NZ239070A - Recovery of titanium values from a complex matrix by chlorinating titanium nitride in the matrix - Google Patents

Description

1 Priority i» .AO:.<39.

Compete SpeciJij: i).

C!a&3: Coic,«loo. .... 2 5 N0V 1992' Pufcnsa«.i«n t?ji£e: P.O. Journal, No: !%kl J2 AMENDED under Section Patents Act 1953 from £ • of tto Z3f 0 / 0 ASSISTANT COMMISSIONED OF PATENTS NEW ZEALAND PATENTS ACT, 1953 j; < No.: |f 22 JUL)99l V.

Date: " COMPLETE SPECIFICATION | PROCESS FOR THE RECOVERY OF TITANIUM VALUES yi We, ANGLO AMERICAN CORPORATION OF SOUTH AFRICA LIMITED, of 44 Main Street, Johannesburg, Transvaal Province, Republic of South Africa, a South African company hereby declare the invention for which ~$r / we pray that a patent may be granted to-*3?w/us, and the method by which it is to be performed, to be particularly described in and by the following statement:- THIS INVENTION relates to a process for the recovery of titanium values, as titanium chloride or, optionally, titanium oxide from a complex matrix comprising titanium nitride as a constituent thereof. More particularly, it relates to a process suitable for the recovery of titanium values as titanium chloride from a said matrix which is obtained by nitriding a complex mineral or metallurgical starting material such as a titaniferous ore or titaniferous slag containing titanium oxide in addition to other metal oxides, especially low-grade titaniferous slags containing 30-80% by mass, or less, titanium expressed as Ti02/ and titaniferous ores which are mixed metal oxides or titanates.

According to the invention there is provided a process for the recovery of titanium values from a complex matrix comprising the steps of: reacting the titanium nitride in the matrix by chlorinating the titanium nitride in the matrix to obtain a reaction product containing titanium chloride; and separating the titanium chloride from the reaction product, the chlorinating of the titanium nitride being by contacting a chlorinating gas with the matrix at a temperature of 200-500°C, to obtain the titanium chloride as TiCl4.

As indicated above, the process is suitable for the of titanium values from matrixes which are obtained by nitriding complex mineral or metallurgical starting materials. Accordingly, the process may include the step of obtaining the matrix containing titanium nitride by nitriding titanium values in a complex titanium-containing starting material. A suitable method for obtaining the matrix containing titanium nitride is disclosed in GB 795386.

Although the process has substantial value for mineral or metallurgical starting materials which can have high titanium values of eg above 8 0% by mass expressed as Ti02, it is particularly useful for metallurgical starting materials such as titaniferous ores or slags which are more or less complex and can have relatively low titanium values of less than 80% by mass, and as low as 30% or even less, expressed as Ti02. Thus, the starting material may be a complex metallurgical titaniferous slag containing at most 80% by mass titanium values; or, instead, the starting material may be selected from the group of ores consisting of rutile, ilmenite, perovskite, armaicoiite, fassaite and mixtures thereof.

As the nitriding step is conveniently carried out by passing nitrogen gas at an elevated temperature through or over the starting material in particulate form, the process may involve nitriding a starting material having a maximum particle size which is as small as feasible or practicable, eg 10 - 2000/im with an average particle size of at most 600/im, with a maximum particle size and average particle size preferably in the range 50 - 100/i m. The process may thus include the step, prior to the nitriding of the titanium values, of size reduction of the starting material to a maximum particle size of at most 2000 /xm and an average particle size of at most 600 /m. Size reduction will typically be by crushing and milling, and the final particle size and particle size distribution chosen will usually depend on economic considerations, milling ...e?p^s* being traded off against increased surface areaVmade available for a rapid and complete nitriding reactioh. 239 07 0 4 As indicated above, the nitriding will typically be by passing nitrogen gas through or over a particulate starting material at an elevated temperature, optionally at atmospheric or elevated pressure, and this may be effected with an excess of nitrogen gas in a reducing environment, provided eg by carbon admixed in particulate form in suitable proportions in the starting material. In other words, the nitriding of the titanium values may be by contacting a stoichiometric excess of nitrogen gas with the starting material at an elevated temperature and in a reducing environment. Surprisingly, the use of a stoichiometric excess of nitrogen can purge carbon dioxide from the reaction zone and can suppress the formation of titanium carbide, which is undesirable. Preferably the gas used for the nitriding comprises at least 25% by volume nitrogen although, naturally, the higher the nitrogen content (up to 100%) the better the nitriding achieved. The nitriding step may be carried out in a suitable metallurgical reactor, such as a rotary or shaft kiln, fluidized bed reactor or the like with a solid starting material. Instead, the starting material may naturally be in a liquid state, the nitriding taking place in a ladle or electric furnace with the nitrogen gas being injected by means of a suitable lance.

Preferably the nitrogen is fed through or over the starting material, after intimate admixing thereof with the carbon to provide a starting mixture, at a temperature of 1000 - 1800°C, preferably 1100 - 1600°C and more preferably 1200 -1350°C. The time required for the nitriding will be inversely related to the temperature and, once again, the precise temperature employed will involve economic considerations, the advantage of employing lower temperatures being traded off against longer nitriding times. Thus, in particular, the contacting of the nitrogen gas with the starting material may take place at a temperature of 1000 - 1800°C, in the presence of carbon which provides the reducing environment, sufficient carbon HOW AMENDED 239 070 »nit in the / Naturally, the rate at which nitrocfen is fed tp the starting mixture should be sufficient tc/take the nitriding to an acceptable degree of completion X/ithin an acceptable time. Mean residence times may be ej^ployed of 2y- 5 hours or less, eg 1 - 3 hrs. Once again, it is expected that there will be an economic trade-off between a/high rate of nitrogen supply, and the cost of/providing the nitrogen and losses of heat and unreacted nitrogen passing through the starting mixture; and it shduld be note^ that, with good gas contact, eg with finely/iivided starting material in a fluidized bed or rotary k/ln, lower residence time of eg l - 2 hours are expected to be sufficient.

The ni / / itrid^'ng reaction/is strongly endothermic. Heat must thus be supplied to the reaction zone to maintain the reaction tempetature. This/can be done via the reactor, eg by using an ,/lectricallwneated furnace or plasma arc / ■ heating, and/or it can be ^!one by preheating the nitrogen. While the nitrogen can be /substantially pure and indirectly heated via a suitable heat exchanger, it is expected that J / any heating thereof wipLl be by means of- a burner, air being used to burn a typically carbonaceous fuel such as producer gas, coal tar fuel,/heavy oil or coal fines, to achieve the ' / required temperature, so that the nitrogen is fed to the starting mixtur.e as a mixture of nitrogen with carbon morioxide and water vapour, in the substantial absence of oxygen. In otlier words, a carbonaceous fuel may be burnt in J / /air to provide a combustion gas which is contacted with the / starting material to provide said elevated temperature, and to provide the carbon required for the reducing environment in the/ form of carbon monoxide. Instead, however, the process may include the step of admixing a carbonaceous AS AMENDED 23 being present to consume any oxygen present in the environment and to provide a stoichiometric excess over that required to reduce the titanium values (as Ti02) in the starting material, to titanium.

Naturally, the rate at which nitrogen is fed to the starting mixture should be sufficient to take the nitriding to an acceptable degree of completion within an acceptable time. Mean residence times may be employed of \ - 5 hours or less, eg 1 - 3 hrs. Once again, it is expected that there will be an economic trade-off between a high rate of nitrogen supply, and the cost of providing the nitrogen and losses of heat and unreacted nitrogen passing through the starting mixture; and it should be noted that, with good gas contact, eg with finely divided starting material in a fluidized bed or rotary kiln, lower residence time of eg l - 2 hours are expected to be sufficient.

The nitriding reaction is strongly endotherrcic. Heat must thus be supplied to the reaction zone to maintain the reaction temperature. This can be done via the reactor, eg by using an electrically heated furnace or plasma arc heating, and/or it can be done by preheating the nitrogen. While the nitrogen can be substantially pure and indirectly heated via a suitable heat exchanger, it is expected that any heating thereof will be by means of a burner, air being used to burn a typically carbonaceous fuel such as producer gas, coal tar fuel, heavy oil or coal fines, to achieve the required temperature, so that the nitrogen is fed to the starting mixture as a mixture of nitrogen with carbon monoxide and water vapour, in the substantial absence of oxygen. In other words, a carbonaceous fuel may be burnt in air to provide a combustion gas which is in contact with the starting material to provide said elevated temperature, and to provide the carbon required for the reducing environment in the form of carbon monoxide ; and the process may include the step of admixing a carbonaceous /■■■>- o ■ \ ' \ i e20DECtr: 239070 6 material in finely divided particulate form with the starting material to provide the reducing environment.

According to another approach, it may be feasible, instead or in addition to other methods of supplying heat, for the nitrogen feed to contain oxygen, air eg being fed to the starting mixture and the starting mixture containing sufficient additional carbon to remove the oxygen from the air by combustion. This can aid in maintaining the heat supply to the nitriding reaction.

When the nitrogen is fed in the substantial absence of oxygen gas, the proportion of carbon admixed with the starting material to form the starting mixture may be 100 -300% of the stoichiometric value, typically 150 - 200% of the stoichiometric value. By 'the stoichiometric value1 is meant the amount of carbon required to reduce the titanium values (expressed as Ti02) in the starting material to TiN, depending on the reaction conditions existing. When air is fed as described above, sufficient additional carbon should be provided to ensure removal of the oxygen from the air, eg a slight stoichiometric excess for this purpose, in addition to the excess required to react with bound oxygen in the starting material during the reduction of oxides therein necessary to nitride the titanium values therein. This approach will naturally require removal of at least some of such excess carbon after the nitriding, if the chlorinating is to take place in a less reducing environment than the nitriding environment, as described hereunder.

The carbon admixed with the starting material may in principle be in the form of coal, anthracite, coke, industrial char, charcoal, graphite or the like, amorphous forms of carbon such as lamp black or soot having been found to lead to acceptable results. The carbon, similarly, should preferably be in finely divided form for intimate admixing with the starting material, the carbon having a 239070 particle size similar to that of the starting material, eg 50 - 100/j.m or less. These small particle sizes facilitate separating of carbon from the nitrided material after the nitriding in a fluidized bed, by fluidizing at a high rate 5 to cause carry-over or elution of carbon particles.

Preferably the chlorinating step takes place in an environment which is less reducing than the environment in which the nitriding takes place.

Encouraging the chlorinating to take place in a less 10 reducing environment than that in which the nitriding takes place can involve, in principle, admixing carbon with the starting material to provide the reducing environment in which the nitriding takes place, in a quantity and/or at a rate such that, after the nitriding step, the proportion of 15 carbon in the nitrided matrix is less than the proportion of carbon mixed with the starting material at the start of the nitriding, and is preferably as low as possible or practicable, substantially all the carbon being oxidized to carbon dioxide during the nitriding, so that the 2 0 environment in which the chlorinating takes place is substantially non-reducing.

If it is desirable to have relatively high proportions of carbon in the starting material to promote rapid and/or complete nitriding of the titanium values, it may not be 2 5 possible to ensure the substantial absence of carbon when the nitriding is complete. In this case the process may involve, instead, separation of carbon from the titanium nitride-containing matrix after the nitriding step and before the chlorinating step. This may be effected by a 3 0 physical separation step, such as blowing off the carbon during fluidization of the titanium nitride-containing matrix with a gas, floating off the carbon during fluidization of the titanium nitride-containing matrix with a liquid, flocculation of the carbon with the titanium 35 nitride-containing matrix suspended in a liquid, followed 23 90 7( 8 by separation of the floes therefrom, eg by flotation, or the like. In other words, the process preferably includes the step, after nitriding and before the chlorinating, of separating carbon from the matrix. Separating the carbon to 5 lessen the reducing nature of the environment can be by gas blowing in a fluidized bed used for the nitriding.

Surprisingly, said lessening of the reducing nature of the environment, before the chlorinating step, can suppress or preferably eliminate the formation, during the 10 chlorinating step, of chlorides of other metal oxide values in the starting material, thereby lessening chlorine / consumption and lessening the production of unwanted chlorides. The Applicant believes that this feature of the process can be advantageous in confining the formation of 15 gaseous metal chlorides to those of titanium, iron and vanadium and limiting the formation of solid chlorides to those of manganese, magnesium and calcium. Chlorides of metals other than titanium are undesirable impurities in the titanium chloride product and can aggravate the 20 possibility of clogging of reactors such as fluidized beds, by melting at the temperatures in question.

As manganese is often present in acceptably small proportions (<1% by mass) in the starting material, and as its chloride has respective melting and boiling points of 25 650°C and 1290°C, it is not regarded as a particularly undesirable impurity of the TiCl4 product as it can easily be separated therefrom. Similar considerations apply to calcium and magnesium which are present in higher quantities but have higher melting points and boiling 30 points. Furthermore, since chlorination of magnesium and calcium is kinetically slower than titanium, the production of gaseous TiCl4 takes place to a much larger extent, resulting in the formation of relatively small amounts of the solid chlorides of magnesium and calcium. This favours 35 the production of TiCl4 at the expense of chlorides of magnesium and calcium, so that these impurities need be present in no more than acceptable proportions.

The chlorination of the titanium nitride, obtained eg from a nitrided starting material, may be by passing a chlorinating gas such as HC1, CC14, SC12 or preferably Cl2 over or through the nitrided matrix, at a suitable temperature, which for Cl2 is 200 - 500°C, preferably 350 -450°C. In other words, the chlorinating of the titanium nitride may be by contacting a chlorinating gas selected from the group consisting of Cl2, HC1, CC14, SC12 and mixtures thereof, with the matrix at a temperature of 350 -450°C, to obtain the titanium chloride as TiCl4. In this regard the Applicant has surprisingly found that suitable selection of the nitriding temperature (eg 12 00 -1350°C) can ensure that the starting material remains in particulate form after the nitriding thereof, of a suitable particle size for the chlorination. No further size reduction thereof is required and it merely requires to be cooled and moved to a suitable reaction vessel, such as a fixed bed, countercurrent cyclone or, conveniently, a fluidized bed. Any metals produced during the nitriding can simply be removed, after said cooling, by magnetic separation and/or by gravimetric separation. Unwanted production of chlorides of the metals can thus be further reduced or preferably eliminated.

The above chlorination temperatures are selected so that the TiN in the nitrided matrix is converted to TiCl4, and at these temperatures the Applicant believes that other major volatile chlorination products which can be produced in any material amounts are transition metal chlorides such as ferric chloride (FeCl3), vanadium chloride (VC14), vanadium oxychloride (V0C13) and silicon chloride (SiCl4) . Any FeCl-, or vanadium chlorides and/or oxychlorides can easily be condensed, together with the TiCl4, from the gas .-i ♦« ,-- j issuing from the chlorination vessel. Any FeCl3 produced can be condensed at atmospheric pressure at a substantially- 2 3 9 0 7( higher temperature than TiCl4 or VOCl3, and can thus easily be removed, eg in a cyclone or the like by separation at 290°C of solid FeCl3 and TiCl4 gas. In this regard it is to be noted that FeCl3 melts at 306°C and at 315 °C it 5 decomposes to FeCl2 and Cl2, FeCl2 having a melting point substantially higher than 315 °C and Cl2 being a gas; TiCl4 boils at 136°C; VOCl3 boils at 126°C; SiCl4 boils at 58°C and VC14 boils at 148°C. The TiCl4 and any V0C13 or VCl4 are thus subsequently condensible together (to separate them eg 10 from any SiCl4 or the like) and are then separable by distillation in known fashion, after which the TiCl4, which is of substantial purity, can easily be oxidized to Ti02, a valuable pigment, in known fashion.

It should be noted that calcium, magnesium and 15 manganese are present in most oxygen-containing mineral complexes. They can thus be present in most starting materials employed by the present process, particularly metallurgical slags. It is a particular and surprising advantage of the present process that the low temperature 2 0 chlorination temperatures employed lead to reduced chlorination of these metals. Furthermore, importantly, the chlorides of these metals are solid at 200 - 500°C. This is a material advantage compared with chlorination at temperatures which are higher and are sufficient to melt 2 5 the chlorides of these metals, which melting can lead to clogging up of reactors such as rotary kilns or fluidized beds.

With regard to the chlorination, it should be noted that this is exothermic. If eg a fluidized bed 30 reactor is used for the chlorination, heat produced can be removed by the fluidizing gas, most of which will be inert carrier gas, and heat can, if desired, be recovered in known fashion from this gas.

The chlorinating gas may be fed over the nitrided 3 5 matrix in diluted form, eg diluted with an inert gas such 11 as argon or nitrogen. When the chlorinating gas is Cl2, it may be mixed with nitrogen in proportions of at least 10% by volume Cl2, eg 20 - 80% by volume Cl2, and it may be fed at atmospheric or elevated pressure. Accordingly, in a 5 particular embodiment, the chlorinating gas may be Cl2 being diluted with nitrogen to form a mixture comprising 20-80% by volume Cl2. The chlorinating gas may be fed over the nitrided matrix for a mean residence time of 10 - 120 minutes, sufficient to chlorinate the TiN in the nitrided 10 material to an acceptable degree of completion in an acceptable time, without employing unnecessarily excessive amounts of chlorinating gas, as dictated by economics. As indicated above, lessening the reducing nature of the environment in the chlorinating step compared with the 15 nitriding step, 'can reduce the proportion of chlorides other than TiCl4 produced, and reaction conditions in the chlorinating step can be selected which lessen the production of such other chlorides bearing in mind the kinetics of the production of such chlorides. 2 0 After the condensation of the TiCl4 and any VOCl3, the chlorinating gas and nitrogen remaining therein, may be recycled to the chlorination vessel, chlorinating gas feed or make-up being added thereto.

The Applicant has found, as discussed in more detail 25 hereunder, that titaniferous slag, obtained from Highveld Steel and Vanadium Corporation Limited, Witbank, as well as rutile and ilmenite, can be nitrided in accordance with the process of the present invention. Nitriding such a slag produces a nitrided matrix which, upon X-ray diffraction 30 analysis, shows a well defined TiN crystalline phase, and very few, if any, other well defined crystalline phases of any material significance. No signs of titanium carbide or titanium carbonitride formation have been noted, nor indeed any other metal carbide or carbonitride formation. It .thus'-. 3 5 appears that the remaining constituents of the starting slag form a glassy, non-crystalline matrix phase during the < r C Z O C.

MOW AMENDED 239070 12 / / nitriding step and that a high proportion (90% bj/ mass or more) of the titanium values can be converted to the nitride. In the subsequent chlorination, the on^y chlorides produced to any material extent are TiCl4, FeyL3 and VOCl3/ and these can easily be condensed and /separated, .as described above.

Between the nitriding and the chlorinating st«=ps, or initially, the process may include a magnetic separation of iron from the material being treated^/ and, to enhance this, 10 the starting material may first be/treated with^carbon and a suitable flux such as CaC03, eg At 800 -1200/C, to reduce / / iron oxides to iron. This step/ can reduce/the amount of FeCl3 waste product eventually produced (see eg MacMillan et al - 'Proposed Process/ for Treatment of Low-Grade / / Titaniferous Ores' US Department of the ^Interior, Bureau of Mines Report of Investigations 4638, January 1950) . i / When the complex/titanium oxide-containing starting material is a mixed m/tal oxide or/titanate, eg an ore such as ilmenite (Fe0T£02), perovskite (Ca0Ti02), fassaite 20 (Ca(Ti,Mg,Al)(Si,Al)206) or' possibly armalcolite (Mg0.2Ti02), the/nitriding step can lead to the production, during the nitriding step; of one or more metals, in metallic forin, from metal values other than titanium present in s-aid mixed metal oxide or titanate.

/ Such1'metals can .be separated from the matrix, before the chlorinating step, by physical methods, eg gravimetric or magnetic separation, or by chemical methods such as leaching, eg employing hydrochloric acid. Thus, in general, wheh the matrix comprising the titanium nitride also 3 0 contains a metal other than titanium, the process may /include they'step, before the chlorinating, of separating i / / the metal from said matrix / Whether lessening of the reducing nature of the i environment before the chlorinating, or the separation of 'AS AMENDED *3 12 nitriding step and that a high proportion (9 0% by mass or more) of the titanium values can be converted to the nitride. In the subsequent chlorination, the only chlorides produced to any material extent are TiCl4, FeCl3 and VOCl3, and these can easily be condensed and separated, as described above.

Between the nitriding and the chlorinating steps, or initially, the process may include a magnetic separation of iron from the material being treated, and, to enhance this, the starting material may first be treated with carbon and a suitable flux such as CaC03, eg at 800 -1200°C, to reduce iron oxides to iron. This step can reduce the amount of FeCl3 waste product eventually produced (see eg MacMillan et al - 'Proposed Process for Treatment of Low-Grade Titaniferous Ores' US Department of the Interior, Bureau of Mines Report of Investigations 4638, January 1950).

When the complex titanium oxide-containing starting material is a mixed metal oxide or titanate, eg an ore such as ilmenite (FeOTiOj) , perovskite (Ca0Ti02) , fassaite (Ca(Ti,Mg,Al)(Si,Al)205) or possibly armalcolite (Mg0.2Ti02), the nitriding step can lead to the production, during the nitriding step, of one or more metals, in metallic form, from metal values other than titanium present in said mixed metal oxide or titanate.

Such metals can be separated from the matrix, before the chlorinating step, by physical methods, eg gravimetric or magnetic separation, or by chemical methods such as leaching, eg employing hydrochloric acid. Thus, in general, when the matrix comprising the titanium nitride also contains a metal other than titanium, the process may include the step, before the chlorinating, of separating the metal other than titanium from the matrix.

Whether lessening of the reducing nature of the environment before the chlorinating, or the separation of »W 4 ' rj •r 20 DEC 1993 HOW AMENDED 13 any metal produced before the chlorinating, or/ both, are employed, as described above, will depend largely^on the nature of the complex titaniferous starting material used, and this c^!n be determined by routine testing. Furthermore/ while it is in / / . principle desirable completely to eliminate,both the reducing / / • environment and any said metals produced before the chlorination, economic considerations may naturally dictate that these steps are not carried out to completion. / / / i / J The invention will now be described by way of / example, with / / reference to the accompanying drawings and Example.

/ In the drawings: /' / / / / / co y u /i AS AMENDED 13 any metal produced before the chlorinating, or both, are employed, as described above, will depend largely on the nature of the complex titaniferous starting material used, and this can be determined by routine testing. Furthermore, while it is in principle desirable completely to eliminate both the reducing environment and any said metals produced before the chlorination, economic considerations may naturally dictate that these steps are not carried out to completion.

The invention also extends to titanium values whenever recovered by the process for the recovery thereof as described above.

The invention will now be described by way of example, with reference to the accompanying drawings and Example.

In the drawings: j C I■* i ^ 239070 14 Figure 1 shows an X-ray diffraction pattern trace of titaniferous slag obtained from Highveld Steel and Vanadium Corporation Limited, for the °20 range of 10-110° using CuKa radiation; Figure 2 shows a similar trace for the °20 range of 32-80° for the slag whose trace is shown in Figure l, but after the slag has been nitrided in accordance with the following Example 1; Figure 3 shows a schematic cross-section of the 10 apparatus used for chlorinating the nitrided slag in accordance with Example 1; and Figure 4 shows a schematic cross-section of an apparatus used for nitriding in accordance with Example 2.

EXAMPLE 1 Titaniferous slag from Highveld Steel and Vanadium Corporation Limited comprising about 30% by mass titanium values (as Ti02) was milled and crushed to a particle size of less than 1000 //. Carbon, in the form of lamp black having an 20 average particle size of 0,5 fj, was intimately mixed with the slag, in a proportion of 20% by mass.

A sample of the mixture of slag and lamp black was loaded into an a-alumina crucible and placed 2 5 in an electrically heated tube furnace. The furnace was repeatedly (4 times) evacuated to a vacuum of about 20 Torr and flushed with high purity (9 9,9998% by volume) nitrogen. A steady stream of this nitrogen was then fed through the 30 furnace at a rate of 40 m£/min.

The furnace was then slowly heated over a period of 5 hrs from ambient to 1550°C at a substantially constant heating rate of 5°C/minute and kept at 1550°C for 10 hrs to nitride the 3 5 starting mixture and obtain a nitrided matrix. 23 9 07 0 \ The furnace was then allowed to cool naturally to ambient and the nitrided matrix was subjected to X-ray diffraction, together with a sample of the starting (un-nitrided) mixture.

The X-ray diffraction trace of the starting mixture is shown in Figure 1, and that of the nitrided matrix in Figure 2. Figure 1 shows that the starting mixture has a relatively high degree of crystallinity, whereas Figure 2 shows that the 10 nitrided matrix is comparatively amorphous, except for a substantial proportion of TiN, indicated by a number of distinct TiN peaks in Figure 2.

Before the nitriding the starting mixture was 15 black and after the nitriding a number of lighter-coloured specks were visible to the naked eye in the matrix.

Referring now to Figure 3, the nitrided matrix was chlorinated in apparatus generally designated 2 0 by reference numeral 10. The apparatus 10 comprises a tubular electrical heater 12, within which is located a tubular glass reaction vessel 14 having a glass inlet tube 16 and a glass outlet tube 18 leading to a glass collection ) 25 flask 20. The flask 20 has a glass gas outlet tube 22 and the vessel 14 is provided with a thermocouple 24 and a porous sintered glass disc 26.

In use of the apparatus 10, 10 g of the nitrided 30 matrix was placed in the vessel 14 on the disc 26 and chlorinating gas in the form of Cl2 was fed via the tube 16 thereto at a rate of 60 m£/min, while the temperature of the chlorinator was increased by means of the heater 12 stepwise from 16 (followed by page 16a) ambient by the steps of about 50°C up to a temperature of 3 50°C, at which stage the Cl2 started to react with the matrix. The reaction was discontinued after 1,5 hours, "when it appeared to be complete.

About 6 g of reaction product was obtained in the product collection flask 20 via the tube 18, in the form of a yellow-brown liquid, together with a small amount of red solid material. The liquid was decanted and subjected to elemental analysis, the analysis being set forth in the following table, Table 1: TABLE 1 Element % by mass CI 75,8 Ti ,9 ±0,3 V 0,93 ±0,03 Si . 0,18 ±0,06 Al 0,01 Fe <0,01 Mg <0,005 Cr not detected Ca not detected From the analysis set forth in Table 1, and ignoring the negligible amounts of Al, Fe, Mg, Cr and Ca detected, it appears that the liquid comprised a mixture of TiCl4, VC14 and/or VOCl3 and SiCl4, with some Cl2 dissolved therein, and having an analysis as set forth in the following table, Table 2: 16(a) TABLE 2 Compound % by mass TiCl4 00 to -0 VC14 and/or VOCI3 3,5 SiCl4 1,1 CI, 12,7 (balance) To test the feasibility of the step of lessening the reducing nature of the environment in which the chlorination took place, pure V205 was chlorinated, in the presence of carbon in the vessel 14 according to the reactions v205 + 3C12 + 3C -» 2VOCI3 + 3CO; and V205 + 3C12 + 5C -+ 2VC13 + 5C0.

S/ w 23 17 The chlorination was carried out at 350°C in each case over a period of 1 hour. In the first case a bright yellow VOCl3 product was formed; and in the second case a dark blue VC13 product.

The tests were repeated in the absence of carbon with no visible reaction, after which the temperature was increased by increments of 50°C and maintained at each increased temperature for a period of 3 0 minutes, up to a maximum temperature of 450°C. No visible reaction occurred whatsoever, indicating that the absence of the reducing environment provided by the carbon, at least as far as V205 is concerned, suppressed the side reactions leading to the production of V0C13 and VC13.

EXAMPLE 2 Complex titanium-containing starting materials, respectively the slag of Example 1 and ilmenite and carbon reductants in the form of coal and char, were crushed and milled to a maximum particle size of less than 53(j.m. The starting materials were then intimately mixed with the \ con 18 carbon reductants in the required proportions to provide starting mixtures.

Samples of various starting mixtures were respectively loaded into two graphite boats in an 5 electrically heated sealed horizontal tube furnace, the boats together containing five samples of 40g each.

The furnace was heated at a rate of 255°C/hr up to its operating temperature of 13 00°C with the 10 samples in place and the operating temperature was maintained during nitriding of the samples for 3 hours, followed by cooling of the furnace at the natural rate. A steady stream of nitrogen (>99% by volume purity) was caused to flow 15 through the furnace throughout the test.

Two starting mixtures were prepared in each case, one containing the stoichiometric proportion of carbon required to reduce the titanium values (as Ti02) in the starting material to titanium, and 20 one containing a 100% excess of carbon.

A sample of 40g of each of the four starting mixtures was placed in the boats and the samples were simultaneously nitrided as described above, using a nitrogen feed rate of 620 m£/minute. 2 5 The matrix reaction products obtained were characterised by X-ray diffraction and quantitative chemical analyses were carried out to determine the quantitative amounts of TiN produced. Titanium contents were determined by 3 0 fusion followed by atomic absorption spectrophotometry and nitrogen present was determined by chemical analysis. c. Q Q 19 The chemical compositions of the slag and ilmenite used are summarised in Table 3 hereunder; and the conversion percentages to TiN obtained are summarised in Table 4 hereunder.

In Figure 4 the same reference numerals are used for the same parts as in Figure 3. The reaction vessel 14 is an aluminosilicate tube and the tubes 16, 18 and 22 and flask 20 are of stainless steel. The graphite boats are shown at 28, and 10 heating elements are shown at 30. Stacks of porous aluminosilicate disc filters are shown at 26, which insulate the inlet and outlet to the reaction vessel 14, the heater 12 as a whole being lagged with insulating material.

TABLE 3 > Starting Material Constituent Titaniferrous Slag (mass %) Ilmenite (mass %) Ti02 , 5a 48,8 Si02 ,75 If 3 MgO 14,10 1,0 CaO 16,8 0, 04 ai2o3 13 , 65 0,7 Cr203 0,19 <0,01 FeO ,15 47,9 v2o3 1,05 0, 12 MnO 0,69 0,82 a Major forms: Fassaite (Ca (Ti, Mg, Al, ) (Si,Al)206) J Perovskite (CaTi03) Minor forms: Pseudobrookite (Fe203Ti02) ; Ulvosjsjkfel (Fe2Ti04). /V ? " ■ ■( / 239 070 TABLE 4 Starting Material Carbon Reductant Reductant Addition (% of stoichiometri c proportion) Conversion to TiN (% by mass) Slag Char 100 73,6 Slag Char 200 92,9 Slag Coal 100 73,8 Slag Coal 200 92,7 Ilmenite Char 100 72,9 Ilmenite Char 200 94,9 Ilmenite Coal 100 75, 8 Ilmenite Coal 200 91,6 Example 1 confirms that the process of the invention is feasible for use with the titaniferous slag obtained from Highveld Steel and Vanadium Corporation Limited. In particular, Figure 2 shows that the nitriding at 1550°C can be employed to nitride an acceptably high proportion of the titanium values present in the slag, with a high degree of selectivity. Table 2 further indicates that a chlorinated product can be obtained of TiCl4 containing only VC14 and/or VOCl3, SiCl4 and Cl2 as impurities, which can easily be separated from the TiCl4 by distillation, to obtain TiCl4 of a high degree of purity. This TiCl4 can easily be converted to Ti02, if required.

Example 2 shows that nitriding the slag in question, and ilmenite, is feasible at 1300°C, and that the use of a stoichiometric excess of nitrogen of 100% leads to high conversions to TiN of above 90% by mass. It is expected that optimization of temperature, proportion of reductant, reaction time, etc will lead to even better conversions. 239 0 71 21 It is a particular advantage of the invention that it provides a process, at least using the slag of the Example, for converting titaniferous slag to a valuable product, namely TiCl4/Ti02. Such slag, produced as a waste-product in steel and vanadium manufacture by Highveld Steel and Vanadium Corporation Limited, but its volume alone, is at least a potential environmental embarrassment. The process reduces the quantity of waste product which has to be dumped, and any wastes produced by the process of the present invention are ecologically acceptable and potentially useful to certain industries such as the cement industries. Furthermore, ores such as ilmenite, containing relatively low proportions of titanium values, can advantageously be used as starting materials for the process.

Claims (15)

22 What */we claim is ;

1. A process for the recovery of titanium values from a complex matrix comprising titanium nitride as a constituent thereof, the process comprising the steps of: reacting the titanium nitride in the matrix by chlorinating the titanium nitride in the matrix to obtain a reaction product containing titanium chloride; and separating the titanium chloride from the reaction product, the chlorinating of the titanium nitride being by contacting a chlorinating gas with the matrix at a temperature of 200-500°C, to obtain the titanium chloride as TiCl4.

2. A process as claimed in claim 1, which includes the step of obtaining the matrix containing titanium nitride by nitriding titanium values in a complex titanium-containing starting material.

3. A process as claimed in claim 2, in which the starting material is a complex metallurgical titaniferous slag containing at most 80% by mass titanium values.

4. A process as claimed in claim 2, in which the starting material is selected from the group of ores consisting of rutile, ilmenite, perovskite, armalcolite, fassaite and mixtures thereof.

5. A process as claimed in any one of claims 2-4, which includes the step, prior to the nitriding of the titanium values, of size reduction of the starting material to a maximum particle size of at most 2000 nm and an average particle size of at most 600 /xm.

6. A process as claimed in any one of claims 2-5, in which the nitriding of the titanium values is by contacting a stoichiometric excess of nitrogen gas with the starting material at an elevated temperature and in a reducing environment.

7. A process as claimed in claim 6, in which the contacting of the nitrogen gas with the starting material takes place at a t:enip.erature HOW AMENDED ^3J0,0 / / 23 / / of 1000 - 1800°C, in the presence of carbon which provides the / reducing environment, sufficient carbon being present/to consume a / oxygen present in the environment and to provide a' stoichiometric /' ' excess over that required to reduce the titanium values (as TiQ2) in 5 the starting material, to titanium. / / / 8. A process as claimed in claim 7, in which a carbona6eous fuel is burnt in air to provide a combustion gas which is contacted with the starting material to provide said elevated temperature, and to provide the carbon required for the reducing environment in the form 10 of carbon monoxide. ^ / / 9. A process as claimed in claim 7, which includes the step of admixing a carbonaceous material in finely divided particulate form with the starting material to/provide the reducing environment. / / / / 10. A process as claimed^in claim 9, which includes the step, after 15 the nitriding and before/the chlorinating, of separating carbon from the matrix. / / / S / 11. A process as ^claimed in any one of the preceding claims, in which the chlorinating of the/ titanium nitride is by contacting a chlorinating ga£ selected from the group consisting of Cl2, HC1, 20 CCl4, SC12 and mixtures thereof, with the titanium nitride at a temperature of 350 - 450°C, to obtain the titanium chloride as TiCl4. / t / / / / 12. A process as claimed in claim 11, in which the chlorinating gas is Cl2/being diluted with nitrogen to form a mixture comprising 20-80% by volume CI,/ / / / 25 13'. A process as claimed in any one of the preceding claims, in .which the matrix comprising the titanium nitride also contains a metal other than titanium, the process including the step, before the chlorinating, of separating the metal other than titanium from said matrix. ■I r:'\ y 12 OCT 1992" f AS AMENDED 23 9 0 23 of 1000-1800°, in the presence of carbon which provides the reducing environment, sufficient carbon being present to consume any oxygen present in the environment and to provide a stoichiometric excess over that required to reduce the titanium values (as Ti02) in the starting material, to titanium.

8. A process as claimed in claim 7, which includes the step of admixing a carbonaceous material in finely divided particulate form with the starting material to provide the reducing environment.

9. A process as claimed in claim 8, which includes the step, after the nitriding and before the chlorinating, of separating carbon from the matrix.

10. A process as claimed in claim 8 or claim 9, in which a carbonaceous fuel is burnt in air to provide a combustion gas which is in contact with the starting material to provide said elevated temperature, and to provide carbon monoxide to contribute to the reducing environment.

11. A process as claimed in any one of the preceding claims, in which the chlorinating of the titanium nitride is by contacting a chlorinating gas selected from the group consisting of Cl2, HCl, CC14, SC12 and mixtures thereof, with the titanium nitride at a temperature of 350 - 450°C, to obtain the titanium chloride as TiCl4.

12. A process as claimed in claim 11, in which the chlorinating gas is Cl2, being diluted with nitrogen to form a mixture comprising 20-80% by volume Cl2.

13. A process as claimed in any one of the preceding claims, in which the matrix comprising the titanium nitride also contains a metal other than titanium, the process including the step, before the chlorinating, of separating the metal other than titanium from said matrix. '• ■ / 3 ? 0 7 0 24

14. A process for the recovery of titanium values from a complex titanium-containing starting material, substantially as described herein.

15. Titanium values whenever recovered by a process as claimed in 5 any one of the preceding claims. ) o;: ' --ry? : 16ST-VVi"""