CA1038630A - Ilmenite beneficiation with fec13 - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

A process for the selective chlorination of the iron constituent of titaniferous ores using FeCl3 as the chlorinating agent, and using a reductant selected from at least one of the group consisting of a solid carbonaceous material and carbon monoxide. The FeCl3 can be produced by oxidizing the FeCl2 resulting from the selective chlo-rination, thereby providing for a recycle operation.

Description

- 103~
For many ye rs, a great deal o~ attention has been devoted to techniques aimed ~t the e~fe^tive separation Or the titanium and iron constituents o~ titaniferous ores such as ilmenite. ~onselective chlorin tion techniques, i.e., in which t}~e two m~tals are chlorinated simultaneously and the chlorides then separated from one another, have proven to be sufriciently effective that they are now practiced in the manu~acture of tltanium dioYide (Ti~2) pigments, particularly ~y the so-called "chloride" process involving the oxidation Or titanium tetrachloride (TiC14). Such techniques are much less efricient than would be desired, however, since dependin~
upon the iron content Or the ore a considerable amount Or costly chlorinating agent, conventionally consisting primarily o~ chlorine, may be consumed in producing iron chlorides as ~y-~roducts, which by-pr~ducts have little commercial value.
Other techniques ror separatlng the iron and titanium constituents Or ores have been devised that involve selectively chlorinating the iron content, thereby leaving an upgraded or benericiated TiO2 fraction. For example, according to a typical technlque for beneficlation, an ore such as ilmenite is mixed with lZ to 12~ by weight Or carbon (based on total weight Or the ore), heated to at least 500~C. and e~posed to a chlorinating agent. The chlorinating agent commonly employed is gaseous chlorine, although other chlorinating agents such as hydrogen chloride and phosgene in con~unction wi~h chlorine are known in the art. Such ;~
benericiation techrliques have achieved some measure Or commerclal importance, but they have not served to lessen the problems associated with the formation Or iron chloride by-products and the attendant consumptlon Or chlorine.

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-2-' ~ '' : '' One apProach to solving the waste disposal problem mi~ht be to convert the iron chlorides to metallic iron or some ~orm of iron oxide thereby reco~ering the chlorlne con-tent as gaseous chlorine, but such conversion is difflcult to achieve in an economic rashlon.
In the specificatlon set ~orth hereina~ter I
describe my rind1ngs of a cyclic process for separating the tltanium and iron constituents ol titaniferous ore by selectively chlorinating the iron constituent utilizing ferric chloride (FeC13). mhis ferric chloride (FeC13) is eenerated in the amount needed to satisfy the requirement Or the process by oxidation of the rerrous chloride (FeC12) produced by chlorination Or the iron constituent of the ore.
In accordance with my inventlon, there is provided a cyclic chlorination/oxidation process for the separation of tltanlum and iron constltuents Or titanirerous materlals in such a way that the iron constituent is chlorinated but there is no appreciable net yield Or titanlum chlorlde rrom the titanium constltuent. The chlorination is carried out ln the presence of a solld carbonaceous materlal or gaseous carbon monoxlde or mlxtures thereo~ as a reductant.
When the reductant conslsts essentially of a solld carbon-aceous materlal, it is utilized in an amount such that the total carbon content thereor ls at least equal to the stolchiometric amount to produce carbon dloxide, based on the oxygen bound to the iron constltuent Or the tltanif-erous materlal, ?nd 'ess than or about equal to the stol-chiometrlc amount to produce carbon mono~ide, based on sald oxygen. When the reductant contains gaseous carbon monoxide, it is fed in an amount greater than requlred to .. . .
. . .

convert the balance Or said oxygen to carbon dioxide. It ~ollows that when essentially no solid carbonaceous mater-ial is present in the reductant ~aseous carbon monoxide is fed in an amount greater than the stoichiometric amount to produce carbon dlo~ide based on said oxygen. The selective chlorination utilizes FeC13 as the chlorinating agent preferably in an amount which is about stoichiometric fDr the iron constituent Or the titanirerous material The temperature maintained durlng the chlorina-tion depends on the dew point Or the FeC12 produced thereby and should be surriclently high to avoid the accumulatlon Or llquld FeC12. In the practice Or this inventlon an elevated temperature of at least 950C. is malntained dur-ing the chlorinatlon. The upper temperature at whlch the chlorinatlon can ta~e place ls limited primarily by energy economlcs and the materlals Or construction Or the vessel ln which the chlorination is conducted. A currently practical llmit is about 1300C. Prererably the tempera-ture maintained during chlorinatlon will be from 1000C. to 1100C.
It is a signiricant reature Or this inventlon that the FeC13, utilized as the chlorinating agent, can be ob-tained by oxidizing the FeC12, which is the iron chloride produced by the selectlve chlorination Or this invention, with a gaseous mlxture containing oxygen. In this way the the FeC12 can be recycled, arter oxidation to Fe203 and FPC13 and removal Or Fe203. The process o~ this invention can also be practiced using FeC13, which is obtained ; directly, as a waste product, rrom the conventional chlo-ride process, thereby enabling the process Or thls 103~630 invention to be operated in combination with the conventional chloride process.
In connection with tne details of the invention hereinarter described it is noted there will be used the ~ormula FeTiO3 which is an idealized formula chosen to repre-sent the titaniferous materials Or interest. The emplrical formula will vary, as is known, from one ore source to another.
In this respect the term "ore'l will be used herein in a gene-ral way since, whlle it is not essential that the titaniferous ~aterial be an ore, normally it will at least be derived from an ore source. The formula FeC13 is used throu~hout this specificatlon for convenience to designate ferric chloride both as such and as the well-known dimer, Fe2C16.
Although it is not essential to separate every rinal trace Or iron in the ore rrom the titanium in the ore, lt ls desirable to separate at least about 75% by weight Or the iron ~n the ore, by conversion Or the iron to FeC12, to pro~lde a high quality benericiate. It is to be understood that conversion Or at least about 75% by weight of the iron in the ore is intended by the express on "essentially completely"
when used in this connection throughout the speci~icatlon.
Ores rrom which at least 85~ by weight of the iron in the ore has been separated Bre decldedly preferred and can nor-.ally be produced without dl~rlculty by the process Or thlsinventlon.
It i8 also noted that when rererence is made hcrel~ to the selectlve chlorinatlon Or the lron constltuent of the ore, this is not intended to be construed as neces-sarlly precluding the net chlorlnatlon of minor quantltles Or other metals ln the ore. Under certain conditions, the .
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iO3863(~
product of the selective chlorination reaction, which is FeC12, or the major chlorinat1ng agent FeC13, can themselves chlorinate so~.e of the titanium in the ore. Of course, any net yield of titanium chloride is a condition which is to be avoided as much as ~osslble since it is desired that as much titanium as possible remain in the beneficiated ore.
A ~udicious selection Or the process conditions in accordance with the dlsclosure herein makes lt readily possible to operate such that the net yield o~ tltanium chlorlde does not exceed about 10% by weight o~ the titaniu~ in the tlta-niferous ore, hence the expresslon "no appreciable net y1eld Or titanium chloride" is employed herein. Most orten, as ls prererred, the percentage will be 5~ or less, an amount whlch ~or all practical purposes can be lgnored. ;~
The process of the invention can be expressed according to the ~ollowlng reactlon (as ln the case Or all reactlons in the specirlcatlon, lt will be rererred to by Roman numeral des~gnatlon):
(I) 4PeT103 + 4C(or CO) + 302 4T102 +
2Fe203 + 4CO(or C02).
Reactlon (I) is the additlve result o~ the selective chlo-rlnatlon Or the iron constltuent Or the FeTiO3 utillzing FeC13, Reaction (II), and the oxldatlon of the FeC12 so produced, Reactlon (III), expressed below ln stolchlometrlc quantlties necessary ~or recycle operation:

(II) 4FeT103 ~ 4C(or CO) + 8FeC13 ' 4T102 +
12FeC12 + 4CO(or C2) tIII) 12FeC12 + 32 ' 2Fe23 + 8FeC13.
Since the titanium present in the ore does not slgnl~lcantly enter the reactlon, lt will be understood .
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103863~ , that ores containing varying ratios Or titanium to iron --can be used and equations (I) to (III) would be modi~ied to represent the composition of the actual reactants.
The pre~erred technique for er~ecting Reaction (II) in accordance with the process o~ this invention lnvolves the use Or FeC13 in the vapor phase. The FeC13 is pre~er-ably produced by the oxidation o~ the FeC12 of Reaction (II) with a gaseous mixture containing o~ygen ln an amount at least 20~ by volume, e.g., alr, according to Reactlon (III). The FeC13 utllized in Reaction tII) can also be generated by dlrect chlorlnation Or the FeC12 with gaseous chlorine, however, this route ls not particularly economi-cally advantageous since chlorine ls a relatively expenslve reactant. The FeC13 can be vaporized dlrectly by heating solid FeC13, obtained rrom any source. The FeC13 vapors are then brought lnto contact with a mixture Or ore and reductant, e.g., carbon or carbon mono~ide, in a reactor.
The FeC12 whlch ~orms during Reactlon (II) approxlmates the amount Or FeC12 that is consumed durlng Reaction (III).
The FeC12 formed during ~eaction (II) can be removed, ~or example, by the ald Or an lnert gas purge, and cond~nsed.
Ir deslred, the ore/reductant mi~ture can ~lrst be heated to a temperature Or 500C. or more out Or contact wlth the FeC13 to lnltlate some prereduction, prlmarlly Or the lron content.
Furthermore, lt has been dlscovered that ratlos Or tco2]/~co] ln e~cess Or O . 01 provlde rOr essentlally complete converslon Or lron wlth no appreclable net yleld titanium chloride. Slnce benerlclatlon increases wlth - 30 lncreasing tCo2~/tCQ] ratlo, lt ls desirable to malntain _7_ , : ..
.: ,;: -,:

, ~ " ~ . . , -,, - ,. , - .: -1038~i30 a substantlal CO2 partial pressure. High CO2 partial pressure can be achleved by a variety Or methods whlch are known to persons skilled in the art.
The FeC12 that forms as a product in equation (II) can undergo an equillbrium reaction wlth TiO2 and carbon to yield TlC14 and Fe at temperatures above 950C. according to the rollowing equatlon:
(IV) TiO2 + 2C + 2FeC12 S TlC14 + 2Fe + 2CO.
The stoichlometry Or the equation shows that excess carbon not consumed in the reduction o~ iron o~ide would result in the formatlon of TlC14, while increasing the amount Or CO, or the partial pressure Or CO, tends to supress the reaction. The presence Or CO2 contributes signiflcantly to supressing Reaction (IV) because CO2 reacts with carbon thereby increaslng the CO partial pressure.
Therefore, when using FeC13 as the chlorlnating agent, it ls advantageous to utllize the least possible amount Or carbon, l.e., about equal to or less than stol-chiometrlc wlth respect to the o~ygen bound to the lron constituent Or the ore.
; The invention wlll be rurther illustrated wlth re~erence to the Drawlngs.
Flgure 1 illustrates on a calculated basls the errect Or the value Or the [C02]/[CO] ratio on the selectivity of the reduction/chlorinatlon process of the inventlon.
Flgures ~, 3 and 4 lllustrate varlous forms Or laboratory apparatus, shown schematically and not to scale, that may be ~sed ror carrylng out the process Or the inventlon.
Rererring to Figure 1, the ratlo of [CO2]/tCO~ ls varied from .001 upward by varying the amount of carbon --ô-- ,.: .

,:, ' ; ' ' ' , . . . . ... ... . . ..
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~38630 added to FeT103 when reacting with FeCl~ at 1050C.
Substantially the same dependence of the chlorinatlon selectivity on the rC02]/[C0] ratio is ~ound at temperatures as high as 1500~.
Referring to Figure 2, there is employed a simple type o~ rlxed bed reactor constituting elongated silica tube 1 in which an lron chloride charge, l.e., FeC13, and an ore/-carbon mixture is placed. These may be maintained in their respective positions by means Or silica wool 2 or simllar oorous material. A stream Or inert gas such as argon, hellum or the like enters through line 3 to serve as a purge in the system to aid in withdrawing and collectin~ ~eC12 produced.
Exit gases are carried out through llne 4. A stationary heater or furnace 5, shown Dartlally cutaway, ls adapted to recelve and enclose the elongated sllica tube 1. The heater, which may be, for example, an electric heater of several sections, wlll typlcally be e~ulpped wlth a thermocouple or other de-vlce not shown, to measure and record a predetermined tem-perature to be applled to the c~arges. In operatlon the charges are placed ln th~ tube as shown, the rlow o~ purge gas ls commenced and the tube ls lnserted sufflclently lnto the heaterthat the ore/carbon blend ls flrst brought to tem-perature. At temperatures below 950C., some reductlon of the ore may commence. The tube ls then rurther inserted lnto the furnace so that the iron chlorlde charge ls caused to vaporlze.
Slow contlnual insertion Or the tube lnto the furnace, l.e., lert to right ln the drawing, results in a stream Or FeC13 vapor being generated and passed lnto contact wlth the ore/- ~`
carbon mixture. Some iron chloride and/or other materlals ~-

3 may be round to be condensed on the walls of tube 1, but ~9~ -:

~03B630 , , .
in any event, an exlt gas results which ls composed Or inert gas, FeCl2, unreacted FeCl3, and possibly so~e tltanium chloride. The exit gas, and more importantly the FeCl2 con-stituent can be collected by any suitable means, not shown.
A slmple ice bath condenser arrangement may be employed ror this purpose. -`
Figure 3 shows a vertical sllica reactor that can be used to react a fixed bed Or ore or ore and carbon ln a steady stream o~ FeCl3. In this case a vertical sllica reactor shown generally as 6 is co~posed Or u~per sections 7 and 8 and a lower section 9 positioned within a rurnace composed of sections lO and ll. A stream of C0 or a mixture CO and C02 in a predetermined a~ount enters the reactor t~rough tube 12 and passes outwardly through perforations 13 in the wall Or tube 14 and through sillca wool 15, then passes into contact with a heated ore or ore~carbon blend ln the lower sectlon 9 o~ the reactor. The heated FeCl2, whlch is held ln place by support 16, ln upper sectlon 7 Or the reactor is reacted wlth a predetermined amount Or 2 or C12 whlch enters the reactor through tube 17. The FeC13 vapor thus rormed passes through support 16 and through sillca wool 15, which ls held ln place by support 18, and passes lnto contact wlth ore or ore/carbon blend ln the lower sectlon 9 o~ the reactor. The FeCl2, e~lt gases, and any minor amounts Or TlCl4 and unreacted FeCl3 ormed rrom the chlorlnatlon reactlon pass through slllca rrlt l9. The FeCl2 is condensed ir. recepta~le 20 ~lle any TlC14 rormed pas~es through tube 21 wlth e~ltlng gases and can be condensed ln an lce/salt bath or any other conventional manner.

~03~0 Figure 4 shows a vert~cal silica reactor that can be used to react a rluidized bed Or Gre and carbon in a steady stream of FeC13. The reactor, shown generally as 22, is composed Or upper section 23, positioned within a furnace composed of sections 24 and 25, and a lower sectlon 26, positioned within ceramic heater 27. In the lower portion of the reactor 26 a bed of solid FeC12 is contacted with a metered quantity Or 2 gas entering through line 28.
Tne two react and the resultant Fe~13 vapors then pass upwardly into contact with the ore/carbon mixture. The ore/-carbon mixture is also contacted ~ith a gaseous mixture contalning inert gas and carbon monoxide entering through line 29. The FeC12 resulting from the selecti~e chlorina-tion Or the ore passes through line 30 and is collected in receptacle 31.
Also in Fi~ure 4, inert gas can be introduced ;. :
at llne 32. The ore/carbon mixture is held in place by ~.
~ coarse silica rrit 33. Silica wool pads 34 are used as ..
: shown to maintain materials in place in reactor 22 and to assist in preventing the passage of blowover particle~
rrom the bed.
In operation Or the device Or Figure 4, ore and ....
carbon in the desired particle size and proportlons are mixed and placed ln upper reactor secti~n 23. The lower ~.
section 26 is rllled wlth a column Or crushed FeC12.
Molsture and FeC13 traces can be removed rrom the reactor .
by applylng heat but bel~w th~ boillng polnt Or FeC12 while ..
an arRon purge ls malntained through line 28. Then the temperature Or the upper section 23 is raised, e.g., to 950C.
30 or above, to commence prereductlon Or the ore, while passlng :-" ,-' .
-11- .
.

., ~ .
,, .. ,., . ,. . , . . ... ., ~ . .

1~3~630 . ., a stream of inert gas through line 29. This heating may be continued for an hour or more to effect reduction.
~idation of the FeC12 is then commenced by metering 2 at the desired rate into the FeCl2 bed through llne 28.
Argon may be passed into the system at 32 to prevent pluggage. While the FeC13 so produced passes lnto contact wlth the ore/carbon mixture, a mixture of argon and carbon monoxide is metered at the desired rate through line 29.
The FeCl2 produced by the selective chlorination Or the iron constituent Or the ore passes through upper silica wool pads 34 and is carried by the argon stream through line 30 to receptacle 31 where it is condensed. The reacted bed is removed from reactor 22, washed with water and analyzed ; ~or iron and titanium. The reacted bed of FeCl2, consist-ing prlmarily Or Fe203 ls removed from reactor lower sectlon 26 and can be replaced with the FeCl2 collected ln 31.
The titanirerous materials employed in the practlce Or the lnventlon may be lron/tltanlum oxldlc ores obtained ~-from a wide variety Or sources or they may be other iron oxide and titanium oxide containln~ materials. It will be apparent that slnce the process Or the invention involves the selectiYe chlorination Or the iron constituent, l.e., beneflclatlon, low grade ores containlng relatively high amounts Or lron can readlly be treated.
, For convenience, the rormula FeTiO3 has been used -,, herein to describe the titanlrerous materials Or interest . ~or practlce Or the invention. This ls the ~ormula typically ;~ ascrlbed to true llmenite ores, whlch contain about equi-! molar amounts Or iron and titanium. In practice, any , 30 titaniferous material may be utllized provlded it contains :- --103~30 : ' sufficient titanium to make its recovery economically attractive. Materials containin~ at least 10%, and prefer-ably at least 20d, by weight o~ titanium are thus best employed. The amount of iron in the material will also usually be at least 10~, typically at least 20%, by weight but there is no practical reason why ores containing much less iron cannot be processed. The oxidic titani~erous ores rererred to generally as ilmenite ores and containing about 20 to 50% titanium and 10 to 50% iron represent a prererred titanlferous material ror use in the inventlon because they are widely available at a relatively low cost such that the recovery of the titanium can be most economi-cally performed. It is to be understood, however, that the various types of ilmenite ores, rutile ores, slags and residues, includln6 mixtures of any such materials, may also be efrectively treated in accordance with the invention.
It will be understood th~t the actual reactlons ~:
which occur ln the course o~ the bene~iciation process o~
the invention can be highly comple~ ones dependlng upon the chemical composition of the titanirerous material employed. In this respect the reactions set rorth in this specification are intended to be representative o~
the primary chemlcal changes which occur and should not , be interpreted as excludlng the posslbility that secondary or slde reactions may also occur.
In general it is desired that the titanlrerous material be in a particulate or at least porous form so that , ~u~icient surface area is accesslble for the reduction and ' selective chlorination reactions to take place at reasonable rates. Sand ores and the like, because o~ their small :. '' .: . . ~.
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1038630 `.
particle size, can typically be used as such wlthout further size reduction. Some form of grinding step is generally necessary with massive ores, however, in which case the extent and cost of grinding will have to be balanced against the extent to which the reaction rate will be beneflted.
Partlcles on the order of 1 mm or less are generally the most useful. For convenience, a particulate material can be formed into briquettes, e.g., w~th carbon and binders lf necessary.
The solld carbonaceous material employed in the practlce Or the inventlon may be car~on as such, e.g., charcoal, coal, or coke, or it may be any other material `~
which on heating wlll produce carbon or carbon compounds in -a rorm suitable as a reduclng agent. .~aterials composed essentially Or carbon are prererred in order to reduce or ellmlnate any slde reactlons. Pre~erably, the solld carbo-naceous material will also be used in partlculate or at least porous ~orm ln order to provide a high degree Or sur~ace area. However, depending upon the apparatus em-20 ployed, powders or other e~cessively small size particles Or carbon, l.e., those below 50 ~, may tend to result in an excesslvely hlgh blowover ~rom the reactor. For thls reason somewhat larger partlcles o~ carbon, i.e., Or 0.1 to 10 mm, are the most userul, especlally when the partlcles are Or a porous character.
3 ~he total amount of chlorlnatlng agent, l.e., 1 FeC13, employed in carrylng out a manuracturln~ process Or the lnvention should, Or cour~e, be surrlclent to permit chlorlnatlon Or essentlally all o~ the lron content Or the 30 ore. Where only FeC12 is produced thls would mean about ~` two FeC13 molecules per iron atom.
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, -14-.. , ~ - . .. . .. .

103S~30 ~ or reasons of efficiency it is desirable, if not necessary, to insure that durin~ the beneficiation process moisture and other materials that might consume a portion o~ the FeC13 are not present in the reactor.
The process of the inventlon can be carried out using a wlde variety Or reactors either on a batch basis or a continuous basls. Fluid bed operations are advantageous for continuous operatlon.
Dependlng upon the type of apparatus empioyed, and -~
the way that the various reactants are supplied and inter-mi~ed, the requisite proportlons of ore, carbon and FeC13 specified herein need not necessarily be maintained throughout the duration of the reactlon. For exam~le, procedures can be devlsed ~or lntermlttent addition Or one or more materials and/or ror the withdrawal and recycling Or one or more materials.
The process Or the inventlon will be exempli~ied by procedures operating at atmospheric pressure, or slightly , thereabove. Subatmospheric or superatmospheric pressure can be used, however.
: It is to be noted that regardless Or the nature o~ the apparatus employed, dlrriculty can be experlenced ln collecting as such the entire quantlty Or FeC12 generated ln the process. Thls ls particularly true ~or la~oratory or other small scale operatlons as the usual condensation techniques tend to allow some FeC12 to be lost, either to the atmosphere or by reaction with moisture. For this reason~
it ls rrequently more accurate to ascertaln ~he percent iron ;
chlorinated ~rom the quantity Or iron which remains as a residue. The e~amples hereinarter indicate conversions which . .

.. . ..
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~03B630 have been determined ln this way. The practice may, on the one hand, involve igniting the res~ue Or the ore/carbon mixture to burn of~ carbon followed by chemical analysis for iron and titanium. These would then be compared with the original ore analysis. Alternatively, the residue may be sub~ected to magnetic separation to remove carbon and other nonmagnetic materials from the iron/titanium portion followed by analysis Or the fractions.
The invention is further illustrated by the following examples in which parts and percentages are by weight unless otherwise specified. .he Ti02 and total Fe values reported for ore analysis should be considered accurate wlthin about one percentage point owing to variations rrom one sample to another. Mesh sizes therein re~er to U.S. Standard Sieve sizes. Gas rlow rates are measured at room temperature.
~xam~le 1 A 50.0 g sample Or a titaniferous sand ore (analyzlng 64.6% TiO2, 22.3% total Fe, 21.5% Fe3+, and containlng mlnor amounts Or SiO2 and other oxides) of mesh slze -60~160 is blended with 3.5 g Or dried partlcu-. late carbon and placed in an elongated sllica tube (or 9 42 mm inside diameter) shown in Flgure 2. The blend, whlch rills the cross section Or the tube,is held ln place with sllica wool.
The carbon ls a standard laboratory grade charcoal (sold by Flsher Sclentirlc Company, Falr Iawn, New ~ersey,^
U.S.A., under the trademark Darco~ G-60 activated carbon).
It is characterized by a particle diameter Or much less 30 than 40Q mesh and a surface area Or about 650 m2/g.
'. .

, 103~30 Then 232 g of a commercially avallable reagent grade anhydrous FeC13 is placed in the tube and heated in portions to 1050C. For 120 minutes the vaporized FeC13 is carrled lnto the reactor by a stream Or argon rlowlng at a rate Or about 200 cc/mln. ~eC12, traces Or TlC14 and unreacted FeC13 are collected by cooling and condensation.
At the end Or the run the argon stream is used to rree the resldual ore/carbon bed Or gaseous chlorides.
The residual ore/carbon bed, weighing 31.9 g, ls separated magnetlcally into two rractions. The magnetic rraction, weighlng 1.0 g, is analyzed and found to contain 80.0% T102 and 13.2~ Fe. The nonmagnetic ~raction is ignlted ln air at about 900C., leaving a beneficiate that welghs 30.3 g and analyzes 94.5~ TlO2 and 3.6Z Fe2O3. On the basls Or the orlginal iron and titanium contents Or the ore and the relative proportions Or each ln both rractlons Or the bed lt ls determlned that the benericlate retalns 9l.1% Or the Ti and 8.o% Or the Fe ln the unreacted ore.
Example 2 The apparatus ls Or the type shown in Flgure 3.
In the lower section Or the reactor ls placed 100 g o~ the titanlferous sand ore descrlbed ln Example 1, blended with ; 7.1 g Or petroleum coke Or mesh slze -80+120 containlng about 2% sulrur as the ma~or impurity. An excess Or 8 .
commerclally avallable, typlcally 99.5% pure, solld partlculate FeC12 ls placed ln the upper sectlon Or the reac'cr.
The ore/carbon blend ls heated to 1050C. in a stream Or argon ~lowing at a rate Or about 100 cc/mln and then contacted with a stream of CO rlowing at a rate Or 17 :
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~03~
about 238 cc/min ~or 15 mlnutes. While continulng the flow Or CO, the blend ls contacted wlth FeC13. The FeC13 is generated rrom FeC12 whlch is preheated to 500C. and contacted wlth a stream o~ C12 flowlng at a rate of 0.301 g/min over a period Or 100 minutes, thus providing 138 g o~ total FeC13. The CO stream provldes a total o~
31.6 g CO during reductlon and chlorlnation.
After completion Or the reaction, the rlow Or argon is resumed for 60 minutes. The reactor is then cooled, after which the residual bed is removed, ignited in air at 900C., and analyzed. A beneficiate is obtained which welghs 64.6 g and ls ~ound to contaln 95.3% TiO2 and 3.0~ Fe203. On the basis Or the original iron and titanium contents Or the ore and the relative proportions - o~ each in the beneficiate, it is determined that the beneficiate retains 95.3S Or the Ti and 6. lZ Or the iron in the unreacted ore.
Example 3 ~i The procedure Or Example 2 is rollowed except that the titanirerous sand ore ls not blended wlth any solid carbon and the CO is replaced by an equal volume o~
a mixture Or CO and C02 contalning about one percent by volume Or C02.
The benericiate removed rrom the reactor weighs 63.9 g and analyzes 95.9% T102 and 1.8% Fe203. It i8 determlned that the benericlate retains 94.9% Or the Ti and 3.6% Or the Fe in the unreacted ore.
Example 4 ; To show that the FeC12 produced by the selective ' 30 chlorinatlon Or this lnvention can be recycled, two ~:
; ., , .~ ' ., ~

103B630 , essentially identical bat~h-type c~lorination runs are carried out using the commercial FeC12 described in Example 2. These runs yield rec~cle FeC12 that is used instead of commercial FeC12 in a subsequent run.
Chlorination with FeC13 from Commerclal FeC12 The procedure of E~ample 2 is rollowed except the FeC13 ls generated by reacting FeC12 with 2 and the CO
flows at a rate Or 60 cc/min ror 15 minutes prior to the chlorination and during the chlorination. A stream Or P2 rlowing at a rate Or 55 cc/min and providing a total Or 11.2 g 2 contacts the FeC12 at 500C. for a total Or 156 minutes. This glves a feed Or about 152 g FeC13 to the reaction chamber.
After coollng the reactor, the resldual bed i8 remoYed J ignited in alr at 900C. and analyzed. The bene-riciate weighs 63.9 g and analyzes 96.0% Ti02 and 2.1S - ` `
Fe203. FeC12 which condenses in receptacle 20 Or Figure 3 ls collected as a starting material ~or a subse~uent run.
The above procedure is repeated and the resulting 20 benericiate weighs 65.9 g and analyzes 92.1% Ti02 and 3.~S

Fe23 - '' Chlorination with FeC13 from recycle FeC12 ., .
The above procedure is repeated using recycle FeC12 obtalned rrom the previous runs. Berore its use, the FeC12 is heated under argon above the melting point to remove traces Or FeC13 and moisture. It is then allowed to soll~lry and is crushed wlth a mortar and pestle.
The resulting beneflclate welghs 64.8 g and analyzes 96.8% T102 and 1.6~ Fe203. It is determined that 30 the benerlclate retalns 97.0% Or the T1 and 3.2% Or the Fe ln the unreacted ore. 1.9 g TiC14 ls also collected. -.' --1 9-- , ,, ~' ,. . . .

~038630 The reacted bed Or FeC12 in the upper section of the reactor ls found to contain unreacted FeC12 and by-product Fe203. The Fe203 is freed from unreacted FeC12 by water-leachlng, ls drled by heating in air, and ls analyzed. It contalns an amount Or lron equivalent to 98.5% Or the amount o~ lron ln the unreacted ore. The welght Or FeC12 condenslng in the receptacle Or Figure 3 eq~als 87.5% Or the weight Or FeC12 consumed by oxidation ln the upper sectlon Or the reactor. PeC12 losses are caused by lnerricient condensation.
ExamPle 5 The apparatus employed is Or the type shown ln Figure 4. 467 g Or commercial FeC12 descrlbed ln Example 2 ls placed ln the lower section Or the reactor. A blend o~
200 g Or the tltanlrerous sand ore described in Example 1, and 14.0 g Or the petroleum coke Or Example 2 ls placed in the upper section of the reactor.
The ore/carbon blend ls rluldized by a stream Or argon gas rlowlng at a rate Or 1120 cc/min. The fluidlzed blend ls heated to 1050C. and held at this temperature for 60 mlnutes. Concurrently, the FeC12 is heated to 500C. 0ver a period Or 60 minutes the heated FeC12 ls contacted with a stream Or 2 rlowlng at a rate Or 263 cc/min, thereby providlng a total Or 20.7 g 2 The o~ldatlon results ln the intermediate rormatlon Or about 280 g o~
FeC13, whlch contacts the ore/carbon blend. Simultaneously, the ~luidlzed ore/carbon blend ls contacted with a ~re~
Or C0 ~lowlng at a rate Or 74 cc/mln ~or 60 mlnutes, thereby provldlng a total Or 5.1 g C0. Fluldlzation of the ore/-3 carbon blend is monitored throughout the re~ctlon and ; no bed stlcking occurs.

- '-- - ~- ~ .

1038630 ' The gas flows Or CO and 2 are then discontinued and the flow of argon ls maintained for another 60 minutes.
The reactor is allowed to cool, after wh~ch the residual bed is removed, lgnited in air at 9~0C. and analyzed.
The bene~iciate weighs 134 g and analyzes 95.2S
TiO2 and 3.4~ Fe203. It is determined that the bene~iclate -retains 98.8S Or the Ti and 7.2~ o~ the Fe in the unreacted ore. The formation o~ TiC14 is found to be negligible. -~
Example 6 The apparatus employed is of the type shown ln Flgure 4. The composition of the ore/carbon blend ls ~ ,.... . .
chosen to simulate the bed compositlon attained in a con-tlnuous bene~iciation process. 565 g Or the FeC12 Or Example 2 is placed in the lower section of the reactor.
A blend Or 100 g of a titaniferous rock ore (analyzlng 32.9% total Fe, 29.0% Fe2~, 44.4~ Ti02 and the balance consisting primarily Or SlO2, A12O3 and MgO) ground to mesh slze -60+160, 100 g Or a benerlclate Or the same ore (analyzing 7.8% Fe203, 76.o% TiO2 and the balance conslst-ing prlmarily Or SiO2, A12O3 and MgO) o~ mesh size -601160, and 9.2 g o~ the petroleum coke described in Example 2.
The ore/carbon blend is nuidized by a stream of argon gas ~lowing at a rate Or 1120 cc/min. The fluidized blend is heated to 1050C. and held at this temperature for 120 minutes. Concurrently, the FeC12 i8 heated to -500C. Over a perlod o~ 60 minutes, the heated FeC12 is contacted with a stream Or 2 rlowing at a rate Or 227 cc/mln, the~by providing a total of 17.8 g 2 The oxidatlon results in the ~ormatlon of about 241 g Or FeC13, whlch contacts the ore/carbon blend. Slmultaneoualy, .`''' ' .,', ' ;. .

., ;
~ .
- . . . . . . . . .. . . . ... .

10~63~
the fluldized ore/carbon blend is contacted with a stream of C0 flowlng at a rate of 74 cc/min for 60 minutes, thereby providing a total of 5.1 g C0. Fluidization of the ore~-carbon blend is monitored throughout the reaction and no bed stlcking occurs.
The gas ~lows o~ C0 and 2 are then discontinued and the ~low of argon is maintalned for another 60 minutes.
The reactor i5 allowed to cool, a~ter which the residual bed is removed, ignited in air at 950C. and analyzed.
The beneficiate so obtained weighs 147 g and analyzes 82.6% TiO2 and 3.2~ Fe2O3. It is calculated that the bene~iciate retains essentially all the Ti and 8.6% Or the Fe ln the starting materials.
The reacted bed Or FeC12 in the upper reactor section is found to contain unreacted FeC12 and by-product ~e203. The Fe203 is freed ~rom unreacted FeC12 by water-leaching, is drled in air and is analyzed. It contalns - an amount Or lron essentially equivalent to the iron content Or the starting materials.
The amount o~ Fe in the FeC12 which condenses ;
in the receptacle Or Figure 3 equals 91.9Z o~ the amount o~ Fe in the FeC12 consumed by oxidation in the upper reaction sectlon. FeC12 losses are caused by lnefricient condenqatlon.
~:
' .. . . .,.. . . . . -, , - ... - . .. .. ~

Claims (3)

1. What is claimed is:
   l. Cyclic process for selectively chlorinating the iron constituent of titaniferous material comprising passing an oxidizing agent to a first reaction zone, said first reaction zone containing ferrous chloride, thereby oxidizing the ferrous chloride to ferric chloride, the temperature in said first reaction zone being maintained above the boiling point of ferric chloride, passing said ferric chloride to a second reaction zone, said second reaction zone containing said titaniferous material and a reductant, said reductant being selected from at least one of the group consisting of solid carbonaceous material and gaseous carbon monoxide, the amount of carbon in said solid carbonaceous material being greater than the stoi-chiometric amount for conversion of the oxygen bound to said iron constituent to carbon dioxide and less than or about equal to the stoichiometric amount for conversion of said oxygen to carbon monoxide, the amount of said gaseous carbon monoxide being at least sufficient to convert the balance of said oxygen to carbon dioxide.
   the temperature in said second reaction zone being at least 950°C., thereby chlorinating the iron constituent in said titaniferous material to form ferrous chloride, and recycling ferrous chloride to said first reaction zone.
2. 2. Process for selectively chlorinating the iron constituent of a titaniferous material without an appreciable net yield of titanium chloride from the titanium constituent of said material by intimately con-tacting said material with FeCl3 at an elevated temperature of at least 950°C. and in the presence of a reductant, said reductant being selected from at least one of the group consisting of solid carbonaceous material and gaseous carbon monoxide, the amount of carbon in said solid carbonaceous material being greater than the stoichiometric amount for conversion of the oxygen bound to said iron constituent to carbon dioxide and less than or about equal to the stoichiometric amount for conversion of said oxygen to carbon monoxide, the amount of said gaseous carbon monoxide being at least sufficient to convert the balance of said oxygen to carbon dioxide.
3. 3. Process according to Claim 2 wherein the FeCl3 is produced by the reaction of FeCl2 with an oxidiz-ing agent selected from the group consisting of gaseous chlorine and a gas containing at least 20% molecular oxygen.