CHLORINATION OF TITANIUM ORES USING LIGNITIC REACTIVE CARBONS

Abstract: Improved process for the chlorination of particulate titaniferous ores using a particulate reactive carbon in a fluidized bed. The particulate reactive carbon is lignite char.

Description: CHL0RINATI0N OF TITANIUM ORES USING LIGNITIC REACTIVE CARBONS This invention relates to the separation of titanium values from vanadium values in mixtures of titanium and vanadium chlorides. BACKGROUND OF THE INVENTION Titaniferous materials are often subjected to chlorina¬ tion, as chlorination is an efficient and economical way to obtain a high purity titanium source for making titanium- alloys, titanium compounds, and especially pigmentary titanium dioxide. Several processes have been described in. the art for the, chlorination of titaniferous materials. Such processes generally react a titanium-containing raw material such as rutile or ilmenite ore, with a chlorine-providing material and a carbon-containing reductant according to one or both of the following equations: Ti0 2 +2Cl 2 (g)+C (s)— ► TiCl 4 (g)+C0 2 ( ) Ti0 2 +2Cl 2 (g)+2C(s)- TiCl 4 (g)+2C0 (g) Iron is a common impurity in titaniferous raw materials , and most chlorination processes are effective for simultaneously chlorinating the Ti and Fe values of these raw materials as shown in the fol¬ lowing reactions : 2FeTi0 3 +6Cl 2 (g)+3C(s) » 2TiCl 4 (g)+3C0 2 (g)+2FeCl 2 FeTi0 3 +3Cl 2 (g)+3C(s) TiCl 4 (g)+3C0 (g)+FeCl 2 O H Chlorination reactions are generally carried out at about 1000°C, but can. be carried out at any temperature in the range from about 400°C. to about 2000°C, using various carbon reductants and chlori¬ ne sources, including chlorine gas and chlorine-containing compounds. The titaniferous raw materials to be chlorinated can be preformed into briquets or the process can be conducted in a fluid bed using granular materials. When a fluid-bed process is used, generally the chlorine-providing material is supplied to the bottom of the bed and product titanium tetrachloride (TiCl 4 ) is removed from the top. Fluidization is generally controlled such that the bed remains fluidized and yet fine, solid particulate materials are not carried out with the product. Selective chlorination processes also exist and are designed to chlorinate only the Ti values or the Fe values of the raw material. A carbon reductant and a chlorine source are used and reaction temperatures are similar to non-selective processes. However, selective processes utilize a chlorine source consisting 3.t. least partially of iron chlorides, react the titaniferous raw materials in a dilute phase, react the titaniferous raw materials at a specially high temperature, or a combination of the above. Titanium raw materials such as rutile and ilmenite ores also usually contain vanadium compounds as impurities which ad¬ versely affect the titanium products produced. For example, pig¬ mentary TiO- can tolerate only about 10 ppm. vanadium in the ti- tanium tetrachloride from which the Ti0„ is made without discolora¬ tion. Removal of such impurities has heretofore been a complicated and burdensome process because of the similarity between the chemi¬ cal and physical characteristics of titanium compounds and vanadium compounds. For example, TiCl 4 melts at -25°C. and boils at 136. °C. and VC1 4 melts at -28°C. and boils at 148.5°C. This parallelism of properties permeates a comparison of the compounds of these two elements. Therefore, in the conventional chlorination process the vanadium values in a titaniferous raw material react in substan¬ tially the same manner as the titanium values, and their respective chlorinated products have nearly identical chemical and physical properties. Accordingly, it is extremely difficult to separate the undesirable chlorinated vanadium values from the desirable titanium values. Fractional distillation, for example, will remove most impurities from TiCl, , but is ineffective for removing vanadium impurities. Processes which are used commercially remove vanadium impurities from TiCl, by refluxing with copper, treating with H„S in the presence of a heavy metal soap, or treating with an alkali metal soap or oil to reduce vanadium impurities to a less volatile form. In each of these processes the treated TiCl is then sub¬ jected to a further distillation. However, the organic materials used tend to decompose and deposit sticky, adhering coatings on heat exchanger surfaces, pipes, and vessel walls. This causes shutdowns of the process and requires frequent maintenance of the equipment. In accordance with this invention, a simple, efficient, and economical process has now been discovered for separating the vanadium values from chlorinated titaniferous materials. The process of this invention utilizes a high sur ace area carbon for reacting with the titaniferous materials during the chlorination process. The use of the high surface area carbonaceous material causes the vanadium values present in the titaniferous material to be reduced to a less volatile form so that they can be easily removed as a solid from the gaseous or liquid TiCl product. One advantage of the present process is that it can be performed in existing equipment for the chlorination of titani¬ ferous material. Another advantage is that it employs economical raw materials. Still another advantage is that the CO value of the tail gas produced is sufficiently enhanced such that said tail gases will support combustion and can be burned to effect complete conversion to CO- and thus eliminate the pollution problem they previously created. These and other advantages will become more apparent in the "Detailed Description of the Invention". Another advantage of this invention is in the surprising beneficial effect of the kind of reactive carbon used in the fluid bed reaction. I have found that a lignite or brown coal char which is a reactive carbon, has an unusual characteristic in that the surface area of the char remains unchanged or actually increases during use providing still better combustibility of the tail gas than heretofore available. Also the greater the surface area of the carbonaceous material in the bed, the more efficient the chlori- ■ nation reaction. When treated anthracite is used in the conventional fluid-bed chlorination of a titaniferous ore, the carbon surface area decreases to a stable equilibrium value. Reactivity is directly related to surface area. If the "as prepared" surface area is high enough, the equilibrium surface area will also be high enough to obtain good chlorination results as shown in Table I below. If the initial surface area of the carbon is lower, the CO level will be lower, and the vanadium impurity level will be higher as shown in Table II below. If the vanadium level is greater than 10 pp , organic additives must be added to crude liquid TiCl 4 to assist in reducing the vanadium level below 10 ppm. TABLE I Using Steam Treated Anthracite 2 Surface Area 481 m /g Chlorination Time, hrs. 15.9 18.9 2 Bed Carbon Surface Area*, m /g 125 130 Average C0 2 /C0 Mole Ratio 0.03 0.02 Soluble V in Crude TiCl 4 , ppm 6 *Method A O H TABLE II Using Steam Treated Anthracite 2 Surface Area 160 m /g Chlorination Time, Hrs. 2.9 9.3 16.7 2 Bed Carbon Surface Area*, m /g 37 21 21 Average C0 2 /C0 Mole Ratio 0.04 0.05 0.11 Soluble V in Crude TiCl 4 , ppm 68 151 424 *Method A Conventional fluid-bed chlorinations have been made using various carbons. Normally, low surface area carbons such as petro¬ leum coke or bituminous coal char change very little in surface area during chlorination. Contrary to the teachings of my prior United States Patents 4,310,495 dated 12 January 1982 and 4,329,322 dated 11 May 1982, instead of using a "high rank" coal char, e.g., anthracite, according to the present invention, I was surprised by the unex¬ pected results that I got when a brown coal char was used. This material is derived from a low rank, lignitic ANSI/ASTM Class IV coal. The surface area of this carbon increased during chlorina¬ tion as shown in Table III. Although the char had an "as prepared" surface area of only 30% of the treated anthracite in Table I, the char gave better chlorination results. TABLE III Using Australian Brown Coal Char 2 Surface Area 147 m /g Chlorination Time, Hrs. 4.0 13.6 20.2 2 Bed Carbon Surface Area*, m /g 189 180 218 Average C0 2 /C0 Mole Ratio 0.005 0.010 0.014 Soluble V in Crude TiCl 4 , ppm <0.5 <0.5 ^0.5 * Method A Brown coal char is available in large quantitites in a size range suitable for fluid-bed chlorinators and at a cost that so far seems very attractive. The relationship between carbonaceous source and surface area changes during chlorination was investigated further. I tried another ANSI/ASTM Class IV lignite-based carbon. As shown in Table IV, the surface area of this carbon also increased during chlori¬ nation. Very high CO levels and low vanadium impurity levels were observed as would be expected from the high equilibrium surface area of the bed carbon. TABLE IV Using a Lignite-Based Carbon 2 Surface Area 625 /g Chlorination Time, Hrs. 3.0 10.9 15.0 27.5 Bed Carbon Surface Area *, 878 856 899 1005 m /g. Average C0 2 /C0 Mole Kc_.:io 0.003 0.002 0.002 0.002 Soluble V in Crude TiCl 4> 0.3 0.3 0.3 ^0.3 ppm. *Method A The chemical and physical properties of reactive carbons are summarized in Table V. TABLE V Steam-Treated Australian. Lignite- Anthracite Brown Coal Based #1 #2 Char Carbon %c 84.5 80.2 91.9 80.0 %H 0.7 0.5 0.9 0.8 %Ash 11.9 17.6 2.3 12.0 % Volatile 0.8 1.1 5.6 6.6 Matter Nominal U. S. Standard 6x50 6x50 8x35 12x20 Sieve Size 2 , * Surface Area, /g 160 481 147 625 *Method A The only change that this invention contemplates from the prior processes is in the carbonaceous material used. The disclosures of the foregoing U. S. Patents are representative of the processes in which the discovery hereof may be used. The best lignite or brown coal char of which I am aware for use in the processes of my prior patents is a brown coal char produced b-' Australian Char Pty. Ltd. and sold under the name "Auschar". The preferred char has the following typical properties: Physical Properties; Average size 0.5 to 2.3 mm Specific Gravity 1.2 Porosity = 33% - Bulk Density = 640 kg/m Proximate Analysis of Dry Char; Ash 2-3% Volatile Matter 2-5% Fixed Carbon 91-95% NOTE; Other sizings are available to meet specific process needs. Surface Area Measurement: (by CO '2, absorption at 0°C) about 750 m /g Ash Fusion Temperatures: In oxidizing atmosphere 1460°C. In reducing atmosphere 1400°C. Gross dry calorific value 7900 kilocalories/ kilogram Although Char is dry as it leaves the retort, it will pick up atmospheric moisture, and, after a time, may contain approximately 10% moisture. The figures quoted above are indicative of low volatile chars produced, and it should be noted that it is possible to vary the analysis to the extent of producing higher volatile materials when required. PROXIMATE ANALYSIS OF DRY CHAR (TYPICAL) Carbon a_ 94.5% Calcium _ 0.08% Hydrogen = . 1.1% Magnesium 0.24% Nitrogen 0.6% Aluminum = 0.06% Sulphur » 0.27% Silicon = 0.05% Iron 0.33% Sodium = 0.11% and traces of Chlorine, Sodium, Potassium, Phosphorous, Titanium and Copper tor details of raw lignite or brown coal, reference may be had to Kirk and Othmer "Encyclopedia of Chemical Technology", Third Edition, Vol. 14, pages 313-343. The chlorination processes of the present invention are to be distinguished from the post-chlorination vanadium removal treatment using activated carbon made from lignite disclosed in my U. S. Patent 4,279,871. In this process a high surface area acti¬ vated carbon made from lignite is entrained in the chlorinated gaseous product stream as it leaves the hot fluid bed. Vanadium impurity levels are vastly reduced by this treatment. In the present process, chlorination is done in a fluid bed composed of lignite or brown coal char and the ore. BRIEF STATEMENT OF THE INVENTION Briefly stated, the present invention is an improvement on prior procedures for chlorinating a titaniferous ore or slag, e.g., rutile, Brookite or ilmenite wherein a low rank lignite or brown coal char is used in place of the prior high rank or anthra¬ cite char. The lignite or brown coal char is utilized in a fluid bed and comingled with particulate -metalliferous ore, particularly a titaniferous ore, in the presence of a chlorinating agent, e.g., chlorine (which may be diluted with an inert gas, e.g., nitrogen). For such fluid bed operation said lignite or brown coal char as used in the processes hereof has a particle size in the range of about -6 mesh (U. S. Standard Screen Size) to about +140 mesh. The char is also characterized in that it initially has a microporous structure wherein from 30% to 95% of the surface area of the carbon is in micropores having a diameter of less than 20 Angstroms. Chlorination is carried out at a temperature in the range of 400° C. to 2000° C. or more specifically in the range of 800° C. to 2000°C, and particularly in the range of 1000°C. to 1600°C. until the metaliferous material is substantially chlorinated. Vanadium impurities contained in titaniferous ores can readily be removed _ substantially completely by a difference in extent of chlorination and consequent difference in boiling point which allows easy separa¬ tion (See U. S. Patent 4,329,322) of vanadium impurities by frac¬ tional condensation from the TiCl, . 4 DETAILED DESCRIPTION OF THE INVENTION As indicated above, this invention is an improvement in prior ore fluid bed chlorinating procedures wherein the high rank char is replaced with a low rank char. The processes with which the advantages of this invention may be realized include the fol- lowing: OMW 1. A low temperature chlorination process at from 400°C. to 800°C. in which a fluidized bed of ore and a porous carbon reductant having internal surface area due to pores of less than 20 Angstroms is reacted with a chlorine-containing gas. This process is disclosed in detail in my U. S. Patent 4,310,495. At the very low temperatures (^600°C.) N0C1 is used alone or with the gaseous chlorine. (See U. S. Patent 2,761,760). 2. A high temperature chlorination process at from 800°C. to 2000°C. in which a fluidized bed or ore and a porous carbon reductant having an internal surface area of at least about 2 2 100 /gtα. of which at least about 10 m /gm. is in micropores having a pore diameter of less than 20 Angstroms is reacted with a chlorine-containing gas. This process is disclosed in my U. S. Patent 4,329,322. Chlorinations were made in a fused quartz fluid-bed reactor of 3 inch outside diameter, which had a porous quartz disc as a gas distributor. The reactor was held at a constant 1000°C. by an electrical furnace around the reactio-. zote. The hot offgas from the fluid bed passed through a cyclone separator held at about 175°C, where most entrained solids were removed. The offgas was further cooled by water-cooled and refrigerated condensers where essentially all remaining condensable vapors (mainly TiCl 4 ) were removed from CO-, CO, and N„, which were discharged to the atmos¬ phere. mixture of carbon and -40 mesh rutile ore was initially charged into the reactor to give a 1 ft. static bed containing 32 wt % carbon. As the mass of the bed decreased due to the chlori¬ nation reaction, fresh carbon and ore were fed continuously to maintain a fairly constant bed mass. The bed mass was so controlled by adjusting the feed rate to maintain the measured pressure drop across the fluid bed constant. The carbon/ore ratio in the bed was held constant by adjusting the carbon/ore ratio in the feed to the carbon/ore ratio being consumed by chlorination. The consumed carbon/ore ratio was calculated from a C0„ and CO analysis of the chlorinator offgas. A mixture of 75 vol % C + 25 vol % N 2 was metered to the reactor at a rate to provide a superficial fluidization velocity of 0.4 feet per second corrected for temperature and pressure. The of gas was analyzed about every 20 minutes for CO-, CO, and N« by gas chromatograph . At regular intervals, the reactor was shut down and allowed to cool. Samples of the +40 mesh bed-material (carbon fraction) were then taken for surface area determination. Solids (which bypassed the cyclone due to its inefficiency) in the crude TiCl were allowed to settle and a sample of the clear supernatant TiCl 4 was taken for vanadium analysis. Surface areas were determined using two commercially available instruments. A Perkin-Elraer Shell Sorpto eter Model 212B was used for rapid surface area determinations (Method A) . A Digisorb 2500 Automatic Multi-gas Surface Area and Pore Volume Analyzer (Micromeritics Instrument Corp., Norcross, Georgia) was used for detailed surface texture studies (Method B) . I do not know why reactive carbons derived from Class I coals decrease in surface area and reactivity during chlorination, whereas carbons from Class IV coals (lignite or brown coal) do not show this decrease. Neither chemical composition, detailed surface texture analyses by Method B, nor X-ray diffraction reveals any property differences that could account for the difference in surface area stability. There are differences in the structure of the carbon atom network, both in microscopic localized areas, and in the boundaries and interfaces between petrographic components ( acerals) . These differences in structure could influence the rate of pore closure and pore formation. Petrography of Class I and IV coals shows them to be quite different. It is therefore reasonable to expect carbons derived from these two classes of coal to be different in this respect also. Brown coal char has a surface texture quite similar to the treated anthracites. Treated anthracite carbons have most of their surface area within micropores of 20 A diameter or less. The maximum pore diameter in these carbons is in the 20-60 A range. The carbon derived from lignite coal differs from the other carbons in surface texture. Most of the surface is within o pores that are greater than 20 A in diameter, and the maximum pore α diameter is 450 A. Analysis of treated anthracite samples taken from equili¬ brium chlorinator beds shows that the surface area has decreased by 70 to 85% and that the microporosity has nearly disappeared. In the lignitic carbons, the microporosity remains rela¬ tively stable as the carbon is consumed during chlorination, and o there is a relatively large increase in pores greater than 20 A in diameter. A summary of surface texture data is given in Table VI. Although lignitic carbons can have a surface texture that is similar or different when compared to anthracitic carbons, the surface texture of lignitic carbons changes during chlorination in a way distinct from anthracitic carbons. TABLE VI* Steam-Treated Australian Lignite- Anthracite Brown Coal Based #1 #2 Char Carbon A. As Prepared -s Surface Area, m /g . m O in < » 20 A pores 215 302 312 206 in 20-600 A pores 10 124 22 382 Total 225 426 334 589 Largest pores, A dia. 26 52 40 450 B. Carbon from Chlorinator Bed Surface Area, m /g in < 20 A. pores 17 45 271 275 ø in 20-600 A pores 19 83 61 768 Total 36 128 332 1043 Largest pores, A dia. 50 70 50 220 Surface Area Change, % -84. -70 0. +77. *A11 data via Method B

Claims: WHAT IS CLAIMED IS: 1. In a process for chlorinating a titaniferous material to form TiCl 4 wherein discrete particles of titaniferous material and discrete particles of porous carbon reductant having a particle size in the range of about -6 mesh +140 mesh characterized in that it has micropores therein having a pore diameter of less than about 20 Angstroms are fluidized and contacted with a chlorine providing material at a temperature of from 400°C. to 2000°C. until the titanium content of the titaniferous material is substantially chlorinated, the improvement which comprises utilizing as the porous carbon reductant a brown coal char or lignite based carbon characterized by a particle size in the range of about -6 mesh +140 mesh and having initially micropores therein having a pore diameter of about 20 Angstroms to the extent of from about 30% to about 95% of the total surface area of the carbon In said porous carbon reductant, whereby vanadium values are substantially removed from the TiCl.. 4 2. A process as defined in Claim 1 wherein the tempera¬ ture is from 400°C. to 800°C. 3. A process as defined in Claim 1 wherein the tempera- ture is from 800°C. to 2000°C. 4. A process as defined in Claim 1 wherein the tempera¬ ture is from 1000°C. to 1600°C. 5. A process as defined in Claim 1 wherein the porous carbon reductant has an internal surface area of at least about 100 M 2 /gm. 6. A process as defined in Claim 5 wherein at least 2 about 10 m /gram of the internal surface area is in micropores having a pore diameter of about 20 Angstroms or less.

Inventors: BONSACK JAMES P, BONSACK, JAMES, P.
Applicants: SCM CORP, SCM CORPORATION
Application year: 1983
Main classification: C01G23
IPC codes: C22B34