WO2023279144A1 - Recovery of vanadium from alkaline slag materials - Google Patents
Recovery of vanadium from alkaline slag materials Download PDFInfo
- Publication number
- WO2023279144A1 WO2023279144A1 PCT/AU2022/050678 AU2022050678W WO2023279144A1 WO 2023279144 A1 WO2023279144 A1 WO 2023279144A1 AU 2022050678 W AU2022050678 W AU 2022050678W WO 2023279144 A1 WO2023279144 A1 WO 2023279144A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- leach
- vanadium
- slurry
- solution
- resin
- Prior art date
Links
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 150
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 238000011084 recovery Methods 0.000 title claims abstract description 37
- 239000002893 slag Substances 0.000 title description 21
- 239000000463 material Substances 0.000 title description 19
- 239000002002 slurry Substances 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 77
- 239000011347 resin Substances 0.000 claims abstract description 66
- 229920005989 resin Polymers 0.000 claims abstract description 66
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 63
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 63
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000007787 solid Chemical group 0.000 claims abstract description 55
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 36
- 238000005549 size reduction Methods 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 30
- 238000000926 separation method Methods 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 15
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000003480 eluent Substances 0.000 claims description 9
- 238000010828 elution Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 95
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 229910052742 iron Inorganic materials 0.000 description 11
- 239000007800 oxidant agent Substances 0.000 description 11
- 230000001590 oxidative effect Effects 0.000 description 11
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 6
- 238000003556 assay Methods 0.000 description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000001117 sulphuric acid Substances 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 102000011045 Chloride Channels Human genes 0.000 description 3
- 108010062745 Chloride Channels Proteins 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- -1 calcium vanadates Chemical class 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 239000001164 aluminium sulphate Substances 0.000 description 2
- 235000011128 aluminium sulphate Nutrition 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 239000001166 ammonium sulphate Substances 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 239000002198 insoluble material Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- DNWNZRZGKVWORZ-UHFFFAOYSA-N calcium oxido(dioxo)vanadium Chemical compound [Ca+2].[O-][V](=O)=O.[O-][V](=O)=O DNWNZRZGKVWORZ-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- MECMQNITHCOSAF-UHFFFAOYSA-N manganese titanium Chemical compound [Ti].[Mn] MECMQNITHCOSAF-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
- C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- 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
Definitions
- the present invention relates to a method for the recovery of vanadium from alkaline feedstocks, particularly secondary materials such as steel slags. More specifically, the method of the present invention is adapted to recover vanadium from such feedstocks through hydrometallurgical processing.
- Vanadium is most prominently found within magnetite iron ore deposits and is typically present in slags generated during iron recovery processes.
- the concentrates or slags are typically processed with the so-called ‘salt roast process’.
- the salt roast process the vanadium slag is mixed with one or more alkali salts and subjected to a roast typically at 800 - 900 °C, to produce sodium metavanadate. These vanadium values are subsequently and selectively leached with water.
- Vanadium values are then recovered in a refining process that includes precipitation from the leach solution as ammonium metavanadate or ammonium polyvanadate, both of which can be treated at high temperature to de-ammoniate and convert to product vanadium pentoxide.
- the process and particularly the initial high temperature salt roast step is highly energy intensive and so the vanadium tenor in the feed needs to be at a particular level to make the process economical.
- a number of alternative hydrometallurgical processes have been employed to process the slags for the recovery of vanadium. Such processes typically comprise an acid leach step in order to extract vanadium into solution.
- the main issue faced with the recovery of vanadium by hydrometallurgical means is that other metals species, such as iron, titanium, calcium, magnesium and silica, are typically co-extracted with the vanadium during the acid leach step.
- the presence of these species in the leach solution must be accounted for when recovering vanadium from the leach solution.
- the separation of vanadium from a leach solution that also contains dissolved iron species poses a significant challenge. Most processes by which this can be achieved are economically challenging.
- CaO and other alkaline materials are also commonly found in slag materials. Consequently, a further problem with the use of an acid leach on these materials is the high consumption of acid as a result of the high alkaline content. Furthermore, when sulphuric acid is used as the leachate, a byproduct of the leach is solid CaSC .xFteO which forms at large volumes. Along with final effluent neutralization solids this product must be adequately disposed of.
- a method for the recovery of vanadium from a vanadium containing feed stream comprising the steps of: subjecting the vanadium feed stream to a leach step, the leach step comprising contacting the vanadium feed stream with an alkaline carbonate leach solution to form a leach slurry comprising a pregnant leach solution containing vanadium and a solid residue; contacting the leach slurry with an ion exchange resin adapted to extract vanadium from the leach slurry, thereby producing a loaded resin; separating the loaded resin from the leach slurry; and recovering vanadium from the loaded resin.
- alkaline carbonate leach of the present invention demonstrates good selectivity of vanadium over other metals and silica that may be found in the feedstock.
- alkaline carbonate leach solution or similar variations, will be understood to refer to an aqueous solution comprising a carbonate or bicarbonate of an alkali metal or a carbonate or bicarbonate of an alkaline earth metal.
- alkaline feedstock will be understood to refer to feedstocks that comprise one or more alkali metal compounds and alkaline earth metal compounds or form an alkaline solution or slurry when mixed with water.
- the method of the present invention is preferably adapted to recover vanadium products from slag materials that result from the steel industry.
- such materials will contain iron, along with other species such as manganese titanium and chromium.
- the method of the present invention allows for vanadium to be leached from such materials with high selectivity over other impurity metals. This has been found to simplify the subsequent recovery of vanadium from the pregnant leach solution.
- the leach slurry is contacted with the ion exchange resin following the completion of the leach step.
- the leach slurry is contacted with the ion exchange resin during the leach step.
- the mixture of the leach slurry and the ion exchange resin is agitated. Agitation has been found to assist in the prevention of the solids settling to the bottom of the tank. Agitation is preferably controlled to prevent attrition and breakdown of the ion exchange resin particles.
- the loaded resin is separated from the leach slurry in a resin recovery step.
- the resin recovery step comprises separation of the loaded resin by way of a screening process.
- the particle size of the ion exchange resin is larger than the particle size of the vanadium feed stream.
- ion exchange resins are typically provided as beads with a narrow band of particle sizes, typically at a size between 0.5 mm and 1.5 mm. This particle size is much larger than the typical particle size of undissolved solids in the leach slurry. This allows the loaded resin to be separated from the other solids in the leach slurry using a screen with a diameter smaller than the particle size of the ion exchange resin and larger than the particle size of the feed stream.
- recovery of vanadium from the loaded resin comprises directing the loaded resin to an elution step in which the loaded resin is contacted with an eluent to recover vanadium into a vanadium eluate.
- the stripped resin is recycled back to the leach step.
- vanadium is recovered from the vanadium eluate.
- the leach slurry is directed to a solid liquid separation step to recover undissolved solids from a leach solution.
- vanadium is recovered from the leach solution.
- the leach solution is combined with the vanadium eluate and vanadium is recovered from the mixed solution.
- the vanadium containing feed stream comprises a steel slag.
- steel slag will be understood to refer to the slag byproduct of a steel manufacturing process.
- the alkaline carbonate leach solution comprises one or more of sodium carbonate (Na2CC>3), sodium bicarbonate (NaHCOa) and sodium hydroxide (NaOH).
- the alkaline carbonate leach solution comprises one or more of potassium carbonate (K2CO3), potassium bicarbonate (KHCO3) and potassium hydroxide (KOH).
- carbonates, bicarbonates and hydroxides exist together in aqueous solutions in a dynamic equilibrium in in the leach solution during the leach step.
- hydroxide and carbonate ion predominates, while in weakly basic conditions the bicarbonate ion is more prevalent.
- the alkaline carbonate leach solution comprises ammonium carbonate.
- the leach step is conducted under oxidative conditions.
- the leach step is conducted in the presence of an oxidant.
- the oxidant is selected from oxygen, air, and hydrogen peroxide.
- the feedstock is combined with an oxidant prior to the leach step.
- Suitable oxidants include Mn02.
- no oxidant is added to the leach step.
- an oxidant is added to the leach step.
- the addition of the oxidant will target a solution Eh of > -100 mV against a Ag/AgCI reference electrode.
- the method further comprises the step of: subjecting the feed stream to a pretreatment process, prior to the step of subjecting the feed stream to the leach step.
- the pre-treatment process comprises one or more size reduction steps. More preferably, the one or more size reduction steps comprise one or more of a crushing step, a grinding step and a milling step. Preferably, the one or more size reduction steps reduce the feedstock particle size to less than particle size of ion exchange resin.
- the pre-treatment process comprises one or more beneficiation steps.
- the one or more beneficiation steps include one or more of a gravity classification step, a magnetic classification step and a flotation step.
- the leach step comprises subjecting the feed stream to a leach process in one or more leach reactors.
- the leach step comprises subjecting the feed stream to a leach process in two or more leach reactors. More preferably, the leach step comprises subjecting the feed stream to a leach process in three or more leach reactors. More preferably, the leach step comprises subjecting the feed stream to a leach process in four or more leach reactors. More preferably, the step comprises subjecting the feed stream to a leach process in five or more leach reactors.
- the step of subjecting the feed stream to a leach step is conducted at atmospheric pressure. In one form of the present invention, the step of subjecting the feed stream to a leach step is conducted at elevated pressure.
- the step of subjecting the feed stream to a leach step is conducted at ambient temperature. In one form of the present invention, the step of subjecting the feed stream to a leach step is conducted at elevated temperature.
- the leach step is conducted at pH above 7.5.
- the pH of the leach step in controlled.
- the leach step is maintained at a pH between 7.5 and 14. More preferably, the leach step is maintained at a pH between 9 and 10.
- a carbon dioxide stream is injected into the leach step.
- the carbon dioxide stream is used to control the pH of the leach step.
- carbonic acid may be added to the leach step.
- At least a portion of the leach slurry is subjected to a size reduction step.
- at least a portion of the leach slurry is transferred to a size reduction step to produce a process stream with a reduced particle size.
- the leach slurry transferred to the size reduction step does not comprise the ion exchange resin.
- the loaded ion exchange resin is separated from the leach slurry and the leach slurry is directed to a size reduction step.
- the process stream is returned to the leach step.
- the process stream is subjected to a secondary leach step.
- the secondary leach step comprises contacting the process stream with an alkaline carbonate leach solution to form a secondary leach slurry comprising a pregnant leach solution containing vanadium and a solid residue.
- the secondary leach step is conducted in the presence of an oxidant.
- a carbon dioxide stream is injected into the secondary leach step.
- the secondary leach slurry is directed to the solid liquid separation step to recover a leach solution.
- the secondary leach slurry is contacted with an ion exchange resin.
- the secondary leach slurry is contacted with the ion exchange resin separated from the leach step prior to the size reduction step.
- the secondary leach slurry is subjected to a size reduction step to produce a process stream with a reduced particle size.
- the leach slurry transferred to the size reduction step does not comprise the ion exchange resin.
- the process stream is subjected to a tertiary leach step.
- the tertiary leach step comprises contacting the process stream with an alkaline carbonate leach solution to form a tertiary leach slurry comprising a pregnant leach solution containing vanadium and a solid residue.
- the tertiary leach slurry is directed to the solid liquid separation step to recover a pregnant leach solution.
- the tertiary leach solution is subjected to one or more further size reduction steps, where each size reduction step is followed by a further leach step.
- the tertiary leach slurry is contacted with an ion exchange resin. More preferably, the secondary leach slurry is contacted with the ion exchange resin separated from the first leach step or the secondary leach step prior to the size reduction step.
- the loaded resin is recovered from the leach slurry prior to the leach slurry being directed to a size reduction step.
- the inventors have found that the size reduction step will lead to the destruction of the ion exchange resins. As such, it should be removed from the leach slurry prior to any size reduction step being undertaken.
- the loaded resin is recovered from the secondary leach slurry.
- the loaded resin is recovered from the tertiary leach slurry.
- ion exchange resin is added at every leach stage. It should be understood that the ion exchange resin is removed at the completion of each leach stage. Alternatively, ion exchange resin is only added to one or more leach stages. Preferably, the ion exchange resin is only added to the first least stage.
- the leach slurry is directed to a classification apparatus with the overflow being directed to the solid liquid separation step and the underflow being recycled back to the leach step or the size reduction step.
- the solid/liquid separation step comprises the treatment of the slurry in a filtration apparatus.
- the solid/liquid separation step comprises a thickening apparatus upstream of the filtration apparatus.
- the solid/liquid separation step comprises the treatment of the slurry in a counter current decantation (CCD) circuit.
- CCD counter current decantation
- the CCD circuit comprises two or more thickeners arranged in series.
- the solids recovered in the solid liquid separation step are subjected to a repulp step to recover further vanadium.
- the step of recovering a vanadium product from the vanadium eluate comprises precipitating a vanadium rich solid and separating the vanadium rich solid from the barren eluate.
- barren eluate will be understood to refer to a eluate to which at least a portion of the vanadium has been recovered. It should be understood to include a solution that contains vanadium.
- a barren eluate results from the step of recovering a vanadium product from the vanadium eluate.
- at least a portion of the barren eluate solution is recycled to the elution step.
- Figure 1 is a flowsheet of the method of the present invention.
- FIG. 2 is flowsheet of an alternative embodiment of the present invention DESCRIPTION OF EMBODIMENTS
- the method of the present invention relates to the recovery of vanadium from a vanadium containing feed stream.
- the method comprises the steps of: subjecting the vanadium feed stream to a leach step, the leach step comprising contacting the vanadium feed stream with an alkaline carbonate leach solution to form a leach slurry comprising a pregnant leach solution containing vanadium and a solid residue; contacting the leach slurry with an ion exchange resin adapted to extract vanadium from the leach slurry, thereby producing a loaded resin; separating the loaded resin from the leach slurry; and recovering vanadium from the loaded resin.
- the carbonate leach of the present invention demonstrates good selectivity of vanadium over other metals that may be found in the feedstock.
- the method of present invention has been found to be suitable for use on alkaline feedstocks.
- the presence of alkaline material in feedstocks presents a problem for the treatment of such feedstocks by hydrometallurgical processes that use acids as the primary leachant.
- the main disadvantage with such processes is that a high amount of acid is consumed by the alkaline material, which increases the operating costs.
- acid soluble impurities are also extracted into the leach solution and further processing is required to remove these.
- large volumes of calcium salts, leach residues and/or effluent neutralization wastes can be generated and the handling of these leads to process inefficiencies and/or added processing costs.
- the present invention may be used to recover vanadium from a range of different sources, including slags, residues and/or other by-products of industrial processes.
- the method of the present invention is preferably adapted to recover vanadium products from slag materials that result from the steel industry. In addition to vanadium, such materials will contain iron, along with other species such as titanium.
- the method of the present invention allows for vanadium to be leached from such materials with high selectivity over other impurity metals. This has been found to simplify the recovery of vanadium from the pregnant leach solution.
- FIG. 1 there is shown a method for the recovery of vanadium 10 from a feed stream 12 in accordance with an embodiment of the present invention the feedstock 12 is subjected to primary milling step 14.
- the feedstock 12 should have a target particle size of ⁇ 200 pm, with a target particle size of ⁇ 100 pm being preferred and ⁇ 75 pm being more preferable.
- the target size of the feedstock 12 should be smaller than the particle size of the ion exchange resin. It is envisaged that conventional crushing and grinding apparatus available to those skilled in the art can be used to reduce the particle size of the feedstock 12.
- the feedstock may be subjected to one or more beneficiation steps (not shown) to remove excess low value bearing components of the feedstock 12.
- the one or more beneficiation steps can include one or more of a gravity classification step, a magnetic classification step and a flotation step.
- the inventors have found that a significant proportion of the vanadium in steel slags may be captured in silica glass.
- the one or more size reduction steps have been found to liberate vanadium from such materials, allowing for subsequent dissolution in the leach step. It is envisaged that both wet and dry particle size reduction apparatus may be utilised.
- the feed stream is directed to leach step 20.
- leach step 20 the feed stream is contacted with an alkaline carbonate leach solution to extract vanadium into the solution.
- the vanadium species in the feed may exist in a number of different forms.
- calcium vanadate species may include Ca(V0 3 )2, CaV2C>6.3Fl20, CaV2C>6.4Fl20, CaV60i6.9Fl20, Ca2V207.9Fl20, Ca 3 Vio028.16Fl20, amongst others.
- the calcium vanadates in the feedstock may react with the alkaline liquor 16 in the leaching process according to the following reactions:
- Additional alkaline liquor or alkaline carbonate leach solution may be directed into leach step 20 to increase the CO3 2 / HCO3 concentration in the leach solution.
- CO3 2 / HC03 r may be regenerated in the solution.
- An oxidant stream may be injected into the leach step 20 to oxidise at least a portion of the components of the feedstock and improve vanadium recovery.
- vanadium in the feedstock may be encapsulated in various Fe(ll) compounds found in the feedstock.
- the inventors have found that the addition of the oxidant will oxidise Fe(ll) to Fe(lll) which can assist in the liberation of vanadium from within these compounds.
- any dissolved Fe(lll) will likely re-precipitate as FeO(OFI) (also written as Fe203.Fl20).
- the oxidant is selected from hydrogen peroxide and potassium permanganate.
- a carbon dioxide stream may be directed into the leach step 20.
- alkaline feedstocks such as steel slags contain a high CaO and Ca(OFI)2 content.
- the Na2CC>3/NaFIC03 in the leach liquor will react with CaO/Ca(OFI)2 to produce solid CaCC>3 and NaOFI.
- the reactions can be summarized by the following simplified reactions: [0055] The inventors have found that carbon dioxide will react with sodium hydroxide and other species in the leach solution to form a reactive carbonate system as represented by the following simplified reactions:
- the pH of the leach solution is controlled throughout the leach step.
- the leach solution is maintained at a pH above 7.5.
- the leach solution is maintained at a pH above 8.
- the leach solution is maintained at a pH above 8.5.
- the leach solution is maintained at a pH above 9.
- the leach solution is maintained at a pH between 7.5 and 14. In one embodiment the pH is maintained between 8 and 11. In one embodiment, the pH is maintained between 9 and 10.
- the inventors have found that the pH of the leach solution will naturally increase throughout the leach process as a result of the formation of NaOH during the reaction of the alkaline carbonates and CaO/Ca(OH)2. However, at pH above 14 silica is increasingly soluble and will be leached into solution. It has also been found that at pH below 9, small quantities of impurities such as manganese, magnesium, iron and titanium begin to dissolve. This will increase the complexity and may impact the subsequent recovery of vanadium form the leach solution.
- the pH is maintained by the addition of carbon dioxide into the leach solution. As discussed above, carbon dioxide will convert NaOH to Na2C03/NaHCC>3. Alternatively, the pH is maintained by the addition of acid.
- the leach step 20 is conduct at a pH of approximately 10 to prevent the above discussed impurities leaching into solution.
- the pH of the pregnant leach solution may then be lowered to between 9-9.5 in order to precipitate at least some silica out of the solution.
- a coagulant may be added to assist in the silica removal.
- the precipitated solids may then be filtered out of the solution.
- the leach step 20 preferably comprises a leach circuit comprising one or more leach vessels arranged in series.
- the feedstock has a particle size of Pso 106 pm. In one embodiment, the feedstock has a particle size of Pso 75 pm. In one embodiment, the feedstock has a particle size of Pso 53 pm. In one embodiment, the feedstock has a particle size of Pioo 25 pm.
- the leach is conducted at ambient temperature. In one embodiment, the leach is conducted at elevated temperature. Preferably, the leach step is conducted at a temperature up to boiling point. In one embodiment, the leach step is conducted at a temperature above 50°C. In one embodiment, the leach step is conducted at a temperature above 60°C. In one embodiment, the leach step is conducted at a temperature above 70°C. In one embodiment, the leach step is conducted at a temperature above 80°C. In one embodiment, the leach step is conducted at a temperature above 90°C.
- the leach step is conducted at ambient pressure. In one embodiment, the leach step is conducted at elevated pressure. It is envisaged that carbon dioxide may be injected into the headspace of the leach reactor.
- the pulp density of the leach step is 10-50%. In one embodiment, the pulp density is 20 - 40 %.
- the Na2C03/NaHC03 concentration in the leach solution is between 2-35 %. In one embodiment, the Na2C03/NaHC03 concentration in the leach solution is at least 50 g/L. In one embodiment, the Na2C03/NaHC03 concentration in the leach solution is at least 75 g/L. In one embodiment, the Na2C03/NaHC03 concentration in the leach solution is at least 125 g/L.
- the Na concentration in the leach solution is at least 40 g/L.
- the residence time of the leach step is greater than 1 hour. In one embodiment, the residence time of the leach step is greater than 2 hours. In one embodiment, the residence time of the leach step is greater than 3 hours. In one embodiment, the residence time of the leach step is greater than 4 hours. In one embodiment, the residence time of the leach step is greater than 5 hours. In one embodiment, the residence time of the leach step is greater than 6 hours. In one embodiment, the residence time of the leach step is greater than 7 hours. In one embodiment, the residence time of the leach step is greater than 8 hours. In one embodiment, the residence time of the leach step is greater than 9 hours. In one embodiment, the residence time of the leach step is greater than 10 hours. In one embodiment, the residence time of the leach step is greater than 11 hours. In one embodiment, the residence time of the leach step is greater than 12 hours.
- a solution Eh of > -100 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > -90 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > -80 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > -70 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > -60 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > -50 mV against a Ag/AgCI reference electrode is maintained.
- a solution Eh of > -40 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > -30 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > -20 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > -10 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > 0 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of >50 mV against a Ag/AgCI reference electrode is maintained.
- a solution Eh of >100 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of >200 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of >300 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of >400 mV against a Ag/AgCI reference electrode is maintained.
- the leach slurry is contacted with an ion exchange resin 22 adapted to selectively extract vanadium from solution.
- the ion exchange resin 22 is introduced into leach step 20. This process is commonly referred to in the art as a ‘resin in pulp’ process. In such a process, the majority of the extracted vanadium species generated in the leach step 20 are extracted from the solution in-situ by the ion exchange resin 22. The contact time between the ion exchange resin 22 and the leach slurry is sufficient to maximise the vanadium loading on the ion exchange resin 22.
- the ion exchange resin 22 is a strongly basic anion exchange resin.
- the ion exchange resin 22 has a particle size of at least 0.5 mm. Preferably, the ion exchange resin 22 has a particle size of at least 0.8 mm
- the leach mixture 24 comprising of leach slurry and ion exchange resin is directed to resin recovery step 26.
- Resin recovery step 26 comprises the separation of the loaded ion exchange resin 28 from the leach slurry 30.
- the resin recovery step 26 comprises the use of a screen to separate the loaded ion exchange resin 28.
- the ion exchange resin 22 preferably has a larger particle size than the undissolved solids in the leach slurry. This allows for the simple separation of the loaded resin 28 from the remaining leach slurry 30 with the use of an appropriately sized screen.
- the loaded resin 28 is directed to a resin elution step 32 where it is contacted with an eluent to recover vanadium from the loaded resin 28 into a vanadium eluate 34.
- the eluent is an aqueous solution.
- the eluent is selected from the group comprising sodium hydroxide and potassium hydroxide.
- the barren ion exchange resin is recycled back to the leach step 20 to recover additional vanadium.
- the vanadium eluate is directed to a vanadium recovery circuit 36 in order to separate out vanadium products.
- the method used will depend on the eluent used.
- the vanadium eluate 34 is directed to a desilication step 38 where it is contacted with an aluminium salt, for example aluminium sulphate to precipitate aluminium silica compounds.
- an aluminium salt for example aluminium sulphate to precipitate aluminium silica compounds.
- Silica removal may require pH adjustment and this is most readily achieved with a small quantity of sulphuric acid.
- the precipitated solids and other insoluble materials are removed in a solid liquid separation step.
- the filtrate 40 is directed to a precipitation step 42 where it is contacted with ammonium sulphate to precipitate ammonium metavanadate.
- Sulphuric acid may be added to precipitation step to control solution pH for optimal vanadium recovery.
- a target pH of between 8 - 9 is preferred.
- the resulting slurry is directed to a filtration step.
- the filtered solids are washed with dilute ammonium sulphate solution to remove any entrained liquors and further purify the filter cake.
- the recovered solids 44 are directed to calcination step 46 for deammoniation and subsequent powder melting and production of solid V2O5 flakes 48.
- Barren liquor 50 from the precipitation step 42 is directed to a crystallisation step 52 to recover sodium sulphate crystals.
- the leach slurry 30 may still include dissolved vanadium which was not recovered by the ion exchange resin.
- the leach slurry 30 is directed to a solid liquid separation step 54 to remove a leach residue 56 from a leach solution 58.
- Wash water (not shown) is used in the solid liquid separation step 54 to ensure the maximum entrained liquids and soluble species are fully separated from the leach residue 56.
- Vanadium may then be recovered from the leach solution 58 by method known to those skilled in the art.
- the leach solution is mixed with the vanadium eluate 34 and the mixed solution is directed to the vanadium recovery circuit 36.
- FIG 2 there is shown a method for the recovery of vanadium 100 from a feed stream 12 in accordance with a further embodiment of the present invention.
- the embodiment shown in Figure 2 shares many similarities with the embodiment shown in Figure 1 and like numerals denote like parts.
- the feed stream 12 is directed to primary milling step 14 to reduce the particle size.
- the resulting stream is then directed to primary leach step 102 where it is contacted with an alkaline carbonate leach solution to produce a primary leach slurry 106.
- Primary leach step 102 is operated under substantially the same conditions as leach step 20 and the above discussion equally applies to primary leach step 102.
- An ion exchange resin 104 is introduced into primary leach step 102. As discussed above, the ion exchange resin 104 is introduced into the primary leach step in order to extract dissolved vanadium species.
- the primary leach slurry 106 is directed to a size reduction step 108.
- the partially loaded ion exchange resin 109 is recovered from the primary leach slurry 106.
- the ion exchange resin may be destroyed in size reduction step and so it is preferably removed prior to size reduction step 108.
- size reduction step 108 the leach mixture is treated to reduce the particle size of undissolved solids in the primary leach slurry 106.
- Na2CC>3 and NaFIC03 will react with CaO to form solid CaCC>3.
- the inventors understand that these species will react with CaO at the exposed surfaces of the feedstock particles or with Ca 2+ in solution to form solid CaC03. At least some of the precipitated CaC03 will form as a coating on the feedstock, thereby hindering further leaching of the vanadium.
- the inventors have found that by subjecting the coated (partially leached) feedstock to a size reduction step 108, at least a portion of the CaCC>3 may be removed, exposing the surface of the feedstock and allowing further leaching of the vanadium.
- Any suitable apparatus may be used in size reductions step 108.
- suitable apparatus include ball mills, rod mills, autogenous grinding (AG) mills, semi- autogenous grinding (SAG) mills, stirred media mills and stirred media detritors.
- the size reduction step reduces the particle size of the undissolved solids to Pso 38 pm. In one embodiment, the size reduction step reduces the particle size of the undissolved solids to P9538 pm. In one embodiment, the size reduction step reduces the particle size of the undissolved solids to Pso 10 pm.
- the treated stream 110 exiting the size reduction step 108 is directed a secondary leach step 112 where it is contacted with an alkaline carbonate leach solution to produce a secondary leach slurry 114 to further extract vanadium.
- the partially loaded resin 109 recovered from the primary leach step 102 is directed to the secondary leach step 112. The ion exchange resin will continue to extract dissolved vanadium from the solution.
- Secondary leach step 112 is operated under substantially the same conditions as leach step 20 and the above discussion applies equally to secondary leach step. Whilst additional alkaline carbonate leach solution may be directed into the secondary leach step 112, it is preferred that a carbon dioxide stream is injected into the secondary leach step 112 to regenerate Na2C03/NaHC03 in the leach solution from NaOH and maintain the desired pH.
- the secondary leach slurry 114 exiting the secondary leach step 112 is directed to a further size reduction step 116 to reduce the particle size of undissolved solids in the leach slurry. Similar to size reduction step 108 size reduction step 116 will remove precipitated species from the surface of the feedstock, therefore allowing further leaching of the vanadium. Prior to proceeding, the partially loaded ion exchange resin 117 is recovered from the secondary leach slurry 114 prior to size reduction step 116.
- the treated stream 118 exiting the size reduction step 116 is directed a tertiary leach step 120 where it is contacted with an alkaline carbonate leach solution to further extract vanadium.
- the partially loaded resin 117 recovered from the secondary leach step 112 is directed to the tertiary leach step 120.
- the ion exchange resin will continue to extract dissolved vanadium from the solution.
- Tertiary leach step 120 is operated under substantially the same conditions as leach step 20 and the above discussion applies equally to secondary leach step.
- additional alkaline carbonate leach solution may be directed into the tertiary leach step 120, it is preferred that a carbon dioxide stream is injected into the tertiary leach step 120 to regenerate Na2C03/NaHCC>3 in the leach solution from NaOH and maintain the desired pH.
- a carbon dioxide stream is injected into the tertiary leach step 120 to regenerate Na2C03/NaHCC>3 in the leach solution from NaOH and maintain the desired pH.
- the process only comprises a primary leach step and a secondary leach step.
- Resin recovery step 26 comprises the separation of the loaded ion exchange resin 28 from the leach slurry 30.
- the resin recovery step 26 comprises the use of a screen to separate the loaded ion exchange resin 28.
- the ion exchange resin 22 preferably has a larger particle size than the undissolved solids in the leach slurry. This allows for the simple separation of the loaded resin 28 from the remaining leach slurry 30 with the use of an appropriately sized screen. It is envisaged that similar resin recovery steps will be utilised between successive leach steps.
- the embodiment shown in Figure 2 shows a co-current resin circuit in which unloaded resin is introduced into the primary leach step 102 and the resulting partially loaded resin is introduced to downstream leach steps.
- the ion exchange resin moves co-currently to the leach slurry.
- the method comprises a counter-current resin circuit. It is envisaged that the barren/unloaded resin may be introduced into the final leach step, for example the tertiary leach step, with the partially loaded resin being introduced into an upstream leach step. As such, the ion exchange resin moves counter-current to the leach slurry.
- the resin recovered from the primary leach step 102 is directed to the resin elution step 32.
- the resulting barren ion exchange resin is then directed to tertiary leach step 120.
- tertiary leach step 120 As would be appreciated by a person skilled in the art, such an arrangement would allow the unloaded resin to contact a leach slurry with the lowest remaining soluble vanadium, leading to increased vanadium loading.
- a further advantage of a counter-current arrangement is that the resulting filtrate from liquid separation step 54 could be recycled to the primary milling step 14. This would reduce the overall volume of the solution progressing towards vanadium recovery.
- the loaded resin 28 is directed to a resin elution step 32 where it is contacted with an eluent to recover vanadium from the loaded resin 28 into a vanadium eluate 34.
- the eluent is an aqueous solution.
- the barren ion exchange resin is recycled back to the leach step 20 to recover additional vanadium.
- the vanadium eluate 34 is directed to a vanadium recovery circuit 36 in order to separate out vanadium products.
- the method used will depend on the eluent used.
- the vanadium eluate 34 is directed to a desilication step 38 where it is contacted with an aluminium salt, for example aluminium sulphate to precipitate aluminium silica compounds.
- an aluminium salt for example aluminium sulphate to precipitate aluminium silica compounds.
- Silica removal may require pH adjustment and this is most readily achieved with a small quantity of sulphuric acid.
- the precipitated solids and other insoluble materials are removed in a solid liquid separation step.
- the filtrate 40 is directed to a precipitation step 42 where it is contacted with ammonium sulphate to precipitate ammonium metavanadate.
- Sulphuric acid may be added to precipitation step to control solution pH for optimal vanadium recovery.
- a target pH of between 8 - 9 is preferred.
- the resulting slurry is directed to a filtration step.
- the filtered solids are washed with dilute ammonium sulphate solution to remove any entrained liquors and further purify the filter cake.
- the recovered solids 44 are directed to calcination step 46 for deammoniation and subsequent powder melting and production of solid V2O5 flakes 48.
- Barren liquor 50 from the precipitation step 42 is directed to a crystallisation step 52 to recover sodium sulphate crystals.
- the leach slurry 30 may still include dissolved vanadium which was not recovered by the ion exchange resin.
- the leach slurry 30 is directed to a solid liquid separation step 54 to remove a leach residue 56 from a leach solution 58.
- Wash water (not shown) is used in the solid liquid separation step 54 to ensure the maximum entrained liquids and soluble species are fully separated from the leach residue 56.
- Vanadium may then be revered from the leach solution 58 by method known to those skilled in the art.
- the leach solution 58 is mixed with the vanadium eluate 34 and the mixed solution is directed to the vanadium recovery circuit 36.
- a test was undertaken to determine to ability of an ion exchange resin to extract vanadium from a leach step in a resin in pulp type arrangement.
- a steel slag sample containing approximately 2.1%V was crushed to particle size of P80: 75 urn.
- the sample was then subjected to a Na2CC>3 leach in the presence of an ion exchange resin.
- the leach parameters were as follows:
- Lixiviant 125 g/L Na2CC>3 / CO2 added to maintain pH 10
- a steel slag sample containing approximately 2.1%V was crushed to particle size of P80: 75 urn.
- the sample was then subjected to a Na2CC>3 leach in the presence of an ion exchange resin.
- the leach parameters were as follows:
- Lixiviant 125 g/L Na2CC>3 / CO2 added to maintain pH 10
Abstract
The present invention relates to a method for the recovery of vanadium from a vanadium containing feed stream, the method comprising the steps of: subjecting the vanadium feed stream to a leach step, the leach step comprising contacting the vanadium feed stream with an alkaline carbonate leach solution to form a leach slurry comprising a pregnant leach solution containing vanadium and a solid residue; contacting the leach slurry with an ion exchange resin adapted to extract vanadium from the leach slurry, thereby producing a loaded resin; separating the loaded resin from the leach slurry; and recovering vanadium from the loaded resin.
Description
Recovery of Vanadium from Alkaline Slag Materials
TECHNICAL FIELD
[0001] The present invention relates to a method for the recovery of vanadium from alkaline feedstocks, particularly secondary materials such as steel slags. More specifically, the method of the present invention is adapted to recover vanadium from such feedstocks through hydrometallurgical processing.
BACKGROUND ART
[0002] The following discussion of the background art is intended to facilitate an understanding of the present invention only. The discussion is not an acknowledgement or admission that any of the material referred to is or was part of the common general knowledge as at the priority date of the application.
[0003] Vanadium is most prominently found within magnetite iron ore deposits and is typically present in slags generated during iron recovery processes. To extract or recover vanadium, the concentrates or slags are typically processed with the so-called ‘salt roast process’. In the salt roast process, the vanadium slag is mixed with one or more alkali salts and subjected to a roast typically at 800 - 900 °C, to produce sodium metavanadate. These vanadium values are subsequently and selectively leached with water. Vanadium values are then recovered in a refining process that includes precipitation from the leach solution as ammonium metavanadate or ammonium polyvanadate, both of which can be treated at high temperature to de-ammoniate and convert to product vanadium pentoxide. The process and particularly the initial high temperature salt roast step is highly energy intensive and so the vanadium tenor in the feed needs to be at a particular level to make the process economical.
[0004] A number of alternative hydrometallurgical processes have been employed to process the slags for the recovery of vanadium. Such processes typically comprise an acid leach step in order to extract vanadium into solution. The main issue faced with the recovery of vanadium by hydrometallurgical means is that other metals species, such as iron, titanium, calcium, magnesium and silica, are typically co-extracted with the vanadium during the acid leach step. The presence of these species in the leach
solution must be accounted for when recovering vanadium from the leach solution. The separation of vanadium from a leach solution that also contains dissolved iron species poses a significant challenge. Most processes by which this can be achieved are economically challenging. Both vanadium and iron can be found in multiple oxidation states and degrees of coordination with varying leach systems and the mixture of species containing these elements alone can be quite complex. As a consequence, many traditional separation techniques and established reagents are unable to efficiently separate vanadium from iron. In order to address this problem, most processes require that the leach solution is first treated to remove these impurities, particularly iron and titanium, before vanadium can be recovered. This adds complexity and overall cost to processes.
[0005] CaO and other alkaline materials are also commonly found in slag materials. Consequently, a further problem with the use of an acid leach on these materials is the high consumption of acid as a result of the high alkaline content. Furthermore, when sulphuric acid is used as the leachate, a byproduct of the leach is solid CaSC .xFteO which forms at large volumes. Along with final effluent neutralization solids this product must be adequately disposed of.
[0006] Basic or alkaline leach systems for the recovery of vanadium from such feedstocks has not been widely applied to industry. The main complications of such systems appear to be the recovery being limited by the poor liberation of vanadium from the feedstock.
[0007] 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.
SUMMARY OF INVENTION
[0008] In accordance with a first aspect of the present invention, there is provided a method for the recovery of vanadium from a vanadium containing feed stream, the method comprising the steps of:
subjecting the vanadium feed stream to a leach step, the leach step comprising contacting the vanadium feed stream with an alkaline carbonate leach solution to form a leach slurry comprising a pregnant leach solution containing vanadium and a solid residue; contacting the leach slurry with an ion exchange resin adapted to extract vanadium from the leach slurry, thereby producing a loaded resin; separating the loaded resin from the leach slurry; and recovering vanadium from the loaded resin.
[0009] The inventors have found that the alkaline carbonate leach of the present invention demonstrates good selectivity of vanadium over other metals and silica that may be found in the feedstock.
[0010] Throughout this specification, unless the context requires otherwise, the term "alkaline carbonate leach solution" or similar variations, will be understood to refer to an aqueous solution comprising a carbonate or bicarbonate of an alkali metal or a carbonate or bicarbonate of an alkaline earth metal.
[0011] The method of present invention has been found to be suitable for use on alkaline feedstocks. It is envisaged that the present invention may be used to recover vanadium from a range of different sources, including slags, residues and other by products of industrial processes. Throughout this specification, unless the context requires otherwise, the term “alkaline feedstock” will be understood to refer to feedstocks that comprise one or more alkali metal compounds and alkaline earth metal compounds or form an alkaline solution or slurry when mixed with water.
[0012] The method of the present invention is preferably adapted to recover vanadium products from slag materials that result from the steel industry. In addition to vanadium, such materials will contain iron, along with other species such as manganese titanium and chromium. The method of the present invention allows for vanadium to be leached from such materials with high selectivity over other impurity metals. This has been
found to simplify the subsequent recovery of vanadium from the pregnant leach solution.
[0013] In one form of the present invention, the leach slurry is contacted with the ion exchange resin following the completion of the leach step. In an alternative form of the present invention, the leach slurry is contacted with the ion exchange resin during the leach step.
[0014] Preferably, the mixture of the leach slurry and the ion exchange resin is agitated. Agitation has been found to assist in the prevention of the solids settling to the bottom of the tank. Agitation is preferably controlled to prevent attrition and breakdown of the ion exchange resin particles.
[0015] In one form of the present invention, the loaded resin is separated from the leach slurry in a resin recovery step. Preferably, the resin recovery step comprises separation of the loaded resin by way of a screening process. Preferably, the particle size of the ion exchange resin is larger than the particle size of the vanadium feed stream. As would be appreciated by a person skilled in the art, ion exchange resins are typically provided as beads with a narrow band of particle sizes, typically at a size between 0.5 mm and 1.5 mm. This particle size is much larger than the typical particle size of undissolved solids in the leach slurry. This allows the loaded resin to be separated from the other solids in the leach slurry using a screen with a diameter smaller than the particle size of the ion exchange resin and larger than the particle size of the feed stream.
[0016] In one form of the present invention, recovery of vanadium from the loaded resin comprises directing the loaded resin to an elution step in which the loaded resin is contacted with an eluent to recover vanadium into a vanadium eluate. Preferably, the stripped resin is recycled back to the leach step.
[0017] In one form of the present invention, vanadium is recovered from the vanadium eluate.
[0018] In one form of the present invention, the leach slurry is directed to a solid liquid separation step to recover undissolved solids from a leach solution. Preferably,
vanadium is recovered from the leach solution. More preferably, the leach solution is combined with the vanadium eluate and vanadium is recovered from the mixed solution.
[0019] In one form of the present invention, the vanadium containing feed stream comprises a steel slag. Throughout this specification, unless the context requires otherwise, the term “steel slag” will be understood to refer to the slag byproduct of a steel manufacturing process. As would be appreciated by a person skilled in the art, when an iron containing material is exposed to high temperatures, at least some impurities or gangue material are separated from the molten metal and are removed as a slag. This slag is subsequently cooled, and a solid material is formed.
[0020] In one form of the present invention, the alkaline carbonate leach solution comprises one or more of sodium carbonate (Na2CC>3), sodium bicarbonate (NaHCOa) and sodium hydroxide (NaOH). In one form of the present invention, the alkaline carbonate leach solution comprises one or more of potassium carbonate (K2CO3), potassium bicarbonate (KHCO3) and potassium hydroxide (KOH). Any reference to sodium salts or species throughout the specification should be understood to be analogous to the use of potassium salts or species and any other alkali or alkaline earth carbonates and bicarbonates or mixtures thereof. As would be appreciated by a person skilled in the art, carbonates, bicarbonates and hydroxides exist together in aqueous solutions in a dynamic equilibrium in in the leach solution during the leach step. In strongly basic conditions, the hydroxide and carbonate ion predominates, while in weakly basic conditions the bicarbonate ion is more prevalent.
[0021] In one form of the present invention, the alkaline carbonate leach solution comprises ammonium carbonate.
[0022] In one form of the present invention, the leach step is conducted under oxidative conditions. Preferably, the leach step is conducted in the presence of an oxidant. More preferably, the oxidant is selected from oxygen, air, and hydrogen peroxide. Alternatively, the feedstock is combined with an oxidant prior to the leach step. Suitable oxidants include Mn02. In an alternative form of the present invention, no oxidant is added to the leach step.
[0023] In one form of the present invention, an oxidant is added to the leach step. Preferably, the addition of the oxidant will target a solution Eh of > -100 mV against a Ag/AgCI reference electrode.
[0024] In one embodiment of the present invention, the method further comprises the step of: subjecting the feed stream to a pretreatment process, prior to the step of subjecting the feed stream to the leach step.
[0025] Preferably, the pre-treatment process comprises one or more size reduction steps. More preferably, the one or more size reduction steps comprise one or more of a crushing step, a grinding step and a milling step. Preferably, the one or more size reduction steps reduce the feedstock particle size to less than particle size of ion exchange resin.
[0026] In one form of the present invention, the pre-treatment process comprises one or more beneficiation steps. Preferably, the one or more beneficiation steps include one or more of a gravity classification step, a magnetic classification step and a flotation step.
[0027] In one form of the present invention, the leach step comprises subjecting the feed stream to a leach process in one or more leach reactors. Preferably, the leach step comprises subjecting the feed stream to a leach process in two or more leach reactors. More preferably, the leach step comprises subjecting the feed stream to a leach process in three or more leach reactors. More preferably, the leach step comprises subjecting the feed stream to a leach process in four or more leach reactors. More preferably, the step comprises subjecting the feed stream to a leach process in five or more leach reactors.
[0028] In one form of the present invention, the step of subjecting the feed stream to a leach step is conducted at atmospheric pressure. In one form of the present invention, the step of subjecting the feed stream to a leach step is conducted at elevated pressure.
[0029] In one form of the present invention, the step of subjecting the feed stream to a leach step is conducted at ambient temperature. In one form of the present invention,
the step of subjecting the feed stream to a leach step is conducted at elevated temperature.
[0030] In one form of the present invention, the leach step is conducted at pH above 7.5.
[0031] In one form of the present invention, the pH of the leach step in controlled. Preferably, the leach step is maintained at a pH between 7.5 and 14. More preferably, the leach step is maintained at a pH between 9 and 10.
[0032] In one form of the present invention, a carbon dioxide stream is injected into the leach step. Preferably, the carbon dioxide stream is used to control the pH of the leach step. Alternatively, carbonic acid may be added to the leach step.
[0033] In one form of the present invention, at least a portion of the leach slurry is subjected to a size reduction step. In one form of the present invention, at least a portion of the leach slurry is transferred to a size reduction step to produce a process stream with a reduced particle size. Preferably, the leach slurry transferred to the size reduction step does not comprise the ion exchange resin. In one form of the present invention, the loaded ion exchange resin is separated from the leach slurry and the leach slurry is directed to a size reduction step. In one form of the present invention, the process stream is returned to the leach step.
[0034] In an alternative form of the present invention, the process stream is subjected to a secondary leach step. Preferably, the secondary leach step comprises contacting the process stream with an alkaline carbonate leach solution to form a secondary leach slurry comprising a pregnant leach solution containing vanadium and a solid residue. In one form of the present invention, the secondary leach step is conducted in the presence of an oxidant. In one form of the present invention, a carbon dioxide stream is injected into the secondary leach step. In one form of the present invention, the secondary leach slurry is directed to the solid liquid separation step to recover a leach solution. Preferably, the secondary leach slurry is contacted with an ion exchange resin. More preferably, the secondary leach slurry is contacted with the ion exchange resin separated from the leach step prior to the size reduction step.
[0035] In one form of the present invention, the secondary leach slurry is subjected to a size reduction step to produce a process stream with a reduced particle size. Preferably, the leach slurry transferred to the size reduction step does not comprise the ion exchange resin. In one form of the present invention, the process stream is subjected to a tertiary leach step. Preferably, the tertiary leach step comprises contacting the process stream with an alkaline carbonate leach solution to form a tertiary leach slurry comprising a pregnant leach solution containing vanadium and a solid residue. In one form of the present invention, the tertiary leach slurry is directed to the solid liquid separation step to recover a pregnant leach solution. In an alternative form of the present invention, the tertiary leach solution is subjected to one or more further size reduction steps, where each size reduction step is followed by a further leach step. Preferably, the tertiary leach slurry is contacted with an ion exchange resin. More preferably, the secondary leach slurry is contacted with the ion exchange resin separated from the first leach step or the secondary leach step prior to the size reduction step.
[0036] Preferably, the loaded resin is recovered from the leach slurry prior to the leach slurry being directed to a size reduction step. The inventors have found that the size reduction step will lead to the destruction of the ion exchange resins. As such, it should be removed from the leach slurry prior to any size reduction step being undertaken. In one form of the present invention, the loaded resin is recovered from the secondary leach slurry. In one form of the present invention, the loaded resin is recovered from the tertiary leach slurry.
[0037] In forms of the present invention where the leach step comprises multiple leach stages, ion exchange resin is added at every leach stage. It should be understood that the ion exchange resin is removed at the completion of each leach stage. Alternatively, ion exchange resin is only added to one or more leach stages. Preferably, the ion exchange resin is only added to the first least stage.
[0038] In one form of the present invention, the leach slurry is directed to a classification apparatus with the overflow being directed to the solid liquid separation step and the underflow being recycled back to the leach step or the size reduction step.
[0039] In one form of the present invention, the solid/liquid separation step comprises the treatment of the slurry in a filtration apparatus. In one embodiment, the solid/liquid separation step comprises a thickening apparatus upstream of the filtration apparatus.
[0040] In an alternative form of the present invention, the solid/liquid separation step comprises the treatment of the slurry in a counter current decantation (CCD) circuit. In one embodiment, the CCD circuit comprises two or more thickeners arranged in series.
[0041] In one form of the present invention, the solids recovered in the solid liquid separation step are subjected to a repulp step to recover further vanadium.
[0042] In one form of the present invention, the step of recovering a vanadium product from the vanadium eluate comprises precipitating a vanadium rich solid and separating the vanadium rich solid from the barren eluate. Throughout the specification, the term “barren eluate” will be understood to refer to a eluate to which at least a portion of the vanadium has been recovered. It should be understood to include a solution that contains vanadium.
[0043] A barren eluate results from the step of recovering a vanadium product from the vanadium eluate. In one form of the present invention, at least a portion of the barren eluate solution is recycled to the elution step.
BRIEF DESCRIPTION OF THE DRAWINGS
[0044] 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:
Figure 1 is a flowsheet of the method of the present invention; and
Figure 2 is flowsheet of an alternative embodiment of the present invention
DESCRIPTION OF EMBODIMENTS
[0045] The method of the present invention relates to the recovery of vanadium from a vanadium containing feed stream. In a very broad sense, the method comprises the steps of: subjecting the vanadium feed stream to a leach step, the leach step comprising contacting the vanadium feed stream with an alkaline carbonate leach solution to form a leach slurry comprising a pregnant leach solution containing vanadium and a solid residue; contacting the leach slurry with an ion exchange resin adapted to extract vanadium from the leach slurry, thereby producing a loaded resin; separating the loaded resin from the leach slurry; and recovering vanadium from the loaded resin.
[0046] The inventors have found that the carbonate leach of the present invention demonstrates good selectivity of vanadium over other metals that may be found in the feedstock.
[0047] The method of present invention has been found to be suitable for use on alkaline feedstocks. The presence of alkaline material in feedstocks presents a problem for the treatment of such feedstocks by hydrometallurgical processes that use acids as the primary leachant. The main disadvantage with such processes is that a high amount of acid is consumed by the alkaline material, which increases the operating costs. Furthermore, acid soluble impurities are also extracted into the leach solution and further processing is required to remove these. In addition, large volumes of calcium salts, leach residues and/or effluent neutralization wastes can be generated and the handling of these leads to process inefficiencies and/or added processing costs.
[0048] It is envisaged that the present invention may be used to recover vanadium from a range of different sources, including slags, residues and/or other by-products of industrial processes.
[0049] The method of the present invention is preferably adapted to recover vanadium products from slag materials that result from the steel industry. In addition to vanadium, such materials will contain iron, along with other species such as titanium. The method of the present invention allows for vanadium to be leached from such materials with high selectivity over other impurity metals. This has been found to simplify the recovery of vanadium from the pregnant leach solution.
[0050] In Figure 1 , there is shown a method for the recovery of vanadium 10 from a feed stream 12 in accordance with an embodiment of the present invention the feedstock 12 is subjected to primary milling step 14. The feedstock 12 should have a target particle size of <200 pm, with a target particle size of <100 pm being preferred and < 75 pm being more preferable. In order to assist with the separation of the loaded resin, the target size of the feedstock 12 should be smaller than the particle size of the ion exchange resin. It is envisaged that conventional crushing and grinding apparatus available to those skilled in the art can be used to reduce the particle size of the feedstock 12. The feedstock may be subjected to one or more beneficiation steps (not shown) to remove excess low value bearing components of the feedstock 12. As discussed previously, the one or more beneficiation steps can include one or more of a gravity classification step, a magnetic classification step and a flotation step. The inventors have found that a significant proportion of the vanadium in steel slags may be captured in silica glass. The one or more size reduction steps have been found to liberate vanadium from such materials, allowing for subsequent dissolution in the leach step. It is envisaged that both wet and dry particle size reduction apparatus may be utilised.
[0051] The feed stream is directed to leach step 20. In leach step 20, the feed stream is contacted with an alkaline carbonate leach solution to extract vanadium into the solution. Depending on the precise feed material being used, the vanadium species in the feed may exist in a number of different forms. For example, calcium vanadate species may include Ca(V03)2, CaV2C>6.3Fl20, CaV2C>6.4Fl20, CaV60i6.9Fl20, Ca2V207.9Fl20, Ca3Vio028.16Fl20, amongst others. By way of illustration, the calcium vanadates in the feedstock may react with the alkaline liquor 16 in the leaching process according to the following reactions:
Ca(V03)2 + M2CO3 CaCOa + 2MVOa
(where M is an alkaline metal or alkaline earth metal)
It would be appreciated by a person skilled in the art the above reactions are included for illustration purposes only and are not an exhaustive list of the reactions occurring during the leach step 20.
[0052] Additional alkaline liquor or alkaline carbonate leach solution may be directed into leach step 20 to increase the CO32 / HCO3 concentration in the leach solution. Alternatively, CO32 / HC03 rmay be regenerated in the solution.
[0053] An oxidant stream may be injected into the leach step 20 to oxidise at least a portion of the components of the feedstock and improve vanadium recovery. Without wishing to be bound by theory, it is believed that at least some of the vanadium in the feedstock may be encapsulated in various Fe(ll) compounds found in the feedstock. The inventors have found that the addition of the oxidant will oxidise Fe(ll) to Fe(lll) which can assist in the liberation of vanadium from within these compounds. Furthermore, any dissolved Fe(lll) will likely re-precipitate as FeO(OFI) (also written as Fe203.Fl20). In one embodiment, the oxidant is selected from hydrogen peroxide and potassium permanganate.
[0054] A carbon dioxide stream may be directed into the leach step 20. As would be appreciated by a person skilled in the art, alkaline feedstocks such as steel slags contain a high CaO and Ca(OFI)2 content. The Na2CC>3/NaFIC03 in the leach liquor will react with CaO/Ca(OFI)2 to produce solid CaCC>3 and NaOFI. The reactions can be summarized by the following simplified reactions:
[0055] The inventors have found that carbon dioxide will react with sodium hydroxide and other species in the leach solution to form a reactive carbonate system as represented by the following simplified reactions:
[0056] The addition of carbon dioxide has therefore been found to regenerate Na2C03/ NaHC03 in the leach solution from the NaOH produced during the reaction of CaO, allowing for further extraction of vanadium from the feedstock.
[0057] In one embodiment, the pH of the leach solution is controlled throughout the leach step. In one embodiment, the leach solution is maintained at a pH above 7.5. In one embodiment, the leach solution is maintained at a pH above 8. In one embodiment, the leach solution is maintained at a pH above 8.5. In one embodiment, the leach solution is maintained at a pH above 9.
[0058] In one embodiment, the leach solution is maintained at a pH between 7.5 and 14. In one embodiment the pH is maintained between 8 and 11. In one embodiment, the pH is maintained between 9 and 10. The inventors have found that the pH of the leach solution will naturally increase throughout the leach process as a result of the formation of NaOH during the reaction of the alkaline carbonates and CaO/Ca(OH)2. However, at pH above 14 silica is increasingly soluble and will be leached into solution. It has also been found that at pH below 9, small quantities of impurities such as manganese, magnesium, iron and titanium begin to dissolve. This will increase the complexity and may impact the subsequent recovery of vanadium form the leach solution. By maintaining a pH between 9 and 14, vanadium extraction can be achieved with minimal silica being leached into solution.
[0059] In one embodiment, the pH is maintained by the addition of carbon dioxide into the leach solution. As discussed above, carbon dioxide will convert NaOH to Na2C03/NaHCC>3. Alternatively, the pH is maintained by the addition of acid.
[0060] In a preferred embodiment, the leach step 20 is conduct at a pH of approximately 10 to prevent the above discussed impurities leaching into solution. Following separation of undissolved solids, the pH of the pregnant leach solution may then be lowered to between 9-9.5 in order to precipitate at least some silica out of the solution. A coagulant may be added to assist in the silica removal. The precipitated solids may then be filtered out of the solution.
[0061] The leach step 20 preferably comprises a leach circuit comprising one or more leach vessels arranged in series.
[0062] In one embodiment, the feedstock has a particle size of Pso 106 pm. In one embodiment, the feedstock has a particle size of Pso 75 pm. In one embodiment, the feedstock has a particle size of Pso 53 pm. In one embodiment, the feedstock has a particle size of Pioo 25 pm.
[0063] In one embodiment, the leach is conducted at ambient temperature. In one embodiment, the leach is conducted at elevated temperature. Preferably, the leach step is conducted at a temperature up to boiling point. In one embodiment, the leach step is conducted at a temperature above 50°C. In one embodiment, the leach step is conducted at a temperature above 60°C. In one embodiment, the leach step is conducted at a temperature above 70°C. In one embodiment, the leach step is conducted at a temperature above 80°C. In one embodiment, the leach step is conducted at a temperature above 90°C.
[0064] In one embodiment, the leach step is conducted at ambient pressure. In one embodiment, the leach step is conducted at elevated pressure. It is envisaged that carbon dioxide may be injected into the headspace of the leach reactor.
[0065] In one embodiment, the pulp density of the leach step is 10-50%. In one embodiment, the pulp density is 20 - 40 %.
[0066] In one embodiment, the Na2C03/NaHC03 concentration in the leach solution is between 2-35 %. In one embodiment, the Na2C03/NaHC03 concentration in the leach solution is at least 50 g/L. In one embodiment, the Na2C03/NaHC03 concentration in the leach solution is at least 75 g/L. In one embodiment, the Na2C03/NaHC03 concentration in the leach solution is at least 125 g/L.
[0067] In embodiments where carbon dioxide is sparged through the leach vessel, the Na concentration in the leach solution is at least 40 g/L.
[0068] In one embodiment, the residence time of the leach step is greater than 1 hour. In one embodiment, the residence time of the leach step is greater than 2 hours. In one embodiment, the residence time of the leach step is greater than 3 hours. In one embodiment, the residence time of the leach step is greater than 4 hours. In one embodiment, the residence time of the leach step is greater than 5 hours. In one embodiment, the residence time of the leach step is greater than 6 hours. In one embodiment, the residence time of the leach step is greater than 7 hours. In one embodiment, the residence time of the leach step is greater than 8 hours. In one embodiment, the residence time of the leach step is greater than 9 hours. In one embodiment, the residence time of the leach step is greater than 10 hours. In one embodiment, the residence time of the leach step is greater than 11 hours. In one embodiment, the residence time of the leach step is greater than 12 hours.
[0069] In one embodiment, a solution Eh of > -100 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > -90 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > -80 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > -70 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > -60 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > -50 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > -40 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > -30 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > -20 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > -10 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of > 0 mV against a Ag/AgCI reference
electrode is maintained. In one embodiment, a solution Eh of >50 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of >100 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of >200 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of >300 mV against a Ag/AgCI reference electrode is maintained. In one embodiment, a solution Eh of >400 mV against a Ag/AgCI reference electrode is maintained.
[0070] In order to recover the extracted vanadium, the leach slurry is contacted with an ion exchange resin 22 adapted to selectively extract vanadium from solution. In the embodiment shown in Figure 1 , the ion exchange resin 22 is introduced into leach step 20. This process is commonly referred to in the art as a ‘resin in pulp’ process. In such a process, the majority of the extracted vanadium species generated in the leach step 20 are extracted from the solution in-situ by the ion exchange resin 22. The contact time between the ion exchange resin 22 and the leach slurry is sufficient to maximise the vanadium loading on the ion exchange resin 22.
[0071] In one embodiment, the ion exchange resin 22 is a strongly basic anion exchange resin.
[0072] In one embodiment, the ion exchange resin 22 has a particle size of at least 0.5 mm. Preferably, the ion exchange resin 22 has a particle size of at least 0.8 mm
[0073] Following the leach step 20, the leach mixture 24 comprising of leach slurry and ion exchange resin is directed to resin recovery step 26. Resin recovery step 26 comprises the separation of the loaded ion exchange resin 28 from the leach slurry 30. Preferably, the resin recovery step 26 comprises the use of a screen to separate the loaded ion exchange resin 28. As discussed above, the ion exchange resin 22 preferably has a larger particle size than the undissolved solids in the leach slurry. This allows for the simple separation of the loaded resin 28 from the remaining leach slurry 30 with the use of an appropriately sized screen.
[0074] The loaded resin 28 is directed to a resin elution step 32 where it is contacted with an eluent to recover vanadium from the loaded resin 28 into a vanadium eluate 34. Preferably, the eluent is an aqueous solution.
[0075] In one form of the present invention, the eluent is selected from the group comprising sodium hydroxide and potassium hydroxide.
[0076] Following the resin elution step 32, the barren ion exchange resin is recycled back to the leach step 20 to recover additional vanadium.
[0077] The vanadium eluate is directed to a vanadium recovery circuit 36 in order to separate out vanadium products. The method used will depend on the eluent used. In the embodiment shown in Figure 1 , the vanadium eluate 34 is directed to a desilication step 38 where it is contacted with an aluminium salt, for example aluminium sulphate to precipitate aluminium silica compounds. Silica removal may require pH adjustment and this is most readily achieved with a small quantity of sulphuric acid. The precipitated solids and other insoluble materials are removed in a solid liquid separation step. The filtrate 40 is directed to a precipitation step 42 where it is contacted with ammonium sulphate to precipitate ammonium metavanadate. Sulphuric acid may be added to precipitation step to control solution pH for optimal vanadium recovery. A target pH of between 8 - 9 is preferred. The resulting slurry is directed to a filtration step. The filtered solids are washed with dilute ammonium sulphate solution to remove any entrained liquors and further purify the filter cake. The recovered solids 44 are directed to calcination step 46 for deammoniation and subsequent powder melting and production of solid V2O5 flakes 48. Barren liquor 50 from the precipitation step 42 is directed to a crystallisation step 52 to recover sodium sulphate crystals.
[0078] The leach slurry 30 may still include dissolved vanadium which was not recovered by the ion exchange resin. The leach slurry 30 is directed to a solid liquid separation step 54 to remove a leach residue 56 from a leach solution 58. Wash water (not shown) is used in the solid liquid separation step 54 to ensure the maximum entrained liquids and soluble species are fully separated from the leach residue 56. Vanadium may then be recovered from the leach solution 58 by method known to those skilled in the art. In the embodiment shown in Figure 1 , the leach solution is mixed with the vanadium eluate 34 and the mixed solution is directed to the vanadium recovery circuit 36.
[0079] In Figure 2, there is shown a method for the recovery of vanadium 100 from a feed stream 12 in accordance with a further embodiment of the present invention. The
embodiment shown in Figure 2 shares many similarities with the embodiment shown in Figure 1 and like numerals denote like parts. The feed stream 12 is directed to primary milling step 14 to reduce the particle size.
[0080] The resulting stream is then directed to primary leach step 102 where it is contacted with an alkaline carbonate leach solution to produce a primary leach slurry 106. Primary leach step 102 is operated under substantially the same conditions as leach step 20 and the above discussion equally applies to primary leach step 102. An ion exchange resin 104 is introduced into primary leach step 102. As discussed above, the ion exchange resin 104 is introduced into the primary leach step in order to extract dissolved vanadium species.
[0081] In the embodiment shown in Figure 2, the primary leach slurry 106 is directed to a size reduction step 108. Prior to proceeding, the partially loaded ion exchange resin 109 is recovered from the primary leach slurry 106. As discussed above, the ion exchange resin may be destroyed in size reduction step and so it is preferably removed prior to size reduction step 108. In size reduction step 108, the leach mixture is treated to reduce the particle size of undissolved solids in the primary leach slurry 106. As discussed above, Na2CC>3 and NaFIC03 will react with CaO to form solid CaCC>3. Without wishing to be bound by theory, the inventors understand that these species will react with CaO at the exposed surfaces of the feedstock particles or with Ca2+ in solution to form solid CaC03. At least some of the precipitated CaC03 will form as a coating on the feedstock, thereby hindering further leaching of the vanadium. The inventors have found that by subjecting the coated (partially leached) feedstock to a size reduction step 108, at least a portion of the CaCC>3 may be removed, exposing the surface of the feedstock and allowing further leaching of the vanadium.
[0082] Any suitable apparatus may be used in size reductions step 108. Examples of suitable apparatus include ball mills, rod mills, autogenous grinding (AG) mills, semi- autogenous grinding (SAG) mills, stirred media mills and stirred media detritors.
[0083] In one embodiment, the size reduction step reduces the particle size of the undissolved solids to Pso 38 pm. In one embodiment, the size reduction step reduces the particle size of the undissolved solids to P9538 pm. In one embodiment, the size reduction step reduces the particle size of the undissolved solids to Pso 10 pm.
[0084] The treated stream 110 exiting the size reduction step 108 is directed a secondary leach step 112 where it is contacted with an alkaline carbonate leach solution to produce a secondary leach slurry 114 to further extract vanadium. In the embodiment shown in Figure 2, the partially loaded resin 109 recovered from the primary leach step 102 is directed to the secondary leach step 112. The ion exchange resin will continue to extract dissolved vanadium from the solution. Secondary leach step 112 is operated under substantially the same conditions as leach step 20 and the above discussion applies equally to secondary leach step. Whilst additional alkaline carbonate leach solution may be directed into the secondary leach step 112, it is preferred that a carbon dioxide stream is injected into the secondary leach step 112 to regenerate Na2C03/NaHC03 in the leach solution from NaOH and maintain the desired pH.
[0085] In the embodiment shown in Figure 2, the secondary leach slurry 114 exiting the secondary leach step 112 is directed to a further size reduction step 116 to reduce the particle size of undissolved solids in the leach slurry. Similar to size reduction step 108 size reduction step 116 will remove precipitated species from the surface of the feedstock, therefore allowing further leaching of the vanadium. Prior to proceeding, the partially loaded ion exchange resin 117 is recovered from the secondary leach slurry 114 prior to size reduction step 116.
[0086] The treated stream 118 exiting the size reduction step 116 is directed a tertiary leach step 120 where it is contacted with an alkaline carbonate leach solution to further extract vanadium. In the embodiment shown in Figure 2, the partially loaded resin 117 recovered from the secondary leach step 112 is directed to the tertiary leach step 120. The ion exchange resin will continue to extract dissolved vanadium from the solution. Tertiary leach step 120 is operated under substantially the same conditions as leach step 20 and the above discussion applies equally to secondary leach step. Whilst additional alkaline carbonate leach solution may be directed into the tertiary leach step 120, it is preferred that a carbon dioxide stream is injected into the tertiary leach step 120 to regenerate Na2C03/NaHCC>3 in the leach solution from NaOH and maintain the desired pH.
[0087] Whilst the embodiment shown in Figure 2 comprises three separate leach steps, it is envisaged that additional leach steps could be included. It is envisaged that a size reduction step should be included between successive leach steps.
[0088] In an alternative form of the present invention, the process only comprises a primary leach step and a secondary leach step.
[0089] Following the tertiary leach step 120, the mixture of leach slurry and ion exchange resin is directed to resin recovery step 26. Resin recovery step 26 comprises the separation of the loaded ion exchange resin 28 from the leach slurry 30. Preferably, the resin recovery step 26 comprises the use of a screen to separate the loaded ion exchange resin 28. As discussed above, the ion exchange resin 22 preferably has a larger particle size than the undissolved solids in the leach slurry. This allows for the simple separation of the loaded resin 28 from the remaining leach slurry 30 with the use of an appropriately sized screen. It is envisaged that similar resin recovery steps will be utilised between successive leach steps.
[0090] The embodiment shown in Figure 2 shows a co-current resin circuit in which unloaded resin is introduced into the primary leach step 102 and the resulting partially loaded resin is introduced to downstream leach steps. As such, the ion exchange resin moves co-currently to the leach slurry. In an alternative embodiment, the method comprises a counter-current resin circuit. It is envisaged that the barren/unloaded resin may be introduced into the final leach step, for example the tertiary leach step, with the partially loaded resin being introduced into an upstream leach step. As such, the ion exchange resin moves counter-current to the leach slurry. In this embodiment, the resin recovered from the primary leach step 102 is directed to the resin elution step 32. The resulting barren ion exchange resin is then directed to tertiary leach step 120. As would be appreciated by a person skilled in the art, such an arrangement would allow the unloaded resin to contact a leach slurry with the lowest remaining soluble vanadium, leading to increased vanadium loading. A further advantage of a counter-current arrangement is that the resulting filtrate from liquid separation step 54 could be recycled to the primary milling step 14. This would reduce the overall volume of the solution progressing towards vanadium recovery.
[0091] The loaded resin 28 is directed to a resin elution step 32 where it is contacted with an eluent to recover vanadium from the loaded resin 28 into a vanadium eluate 34. Preferably, the eluent is an aqueous solution.
[0092] Following the resin elution step 32, the barren ion exchange resin is recycled back to the leach step 20 to recover additional vanadium.
[0093] The vanadium eluate 34 is directed to a vanadium recovery circuit 36 in order to separate out vanadium products. The method used will depend on the eluent used. In the embodiment shown in Figure 1 , the vanadium eluate 34 is directed to a desilication step 38 where it is contacted with an aluminium salt, for example aluminium sulphate to precipitate aluminium silica compounds. Silica removal may require pH adjustment and this is most readily achieved with a small quantity of sulphuric acid. The precipitated solids and other insoluble materials are removed in a solid liquid separation step. The filtrate 40 is directed to a precipitation step 42 where it is contacted with ammonium sulphate to precipitate ammonium metavanadate. Sulphuric acid may be added to precipitation step to control solution pH for optimal vanadium recovery. A target pH of between 8 - 9 is preferred. The resulting slurry is directed to a filtration step. The filtered solids are washed with dilute ammonium sulphate solution to remove any entrained liquors and further purify the filter cake. The recovered solids 44 are directed to calcination step 46 for deammoniation and subsequent powder melting and production of solid V2O5 flakes 48. Barren liquor 50 from the precipitation step 42 is directed to a crystallisation step 52 to recover sodium sulphate crystals.
[0094] The leach slurry 30 may still include dissolved vanadium which was not recovered by the ion exchange resin. The leach slurry 30 is directed to a solid liquid separation step 54 to remove a leach residue 56 from a leach solution 58. Wash water (not shown) is used in the solid liquid separation step 54 to ensure the maximum entrained liquids and soluble species are fully separated from the leach residue 56. Vanadium may then be revered from the leach solution 58 by method known to those skilled in the art. In the embodiment shown in Figure 2, the leach solution 58 is mixed with the vanadium eluate 34 and the mixed solution is directed to the vanadium recovery circuit 36.
EXAMPLE 1
[0095] A test was undertaken to determine to ability of an ion exchange resin to extract vanadium from a leach step in a resin in pulp type arrangement.
[0096] A steel slag sample containing approximately 2.1%V was crushed to particle size of P80: 75 urn. The sample was then subjected to a Na2CC>3 leach in the presence of an ion exchange resin. The leach parameters were as follows:
Lixiviant: 125 g/L Na2CC>3 / CO2 added to maintain pH 10
% solids: 30.0%
Temp: 70°C
Time: 8 hrs
Resin Purolite A500/2788 - 300mL
[0097] Liquor and residue assays were taken every hour and the results are shown in Table 1 - Table 3:
Table 1 : Liquor Assays
Table 2: Residue Assay
Table 3: Extraction
[0098] The results indicated a vanadium extraction of approximately 67% vanadium after 4 hours. Resin loading was approximately 3.8 g/L.
EXAMPLE 2
[0099] A further test was undertaken to determine to ability of an ion exchange resin to extract vanadium from a leach step in a resin in pulp type arrangement.
[00100] A steel slag sample containing approximately 2.1%V was crushed to particle size of P80: 75 urn. The sample was then subjected to a Na2CC>3 leach in the presence of an ion exchange resin. The leach parameters were as follows:
Lixiviant: 125 g/L Na2CC>3 / CO2 added to maintain pH 10
% solids: 30.0%
Temp: 70C
Time: 8 hrs
Resin Purolite MTA8000PPS04: 500mL
[00101] Liquor and residue assays were taken every hour and the results are shown in Table 4 - Table 6:
Table 4: Liquor Assay
Table 5: Residue Assay
Table 6: Extraction
[00102] The results demonstrated 65% extraction of vanadium from feed. Resin loading was approximately 6.8 g/L.
[00103] Those skilled in the art will appreciate that the invention described herein is susceptible to variations and modifications other than those specifically described. The invention includes all such variation and modifications. The invention also includes all of the steps, features, formulations and compounds referred to or indicated in the specification, individually or collectively and any and all combinations or any two or more of the steps or features.
Claims
1. A method for the recovery of vanadium from a vanadium containing feed stream, the method comprising the steps of: subjecting the vanadium feed stream to a leach step, the leach step comprising contacting the vanadium feed stream with an alkaline carbonate leach solution to form a leach slurry comprising a pregnant leach solution containing vanadium and a solid residue; contacting the leach slurry with an ion exchange resin adapted to extract vanadium from the leach slurry, thereby producing a loaded resin; separating the loaded resin from the leach slurry; and recovering vanadium from the loaded resin.
2. A method according to claim 1 , wherein the leach slurry is contacted with the ion exchange resin following the completion of the leach step.
3. A method according to claim 1 , wherein the leach slurry is contacted with the ion exchange resin during the leach step.
4. A method according to any one of the preceding claims, wherein the mixture of the leach slurry and the ion exchange resin is agitated.
5. A method according to any one of the preceding claims, wherein the loaded resin is separated from the leach slurry in a resin recovery step.
6. A method according to any one of the preceding claims, wherein the particle size of the ion exchange resin is larger than the particle size of the vanadium feed stream.
7. A method according to any one of the preceding claims, wherein recovery of vanadium from the loaded resin comprises directing the loaded resin to an elution
step in which the loaded resin is contacted with an eluent to recover vanadium into a vanadium eluate.
8. A method according to claim 7, wherein the vanadium is recovered from the vanadium eluate.
9. A method according to any one of the preceding claims, wherein following the separation of the loaded resin, the leach slurry is directed to a solid liquid separation step to recover undissolved solids from a leach solution.
10. A method according to claim 9, wherein vanadium is recovered from the leach solution.
11. A method according to any one of the preceding claims, wherein the alkaline carbonate leach solution comprises one or more of sodium carbonate (Na2CC>3), sodium bicarbonate (NaHCC>3) and sodium hydroxide (NaOH).
12. A method according to any one of the preceding claims, wherein a carbon dioxide stream is injected into the leach step.
13. A method according to any one of the preceding claims, wherein at least a portion of the leach slurry is transferred to a size reduction step to produce a process stream with a reduced particle size.
14. A method according to claim 13, wherein the process stream is returned to the leach step.
15. A method according to claim 13, wherein the process stream is subjected to a secondary leach step.
16. A method according to any one of the preceding claims, wherein the step of recovering a vanadium product from the vanadium eluate comprises precipitating a vanadium rich solid and separating the vanadium rich solid from the barren eluate.
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| AU2021902087A AU2021902087A0 (en) | 2021-07-08 | Recovery of Vanadium from Alkaline Slag Materials | |
| AU2021902087 | 2021-07-08 |
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| WO2023279144A1 true WO2023279144A1 (en) | 2023-01-12 |
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