EP0324843A1 - Procede d'extraction d'ions metalliques contenus dans des solutions aqueuses - Google Patents

Procede d'extraction d'ions metalliques contenus dans des solutions aqueuses

Info

Publication number
EP0324843A1
EP0324843A1 EP88907053A EP88907053A EP0324843A1 EP 0324843 A1 EP0324843 A1 EP 0324843A1 EP 88907053 A EP88907053 A EP 88907053A EP 88907053 A EP88907053 A EP 88907053A EP 0324843 A1 EP0324843 A1 EP 0324843A1
Authority
EP
European Patent Office
Prior art keywords
phase
membrane
nickel
stage
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.)
Withdrawn
Application number
EP88907053A
Other languages
German (de)
English (en)
Inventor
Rolf Marr
Heinz Lackner
Hans-Jörg BART
August Nickl
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.)
M&T Chemicals Inc
Original Assignee
M&T Chemicals 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 M&T Chemicals Inc filed Critical M&T Chemicals Inc
Publication of EP0324843A1 publication Critical patent/EP0324843A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0415—Solvent extraction of solutions which are liquid in combination with membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/38—Liquid-membrane separation
    • B01D61/40—Liquid-membrane separation using emulsion-type membranes
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to a process for separating metal ions, in particular nickel ions, from aqueous solutions, in which the solutions are subjected to liquid membrane permeation in a first stage and the depleted solutions are subjected to conventional solvent extraction in a second stage, the membrane phase from the first stage is used as the solvent phase of the second stage.
  • the nickel can be separated from wash water in the electroplating industry using known techniques. Evaporation, electrolysis, precipitation, liquid-liquid extraction, processes using solid ion exchangers and, in particular, membrane separation processes are suitable (Ullmanns Enzyklo ⁇ ubendie der technical chemistry, 4th edition, vol. 17). In the case of very dilute solutions, membrane processes are particularly economical since, as a rule, less equipment and operating resources are to be expected based on the substance to be separated (J. Draxler, R. Marr: Emulsion Liquid Membranes, Part I: Phenomenon and Industrial Application, Chem. Eng. Process., 20 (1986) 319-329).
  • the removal of nickel from dilute aqueous solutions should be designed in such a way that, with simple process control, a good removal is obtained which is selective and provides a product which can be used.
  • the treated wastewater should be cleaned to such an extent that the various state guidelines can be safely adhered to.
  • the legislative in Austria has set the permissible nickel content in waste water to a maximum of 3 pp (guidelines for limiting waste water emissions, Federal Ministry of Agriculture and Forestry Vienna, September 1981). Extraction methods which work with strong ion exchangers are suitable for such extensive separation.
  • the choice of a strongly acidic ion exchanger is expedient since it is possible to obtain metal directly without additional steps, such as pH adjustment, for example.
  • Comparative example 1 describes an extraction process for nickel.
  • the re-extraction takes place with hydrochloric acid. According to this process, it is possible to separate nickel from the waste water to the required extent and to selectively obtain it as a NiCl 2 solution.
  • nickel chloride solutions can only be used to a very limited extent there, since the nickel plating baths work in a sulfate environment. Carryover of nickel sulfate into the washing solutions creates an additional need for nickel sulfate, while the electrolysis itself creates an acid requirement. Although small amounts of chloride are metered into the bath, the amounts of nickel chloride solutions obtained during the extraction of the waste water could not be consumed in this way.
  • a stripping of the nickel from the extract phase with sulfuric acid instead of hydrochloric acid is not technically feasible, since it was found that even after hours of contact, no significant amount of nickel can be obtained from the organic extract phase.
  • a process control with sulfuric acid is therefore not useful.
  • sulfuric acid is used with an ion exchanger other than bis-2-ethylhexyldithiophosphoric acid, a weaker ion exchanger must then be used, so that the requirement mentioned above for high performance can no longer be met at low pH values.
  • Comparative example 2 shows the results for a single-stage and comparative example 3 for a two-stage permeation system.
  • the advantage of the method is that an aqueous sulfuric acid can be used as the stripping phase, which has a concentration of at least 1 mol / 1 H ⁇ SO., But preferably 5 mol / 1. Higher sulfuric acid concentrations would favor the stripping operation, but they would damage the ion exchangers and reduce their capacity over longer periods of time.
  • the phase ratio in the process can be set so that the emulsion phase, which consists of the stripping and membrane phases, can always be used in a ratio of less than one compared to the waste water phase.
  • the membrane phase is thus small in quantity. This has a positive effect on the costs of the procedure.
  • FMP is best carried out in a two-stage process control in equipment of the mixer-separator type.
  • various types of apparatus are known from conventional liquid-liquid extraction (Handbook of Solvent Extraction, Ed. T.C. Lo et al., John Wiley & Sons, New York 1982).
  • the FMP is thus a membrane process which, with the simultaneous use of specific ion exchangers, enables very selective metal separation.
  • the advantage of this design of the apparatus is that the proportion of the dispersion in the apparatus can be influenced not only as a function of the usual parameters throughput, phase relationships, apparatus volume and number of revolutions and type of stirrer, but also by the height difference between Mixer and separator.
  • the separation of the mixing chamber and settling chamber makes it possible to set any hydrostatic counterpressure, which represents a further degree of freedom for regulating the residence times and the disperse phase portion in the mixing chamber.
  • Fig. 1 shows such an apparatus with a separation of the mixing chamber and settling chamber.
  • FIG. 2 shows a graphical representation which shows the increase in nickel in the stripping phase with increasing dwell time.
  • nickel is initially transported through the membrane transport into the stripping phase and concentrated there. Due to the increasing nickel concentration, however, an osmotic gradient arises, which entails water transport, which redilutes the stripping solution again. A clear maximum of the nickel concentration at 7 minutes can therefore be seen in FIG. 2.
  • the emulsion In order to obtain a stripping phase with the highest possible nickel concentration, the emulsion must not remain in the mixing chamber longer than until the maximum concentration is reached.
  • the required dwell time of e.g. B. 7 minutes can be set in a very exact way by choosing the above freely selectable parameters.
  • the solutions containing metal ions, in particular nickel ions are subjected to a liquid membrane permeation in a first stage and the depleted solutions are subjected to a conventional solvent extraction in a second stage, the membrane phase from the first stage being the solvent phase in the second stage.
  • the method according to the invention being particularly characterized in that for the removal of nickel
  • the membrane phase contains a sulfur-containing organophosphorus compound
  • the aqueous stripping phase contains a mineral acid content between 1 and 5 mol / 1,
  • liquid membrane permeation and the solvent extraction are carried out in an apparatus of the mixer-settler type, vertical settlers being used and the static height difference between the mixer and settler being freely selectable.
  • the advantage is that in a first permeation stage a major part of the nickel is optimally separated.
  • a second stage in which little residual nickel and a lot of water would be transported through the membrane during permeation, the use of a conventional liquid-liquid extraction leads to an extraction of the residual nickel into the organic phase, so that the nickel concentration in the raffinate can be reduced to the required values.
  • the organic phase preloaded with nickel can easily be used for membrane production for the FMP, without the permeation being significantly affected thereby.
  • FIG. 1 shows an apparatus with a separate mixing and separating chamber for liquid membrane permeation with a standing separator according to the present invention
  • Fig. 2 is a graphical representation of the dependence of
  • Nickel enrichment in the emulsified stripping phase depending on the contact time between the wastewater to be cleaned and the membrane and stripping phase in liquid membrane permeation
  • 3a shows the flow diagram of a two-stage liquid membrane permeation process
  • 3b shows the flow diagram of the method according to the invention with a liquid membrane permeation in the first stage and a conventional liquid-liquid extraction in the second stage.
  • a freshly prepared emulsion (stripping acid in organic membrane phase) is permeated in a first step. This leads to the transport of nickel ions and water through the liquid membrane.
  • the emulsion is then broken down according to known methods.
  • the aqueous product phase is fed to the nickel bath.
  • the organic membrane phase which contains the ion exchanger
  • the waste water is subjected to a conventional liquid-liquid extraction in a second step.
  • the small amount of residual nickel from the permeation stage is extracted completely. No water is transported during the extraction.
  • the wastewater obtained (raffinate) then has the required low final nickel concentrations.
  • a new emulsion is then produced from the loaded organic membrane phase using fresh acid.
  • the membrane phase is regenerated and the emulsion used in the permeation stage already has a slight preload.
  • this pre-loading does not affect the effectiveness of the permeation stage to a detectable extent.
  • an organic extract phase is required which can be used both in the extraction and in the permeation.
  • the phase preferably contains 2 to 7% bis-2-ethylhexyl-dithiophosphoric acid dissolved in technically customary aromatic or aliphatic hydrocarbons.
  • An oil-soluble surfactant is also added to stabilize the emulsion.
  • the sulfur-containing organophosphorus compound, the bis-2- ethy] exyl-dithiophosphoric acid, extracts nickel even at low pH values down to low raffinate concentrations;
  • a sulfuric acid solution can be used as the stripping phase
  • the process is able to guarantee, on the one hand, the officially required low raffinate concentrations and, on the other hand, to produce selectively enriched, acidic nickel sulfate solutions;
  • an aqueous nickel phase which contains 2 g / 1 of nickel and has a pH of 4.5 are treated with 3.5 parts of an organic phase which comprises 15% bis-2- contains lo-ethylhexyl-dithiophosphoric acid, 15% isotridekanol and 70% undecane.
  • the initially nickel-free organic phase contains 7.0 g / 1 nickel, and 0.003 g / 1 nickel remain in the aqueous raffinate phase.
  • the organic extract phase loaded with nickel is regenerated with 10 mol / 1 HC1.
  • 1 part of aqueous phase with 3.5 parts of organic phase are contacted in two countercurrent stages for 5 minutes each.
  • the organic phase obtained has a nickel concentration of 0.5 g / 1 Ni, the aqueous stripping phase has been enriched to a content of 22.75 g / 1 nickel.
  • aqueous nickel phase which contains 2 g / 1 nickel and has a pH of 4.5 is treated with an emulsion phase whose organic membrane phase contains 5% bis-2-ethylhexyldithiophosphoric acid, 3% oil-soluble surfactant Paranox 100 (Esso Chem.) And 92% undecane and their aqueous stripping phase contains 250 g / 1 H_S0 4 .
  • the ratio of aqueous nickel phase to membrane phase to stripping phase is 30: 3.5: 1. After a contact time of 5 minutes, the initially nickel-free stripping phase contains 50 g / 1 nickel, and 0.17 g / 1 Ni remains in the aqueous raffinate phase .
  • An aqueous nickel phase which contains 2 g / 1 nickel and has a pH of 4.5 is treated in a two-stage countercurrent with an emulsion phase, the organic membrane phase of which is 5% bis-2-ethylhexyldithiophosphoric acid, 3% contains oil-soluble surfactant Paranox 100 (Esso Chem.) and 92% undecane, and whose stripping phase contains 250 g / 1 H 2 S04.
  • the ratio of the aqueous nickel phase to the membrane phase to the stripping phase is set to 30: 3.5: 1. After a contact time of 5 minutes each, the nickel concentration is 0.2 g / 1 in the first countercurrent stage and 0.003 g / 1 in the second. The degree of nickel recovery is therefore 99.85%. - u -
  • the nickel concentration in the stripping phase is 30 g / 1.
  • An aqueous nickel phase which contains 2 g / 1 of nickel and has a pH of 4.5, is treated in countercurrent in two stages, first in a permeation stage and then in an extraction stage.
  • the organic membrane or organic extract phase contains 5% bis-2-ethylhexyldithiophosphoric acid, 3% oil-soluble surfactant Paranox 100 (Esso Chem.) And 92% undecane.
  • the stripping phase of the emulsion contains 250 g / 1 H 2 S0 4 .
  • the ratio of the aqueous nickel phase to the membrane phase to the stripping phase is set to 30: 3.5: 1.
  • the nickel content in the aqueous raffinate phase is only 0.08 g / l. This amount of residual nickel is subjected to a subsequent liquid-liquid extraction.
  • the phase ratio of aqueous to organic extract phase is 3.5: 1.
  • a raffinate concentration of 0.003 g / 1 nickel is found.
  • the organic extract phase is regenerated in the emulsion preparation with 250 g / 1 H 2 S0 4 .
  • the aqueous stripping phase then contains a product concentration of 55 g / 1 nickel. The degree of recovery of nickel is therefore 99.85%.
  • the product solution has a concentration of 2750% compared to the input solution.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Water Supply & Treatment (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Extraction Or Liquid Replacement (AREA)

Abstract

Selon un procédé d'extraction d'ions métalliques, notamment d'ions de nickel, contenus dans des solutions aqueuses, on soumet les solutions pendant une première étape à une perméation fluide à travers une membrane, puis on soumet les solutions ainsi enrichies pendant une deuxième étape à une extraction usuelle à l'aide d'un solvant. La phase de la membrane utilisée pendant la première étape est utilisée comme phase solvante pendant la deuxième étape. La phase de la membrane contient un composé organophosphorique sulfureux, la phase aqueuse d'extraction a une teneur en acide minéral comprise entre 1 et 5 mol/l, le rapport entre la phase aqueuse de solution utilisée d'une part et la phase de solvant et de membrane d'autre part est toujours supérieur à 1. La perméation fluide et l'extraction par solvant se font dans un appareil du type mélangeur-séparateur, avec des séparateurs verticaux, la hauteur différentielle statique entre le mélangeur et le séparateur étant librement sélectionnable.
EP88907053A 1987-07-13 1988-07-13 Procede d'extraction d'ions metalliques contenus dans des solutions aqueuses Withdrawn EP0324843A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT0176387A AT391464B (de) 1987-07-13 1987-07-13 Verfahren zur abtrennung von nickelionen aus waesserigen loesungen
AT1763/87 1987-07-13

Publications (1)

Publication Number Publication Date
EP0324843A1 true EP0324843A1 (fr) 1989-07-26

Family

ID=3520483

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88907053A Withdrawn EP0324843A1 (fr) 1987-07-13 1988-07-13 Procede d'extraction d'ions metalliques contenus dans des solutions aqueuses

Country Status (4)

Country Link
EP (1) EP0324843A1 (fr)
JP (1) JPH02500452A (fr)
AT (1) AT391464B (fr)
WO (1) WO1989000444A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT395409B (de) * 1988-07-11 1992-12-28 Rolf Dipl Ing Dr Techn Marr Verfahren zur abtrennung von nickel aus waesserigen loesungen
US5095170A (en) * 1990-12-05 1992-03-10 Exxon And Research And Engineering Company Intergrated membrane pre-extraction/solvent extraction of distillates
PH31603A (en) * 1994-03-22 1998-11-03 Goro Nickels S A Process for the extraction and separation of nickel and/or cobalt.
JP2013057115A (ja) * 2011-09-09 2013-03-28 Kanazawa Inst Of Technology Ｓｃ３＋とＳｃ３＋以外の金属イオンとを含む水溶液からＳｃ３＋を分離するための方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE30179E (en) * 1970-04-13 1979-12-25 Exxon Research & Engineering Co. Common ion effect to assist LM separation
US3617546A (en) * 1970-04-13 1971-11-02 Exxon Research Engineering Co Removal of organic compounds by liquid membrane
DE3018862A1 (de) * 1975-01-27 1982-01-21 A.T. Ramot Plastics Ltd., Tel Aviv Aromatische araliphatische polymere und copolymere und daraus hergestellte produkte
US4010099A (en) * 1975-07-10 1977-03-01 Continental Oil Company Settlers for copper liquid extraction systems
SE398299B (sv) * 1976-04-21 1977-12-19 Berol Kemi Ab Forfarande och reagensblandning for avlegsnande av metalljoner ur en vattenlosning medelst vetskeextraktion
US4086163A (en) * 1976-09-29 1978-04-25 Exxon Research & Engineering Co. Metal extraction by combined solvent and LM extraction
US4353883A (en) * 1980-08-28 1982-10-12 American Cyanamid Company Selective extraction of cobalt(II) from aqueous solutions with phosphinic acid extractants
AT373859B (de) * 1982-06-04 1984-02-27 Chemiefaser Lenzing Ag Verfahren zur gewinnung von zink

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8900444A1 *

Also Published As

Publication number Publication date
JPH02500452A (ja) 1990-02-15
ATA176387A (de) 1990-04-15
AT391464B (de) 1990-10-10
WO1989000444A1 (fr) 1989-01-26

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