US3787139A - Process for the preparation of titaniun concentrates from iron-containing titanium ores - Google Patents

Process for the preparation of titaniun concentrates from iron-containing titanium ores Download PDF

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US3787139A
US3787139A US3787139DA US3787139A US 3787139 A US3787139 A US 3787139A US 3787139D A US3787139D A US 3787139DA US 3787139 A US3787139 A US 3787139A
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mixture
hydrochloric acid
water
iron
vapors
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F Oster
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FAB DE PROD CHIMIQUES DE THANN ET DE MULHOUSE FR
THANN FAB PROD CHEM
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THANN FAB PROD CHEM
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    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C22B1/08—Chloridising roasting
    • 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
    • C22B34/1204—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 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
    • C22B34/1213—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 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by wet processes, e.g. using leaching methods or flotation techniques

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  • ABSTRACT A titanium concentrate is made from an ilmenite or other iron-containing titanium ore by treatment with aqueous hydrochloric acid of the azeotropic concentration while maintaining this concentration by contin- 9 Claims, Drawing Figures PATENTED JAN22 I974 SHEET 1 [IF FIG].
  • Hydrochloric acid has been used in different ways for this deferrization of titanium ores, particularly of different types of ilmenites.
  • a sand containing from 40 percent to 60 percent of titanium dioxide it has been possible to obtain concentrates containing more than 90 percent thereof.
  • a wide variety of methods, proportions and concentrations of hydrochloric acid have 'been used.
  • hydrochloric acid and its concentration are determining-factors for the selective solution of the iron in the ilmenites.
  • concentrated (35 percent) hydrochloric acid is less suitable for the selective solubilization of the iron of the ilmenites than it is for complete solubilization of both iron and titanium.
  • Wilska proposes to carry out the operation in three steps with countercurrent extraction of the ore with the acid, but this increases the loss of acid and triples the costof the installation.
  • An object of the present invention is to provide a process for the deferrization of titanium ores which is both rapid and capable of giving concentrates with a high titanium dioxide content with small losses of titanium, without the necessity of a preliminary treatment of the ore apart from crushing as necessary.
  • the invention comprises a process for the production of titanium dioxide concentrates from iron-containing titanium ores, particularly from various types of ilmenites, by the action of azeotropic hydrochloric acid on the ore, in which the titanium ore is treated with hydrochloric acid of concentration which initially is not substantially above the azeotropic concentration, in amount at least twice the 'quantity theorectically needed to transform all the iron in the ore into iron chloride and maintaining the concentration of the free hydrochloric acid substantially at the azeotropic level for at least the major part of the duration of the reaction by continuously distilling off excess water and water formed in the process.
  • the initial concentration ofthe acid is preferably either at or a little below the azeotropic level, so that the latter is rapidly reached in the early stages of the treatment.
  • a preferred method of carrying out the above process comprises first boiling the reaction mixture under total reflux for 1% hours from the commencement of the heating and then continuing the boiling under, running conditions for the fractional distillation of the said excess water, usually for about 11% hours from the commencement of the heating. At the end of this time water is added to precipitate by hydrolysis such titanium dioxide as has dissolved, the amount of water added being nearly equivalent to that which has been eliminated by distillation, and boiling is continued for another half an hour or so under complete reflux, as at the start.
  • the water which has distilled off in the main reaction is returned to the mixture for the final boiling under reflux; this has the double advantage of recovering such small quantities of hydrochloric acid as may have been entrained in this distillation, and also of saving-heat, to which end the distillate is preferably condensed at as high a temperature as possible.
  • reaction mixture is then cooled to separate it into a solid and a liquid phase
  • the solid titanium dioxide concentrate is washed first with azeotropic hydrochloric acid and then with water and then according to circumstances, dried and calcined, and the liquid phase is treated to recover the hydrochloric acid for re-use.
  • the invention comprises also equipment for carrying the above process into effect which comprises a plurality of reaction vessels each provided with an agitator, and with discharge means at the bottom, a fractionating column communicating with the upper part of each reaction vessel, means for adjusting the reflux rates in each column from I percent downwards and capable of causing the column to separate material of boiling point 100 C. from material of boiling point 1 C., a condenser communicating with the upper end of each column, a reservoir adapted to receive and store liquid from each of said condensers, and a valved conduit from each such reservoir to the upper part of the corresponding reaction vessel.
  • FIG. 1 shows diagrammatically a laboratory apparatus
  • FIG. 2 shows diagrammatically a plant-scale installation.
  • the device illustrated in FIG. 1 comprises a reactor R equipped with an agitator B and connected by a distillation column C provided with a dephlogmator D to a condenser A for condensing the aqueous distillate; the condensate is collected in a receptacle E.
  • the industrial installation illustrated in FIG. 2 comprises three reactors R, R, R with their agitators and three distillation columns C, C, C" with the corresponding dephlegmators D, D, D" connected to condensers A, A, A", which are themselves connected to storage reservoirs E, E, E receiving the aqueous distillates; the reservoirs in turn communicate with the corresponding reactors by return conduits L, L, L.
  • the reaction products can be transferred from the reactors R, R, R" into coolers K, K, K" which all feed to a single separating plant F, in which the product is separated into a liquid and a solid phase.
  • the liquid phase can be forwarded by a pump P to an acid regenerating plant G, which is connected to a reservoir T for the storage of azeotropic hydrochloric acid.
  • the invention makes it possible to dispense with a preliminary reduction treatment of the ore, and at the same time to use an azeotropic hydrochloric acid which does not liberate any harmful and corrosive hydrogen chloride gas.
  • the used acid can easily be regenerated by methods such as the Ruthner process, which permits the simultaneous recovery of the free acid and acid combined with iron in the deferrization liquor.
  • the process of theinvention can be carried out in a single stage lasting only about 12 hours, the speed of reaction always being kept high. While ferric iron is generally extracted less well than ferrous iron, its preliminary reduction, as already stated, is not necessary. Operation in a single stage means that the installation can be very much simplified and cheapened. As regards effectiveness, concentrates can 'be obtained which have titanium dioxide contents substantially exceeding 90 percent, the losses of titanium being very small.
  • reaction speed decreases to the point that, to eliminate another 15 percent of iron, it has in the past been necessary to extend the treatment to 20 hours.
  • the Applicants aim at maintaining as long as possible a high initial deferrization speed beyond the aforesaid 3 hours.
  • the maintenance of the acid concentration could reduce the selectivity of its dissolving action as between iron and titanium, if only by reducing the hydrolyzing effect of the water present which tends to prevent solution of the titanium.
  • This effect is overcome by the final step in the preferred process, in which about as much water as has been removed is returned, and boiling continued for a short time, usually one-half to 1 hour, under total reflux. This may thus be termed a hydrolytic boil.
  • the total reflux is readily effected simply by increasing the supply of cooling water through the dephlegrnator of the column above the reactor.
  • the invention is illustrated by the following Example.
  • titanium dioxide concentrate containmg 92.2 percent of Ti0 and 3.37 percent of total iron (ferrous iron plus ferric iron) b. 1,124 cc. of concentrated deferrization liquid of density 1.205, containing: 1 g/l of Tim 67.41 g/l of total Fe (ferrous plus ferric) 206.0 g/l of C1 anion c. concentrated and dilute washing waters.
  • the concentrate can serve for the preparation of a pure titanium dioxide.
  • the ferric oxide is slightly charged with titanium dioxide and also represents a product which can be exploited.
  • the effeciency of the deferrization was 96.29 percent, leaving only 3.71 percent of the initial iron in the concentrate. lt can be established by analysis that, during the operation, the proportion of ferric iron originally present has been slightly increased by oxidation of a corresponding part of the ferrous iron.
  • titanium dioxide concentrates which exceed percent of titanium dioxide and which, in the best cases (presence of little ferric iron in the ore) can reach up to 94 percent of titanium dioxide.
  • the corresponding deferrization yield is between 90 and 97 percent.
  • the loss of titanium dioxide by solubilization as recorded is a maximum of only 1 percent.
  • Azeotropic hydrochloric acid is used in the form which has been recovered from deferrization liquors,
  • the industrial installation illustrated in FIG. 2 can be operated as follows.
  • the three equivalent reactors R, R, R are charged with 20.2 percent azeotropic hydrochloric acid (or an acid of slightly lower concentration) coming from the storage reservoir T, and the agitators are rotated.
  • the crushed ilmenite is added to the hydrochloric acid.
  • heating is started.
  • the delivery of cold water through the dephlegmators in the top of the Raschig ring columns C, C, C" is regulated so that all the vapour which is produced is condensed and returns to the reactors.
  • the flow of cooling water is reduced to that necessary to ensure the separation of water vapour from the azeotropic acid of boiling point C.
  • the cooled material is passed to the rotary filter F,
  • the concentrate is washed with water on the filter by means of two rows of sprinklers S.
  • the deferrization liquid is sent by the pump P to the regenerator G, which in turn supplies azeotropic hydrochloric acid to the reservoir T ready for re-use.
  • a process for the, production ofa titanium dioxide concentrate from iron-cntaining titanium ore, whereby the speed of deferrization of the ore is kept high which comprises forming a reaction mixture consisting essentially of a quantity of said ore and an aqueous solution of hydrochloric acid having a concentration approximating the azeotropic HCl concentration of 20.24 percent by weight, the amount of said acid solution being at least twice that theoretically required to transform the iron oxide content of said ore quantity into iron chloride, boiling said mixture for reaction of the acid with the ore therein-and to selectively dissolve the iron content of the ore until 90 to 97 percent of said iron oxide content has been extracted into the liquid phase of the reaction mixture, and during at least the major part of the period of said boiling maintaining the hydrochloric acid in the reaction mixture at substantially said azeotropic concentration by continuously removing from the reaction mixture the amount of water being formed and present therein in excess of the amount of water required therein to maintain the hydrochloric acid therein
  • a process according to claim 1, said removing of water being effected by conducting the vapors boiled from said mixture into a condensation zone and fractionally condensing in said zone and returning as condensate into said mixture the azeotropic HCl content of said vapors while passing the remaining water vapor content of said vapors through said zone and away from said mixture.
  • washing being effected first with hydrochloric acid of said azeotropic concentration and then with water.
  • a process for the production'of a titanium dioxide concentrate form iron-containing titanium ore

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
US3787139D 1968-03-26 1971-10-15 Process for the preparation of titaniun concentrates from iron-containing titanium ores Expired - Lifetime US3787139A (en)

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FR68001860 1968-03-26

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US (1) US3787139A (enrdf_load_stackoverflow)
BE (1) BE729171A (enrdf_load_stackoverflow)
FR (1) FR1566670A (enrdf_load_stackoverflow)
GB (1) GB1251868A (enrdf_load_stackoverflow)
LU (1) LU58175A1 (enrdf_load_stackoverflow)
NL (1) NL163268C (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3856918A (en) * 1973-03-28 1974-12-24 American Cyanamid Co Process for the beneficiation of titaniferous ores utilizing hot wall continuous plasma reactor
US4119696A (en) * 1977-11-14 1978-10-10 Uop Inc. Production of titanium metal values
US4197276A (en) * 1978-07-31 1980-04-08 Uop Inc. Recovery of titanium metal values
US20050142051A1 (en) * 2003-11-19 2005-06-30 Process Research Ortech, Inc. Process for the recovery of titanium in mixed chloride media
WO2023075738A1 (en) 2021-10-26 2023-05-04 Velta Holding Us Inc Method for integrated processing of titanium-containing feedstock to obtain high value-added products based on titanium, iron, calcium and nitrogen

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1294703A (en) * 1970-05-16 1972-11-01 British Titan Ltd Process for the removal of dissolved titaniferous solution

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1325561A (en) * 1919-12-23 norway
US2167628A (en) * 1937-10-06 1939-08-01 Nat Lead Co Preparation of titanium dioxide pigments
US2439895A (en) * 1942-01-09 1948-04-20 Du Pont Titanium oxide pigment production
US2441856A (en) * 1942-08-01 1948-05-18 Nat Lead Co Cyclical process for the manufacture of titanium dioxide
US2804375A (en) * 1953-05-28 1957-08-27 Nat Distillers Chem Corp Cyclic process for the beneficiation of titania ores and slags
US3006728A (en) * 1959-09-10 1961-10-31 Horizons Inc Preparation of ceramic grade titanium dioxide
US3193376A (en) * 1961-12-04 1965-07-06 Wah Chang Corp Beneficiation of ilmenite
US3236596A (en) * 1961-08-05 1966-02-22 Bayer Ag Process for the decomposition of titanium dioxide-containing minerals with hydrochloric acid
GB1023275A (en) * 1964-01-21 1966-03-23 British Titan Products Production of titanium dioxide

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1325561A (en) * 1919-12-23 norway
US2167628A (en) * 1937-10-06 1939-08-01 Nat Lead Co Preparation of titanium dioxide pigments
US2439895A (en) * 1942-01-09 1948-04-20 Du Pont Titanium oxide pigment production
US2441856A (en) * 1942-08-01 1948-05-18 Nat Lead Co Cyclical process for the manufacture of titanium dioxide
US2804375A (en) * 1953-05-28 1957-08-27 Nat Distillers Chem Corp Cyclic process for the beneficiation of titania ores and slags
US3006728A (en) * 1959-09-10 1961-10-31 Horizons Inc Preparation of ceramic grade titanium dioxide
US3236596A (en) * 1961-08-05 1966-02-22 Bayer Ag Process for the decomposition of titanium dioxide-containing minerals with hydrochloric acid
US3193376A (en) * 1961-12-04 1965-07-06 Wah Chang Corp Beneficiation of ilmenite
GB1023275A (en) * 1964-01-21 1966-03-23 British Titan Products Production of titanium dioxide

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3856918A (en) * 1973-03-28 1974-12-24 American Cyanamid Co Process for the beneficiation of titaniferous ores utilizing hot wall continuous plasma reactor
US4119696A (en) * 1977-11-14 1978-10-10 Uop Inc. Production of titanium metal values
US4197276A (en) * 1978-07-31 1980-04-08 Uop Inc. Recovery of titanium metal values
US20050142051A1 (en) * 2003-11-19 2005-06-30 Process Research Ortech, Inc. Process for the recovery of titanium in mixed chloride media
US7803336B2 (en) 2003-11-19 2010-09-28 Process Research Ortech, Inc. Process for the recovery of titanium in mixed chloride media
WO2023075738A1 (en) 2021-10-26 2023-05-04 Velta Holding Us Inc Method for integrated processing of titanium-containing feedstock to obtain high value-added products based on titanium, iron, calcium and nitrogen

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NL6902622A (enrdf_load_stackoverflow) 1969-09-30
DE1906689A1 (de) 1969-10-09
DE1906689B2 (de) 1977-06-23
NL163268C (nl) 1980-08-15
GB1251868A (enrdf_load_stackoverflow) 1971-11-03
LU58175A1 (enrdf_load_stackoverflow) 1969-07-10
BE729171A (enrdf_load_stackoverflow) 1969-08-01
FR1566670A (enrdf_load_stackoverflow) 1969-05-09
NL163268B (nl) 1980-03-17

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