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EP0267858B1 - Verfahren zur Herstellung von Vanadiumtrichlorid in wässriger Lösung - Google Patents

Verfahren zur Herstellung von Vanadiumtrichlorid in wässriger Lösung Download PDF

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Publication number
EP0267858B1
EP0267858B1 EP19870420284 EP87420284A EP0267858B1 EP 0267858 B1 EP0267858 B1 EP 0267858B1 EP 19870420284 EP19870420284 EP 19870420284 EP 87420284 A EP87420284 A EP 87420284A EP 0267858 B1 EP0267858 B1 EP 0267858B1
Authority
EP
European Patent Office
Prior art keywords
vanadium
process according
solution
ions
aqueous solution
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.)
Expired - Lifetime
Application number
EP19870420284
Other languages
English (en)
French (fr)
Other versions
EP0267858A1 (de
Inventor
Guy Bernard
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.)
Metaux Speciaux SA
Original Assignee
Metaux Speciaux SA
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 Metaux Speciaux SA filed Critical Metaux Speciaux SA
Publication of EP0267858A1 publication Critical patent/EP0267858A1/de
Application granted granted Critical
Publication of EP0267858B1 publication Critical patent/EP0267858B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • 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

Definitions

  • the present invention relates to a process for the manufacture of vanadium trichloride in aqueous solution.
  • Vanadium trichloride in aqueous solution is used as a catalyst in the manufacture of certain elastomers.
  • vanadium tetrachloride VCI 4 is an intermediate product in the manufacture of anhydrous vanadium trichloride VCl 3 , because it is an unstable compound which decomposes slowly into VC1 3 and into chlorine at temperatures below 63 ° C.
  • the invention therefore consists in using a solution containing pentavalent and / or tetravalent vanadium ions.
  • VCI 4 is available because it is, in general, a relatively pure product, unlike V 2 O 5 which requires purification prior to its dissolution in acid. hydrochloric.
  • VCI 2 vanadium ions are partially tetravalent in the case of the dissolution of V 2 0s in VCI 2 acidified by hydrochloric acid.
  • This VCI 2 can be easily obtained by advanced electrolytic reduction of pentavalent vanadium ions, for example.
  • the merit of the invention is to have developed a process which leads to VC1 3 free of other chlorides and which perfectly meets the requirements of users, in particular from the point of view of concentration of trivalent ions.
  • the demandeesae has developed the reduction in an electrolysis cell where the catholyte and the anolyte are separated by an anionic membrane. Indeed, it found that with this means the VCls solution obtained was particularly pure. This is due, it seems, to the fact that the membrane avoids reoxidation of the ionium vanadium as well as a possible migration of oxidation by-products which risk polluting the catholyte. This membrane must nevertheless allow excess CI- ions to pass after the reduction reaction.
  • anionic membranes are commercially available. They must be chosen here according to their mechanical and corrosion resistance in an acid medium and their electrical resistivity.
  • those which are made of polyvinyl chloride and whose resistivity is between 1 and 3 ⁇ / cm 2 are chosen.
  • the reduction rate is controlled by means of a platinum electrode immersed in the electrolyte solution, the potential of which is measured compared to a conventional calomel electrode.
  • This potential initially between 400 and more than 1000 mV drops during the reduction and suddenly between 100 and -200 mV which indicates then that the only trivalent ions are present in the solution and that one can thus stop the reduction.
  • this reduction is carried out at the lowest possible temperature, at most 30 ° C., to reduce the evolution of hydrogen and improve the current efficiency of the cell.
  • This reduction can be carried out both in batch and continuously.
  • a PVDF filter press type cell having a graphite cathode of 1 dm 2 of surface, a rhodium titanium anode of 1 dm 2 of surface separated by an anionic polyvinyl chloride membrane of 1 dm 2 of surface and resistivity 1.5 ⁇ / dm 2 , circulate 1 1 of VCI 4 solution containing 113.7 g of vanadium per liter, at a flow rate of 3 liters per hour and feed this cell with a direct current of 6 amperes at 9 volts of voltage.
  • the voltage across a platinum electrode relative to a calomel electrode immersed in the solution was initially 900 mV. After 11.5 h, this voltage dropped to -200 mV.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Claims (8)

1. Verfahren zur Herstellung von Vanadiumtrichlorid in wässeriger Lösung, dadurch gekennzeichnet, daß man elektrolytisch eine fünfwertige und/oder vierwertige Vanadiumionen enthaltende Lösung in einer Zelle reduziert, wo der Katholyt und der Anolyt durch eine anionische Membran getrennt sind, und daß man die Elektrolyse durchführt, bis das Potential einer in die Lösung eintauchenden Platinelektrode bezüglich einer Calomelelektrode im Bereich von 100 bis -200 mV ist.
2. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß die die Vanadiumionen enthaltende Lösung durch Bringen von VCI4 in wässerige Lösung erhalten wird.
3. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß die die Vanadiumionen enthaltende Lösung durch Auflösung von Vanadiumpentoxid in Salzsäure erhalten wird.
4. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß die die Vanadiumionen enthaltende Lösung durch Auflösung von Vanadiumpentoxid in angesäuertem Vanadiumdichlorid.erhalten wird.
5. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß man während der Elektrolyse die Lösung auf einer Temperatur unter 30°C hält.
6. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß die Lösung 100 bis 120 g/I Vanadium enthält.
7. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß man den Strom dem Katholyten mittels einer Graphitelektrode zuführt.
8. Verfahren nach dem Anspruch 1, dadurch gekennzeichnet, daß man den Strom dem Anolyten mittels einer Elektrode aus rhodiniertem Titan zuführt.
EP19870420284 1986-10-22 1987-10-21 Verfahren zur Herstellung von Vanadiumtrichlorid in wässriger Lösung Expired - Lifetime EP0267858B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8614854 1986-10-22
FR8614854A FR2605622B1 (fr) 1986-10-22 1986-10-22 Procede de fabrication de trichlorure de vanadium en solution aqueuse

Publications (2)

Publication Number Publication Date
EP0267858A1 EP0267858A1 (de) 1988-05-18
EP0267858B1 true EP0267858B1 (de) 1990-03-07

Family

ID=9340195

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19870420284 Expired - Lifetime EP0267858B1 (de) 1986-10-22 1987-10-21 Verfahren zur Herstellung von Vanadiumtrichlorid in wässriger Lösung

Country Status (3)

Country Link
EP (1) EP0267858B1 (de)
DE (1) DE3761824D1 (de)
FR (1) FR2605622B1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989005363A1 (en) * 1987-12-10 1989-06-15 Unisearch Limited Vanadium compound dissolution processes
AU649272B2 (en) * 1990-10-15 1994-05-19 Director-General Of Agency Of Industrial Science And Technology Method for producing vanadium electrolytic solution
CN102978664B (zh) * 2011-09-05 2015-12-02 攀钢集团攀枝花钢铁研究院有限公司 一种金属钒的制备方法及由该方法得到的金属钒

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1053107A (de) * 1964-09-14
US3494729A (en) * 1967-08-18 1970-02-10 Stauffer Chemical Co Process for the production of vanadium trichloride

Also Published As

Publication number Publication date
EP0267858A1 (de) 1988-05-18
FR2605622A1 (fr) 1988-04-29
DE3761824D1 (de) 1990-04-12
FR2605622B1 (fr) 1989-05-19

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