DE2417510A1 - PROCESS FOR EXTRACTION OF METALS FROM Aqueous SOLUTIONS WITH ACID PHOSPHORUS COMPOUNDS - Google Patents

PROCESS FOR EXTRACTION OF METALS FROM Aqueous SOLUTIONS WITH ACID PHOSPHORUS COMPOUNDS

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Publication number
DE2417510A1
DE2417510A1 DE2417510A DE2417510A DE2417510A1 DE 2417510 A1 DE2417510 A1 DE 2417510A1 DE 2417510 A DE2417510 A DE 2417510A DE 2417510 A DE2417510 A DE 2417510A DE 2417510 A1 DE2417510 A1 DE 2417510A1
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extraction
salts
metals
acidic phosphorus
acid
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German (de)
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Johannes Dr Kaschuba
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Bayer AG
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Bayer AG
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Priority to DE2417510A priority Critical patent/DE2417510A1/en
Priority to NO751058A priority patent/NO751058L/no
Priority to NL7504124A priority patent/NL7504124A/en
Priority to JP50041924A priority patent/JPS50141579A/ja
Priority to LU72237A priority patent/LU72237A1/xx
Priority to BE155231A priority patent/BE827731A/en
Priority to SE7504086A priority patent/SE388129B/en
Priority to ZA00752252A priority patent/ZA752252B/en
Priority to FR7511270A priority patent/FR2267380A1/en
Publication of DE2417510A1 publication Critical patent/DE2417510A1/en
Pending legal-status Critical Current

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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
    • 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
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/385—Thiophosphoric acids, or esters thereof
    • 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
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
    • 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
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
    • 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
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
    • 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
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/387—Cyclic or polycyclic compounds
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Description

/O IU Patente, Marken/ O IU patents, trademarks

und Lizenzenand licenses

Br-her 509 Leverkusen. BayerwerkBr-her 509 Leverkusen. Bayerwerk

9. April9th April

Verfahren zur Extraktion von Metallen aus wäßrigen LösungenProcess for the extraction of metals from aqueous solutions

mit sauren Phosphorverbindungenwith acidic phosphorus compounds

Die vorliegende Erfindung betrifft ein verbessertes Verfahren zur Extraktion von Metallen aus wäßrigen Lösungen mit sauren Phosphorverbindungen der allgemeinen FormelThe present invention relates to an improved method for extracting metals from aqueous solutions with acidic phosphorus compounds of the general formula

ρ; ■ (Dρ; ■ (D

OHOH

wobei R1 und R2 gleich oder verschieden sein können und für einen linearen oder verzweigten, gegebenenfalls substituierten aliphatischen, einen gegebenenfalls substituierten araliphatischen oder aromatischen Rest mit bis zu 18 C-Atomen stehen und wobei die organischen Reste unmittelbar oder über ein Sauerstoffatom an den Phosphor gebunden sein können.where R 1 and R 2 can be the same or different and represent a linear or branched, optionally substituted aliphatic, an optionally substituted araliphatic or aromatic radical with up to 18 carbon atoms and the organic radicals directly or via an oxygen atom to the phosphorus can be bound.

Die Extraktion von Metallen aus wäßrigen Lösungen mit sauren Phosphorverbindungen der obengenannten Art ist an sich bekannt (siehe z.B. Peter Markl, "Extraktion und Extraktionschronatographie in der anorganischen Analytik", Band I5 in der Reihe "Methoden der Analyse in der Chemie",The extraction of metals from aqueous solutions with acidic phosphorus compounds of the type mentioned above is on known (see e.g. Peter Markl, "Extraktion und Extraction chromatography in inorganic analysis ", Volume I5 in the series "Methods of Analysis in Chemistry",

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509844/0497509844/0497

Akademische V^rlagsgesellschaft Prankfurt/Main, 1972). Es ist auch bekannt, daß die Metallextraktion mit solchen sauren Phosphorverbindungen vom pH-Wert abiJIngig ist. Im allgemeinen kann ein gegebenes Metall bei höheren pH-Werten in der Lösung besser extrahiert werden als bei niedrigem pH-Wert (K. Kimura, Bull. Chem. Soc. Japan 33, IO38 ff (i960)). So verbessern z.B. basische Zusätze wie NaOH, CaO, CaCO^, Na2HPO^, Na^PO^ das Extraktionsverhalten.Akademische V ^ rlagsgesellschaft Prankfurt / Main, 1972). It is also known that metal extraction with such acidic phosphorus compounds is dependent on the pH value. In general, a given metal can be extracted better at higher pH values in the solution than at low pH values (K. Kimura, Bull. Chem. Soc. Japan 33, IO38 ff (1960)). For example, basic additives such as NaOH, CaO, CaCO ^, Na 2 HPO ^, Na ^ PO ^ improve the extraction behavior.

Gegenstand der vorliegenden Erfindung ist nun ein Verfahren zur Extraktion von mehrwertigen Metallionen aus wäßrigen Lösungen oder Suspensionen ihrer Salza mit in Wasser schwerlöslichen sauren Phosphorverbindungen der allgemeinen Formel I, gegebenenfalls in Gegenwart von organischen Lösungsmitteln, dadurch gekennzeichnet, daß die Metallionen aus Lösungen oder Suspensionen extrahiert werden, die eines oder mehrere neutrale Salze der Salzsäure oder der Schwefelsäure in einer Konzentration von 0,01 Mol/l bis zur Löslichkeitsgrenze der neutralen Salze enthalten.The present invention now relates to a process for the extraction of polyvalent metal ions from aqueous solutions or suspensions of their salts with acidic phosphorus compounds that are sparingly soluble in water of the general formula I, optionally in the presence of organic solvents, characterized in that that the metal ions are extracted from solutions or suspensions which are one or more neutral Salts of hydrochloric acid or sulfuric acid in one concentration from 0.01 mol / l to the solubility limit of the neutral salts.

Überraschend hat sich herausgestellt, daß neutrale Ammonium-, Alkali- oder Erdalkalisalze der genannten Mineralsäuren wie z.B. NaCl, NH^Cl, Na3SO^, K2SO^, (Kffi^) 2S0^, CaCl2, MgSOj. die Extraktion von Metallen aus wäßrigen Lösungen mit sauren Phosphorverbindungen noch erheblich verbessern können.It has surprisingly been found that neutral ammonium, alkali or alkaline earth salts of the mineral acids mentioned, such as NaCl, NH ^ Cl, Na 3 SO ^, K 2 SO ^, (Kffi ^) 2 S0 ^, CaCl 2 , MgSOj. the extraction of metals from aqueous solutions with acidic phosphorus compounds can still improve considerably.

Die extraktionsfördernde Wirkung der angegebenen neutralen Salze starker Mineralsäuren ist eine neue Art von Synergismus und war nach den bisherigen Kenntnissen über den Extraktionsmechanismus nicht zu erwarten.The extraction-promoting effect of the stated neutral salts of strong mineral acids is a new kind of Synergism and was not to be expected based on the previous knowledge about the extraction mechanism.

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Während organische Zusätze, die in Verbindung mit einem Extraktionsmittel synergistisch wirken, die Extraktion fördern, aber dafür die Reextraktion erschweren (z.B. Zusätze von Trialkylphosphaten zu Dialkylphosphaten), haben die erfindungsgemäßen extraktionsfördernden Zusätze den letztgenannten Nachteil nicht, da sie selber kaum extrahiert werden und deshalb in der wäßrigen Phase zurückbleiben. Gegenüber basischen Zusätzen haben die extraktionsfördernden Salze den Vorteil, daß sie beim Extraktionsprozeß nur anwesend sein müssen, aber dabei nicht verbraucht werden.While organic additives that are used in conjunction with an extractant act synergistically, promote extraction, but make re-extraction more difficult (e.g. additives from trialkyl phosphates to dialkyl phosphates), the extraction-promoting additives according to the invention have not the last-mentioned disadvantage, since they are hardly extracted themselves and therefore remain in the aqueous phase. Compared to basic additives, the extraction-promoting salts have the advantage that they only have to be present during the extraction process, but are not consumed in the process will.

Ein weiterer Vorteil des erfindungsgemäßen Verfahrens besteht darin, daß ein gegebenes extraktionsförderndes Salz die Verteilungskoeffizienten zweier Metalle in der Regel unterschiedlich verändert. Daraus resultiert die Möglichkeit, die extraktive Trennung von Metallen durch Zugabe eines geeigneten extraktionsfördernden Salzes zu verbessern.Another advantage of the method according to the invention is that a given extraction-promoting Salt usually changes the distribution coefficients of two metals differently. This results in the Possibility of extractive separation of metals by adding a suitable extraction-promoting salt to enhance.

Die extraktionsfordernde Wirkung der Neutralsalze wird mit Zusätzen von etwa 0,01 Mol pro 1 Lösung bzw. Suspension bis zur Löslichkeitsgrenze der Zusätze erreicht; bevorzugt werden etwa 0,05 - 0,5 Mol zugegeben.The extraction promoting effect of the neutral salts is with Additions of about 0.01 mol per 1 solution or suspension reached up to the solubility limit of the additives; preferred about 0.05-0.5 moles are added.

Das erfindungsgemäße Verfahren eignet sich prinzipiell für die Extraktion sämtlicher Metalle, besonders geeignet ist es jedoch für Lösungen, die Zink und/oder dreiwertiges Eisen enthalten.The method according to the invention is suitable in principle for the extraction of all metals, but it is particularly suitable for solutions containing zinc and / or trivalent Contain iron.

Die Extraktion wird bei Temperaturen zwischen O0C und 75°C durchgeführt, bevorzugt wird jedoch im Temperaturbereich zwischen 15°C und 250C gearbeitet.The extraction is carried out 0 C and 75 ° C at temperatures between O, however, and is preferably carried out 25 0 C in the temperature range between 15 ° C.

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5 0-9844/049750-9844 / 0497

Als Phosphorverbindungen kommen z.B. folgende infrage:Possible phosphorus compounds include, for example, the following:

Phosphorsäure-di butylester Phosphorsäure-di-i/~"2-äthylhexyl-(l)_7-ester (DEHP) Phosphorsäure-phenyl-z/~2-äthylhexyl-(l)_/-ester (PEHP) Phosphorsäure-isodecyl-pentyl-ester Butanphosphonsäure-butylester Butanphosphonsäure-isobutylester 2-Methylpropan-phosphonsäure-butylester Pentanphosphonsäure-pentylester 2-Methylbutan-phosphonsäure-2-methylpropylester Hexanphosphonsäure-butylester Hexanphosphonsäure-hexylester (HHP) Isodecanphosphonsäure-butylester Octan-phosphonsäure-butylester Octan-phosphonsäure-octylester Benzylphosphonsäure-butylester Benzolphosphonsäure-pentylester Phenyl-butyl-phosphinsäure Dioctylphosphinsäure (DOP)Phosphoric acid di butyl ester Phosphoric acid di- i / ~ "2-ethylhexyl- (l) _7-ester (DEHP) Phosphoric acid phenyl- z / ~ 2-ethylhexyl- (l) _ / - ester (PEHP) Phosphoric acid isodecyl pentyl ester butyl phosphonic acid butyl ester butyl phosphonic acid isobutyl ester 2-methylpropane phosphonic acid butyl ester pentyl phosphonic acid pentyl ester 2-methylbutane phosphonic acid 2-methylpropyl ester hexanephosphonic acid butyl ester hexanephosphonic acid-butyl ester hexanephosphonic acid-octyl-phosphonate-octyl-phosphonate-butyl-phosphonate-octane-butyl-phosphonate (H-phosphonate-octyl-phosphonate-octane-phosphonate-octylphosphonate-octanylphosphonate-octanylphosphonate-octylphosphonate-butyl-phosphonate Benzylphosphonic acid butyl ester Benzene phosphonic acid pentyl ester Phenyl butyl phosphinic acid Dioctylphosphinic acid (DOP)

Die sauren Phosphorverbindungen können unverdünnt oder in einem wasserunlöslichen Lösungsmittel verwendet werden. Als Lösungsmittel kommen z.B. infrage: Benzol, Toluol, Xylole, Hexan, Cyclohexan, Heptan.The acidic phosphorus compounds can be used neat or in a water-insoluble solvent. Possible solvents are, for example: benzene, toluene, xylenes, hexane, cyclohexane, heptane.

Besonders geeignete Lösungsmittel sind hochsiedende, schwer entflammbare Fraktionen, wie sie bei der Erdöldestillation anfallen. Solche Erdölfraktionen werden z.B. unter den Handelsnamen Shellsol, Solvesso, Escaid angeboten.Particularly suitable solvents are high-boiling, flame-retardant fractions, such as those in petroleum distillation attack. Such petroleum fractions are offered, for example, under the trade names Shellsol, Solvesso, Escaid.

Die erfindungsgemäßen extraktionsfördernden Salze können prinzipiell in allen pH-Bereichen verwendet werden. Beson-The extraction-promoting salts according to the invention can in principle be used in all pH ranges. Special

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2A1751O2A1751O

ders vorteilhaft ist ihr Einsatz im eauren pH-BereichTheir use in the acidic pH range is also advantageous

(0 < pH <■ 5), weil hier die Verteilungskoeffizienten vieler(0 <pH <■ 5), because here the distribution coefficients of many

Metalle in Abwesenheit der genannten Salze zu niedrig liegen.Metals are too low in the absence of the salts mentioned.

Das erfindungsgemäße Verfahren soll nun anhand der folgenden Beispiele noch näher erläutert werden:The method according to the invention will now be based on the following Examples are explained in more detail:

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Beispiele:Examples:

a) Ausgangslösungen:a) Starting solutions:

Die wäßrigen Ausgangslösungen enthielten im Liter jeweils 0,1 Mol des zu extrahierenden Metalls in Form von Chlorid oder Sulfat und wechselnde, in der Tabelle angegebene Mengen eines "extraktionsfordernden Salzes". Weitere Stoffe waren darin nicht enthalten.The aqueous starting solutions each contained 0.1 mol per liter of the metal to be extracted in the form of chloride or sulfate and varying amounts of an "extraction-promoting salt" given in the table. More fabrics were not included.

Die organischen Lösungen enthielten in 1 Liter im Falle der Dioctylphosphinsäure 0,2 Mol, in allen anderen Fällen 1 Mol der sauren Phosphorverbindung, Als Lösungsmittel wurde in allen Fällen ein Kohlenwasserstoff-Gemisch benutzt (Shellsol RA). Dieses Kohlenwasserstoff-Gemisch mit der Dichte 0,904 enthält 99 % Aromaten, hat einen Flammpunkt von 68°C und einen Siedebereich von I83 - 312°C.The organic solutions contained in 1 liter in the case of dioctylphosphinic acid 0.2 mol, in all other cases 1 mol of the acidic phosphorus compound. A hydrocarbon mixture was used as solvent in all cases (Shellsol RA). This hydrocarbon mixture with a density of 0.904 contains 99 % aromatics, has a flash point of 68 ° C and a boiling range of I83 - 312 ° C.

b) Versuchsdurchführung:b) Carrying out the experiment:

50 ml der wäßrigen Ausgangslösung und 50 ml der organischen Extraktionsmittel-Lösung wurden in Schütteltrichtern mittels einer Maschine ^O Minuten lang intensiv geschüttelt. Obwohl die Metallverteilung nach 2 Minuten und nach 30 Minuten Schüttelzeit innerhalb der Analysengenauigkeit gleich war, wurden die Gemisch 30 Minuten geschüttelt, um eine vollkommenere Gleichgewichtseinstellung zu erreichen.50 ml of the aqueous starting solution and 50 ml of the organic extractant solution were placed in separating funnels Shaken vigorously by means of a machine for ^ 0 minutes. Although the metal distribution after 2 minutes and after 30 minutes of shaking time is within the accuracy of the analysis was the same, the mixtures were shaken for 30 minutes to allow a more perfect equilibrium to reach.

Nach der Phasentrennung wurden die Metallgehalte in beiden Phasen mittels der Atomabsorptionsphotometrie bestimmt. After the phase separation, the metal contents in both phases were determined by means of atomic absorption photometry.

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c) Ergebnisse:c) Results:

Aus den gemessenen Konzentrationen CM der Metalle wurden die in der folgenden Tabelle angegebenen Verteilungskoeffizienten der Metalle d.. nach der FormelFrom the measured concentrations C M of the metals, the distribution coefficients of the metals indicated in the table below were obtained according to the formula

Cw (organische Phase) d.Cw (organic phase) d.

Me
berechnet.Me
calculated.

Me . CM (wäßrige Phase)Me. C M (aqueous phase)

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Tabelle:Tabel: Verteilungskoeffizienten von Metallen in Abwesenheit und in Gegenwart "extraktionsfördernderPartition coefficients of metals in the absence and in the presence of "extraction-promoting

Salze":Salts ":

zu extrahierendes
Metallsalz/Konzentra-
0,1 Mol Metall/l tion
der wäßr. Phase to be extracted
Metal salt / concentrate
0.1 mol metal / liter
the water phase ZnSO^ZnSO ^ extraktionsforderndes
Salz extraction demanding
salt Q
wäßr. Phase
i/~~Mol/l_/7' Q
aq. phase
i / ~~ Mol / l_ / 7 ' saure Phosphor
verbindung/Kon
zentration in
der org. Phaseacidic phosphorus
connection / con
centering in
the org. phase Verteilungs
koeffizient
CMe(org.)Distribution
coefficient
C Me (org.) cn ZnSO j,
σ
CD
OOcn ZnSO j,
σ
CD
OO Substanz
formelsubstance
formula 0,0
0,1
0,50.0
0.1
0.5 DEHP
1-molarDEHP
1 molar dMe c MeCwäßr.) d ec M Me C w äßr.) OO •IN Q. /~i ώ \J ) ■
1 • IN Q. / ~ i ώ \ J ) ■
1 0,0
0,940.0
0.94 HHP
1-molarHHP
1 molar dZn = !'56
2,04
2,92 d Zn =! '56
2.04
2.92 COCO K2SO4 K 2 SO 4 0,0
0,940.0
0.94 PEHP
1-molar.PEHP
1 molar. dZn = I'2*?
2,0 d Zn = I ' 2 *?
2.0 0,0
0,940.0
0.94 DOP
0,2-molarDOP
0.2 molar d7n = 4,91
^n
10,3 d 7n = 4.91
^ n
10.3 0,0
0,1
0,5
1,00.0
0.1
0.5
1.0 DEHP
1-molarDEHP
1 molar d^^ = 0,92
Zn 'J
1,54 d ^^ = 0.92
Zn ' J
1.54 dZn - X'56
1,89
2,50
3,54 d Zn - X '56
1.89
2.50
3.54

Le A 15 651Le A 15 651

zu extrahierendes
Metallsalz/Konzentra-
0,1 Mol Metall/l tion
der wäßr. Phaseto be extracted
Metal salt / concentrate
0.1 mol metal / liter
the water phase cn
σcn
σ extraktionsförderndes
Salzextraction-promoting
salt Q
wäßr. Phase
j/~Mol/l_J7 Q
aq. phase
j / ~ mol / l_J7 saure Phosphor
verbindung/ Kon
zentration in
der org. Phaseacidic phosphorus
connection / con
centering in
the org. phase Verteilungs
koeffizient
CMe(org.)Distribution
coefficient
C Me (org.) ZnSO4 ZnSO 4 CXJ1 "
ex» Na2MoO4 CXJ 1 "
ex »Na 2 MoO 4 Substanz
formelsubstance
formula 0,0
0,1
0,50.0
0.1
0.5 DEHP
1-molarDEHP
1 molar aMe CMe(wäßr.) a Me C Me (aq.) 0 Pe2(SO4),
■P-» ^
CO 0 Pe 2 (SO 4 ),
■ P- » ^
CO 0,0
1,00.0
1.0 DEHP
1-molarDEHP
1 molar dZn - 1^
2,02
2,96 d Zn - 1 ^
2.02
2.96 MgSO4 MgSO 4 0,0
1,00.0
1.0 DEHP
1-molarDEHP
1 molar 2,072.07 Na3SO4 Na 3 SO 4 0,0
1,00.0
1.0 DEHP
1-molarDEHP
1 molar dMc = °'7
1,0 d Mc = ° ' 7
1.0 FeCl3 FeCl 3 NaClNaCl 0,0
1,00.0
1.0 DEHP
1-molarDEHP
1 molar Se = 2,23
6,14Se = 2.23
6.14 NH4ClNH 4 Cl 0,0
1,00.0
1.0 DEHP
1-molarDEHP
1 molar Se = 5,23
3,81Se = 5.23
3.81 MgCl2 MgCl 2 0,0
1,00.0
1.0 DSHP
1-molarDSHP
1 molar Se - 3,23
18,0Se - 3.23
18.0 MgCl2 MgCl 2 0,0
1,00.0
1.0 DEHP
1-molarDEHP
1 molar Se = 2δ'4
257,5 Se = 2δ ' 4
257.5 CaCl2 CaCl 2 dFe = 28,4
171,7d Fe = 28.4
171.7

Le A 15 651Le A 15 651

cn ο co ex»cn o co ex »

COCO

zu extrahierendes
Metallsalz/Konzentra-
O',l Mol Metall/l tioi
der wäßr. Phase to be extracted
Metal salt / concentrate
O ', l mole of metal / l tioi
the water phase extraktionsforderndes
Salzextraction demanding
salt Q
wäßr. Phase
/^"Mol/lJ7Q
aq. phase
/ ^ "Moles / lJ7 saure Phosphor
verbindung/Kon
zentration in
der org. Phaseacidic phosphorus
connection / con
centering in
the org. phase Verteilungs
koeffizientDistribution
coefficient SbCl,SbCl, Substanz
formelsubstance
formula 0,0
1,00.0
1.0 DEHP
1-molarDEHP
1 molar NaClNaCl 0,0
1,00.0
1.0 DEHP
1-molarDEHP
1 molar Me CMe(wäßr.)Me C Me (aq.) TiOSO4 TiOSO 4 NH4ClNH 4 Cl 0,00.0 DEHP
1-molarDEHP
1 molar dsb = 0,091
0,126d sb = 0.091
0.126 'dsb = 0,091'd sb = 0.091 dTi - 1550d Ti - 1550

CDCD

Le A 15 65 ΓLe A 15 65 Γ

- 10 -- 10 -

Claims (1)

Pa tentansprüche:Patent claims: 1) Verfahren zur Extraktion von mehrwertigen Metallionen aus wäßrigen Lösungen oder Suspensionen ihrer Salze, gegebenenfalls in Gegenwart von organischen Lösungsmitteln, mit in Wasser schwerlöslichen sauren Phosphorverbindungen der allgemeinen Formel1) Method of extracting polyvalent metal ions from aqueous solutions or suspensions of their salts, optionally in the presence of organic solvents, with acidic phosphorus compounds of the general formula that are sparingly soluble in water R2 ^ P"^ OHR 2 ^ P "^ OH wobeiwhereby R, und R2 gleich oder verschieden sein können und für einen linearen oder verzweigten, gegebenenfalls substituierten aliphatischen, einen gegebenenfalls substituierten araliphatischen oder aromatischen Rest mit bis zu 18 C-Atomen stehen und wobei die organischen Reste unmittelbar oder über ein Sauerstoffatom an den Phosphor gebunden sein können, dadurch gekennzeichnet, daß die Metallionen aus Lösungen oder Suspensionen extrahiert werden, die eines oder mehrere neutrale Salze der Salzsäure oder der Schwefelsäure in einer Konzentration von 0,01 Mol/l bis zur Löslichkeitsgrenze der neutralen Salze enthalten. R, and R 2 can be identical or different and represent a linear or branched, optionally substituted aliphatic, an optionally substituted araliphatic or aromatic radical with up to 18 carbon atoms and the organic radicals being bonded directly or via an oxygen atom to the phosphorus can be, characterized in that the metal ions are extracted from solutions or suspensions which contain one or more neutral salts of hydrochloric acid or sulfuric acid in a concentration of 0.01 mol / l up to the solubility limit of the neutral salts. 2) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als saure Phosphorverbindung Phosphorsäure-di-/~2-äthylhexyl-(l)_7-ester verwendet wird.2) Method according to claim 1, characterized in that the acidic phosphorus compound is phosphoric acid di- / ~ 2-ethylhexyl- (l) _7-ester is used. >) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als saure Phosphorverbindung Phosphorsäure-phenyl-^2-äthylhexyl-(l)_7-ester verwendet wird.>) Method according to claim 1, characterized in that as an acidic phosphorus compound, phosphoric acid-phenyl- ^ 2-ethylhexyl- (1) _7-ester is used. Le A 15 65I - 11 -Le A 15 65I - 11 - 509844/0497509844/0497 4) Verfahren nach einem der Ansprüche 1 bis 3> dadurch gekennzeichnet, daß als extraktionsfördernde Salze eines oder mehrere Salze aus der Gruppe Natriumchlorid, Ammoniumchlorid, Natriumsulfat, Ammoniumsulfat verwendet werden.4) Method according to one of claims 1 to 3> characterized in that one or more salts from the group of sodium chloride, ammonium chloride, Sodium sulfate, ammonium sulfate can be used. 5) Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Extraktion des dreiwertigen Eisens durch Zusatz von Natriumchlorid und/oder Ammoniumchlorid und/oder Calciumchlorid verbessert wird.5) Method according to one of claims 1 to 4, characterized in that that the extraction of trivalent iron by adding sodium chloride and / or ammonium chloride and / or calcium chloride is improved. 6) Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Extraktion des Zinks durch Zusatz von Natriumsulfat und/oder Ammoniumsulfat verbessert wird.6) Method according to one of claims 1 to 4, characterized in that that the extraction of the zinc is improved by adding sodium sulfate and / or ammonium sulfate. Le A 15 651 - 12 -Le A 15 651 - 12 - 5098A4/04975098A4 / 0497
DE2417510A 1974-04-10 1974-04-10 PROCESS FOR EXTRACTION OF METALS FROM Aqueous SOLUTIONS WITH ACID PHOSPHORUS COMPOUNDS Pending DE2417510A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
DE2417510A DE2417510A1 (en) 1974-04-10 1974-04-10 PROCESS FOR EXTRACTION OF METALS FROM Aqueous SOLUTIONS WITH ACID PHOSPHORUS COMPOUNDS
NO751058A NO751058L (en) 1974-04-10 1975-03-26
NL7504124A NL7504124A (en) 1974-04-10 1975-04-07 PROCEDURE FOR EXTRACTING POLYVALENT METAL IONS FROM WATER CONTAINING SOLUTIONS OR SUSPENSIONS OF ITS SALTS.
JP50041924A JPS50141579A (en) 1974-04-10 1975-04-08
LU72237A LU72237A1 (en) 1974-04-10 1975-04-08
BE155231A BE827731A (en) 1974-04-10 1975-04-09 EXTRACTION OF VERSATILE METAL IONS WITH ACID AND PHOSPHORUS COMPOUNDS AND NEUTRAL CHLORIDES AND / OR SULPHATES
SE7504086A SE388129B (en) 1974-04-10 1975-04-09 WAY TO EXTRACT POLYVALENTAL METAL IONS FROM AUTOMATIC SOLUTIONS OR SUSPENSIONS OF THEIR SALTS THROUGH ACID PHOSPHORIUM COMPOUNDS
ZA00752252A ZA752252B (en) 1974-04-10 1975-04-09 Extracting polyvalent metal ions with acid phosphorus and neutral chlorides and/or sulfates
FR7511270A FR2267380A1 (en) 1974-04-10 1975-04-10 Extracting polyvalent metal ions from aqs. soln. - with phosphorus acid cpds. in presence of a neutral sulphate of chloride salt

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DE2417510A DE2417510A1 (en) 1974-04-10 1974-04-10 PROCESS FOR EXTRACTION OF METALS FROM Aqueous SOLUTIONS WITH ACID PHOSPHORUS COMPOUNDS

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DE (1) DE2417510A1 (en)
FR (1) FR2267380A1 (en)
LU (1) LU72237A1 (en)
NL (1) NL7504124A (en)
NO (1) NO751058L (en)
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ZA (1) ZA752252B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4246240A (en) * 1978-07-24 1981-01-20 Nippon Mining Co., Ltd. Process for separating cobalt and nickel from a solution containing cobalt and nickel
DE3140380A1 (en) * 1981-10-10 1983-04-28 Gebrüder Sulzer AG, 8401 Winterthur Process for producing nickel, highly pure magnesium oxide and cement
DE3523624A1 (en) * 1984-07-03 1986-01-09 Outokumpu Oy, Helsinki METHOD FOR REMOVING AND RECOVERY METALS FROM AQUEOUS SOLUTIONS BY EXTRACTION

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4053552A (en) * 1976-03-15 1977-10-11 General Mills Chemicals Co. Solvent extraction of zinc from sulfite-bisulfite solution
FR2462481A1 (en) * 1979-07-30 1981-02-13 British Petroleum Co METHOD FOR THE LIQUID-LIQUID EXTRACTION OF AQUEOUS SOLUTION-BASED METALS USING ORGANOPHOSPHORUS DERIVATIVES
MA19258A1 (en) * 1980-08-28 1982-04-01 Canada Cyanamid PROCESS FOR SELECTIVE SEPARATION OF COBALT (II) FROM AQUEOUS SOLUTIONS.
FR2562059B1 (en) * 1984-04-02 1989-12-01 Rhone Poulenc Spec Chim PROCESS FOR SEPARATING RARE EARTH BY LIQUID-LIQUID EXTRACTION
CN107074890B (en) 2014-10-17 2019-09-24 默克专利股份公司 Alkenyl (perfluoroalkyl) phosphinic acids

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4246240A (en) * 1978-07-24 1981-01-20 Nippon Mining Co., Ltd. Process for separating cobalt and nickel from a solution containing cobalt and nickel
DE3140380A1 (en) * 1981-10-10 1983-04-28 Gebrüder Sulzer AG, 8401 Winterthur Process for producing nickel, highly pure magnesium oxide and cement
DE3523624A1 (en) * 1984-07-03 1986-01-09 Outokumpu Oy, Helsinki METHOD FOR REMOVING AND RECOVERY METALS FROM AQUEOUS SOLUTIONS BY EXTRACTION

Also Published As

Publication number Publication date
FR2267380B1 (en) 1979-03-09
JPS50141579A (en) 1975-11-14
LU72237A1 (en) 1976-03-17
BE827731A (en) 1975-10-09
NL7504124A (en) 1975-10-14
FR2267380A1 (en) 1975-11-07
NO751058L (en) 1975-10-13
SE388129B (en) 1976-09-27
ZA752252B (en) 1976-03-31
SE7504086L (en) 1975-10-13

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