US3486847A - Process for automatically regulating the reduction of the iron and titanium values in a digestion liquor - Google Patents

Process for automatically regulating the reduction of the iron and titanium values in a digestion liquor Download PDF

Info

Publication number
US3486847A
US3486847A US3486847DA US3486847A US 3486847 A US3486847 A US 3486847A US 3486847D A US3486847D A US 3486847DA US 3486847 A US3486847 A US 3486847A
Authority
US
United States
Prior art keywords
reduction
iron
titanium
digestion
liquor
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
Other languages
English (en)
Inventor
Helmut Steinhausen
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.)
Titan GmbH
NL Chemicals Inc
Original Assignee
Titan GmbH
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 Titan GmbH filed Critical Titan GmbH
Application granted granted Critical
Publication of US3486847A publication Critical patent/US3486847A/en
Assigned to NL CHEMICALS, INC., A CORP. OF DE. reassignment NL CHEMICALS, INC., A CORP. OF DE. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: NL INDUSTRIES, INC.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
    • C22B34/1259—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching treatment or purification of titanium containing solutions or liquors or slurries
    • G—PHYSICS
    • G05—CONTROLLING; REGULATING
    • G05D—SYSTEMS FOR CONTROLLING OR REGULATING NON-ELECTRIC VARIABLES
    • G05D21/00—Control of chemical or physico-chemical variables, e.g. pH value
    • G05D21/02—Control of chemical or physico-chemical variables, e.g. pH value characterised by the use of electric means
    • 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 covers a process for the continuous and fully automatic reduction of the iron and titanium values in digestion of liquors produced from titanium ores, titanium ore concentrates and titanium slags with the aid of a regulating device which controls the rate of flow of the digestion liquor through a reductor filled with a reducing agent by measuring the oxidation-reduction potential of the liquor which is dependent upon the amount of tri-valent titanium ions formed during the reduction.
  • the control of the Ti value must therefore always be carried out; it is mostly carried out by titration with an iron (III) sulfate solution of known content using thiocyanate solution as indicator.
  • This analytical method of determination requires quite some time so that a rapid and/or continuous reduction is not very well controllable in this manner.
  • FIGURE 1 is presented to show the rapid jump in potential which takes place in an iron sulfate-titanium sulfate solution when all of the iron values have been reduced to the ferrous state and a small amount of trivalent titanium is formed.
  • FIGURE 2 represents a schematic drawing of apparatus for carrying out the continuous and automatic reduction of the iron sulfate-titanium sulfate solution to obtain the desirable degree of reduction.
  • the degree of reduction is measured by the oxidation-reduction potential of the solution.
  • the amount of Ti+ reduced to Ti+ is measured exactly and rapidly by a change in the potential.
  • the dependence of the oxidation-reduction potential T i +/Ti is surprisingly large in the range up to about 5 g.p.l. Ti calculated as TiO so that it is easily possible to coordinate each measured potential with a definite content of Ti ions.
  • the potential curve must, of course, be determined separately for each digestion liquor produced according to a particular digestion process from a particular titaniferous material. However with each identical starting material and identical digestion procedure, the same standardizing curve may be used each time.
  • Such an automatic control of the continuous reduction may be carried out, for example, by means of the apparatus described in FIG. 2.
  • the apparatus consists of a bufl er and mixing tank 2 fitted with a stirrer.
  • the unreduced digestion liquor is fed into this mixing tank through the inlet 1.
  • the amount of liquor fed may be regulated by valve V
  • the sufi'iciently reduced liquor is transferred from the mixing tank into the clarifying tank through outlet 11, whereby the effluent amount may also be controlled by valve V
  • the liquor is pumped through pipe 3 from the mixing tank 2 into the reductor 5 by means of pump 4 for reduction; the reductor has a vent 6.
  • the amount flowing through is regulated by valve V From there the reduced solution flows through pipe 7 again into the mixing tank 2 into which the electrodes 8 connected with the potentiometer 9 are immersed directly in front of the outlet.
  • the potentiometer is connected with the regulator 10 which controls the regulating valves V V and V
  • the unreduced digestion liquor coming from the digestion tank is brought to the temperature necessary for reduction and collected in the mixing tank. From there it is pumped in portions into the reductor which is filled with loose scrap iron, where it emanates from a ring-shaped pipe with many bore holes like a sprinkler, and flows over the scrap iron.
  • the reductor which is expediently suspended in an elevated frame, can be refilled with scrap iron from above.
  • the reduced solution is recycled into the mixing tank again through the bottom outlet of the reductor and mixed there with the remaining solution.
  • the potential of this solution measured by the oxidation-reduction electrode measuring device is indicated by the potentiometer and effects the control of the regulating valve V via the regulator, whereby the ratio of flow through the reductor to the total amount of flow through the mixing tank is regulated corresponding to the content of Ti ions.
  • the regulator causes, furthermore, closing of the regulating valve V in the inlet of the mixing tank when the Ti ion content has been decreased below a certain minimum value, and a closing of the regulating valve V when the Ti ion content has risen above a certain value. Since in this case unreduced liquor is added without reduced liquor being removed, it may be necessary to close the influx to the tank by means of a floating hook-up at a certain level of filling.
  • the electrode measuring combination may be immersed, instead of into the mixing tank directly before the outlet, into the outlet itself even before the regulating valve V
  • the flow through the reductor may be carried out with potentiometric control in other form also in the main circuit and/ or shunt circuit.
  • the redox electrode measuring combination may be the combination of a platinum electrode immersed into the measuring solution and a reference electrode which is separated from the measuring solution by a suitable salt bridge; as reference electrode, for example, a calomel electrode or another reference electrode which operates reversibly at elevated temperature is applicable.
  • Reference electrodes need some attention in continuous operation.
  • it is advantageous in certain cases to use the quite constant oxidation-reduction potential of the unreduced starting solution as reference potential i.e. to employ two platinum electrodes of which one is immersed in the unreduced digestion liquor and the other inthe reduced digestion liquor which is, as the case may be, connected with the unreduced liquor via a diaphragm. In this manner the reduction may be carried out up to a definite potential difference which must be determined empirically.
  • the process according to the invention is not only limited to sulfuric acid digestion liquors. It may, in the same manner, be applied to hydrochloric acid solutions.
  • one electrode is platinum and the other electrode is a calomel electrode.

Landscapes

  • Engineering & Computer Science (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Automation & Control Theory (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Electrolytic Production Of Metals (AREA)
US3486847D 1967-01-24 1967-09-15 Process for automatically regulating the reduction of the iron and titanium values in a digestion liquor Expired - Lifetime US3486847A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DET0033053 1967-01-24

Publications (1)

Publication Number Publication Date
US3486847A true US3486847A (en) 1969-12-30

Family

ID=7557474

Family Applications (1)

Application Number Title Priority Date Filing Date
US3486847D Expired - Lifetime US3486847A (en) 1967-01-24 1967-09-15 Process for automatically regulating the reduction of the iron and titanium values in a digestion liquor

Country Status (7)

Country Link
US (1) US3486847A (ja)
BE (1) BE709168A (ja)
ES (1) ES349610A1 (ja)
FR (1) FR1554954A (ja)
GB (1) GB1191981A (ja)
NL (1) NL6800989A (ja)
NO (1) NO119836B (ja)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3728431A (en) * 1970-03-28 1973-04-17 Bayer Ag Production of titanyl sulfate solutions
US3853984A (en) * 1973-10-17 1974-12-10 Huber Corp J M Controlling the leaching of kaolin clay
US3880653A (en) * 1971-03-18 1975-04-29 Falconbridge Nickel Mines Ltd Chlorine leach process
US3883421A (en) * 1972-09-12 1975-05-13 Dale Emerson Cutting Measurement of oxidation reduction potential in ore beneficiation

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1333849A (en) * 1917-10-12 1920-03-16 Titan Co As Solution of titanium and iron salts and the process of preparing same
US1916236A (en) * 1928-03-27 1933-07-04 Titanium Pigment Co Inc Method of precipitating titanium compounds
US3199948A (en) * 1961-06-28 1965-08-10 Sincat Soc Ind Catanese S P A Processing of kainitic minerals
US3218131A (en) * 1961-01-27 1965-11-16 Independence Foundation Process for recovery of titania values
US3368870A (en) * 1963-12-06 1968-02-13 Soloducha Nicolas Method of producing titanium hydroxide and high grade pigments produced therefrom

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1333849A (en) * 1917-10-12 1920-03-16 Titan Co As Solution of titanium and iron salts and the process of preparing same
US1916236A (en) * 1928-03-27 1933-07-04 Titanium Pigment Co Inc Method of precipitating titanium compounds
US3218131A (en) * 1961-01-27 1965-11-16 Independence Foundation Process for recovery of titania values
US3199948A (en) * 1961-06-28 1965-08-10 Sincat Soc Ind Catanese S P A Processing of kainitic minerals
US3368870A (en) * 1963-12-06 1968-02-13 Soloducha Nicolas Method of producing titanium hydroxide and high grade pigments produced therefrom

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3728431A (en) * 1970-03-28 1973-04-17 Bayer Ag Production of titanyl sulfate solutions
US3880653A (en) * 1971-03-18 1975-04-29 Falconbridge Nickel Mines Ltd Chlorine leach process
US3883421A (en) * 1972-09-12 1975-05-13 Dale Emerson Cutting Measurement of oxidation reduction potential in ore beneficiation
US3853984A (en) * 1973-10-17 1974-12-10 Huber Corp J M Controlling the leaching of kaolin clay

Also Published As

Publication number Publication date
FR1554954A (ja) 1969-01-24
GB1191981A (en) 1970-05-13
BE709168A (ja) 1968-05-16
ES349610A1 (es) 1969-10-01
NO119836B (ja) 1970-07-13
NL6800989A (ja) 1968-07-25

Similar Documents

Publication Publication Date Title
Schumb et al. The measurement of the molal ferric-ferrous electrode potential
US3486847A (en) Process for automatically regulating the reduction of the iron and titanium values in a digestion liquor
Sinkov et al. Americium (III) oxidation by copper (III) periodate in nitric acid solution as compared with the action of Bi (V) compounds of sodium, lithium, and potassium
CN102183574A (zh) 测定铬矿石中氯离子的方法
US4279705A (en) Process for oxidizing a metal of variable valence by constant current electrolysis
PL110331B1 (en) Method for mud polluting prevention during electroliticpickling of alloy containing chromium
Visco Kinetics and Equilibria of the System Indium (III)-Indium (I)-Indium (O) in Acidic Solution
Luke et al. Photometric Determination of Aluminum in Manganese Bronze, Zinc Die Casting Alloys, and Magnesium Alloys
CN107814411A (zh) 三价钛溶液的制备方法
Norwitz Electrolytic investigations: Electrolytic determination of selenium and tellurium and the separation of copper from selenium and tellurium
Pariona et al. An electrochemical study of the crevice corrosion of titanium
US2288503A (en) Electrolytic basic metal chromate pigment manufacture
Kirshin et al. Recovery of Pd from spent fuel: 1. Electrochemical recovery of palladium from nitric acid solutions
Hirato et al. Electrolytic reduction of Eu (III) to Eu (II) in acidic chloride solutions with titanium cathode
Kirby et al. Polarography of Niobium-EDTA Complexes.
US20200333289A1 (en) Apparatus, systems and methods for in situ measurement of an oxidation / reduction potential and ph of a solution
Hopkins et al. The critical factors influencing uranium precipitation by hydrogen peroxide: The use of experimental design techniques
US3853984A (en) Controlling the leaching of kaolin clay
Xu et al. Effects of F-on the electrochemical properties and electrodeposition nucleation mechanism of Ce (III) in LiCl-KCl melts
US4065348A (en) Method and apparatus for detecting and controlling the caustic in paper pulp bleaching
JPH01222099A (ja) めっき液中のＦｅイオン除去方法
Ekstrom et al. Kinetics and mechanisms of the reactions of uranium (III) with vanadium (III), vanadium (IV) and iron (III) in perchlorate media
JPS60235000A (ja) 表面処理液の制御方法
Byars et al. A more environmentally acceptable determination of iron in an ore
El Din et al. Corrosion Behaviour of Manganese‐Containing Stainless Steels. II. Potentiodynamic measurements in H2SO4 solutions

Legal Events

Date Code Title Description
AS Assignment

Owner name: NL CHEMICALS, INC., A CORP. OF DE., NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:NL INDUSTRIES, INC.;REEL/FRAME:004661/0323

Effective date: 19861118

Owner name: NL CHEMICALS, INC., 1230 AVENUE OF THE AMERICAS, N

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:NL INDUSTRIES, INC.;REEL/FRAME:004661/0323

Effective date: 19861118