraction of the silicate material-based operative metal material fraction from the operative metal material-comprising silicate material.
[0030] In some embodiments, for example, the contacting of an operative metal material-comprising silicate material 10 with at least one halide ion-donating agent 18 is effected within a halide ion donating agent contacting zone 22 that is disposed at a temperature of at least 100 degrees Celsius and at a pressure of at least atmospheric pressure. In some embodiments, for example, the pressure within the contacting zone 22 is less than one (1) bar.
[0031] In some embodiments, for example, the pre-reduction operative metal material-comprising material 20 includes one or more respective halides of at least one of the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction. In some of these embodiments, for example, the pre-reduction operative metal material-comprising material includes one or more respective halides of each one of the at least one operative metallic elements of the operative metal material of the silicate material-based operative metal material fraction.
[0032] When the operative metal material of the operative metal material of the silicate material-based operative metal material fraction is defined by two or more operative metallic elements, in some embodiments, for example, the pre-reduction operative metal material-comprising material 20 includes one or more respective halides of at least two of the operative metallic elements of the operative metal material of the silicate material-based operative metal material fraction. In some of these embodiments, for example, the pre-reduction operative metal material-comprising material 20 includes one or more halides of each one of the operative metallic elements of the operative metal material of the silicate material-based operative metal material fraction.
[0033] After the contacting of a operative metal material-comprising silicate material 10 with at least one halide ion-donating agent 18 to effect production of a pre-reduction operative metal material-comprising material 20, the pre-reduction operative metal material-comprising material 20 is contacted with at least one reducing agent 24 so as to effect production of a pre-carbonylation operative metal material-comprising material 26. The pre-carbonylation operative metal material-comprising material 26 includes a pre- carbonylation material-based operative metal material fraction that includes at least a fraction of the pre-reduction material -based operative metal material. In some of these embodiments, for example, the pre-carbonylation operative metal material-comprising material includes a pre-carbonylation material-based operative metal material fraction that is defined by at least a fraction of the pre-reduction material-based operative metal material.
[0034] The pre-carbonylation material-based operative metal material fraction includes at least one of the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction. In some of these embodiments, for example, the pre-carbonylation material-based operative metal material fraction is defined by at least one of the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction. In some embodiments, for example, the pre-carbonylation material-based operative metal material fraction includes each one of the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction. In some embodiments, for example, the pre-carbonylation material-based operative metal material fraction is defined by the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction.
[0035] When the operative metal material of the silicate material-based operative metal material fraction is defined by two or more operative metallic elements, in some embodiments, for example, the pre-carbonylation material-based operative metal material fraction includes at least two of the operative metallic elements. In some embodiments, for example, the pre-carbonylation material-based operative metal material fraction is defined by at least two of the operative metallic elements.
[0036] In some embodiments, for example, when the contacting of an operative metal material-comprising silicate material 10 is with at least one halide ion-donating agent 18 that is disposed in a liquid solution (such as an aqueous solution), prior to the contacting of the pre-reduction operative metal material-comprising material 20 with at least one reducing agent 24, the material, produced from the contacting of an operative metal material-comprising silicate material 10 with at least one halide ion-donating agent 18, is subjected to drying 28 so as to effect separation of any solvent component which remains after the contacting of an operative metal material-comprising silicate material with at least one halide ion-donating agent that is disposed in a liquid solution. In some of these embodiments, for example, after the drying and prior to the contacting of the pre-reduction operative metal material-comprising material 20 with at least one reducing agent 24, the dried material is, in sequence, subjected to size reduction (for example, by grinding 16), and then separated into oversize and undersize fractions 30, 32 within a classifier 33, with the undersize fraction 32 defining the pre-reduction operative metal material-comprising material 20 which is subjected to the contacting with at least one reducing agent 24. In some embodiments, for example, the oversize fraction 30 may be recycled for further size reduction.
[0037] In some embodiments, for example, at least one of the at least one reducing agent is gaseous.
[0038] In some embodiments, for example, one of the at least one reducing agent is gaseous diatomic hydrogen.
[0039] In some embodiments, for example, the ratio of moles of atomic oxygen within the silicate material 10 to moles of the at least one reducing agent is at least 3: 1. In some embodiments, for example, this ratio is at least 5: 1.
[0040] In some embodiments, for example, the contacting of the pre-reduction operative metal material-comprising material 20 with at least one reducing agent 24 is effected within a reducing agent contacting zone 34 that is characterized by a temperature of less than 750 degrees Celsius. In some embodiments, for example, the reducing agent contacting zone is characterized by a temperature of between 550 degrees Celsius and 750
degrees Celsius. In some embodiments, for example, the reducing agent contacting zone is characterized by a pressure of between atmospheric pressure and one bar.
[0041] In some embodiments, for example, and referring to Figure 1, the contacting of an operative metal material-comprising silicate material 10 with at least one halide ion- donating agent 18 is effected in a separate contacting zone 22 from the contacting zone 34 in which the contacting of a pre-reduction operative metal material-comprising material 20 with at least one reducing agent 24 is effected. In some embodiments, for example, and referring to Figure 2, the contacting of a operative metal material-comprising silicate material 10 with at least one halide ion-donating agent 18 is effected in the same contacting zone 35 as that in which the contacting of a pre-reduction operative metal material-comprising material 20with at least one reducing agent 24 is effected.
[0042] In those embodiments where the contacting of an operative metal material- comprising silicate material 10 with at least one halide ion-donating agent 18 is effected in a separate contacting zone 22 from the contacting zone 34 in which the contacting of a prereduction operative metal material-comprising material 20 with at least one reducing agent 24 is effected, each one of the halide ion-donating agent is, independently, either gaseous or disposed in a liquid (for example, aqueous) solution.
[0043] In those embodiments where the contacting of an operative metal material- comprising silicate material 10 with at least one halide ion-donating agent 18 is effected in the same contacting zone 35 as that in which the contacting of a pre-reduction operative metal material-comprising material 20 with at least one reducing agent 24 is effected, both of: (i) the contacting of an operative metal material-comprising silicate material with at least one halide ion-donating agent, and (ii) the contacting of a pre-reduction operative metal material-comprising material with at least one reducing agent, is effected by supplying a reagent mixture including the at least one halide-ion donating agent and the at least one reducing agent to a contacting zone, and effecting contacting of the reagent mixture with the operative metal material-comprising silicate material. In some of these embodiments, for example, the contacting zone is characterized by a temperature of less than 750 degrees Celsius. In some of these embodiments, for example, the contacting zone
is characterized by a temperature of between 550 degrees Celsius and 750 degrees Celsius. In some of these embodiments, for example the contacting zone is characterized by a pressure of between atmospheric pressure and one bar. In those embodiments where the contacting zone is characterized by a temperature of between 550 degrees Celsius and 750 degrees Celsius, and a pressure of between atmospheric pressure and one bar, for example, the at least one halide-ion donating agent is gaseous.
[0044] In some embodiments, for example, the contacting of the pre-reduction operative metal material-comprising material 20 with at least one reducing agent 24 effects reduction of at least a fraction of the pre-reduction material-based operative metal material fraction
[0045] In some embodiments, for example, the pre-carbonylation material-based operative metal material fraction 26 includes at least a fraction of at least a fraction of the pre-reduction material-based operative metal material fraction that is defined by the silicate material-based operative metal material fraction that has been halidized by the contacting of a operative metal material-comprising silicate material 10 with at least one halide ion- donating agent 18.
[0046] After the contacting of the pre-reduction operative metal material-comprising material 20 with at least one reducing agent 24 so as to effect production of a pre- carbonylation operative metal material-comprising material 26, at least a fraction of the pre-carbonylation material-based operative metal material fraction 26 is carbonylated. The carbonylation is effected in a carbonylation zone 38.
[0047] In this respect, in another related aspect, there is provided a process for treating metallic material, comprising carbonylating at least a fraction of the pre- carbonylation material-based operative metal material fraction.
[0048] In some embodiments, for example, the carbonylation effects production of a post-carbonylation gaseous mixture 40. In some embodiments, for example, the carbonylation is effected by contacting of the pre-carbonylation operative metal material- comprising material with a carbonylation agent 42, such as carbon monoxide.
[0049] In some embodiments, the post-carbonylation gaseous mixture includes a post-carbonylation gaseous mixture-based operative metal material fraction, wherein the post-carbonylation gaseous mixture-based operative metal material fraction includes at least a fraction of the pre-carbonylation material-based operative metal material fraction. In some of these embodiments, for example, the post-carbonylation gaseous mixture-based operative metal material fraction is defined by at least a fraction of the pre-carbonylation material-based operative metal material fraction.
[0050] The post-carbonylation gaseous mixture-based operative metal material fraction includes at least one of the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction. In some of these embodiments, for example, the post-carbonylation gaseous mixture-based operative metal material fraction is defined by at least one of the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction.
[0051] In some embodiments, for example, the post-carbonylation gaseous mixture- based operative metal material fraction includes each one of the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction. In some of these embodiments, for example, the post- carbonylation gaseous mixture-based operative metal material fraction is defined by the at least one operative metallic element of the operative metal material of the silicate material- based operative metal material fraction.
[0052] When the operative metal material of the silicate material-based operative metal material fraction is defined by two or more operative metallic elements, in some embodiments, for example, the post-carbonylation gaseous mixture-based operative metal material fraction includes at least two of the operative metallic elements. In some of these embodiments, for example, the post-carbonylation gaseous mixture-based operative metal material fraction is defined by at least two of the operative metallic elements.
[0053] In some embodiments, for example, the post-carbonylation gaseous mixture 40 includes one or more respective carbonyls of at least one of the at least one operative
metallic element of the operative metal material of the silicate material-based operative metal material fraction. In some of these embodiments, for example, the post- carbonylation gaseous mixture 40 includes one or more respective carbonyls of each one of the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction.
[0054] When the operative metal material of the silicate material-based operative metal material fraction is defined by two or more operative metallic elements, in some embodiments, for example, the post-carbonylation gaseous mixture 40 includes one or more respective carbonyls of at least two of the operative metallic elements of the operative metal material of the silicate material-based operative metal material fraction. In some of these embodiments, for example, the post-carbonylation gaseous mixture 40 includes one or more carbonyls of each one of the operative metallic elements of the operative metal material of the silicate material-based operative metal material fraction.
[0055] In some embodiments, for example, after the carbonylating of at least a fraction of the pre-carbonylation material-based operative metal material fraction, separation, from the post-carbonylation gaseous mixture 40, of a relatively more volatile fraction 44 and of a relatively less volatile fraction 46 is effected. In some embodiments, for example, a plurality of fractions may be separated from the post-carbonylation gaseous mixture, each one of the fractions including a respective volatility that is different from the respective volatility of every other one of the fractions. The separation is based on the relative volatility as between each one of the separated fractions. In some embodiments, for example, the separation includes fractional distillation 48. The concentration of one of the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction is greater within one of the relatively more volatile fraction and the relatively less volatile fraction than within the other one of the relatively more volatile fraction and the relatively less volatile fraction.
[0056] When the operative metal material of the silicate material-based operative metal material fraction is defined by two or more operative metallic elements, and the post- carbonylation gaseous mixture-based operative metal material fraction includes, or is
defined by, at least two of the operative metallic elements, in some embodiments, for example, the relatively more volatile fraction 44 includes a relatively more volatile fraction-based operative metal material fraction and the relatively less volatile fraction 46 includes a relatively less volatile fraction-based operative metal material fraction. Each one of the relatively more volatile fraction-based operative metal material fraction and the relatively less volatile fraction-based operative metal material fraction includes a corresponding fraction of the post-carbonylation gaseous mixture-based operative metal material fraction. In some of these embodiments, for example, each one of the relatively more volatile fraction-based operative metal material fraction and the relatively less volatile fraction-based operative metal material fraction is defined by a corresponding fraction of the post-carbonylation gaseous mixture-based operative metal material fraction. Each one of the relatively more volatile fraction-based operative metal material fraction and the relatively less volatile fraction-based operative metal material fraction includes, and, in some embodiments, is defined by, independently, at least one of the two or more operative metallic elements of the post-carbonylation gaseous mixture-based operative metal material fraction, such that, for the relatively more volatile fraction-based operative metal material fraction, at least one relatively more volatile fraction-based operative metallic element is thereby defined, and for the relatively less volatile fraction-based operative metal material fraction, at least one relatively less volatile fraction-based operative metallic element is thereby defined. In some embodiments, the at least one relatively more volatile fraction-based operative metallic element is the same as the at least one relatively less volatile fraction-based operative metallic element. In some embodiments, the at least one relatively more volatile fraction-based operative metallic element is different from the at least one relatively less volatile fraction-based operative metallic element. The ratio, of moles of one of the two or more operative metallic elements of the post-carbonylation gaseous mixture-based operative metal material fraction to moles of another one of the two or more operative metallic elements of the post- carbonylation gaseous mixture-based operative metal material fraction is greater within one of the relatively more volatile fraction 44 and the relatively less volatile fraction 46 than within the other one of the relatively more volatile fraction 44 and the relatively less volatile fraction 46.
[0057] When the operative metal material of the silicate material-based operative metal material fraction is defined by two or more operative metallic elements, and the post- carbonylation gaseous mixture-based operative metal material fraction includes, and, in some embodiments, is defined by, at least two of the operative metallic elements, in some embodiments, for example, the post carbonylation gaseous mixture includes a relatively more volatile metal carbonyl and a relatively less volatile metal carbonyl, wherein each one of the relatively more volatile metal carbonyl and the relatively less volatile metal carbonyl includes, independently, at least one of the at least two operative metallic elements of the post-carbonylation gaseous mixture-based operative metal material fraction. In some embodiments, for example, the ratio of moles of the one or more operative metallic elements respective to the more volatile metal carbonyl to the moles of the one or more operative metallic elements respective to the less volatile metal carbonyl is greater within the relatively more volatile fraction 44 than within the relatively less volatile fraction 46.
[0058] When the operative metal material includes nickel and iron, and the post- carbonylation gaseous mixture 40 includes nickel carbonyl and iron carbonyl, in some embodiments, for example, the ratio of moles of nickel to moles of iron is greater within the relatively more volatile fraction 44 than within the relatively less volatile fraction 46.
[0059] In some embodiments, for example, at least one of the relatively more volatile fraction 44 and the relatively less volatile fraction 46 is subjected to thermal decomposition in a respective decomposition zone 50, 52 to effect recovery of the pure form of its respective operative metallic elements 54, 56.
[0060] In some embodiments, for example, when the operative metal material includes nickel and iron, and the post-carbonylation gaseous mixture 40 includes nickel carbonyl and iron carbonyl, the relatively more volatile fraction 44 is a nickel carbonyl- rich fraction and the relatively less volatile fraction 46 is an iron carbonyl-rich fraction. Each of the iron carbonyl-rich fraction 46 and the nickel carbonyl-rich fraction 44 is supplied to a respective decomposition zone 52, 50, so as to effect its respective decomposition into a substantially pure form of the respective metal (ie. iron carbonyl of
the iron carbonyl-rich fraction 46 is decomposed within its respective decomposition zone 52 so as to produce substantially pure iron 56, and nickel carbonyl of the nickel carbonyl- rich fraction 44 is decomposed within its respective decomposition zone 50 so as to produce substantially pure nickel 54). In some embodiments, for example, each of the decomposition zones is disposed at a temperature of between 220 degrees Celsius and 500 degrees Celsius, which is sufficient to effect the decompositions.
[0061] In some embodiments, for example, the carbonylation additionally effects production of a solid residue. In some of these embodiments, for example, the solid residue includes other desirable metallic elements, such as copper and cobalt. In some of these embodiments, recovery of these other desirable metallic elements, from the solid residue, is effected, for example, by magnetic separation.
Second aspect
[0062] In another aspect, and referring to Figure 3, there is provided a process for treating silicate material, and the process includes contacting an operative metal material- comprising silicate material 10 with a reagent mixture 25 so as to effect production of a pre-carbonylation operative metal material-comprising material 26. The reagent mixture 25 includes at least one halide ion-donating agent and at least one reducing agent.
[0063] An operative metal material is defined by at least one operative metallic element. In some embodiments, for example, the operative metal material is defined by two or more operative metallic elements, such that, in these embodiments, the at least one operative metallic element is two or more operative metallic elements. The operative metallic elements are defined by nickel, iron, and cobalt. In some embodiments, for example, the operative metal material is defined by nickel and iron. In some embodiments, for example, the operative metal material is defined by cobalt and nickel. In some embodiments, for example, the operative metal material is defined by cobalt and iron. In some embodiments, for example, the operative metal material is defined by nickel, cobalt and iron.
[0064] The operative metal material-comprising silicate material 10 includes the operative metal material to thereby define a silicate material-based operative metal material fraction. The pre-carbonylation operative metal material-comprising material 26 includes a pre-carbonylation material-based operative metal material fraction that includes at least a fraction of the silicate material-based operative metal material. In some embodiments, for example, the pre-carbonylation operative metal material-comprising material 26 includes a pre-carbonylation material-based operative metal material fraction that is defined by at least a fraction of the silicate material-based operative metal material.
[0065] In some embodiments, for example, the at least one halide ion-donating agent is gaseous.
[0066] In some embodiments, for example, the halide ion is a chloride ion. In some of these embodiments, for example, one of the at least one halide ion donating agent is hydrochloric acid. Other suitable halide donating agents include calcium chloride and other halides of alkali and alkaline earth metals.
[0067] In some embodiments, for example, the at least one reducing agent is gaseous.
[0068] In some embodiments, for example, one of the at least one reducing agent is diatomic hydrogen.
[0069] In some embodiments, for example, the contacting of a operative metal material-comprising silicate material 10 and the reagent mixture 25 is effected within a reagent mixture contacting zone 351. In some of these embodiments, within the reagent mixture contacting zone 351 , the ratio of [moles of halide ion of the at least one halide ion donating agent] to the [moles of the operative metal material] is between 0.5 and 15. In some of these embodiments, for example, the ratio of moles of atomic oxygen within the operative metal material-comprising silicate material 10 to moles of the at least one reducing agent is at least 3: 1. In some embodiments, for example, this ratio is 5 : 1.
[0070] In some embodiments, for example, the contacting is effected within a reagent mixture contacting zone 351 that is characterized by a temperature of less than 750 degrees Celsius. In some embodiments, for example, the reagent mixture contacting zone is
characterized by a temperature of between 550 degrees Celsius and 750 degrees Celsius. In some embodiments, for example, the reagent mixture contacting zone 351 is characterized by a pressure of between atmospheric pressure and one bar.
[0071] The pre-carbonylation material-based operative metal material fraction includes at least one of the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction. In some of these embodiments, for example, the pre-carbonylation material-based operative metal material fraction is defined by at least one of the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction. In some embodiments, for example, the pre-carbonylation material-based operative metal material fraction includes each one of the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction. In some embodiments, for example, the pre-carbonylation material-based operative metal material fraction is defined by the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction.
[0072] When the operative metal material of the silicate material-based operative metal material fraction is defined by two or more operative metallic elements, in some embodiments, for example, the pre-carbonylation material-based operative metal material fraction includes at least two of the operative metallic elements. In some embodiments, for example, the pre-carbonylation material-based operative metal material fraction is defined by at least two of the operative metallic elements.
[0073] After the contacting of the operative metal material-comprising silicate material 10 with a reagent mixture 25 so as to effect production of a pre-carbonylation operative metal material-comprising material 26, at least a fraction of the pre-carbonylation material-based operative metal material fraction is carbonylated. The carbonylation is effected in a carbonylation zone 38.
[0074] In this respect, in another related aspect, there is provided a process for treating metallic material, comprising carbonylating at least a fraction of the pre- carbonylation material-based operative metal material fraction.
[0075] In some embodiments, for example, the carbonylation effects production of a post-carbonylation gaseous mixture 40. In some embodiments, for example, the carbonylation is effected by contacting of the pre-carbonylation operative metal material- comprising material 26 with a carbonylation agent 42, such as carbon monoxide.
[0076] In some embodiments, the post-carbonylation gaseous mixture 40 includes a post-carbonylation gaseous mixture-based operative metal material fraction, wherein the post-carbonylation gaseous mixture-based operative metal material fraction includes at least a fraction of the pre-carbonylation material-based operative metal material fraction. In some of these embodiments, for example, the post-carbonylation gaseous mixture-based operative metal material fraction is defined by at least a fraction of the pre-carbonylation material-based operative metal material fraction.
[0077] The post-carbonylation gaseous mixture-based operative metal material fraction includes at least one of the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction. In some of these embodiments, for example, the post-carbonylation gaseous mixture-based operative metal material fraction is defined by at least one of the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction.
[0078] In some embodiments, for example, the post-carbonylation gaseous mixture- based operative metal material fraction includes each one of the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction. In some of these embodiments, for example, the post- carbonylation gaseous mixture-based operative metal material fraction is defined by the at least one operative metallic element of the operative metal material of the silicate material- based operative metal material fraction.
[0079] When the operative metal material of the silicate material-based operative metal material fraction is defined by two or more operative metallic elements, in some embodiments, for example, the post-carbonylation gaseous mixture-based operative metal material fraction includes at least two of the operative metallic elements. In some of these
embodiments, for example, the post-carbonylation gaseous mixture-based operative metal material fraction is defined by at least two of the operative metallic elements.
[0080] In some embodiments, for example, the post-carbonylation gaseous mixture 40 includes one or more respective carbonyls of at least one of the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction. In some of these embodiments, for example, the post- carbonylation gaseous mixture includes one or more respective carbonyls of each one of the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction.
[0081] When the operative metal material of the silicate material-based operative metal material fraction is defined by two or more operative metallic elements, in some embodiments, for example, the post-carbonylation gaseous mixture 40 includes one or more respective carbonyls of at least two of the operative metallic elements of the operative metal material of the silicate material-based operative metal material fraction. In some of these embodiments, for example, the post-carbonylation gaseous mixture 40 includes one or more carbonyls of each one of the operative metallic elements of the operative metal material of the silicate material-based operative metal material fraction.
[0082] In some embodiments, for example, after the carbonylating of at least a fraction of the pre-carbonylation material-based operative metal material fraction, separation, from the post-carbonylation gaseous mixture 40, of a relatively more volatile fraction 44 and of a relatively less volatile fraction 46 is effected. In some embodiments, for example, a plurality of fractions may be separated from the post-carbonylation gaseous mixture, each one of the fractions including a respective volatility that is different from the respective volatility of every other one of the fractions. The separation is based on the relative volatility as between each one of the separated fractions. In some embodiments, for example, the separation includes fractional distillation 48. The concentration of one of the at least one operative metallic element of the operative metal material of the silicate material-based operative metal material fraction is greater within one of the relatively more
volatile fraction 44 and the relatively less volatile fraction 46 than within the other one of the relatively more volatile fraction 44 and the relatively less volatile fraction 46.
[0083] When the operative metal material of the silicate material-based operative metal material fraction is defined by two or more operative metallic elements, and the post- carbonylation gaseous mixture-based operative metal material fraction includes, or is defined by, at least two of the operative metallic elements, in some embodiments, for example, the relatively more volatile fraction 44 includes a relatively more volatile fraction-based operative metal material fraction and the relatively less volatile fraction 46 includes a relatively less volatile fraction-based operative metal material fraction. Each one of the relatively more volatile fraction-based operative metal material fraction and the relatively less volatile fraction-based operative metal material fraction includes a corresponding fraction of the post-carbonylation gaseous mixture-based operative metal material fraction. In some of these embodiments, for example, each one of the relatively more volatile fraction-based operative metal material fraction and the relatively less volatile fraction-based operative metal material fraction is defined by a corresponding fraction of the post-carbonylation gaseous mixture-based operative metal material fraction. Each one of the relatively more volatile fraction-based operative metal material fraction and the relatively less volatile fraction-based operative metal material fraction includes, and, in some embodiments, is defined by, independently, at least one of the two or more operative metallic elements of the post-carbonylation gaseous mixture-based operative metal material fraction, such that, for the relatively more volatile fraction-based operative metal material fraction, at least one relatively more volatile fraction-based operative metallic element is thereby defined, and for the relatively less volatile fraction-based operative metal material fraction, at least one relatively less volatile fraction-based operative metallic element is thereby defined. In some embodiments, the at least one relatively more volatile fraction-based operative metallic element is the same as the at least one relatively less volatile fraction-based operative metallic element. In some embodiments, the at least one relatively more volatile fraction-based operative metallic element is different from the at least one relatively less volatile fraction-based operative metallic element. The ratio, of moles of one of the two or more operative metallic elements of the post-carbonylation gaseous mixture-based operative metal material fraction
to moles of another one of the two or more operative metallic elements of the post- carbonylation gaseous mixture-based operative metal material fraction is greater within one of the relatively more volatile fraction 44 and the relatively less volatile fraction 46 than within the other one of the relatively more volatile fraction 44 and the relatively less volatile fraction 46.
[0084] When the operative metal material of the silicate material-based operative metal material fraction is defined by two or more operative metallic elements, and the post- carbonylation gaseous mixture-based operative metal material fraction includes, and, in some embodiments, is defined by, at least two of the operative metallic elements, in some embodiments, for example, the post carbonylation gaseous mixture 40 includes a relatively more volatile metal carbonyl and a relatively less volatile metal carbonyl, wherein each one of the relatively more volatile metal carbonyl and the relatively less volatile metal carbonyl includes, independently, at least one of the at least two operative metallic elements of the post-carbonylation gaseous mixture-based operative metal material fraction. In some embodiments, for example, the ratio of moles of the one or more operative metallic elements respective to the more volatile metal carbonyl to the moles of the one or more operative metallic elements respective to the less volatile metal carbonyl is greater within the relatively more volatile fraction 44 than within the relatively less volatile fraction 46.
[0085] When the operative metal material includes nickel and iron, and the post- carbonylation gaseous mixture 40 includes nickel carbonyl and iron carbonyl, in some embodiments, for example, the ratio of moles of nickel to moles of iron is greater within the relatively more volatile fraction 44 than within the relatively less volatile fraction 46.
[0086] In some embodiments, for example, at least one of the relatively more volatile fraction 44 and the relatively less volatile fraction 46 is subjected to thermal decomposition in a respective decomposition zone 50, 52 to effect recovery of the pure form of its respective operative metallic elements.
[0087] In some embodiments, for example, when the operative metal material includes nickel and iron, and the post-carbonylation gaseous mixture 40 includes nickel
carbonyl and iron carbonyl, the relatively more volatile fraction 44 is a nickel carbonyl- rich fraction and the relatively less volatile fraction 46 is an iron carbonyl-rich fraction. Each of the iron carbonyl-rich fraction 46 and the nickel carbonyl-rich fraction 44 is supplied to a respective decomposition zone 52, 50, so as to effect its respective decomposition into a substantially pure form of the respective metal (ie. iron carbonyl of the iron carbonyl-rich fraction 46 is decomposed within its respective decomposition zone 52 so as to produce substantially pure iron 56, and nickel carbonyl of the nickel carbonyl- rich fraction 44 is decomposed within its respective decomposition zone 50 so as to produce substantially pure nickel 54). In some embodiments, for example, each of the decomposition zones is disposed at a temperature of between 220 degrees Celsius and 500 degrees Celsius, which is sufficient to effect the decompositions.
[0088] In some embodiments, for example, the carbonylation additionally effects production of a solid residue. In some of these embodiments, for example, the solid residue includes other desirable metallic elements, such as copper and cobalt. In some of these embodiments, recovery of these other desirable metallic elements, from the solid residue, is effected, for example, by magnetic separation.
[0089] There will now be described several non-limitative examples.
Examples
[0090] Example #1 :
34.4g of Chloride was mixed with 30g of Saprolite and pass through 20 mesh screen. This material was reduced at 600-800°C in Hydrogen reducing atmosphere. The reduced material was then Carbonylated at 120-160°C and 450-750 psi Carbon Monoxide pressure for 72 hours. 97% Nickel and 85% Iron, by weight, was extracted from the feed material.
[0091] Example #2:
The Example #1 was repeated to see the repeatability of the method, and 96% of Nickel and 84% of Iron, by weight, was extracted from the feed material.
[0092] Example #3:
34.4g of Chloride was mixed with 60g of Saprolite and passed through 20 mesh screen. This material was reduced at 600-800°C in Hydrogen reducing atmosphere. The reduced material was then carbonylated at 120-160°C and 450-750 psi Carbon Monoxide pressure for around 72 hours. 91% Nickel and 58% Iron, by weight, was extracted from the feed material.
[0093] Example #4:
17.2g of Chloride was mixed with 60g of Saprolite and passed through 20 mesh screen. This material was reduced at 600-800°C in Hydrogen reducing atmosphere. The reduced material was then Carbonylated at 120-160°C and 450-750 psi Carbon Monoxide pressure for around 72 hours. 85% Nickel and 25% Iron, by weight, was extracted from the feed material.
[0094] Example #5:
4.3g of Chloride was mixed with 60g of Saprolite and pass through 20 mesh screen. This material was reduced at 600-800°C in Hydrogen reducing atmosphere. The reduced material was then carbonylated at 120-160°C and 450-750 psi Carbon Monoxide pressure for around 72 hours. 68% Nickel and 5% Iron, by weight, was extracted from the feed material.
Table 1 , below, provides all the test results, and Figure 4 illustrates the effect of chloride addition on nickel and iron extraction from saprolite.
Ratio
Nickel Iron
Test # cr
Extraction Extraction
/Feed
1 1.15 97% 85%
2 1.15 96% 84%
3 0.57 91% 58%
4 0.29 85% 25%
5 0.07 68% 5%
[0095] In the above description, for purposes of explanation, numerous details are set forth in order to provide a thorough understanding of the present disclosure. However, it will be apparent to one skilled in the art that these specific details are not required in order to practice the present disclosure. Although certain dimensions and materials are described for implementing the disclosed example embodiments, other suitable dimensions and/or materials may be used within the scope of this disclosure. All such modifications and variations, including all suitable current and future changes in technology, are believed to be within the sphere and scope of the present disclosure. All references mentioned are hereby incorporated by reference in their entirety.