WO2002018663A2 - Recuperation selective de metaux a partir d'une composition catalytique usee - Google Patents

Recuperation selective de metaux a partir d'une composition catalytique usee Download PDF

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Publication number
WO2002018663A2
WO2002018663A2 PCT/ZA2001/000128 ZA0100128W WO0218663A2 WO 2002018663 A2 WO2002018663 A2 WO 2002018663A2 ZA 0100128 W ZA0100128 W ZA 0100128W WO 0218663 A2 WO0218663 A2 WO 0218663A2
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Prior art keywords
cobalt
solution
platinum
aluminium
catalyst composition
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PCT/ZA2001/000128
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English (en)
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WO2002018663A3 (fr
WO2002018663A8 (fr
Inventor
Ratale Henry Matjie
Ewald Watermeyer De Wet
Masikana Millan Mdleni
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Sasol Technology (Pty) Ltd
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Priority to US10/363,491 priority Critical patent/US20040219082A1/en
Priority to AU2001295097A priority patent/AU2001295097A1/en
Publication of WO2002018663A2 publication Critical patent/WO2002018663A2/fr
Publication of WO2002018663A3 publication Critical patent/WO2002018663A3/fr
Publication of WO2002018663A8 publication Critical patent/WO2002018663A8/fr

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    • 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
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes
    • C22B11/042—Recovery of noble metals from waste materials
    • C22B11/048—Recovery of noble metals from waste materials from spent catalysts
    • 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C22B23/026—Obtaining nickel or cobalt by dry processes from spent catalysts
    • 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
    • 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

  • This invention relates to the selective recovery of metal values from a spent catalyst composition.
  • this invention relates to a process for the selective recovery of aluminium, Cobalt and Platinum and/or compounds thereof, from a spent catalyst composition.
  • the specific spent catalyst composition of the current invention is obtained from Fischer Tropsch synthesis reactions for the production of predominantly paraffinic hydrocarbons.
  • the catalyst is an impregnated Fischer Tropsch Catalyst comprising an alumina carrier and active component selected from the group consisting of cobalt and/or iron and mixtures thereof.
  • the catalyst may also comprise of a group VIM noble metal as promoter.
  • the Fischer-Tropsch process is used to produce hydrocarbons from carbon monoxide and hydrogen.
  • a cobalt catalyst may be used to activate the catalytic reaction.
  • This catalyst may be prepared with a cobalt nitrate and tetra amine platinum nitrate that are used as cobalt and platinum precursors respectively. Aluminium oxide may be used as a support.
  • Continual processing causes a drop in the activity of the catalyst mainly due to sulphur, which is originally present in the mixture of gases, which may accumulate on the surface of the catalyst to form either cobalt sulphide or platinum sulphide during the process. Coke formation may also be experienced during the process and subsequently the catalyst reaches a stage of deactivation and becomes a spent catalyst.
  • the spent catalyst typically contains organic material, cobalt oxide, platinum and aluminium oxide.
  • organic content in the catalyst coupled with the fact that both cobalt and platinum are considered to be environmentally toxic, dumping is not a viable option.
  • the chemical fixation method should be recommended. In this method, which is very expensive, the pollutants like heavy and base metals can react with cement or pozzolanic materials to form water insoluble compounds. This encapsulation of heavy and base metals on the spent catalyst is efficacious only if the heavy metals are not absolutely leached out in the soil by water. To avoid the disposal of the spent catalyst or encapsulated deactivated catalyst in the landfills, the recovery of these high value metals is important.
  • the inventor is aware that the above catalyst composition contains valuable metal values which, if recovered, could lead to a substantial profit and also to eliminate the existing environmental problems. At present the catalyst composition is disposed of without substantial recovery thereof.
  • either the mixture of spent catalyst and sodium carbonate or the spent catalyst containing organic material is calcined at different temperatures in the presence of air to oxidise the organic material.
  • metal oxides such as cobalt oxide (CoO and C03O4), cobalt aluminate (C02AIO4) and sodium aluminate (Na2Al 2 ⁇ 4 ) are formed.
  • a solution of caustic soda (sodium hydroxide) is used to selectively and efficiently dissolve aluminium oxide at a relatively high temperatures (ranging from 110 to 220 Degrees Celsius) and pressures (ranging from 5 to 20 bars) with substantially no dissolution of cobalt and platinum from the spent catalyst.
  • the pH of the mixture is around 13.
  • water leaching may be used to solubilise sodium aluminate formed during the calcination step.
  • This sodium aluminate solution which is formed during the leaching step may be used in the precipitation step of the aluminium hydroxide.
  • the cobalt and platinum which are theoretically insoluble in a solution of sodium hydroxide under afore-given conditions, remain in the leached residue after the base leaching.
  • This leached residue containing mainly platinum and cobalt are dissolved in a solution of nitric acid to form cobalt nitrate while the platinum remains in the acid-residue after the acid leaching step.
  • This acid residue may be dissolved in the aqua regia (a solution of nitric acid and hydrochloric acid) to form chloroplatinic acid.
  • aqua regia a solution of nitric acid and hydrochloric acid
  • purification methods such as solvent extraction and selective precipitation may be used to selectively remove impurities or the desired metal ions from the leach liquors of the basic residue and acidic residue.
  • the purified leach liquors may be reserved for the crystallisation method. In this method, chemically pure crystalline cobalt nitrate or diammonium hexachloroplatinate are formed.
  • the platinum salts are important in the purification of platinum metal and sponge while the cobalt nitrate is commercially used in the production of high purity cobalt, in the electronics and chemical industries.
  • a process for the selective recovery of aluminium, cobalt and platinum, and compounds thereof, from a catalyst composition including aluminium, cobalt and platinum including the steps of: treating the catalyst composition to selectively get ions of substantially only one of the aluminium, cobalt and platinum into solution; recovering, in separate process steps, the thus treated aluminium, cobalt, or platinum in salt or metal form; and repeating the treating and recovering steps for each of the aluminium, cobalt and platinum.
  • the treating steps may include process steps such as leaching, washing, dissolving, stripping, and the like.
  • the recovery steps may include filtration, precipitation, separation, flocculation, and the like.
  • a process for the selective recovery of aluminium, cobalt and platinum, and compounds thereof, from a catalyst composition including aluminium, cobalt and platinum including the steps of: oxidising substantially all organic material present with the catalyst composition; leaching the aluminium and/or compounds thereof from the oxidised catalyst composition with a strong or weak base to form an aluminium containing product and a filtrate; filtering of alkali insoluble residue from the filtrate; washing of the alkali insoluble residue with water to remove the residual alkali aluminate solution; - precipitating of silica from alkali aluminate with slaked lime or quicklime; filtering of insoluble silicate from alkali aluminate; crystalising aluminium trihydrate from the alkali aluminate solution; - filtering aluminium trihydrate crystals from the alkali aluminate solution recycling of the alkali solution to the leaching step; dissolving the cobalt and compounds thereof
  • a flocculation step may be included to remove ultra fine solids which inhibit efficient filtration.
  • a flocculation step may be included to remove ultra fine solids which may inhibit efficient separation.
  • the flocculation for an alkali slurry may be carried out with the aid of flocculating agents, such as modified anionic polyacrylamides.
  • the flocculation may be carried out at a pH of about 12.
  • the flocculation may assist the sedimentation rate and filterability of suspended ultra fine solid particles from the slurry
  • the flocculation for an acidic slurry may be carried out with the aid of flocculating agents such as cationic a flocculant.
  • the flocculation may carried out at a low pH about 1.5.
  • the flocculation may assist the sedimentation rate and filterability of suspended ultra fine solid particles from the slurry.
  • the catalyst composition may be in the form of waxy lumps of spent catalyst composition from a hydrocarbon processing reactor.
  • the oxidising step may be performed by heating the catalyst composition and contacting it with oxygen.
  • the catalyst composition is heated to a temperature of between 600°C and 1400°C, generally between 700°C and 1000°C. In specific embodiments of the invention the catalyst composition was heated to 700°C, 800°C, 900°C and 1000°C.
  • the oxidised spent catalyst composition typically contains about from 0.0125 g Pt per 100 g AI 2 O 3 to 0.175 g Pt per 100 g AI 2 O 3 and from 5 g Co per 100 g AI 2 O 3 to 70 g Co per 100 g AI 2 O .
  • the leaching of the aluminium and/or the aluminium compounds, such as AI2O 3 , from the oxidised spent catalyst composition may be carried out with a solution of sodium hydroxide of about 20% to 50% w/w NaOH, typically 25%. This selectively and efficiently dissolves aluminium oxide at a relatively high temperature ranging from 1 10°C to 250°C, typically 200°C, and at a high pressure ranging from 5 to 20 bar, typically 15 bar, with substantially no dissolution of cobalt and platinum from the spent catalyst composition.
  • the leachate may be in the form of slurry.
  • the flocculation of the slurry prior to filtration may be carried out using approximately 2 % w/w of flocculant prepared using a solution of sodium hydroxide of about 2 % w/w NaOH, whereafter the flocculant solution is conditioned at ambient temperature for one hour to form homogeneous solution, whereafter it is diluted with a solution of sodium hydroxide of 2 % w/w NaOH to produce a final solution containing about 0.25 % w/w of the flocculant.
  • Approximately 3000 to 6000 g/t of the final solution heated to 90 degrees Celsius may be added to the slurry and mixed thoroughly until floes form. These floes may be separated from the mixture by filtration and eventually washed with water to remove aluminium-containing filtrate absorbed during the filtration.
  • water leaching could also be used to selectively solubilize sodium aluminate formed during the oxidising of the spent catalyst in the presence of either sodium carbonate or sodium chloride.
  • the water leaching may be carried out at any temperature and pressure, and 50°C at atmospheric pressure has been found to be satisfactory.
  • a solution of sodium aluminate from the water leaching step may be reserved for the precipitation of aluminium hydroxide while the water- washed base insoluble residue may be used in the strong or weak inorganic acid cobalt dissolving step.
  • the leached residue recovered from the aluminium leaching step typically contains 51 % w/w cobalt, 0.124% w/w platinum and 4.9% w/w aluminium.
  • Cobalt and platinum are currently considered to be environmentally toxic and thus dumping of this leached residue is not a viable option. Also, both cobalt and platinum are high value products.
  • Cobalt recovery is initiated by dissolving the cobalt and compounds thereof present in the water- washed leached residue of the oxidised catalyst composition with a strong acid such as nitric acid.
  • the water washed-leached residue may be contacted with a solution of nitric acid of about 55 % w/v HNO 3 at a temperature of between 80°C and 200°C and at a pressure of between 1 bar and 20 bar, in order to selectively dissolve cobalt.
  • this cobalt dissolution step is carried out at 100° and 1 atmospheric pressure.
  • the impure cobalt nitrate may be used in the chemical, ceramics Industries and the production of high purity cobalt for use in the electronics and related industries.
  • the washed nitric acid insoluble residue which is mainly composed of platinum compounds and impurities, may be used in the step of producing platinum compound.
  • the process includes the separating of a substantial portion of the impure cobalt nitrate, i.e. the cobalt rich solution, from the strong acid insoluble residue, i.e. the solid component present after the dissolving step.
  • This separation may include a precipitation step during which impurities such as Aluminium and Iron are precipitated out of the cobalt rich solution.
  • the separation may be aided by flocculating ultra fine solids using a suitable flocculant, such as ZN92V Zetafloc produced by Zetachem Company.
  • a suitable flocculant such as ZN92V Zetafloc produced by Zetachem Company.
  • the flocculant may be used as 0.1 % w/w solution.
  • the still impure cobalt rich solution is then purified by selectivley removing substantially all only cobalt ions from the cobalt rich solution by solvent extraction.
  • the impurities may remain in the aqueous phase after the solvent extraction step.
  • the cobalt rich solution from the precipitation step typically contains Co, Pt, Al, Fe, NO3 " and NH 4 + ions.
  • a suitable type of an acidic extractant like di- (2-ethylhexyl) phosphoric acid (DEHPA) and tributylphosphate (TBP) as a modifier in illuminating paraffin for extracting Co ions from the cobalt rich solution may be used.
  • DEHPA di- (2-ethylhexyl) phosphoric acid
  • TBP tributylphosphate
  • this solvent extractant is used as an ammonium salt which assists in keeping the pH of the mixture relatively constant after contacting the acidic cobalt rich solution with the organic extractant phase.
  • the aqueous phase recovered from the solvent extraction may be used in the precipitation of Fe and Al ions step, while the loaded organic phase (containing mainly Co ions) is reserved for a stripping step.
  • the Co loaded organic phase is contacted with a solution of the stripping agent, such as a solution of nitric acid, to remove the extracted species i.e. Co ions.
  • a solution of the stripping agent such as a solution of nitric acid
  • the purified cobalt rich solution is finally crystallised to form a red- brown crystalline cobalt nitrate salt, Co(NO 3 )2.6H 2 O or Co(NO 3 )z4H2O depending on the retention time when heating the crystals at 55°C.
  • This salt is currently used in the production of high purity cobalt and also electronics and chemical industries.
  • the crystallisation liquor containing free water and nitric acid may be utilised in the crystallisation step of cobalt nitrate or in the dissolution step of cobalt from the washed insoluble basic residue.
  • Platinum is recovered from the nitric acid insoluble solid component from the cobalt dissolution step by dissolving the platinum and compounds thereof, as well as non-cobalt and /or non-cobalt compound impurities from the cobalt rich solution out of the solid component to obtain a platinum rich solution.
  • the dissolving of platinum may be achieved by a mixture of HCl and HNO 3 or by using H 2 O 2 and HCl or HCl and Cl 2
  • the dissolved platinum may be precipitated out of the platinum rich solution by using NaOH and/or NH 4 CI to form platinum salts complex which can be recovered by a liquid: solid separation process such as filtration.
  • the recovered aluminium, cobalt and platinum, and/or compounds or salts thereof may be further processed. Specific Description and Examples
  • the spent catalyst composition from a Fischer-Tropsch reaction for the industrial synthesis of certain hydrocarbons from carbon monoxide and hydrogen typically contains about 60 to 75 % of the organic content.
  • This spent catalyst is initially heated to a temperature ranging from 700 to 1000°C at atmospheric pressure for 2 to 6 hr in the presence of air to oxidise the organic material.
  • a high temperature furnace maximum temperature of the furnace is 1400°C was used for the heating.
  • the spent catalyst composition was oxidised in the presence of either sodium carbonate or sodium chloride to prevent the formation of the spinels such as cobalt aluminate (C0 2 AIO 4 ) and cobalt (II) dicobalt (III) oxide (Co 3 O 4 ) during the oxidising step.
  • the aluminium oxide or cobalt oxide that is present in the spinels may possibly dissolve with difficulty in a solution of sodium hydroxide or mineral acid solution.
  • sodium oxide from either sodium carbonate or sodium chloride could possibly react with water-insoluble aluminium oxide to form water-soluble compounds such as sodium aluminate or silicate.
  • the oxidised spent catalyst composition sample produced in this step is digested with either water or a weak solution of sodium hydroxide (approximately 10 to 25 % w/w NaOH) at a relatively high temperature ranging from 90 to 230°C and at high pressure ranging from 1 to 20 bars.
  • a weak solution of sodium hydroxide approximately 10 to 25 % w/w NaOH
  • the main objective of the oxidising step is to burn out almost all of the organic material present in the spent catalyst composition prior to the leaching step as this organic material can decompose the lixiviant reagents during the leaching step.
  • a second sample of free flowing powder and sodium carbonate or sodium chloride were mixed together using solid to solid ratio of 1 :1 (a sample of flowing powder: either sodium carbonate or sodium chloride) and finally, reoxidised under the above conditions. Subsequently, a sample of free flowing powder produced after a self-supporting combustion and a sample after oxidising the spent catalyst at various temperatures were submitted for the organic carbon analysis.
  • the loss on ignition (L.O.I) analysis of a free flowing powder formed during self-supporting combustion was determined to be 2.7 %. This implies that the organic material was still contained in the free flowing powder after the self-supporting combustion.
  • the L.O.I of the final oxidised spent catalyst was determined to be ⁇ 0.1. This implies that all of the residual carbon was effectively removed after the second oxidising step.
  • the oxidised spent catalyst from the waxy lumps of the spent catalyst composition typically contains about 60 to 65 % AI 2 O3, 18.7 to 19.6 % w/w Co and 0.046 to 0.05 % w/w Pt.
  • a solution of sodium hydroxide of about 20 to 50% w/w NaOH was used to selectively and efficiently dissolve aluminium oxide at relatively high temperatures ranging from 1 10 to 170°C and at high pressures ranging from 5 to 20 bars with substantially no dissolution of cobalt and platinum from the spent catalyst.
  • water leaching was used to selectively solubilize sodium aluminate formed during the calcination of the spent catalyst in the presence of either sodium carbonate or sodium chloride.
  • the spent catalyst sample which was oxidised in the presence of either sodium carbonate or sodium chloride was digested with water at 90°C at atmospheric pressure to remove water soluble sodium aluminate.
  • the sodium hydroxide-insoluble residue was separated from the leach liquor by normal filtration and washed thoroughly with enough water to remove the residual leach liquor from the filtercake.
  • two steps of leaching were used. In these two steps of leaching, the filtercake from the first leaching step was contacted with a fresh solution of sodium hydroxide and leached under above-mentioned conditions.
  • the water -washed residue was dried at 90°C to remove free water.
  • Cytec flocculant Approximately 2 % w/w of Cytec flocculant was prepared using a solution of sodium hydroxide (about 2 % w/w NaOH). The solution was then conditioned at ambient temperature for one hour to form homogeneous solution. It was further diluted with a solution of sodium hydroxide (2 % w/w NaOH) to produce a final solution containing about 0.25 % w/w of the flocculant.
  • the turbidity value of the original slurry prior to the flocculation was measured to 3000 NTU.
  • the leach liquor containing mainly sodium aluminate was produced. This solution was stored in a one-litre container for a period of one month. Visual observation indicated that white crystals were formed after keeping the solution for a month. After filtering, washing and drying of the crystals, the final solid sample was submitted for XRD analysis and sent for elemental analysis. Eventually, the filtrate containing mainly sodium hydroxide and small amounts of sodium aluminate can be recycled to the leaching step where it utilizes as a lixiviant.
  • Aluminium trihydrate produced during the crystallisation step was calcined at various temperatures (ranging from 400 to 600 Degrees Celsius) in the presence of air. Following the calcination a white powdered product was formed. Subsequently, both product and alumina were submitted for XRD analysis.
  • the water washed leached residue recovered from the base leaching step typically contains 51 % w/w cobalt, 0.124% w/w platinum and 4.9% w/w aluminium.
  • the leached residue is contacted with a solution of nitric acid of about
  • nitric acid comprising of about 400 g of 55 % w/v of nitric acid at 100°Celsius for 4 hr. The experiment was conducted at atmospheric pressure.
  • the slurry formed from this leaching step was filtered at room temperature to obtain a filtercake.
  • a washing step was included in the experiment using a filtercake to water ratio of 1 :4 to remove the residual leach liquor retained after the leaching step.
  • the wash solution was then combined with the leach liquor to form the final parent solution. After drying the washed filtercake, the leached residue was weighed out prior to the cobalt, platinum and aluminium analysis.
  • a second leaching step was conducted on the leached residue.
  • the leached residue was contacted with fresh nitric acid solution and the leaching of the mixture was then carried out under above-mentioned leaching conditions
  • impure acid leach liquor typically contained 68,3 g/l Co, 5,2 g/l Al, 65 mg/l Pt while the purified acid leach liquor contained 326 mg/l Fe, and 7,7 g/l Co, 18 mg/l Al, 3 mg/l Pt and 4 mg/l Fe.
  • the leach liquor was heated to 90°C until its volume was reduced by 50%.
  • the concentrated leach liquor was then added to a 250-ml crystalliser and on cooling off the solution, red -brown crystals were formed.
  • the crystals were separated by normal filtration and dried at 55°C to further improve their crystallinity. Subsequently, the dried crystals were submitted to XRD analysis and elemental analysis. Concentrations of the substances present in the crystals were reported as percentage (% w/w) in
  • Table 9 Composition of crystallised and commercially available cobalt nitrate.
  • the retention time of the crystal at 55°C may be increased. This may remove free water retained in the crystals after the filtration. Eventually, an excess of nitric acid should be used during the crystallisation step. 9 Precipitation Of Fe And Al Ions From The Impure Cobalt Nitrate Containing Solution.
  • the precipitation of both Fe and Al ions from the impure cobalt containing solution should be firstly conducted.
  • the impure cobalt containing solution from the dissolution of the base leached residue step typically 5.2 g/l Al , 0.065 g/l Pt, 0.326 g/l Fe and 68 g/l Co.
  • a solution of ammonium hydroxide (about 25 % w/v NH 4 OH) would be used to selectively precipitate both Fe and Al ions from the cobalt-containing solution.
  • the filtrate produced in this way could be used in the solvent extraction step where the cobalt ions will be selectively loaded into an organic phase under certain conditions.
  • the precipitate containing both Fe and Al formed after the addition of ammonium hydroxide to the impure cobalt-containing solution will be dissolved in a solution of sodium hydroxide to form sodium aluminate.
  • This aluminate can be recycled in the precipitation of aluminium hydroxide step.
  • a dumping option should be considered for sodium hydroxide insoluble precipitate containing mainly iron hydroxide, which is environmentally friendly by-product.
  • the sodium hydroxide insoluble precipitate may be reserved for the platinum dissolution
  • the precipitate containing typically Fe and Al was allowed to react with sodium hydroxide (about 25% m/v of NaOH) to form sodium aluminate which is eventually recycled to the precipitation of aluminium hydroxide step. While the sodium hydroxide insoluble precipitate, which contains Fe, may possibly be dumped or dissolved in a solution of sulphuric acid or nitric acid to form iron salts that are suitable for water purification.
  • Table 11 The precipitation efficiency of metal ions at various pH when using ammonium hydroxide.
  • the original aqueous filtrate from the precipitation step typically contains Co, Pt, Al, Fe, NO 3 " and NH 4 + ions.
  • the organic phase salt which is suitable for the extraction of the Co ions was prepared as follows: 1000 ml of ammonium hydroxide solution (about 12.5 % w/v NH 4 OH was contacted with an equal volume of the organic phase containing 40% w/w DEHPA, 20 % w/w TriButylPhosphate (TBP) and 40 % w/w illuminating paraffin at room temperature. This mixture was stirred for 15 min. The two phases were allowed to separate at room temperature. The organic phase salt produced in this way contains ammonium ions and is suitable for the extraction of Co ions from the filtrate at pH 4.
  • the loaded organic phase produced in this experiment could possibly be utilised in the stripping step where finally cobalt nitrate will be produced.
  • the colour of the mixture (organic phase and aqueous phase) turned to pink at low temperature (ranging from 30 to 45°C) during the solvent extraction experiment.
  • low temperature ranging from 30 to 45°C
  • high temperature ranging from 50 to 90°C
  • the pink colour indicates the presence of octahedral cobalt complex in the mixture whilst the blue indicates tetrahedral cobalt complex. It is therefore considered that the colour change is definitely attributed to a change in co-ordination state of the cobalt complex.
  • the colour of the loaded organic phase still remained blue even if the temperature of the loaded organic phase was lowered to an ambient temperature.
  • Table 12 Extraction efficiency of metal ions from the original aqueous filtrate by solvent extraction.
  • solvent extraction method gave good performance in terms of both Co and Pt ions extraction efficiency and phase separation when using di-(2-ethylhexyl) phosphoric acid as an extractant and tributyl phosphate as a modifier.
  • PGM Group Metals
  • Pt can dissolve in 6 to 18 M aqua regia at 80 to 90 Degrees Celsius at atmospheric pressure to form a chloroplatinic acid, H 2 PtCl 6 .
  • 6 M acid solution is used.
  • the platinum acid obtained in this fashion could be reserved for the preparation of platinum sponge and various salts.
  • the platinum dissolution in aqua regia is preferred because the yield of the Pt from the ore is around 99%.
  • the residue produced during the nitric acid leaching was firstly calcined at 700 °C for 6 h to oxidise the flocculant present in the residue. Subsequently 20 g of the nitric acid insoluble residue containing 7.67% Pt was dissolved in 1000ml of aqua regia (3HCI: 1 HNO 3 ) at 80 °C to 90 °C at atmospheric pressure for 4 hr to form a chloroplatinic acid, H 2 PtCI 6 . The latter was separated from the aqua regia insoluble residue through filtration. The platinum acid obtained in this fashion could be reserved for the preparation of platinum sponge and various salts. The blue insoluble residue formed during the dissolution of platinum was dried at 90 °C prior to the submission for XRD analysis. Results
  • Table 13 Composition of residue obtained after leaching nitric acid residue with aqua-regia solution.
  • a solution of ammonium chloride (about 25%) is used to quantitatively precipitate the Pt(iv) from a platinic acid at 50 to 70 Degrees Celsius in the form of ammonium chloroplatinate, (NH4)2PtCl ⁇ (deep-yellow colour).
  • the deep-yellow crystals are recovered with a purity of 99 to 99.5% in greater than
  • Table: 14 Composition of diammoniumhexachloroplatinate produced through the sodium-nitric acid leaching process.
  • Table 15 The extraction efficiency of metal ions during the Sodium hydroxide-nitric acid-aqua regia leaching process.

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Abstract

L'invention concerne un procédé de récupération sélective, d'aluminium, de cobalt et de platine, ainsi que de leurs composés, à partir d'une composition catalytique comprenant aluminium, cobalt et platine. Ce procédé consiste à traiter la composition catalytique afin d'obtenir de façon sélective des ions de pratiquement un seul métal parmi aluminium, cobalt et platine dans une solution, à récupérer dans des étapes séparées, l'aluminium, le cobalt ou le platine traités sous forme de sel ou de métal et à renouveler les phases de traitement et de récupération pour chacun des métaux aluminium, cobalt et platine. Les étapes de traitement peuvent consister en des étapes de lixiviation, lavage, dissolution ou désorption. Les étapes de récupération peuvent consister en des étapes de filtration, précipitation, séparation ou floculation.
PCT/ZA2001/000128 2000-08-29 2001-08-29 Recuperation selective de metaux a partir d'une composition catalytique usee WO2002018663A2 (fr)

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US10/363,491 US20040219082A1 (en) 2000-08-29 2001-08-29 Selective recovery of aluminium, cobalt and platinum values from a spent catalyst composition
AU2001295097A AU2001295097A1 (en) 2000-08-29 2001-08-29 Selective recovery of aluminium, cobalt and platinum values from a spent catalyst composition

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US7754635B2 (en) 2006-03-03 2010-07-13 Johnson Matthey Plc Catalyst reprocessing
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EP2170479A4 (fr) * 2007-06-18 2012-04-11 Crisolteq Oy Procédé de récupération
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