AU661486B2 - Recovery of vanadium and aluminium values - Google Patents
Recovery of vanadium and aluminium values Download PDFInfo
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- AU661486B2 AU661486B2 AU17118/92A AU1711892A AU661486B2 AU 661486 B2 AU661486 B2 AU 661486B2 AU 17118/92 A AU17118/92 A AU 17118/92A AU 1711892 A AU1711892 A AU 1711892A AU 661486 B2 AU661486 B2 AU 661486B2
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- temperature
- pregnant liquor
- alumina
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- 229910052720 vanadium Inorganic materials 0.000 title claims description 49
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims description 49
- 239000004411 aluminium Substances 0.000 title claims description 17
- 229910052782 aluminium Inorganic materials 0.000 title claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 17
- 238000011084 recovery Methods 0.000 title description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 238000005349 anion exchange Methods 0.000 claims description 22
- 125000000129 anionic group Chemical group 0.000 claims description 22
- 150000003388 sodium compounds Chemical class 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 17
- 229910001710 laterite Inorganic materials 0.000 claims description 16
- 239000011504 laterite Substances 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910052723 transition metal Inorganic materials 0.000 claims description 11
- 150000003624 transition metals Chemical class 0.000 claims description 11
- 239000003518 caustics Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 238000010899 nucleation Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- -1 hydroxide ions Chemical class 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 150000003868 ammonium compounds Chemical class 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000003841 chloride salts Chemical group 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000012047 saturated solution Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 9
- 238000000638 solvent extraction Methods 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 229910001570 bauxite Inorganic materials 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000002203 pretreatment Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical group [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 230000029087 digestion Effects 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 150000004684 trihydrates Chemical class 0.000 description 4
- 239000000428 dust Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 3
- 229940039790 sodium oxalate Drugs 0.000 description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001784 vanadium mineral Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Description
661486
AUSTRALIA
Patents Act 1990 COMPLETE SPECIFICATION For a Standard Patent
ORIGINAL
TO BE COMPLETED BY APPLICANT
C
Name of Applicant: Actual Inventor: RAMSAY EL GIMIAM RAMSAY EL GAMMEL Address for Service: WRAY ASSOCIATES, Primary Industry Terrace, Perth, Western Australia, 6000.
House, 239 Adelaide
C
Attorney code, WR Invention Title: "RECOVERY OF VANADIUM AND ALUMINIUM VALUES"
C
Details of Associated Provisional Application No: PK7323 The following statement is a full description of this invention, including the best method of performing it known to me:- 1
C
2 This invention relates to the parallel recovery of vanadium and aluminium values from ores bearing the same, although the invention also has application in the recovery of transition metal values and aluminium values from bauxitic laterites.
Vanadium minerals are often found in bauxitic laterites which overlie primary ores. These bauxitic laterites are often known as cap rocks. While the recovery of vanadium from primary ore, which consists of magnetites, is well established technology, recovery of vanadium from bauxitic laterites is not well defined.
A difference between bauxitic laterites and primary ores Sresides in their iron component. Iron is largely present in bauxitic laterites as haematite and geothite, whilst in the primary ore iron is present as magnetite. Magnetite responds to upgrading by magnetic separation, but the bauxitic laterite iron values are non magnetic.
The bauxitic laterite has been subject to weathering which has removed some of the silica ore components leaving a 20 difference in composition from the magnetite primary ores, in particular, the bauxitic laterite has higher levels of vanadium oxides, bauxite, and titaniferous sands. As a result of intensive weathering, a bauxite with low iron content will result.
The following table (overleaf) shows the differences between bauxitic laterites primary (magnetite) ores and bauxite ores.
3 Table 1 Chemical Composition of Caprock, Primary Ores and Bauxite Chemical Compositions Bauxitic Primary Bauxite (expressed as oxides) Laterite "Fe203" 15.0-60.0 34.7 5-55 "V205" 0.6-2.3 0.5 0.1-0.5 "Al 203 7.0-45.0 15.0 35-60 "SiO2" 1.0-12.0 33.0 2-10 "TiO 2 9.0-35.0 5.0 1-10 "MgO" 0.1-0.2 2.5 "CaO" 0.1-0.5 7.5 L.O.I. 12.0-15.0 9-13 Most major vanadium producers adopt the pyrometalurgical route for the recovery of vanadium from primary concentrate containing less than 2% silica. This concentrate can be achieved by magnetic separation of the primary ore.
The concentrate is mixed with sodium salts, for example sodium carbonate, and pelletised. The pellets are then roasted at high temperature, around 1,000 0 C, to produce water soluble vanadate. Sodium salt consumption is low due to the low silica content, and on leaching, a higher vanadium concentration in the pregnant liquor is achieved.
e* Unfortunately, this high temperature pyrometalurgical route is not feasible for bauxitic laterites for the following reasons. Bauxitic laterites are non magnetic, thus making it impossible to concentrate the ore or otherwise exclude the silica. Silica control can only be achieved by selective mining. The vanadium content of bauxitic laterite ore is only 60% that of the concentrate. This adds extra cost for fuel consumption and material handling per tonne of vanadium pentoxide produced. The high silica content causes a sticky phase at high temperatures, adding 4 extra costs due to down time and loss of availability of equipment. In addition the pebble or pellet feed of bauxitic laterites has weak strength and is unable to withstand elutriation during roasting. Further, the high temperature tends to disintegrate the ore and generate dust, causing blockage of gas passages in the roaster and difficulty in subsequent leaching.
Clearly the conventional pyrometalurgical route is not suitable for bauxitic laterite ores of the type hereinbefore described.
In accordance with one aspect of the invention there is provided a method of recovering aluminium values and vanadium values from a bauxitic laterite ore containing s. aid values comprising:crushing said ore to a particle size of less than 2mm; adding a sodium compound in proportion of greater than
S.
0.1% by weight; roasting said ore at a temperature between 500 C and 750 C in an oxidising atmosphere; 0 digesting said ore in a caustic solution at a second temperature of between 100 C and 160°C to obtain a pregnant liquor bearing vanadium and aluminium as anionic values; e.
cooling said pregnant liquor to a third temperature of between 600C and 850C and maintaining said pregnant liquor at a sufficient temperature to prevent crystalisation of alumina therefrom; treating said pregnant liquor with an anion exchange solvent to remove anionic vanadium values therefrom, whilst maintaining said pregnant liquor at said third temperature; cooling said pregnant liquor and seeding the remaining pregnant liquor with alumina crystals in order to crystalise alumina therefrom, and recovering vanadium values Lrom said quarternary ammonium anion exchange solvent.
In accordance with another aspect of the present invention there is provided a method of recovering aluminium values and vanadium values from a bauxitic laterite ore containing said values comprising: crushing said ore to a particle size of less than 2mm; adding a sodium compound in proportion of greater than 0.1% by weight; roasting said ore at a temperature between 500 0
C
and 750 C in an oxidising atmosphere; digesting said ore in a caustic solution at a second temperature of between 100 0 C and 160 C to obtain a pregnant liquor bearing vanadium and aluminium as anionic values; cooling said pregnant liquor to a third 20 temperature of between 60 0 C and 85 C and seeding said pregnant liquor with alumina crystals in order to crystalise alumina therefrom; treating said pregnant liquor with an anion exchange solvent to remove anionic vanadium values S* 25 therefrom; and recovering vanadium values from said anion exchange solvent.
Preferably the amount of sodium compound added to said ore is equivalent to between 0.5% and 3% by weight, Preferably the amount of sodium compound added to said ore is equivalent to approximately 1% by weight, Na 2
O.
Preferably said temperature is between 600 0 C and 700°C.
6 Preferably said temperature is about 650 0
C.
Preferably said oxidising atmosphere comprises air.
Preferably said second temperature lies between 120°C and 150 0
C.
Preferably said second temperature is about 145 0
C.
Preferably the concentration of said caustic solution is between 80g/l and 120g/l.
Preferably said third temperature is about 80 C.
Preferably said anion exchange solvent is a quarternary ammonium compound.
Preferably said anion exchange solvent is a quarternary ammonium chloride treated with hydroxide ions to replace the chloride ions thereof.
Preferably said method includes, prior to the step of 15 treating said pregnant liquor with an anion exchange solvent, the step of adjusting the pH of said pregnant liquor to a value of greater than 9 whilst maintaining said
S.
third temperature.
Preferably said value of pH is greater than 12.
In accordance with a further aspect of the present invention there is provided a method of treating a bauxitic laterite ore containing transition metal values and silica values, in order to maximise the recovered yield of said transition metal values and alumina, said method comprising:- 7 crushing said ore to a particle size of less than 2mm; adding a sodium compound in an amount of greater than 0.1% by weight; roasting said ore at a temperature of between 500°C and 750 C in an oxidising atmosphere before digesting said ore to extract alumina and said transition metal values therefrom.
Preferably said transition metal values are characterised by being able to form complex anionic values.
10 Preferably the amount of sodium compound added to said ore is between 0.5% and 3% by weight, expressed as Na 2 O0.
Preferably the amount of sodium compound added to said ore is approximately 1% by weight, expressed as Na 2 O0.
Preferably said temperature is between 600 0 C and 700 0
C.
Preferably said temperature is about 650°C.
Preferably said oxidising atmosphere comprises air.
0 Preferably said oxidising atmosphere is continually replenished.
*0 The invention will be better understood by reference to the following description of one specific embodiment thereof and reference to the drawing figure which shows a flow chart for processing bauxitic laterite or containing aluminium and vanadium values and recovering vanadium pentoxide and alumina tri-hydrate therefrom.
The process comprises feeding ore from an ore feed stock 11 to a crushing apparatus 13 where the ore is crushed to a nominal size of less than 2.0mm. The crushed ore is 8 screened through a screen 15; that ore which passes through being of a size of less than 2.0mm, is mixed with a sodium compound such as soda ash or sodium oxalate, and fed into a fluidised bed roaster 17. The crushed ore a size greater than 2mm is caught by the screen 15 and returned to the crushing apparatus 13 for re-crushing.
The amount of sodium compound added is based on 0.5% to 3% W/W expressed as Na 2 0, preferably 1% W/W expressed as Na 2 0.
When soda ash (anhydrous sodium carbonate) is utilised, an amount of between 0.8% and 5.2% W/W, preferably 1.5% W/W, is used. When sodium oxalate is utilised, an amount of between 1% and 6.5% W/W, preferably 1.8% W/W, is used.
4 The fluidised bed roaster 17 is operated at a temperature of about 650°C, and the crushed ore mixed with the sodium compound is roasted for a period of thirty minutes in an atmosphere of air, which is replenished at a rate sufficient to ensure an oxidising atmosphere.
The roasted ore is then digested in a sodium hydroxide S.solution of concentration between 2 mol/litre and 4 mol/ litre, 2.5 mol/litre (100 gram/litre) being preferred, for a period of one hour at a temperature of 145 0 C. The optimum roasted or pulp density is 35% by weight. The digestion is carried out in an appropriate digesting vessel 19.
When the digestion is complete, the pregnant liquor resulting and the residue are transferred to a separating tank 21. The residue is transferred to a settling tank 23 where it is further washed with water. The aqueous overflow from the settling tank 23, and indeed the aqueous component thereof is eventually transferred, together with any dissolved solute, to the digesting vessel 19 where it is further made up with aqueous sodium hydroxide as 9 necessary, in order to give the required sodium hydroxide concentration therein.
The residue, which comprises primarily silicates, alumina silicates, and perhaps titaniferous and ferric oxides is collected in a vessel 25 for subsequent treatment.
The aqueous pregnant liquor separated from the residue in the separating tank 21 proceeds to a counter current mixersettler system solvent extraction plant 27 in which a quarternary ammonium anion exchange solvent such as 10 "ALIQUAT 336" (trade mark) or "ADOGEN 464" (trade mark) is e used. These anion exchange solvents exchange chloride ions for anions containing vanadium. The vanadium is extracted as one of several species which may exist, depending upon the pH, a pH 13 or greater being preferred but a pH of 9 or greater being effective. Before the anion exchange solvent is used it is pre-treated in a pre-treatment vessel 29 with a 0.75 mol/litre sodium hydroxide solution 31 in order to exchange chloride ions associated with the anion exchange solvent for hydroxide ions. This pre-treatment prevents hydroxide ions in the aqueous pregnant liquor competing with anionic vanadium species for sites which would be otherwise occupied by chloride ions on the anion exchange solvent, thus optimising the yield of anionic vanadium species extracted by the anionic exchange solvent. The extraction of anionic vanadium species is carried out at a temperature of 80 0 C. The anion exchange solvent is diluted with a solvent having a flash point sufficiently higher than the operation temperature of 80 0 C in order to minimise the chance of explosion. A suitable diluent is "SHELLSOL" 2046 (trade mark) which is a high flashpoint kerosene developed for solvent extraction. In addition, iso-decanol is recommended at 5% by volume, as a phase modifier to inhibit the formation of emulsions, and improve the settling characteristics of any dispersion between the 10 aqueous and organic phases after mixing.
The aqueous solution recovered from the solvent extraction plant 27 is transferred to an evaporator 32 to concentrate the aqueous solution, and the transferred to a crystallisation tank 33 where the solution is then cooled to a temperature of approximately 65 C and seeded with crystals of alumina tri-hydrate which causes crystallisation of alumina tri-hydrate from the aqueous solution. Upon completion of crystallisation, which is expected to yield greater than 50% of dissolved alumina, the crystaline product is collected, and the remaining aqueous solution which contains sodium hydroxide and sodiium aluminate is recycled to the digesting vessel 19 for reuse.
.o The loaded anion exchange solvent is stripped in a stripping stage using a strip solution of 1.25 mol/litre sodium hydroxide and 1.7 mol/litre sodium chloride. The aqueous solution containing anionic vanadium species is then transferred to a precipitation tank 39 where the pH is adjusted to a value between 8 and 9. An aqueous ammonia solution is added, and ammonium metavanadate and perhaps other anionic vanadium species are precipitated.
The precipitated anionic vanadate species can then be calcined at 690°C for two hours to produce vanadium pentoxide, following the removal of ammonia by heating the recovered dried precipitate at a lower temperature prior to performing the calcination. The ammonia can be recovered from this step of the process and reused.
There is much scope for reuse of other waste products, for example the aqueous output of the pre-treatment vessel which would comprise sodium chloride and sodium hydroxide solution can be recycled for use in the strip solution 37.
In addition, the sodium compound added to the crushed ore 11 prior to roasting can be obtained from elsewhere in the plant, or from waste from other plants or industries.
It should be noted that it is important that the crushing apparatus 13 is operated in such a manner so as to reduce the generation of fine dust. Excessive fine dust generation during the crushing stage will result in reduced ore reserve or reduced efficiency, unless the plant is designed to handle fine ore stock feed.
The roasting process achieves two objectives. Firstly .10 trivalent vanadium species are converted to pentavalent vanadium species, which are soluble. Secondly, organics Ssuch as humic acids and wood products naturally present in the bauxitic laterite ores are burnt off in the roasting •too process, which makes the subsequent alumina recovery easier and cheaper, and gives rise to a purer product.
Experimentation indicates that the roasting can be carried out at a temperature of between 500 0 C and 750 0 C. The optimum temperature has been determired to be 650 0 C, Below 500 C, not all trivalent vanadium is converted to the .o0 soluble pentavalent state. Above 700 0 C, amount of vanadium recoverable from the roasted ore falls, as it appears that sintering decreases the porosity of the ore and causes the vanadium to be "locked up". The air flow rate in the roasting stage should be adjusted to give approximately 4% free oxygen.
There are other Advantages of utilising a low temperature roast approach, these being that the roasting temperature is below the sticky temperature of both sodium vanadate and silicates. Accordingly agglomeration of ore in the fluidised bed roaster is avoided. As the silica is not activated by such low temperature roasting, for example quartz becomes reactive at temperatures greater than 1000 0 C, this results in the consumption of sodium hydroxide 12 being minimised as the non reactive silicate forms tend not to form sodium alumino-silicates. Additionally, the remaining alumina is still reactive and soluble in the caustic solution. Alumina becomes non reactive after roasting at 1000 0 C dae to a change in crystal phase which occurs at a temperature of approximately 800°C. An important consideration regarding the economics of the process is that each tonne of reactive silica contained in the ore will consume approximately one tonne of caustic and one tonne of alumina.
Referring now to the digestion stage, it has been found e tPat approximately 90% or more aluminium and approximately of vanadium is readily extracted in roasted ore of pulp *densities up to 40% by weight. The extraction is not favourable as the pulp density approaches 50% by weight.
It is important that the aqueous phases are maintained at a temperature of 80 C until such time ae the aqueous solutions are ready for crystallising. This is to avoid crystalisation of alumina from the aqueous pregnant liquor.
".20 The exact temperature obviously is determined by the concentration of alumina in the caustic solution.
It should be noted that the crystallisation of the alumina tri-hydrate may take place before the solvent extraction of the anionic vanadium values. However as it has been discovered that the solrvent extraction can operate at the temperature required to prevent premature crystallisation of alumina, it is preferable to crystalise the alumina after recovery of the vanadium values in the solvent extraction stage. It is more efficient to carry out the crystallisation of the alumina after the solvent extraction of the anionic vanadium values. Tests indicate that the solvent extraction can withstand concentrations of alumina up to 100 grams per litre and free sodium hydroxide 13 up to 40 grams per litre.
Before the ore is roasted in the fluidised bed roaster 17 the addition of a sodium compound, most preferably sodium carbonate and/or sodium oxalate but for practical reasons sodium chloride is effective, in an amount of 1% by weight expressed as sodium oxide, results in increased yield of alumina and vanadium pentoxide available for extraction at the digesting stage. Alumina yields can be expected to be greater than or equal to 90%, and vanadium pentoxide yields can be expected to be greater than or equal to 70%, these values being available for extraction during the digestion stage. It has also been established that 85% of the aqueous vanadium can be solvent extracted with "ALIQUOT 336" which has been treated with sodium hydroxide solution S1 at the pre-treatment stage (pre-treatment vessel 29), when the aqueous liquors contain 100 grams per litre of sodium aluminate and 30 grams per litre of sodium hydroxide, when the solvent extraction is carried out utilising shake out Stests. Utilising shake out tests, the vanadium yield of 6* o 85% can be obtained after five stages. These figures apply for solvent extraction conducted at a temperature of 80 0
C.
On a larger scale it would appear that direct stripping of anionic vanadate species in precipitate form, would appear feasible utilising stripping of the solvent with for example aqueous ammonia and ammonium chloride solutions.
It should appreciated that the invention should not be limited to the scope of the embodiment described herein.
Claims (20)
1. A method of recovering aluminium values and vanadium values from a bauxitic laterite ore containing said values comprising:- crushing said ore to a particle size of less than 2mm; adding a sodium compound in proportion of greater than 0.1% by weight; roasting said ore at a temperature between 500°C and 750°C in an oxidising atmosphere; digesting said ore in a caustic solution at a second temperature of between 100 C and 160 C to obtain a pregnant liquor bearing vanadium and aluminium as 0 anionic values; cooling said pregnant liquor to a third temperature of between 60°C and 85°C and maintaining said pregnant liquor at a sufficient temperature to prevent crystalisation of alumina therefrom; treating said pregnant liquor with an anion exchange solvent to remove anionic vanadium values therefrom, whilst maintaining said pregnant liquor at said third temperature; cooling said pregnant liquor and seeding the remaining pregnant liquor with alumina crystals in order to "crystalise alumina therefrom, and recovering vanadium values from said quarternary ammonium anion exchange solvent.
2. A method of recovering aluminium values and vanadium values from a bauxitic laterite ore containing said values comprising: crushing said ore to a particle size of less than 2mm; adding a sodium compound in proportion of greater than 0.1% by weight; roasting said ore at a temperature between 500°C and 750 0 C in an oxidising atmosphere; digesting said ore in a caustic solution at a second temperature of between 100 0 C and 160°C to obtain a pregnant liquor bearing vanadium and aluminium as anionic values; cooling said pregnant liquor to a third temperature of between 60 C and 85 C and seeding said pregnant liquor with alumina crystals in order to crystalise alumina therefrom; treating said pregnant liquor with an anion exchange solvent to remove anionic vanadium values therefrom; and recovering vanadium values from said anion exchange solvent.
3. A method as claimed in claim 1 or 2 wherein the amount of sodium compound added to said ore is equivalent to between 0.5% and 3% by weight, Na 2 0. S e0 4. A method as claimed in claim 3 wherein the amount of sodium compound added to said ore is equivalent to S. approximately 1% by weight, Na 2 0. 0 e*
5. A method as claimed in any one of the preceding claims wherein said temperature is between 600 0 C and 700 C.
6. A method as claimed in claim 5 wherein said temperature is about 650°C.
7. A method as claimed in any one of the preceding claims wherein said oxidising atmosphere comprises air. -16-
8. A method as claimed in any one of the preceding claims wherein said second temperature lies between 120 0 C and 150 C.
9. A method as claimed in claim 8 wherein said second temperature is about 145 0 C. A method as claimed in any one of the preceding claims wherein the concentration of said caustic solution is between 80g/l and 120g/l.
11. A method as claimed in any one of the preceding claims wherein said third temperature is about 80 C.
12. A method as claimed in any one of the preceding claims wherein said anion exchange solvent is a quarternary ammonium compound. 4*
13. A method as claimed in claim 12 wherein said anion 15 exchange solvent is a quarternary ammonium chloride treated with hydroxide ions to replace the chloride S. ions thereof.
14. A method as claimed in any one of the preceding claims wherein said method includes, prior to the step 20 of treating said pregnant liquor with an anion exchange solvent, the step of adjusting the pH of said pregnant liquor to a value of greater than 9 whilst maintaining said third temperature. A method as claimed in claim 14 wherein said value of pH is greater than 12.
16. A method as claimed in any one of the preceding claims wherein said method includes, prior to the step of cooling said pregnant liquor to crystalise alumina, AL concentrating said pregnant liquor to form a saturated 3k or near saturated solution of solute values. -17-
17.A method of treating a bauxitic laterite ore containing transition metal values and silica values, in order to maximise the recovered yield of said transition metal values and alumina, said method comprising:- crushing said ore to a particle size of less than 2mm; adding a sodium compound in an amount of greater than 0.1% by weight; roasting said ore at a temperature of between 500 C and 750 0 C in an oxidising atmosphere before digesting said ore to extract alumina and said transition metal values therefrom.
18. A method as claimed in claim 17 wherein said transition metal values are characterised by being able to form complex anionic values.
19. A method as claimed in claim 17 or 18 wherein the amount of sodium compound added to said ore is between and 3% by weight, expressed as Na 0. 2 A method as claimed in claim 19 wherein the amount of 20 sodium compound added to said ore is approximately 1% by weight, expressed as 0
21. A method as claimed in any one of claims 17 to wherein said temperature is between 6000C and 700 0 C.
22. A method as claimed in claim 21 wherein said temperature is about 650 0 C.
23. A method of recovering aluminium values and vanadium values from a bauxitic laterite ore containing said values substantially as herein described with reference S A to the description of the embodiement. -18-
24. A method of treating a bauxitic laterite ore containing transition metal values and silica values, in order to maximise the recovered yield of said transition metal values and alumina, substantially as herein described with reference to the description of the embodiment. Dated this EIGHTH day of MAY 1995. S S. S S *4 5 S S.C. es S S S. S 5* 555 5 S. OS S S. CLOUGH RESOURCES LIMITED Applicant WRAY ASSOCIATES, Perth, Western Australia, Patent Attorneys for the Applicant. ABSTRACT A method of recovering aluminium values and vanadium values from a bauxitic literite ore containing the values. The method includes crushing the ore, adding a sodium compound, roasting the ore, digesting the ore in a caustic solution to obtain a pregnant liquor bearing vanadium and aluminium as anionic values, cooling the pregnant liquor and maintaining it at a sufficient temperature to prevent crystalisation of alumina, treating the pregnant liquor with an anion exchange solvent to remove anionic vanadium values, cooling the pregnant liquor and seeding the .o remaining pregnant liquor with alumina crystals in order to crystalise alumina, and recovering vanadium values from the quarternary ammonium anion exchange solvent. Alternatively, when the pregnant liquor is cooled, it is seeded with alumina crystals in order to crystalise alumina from it, without maintaining the pregnant liquor at a sufficient temperature to prevent crystallisation of the alumina. eo 0 0e
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU17118/92A AU661486B2 (en) | 1991-07-19 | 1992-05-22 | Recovery of vanadium and aluminium values |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPK732391 | 1991-07-19 | ||
| AUPK7323 | 1991-07-19 | ||
| AU17118/92A AU661486B2 (en) | 1991-07-19 | 1992-05-22 | Recovery of vanadium and aluminium values |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU1711892A AU1711892A (en) | 1993-02-11 |
| AU661486B2 true AU661486B2 (en) | 1995-07-27 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU17118/92A Ceased AU661486B2 (en) | 1991-07-19 | 1992-05-22 | Recovery of vanadium and aluminium values |
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| Country | Link |
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| AU (1) | AU661486B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116640936B (en) * | 2023-05-25 | 2024-07-16 | 中铝郑州有色金属研究院有限公司 | A method for producing high-grade vanadium concentrate |
| GB202319943D0 (en) * | 2023-12-22 | 2024-02-07 | Imperial College Innovations Ltd | Vanadium extraction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3376105A (en) * | 1964-05-13 | 1968-04-02 | Union Carbide Corp | Ion exchange extraction of vanadium |
| US4051221A (en) * | 1975-04-16 | 1977-09-27 | Akzona Incorporated | Process for the separate recovery of vanadium and molybdenum |
| AU594035B2 (en) * | 1985-01-17 | 1990-03-01 | Alcoa Chemie G.M.B.H. | Process for the production of aluminium hydroxide with low content of impurities, especially of iron, and with high degree of whiteness |
-
1992
- 1992-05-22 AU AU17118/92A patent/AU661486B2/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3376105A (en) * | 1964-05-13 | 1968-04-02 | Union Carbide Corp | Ion exchange extraction of vanadium |
| US4051221A (en) * | 1975-04-16 | 1977-09-27 | Akzona Incorporated | Process for the separate recovery of vanadium and molybdenum |
| AU594035B2 (en) * | 1985-01-17 | 1990-03-01 | Alcoa Chemie G.M.B.H. | Process for the production of aluminium hydroxide with low content of impurities, especially of iron, and with high degree of whiteness |
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| Publication number | Publication date |
|---|---|
| AU1711892A (en) | 1993-02-11 |
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