EP1297199B1 - Verfahren zur herstellung von metallhydroxiden oder basischen metallcarbonaten - Google Patents

Verfahren zur herstellung von metallhydroxiden oder basischen metallcarbonaten Download PDF

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Publication number
EP1297199B1
EP1297199B1 EP01943480.2A EP01943480A EP1297199B1 EP 1297199 B1 EP1297199 B1 EP 1297199B1 EP 01943480 A EP01943480 A EP 01943480A EP 1297199 B1 EP1297199 B1 EP 1297199B1
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EP
European Patent Office
Prior art keywords
metal
chamber
process according
precipitation
salt solution
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Expired - Lifetime
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EP01943480.2A
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German (de)
English (en)
French (fr)
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EP1297199A1 (de
Inventor
Armin Olbrich
Astrid GÖRGE
Frank Schrumpf
Juliane Meese-Marktscheffel
Viktor Stoller
Gerhard Gille
Josef Schmoll
Michael Kruft
Dirk Naumann
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HC Starck GmbH
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HC Starck GmbH
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/135—Carbon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/40—Cells or assemblies of cells comprising electrodes made of particles; Assemblies of constructional parts thereof

Definitions

  • the present invention relates to a process for the preparation of metal hydroxides and / or metal carbonates by anodic dissolution of corresponding metals and precipitation of the hydroxides or basic carbonates in an aqueous medium.
  • Metal hydroxides or basic metal carbonates are usually prepared by precipitation from corresponding aqueous metal salt solutions by reaction with alkali metal hydroxides or alkali metal bicarbonates. This stoichiometric amounts of neutral salts, which must be worked up or disposed of.
  • EP-A 684 324 It has been proposed to circulate separate anolyte and catholyte circuits in a two-compartment electrochemical cell partitioned by an anionic ion exchange membrane, anodically dissolving nickel in the anode compartment, containing anolyte ammonia as a complexing agent, generating hydroxyl ions in the cathodic compartment, and into the anode compartment through the membrane be converted, are hydrolyzed in the anolyte by increasing the temperature of the nickel ammine complexes and nickel hydroxide is precipitated and separated from the anolyte.
  • the process makes it possible to control the particle size of the nickel hydroxide in a wide range by controlling the hydrolysis process.
  • the process is cost-intensive and prone to failure due to the still insufficient service life of commercially available membranes.
  • the object of the invention is to provide a process for the preparation of metal hydroxides, which does not have the disadvantages mentioned.
  • the process according to the invention also permits the preparation of basic metal carbonates essentially without neutral salt attack.
  • metal hydroxides or basic metal carbonates in a two-stage process by obtaining a metal salt solution in an initial stage using an alkali salt solution by anodic dissolution of the metal and an alkaline alkali metal salt solution by cathodic hydrogen evolution Stage are combined to precipitate the metal hydroxide.
  • the alkali metal salt solution obtained after separation of the metal hydroxide precipitate is returned to the electrolytic cell. This is achieved by using a three-chamber electrolysis cell, in which the chambers are separated by porous membranes, with introduction of an alkali metal salt solution in the intermediate chamber between the cathode and anode chamber. Upon additional introduction of carbon dioxide into the cathodic compartment or into the second stage precipitation reactor, basic carbonates are obtained.
  • the present invention accordingly provides a process for the preparation of metal hydroxides or basic metal carbonates by anodic dissolution of corresponding metals and precipitation of the hydroxides or basic carbonates in an aqueous medium, which is characterized in that the anodic dissolution of the metal component takes place in the anode chamber of a three-chamber electrolysis cell, arranged between the anode chamber and cathode chamber and of an aqueous auxiliary salt solution is continuously fed to this intermediate chamber separated by porous membranes, the anode chamber is continuously withdrawn an at least non-alkaline metal salt solution, the alkaline chamber is continuously withdrawn from the cathode chamber, and the at least non-alkaline metal salt solution and the alkaline auxiliary salt solution outside the electrolytic cell to precipitate metal hydroxides or basic metal carbonates are combined.
  • an alkali hydroxide solution for adjusting the desired precipitation pH and a solution with a complexing agent, for example a NH 3 solution for producing spherical precipitates are fed.
  • Basic metal carbonates are easily obtained by introducing carbon dioxide into either the cathodic compartment or the combined precipitating solution.
  • Suitable metals are those which form salts which are soluble in the aqueous medium, can be precipitated in neutral or alkaline medium as hydroxides and / or basic carbonates and which do not form non-conductive surface layers in the electrolysis cell as anodes (oxides).
  • the metals used are particularly preferably Fe, Co, Ni, Cu, In, Mn, Sn, Zn, Cd and / or Al. Preference is given to using nickel or cobalt anodes.
  • auxiliary salts to be introduced into the intermediate chamber of the electrolytic cell chlorides, nitrates, sulfates, acetates and / or formates of the alkali metals and / or alkaline earth metals are suitable. Preference is given to sodium chloride and sodium sulfate.
  • the auxiliary salt solution preferably has a concentration of 1 to 3 mol / l.
  • auxiliary salt solution flows through the porous membranes to the anode chamber and the cathode chamber, wherein by the effect the electric field, a partial ion separation of the auxiliary salt solution in a portion with an excess of anion, which flows to the anode and a share with cation excess, which flows to the cathode takes place.
  • the auxiliary salt solution is preferably introduced into the intermediate chamber under such a pressure that the flow velocity through the porous membranes is greater than the migration rate of the anodically generated metal ions and the cathodically generated OH - ions in the respective solution, so that the anodically generated metal ions and the cathodic generate OH - ions can not get into the intermediate chamber.
  • the separation of the auxiliary salt solution in anion and cation excess proportion is the better, that is, the transport of neutral auxiliary salt into the anode and cathode chamber the lower, the lower the flow rate of the auxiliary salt solution through the membranes.
  • Optimum conditions can be determined by simple preliminary tests depending on the structural properties of the separation medium or its permeability or flow resistance. With regard to the separation effect and the electrical energy to be used, it is possible to set an optimum, which is determined by the type and concentration of the electrolyte. The inflow rate of the electrolyte must be chosen so that the ions with the higher mobility are in any case prevented from passing into the central space.
  • the ratio of anions to cations of the auxiliary salt solution passing through the membrane to the anode side is about 1.5 to 3, and conversely, the ratio of cations to anions of the auxiliary salt solution passing through the membrane to the cathode chamber is about 1.2 to 3.
  • all of the auxiliary salt solution introduced into the intermediate chamber passes through the porous membranes.
  • Suitable membranes are porous, preferably woven cloths or nets made of materials which are resistant to the auxiliary salt solutions, the anolytes and the catholytes.
  • cloths made of polypropylene can be used as described by the company SCAPA FILTRATION GmbH under the Designation Propex are offered.
  • Suitable wipes preferably have a pore radius of 10 to 30 microns. The porosity can be 20 to 50%.
  • the auxiliary salt solution with an excess of anions passing through the middle space in the anode space is substantially neutralized by the anodic dissolution of the metal anode and continuously discharged as anolyte.
  • a small amount of acid may be fed to the anode chamber, preferably by feeding in an acid containing the anion of the auxiliary salt solution.
  • the effluent from the anode chamber anolyte preferably has a metal salt content of 0.5 to 2 mol / l. Hydrogen and OH - ions are formed at the cathode in accordance with the excess of cations of the auxiliary salt which has passed through the membrane to the cathode space. From the cathode chamber so runs an alkaline auxiliary salt solution (catholyte).
  • Anolyte and catholyte are then brought to the precipitation reaction in a precipitation reactor.
  • a hydroxide solution may be carried out to adjust the precipitation pH and, if desired, complexing agents such as ammonia may be added to achieve a spherical shape of the precipitates.
  • carbon dioxide is passed into the catholyte or directly into the precipitation reactor. After separation of the precipitate remains an optionally alkaline auxiliary salt solution, which is preferably recycled after neutralization in the intermediate chamber of the electrolysis. It is also possible to store anolyte and catholyte in intermediate containers and carry out the precipitation discontinuously.
  • corresponding metal salt solutions of salts of the doping metals can be introduced into the precipitation reactor, wherein the demand for the precipitation reactor supplied alkali metal hydroxide to adjust the precipitation pH molar increases according to the amount of the doping salts. It Thus, a corresponding excess Neutralsalzanfall, which can not be returned to the intermediate chamber of the electrolysis cell.
  • the precipitation reaction may also be controlled by the presence of complexing agents, for example ammonia, in the precipitation reactor.
  • complexing agents for example ammonia
  • Amphoteric doping metals e.g. Aluminum
  • Aluminum can be introduced as aluminum salt or aluminates in the catholyte.
  • the precipitate is separated from the combined auxiliary salt solution (mother liquor). This can be done by sedimentation, by cyclones, by centrifugation or filtration. The separation can be carried out in stages, the precipitate being fractionated by particle size. Further, it may be appropriate to recycle a portion of the mother liquor after separation of the large metal hydroxide particles with the small metal hydroxide particles as nuclei in the precipitation reactor.
  • the liberated from the precipitate mother liquor is returned, optionally after a workup, in the intermediate chamber of the three-chamber electrolysis cell.
  • the workup serves to remove residual metal ions, to prevent the accumulation of impurities and to reinstate the concentration and composition of the auxiliary salt solution, for example the stripping of any complexing agent introduced for the precipitation.
  • the work-up of the mother liquor can be carried out in part stream.
  • the process is insensitive to the processing of the auxiliary salt solution. Thus, it is generally harmless if the complexing agent is recycled with the mother liquor in the intermediate chamber. Also, the process is hardly affected by the introduction of small amounts of metal ions in the intermediate chamber.
  • the metal ions precipitate in the intermediate chamber or in the catholyte as optionally sedimenting hydroxide sludge or are discharged with the catholyte as feinstteiliges hydroxide in the precipitation reactor.
  • the method according to the invention is an extremely flexible electrolytic process for the production of metal hydroxides are available in which essentially in addition to the starting materials of the anode metal and water and small amounts of acids and / or bases for pH regulation, no further starting materials are required and accordingly also no by-products arise.
  • the flexibility follows from the electrolytic separation of a recirculatable, neutral auxiliary salt solution into an acidic and alkaline fraction when passing through robust porous, electrochemically inactive membranes. In this way it is possible to discharge the metal ions and the hydroxide ions in the form of separate solutions from the electrolysis cell and to reunite them only for the precipitation. As a result, the precipitation is independently controllable without any influence on or retroactivity by the electrolysis process.
  • the process of the invention accordingly provides an extremely flexible process for the preparation of metal hydroxides or basic carbonates.
  • the person skilled in the art will readily be able to make further variations adapted to the particular requirements of the production of a specific product.
  • the middle space can also be separated on the cathode and anode sides by different separation media (filter cloths, diaphragms, etc.) in order to allow different flow conditions (velocities) into the cathode and anode spaces.
  • the electrodes may be arranged concentrically as in a tube condenser.
  • the counter electrode is formed concentrically to this center electrode as a tube.
  • the central space which consists of two parallel, tubular filter cloths, diaphragms or the like. Separation media is formed.
  • the invention further provides an apparatus for producing metal hydroxides, comprising a three-compartment electrolysis cell, a precipitation reactor and means for separating solids from the effluent of the precipitation reactor, wherein the electrolysis cell is divided by porous membranes in an anode chamber, an intermediate chamber and a cathode chamber, an inlet to the intermediate chamber, a drain from the anode chamber and a drain from the cathode chamber, an inlet of the precipitation reactor is connected to the drain from the anode chamber and another inlet of the precipitation reactor is connected to the drain from the cathode chamber.
  • the cathode chamber also has a vent for cathodically generated hydrogen.
  • feed-in options for subordinate quantities may be required
  • auxiliary reagents such as acid in the anode chamber, base in the precipitation reactor, both for pH adjustment, as well as complexing and doping agent may be provided in the precipitation reactor.
  • carbon dioxide can be introduced via line 17 for the production of basic metal carbonates.
  • the processes 41 and 42 from the electrolytic cell 1 are introduced into the precipitation reactor 2.
  • the precipitation reactor contains, for example, a high-speed agitator 21.
  • the precipitation reactor can also be used as a loop or jet propellant reactor or in be executed of a different type.
  • the precipitation suspension passes from the precipitation reactor in line 43.
  • introduction devices 22, 23 and 24 may be provided to provide auxiliaries and modifiers, such as for adjusting the pH, doping and / or influencing the precipitation by introducing complexing agent or introducing CO 2 to produce basic carbonates.
  • the precipitation reactor 2 can also be designed as a reactor cascade, with partial streams of the electrolysis cell effluents 41 or 42 being introduced into the individual reactors of the cascade.
  • the precipitation suspension passes via line 43 into the separating device 3 shown here as a hydrocyclone, from which the precipitated solid is largely withdrawn via the lower run 31 and via line 44 the precipitated mother liquor freed from solids overflows for workup 45.
  • Arrow 48 indicates schematically the introduction of work-up reagents and the separation of any interfering components.
  • the reclaimed mother liquor can be returned via line 47 and pump 46 in the intermediate chamber I.
  • the anode and cathode areas were each 7.5 dm 2 .
  • the distance between the electrodes was 4 cm.
  • the porous membranes used were polypropylene wipes having an average pore diameter of 26 .mu.m and a porosity of 28% calculated from the density determination of the wipe, as available from SScapa Filtration GmbH (Propex E14K).
  • the anode was made of pure nickel.
  • the cathode used was also a nickel electrode.
  • the intermediate chamber of the cell was fed per hour 8.18 1 sodium chloride solution containing 80 g / l sodium chloride. Further, 25 ml of a 1-normal hydrochloric acid solution was introduced into the anode compartment every hour.
  • the anodic current was 1000 A / m 2 . Between anode and cathode, a voltage of 7.3 V was measured. After reaching the steady state flowed from the anode chamber hourly 3.67 1 anolyte and from the cathode chamber 4.53 1 catholyte over.
  • Anolyte and catholyte were continuously introduced into a Rendingungsrroundreaktor, in the additionally hourly 184 ml of ammonia solution with 220 g / l NH 3 and 107 ml / h sodium hydroxide solution containing 200 g / l NaOH and 71.4 ml of a doping solution containing 20g / l cobalt and 100 g / l zinc were introduced in the form of their chloride salts.
  • the alkaline mother liquor was introduced into a stripping column to remove the ammonia, then neutralized and returned to the reservoir from which the auxiliary salt solution was withdrawn.
  • a spherical nickel hydroxide excellent in the use as a positive electrode material for rechargeable batteries having a mean particle diameter of 12 ⁇ m was obtained.
  • Example 1 was repeated with the difference that an auxiliary salt solution was used which contains 4.5 g / l NH 3 in addition to 80 g / l NaCl.
  • the introduction of ammonia solution into the precipitation reactor was dispensed with.
  • Example 2 was repeated with the difference that in the anode chamber additional cobalt and Zinkelektroden be attached and these were applied to currents corresponding to the desired molar ratio of Co and Zn in nickel hydroxide.
  • the workup of the mother liquor from the precipitation reactor consisted only in an addition of spent water.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP01943480.2A 2000-06-19 2001-06-06 Verfahren zur herstellung von metallhydroxiden oder basischen metallcarbonaten Expired - Lifetime EP1297199B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10030093 2000-06-19
DE10030093A DE10030093C1 (de) 2000-06-19 2000-06-19 Verfahren und Vorrichtung zur Herstellung von Metallhydroxiden oder basischen Metallcarbonaten
PCT/EP2001/006420 WO2001098559A1 (de) 2000-06-19 2001-06-06 Verfahren zur herstellung von metallhydroxiden oder basischen metallcarbonaten

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EP1297199A1 EP1297199A1 (de) 2003-04-02
EP1297199B1 true EP1297199B1 (de) 2016-11-16

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US (1) US7048843B2 (enExample)
EP (1) EP1297199B1 (enExample)
JP (1) JP4801312B2 (enExample)
KR (1) KR100809121B1 (enExample)
CN (1) CN1220793C (enExample)
AU (1) AU2001266051A1 (enExample)
CA (1) CA2412927C (enExample)
CZ (1) CZ300272B6 (enExample)
DE (1) DE10030093C1 (enExample)
ES (1) ES2612928T3 (enExample)
MY (1) MY140696A (enExample)
PT (1) PT1297199T (enExample)
TW (1) TW572844B (enExample)
WO (1) WO2001098559A1 (enExample)

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US8822030B2 (en) 2006-08-11 2014-09-02 Aqua Resources Corporation Nanoplatelet metal hydroxides and methods of preparing same
US20100239467A1 (en) 2008-06-17 2010-09-23 Brent Constantz Methods and systems for utilizing waste sources of metal oxides
AU2009270879B2 (en) 2008-07-16 2013-07-18 Eleryc, Inc. CO2 utilization in electrochemical systems
US8869477B2 (en) 2008-09-30 2014-10-28 Calera Corporation Formed building materials
CN101878327A (zh) * 2008-12-23 2010-11-03 卡勒拉公司 低能电化学氢氧根系统和方法
WO2010093716A1 (en) 2009-02-10 2010-08-19 Calera Corporation Low-voltage alkaline production using hydrogen and electrocatlytic electrodes
US8883104B2 (en) 2009-03-02 2014-11-11 Calera Corporation Gas stream multi-pollutants control systems and methods
CN102249349B (zh) * 2011-04-26 2013-06-05 北京化工大学 一种化学和电化学联用法合成多元掺杂球形纳米氢氧化镍
KR102614113B1 (ko) * 2013-10-23 2023-12-13 네마스카 리튬 인코포레이션 리튬 카보네이트의 제조방법
JP6119622B2 (ja) * 2014-01-29 2017-04-26 住友金属鉱山株式会社 水酸化インジウム粉の製造方法及び陰極
KR101903004B1 (ko) * 2014-08-22 2018-10-01 한국과학기술원 탄산염의 제조 방법
CN107177858B (zh) * 2017-05-10 2019-02-05 东北大学 一种氯化铝电转化为氧化铝的方法
CN107512811B (zh) * 2017-07-31 2020-06-23 四川思达能环保科技有限公司 球形氢氧化镍生产工艺过程废水的处理方法
DE102018000672A1 (de) * 2018-01-29 2019-08-14 Rheinisch-Westfälische Technische Hochschule (Rwth) Aachen Verfahren zur Übertragung eines Zielstoffs zwischen zwei flüssigen Phasen
CN108217856B (zh) * 2018-01-30 2024-02-20 武汉工程大学 一种电化学水处理系统及其水处理方法
EP4052313B1 (en) * 2019-10-29 2024-04-03 Carnegie Mellon University Electrochemical synthesis of cementitious compounds
WO2022036006A1 (en) * 2020-08-11 2022-02-17 The Regents Of The University Of California Chemical calcium hydroxide manufacturing for cement production using electrochemical separation devices
WO2023137553A1 (en) * 2022-01-20 2023-07-27 The University Of British Columbia Methods and apparatus for converting metal carbonate salts to metal hydroxides
KR102878258B1 (ko) * 2023-08-29 2025-11-06 한국에너지기술연구원 금속의 기전력을 이용한 이산화탄소 전환 시스템 및 방법
KR20250092402A (ko) 2023-12-14 2025-06-24 주식회사 디에스엔텍 방사성 이산화탄소 제거용 필터의 제조 방법 및 방사성 이산화탄소 제거 장치

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CZ300272B6 (cs) 2009-04-08
CN1437660A (zh) 2003-08-20
JP2004501281A (ja) 2004-01-15
PT1297199T (pt) 2017-01-04
AU2001266051A1 (en) 2002-01-02
CZ20024119A3 (cs) 2003-04-16
EP1297199A1 (de) 2003-04-02
CA2412927C (en) 2009-11-17
TW572844B (en) 2004-01-21
DE10030093C1 (de) 2002-02-21
MY140696A (en) 2010-01-15
JP4801312B2 (ja) 2011-10-26
ES2612928T3 (es) 2017-05-19
US7048843B2 (en) 2006-05-23
KR100809121B1 (ko) 2008-02-29
US20030141199A1 (en) 2003-07-31
CN1220793C (zh) 2005-09-28
CA2412927A1 (en) 2002-12-16
WO2001098559A1 (de) 2001-12-27
KR20030019435A (ko) 2003-03-06

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