Patent Application
20210070624
A method for controlling the concentration of impurities in Bayer liquors.
The Bayer process is widely used for the production of alumina from alumina containing ores, such as bauxite. The process involves contacting alumina containing ores with recycled caustic aluminate solutions, at elevated temperatures, in a process commonly referred to as digestion. Solids are removed from the resulting slurry, and the solution cooled.
Aluminium hydroxide is added to the solution as seed to induce the precipitation of further aluminium hydroxide therefrom. The precipitated aluminium hydroxide is separated from the caustic aluminate solution, with a portion of the aluminium hydroxide being recycled to be used as seed and the remainder recovered as product. The remaining caustic aluminate solution is recycled for further digestion of alumina containing ore.
Bauxite ore generally contains inorganic impurities, the amounts of which are specific to the bauxite source. As aluminium hydroxide is precipitated and bauxite dissolved, the concentrations of sodium hydroxide present in the process solution decrease, whilst concentrations of impurities increases, reducing the efficacy of the solution for digestion of further aluminium-containing ore. Accordingly, processes aimed at removing impurities from Bayer liquors have been developed.
Alumina refineries have developed numerous methods to address impurities in liquors and reduce their build up. Most impurity removal techniques are specific to the impurity in question, thereby complicating the entire circuit. For example, silicon may be removed via precipitation of desilication product, phosphorus by the addition of lime to form hydroxyapatite and vanadium by the formation of fluovanadate salts.
Layered Double Hydroxides (LDHs) are a family of lamellar minerals composed of positively charged layers charge balanced with hydrated weakly bound anions located in the interlayer spaces. Most LDHs are binary systems where the charge on the layers is due to the substitution of some of the divalent cation sites within the lattice by mono- and/or tri-valent cations, giving a general formula of:
[MII1-xMIIIx(OH)2]q+(An−)x/n.yH2O or
[MIMIII2(OH)6](An−)1/n.yH2O
where MI, MII and MIII represents the mono-, di- and tri-valent metal cations within the layers respectively and A represents the interlayer anion(s).
In the above formula, ‘A’ may be mono-, di- or multi-valent as long as the overall charge of the structure is neutral.
The most common naturally occurring LDHs are members of the Hydrotalcite (HTC) group, characterised by M2+:M3+=3:1. The name-sake of this group, hydrotalcite, is a Mg—Al structure and has the general formula of [Mg3Al(OH)6]2.X.nH2O, where ‘X’ represents the charge balancing anion(s).
Another group of LDHs referred to in this specification is the Hydrocalumite (HCM) group, which is characterised by M2+:M3+=Ca2+:Al3+=2:1. Hydrocalumite has the general formula of [Ca2Al(OH)6]x.X.nH2O, where ‘X’ is more specifically, one formula unit of a singly charged anion or half of a doubly charged anion. It will be appreciated that this is a general formula only and that X may be a combination of anions.
Throughout the specification, unless the context requires otherwise, the word “comprise” or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.
Throughout the specification, unless the context requires otherwise, the word “solution” or variations such as “solutions”, will be understood to encompass slurries, suspensions and other mixtures containing undissolved solids.
The preceding discussion of the background to the invention is intended to facilitate an understanding of the present invention. However, it should be appreciated that the discussion is not an acknowledgement or admission that any of the material referred to was part of the common general knowledge in Australia or any other country as at the priority date.
In accordance with the present invention, there is provided a method for controlling the concentration of impurities in Bayer liquors, the method comprising the steps of:
In accordance with the present invention, there is provided a method for controlling the concentration of impurities in Bayer liquors, the method comprising the steps of:
An important property of a Bayer liquor is its alkalinity, the total amount of alkali chemicals in the liquor. Most of the liquor alkalinity comes from the sodium hydroxide present, the other major contributor being sodium carbonate. The total alkalinity of a Bayer liquor is commonly described in terms of its TA which is measured in gL−1 expressed as Na2CO3.
In the context of the present invention, the term incorporation shall be understood to include intercalation of impurities and adsorption of impurities.
It will be appreciated that the impurities may exist in many forms in a Bayer liquor, including as oxyanions.
Preferably, the desired TA is less than 160 gL−1.
In one form of the invention, the method comprises the further step of monitoring the concentration of at least one impurity in a Bayer circuit. Monitoring the concentration of at least one impurity in a Bayer circuit may comprise measuring the concentration of at least one impurity at any location within the Bayer circuit.
In one form of the invention, the method comprises the further step of measuring the concentration of at least one impurity in the Bayer liquor with a desired TA.
In one form of the invention, the method comprises the further step of:
In one form of the invention, the method comprises the further step of:
In one form of the invention, the method comprises the further step of:
Advantageously, the concentration of at least one impurity in the Bayer liquor after the formation of the layered double hydroxide is less than the concentration of at least one impurity prior to the step of adding an oxide and/or a hydroxide of a metal other than aluminium to a Bayer liquor.
In one form of the invention, the method comprises the step of:
obtaining a Bayer liquor with a desired TA.
In one form of the invention, the method comprises the step of:
treating the Bayer liquor to provide a Bayer liquor with a desired TA.
The Bayer liquor may be treated prior to the step of adding an oxide and/or a hydroxide of a metal other than aluminium to the Bayer liquor, to reduce the TA of the Bayer liquor. Treatment of the Bayer liquor to reduce the TA may include dilution the Bayer liquor with water or a second Bayer liquor.
In one form of the invention, the method comprises the further step of:
Advantageously, the degree of incorporation of at least one impurity increases with liquor dilution.
In one form of the invention, the TA is set to a predetermined value to maximise the incorporation of at least one target impurity.
In one form of the invention, the step of incorporating at least one impurity in said layered double hydroxide results in a reduction of the concentration of the at least one impurity of at least 10%. In one form of the invention, the step of incorporating at least one impurity in said layered double hydroxide results in a reduction of the concentration of the at least one impurity of at least 20%. In one form of the invention, the step of incorporating at least one impurity in said layered double hydroxide results in a reduction of the concentration of the at least one impurity of at least 30%. In one form of the invention, the step of incorporating at least one impurity in said layered double hydroxide results in a reduction of the concentration of the at least one impurity of at least 40%. In one form of the invention, the step of incorporating at least one impurity in said layered double hydroxide results in a reduction of the concentration of the at least one impurity of at least 50%. In one form of the invention, the step of incorporating at least one impurity in said layered double hydroxide results in a reduction of the concentration of the at least one impurity of at least 60%. In one form of the invention, the step of incorporating at least one impurity in said layered double hydroxide results in a reduction of the concentration of the at least one impurity of at least 70%. In one form of the invention, the step of incorporating at least one impurity in said layered double hydroxide results in a reduction of the concentration of the at least one impurity of at least 80%. In one form of the invention, the step of incorporating at least one impurity in said layered double hydroxide results in a reduction of the concentration of the at least one impurity of at least 90%.
The inventors have identified that when the TA of the Bayer liquor is below 160 gL−1, it is possible to incorporate phosphorus, silicon and vanadium into layered double hydroxides thereby removing them from the Bayer liquor. The degree of incorporation increases as the TA is reduced. The present invention makes it possible to target and remove these impurities in Bayer liquors. Under certain conditions, it is possible to remove these impurities in preference to other impurities.
In one form of the invention, the method comprises the further step of:
prior to the step of:
Preferably, the step of:
Preferably, the at least one impurity added to the Bayer liquor is the same as the at least one impurity incorporated into the layered double hydroxide.
In one form of the invention, the method comprises the further step of:
Preferably, the impurity depleted liquor is returned to the Bayer circuit.
In preferred forms of the invention, the formation of a layered double hydroxide under the conditions of the desired TA facilitates the incorporation of at least one impurity over at least one other impurity.
In the context of the present specification, the term facilitate shall not be limited to the incorporation of one impurity to the exclusion of others.
In preferred forms of the invention, the desired TA favours the incorporation of at least one impurity over at least one other impurity.
In the context of the present specification, the term favour shall not be limited to the incorporation of one impurity to the exclusion of others.
It will be appreciated that the step of incorporating at least one impurity in said layered double hydroxide will not necessarily mean that all of said impurity in the Bayer liquor is incorporated into said layered double hydroxide.
Preferably, the Bayer liquor is a washer overflow, diluted spent liquor, diluted green liquor or lakewater.
It will be appreciated that the oxide and/or a hydroxide of a metal other than aluminium will need to be one that can form a layered double hydroxide. In preferred forms of the invention, the metal other than aluminium is selected from the group comprising calcium and magnesium.
Preferably, the layered double hydroxide is hydrocalumite and/or hydrotalcite.
Preferably, the metal oxide other than aluminium is calcium hydroxide. Preferably, the calcium hydroxide is prepared by slaking calcium oxide. Preferably, the calcium oxide is slaked in lakewater. It will be appreciated that the addition of slaked lime to the Bayer liquor will decrease the TA of said liquor.
It will be appreciated that the lime charge will be dependent on the liquor type and concentration. While it is desirable to maximise the conversion to hydrocalumite, care should be taken not to deplete the liquor of alumina or carbonate.
In one form of the invention, the Bayer liquor has a TA less than 100 gL−1. In an alternate form of the invention, the Bayer liquor has a TA less than 75 gL−1.
In an alternate form of the invention, the Bayer liquor has a TA between 50 and 100 gL−1.
It will be appreciated that the desired TA will be influenced by the choice of liquor. Where the liquor is a washer overflow, diluted spent liquor or diluted green liquor, the TA is preferably between 50 and 75 gL−1. Where the liquor is a lakewater, the TA is preferably less than 50 gL−1.
Given that the incorporation of phosphorous, silicon and vanadium ions are favoured by lower TA's, it is possible using the method of the present invention to target these impurities over others in Bayer liquors.
Advantageously, the present invention allows a user to choose a TA that provides the best absolute or relative removal of at least one impurity over at least one other impurity.
Advantageously, the method of the present invention provides the vehicle to remove target impurities in Bayer liquors. To date, this has not been achievable as the relationship of impurity incorporation in layered double hydroxides with TA was not known. By controlling the TA of the Bayer liquor it is now possible to change the selectivities of layered double hydroxides for some impurities.
The method of the present invention may be used to prepare impurity-substituted layered double hydroxides.
Further features of the present invention are more fully described in the following description of several non-limiting embodiments thereof. This description is included solely for the purposes of exemplifying the present invention. It should not be understood as a restriction on the broad summary, disclosure or description of the invention as set out above. The description will be made with reference to the accompanying drawings in which:
Throughout this specification, unless the context requires otherwise, the word “comprise” or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.
Those skilled in the art will appreciate that the invention described herein is amenable to variations and modifications other than those specifically described. It is to be understood that the invention includes all such variations and modifications. The invention also includes all of the steps, features, compositions and compounds referred to or indicated in the specification, individually or collectively and any and all combinations or any two or more steps or features.
To further describe the invention, a series of experiments will now be described. It must be appreciated that the following description of the experiments is not to limit the generality of the above description of the invention.
Experiments were conducted in 3 L stainless steel water jacketed vessels with constant stirring at 1000 RPM. The temperature was maintained at 60° C. and the vessels contained baffles to ensure good mixing. The duration of each experiment was one hour.
Liquors from three alumina refineries (hereinafter the 1st Refinery, the 2nd Refinery and the 3rd Refinery) were used and slaked lime was sourced from the 2nd Refinery. The slaked lime typically had a solids concentration of 250 gL−1 with an available CaO content of approximately 56%. This lime had been produced by slaking in 2nd Refinery lakewater.
The ratios of lime to liquor were kept constant and the TA was varied by changing the amount of distilled water added to the reaction mixture. The total reaction volume was approximately 2 L.
The concentration of impurity in the original spent liquor and the exit liquor was determined by ICP-OES. The amount of the impurities removed was calculated from a mass balance of the total impurities in the feed streams (liquor and lake water from slaked lime) compared to the total impurities present in the exit liquor. The difference between the feed and exit was assumed to be due to incorporation into the hydrocalumite. Due to a significant volume change during the reaction, an internal standard had to be used to determine volume of the exit liquor. Sodium malonate was used as the internal standard as it is not incorporated into the hydrocalumite.
The effect of TA on the uptake of P2O5, SiO2 and V2O5 was investigated with spent liquors from all three refineries and green liquor from the 1st refinery.
The concentration of lime added to the reaction mixture was 100 g CaOL−1 of spent liquor for the 1st refinery (both spent and green liquors) and the 2nd refinery experiments, and 125 g CaOL−1 of spent liquor from the 3rd refinery. The total liquid volume was approximately 2 L (liquor plus distilled water plus lime slurry lake water [88% of lime slurry volume]).
This sample of 1st refinery spent liquor had a TA of 262 gL−1 (as Na2CO3). This liquor was diluted according to Table 1, to produce a series of liquors with decreasing TA. The actual TA of the reaction mixtures (reaction TA) was less than the water dilution alone due to the extra dilution caused by the lake water contained in the lime slurry. The lime slurry added was proportional to the original feed spent liquor added, which is why the lime slurry volume and lime concentration in the reactor decreases through the experimental runs. The CaO added was relatively constant when proportioned to the feed liquor (approximately 104 gL−1).
The concentration of P2O5 and SiO2 in the feed liquor was 168 mgL−1 and 715 mgL−1. The percentage removed at the lowest TA was 75% for P2O5 and 67% for SiO2. In the lowest TA run, there were small amounts of P2O5 and SiO2 left in the product liquor at the end of the experiment (4.6 mgL−1 P2O5 and 25.7 mgL−1 SiO2 remaining).
The uptake of SiO2 and P2O5 was also tested in 2nd refinery spent liquor (see Table 2 for liquor conditions), showing a similar increase in uptake with decreasing TA (
In this liquor, the concentration of P2O5 was 149 mgL−1 and the concentration of SiO2 was 765 mgL−1 with 70% and 63% of the impurities removed at the lowest TA run. SiO2 uptake was higher in the 2nd refinery liquor than the 1st refinery liquor which agrees with the concentration of SiO2 in the starting liquors with the 2nd refinery liquor having a higher SiO2 concentration (765 mgL−1 vs 715 mgL−1). Uptakes were similar for P2O5 where 1st refinery had a slightly higher P2O5 concentration compared to the 2nd refinery, 168 mgL−1 vs 149 mgL−1.
The experiments were repeated with the 3rd refinery spent liquor; this time at a higher CaO charge. Experimental liquor conditions are shown in Table 3. The initial TA of this liquor was 272 gL−1. These results also include V2O5 as a part of the ICP-OES analysis suite.
For all three impurities, the uptake into the hydrocalumite increased with decreasing TA (
The uptake of SiO2 and P2O5 was also tested in 1st refinery green liquor (see Table 4 for liquor conditions), showing a similar increase in uptake with decreasing TA (
Phosphorus uptake increased as TA decreased like the spent liquors, but uptake in the green liquor was significantly higher for P2O5. SiO2 uptake also show the trend of increasing uptake with decreasing TA, although SiO2 uptake was lower in the 1st refinery green liquor than the 1st refinery spent liquor.
The uptake of the three impurities was investigated in 1st refinery and 3rd refinery lakewaters with TA's of 27 gL−1 and 23 gL−1 respectively. Unlike the previous suite of experiments, where water was added to lower the TA, the amount of lime slurry added was adjusted to 20 gL−1 (based on reactor volume) which was similar to the amount of lime added for the spent liquor experiments at the lowest TA. No additional water was added to the reaction solution. Reaction conditions and the uptakes for P2O5 and V2O5 are shown in Table 5. Due to SiO2 levels in the lakewater being close to the detection limit of the ICP-OES, results from SiO2 were excluded from the impurity removal calculation. Comparing the uptake of P2O5 in the 1st refinery lake water to the lowest dilution spent liquor, showed a lower uptake in the lakewater than the spent liquor. This difference could be due to the lakewater start and end liquor being at the low end of the analytical range of analysis, where the diluted 45E liquor mass balance was calculated based on an analysis of the neat liquor. Results for P2O5 and V2O5 were more comparable when comparing diluted 3rd refinery spent liquor and lakewater.
To further investigate the uptake of phosphorus, P2O5 was spiked into some neat 1st refinery spent liquor and some diluted 1st refinery spent (low TA conditions). Three liquor solutions were prepared: 2 litres of neat liquor, 2 litres of liquor with 50 mgL−1 P2O5 added and 2 litres of liquor with 100 mgL−1 P2O5 added. The P2O5 addition was by the addition of 5 or 10 mL of a 20 mgmL−1 P2O5 stock solution (107.13 gL−1 Na3PO4.12H2O). These three liquors with 0, 50 or 100 mgL−1 of additional P2O5 were used undiluted or diluted to 25% strength with the addition of water (Table 6).
Table 7 shows the concentration of P2O5 in the starting liquor (without the dilution due to the lime and the water [for runs 4-6]), P2O5 in the end liquor (both raw and corrected back to neat liquor conditions with a malonate normalisation), the difference in concentration and impurity removal based on the mass balance.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2018901884 | May 2018 | AU | national |
This application is a continuation of International Patent Application No. PCT/AU2019/050477, filed May 17, 2019, which claims priority to Australian Patent Application No. 2018901884, filed May 28, 2018, entitled “Method for Controlling the Concentration of Impurities in Bayer Liquors”, each of which is incorporated herein by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/US2019/050477 | May 2019 | US |
| Child | 17101496 | US |
