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WO1993001135A1 - Apparatus and process for removal of dissolved metal forms - Google Patents

Apparatus and process for removal of dissolved metal forms Download PDF

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Publication number
WO1993001135A1
WO1993001135A1 PCT/CS1992/000018 CS9200018W WO9301135A1 WO 1993001135 A1 WO1993001135 A1 WO 1993001135A1 CS 9200018 W CS9200018 W CS 9200018W WO 9301135 A1 WO9301135 A1 WO 9301135A1
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WO
WIPO (PCT)
Prior art keywords
metal
separated
electrochemical
particular form
particles
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/CS1992/000018
Other languages
French (fr)
Inventor
Miroslav KOLLÁR
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.)
Vy^ Skumny Ustav Vodneho Hospodarstva
Original Assignee
Vy^ Skumny Ustav Vodneho Hospodarstva
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
Priority claimed from CS200491 external-priority patent/CZ9102004A3/en
Priority claimed from CS200591 external-priority patent/CZ9102005A3/en
Application filed by Vy^ Skumny Ustav Vodneho Hospodarstva filed Critical Vy^ Skumny Ustav Vodneho Hospodarstva
Publication of WO1993001135A1 publication Critical patent/WO1993001135A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C02F1/705—Reduction by metals
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • C22B15/0091—Treating solutions by chemical methods by cementation
    • 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 apparatus for continuous removal of dissolved metal forms from solutions, which is suitable mainly as part of the technologic line for purification of waste water containing these metal forms or may be used in the hydrometallurgy, as well as to the procces of metal removal realized in this apparatus.
  • the dissolved metal forms are removed from the solutions in which they are contained mainly by :
  • the electrochemical cementation belongs, where the metal containing solutions, e.g. waste water, are contacted with a metal having a lower electrochemical potential than that of the metal contained in the solution.
  • the process is conductet in charged vessels, where the water under treatment flows positively onto the metal layer with a lower electrochemical potential forming the charge.
  • the efficiency of separating the metal which is to be removed is very good at the beginning, then it decreases, because the separated metal forming a layer on the surface of charge of metal with a lower electrochemical potential hinders the further exchange.
  • the soluble metal forms can be removed from solutions continuously, using the process of electrochemical cementation in an apparatus suitable mainly as part of the technologic line for waste water treatment and with the possibility to use in the hydrometallurgy.
  • This apparatus is formed by a fluid reactor charged with a lower electrochemical potential than that of the metals contained in the solution, further by separator of the particular form of the removed metal and by a metering device for the particular form of the removed metal, interconected by a circulating pipeline.
  • the electrochemical cementation process with fluidized metal particles is realized, in which the metal with the higher electrochemical potential is reduced by its own electrochemical reaction and it is separated in solid form. Due to mutual abrasion of particles in the fluid bed the removed metal is separated from the surface of the fluidized bed filling particles. Due to mutual contact of particles of both of the metals the potential is transferred from the more electronegative metal particles to the more electropositive metal particles, whereby conditions are formed for the reduction of the separated metal on its own particles, too.
  • the concentration of particles with a higher electrochemical potential catalyzes the reaction up to the reaching the limit concentration of the particular form.
  • the purified water flows from the fluid reactor into the separator and entrains the separated particles of particular metal, which are separated from purified water in this separator.
  • the separated metal particles are back-dosed into the fluid reactor by the metering device so that the parti cular form in the fluid bed should not exceed the limit concentration.
  • the metal with a higher electrochemical potential in the particular form autocatalyzes at the electrochemical cementation the separation itself on the metal with a lower electrochemical potential.
  • the separated metal immediately takes part in the reaction as a catalyst, whereby the metal separation rate is directly proportional to the concentration of the metal particular form present in the fluidized layer.
  • the catalytic effect of the given concentration of the particular metal form with a higher electrochemical potential is limited by the range of concentration variations of the removed metal. After exceeding the limit concentration of the particular form of separated metal the reaction rate constant decreases.
  • fluid reactors e.g. cylindrical, conical, tapered, pyramidal, slot reactors or those with perforated grate or with a counter-current mushroom.
  • filtration or sedimentation basins a hydrocyclone etc. can be used as separator and metering pump with controlled mode is suitable as the doser.
  • Fig.1 shows the section of one of the examples of apparatus according to this invention.
  • the apparatus for continuous removal of dissolved metal forms from solutions consists of the fluid reactor 1 filled with charge 11 consisting of 500g steel granulate, with 20% expansion of the fluid bed mantained in the course of apparatus operation.
  • the fluid reactor 1 is conected with the separator 2 formed by the sedimentation basin and with the metering pump 3 - doser of particular form of the separated metal, which is a metering pump. All parts of the apparatus are interconnected with a circulating pipeline 4.
  • This apparatus is a part of the technologic line for purification of waste water from metalworking industry containig dissolved copper in concentrations up to 400 mg.l -1 , whereby the volume of the whole system amounts to 15 litres.
  • the waste water under purification was brought into the fluid reactor 1 where the process of electrochemical cementation in the fluidized bed of steel granulate was carried out.
  • the copper is reduced by its own electrochemical reaction and is separated in solid form.
  • the copper Due to mutual abrasion of particles in the fluid bed the copper is separated from the surface of the fluidized filling particles. Due to mutual contact of particles of both of the metals the potential is transferred from the more electronegative steal particles to the more electropositive copper particles. Then the purified water was transfered from the fluid reactor 1 into the separator - sedimentation basin 2, where the particular form of the separated copper was separated by sedimentation, which was back-dosed into the fluid reactor by the help of the metering pump 3, whereby for copper concentrations from 100 to 400 mg.l -1 the limit particular concentration of the particular copper 4, 25 g.l -1 was maintained in the fluid bed controlled by back-dosing and for copper concentration below 20 mg.l -1 the limit concentration 2,9 g.l -1 was maintained.
  • the limit concentration of the particular form of separated copper was determined experimentally by watching the kinetics of coppper concentration changes in the solution at various concentrations of particular copper.
  • the apparatus and process according to this invention can be used mainly for purification of waste water containing dissolved metal forms and in the hydrometallurgy, especially for recovery of rare metals.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

Apparatus is suitable mainly as part of the technologic line for purification of waste water containing dissolved metal forms or for the use in the hydrometalurgy. It consists of the fluid reactor (1) filled with a charge (11) of metal particles with a lower electrochemical potential than that of the separated metal, further of the separator (2) of the particular form of separated metal and the metering device of the particular form of separated metal. The apparatus parts are interconnected with a circulating pipeline (4). The solution containing dissolved metal forms is brought into the fluid reactor (1). The electrochemical cementation process with fluidized metal particles is realized, in which the metal with the higher electrochemical potential is reduced by its own electrochemical reaction and it is separated in solid form. The process of electrochemical cementation is autocatalysed by the controlled metering of the particular form of separated metal.

Description

APPARATUS AND PROCESS FOR REMOVAL OF DISSOLVED METAL FORMS.
FIELD OF INVENTION
This invention relates to the apparatus for continuous removal of dissolved metal forms from solutions, which is suitable mainly as part of the technologic line for purification of waste water containing these metal forms or may be used in the hydrometallurgy, as well as to the procces of metal removal realized in this apparatus.
BACKGROUND OF THE INVENTION
At present, the dissolved metal forms are removed from the solutions in which they are contained mainly by :
- precipitation under forming insoluble hydroxides,
- precipitation with the use of inorganic sulphides or organosulphates under forming insoluble metal sulphides or their complexes,
- electrochemical methods using various types of electrσlyzers,
- removal of these metals by exchange for another metal, whereby this process runs in static conditions on large surface metal materials.
To the mentioned methods also the electrochemical cementation belongs, where the metal containing solutions, e.g. waste water, are contacted with a metal having a lower electrochemical potential than that of the metal contained in the solution. The process is conductet in charged vessels, where the water under treatment flows positively onto the metal layer with a lower electrochemical potential forming the charge. When removing metals from waste water by this process, the efficiency of separating the metal which is to be removed is very good at the beginning, then it decreases, because the separated metal forming a layer on the surface of charge of metal with a lower electrochemical potential hinders the further exchange. SUMMARY OF THE INVENTION
The soluble metal forms can be removed from solutions continuously, using the process of electrochemical cementation in an apparatus suitable mainly as part of the technologic line for waste water treatment and with the possibility to use in the hydrometallurgy.
This apparatus is formed by a fluid reactor charged with a lower electrochemical potential than that of the metals contained in the solution, further by separator of the particular form of the removed metal and by a metering device for the particular form of the removed metal, interconected by a circulating pipeline.
The solution containing the dissolved metal forms in brought to the fluid reactor charged with metal particles with a lower electrochemical potential than that of the metal removed from the purified solution. The electrochemical cementation process with fluidized metal particles is realized, in which the metal with the higher electrochemical potential is reduced by its own electrochemical reaction and it is separated in solid form. Due to mutual abrasion of particles in the fluid bed the removed metal is separated from the surface of the fluidized bed filling particles. Due to mutual contact of particles of both of the metals the potential is transferred from the more electronegative metal particles to the more electropositive metal particles, whereby conditions are formed for the reduction of the separated metal on its own particles, too. The concentration of particles with a higher electrochemical potential catalyzes the reaction up to the reaching the limit concentration of the particular form.
The purified water flows from the fluid reactor into the separator and entrains the separated particles of particular metal, which are separated from purified water in this separator. The separated metal particles are back-dosed into the fluid reactor by the metering device so that the parti cular form in the fluid bed should not exceed the limit concentration.
It is possible to optimize the process of electrochemical cementation which is realized in the apparatus according to this invention in such a way, that first the limit concentration of the particular form of the separated metal for the realizing process is determined and then by back controlled metering of the paricular form of separated metal the rate of its separation is optimized.
As mentioned above, the metal with a higher electrochemical potential in the particular form autocatalyzes at the electrochemical cementation the separation itself on the metal with a lower electrochemical potential. In conditions of fluidization realized in the apparatus according to this invention the separated metal immediately takes part in the reaction as a catalyst, whereby the metal separation rate is directly proportional to the concentration of the metal particular form present in the fluidized layer.
The catalytic effect of the given concentration of the particular metal form with a higher electrochemical potential is limited by the range of concentration variations of the removed metal. After exceeding the limit concentration of the particular form of separated metal the reaction rate constant decreases.
The logarithm of limit concentrations of the particular metal form with a higher electrochemical potential is a linear function of its concentration.
Under operational conditions, with the application of the mentioned knowledge, it is possible to use the combination of fluid reactor with various concentrations of the particular form of the separated metal and to reach a maximum rate of the realised process with the use of minimum reaction space. In addition, by application of this way simultaneously the problem of passivating of metal with a lower electrochemical potential than that of the separated metal is eliminated.
Various equipments securing the required fluidized charge state can be used as fluid reactors, e.g. cylindrical, conical, tapered, pyramidal, slot reactors or those with perforated grate or with a counter-current mushroom.
For instance, filtration or sedimentation basins, a hydrocyclone etc. can be used as separator and metering pump with controlled mode is suitable as the doser.
BRIEF DESCRIPTION OF THE DRAWINGS
Present invention is explained by the help of the drawing where Fig.1 shows the section of one of the examples of apparatus according to this invention.
DESCRIPTION OF THE PREFERED EMBODIMENT OF THE INVENTION
The apparatus for continuous removal of dissolved metal forms from solutions consists of the fluid reactor 1 filled with charge 11 consisting of 500g steel granulate, with 20% expansion of the fluid bed mantained in the course of apparatus operation. The fluid reactor 1 is conected with the separator 2 formed by the sedimentation basin and with the metering pump 3 - doser of particular form of the separated metal, which is a metering pump. All parts of the apparatus are interconnected with a circulating pipeline 4. This apparatus is a part of the technologic line for purification of waste water from metalworking industry containig dissolved copper in concentrations up to 400 mg.l-1, whereby the volume of the whole system amounts to 15 litres.
The waste water under purification was brought into the fluid reactor 1 where the process of electrochemical cementation in the fluidized bed of steel granulate was carried out. In this process the copper is reduced by its own electrochemical reaction and is separated in solid form.
Due to mutual abrasion of particles in the fluid bed the copper is separated from the surface of the fluidized filling particles. Due to mutual contact of particles of both of the metals the potential is transferred from the more electronegative steal particles to the more electropositive copper particles. Then the purified water was transfered from the fluid reactor 1 into the separator - sedimentation basin 2, where the particular form of the separated copper was separated by sedimentation, which was back-dosed into the fluid reactor by the help of the metering pump 3, whereby for copper concentrations from 100 to 400 mg.l-1 the limit particular concentration of the particular copper 4, 25 g.l-1was maintained in the fluid bed controlled by back-dosing and for copper concentration below 20 mg.l-1 the limit concentration 2,9 g.l-1 was maintained.
The limit concentration of the particular form of separated copper was determined experimentally by watching the kinetics of coppper concentration changes in the solution at various concentrations of particular copper.
INDUSTRIAL USE
The apparatus and process according to this invention can be used mainly for purification of waste water containing dissolved metal forms and in the hydrometallurgy, especially for recovery of rare metals.

Claims

1. Apparatus for continuoous removal of dissolved metal forms from solutions, suitable mainly as a part of the technologic line for purification of waste water containing these metal forms or for the use in the hydrometallurgy, characterized by the fact that it consist of the fluid reactor /1/ filled with a charge /11/ of metal particles with a lower electrochemical potential than that of the separated metal, further of the separator /2/ of the particular form of separated metal and the metering device /3/ of the particular form of separated metal, which are interconected with a circulating pipeline /4/.
2. Process for continuous removal of dissolved metal forms from solutions by electrochemical cementation, characterized by the fact that the electrochemical cementation of the solution containing dissolved metal forms is carried out under contact with the fluidized layer of metal particles with a lower electrochemical potential than that of the separated metal and the particular form of the separated metal, which autocatalyzes the process of electrochemical cementation, is back-dosed into this process, whereby the metering is controled by the experimentally determined limit concentration value of the particular form of metal separated in this process.
PCT/CS1992/000018 1991-07-01 1992-06-30 Apparatus and process for removal of dissolved metal forms Ceased WO1993001135A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CSPV2004-91 1991-07-01
CSPV2005-91 1991-07-01
CS200491 CZ9102004A3 (en) 1991-07-01 1991-07-01 Continuous removal device
CS200591 CZ9102005A3 (en) 1991-07-01 1991-07-01 A method for optimizing the removal of dissolved metal forms from solutions

Publications (1)

Publication Number Publication Date
WO1993001135A1 true WO1993001135A1 (en) 1993-01-21

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CS1992/000018 Ceased WO1993001135A1 (en) 1991-07-01 1992-06-30 Apparatus and process for removal of dissolved metal forms

Country Status (2)

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AU (1) AU2164892A (en)
WO (1) WO1993001135A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2447220A1 (en) * 2010-11-02 2012-05-02 Montanuniversität Leoben Removing contaminants from aquatic fluids

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3154411A (en) * 1962-03-20 1964-10-27 Kennecott Copper Corp Process and apparatus for the precipitation of copper from dilute acid solutions
US4027864A (en) * 1975-03-03 1977-06-07 Cities Service Company Process and apparatus for recovering dissolved copper from solutions containing copper

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3154411A (en) * 1962-03-20 1964-10-27 Kennecott Copper Corp Process and apparatus for the precipitation of copper from dilute acid solutions
US4027864A (en) * 1975-03-03 1977-06-07 Cities Service Company Process and apparatus for recovering dissolved copper from solutions containing copper

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZEITSCHRIFT FUR METALLKUNDE. vol. 79, no. 8, August 1988, STUTTGART DE pages 544 - 546; YEHYAA, EL-TAWIL: 'CEMENTATION OF CUPRIC IONS FROM COPPER SULPHATE SOLUTION USING FLUIDIZED BED OF ZINC POWDER' *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2447220A1 (en) * 2010-11-02 2012-05-02 Montanuniversität Leoben Removing contaminants from aquatic fluids
WO2012059480A1 (en) * 2010-11-02 2012-05-10 Montanuniversitaet Leoben Installation and process for removing contaminants from aquatic fluids
CN103347819A (en) * 2010-11-02 2013-10-09 莱奥本矿冶大学 Installation and process for removing contaminants from aquatic fluid

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Publication number Publication date
AU2164892A (en) 1993-02-11

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