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EP0291416B1 - Procédé pour la réduction d'une solution comprenant du titane et du fer - Google Patents

Procédé pour la réduction d'une solution comprenant du titane et du fer Download PDF

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Publication number
EP0291416B1
EP0291416B1 EP88401168A EP88401168A EP0291416B1 EP 0291416 B1 EP0291416 B1 EP 0291416B1 EP 88401168 A EP88401168 A EP 88401168A EP 88401168 A EP88401168 A EP 88401168A EP 0291416 B1 EP0291416 B1 EP 0291416B1
Authority
EP
European Patent Office
Prior art keywords
solution
cathode
process according
abovementioned
titanium
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
EP88401168A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0291416A1 (fr
Inventor
Jean Bachot
Olivier Le Roux
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.)
Rhodia Chimie SAS
Original Assignee
Rhone Poulenc Chimie 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 Rhone Poulenc Chimie SA filed Critical Rhone Poulenc Chimie SA
Publication of EP0291416A1 publication Critical patent/EP0291416A1/fr
Application granted granted Critical
Publication of EP0291416B1 publication Critical patent/EP0291416B1/fr
Anticipated expiration legal-status Critical
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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

Definitions

  • the present invention relates to a process for the reduction of a solution comprising titanium and iron and in particular of a solution resulting from a sulfuric attack of ilmenite.
  • titanium dioxide involves an attack by a sulfuric acid solution of a titaniferous mineral of the ilmenite, anatase or rutile type. After this attack, a solution is obtained which contains titanyl sulfate and especially ferric and ferrous iron sulfates.
  • This method has various drawbacks. In particular, it is discontinuous. On the other hand, it requires a subsequent separation of large quantities of iron giving in particular ferrous sulphate waste.
  • the main object of the invention is therefore an electrolysis process making it possible to work with a high current density and efficiency.
  • a method for the electrolytic reduction of ferric ions to ferrous ions in a solution further comprising titanium ions, by passing said solution through the cathode compartment of an electrolysis cell comprising a compartment. anode, a cathode compartment and an ion exchange membrane separating the two compartments, said method being characterized in that a cationic membrane is used.
  • This cell has two compartments, an anode, a cathode separated by an ion exchange membrane.
  • this membrane is of the cationic type, in particular with strong acid groups of the sulfonic type, for example.
  • membranes of this species mention may be made, for example, of those sold under the brands NAFION® and SELEMION®.
  • a cationic membrane brings about a certain number of advantages linked to the very qualities of this type of membrane. In fact, their superior strength to that of anionics makes the cell less fragile. It is also possible to operate with higher current intensities.
  • the cathode can be based on different materials.
  • a copper-based cathode is used, this type of cathode offering the highest faradaic yields thanks to the excellent mass transfer on this material.
  • cathode based on at least one material chosen from the group comprising lead, titanium, special steels.
  • lead or titanium cathodes alone, or lead on a suitable substrate, for example lead on titanium or lead on copper, or even titanium coated with at least one precious metal.
  • precious metals mention may be made of platinum, iridium, palladium and, for example, a 0.2% palladium titanium cathode can be used.
  • anode As regards the anode, the nature of this is not critical insofar as it exhibits sufficient chemical resistance during the oxidation of water in an acid medium.
  • titanium coated with precious metals or oxides of precious metals as defined above is used.
  • the electrodes can be in different forms, for example planar, perforated, deployed.
  • the membrane can be placed in abutment on the anode.
  • Turbulence promoters can be placed in the compartments of the cell.
  • This process essentially consists in circulating in the cathode compartment of the cell which has just been described the solution to be treated.
  • Titanium is essentially present in the form of titanium IV, the Fe II / Fe III ratio can be variable.
  • This solution may also contain H+ ions and anions of the sulfate type.
  • the process for preparing titanium dioxide essentially comprises the following stages.
  • the first step consists in attacking the titaniferous ore with a sulfuric acid solution.
  • the etching solution thus obtained is reduced in a second step and then clarified in a third, steps 2 and 3 can be reversed.
  • a fourth step consists in crystallizing and then in separating part of the ferrous sulfate in solution.
  • the solution thus obtained undergoes a concentration in a fifth step then, in a last and sixth step, the titanyl sulfate is hydrolyzed and the titanium hydroxide is separated, which will then be calcined.
  • the cell and the method of the invention apply very particularly to the reduction of the solution from the first aforementioned step, that is to say of the sulfuric attack on the titaniferous ore of the ilmenite type in particular.
  • the process reduction step (second step) is carried out entirely by electrolytic means.
  • the solution circulating in the cathode compartment can be recycled there at the outlet thereof.
  • the solution to be treated is separated into a first and a second part, the second part is treated by passage through the cathode compartment of the aforementioned cell, the solution thus treated is stored in a reserve and the solution resulting from this reservation is combined with the aforementioned first part.
  • the solution to be treated arrives at 1, a first main part 2 continues in the process while a second part 3 will undergo the electrolytic treatment.
  • the stream 3 is divided into two parts 4 and 5 and feeds the cathode compartments of the two cells 6 and 7 according to the invention mounted in parallel.
  • the two parts of this same flow are combined at the outlet at 8 and open into a reserve 9.
  • Lines 12 and 11 allow at least part of the solution from the reserve 9 to be recycled into the cathode compartment (s) of at least one of cells 6 and 7.
  • Such a system with reserve and two cells makes it possible to have greater stability of operation of the cells even in the event instability of the Fe II / Fe III ratio of the main flux. It is also possible, thanks to this system, to treat only part of the main flow insofar as the reduction of titanium has been carried out quite far, for example of the order of 100 g / l.
  • a catholyte of the following composition is obtained at the exit from the cathode compartment: Ti4+ 104 g / l, Fe2+ 48 g / l, Ti3+ 16 g / l
  • the cathodic faradic yield is 99%.
  • the operating conditions are as follows:
  • This example shows the possibility of obtaining with the cell of the invention solutions highly concentrated in Ti3+.
  • a catholyte of the following composition is obtained at the outlet: Ti4+ 46.4 g / l Fe2+ 49.1 g / l Ti 3+ 73.6 g / l.
  • the cathodic faradic yield is 97.5%.
  • a catholyte of the following composition is obtained at the exit from the cathode compartment: Ti4+ 104 g / l, Fe2+ 48 g / l, Ti3+ 8 g / l.
  • the cathodic faradic yield is 80%.
  • a catholyte of the following composition is obtained at the exit from the cathode compartment: Ti4+ 120 g / l, Fe2+ 48 g / l, Ti3+ 9 g / l.
  • the faradic cathodic yield is 90%.

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 Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
EP88401168A 1987-05-15 1988-05-13 Procédé pour la réduction d'une solution comprenant du titane et du fer Expired - Lifetime EP0291416B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8706818 1987-05-15
FR8706818A FR2615204B1 (fr) 1987-05-15 1987-05-15 Cellule d'electrolyse et procede pour la reduction d'une solution comprenant du titane et du fer

Publications (2)

Publication Number Publication Date
EP0291416A1 EP0291416A1 (fr) 1988-11-17
EP0291416B1 true EP0291416B1 (fr) 1991-11-21

Family

ID=9351118

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88401168A Expired - Lifetime EP0291416B1 (fr) 1987-05-15 1988-05-13 Procédé pour la réduction d'une solution comprenant du titane et du fer

Country Status (9)

Country Link
US (1) US4919772A (ja)
EP (1) EP0291416B1 (ja)
JP (1) JPS6456890A (ja)
CA (1) CA1328421C (ja)
DE (1) DE3866279D1 (ja)
ES (1) ES2039659T3 (ja)
FI (1) FI86561C (ja)
FR (1) FR2615204B1 (ja)
SU (1) SU1720495A3 (ja)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4129308C2 (de) * 1991-09-03 1994-07-07 Metallgesellschaft Ag Verfahren zur Herstellung einer Titan(III)-Sulfatlösung sowie deren Verwendung
US5227032A (en) * 1991-09-24 1993-07-13 The United State Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Method for producing oxygen from lunar materials
US9856569B2 (en) 2012-07-03 2018-01-02 Field Upgrading Limited Apparatus and method of producing metal in a nasicon electrolytic cell
US9577257B2 (en) * 2013-09-18 2017-02-21 Guiqing Huang Methods of making low cost electrode active materials for secondary batteries from ilmenite
CN106048641A (zh) * 2016-07-06 2016-10-26 扬州大学 一种成对电化学制备Fe3+和H2的工艺方法
CN105925999B (zh) * 2016-07-06 2018-06-15 扬州大学 一种Fe2+阳极氧化及阴极还原并联产H2的工艺方法
CN113697854A (zh) * 2021-09-16 2021-11-26 山东晟融泰新材料科技有限责任公司 硫酸法钛白电解三价钛工艺
CN113818037B (zh) * 2021-09-16 2024-07-16 山东晟融泰新材料科技有限责任公司 一种硫酸法钛白电解三价钛的电解装置
CN113929132A (zh) * 2021-09-24 2022-01-14 东华工程科技股份有限公司 一种硫酸法钛白粉偏钛酸漂白方法及系统

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1017744A (en) * 1972-06-21 1977-09-20 E.R. Squibb And Sons Perhydrofluorenetetrol and perhydrophenanthrenetetrol derivatives
CH610935A5 (en) * 1976-09-03 1979-05-15 Battelle Memorial Institute Electrochemical reactor intended to be incorporated into a plant for the production of titanium dioxide from ilmenite by the sulphate process
JPS5346484A (en) * 1976-10-12 1978-04-26 Tokuyama Soda Co Ltd Electrolytic cell
FR2418773A1 (fr) * 1978-03-02 1979-09-28 Thann & Mulhouse Procede d'utilisation de sulfate ferreux dans la fabrication de bioxyde de titane pigmentaire par la voix sulfurique
US4175014A (en) * 1978-03-06 1979-11-20 Amax Inc. Cathodic dissolution of cobaltic hydroxide
US4230542A (en) * 1978-10-13 1980-10-28 Oronzio De Nora Impianti Elettrochimici S.P.A. Electrolytic process for treating ilmenite leach solution
SU996523A1 (ru) * 1981-05-21 1983-02-15 Усть-Каменогорский Строительно-Дорожный Институт Нерастворимый анод дл получени электролизом из водных электролитов металлов
JPS591688A (ja) * 1982-06-28 1984-01-07 Asahi Glass Co Ltd 鉄塩の還元方法
JPS6013087A (ja) * 1983-07-05 1985-01-23 Kawasaki Kasei Chem Ltd 硫酸第一セリウムの電解法
SU1217927A1 (ru) * 1984-06-22 1986-03-15 Химико-металлургический институт АН КазССР Способ электролитического восстановлени трехвалентного катиона железа

Also Published As

Publication number Publication date
FI882264L (fi) 1988-11-16
JPH0220712B2 (ja) 1990-05-10
FR2615204A1 (fr) 1988-11-18
FI882264A0 (fi) 1988-05-13
ES2039659T3 (es) 1993-10-01
EP0291416A1 (fr) 1988-11-17
FR2615204B1 (fr) 1991-06-14
FI86561C (fi) 1992-09-10
CA1328421C (fr) 1994-04-12
US4919772A (en) 1990-04-24
FI86561B (fi) 1992-05-29
JPS6456890A (en) 1989-03-03
SU1720495A3 (ru) 1992-03-15
DE3866279D1 (de) 1992-01-02

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