[go: up one dir, main page]

WO2008157275A1 - Extraction de titane par solvant en utilisant un diluant aromatique - Google Patents

Extraction de titane par solvant en utilisant un diluant aromatique Download PDF

Info

Publication number
WO2008157275A1
WO2008157275A1 PCT/US2008/066811 US2008066811W WO2008157275A1 WO 2008157275 A1 WO2008157275 A1 WO 2008157275A1 US 2008066811 W US2008066811 W US 2008066811W WO 2008157275 A1 WO2008157275 A1 WO 2008157275A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
organic phase
titanium
stripped
aqueous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2008/066811
Other languages
English (en)
Inventor
Bob Zhengqi Wang
Bruce James Sabacky
Dirk Edmond Verhulst
Jacob R. Ward
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Altair Nanotechnologies Inc
Original Assignee
Altair Nanotechnologies Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Altair Nanotechnologies Inc filed Critical Altair Nanotechnologies Inc
Publication of WO2008157275A1 publication Critical patent/WO2008157275A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/001—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide

Definitions

  • the present invention relates to the processing of titaniferous ores or ore concentrates to titanium dioxide or titanium metal. Particularly, the process relates to solvent extraction of titanium from an aqueous solution and the transfer of titanium into a concentrated and purified titanium stream.
  • US Patent 6,375,923 teaches a process to make TiO 2 pigment from ilmenite ore by digestion and separation by solvent extraction followed by spray hydrolysis and calcination.
  • the present invention presents an improved method for the solvent extraction step.
  • the preferred extractant is a tri-alkyl phosphine oxide (commercial name: Cyanex 923).
  • the preferred diluents are kerosene or Orfom SX-11 (Chevron-Phillips). This system has good extraction and stripping characteristics, but the organic phase is relatively viscous, and requires a temperature of at least 40° C to achieve a sufficiently fast phase separation between the organic and the aqueous phases. Heating to a higher temperature improves phase separation but increases the HCI partial pressure, requiring ventilation of all solutions to a scrubber and causing significant losses of HCI.
  • a higher temperature increases the tendency of the solutions to hydrolyze, forming solid TiO 2 deposits which impede the flow of solution, may cause plugging of the lines and contribute to titanium losses.
  • the diluent is xylene, but other low-viscosity aromatic compounds may be used.
  • the amount of iron is adjusted in such a way that a concentration of about 3 g/l Ti(III) is obtained.
  • the titanous ion also insures that V and Cr are present in the (III) oxidation state and Mn and Fe are present in the (II) oxidation state.
  • metallic iron other reactive metals such as aluminum may be used to achieve the same effect. Scrubbing of Loaded Organic
  • the loaded organic phase contains significant amounts of impurities, particularly coloring impurities that may be extracted into the organic phase or entrained as a dispersed aqueous phase into the organic.
  • the most important coloring impurities are Cr, Fe, V and Mn. Therefore, a scrubbing step is introduced.
  • the scrubbing step the loaded organic is brought into contact with a HCI solution at high concentration (typically 9 M). In these conditions, the impurities are stripped preferentially.
  • the scrubbing step is conducted in a mixer-settler. The mixing and settling actions also promote removal of the aqueous phase entrained in the organic phase.
  • the new diluent (xylene, etc.) provides a satisfactory eluate that can be treated further in the process
  • the titanium concentration of the eluate is generally lower than what is achieved with the preferred diluents in US patent 6,375,923.
  • the inventors believe that the less favorable stripping conditions are due to the higher HCI loading observed in the presence of aromatic diluents in general, and particularly in the case of xylene.
  • HCI is preferentially stripped.
  • the HCI concentration in the actual stripping stage is lower and higher titanium concentrations, together with lower HCI concentrations, can be obtained in the stripping step.
  • the loaded organic phase is placed in a condition where a substantial vapor pressure of HCI is in equilibrium with this phase and where a substantial amount of HCI can be removed by sweeping the gas phase. This method allows the removal of chloride without entraining any titanium. Scrubbing of the Stripped Organic Phase
  • Fig. 1 is a general flow sheet of the solvent extraction of titanium, showing, by way of example, two extraction stages and four stripping stages.
  • Fig. 2 is a flow sheet of an embodiment of the process according to the present invention, showing additional steps of pre-reduction, pre-stripping, scrubbing of the loaded organic and scrubbing of the stripped organic.
  • Fig. 3 is a schematic drawing showing the principle of pre-stripping by vacuum evaporation.
  • Fig. 4 shows an embodiment of the pre-stripping unit including vacuum evaporation and condensation, where HCI gas is removed from the loaded organic phase and is redissolved in a dilute HCI solution in a condensation column.
  • Fig. 5 shows the effect of the HCI concentration in the pre-stripping solution on the titanium concentration in the pre-stripping eluate.
  • Fig. 6 shows the molar ratio of the amount of Cl to Ti stripped from the organic phase as a function of the ratio of the organic phase to aqueous phase.
  • the present invention is a solvent extraction process for extracting titanium from an aqueous feed solution and transferring it to a product solution or eluate.
  • the solvent extraction process may be part of a processing method to make T1O 2 pigment, TiC" 2 nanoparticles, or another form of Ti ⁇ 2 from a titaniferous ore.
  • the method of the present invention is an inventive improvement over the solvent extraction step taught in US Patent 6,375,923.
  • the solvent extraction process may include a number of loading steps and a number of stripping steps. The loading steps and the stripping steps may take place in mixer-settlers. The loading and stripping steps may also take place in columns.
  • the object of the present invention is an improved organic mixture that allows better separation of phases while keeping good extraction and stripping characteristics.
  • This central idea becomes more valuable and leads to a better process when it is associated with the other features of the invention.
  • the improvements of the present invention comprise a pre-reduction step, a loaded organic scrubbing step (scrubbing 1), a pre-stripping step, and a stripped organic scrubbing step (scrubbing 2).
  • Figure 1 shows a general flow sheet of a solvent extraction process.
  • Figure 2 is the same solvent extraction process but with the addition of the extra steps of the present invention.
  • the feed solution to the titanium solvent extraction process of the present invention is an aqueous, acidic solution of titanium.
  • the solution may be obtained by digestion of a titaniferous ore according to the process of US Patent 6,375,923 or by any other suitable process that provides an aqueous, acidic soultion of titanium.
  • the solution contains titanium chlorides or oxychlorides, hydrochloric acid and impurities.
  • the impurities may be Fe, Mn, V, Cr, Mg, Ca and other impurities present in titanium ores.
  • the impurities are also generally present as chlorides or oxychlorides.
  • the organic phase is a mixture of an extractant, a diluent and, optionally, a modifier.
  • the extractant is a chemical compound capable of binding titanium from an aqueous solution.
  • the diluent is added for purposes of viscosity.
  • the modifier is primarily added to prevent the formation of a third phase. It may also influence the behavior of the extractant, in such a way that the loading capacity of the mixture is higher than the loading capacity of the extractant taken alone.
  • the present process is directed to an organic phase mixture that allows the process to be operated at or close to room temperature.
  • the extractant is desirably an organic phosphorus compound or a mixture of two or more organic phosphorous compounds.
  • the organophosphorus compound may have the general formula (I)
  • R 1 R 2 R3PO where R 1 , R 2 , and R 3 may be the same or different and are each a hydrogen atom, a substituted or unsubstituted linear or branched chain, a cyclic, saturated, or unsaturated hydrocarbon radical, with the proviso that the sum of the carbon atoms of the radicals Ri, R 2 , and R 3 is equal to at least 12 carbon atoms.
  • organophosphorus compound(s) will have the formula (II) R 4 R 5 RePO where R 4 , R 5 , and R 6 may be the same or different and are each a hydrogen atom, a substituted or unsubstituted linear or branched chain, a cyclic, saturated, or unsaturated hydrocarbon radical, with the proviso that the sum of the carbon atoms of the radicals R 4 , R 5 , and Re is equal to at least 12 carbon atoms.
  • Exemplary radicals Ri, R 2 , R3, R 4 , R 5 , and R 6 include but are not limited to methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1 -methyl- butyl, isopentyl, tert-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, n-n-nonyl, n-decyl, n- undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, and n-octadecyl, together with the corresponding branched
  • the extractant is a mixture of an organophosphorus extractant of formula (I) and (II), where Ri, R 2 , and R 3 are identical linear alkyl radicals and where
  • R 4 , R 5 , and R 6 are identical linear alkyl radicals but different from those of the Ri, R 2 , and R 3 radicals.
  • the proportion of the two organic phosphorus compounds of formulae (I) and (II) is determined such that a phosphine oxide mixture exists that is liquid at ambient temperature.
  • the organophosphorus extractant is a mixture of the phosphine oxides tri(n-hexyl)phosphine oxide and tri(n-octyl)phosphine oxide and is commercially available from Cytec under the trade designation CYANEX 923.
  • the diluent is xylene, mesitylene, or other suitable dilutent for the extractant that allows the organic phase to be contacted with and to load the titanium at or close to room temperature.
  • Modifying agents are generally added to improve the hydrodynamic properties of the system without adversely affecting the extracting properties of the organic phosphorus compounds.
  • An example of such modifying agents includes alcohols having from 4 to 15 carbon atoms, phenols, and the like. While a modifying agent may be optionally incorporated into the organic phase mixture, it is believed that a modifying agent is not necessary when the amounts of the organic phosphorous compounds are incorporated within the range contemplated by the present invention.
  • the organic phase includes from about 5-15% or greater than 35% of an organophosphorous extractant, e.g, Cyanex 923, with the balance being a diluent, e.g., xylene. It has been found that when the organic phase contains from about 20 to
  • Phosphine oxides such as Cyanex 923 generally load elements better when the elements are in their oxidized state rather than in their reduced state.
  • impurities such as Fe, Cr, V and Mn
  • Pre-reduction is achieved by adding a reactive metal phase. In practice, iron powder or aluminum flakes have been found to be the most effective.
  • Good prereduction conditions correspond to a redox potential between about 0.0 and about 0.35 V versus a standard Ag/AgCI electrode and suitably between about 0.2 to about 0.3 V.
  • This redox level corresponds to the formation of about 1 to 4 g/L Ti(III) in the feed solution.
  • Control of the redox potential is particularly important in the conditions of the present invention. Since the use of an aromatic diluent leads to somewhat lower titanium concentrations in the eluate, the impurity levels also have to be kept lower such that the impurity level in the final titanium dioxide product, proportional to the impurity/Ti ratio, does not increase. Loading
  • the pre-reduced solution is brought into contact with the organic extractant phase described previously.
  • the contact may occur by any means that ensures good contact between the phases.
  • Industrial equipment used in solvent extraction such as a series of mixer settlers or a solvent extraction column may be used.
  • the number of equilibrium stages needed is generally between 2 and 4.
  • the contacting is typically conducted at a temperature less than about 35° C, desirably between about 10° and 30° C, and in one aspect about 25° C.
  • a loading concentration of about 10 to 20 g/l Ti is achieved in the organic phase, and in some instances, about 15 g/l Ti. If the feed solution contains significant levels of impurities, some of these impurities will be transferred with the organic phase.
  • the impurities may be present as dissolved species in the organic phase, or they may be present in an entrained aqueous phase.
  • the organic phase is therefore brought into contact with a concentrated solution of HCI.
  • a concentration of about 6 to 9 M HCI is used. Impurities which have a smaller extraction coefficient than Ti will be stripped while Ti will not be substantially stripped. The process will also liberate entrained aqueous particles from the organic phase and thereby decrease the level of elements which are not chemically extracted in the organic phase.
  • the loaded organic phase, containing extracted titanium and chloride is transferred to the stripping section. It has been found that in the conditions of the present invention, Cl tends to strip before Ti, therefore limiting the concentration of Ti that can be obtained. This is particularly true of the xylene system. To compensate for this effect, a pre-stripping section is introduced. [0038] The purpose of the pre-strip section is to remove a significant fraction of the Cl from the organic phase, without removing a significant amount of Ti. In the subsequent stripping section, a higher concentration of Ti and a lower concentration of Cl will therefore be obtained.
  • the definition of pre-stripping as it is understood in the context of the present invention is that it is a solvent extraction step where Cl is removed preferentially to Ti.
  • Pre-stripping can be achieved by any suitable process that provides preferential removal of Cl with respect to Ti. Two means of pre-stripping are described below.
  • the loaded solution is subjected to conditions where the vapor pressure of HCI gas over the organic solution is greater than the total pressure over the organic phase.
  • This condition can be achieved by applying a vacuum to the loaded organic phase, or by increasing the temperature of this phase, or by a combination of both.
  • Fig. 3 and 4 show two embodiments of a pre-stripping by evaporation process.
  • the pre-stripped organic phase undergoes stripping by an aqueous solution with a low chloride concentration.
  • concentration of the stripping solution is generally in the range 0.25 to 2 M HCI. If the concentration is too high, stripping is less effective. If the concentration is too low, significant hydrolysis occurs. Stripping produces a solution containing 25 to 60 g/L Ti, which is further concentrated before going to spray hydrolysis. Scrubbing of Stripped Organic Phase
  • Equal volumes (100 ml) of a feed solution containing 50 g/L Ti and 400 g/L Cl, and stripped organic phase (containing 15% Cyanex 923 in xylene) were mixed by shaking for 1 min in a decanting flask at room temperature to simulate loading. After shaking, the time needed for separation of the phases was observed.
  • the separated loaded organic phase was put in contact with an equal volume of a 0.5 M HCI solution and shaken in the same fashion as for the loading part. Whereas separation time after loading was always reasonabley fast, and increased with the proportion of extractant, it appeared that the separation time after stripping was higher in an intermediate concentration range, i.e., 20-30%.
  • Table Ia shows that the separation time after shaking for loading took between about 1 min and 5.5 min, with the separation time increasing with the extractant concentration. For stripping, however, the separation time is much longer (> 1 h) at the intermediate range of 20-30% Cyanex in the organic phase mixture.
  • Table Ib shows the separation time after stripping. In general, the ranges 5 to 15% and 35-50% Cyanex have been shown to give favorable separation times.
  • a feed solution to the solvent extraction step of the process of the present invention contained 55 g/L Ti, 400 g/L Cl, 5 g/L Fe and less than 5 g/L each of the impurities Cr, V, Mn and Mg.
  • the redox potential of the solution, measured with a standard Ag/AgCI electrode was 35OmV vs Ag/AgCI (or 570 mV vs a standard H2 electrode).
  • Aluminum chips were added to the solution until the measured potential droped to 225 mV vs Ag/AgCI. Chemical analysis showed that the solution after reduction contained 3 g/L of Ti in the titanous (Ti(III)) form.
  • Example 3 Comparitive Example - Loading and Stripping Without Scrubbing.
  • the feed solution from example 1 was fed to the top of a solvent extraction column with an internal diameter of 40 mm and a height of 8 m.
  • An organic mixture consisting of 15% Cyanex 923 and 85% xylene was fed at the bottom. Titanium was loaded on the organic phase whereas the impurities were not.
  • the loaded organic phase was stripped by passing it through a second column, fed with a dilute (1.5 M) HCI solution.
  • the aqueous product of the stripping column (eluate) contained 28 g/L Ti, 21 mg/L Mn, 0.76 mg/L Cr and 0.69 mg/L V.
  • Example 4 Effect of Loaded Organic Scrubbing Stage
  • a scrubbing stage consisting of a mixer-settler
  • the scrubbing stage was fed with a small stream of 9 M HCI.
  • the eluate in the present example contained 27.1 g/L Ti, 2 mg/L Mn, 0.5 mg/L Cr and 0.4 mg/L V, showing the marked improvement in the impurity levels achieved, particularly for Mn.
  • Example 5 Pre-Stripping by Vacuum Evaporation
  • a volume of 300 ml of the organic phase produced by loading the organic phase as in Example 3 was placed in a spherical, air-tight glass flask and heated to 60 °C.
  • the flask was connected through a cooler to a conical flask containing water to a source of vacuum.
  • a vacuum of about 0.1 atm was maintained in the spherical flask.
  • Samples were taken out of the conical flask at intervals and their chloride concentration was determined.
  • a chlorine mass balance showed that 20% of the amount of chloride in the organic phase was removed in 20 min. No titanium or other metal compounds were recovered in the conical flask.
  • a volume of 100 ml of the same loaded solution used in Example 4 was equilibrated with different amounts of HCI solutions of different molarities.
  • the amounts of HCI solution were 100, 20, 10 and 5 ml respectively, i.e. the organic to aqueous (O/A) ratio was 1 , 5, 10 and 20 respectively.
  • This series of tests was repeated with different concentrations of the HCI solution.
  • the HCI concentrations varied between 0.5 and 9 M HCI.
  • Figs. 5 and 6 summarize the results obtained. Fig.
  • Fig. 6 is calculated from the Cl and Ti mass balances of the tests. As the O/A ratio is increased, relatively more Cl and less Ti is transferred from the organic to the aqueous phase. At an O/A ratio in the range 1 to 3, the Cl/Ti ratio stripped from the organic phase corresponds approximately to the formula TiCI 4 . At higher O/A, the amount of chloride stripped can be up to 3 times as high. Preferential removal of HCI in the pre-stripping step makes it possible to achieve a higher Ti concentration in the subsequent stripping operation.
  • Example 7 Scrubbing of Stripped Organic Phase (Scrubbing 2)
  • a series of lab-scale mixers and settlers were connected to form four loading stages and four stripping stages.
  • the organic phase from the fourth stripping stage was fed to an additional mixer and settler to form a scrubbing stage 2 .
  • the aqueous feed solution to the solvent extraction system contained 71 g/L Ti and 397 g/L Cl and was maintained at a feed rate of 10 ml/min.
  • a stream of 0.91 ml/min of dilute HCI solution (1.5 M) was fed to scrubbing stage 2.
  • the aqueous product of scrubbing stage 2 contained 56.8 g/L Ti.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention concerne un procédé amélioré d'extraction de titane par solvant d'une solution aqueuse dans une phase organique contenant un diluant aromatique. Le procédé comprend la préréduction, le chargement, le lavage des composés organiques chargés, la pré-extraction, l'extraction et le lavage des composés organiques extraits, et produit des solutions de titane pures avec de bonnes cinétiques ainsi qu'une séparation de phases et une pureté améliorées.
PCT/US2008/066811 2007-06-14 2008-06-13 Extraction de titane par solvant en utilisant un diluant aromatique Ceased WO2008157275A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US94391707P 2007-06-14 2007-06-14
US60/943,917 2007-06-14

Publications (1)

Publication Number Publication Date
WO2008157275A1 true WO2008157275A1 (fr) 2008-12-24

Family

ID=39712308

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2008/066811 Ceased WO2008157275A1 (fr) 2007-06-14 2008-06-13 Extraction de titane par solvant en utilisant un diluant aromatique

Country Status (1)

Country Link
WO (1) WO2008157275A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140322110A1 (en) * 2011-11-03 2014-10-30 Advance Lithium Projects Ltd. Processes for metal ions removal of from aqueous solutions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4269809A (en) * 1979-12-19 1981-05-26 Uop Inc. Recovery in titanium metal values by solvent extraction
EP0273244A2 (fr) * 1986-12-20 1988-07-06 Bayer Antwerpen N.V. Procédé de fabrication de bioxyde de titane de haute qualité par le procédé au sulfate
US6375923B1 (en) * 1999-06-24 2002-04-23 Altair Nanomaterials Inc. Processing titaniferous ore to titanium dioxide pigment
US20050142051A1 (en) * 2003-11-19 2005-06-30 Process Research Ortech, Inc. Process for the recovery of titanium in mixed chloride media

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4269809A (en) * 1979-12-19 1981-05-26 Uop Inc. Recovery in titanium metal values by solvent extraction
EP0273244A2 (fr) * 1986-12-20 1988-07-06 Bayer Antwerpen N.V. Procédé de fabrication de bioxyde de titane de haute qualité par le procédé au sulfate
US6375923B1 (en) * 1999-06-24 2002-04-23 Altair Nanomaterials Inc. Processing titaniferous ore to titanium dioxide pigment
US20050142051A1 (en) * 2003-11-19 2005-06-30 Process Research Ortech, Inc. Process for the recovery of titanium in mixed chloride media

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140322110A1 (en) * 2011-11-03 2014-10-30 Advance Lithium Projects Ltd. Processes for metal ions removal of from aqueous solutions
US10604822B2 (en) * 2011-11-03 2020-03-31 Eyal Hahn Processes for metal ions removal from aqueous solutions

Similar Documents

Publication Publication Date Title
EP1194379B1 (fr) Traitement de minerai titanifere afin de produire un pigment dioxyde de titane
Liu et al. Recovery and separation of gallium (III) and germanium (IV) from zinc refinery residues: Part I: Leaching and iron (III) removal
Zhu et al. A literature review of titanium solvent extraction in chloride media
US10260127B2 (en) Method for recovering scandium values from leach solutions
Yu et al. Recovery of rare earth metal oxides from NdFeB magnet leachate by hydrophobic deep eutectic solvent extraction, oxalate stripping and calcination
US4269809A (en) Recovery in titanium metal values by solvent extraction
Wang et al. Simultaneous oxidation and extraction of iron from simulated ilmenite hydrochloric acid leachate
JP5103541B2 (ja) ニオブの分離精製方法及び製造方法
US4125586A (en) Removal of AlCl3 from crude TiCl4 by addition of H2 O and NaCl
Wang et al. Combined oxidation and 2-octanol extraction of iron from a synthetic ilmenite hydrochloric acid leachate
AU620148B2 (en) Improved process for obtaining impurity-free compounds of ta and/or nb from materials containing these metals
WO2008157275A1 (fr) Extraction de titane par solvant en utilisant un diluant aromatique
JPS60255621A (ja) 溶媒抽出によるジルコニウムの回収法
US10988828B2 (en) Extraction of scandium values from copper leach solutions
EP0046974A2 (fr) Procédé de préparation de fer métallique très pur
AU649676B2 (en) Method for stripping metals in solvent extraction
JP7463180B2 (ja) レアメタルの回収方法
JP7463182B2 (ja) レアメタルの回収方法
EP0046973B1 (fr) Procédé pour la production d'oxyde de fer de grande pureté
US20150315677A1 (en) Process for the separation of iron in extraction of titanium in mixed chloride media
JPS63227727A (ja) クエン酸部分エステル系鉄抽出剤
Lakshmanan et al. Separation and purification of zirconium with amines from sulphuric acid system: a review
Sato et al. Liquid-liquid extraction of tin (IV) from hydrochloric acid solutions by di (2-ethylhexyl) phosphoric acid
CN120081761A (zh) 一种酰胺夹醚型羟肟酸类化合物及其制备方法和应用
CN118006938A (zh) 一种氯化废酸浸出熔盐渣富集钪的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08770923

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08770923

Country of ref document: EP

Kind code of ref document: A1