WO1990013680A1

WO1990013680A1 - A process for jointly producing metal chlorides

Info

Publication number: WO1990013680A1
Application number: PCT/US1990/002107
Authority: WO
Inventors: Kenneth J. Richards; Theodore A. Rado
Original assignee: Kerr-Mcgee Chemical Corporation
Priority date: 1989-05-12
Filing date: 1990-04-20
Publication date: 1990-11-15

Abstract

A process for producing volatile metal chlorides jointly with titanium tetrachloride is provided. The process comprises chlorinating a reactive mixture of metal component- and titanium dioxide-containing materials under reducing conditions to produce a vaporous product mixture containing volatilized metal chloride and titanium tetrachloride reaction products. The vaporous product mixture then is subjected to condensation to condense at least one of the volatilized metal chloride or titanium tetrachloride reaction products contained therein. The resulting condensed mixture then is subjected to separation to recover at least one condensed reaction product therefrom.

Description

A Process for Jointly Producing Metal Chlorides

Field of the Invention

The invention relates to the production of volatile metal chlorides and more particularly to the production of volatile metal chlorides jointly with titanium tetra- chloride.

Background of the Invention

Volatile metal chlorides and methods for their manufacture are known. In this respect, the simplest, most widely employed method is the direct chlorination of the metals themselves. For example, tin tetrachlor¬ ide, which is a liquid at room temperature and atmos¬ pheric pressure, is prepared commercially either by direct chlorination of tin metal in a molten state or of finely divided tin metal suspended in a suitable medium such as tin tetrachloride.

Regardless of the particular method employed to produce the volatile metal chlorides, the quantities of volatile metal chlorides produced annually are rela- tively small. This particularly is true when compared to, for instance, the quantities of titanium tetrachlor¬ ide manufactured each year. The production of such relatively small quantities is necessitated by the limited demand and uses for these volatile metal chlor- ides. Unfortunately, it is the production of such small scale quantities which results in the high unit production costs for these materials. A process whereby these volatile metal chlorides could be produced in such relatively small quantities but at lower unit production costs, such as those associated with the large scale manufacture of titanium tetrachloride, would offer a significant economic advantage. The process constituting the present invention offers such an advantage.

Summary of the Invention A process now has been discovered for advantageous¬ ly and economically producing volatile metal chlorides jointly with the production of titanium tetrachloride.

In accordance with the process of this invention, a reactive mixture comprised of a metal component-contain- ing material, a titanium dioxide-containing material and a carbonaceous reducing agent first is formed in a suit¬ able chlorination zone. This mixture is reacted within the chlorination zone by contacting the mixture with a chlorinating agent at an elevated temperature sufficient to effect reduction and chlorination of the metal com¬ ponent containing material and titanium dioxide-contain¬ ing material and produce a vaporous product mixture of volatilized metal chloride and titanium tetrachloride reaction products. The vaporous product mixture is recovered from the chlorination zone and subjected to condensation under conditions whereby at least one of the metal chloride and the titanium tetrachloride reaction products con¬ tained therein is condensed. Following the condensation of the vaporous product mixture, the condensed metal chloride, titanium tetrachloride, or both are recovered therefrom.

Description of the Drawing The single Figure presents a diagrammatical illus¬ tration of the use of the process of the present inven¬ tion to produce and recover a volatile metal chloride thereby. Detailed Description of the Invention

The process constituting the present invention broadly is applicable to the production of any metal chloride from a metal component-containing material and which metal chloride is volatile at the operating temperatures utilized in the process and particularly at the temperatures employed in the hereinafter described chlorination step of the process. For all practical purposes, the metal chlorides which can be produced by the process of this invention generally can be any metal chloride which possesses a vapor pressure, at the chlor¬ ination temperatures employed, of at least about 20 mm Hg. While it is feasible to utilize the process of this invention to produce metal chlorides possessing vapor pressures below the above specified minimum vapor pressure, generally such metal chlorides either will not be sufficiently volatile, without the use of excessive chlorination temperatures, to be readily recoverable from the chlorination zone or must be prepared in such small quantities as to render their manufacture economi¬ cally impractical at present.

In a preferred embodiment, the process of the present invention is particularly applicable to the production of the various chlorides of the metals of Groups lb, lib. Ilia, IVa, Va, Via and VIII of the

Periodic Table of the Elements. The chlorides of the metals of these Groups all possess vapor pressures considerably in excess of the above specified minimum vapor pressure at the chlorination temperatures employed and thus, all are readily recoverable from a chlorina¬ tion zone and can be produced in economically practical quantities. Representative, but nonlimiting examples, of the metals within these Groups are, for instance, copper, zinc, cadmium, boron, aluminum, gallium, indium, silicon, germanium, tin, lead, arsenic, antimony, bis¬ muth, iron, selenium and the like. Although the chlor¬ ides of these metals may themselves be either solids or liquids at room temperature and atmospheric pres- sure, they all are essentially completely volatile at the chlorination temperatures hereinafter disclosed, thereby rendering them readily recoverable.

A more preferred application of the process of this invention is in the preparation of the various chlorides of the metals of Groups IVa and Va of the Periodic Table of Elements. These groups include, for instance, such metals as germanium, tin, silicon, antimony and arsenic. The use of the process of this invention to produce the chlorides of these metals is most advantageous since such chlorides are readily volatilized and many are liquids at room temperature and atmospheric pressure. Thus, not only can these materials be economically pro¬ duced utilizing the process described herein, but many also can be easily separated from the coproduced titanium tetrachloride and purified using simple frac- tionation techniques well-known to those of ordinary skill in this art.

As disclosed hereinabove, the present invention broadly is applicable to the preparation of any volatile metal chloride from any metal component-containing material. As used herein and in the appended claims, the term "metal component-containing materials" means any ore, ore concentrate or other material derived therefrom in which the metal component can be present therein in the form of the free or elemental metal or is chemically bound to a nonmetallic moiety including, but by no means limited to, oxygen, sulfur, carbon and the like, and mixtures thereof. Thus, the metal components contained in the metal component-containing material can comprise the free or elemental metal itself or the oxides, sulfides and carbides thereof.

In accordance with the process of this invention the preparation of the volatile metal chlorides is carried out jointly with the preparation of titanium tetrachloride using any of the static or fluidized bed or molten salt bath chlorination techniques known in this technical field. However, for the sole purpose of simplifying the description and explanation of the use and operation of the process comprising the present invention, the process is described below particularly with regard to the preparation of tin tetrachloride (a volatile, metal chloride which is liquid at room tem¬ perature and atmospheric pressure) jointly with titanium tetrachloride employing fluidized bed chlorination techniques.

With reference to the single Figure, a titanium dioxide-containing material, a tin dioxide-containing material (i.e., the metal component-containing material) and a carbonaceous reducing agent individually are introduced, via inlet conduits 10, 12 and 14 respec¬ tively, into .a chlorination zone 18 to provide therein a reactive mixture. Each of the titanium dioxide- and tin dioxide-containing materials and the carbonaceous redu- cing agent will be introduced into the chlorination zone 18 in the form of particulate solids and be of a size capable of ready fluidization. To facilitate the fluid- ization of this reactive mixture, the size of the par¬ ticulate titanium dioxide- and tin dioxide-containing materials contained therein will range from about minus

28 to about plus 270 mesh (Tyler Standard Screen Scale Sieves) and preferably from about minus 42 to about plus 150 mesh.

The sources of the titanium dioxide- and tin dioxide-containing materials employed to provide the readily fluidizable reactive mixture within the chlor¬ ination zone 18 are not critical. Generally, the titanium dioxide- and tin dioxide-containing materials which can be used in the practice of this invention can include any of the known materials containing these particular metal oxide constituents. Representative, but nonlimiting, examples of useful titanium dioxide- containing materials include, for instance, rutile, ilmenite and Brookite ores and the like, titanium dioxide enriched ore concentrates resulting from the beneficiation of any of the above disclosed ores and titanium dioxide-rich slags such as, for instance, slags produced by the electrosmelting of the naturally occurring ores or ore concentrates. Representative, but nonlimiting, examples of useful tin dioxide-containing materials include cassiterite ore and other tin dioxide-containing ores found in low grade alluvial or eluvial placer deposits as well as ore concentrates thereof. In general, the concentration of the titanium dioxide and tin dioxide present in the particular materials being employed can vary widely depending upon the nature of these materials. For example, with regard to titanium dioxide-containing materials the concentration of the titanium dioxide present in such materials can range broadly from about 50 to about 95 weight percent based upon the total weight of the material utilized depending upon whether this material is an ore, ore concentrate, or slag. Most usually, however, it is preferred to employ upgraded titanium dioxide-containing materials (i.e., ore concentrates) such as synthetic rutiles prepared, for instance, by the acid leaching of ilmenite. The titanium dioxide concen¬ tration in these synthetic rutiles typically can range from about 90 to about 95 weight percent or higher. With regard to tin dioxide-containing materials, such as the cassiterite ores, the tin dioxide concen¬ tration present therein also can vary widely. In general, the tin dioxide concentration of cassiterite ores can range from about 10 to about 100 weight percent based upon the total weight of the ore. This same broad concentration range also is typical of other metal com¬ ponent-containing materials which can be employed in the process of this invention to produce volatile chlorides of the other metals disclosed hereinabove. Representa¬ tive examples of such other metal component-containing materials include, but are not limited to, naturally occurring zincite (ZnO) , wurtzite (ZnS) , corundum (AI2O3) , quartz (Siθ2) , moissanite (SiC) , litharge (PbO) , galena (PbS) , Plattnerite (Pb02) , galenabismuthite

(PbBi∑SA) , arsenolite (As2θ3) , realgar (AsS) valentinite (Sb203) , stibnite (Sb2S3) , wuestite (FeO) , pyrite (FeS2) , hematite (Fe2θ3) , chalcopyrite (CuFeS2) and the like, to name but a few. Mixtures of such metal component- containing materials also can be employed. However, it generally will be preferred to employ materials contain¬ ing, as the metal component, a metal oxide. Thus, when the metal component contained in the metal component- containing material is a metal sulfide it usually will be preferred to first convert the metal sulfide to the corresponding metal oxide. This readily can be accom¬ plished by methods known to those skilled in this art such as, for example, by roasting the metal sulfide- containing ore or ore concentrate under oxidizing conditions.

Referring again to the single Figure, the particu- late titanium dioxide- and tin dioxide-containing materials will be introduced into the chlorination zone 18 in quantities sufficient to provide, within the reactive mixture, a weight ratio of the titanium dioxide to the tin dioxide of at least about 1:1 and preferably at least about 2:1. Most usually the quantities of the titanium dioxide- and tin dioxide-containing ores or ore concentrates or other metal component-containing mater- ials will be amounts sufficient to provide weight ratios of the titanium dioxide to the tin dioxide or other metal component-containing material ranging from about

2:1 to about 20:1.

The exact type and composition of the carbonaceous reducing agent introduced via an inlet conduit 14 into the chlorination zone 18 also generally will not be critical. However, this reducing agent preferably should be low in ash and free of hydrogen since the presence of the latter readily can lead to the produc- tion of hydrogen chloride. In this regard, calcined petroleum coke generally is the carbonaceous reducing agent of choice since it is both substantially free of ash and hydrogen. Typically, the carbonaceous reducing agent will be in the form of particulate solids ranging from about minus 10 to about plus 150 mesh in size and will be added to the reactive mixture in at least a stoichiometric amount based upon the equivalents of the titanium dioxide and tin dioxide present therein.

Once a bed of the reactive mixture of the titanium dioxide- and tin dioxide-containing materials and the car¬ bonaceous reducing agent is formed in the chlorination zone 18 and the temperature thereof brought to at least about 600°C, a chlorinating agent is introduced via an inlet conduit 16 into the chlorination zone 18. The rate of flow of the chlorinating agent through the inlet conduit 16 and into the chlorination zone 18 will be such, generally, to provide fluidization of the bed of the reactive mixture without excessive blowover of the bed from the chlorination zone 18. The extent of blow- over of the bed generally will depend on such factors as the depth of the bed and the density and other physical characteristics (including the particle size) of the particulate titanium dioxide- and tin dioxide-containing materials and the carbonaceous reducing agent present in the bed. However, for any given bed depth and knowing the density and other physical characteristics (includ¬ ing the particle size) of the particulate titanium dioxide- and tin dioxide-containing materials (or other metal component-containing material) and the carbona- ceous reducing agent, one of ordinary skill in this field readily can determine, without undue experi¬ mentation, the flow rate required for the chlorinating agent to avoid excessive blowover of the bed materials. The chlorination of the titanium dioxide- and tin dioxide-containing materials within the fluidized reactive mixture can be accomplished by any suitable chlorinating agent such as, for example, chlorine or a source of chlorine. Preferably, however, the chlor¬ inating agent of choice is anhydrous chlorine gas. The chlorinating agent can be introduced into the chlorina¬ tion zone 18 at ambient temperatures or at elevated temperatures although ambient temperatures typically are employed.

Within the chlorination zone 18 the temperature of the fluidized reactive mixture of titanium dioxide and tin dioxide-containing materials and carbonaceous reduc¬ ing agent will be maintained at a temperature of at least about 600^*C and above. Preferably, the chlorina¬ tion temperatures will range from about 800^βC to about 1200^βC. At these temperatures the reduction/chlorina¬ tion reaction is self-sustaining.

To initiate the chlorination of the reactive mix¬ ture of the titanium dioxide- and tin dioxide-containing materials and carbonaceous reducing agent, the chlorina- tion zone 18 containing this reactive mixture is brought up to the above disclosed operating temperatures utili¬ zing known techniques. For example, one such technique includes igniting and burning any convenient solid fuel within the chlorination zone 18 until the desired operating temperature is obtained. During this initial heat-up, air can be introduced through the bottom of the chlorination zone 18 (by means not shown) to fluidize the reactive mixture contained therein. After fluidization is accomplished and heat-up completed, the chlorinating agent (e.g., chlorine gas) gradually is substituted for the air.

As the introduction of the chlorinating agent into the chlorination zone is continued, the titanium dioxide- and tin dioxide-containing materials within the fluidized reactive mixture undergo reduction and chlor¬ ination to form a vaporous product mixture containing volatilized titanium and tin tetrachloride products. This vaporous mixture may also contain other volatilized metal halides which may be formed from other metal components present as incidental impurities in the original titanium dioxide- and tin dioxide-containing materials. The vaporous product mixture, containing the volatilized titanium and tin tetrachlorides and any other volatilized metal halides present as impurities therein, together with any gaseous components such as carbon monoxide and carbon dioxide formed during the chlorination, is removed from the chlorination zone 18 by way of an outlet conduit 20.

The vaporous product mixture removed from the chlorination zone 18 also may contain entrained particulate solid materials such as, for instance, a portion of the carbonaceous reducing agent, a portion of the residues remaining from the chlorination of the titanium dioxide- and tin dioxide-containing materials and the like. To remove these entrained particulate solid materials, the vaporous product mixture flowing through the outlet conduit 20 is passed to a gas/solids separation zone 22. Within the gas/solids separation zone 22, which can comprise any of a number of different conventional separation devices such as gravity collec¬ tors, impingement separators or cyclone separators, the entrained particulate solid materials are separated from the vaporous product mixture, settled into a lower section of the gas/solids separation zone 22 and are removed therefrom via a solids outlet conduit 24.

The vaporous product mixture, now substantially free of the entrained particulate solid materials, is removed from an upper section of the gas/solids separa¬ tion zone 22 via a vapor outlet conduit 26. The vapor- ous product mixture removed from the upper section of the gas/solids separation zone 22 is conveyed through the conduit 26 to a condensation zone 28 wherein the vaporous mixture is condensed by means of either direct or indirect heat exchange. Generally, where the metal chloride co-product is a liquid at room temperature and atmospheric pressure, as is tin tetrachloride, the condensation of the vaporous product mixture can be effected through the use of indirect heat exchange employing a suitable cooling medium. Typical of indirect heat exchange apparatus for use in the condensation zone 28 are, for example, conventional shell-and-tube type heat exchangers as well as plate type heat exchangers. Suitable cooling medium for use in such heat exchangers can include, for instance, water or various process streams such as the liquid titanium tetrachloride and tin tetrachloride products produced in the process. The temperature of the cooling medium will be such as to provide for cooling and thereby a conden¬ sation of the condensable constituents in the vaporous product mixture, i.e., the titanium tetrachloride and tin tetrachloride chlorination products. In this regard, the temperature of the cooling medium will be a temperature which, upon indirect heat exchange with the vaporous product mixture, is sufficient to cool the vaporous product mixture to a temperature below about the dew point temperature of at least the volatilized titanium tetrachloride and tin tetrachloride contained therein. As a result of this cooling, at least the titanium and tin tetrachlorides will be condensed and will collect in a lower section of the condensation zone 28 as a liquid product mixture. Any noncondensable con¬ stituents such as, for example, carbon monoxide and carbon dioxide, will be collected in an upper section of the condensation zone 28 and will be removed therefrom via a conduit 30.

The condensed liquid product mixture, which prin¬ cipally is comprised of liquid titanium tetrachloride and liquid tin tetrachloride, is removed from the lower section of the condensation zone 28 by way of an outlet conduit 32 and conveyed through the conduit 32 to a fractionation zone 34. The fractionation zone 34 typi¬ cally can be a distillation column or tower such as, for instance, conventional packed or plate type towers. In general, the fractionation zone 34 will be maintained at a temperature sufficient to effect a fractionation of the liquid product mixture through revolatilization of the lowest boiling point metal chloride constituent present in this mixture. In the particular embodiment herein being described, i.e., the joint production of liquid titanium tetrachloride and tin tetrachloride, the fractionation zone 34 will be operated at a temperature above about 11 ^βC, the boiling point of the tin tetra¬ chloride, and below about 136°C, the boiling point of the titanium tetrachloride. It is, of course, apparent to one of skill in this field that the precise tempera¬ ture or range of temperatures which can be utilized for carrying out the fractionation of liquid product mix¬ tures will vary depending upon the particular liquid metal chloride being co-produced together with the titanium tetrachloride.

A vaporous stream containing the revolatilized tin tetrachloride and any other volatilizable metal chlor¬ ides which may be present in the liquid reaction mixture and which have boiling points lower than that of titan¬ ium tetrachloride is removed from the fractionation zone 34 via a conduit 38 while a liquid effluent stream com¬ prised of the condensed titanium tetrachloride and any other nonvolatilized metal chlorides present having boiling points higher than that of titanium tetrachlor¬ ide, is removed from the fractionation zone 34 via a conduit 36. The vaporous stream removed from the frac¬ tionation zone 34 via conduit 38 then is recondensed and subjected to purification (by means not shown) to reco- ver the tin tetrachloride contained therein as one principal product of the process. The liquid effluent stream, containing the titanium tetrachloride and any other nonvolatilized metal chlorides, also is subjected to further purification (by means not shown) and finally recovered as another principal product of the process. The process of this invention has been described above particularly with respect to the production of tin tetrachloride. As is known to those skilled in this art, this particular metal chloride is volatile at the elevated temperatures employed in the chlorination step and also is a liquid at room temperature and atmospheric pressure. However, as aforementioned, the process of this invention also is applicable to the production of various other metal chlorides which, although volatile at the chlorination temperatures employed, can be solids at room temperature and atmospheric pressure. In such event, the metal chlorides can form particulate solids at temperatures significantly higher than the dew point (or condensation) temperature of the titanium tetra- chloride being co-produced therewith permitting the condensation, precipitation and separation of such volatilized metal chlorides from the remainder of the vaporous product mixture to be carried out simultane¬ ously. With regard to the above and referring, once again, to the single Figure, the simultaneous condensation, precipitation and separation of such volatilized, metal chlorides can be effected in the gas/solids separation zone 22 and the separated solid metal chloride recovered therefrom via the solids outlet conduit 24. Depending upon the dew point (or condensation) temperature and freezing point temperature of the particular volatilized metal chloride contained in the vaporous product mix¬ ture, the condensation and precipitation of the metal chloride into a particulate solid can be carried out by cooling of the vaporous product mixture either through the natural heat losses which occur within the conduit 20 or by spraying a liquid coolant such as liquid titanium tetrachloride into the vaporous product mixture. One example of the latter technique for cool¬ ing a vaporous stream to condense the metal chlorides contained therein is U.S. Patent No. 4,066,424, the teachings of which are incorporated herein in their entirety, by reference. Where the dew point and freezing point temperatures of the volatilized metal chloride being produced jointly with the titanium tetrachloride are such that condensa¬ tion and precipitation thereof cannot be accomplished by cooling through the natural heat losses which occur within the conduit 20, then artificial cooling in a manner such as described in the above identified U.S. patent will be required. However, in this instance, it may be desirable to effect the cooling downstream of the gas/solids separation zone 22 to maintain the volatil- ized metal chloride, once solidified, separate from the entrained particulate solids removed from the vaporous product mixture in the gas/solids separation zone 22.

For example, utilizing the cooling technique described in the above identified U.S. patent, liquid titanium tetrachloride can be sprayed into the conduit 26 (by means not shown) to condense and precipitate, as a particulate solid, the volatilized metal chloride contained in the vaporous product mixture and the solid metal chloride separated therefrom in an additional gas/solids separation zone (not shown) installed in the conduit 26. The remainder of the vaporous product stream, comprising principally the volatilized titanium tetrachloride, then will be removed from this additional gas/solids separation zone (not shown) and will be continued to be treated in accordance with the process of this invention.

From the foregoing description it will be apprecia¬ ted that through the use of the process of the present invention relatively small scale quantities of volatile metal chlorides of metals other than titanium can be prepared in a more economical and advantageous manner than heretofore possible. Particularly, the process of the present invention permits the production of rela¬ tively small scale quantities of other desirable vola- tile metal chlorides jointly with the production of titanium tetrachloride whereby advantage readily can be taken of the economics of scale associated with the manufacture of titanium tetrachloride.

While the above description sets forth what can be considered to represent certain preferred embodiments of the present invention, changes may be made in the arrangement and operation of the various parts, elements and procedures described herein without departing from the spirit and scope of the invention as defined in the following claims.

Claims

1. A process for producing volatile metal chlorides jointly with titanium tetrachloride comprising the steps of: forming a reactive mixture comprised of a metal component-containing material, a titanium dioxide-containing material and a carbonaceous reducing agent; contacting said reactive mixture with a chlorinating agent, said contact being carried out at an elevated temperature sufficient to effect a reduction and chlorination of said metal component- and titanium dioxide-containing materials in said reactive mixture and to produce a vaporous product mixture comprised of volatilized metal chloride and titanium tetrachloride reaction products; subjecting said vaporous product mixture to condensation whereby at least one of said volatile metal chloride and said titanium tetrachloride reaction products is condensed; and separating said condensed vaporous product mixture to individually recover said at least one condensed reaction product therefrom.

2. The process of claim 1 wherein said volatile metal chlorides are characterized by a vapor pressure of at least about 20 mm Hg pressure as said elevated temperature.

3. The process of claim 1 wherein said metal component in said metal component-containing material is selected from the group consisting of an elemental metal and oxides, sulfides and carbides of said metal.

4. The process of claim 3 wherein said metal in said metal component-containing material is a metal selected from Groups lb, lib. Ilia, IVa, Va, Via and VIII of the Periodic Table of the Elements.

5. The process of claim 4 wherein said metal is selec¬ ted from Groups IVa and Va of the Periodic Table of the Elements.

6. The process of claim 5 wherein said metal is selec¬ ted from the group consisting of tin, silicon, antimony and arsenic and wherein said metal is present in said metal component-containing material as a metal oxide.

7. The process of claim 1 wherein said chlorinating agent contacted with said reactive mixture is chlorine gas.

8. The process of claim 1 wherein said metal compon¬ ent- and said titanium dioxide-containing materials are present in said reactive mixture in amounts sufficient to provide a weight ratio of said titanium dioxide to said metal component contained in said materials of at least about 1:1.

9. The process of claim 1 wherein said contact of said mixture with said chlorinating agent is carried out at a temperature of at least about 600"C.

10. The process of claim 9 wherein said contact is carried out at a temperature from about 800°C to about 1200*C.

11. The process of claim 1 wherein said carbonaceous reducing agent contained in said reactive mixture is present therein in at least a stoichiometric amount based upon the total equivalents of said metal component and said titanium dioxide contained in said reactive mixture.

12. The process of claim 1 wherein said metal component- containing material is an ore or ore concentrate containing from about 10 to about 100 weight percent of said metal component.

13. The process of claim 1 wherein said titanium diox¬ ide-containing material is an ore or ore concen- trate containing from about 50 to about 95 weight percent of said titanium dioxide.

14. The process of claim 1 wherein said metal compon¬ ent- and titanium dioxide-containing materials are present in said reactive mixture as solid particles ranging in size from about minus 28 mesh to about plus 270 mesh.

15. The process of claim 1 wherein said carbonaceous reducing agent is present in said reactive mixture as solid particles ranging in size from about minus 10 mesh to about plus 150 mesh.

16. The process of claim 1 wherein said vaporous product mixture is condensed by cooling said vaporous product mixture to a temperature below about the dew point temperature of at least one of said volatilized metal chloride and titanium tetrachloride reaction products contained therein.

17. A process for producing volatile, liquid metal chlorides jointly with titanium tetrachloride comprising: forming a reactive mixture comprised of a metal component-containing material wherein the metal component in said metal component-containing mater¬ ial is an oxide of a metal selected from Groups IVa and Va of the Periodic Table of the Elements, a titanium dioxide-containing material and a carbonaceous reducing agent; contacting said mixture with a chlorinating agent, said contact being carried out at a tempera¬ ture of at least about 600°C to effect reduction and chlorination of said metal oxide and titanium dioxide contained therein to produce a vaporous product mixture containing volatilized metal chlor¬ ide and titanium tetrachloride reaction products; condensing said vaporous product mixture to form a liquid product mixture containing liquid metal chloride and liquid titanium tetrachloride reaction products; and fractionating said liquid product mixture to separate said condensed liquid metal chloride reaction product therefrom.

18. The process of claim 17 wherein the metal oxide in said metal component-containing material is an oxide of a metal selected from the group consisting of tin, silicon, antimony and arsenic.

19. The process of claim 18 wherein said metal oxide is tin dioxide.

20. The process of claim 17 wherein said chlorinating agent contacted with said reactive mixture is chlorine gas.

21. The process of claim 17 wherein said reactive mixture is reacted at a temperature ranging from about 800'C to about 1200'C.

22. The process of claim 17 wherein said carbonaceous reducing agent is coke.

23. The process of claim 17 wherein said carbonaceous reducing agent is present in said reactive mixture in at least a stoichiometric amount based on the total equivalent of said metal oxide and titanium dioxide contained in said reactive mixture.

24. The process of claim 17 wherein said metal component- containing material is an ore or ore concentrate containing from about 10 to about 100 weight percent of said metal oxide.

25. The process of claim 17 wherein said titanium dioxide-containing material is an ore or ore concentrate containing from about 50 to about 95 weight percent of said titanium dioxide.

26. The process of claim 17 wherein said metal oxide and said titanium dioxide-containing materials are present in said reactive mixture in amounts suffi¬ cient to provide a weight ratio of said titanium dioxide to said metal oxide therein of from about 2:1 to about 20:1.

27. The process of claim 17 wherein said metal oxide and said titanium dioxide-containing materials are present in said reactive mixture as solid particles of said materials ranging in size from about minus 28 mesh to about plus 270 mesh.

28. The process of claim 17 wherein said carbonaceous reducing agent is present in said reactive mixture as solid particles ranging in size from about minus 10 to about plus 150 mesh.

29. The process of claim 17 wherein said vaporous product mixture is condensed to form said liquid product mixture by cooling said vaporous product mixture to a temperature below about the dew point temperatures of both the volatilized metal chloride and the titanium tetrachloride reaction products contained therein.

30. The process of claim 17 wherein said liquid product mixture is fractionated to separate said condensed liquid metal chloride reaction product therefrom by revolatilizing said condensed liquid metal chloride product.

31. The process of claim 17 wherein said liquid metal chloride is tin tetrachloride.