PROCESS FOR PARTIAL OXIDATION OF FECL2 TO FECL3

Abstract: There is provided a process for the partial oxidation of solid ferrous chloride in the presence of carbon with mole­ cular oxygen in counter-current flow at 350°C. to 675°C., to produce ferric oxide and ferric chloride vapor without producing elemental chlorine.

Description: PROCESS FOR PARTIAL OXIDATION OF FeC12 TO FeC13 This invention relates to a process for partial oxidation of solid ferrous chloride to ferric chloride. This process has particular utility as a step in a process for making TiC14 in plural stages in one of which FeC12 is a by-product of fluidized bed chlorination of ilmenite and the second of which FeC12 is a by-product of a dilute phase process for chlorinating ilmenite using Fecal3 as the chlorinating agent. Such a process utilizes substantially all the chlorine to produce TiC14 and converts the iron in the ilmenite into a readily disposible form of iron oxide. The benefits of a packed bed reactor include greater efficiency over a fluidized system because residual oxygen as it moves through the bed contacts only fresh Fed2 feed unlike the fluidized bed system where oxygen is always in contact with relatively more product Fe203 than Fed2 reactant. The present process allows product Fe2O3 to be discharged continuously without having fresh FeCl2 feed mixed with it. BACKGROUND OF THE INVENTION AND PRIOR ART Conversion of the titanium values in various titaniferous ores has been accomplished heretofore mainly by chlorination of an ore/carbon mixture under fluidized bed conditions. Usually, the chlorination agent has been elemental chlorine. By-product iron chlorides from titaniferous ores containing iron pose a problem in disposal and waste valuable chlorine. Previously chlorine values in by-product iron chlorides have been recovered by full oxidation thereof with air or oxygen to Fe2O3 and Cl2. In the present process, advantages are obtained by partial oxidation of the iron chloride as distinct from the complete oxidation contemplated in prior efforts. Instead of a single stage chlorination to produce TiC14 as most often practiced heretofore, the present invention lends itself well to a two stage process. In the first stage, a major part of the ore to be processed is chlorinated in a conventional fluidized bed reactor yielding TiCl4 and iron chloride, mainly FeC12. A second smaller portion of the ore is ground (-325 mesh) and chlorinated in an entrained flow reactor with FeCl3 vapor. The process is successful because the chlorine values are readily recovered by partial oxidation of the Fecal2 to FeC13 and Fe203. There is a large amount of prior art directed to the oxidation of Fecal2 or FeCl3 to C12 that attempts to solve problems inherent in this reaction. The main problem with the full oxidation of FeCl2 or FeCl3 to C12 is that at low temperatures where the thermodynamics are favorable, the reaction is slow. At higher temperatures where the reaction proceeds at a practical rate, the tbo=nenue & are unfavorable and the reaction is far from complete. To overcome this problem, Dunn U.S. Patent 3,887,694 and 3,376,112 and Bonsack U.S. Patent 3,944,647 and 3,919,400 taught the use of catalysts to speed up the reaction at lower temperatures where the thermodynamics are more favorable. Dunn U.S. Patent 3,865,920 and Bonsack U.S. Patent 4,094,854 also suggest systems operating at higher temperatures where unreacted FeC13 is separated and recycled back to the oxidation zone. Dunn U.S. Patent 3,865,920 also suggests the use of a very long "flue pipe" on the oxidation zone discharge that is held at a lower temperature. Another severe problem with FeC12 or Fecal3 oxidation to C12 is the formation of hard, dense Fe203 deposits on the inner walls especially near the oxidation zone discharge. Attempts to solve this problem were the subjects of U.S. Patents to Sawyer 2,642,339; Nelson, 3,050,365 and 3,092,456; Reeves, 3,793,444; and Mitsubishi, 4,073,874. Nelson 3,092,456 introduces carbon in the discharge line of the oxidizer. I have found it to be essential to have carbon in the reaction zone itself. In Nelson's process the reaction is essentially complete. Moreover, Nelson is oxidizing iron chloride to chlorine in a gas-gas reaction rather than a gas-solid reaction as I use. The following is a more detailed review of prior art in this field: U.S. Patent 2,642,339 to Sawyer teaches a process for oxidizing iron halides to produce iron oxide and chlorine comprising reacting ferric chloride with dry air in the vapor phase at a temperature of from 600 to 8000C. in a vertical reaction zone containing a bed of finely divided catalytic iron oxide under conditions that prevent substantial be'ill up of reaction product on the inner surfaces of the reactor. U.S. Patent 2,657,976 to Rowe et al show a process for producing iron oxide and titanium tetrachloride from titaniferous iron ores. According to this process, the titanium ore containing iron is subdivided, mixed with carbon and placed in a chamber. Chlorine and moist air are introduced into the chamber to produce at an elevated temperature volatile ferric chloride substantially free from titanium tetrachloride. The amount of chlorine added is the theoretical amount required to react with the iron values but not with the titanium values. Moist air is also added. Ferric chloride is volatilized and separated from the titanium concentrate, and the ferric chloride reacted immediately with oxygen to produce ferric oxide and chlorine gas. The ferric oxide and chlorine so produced are separated and the chlorine returned to react with the titanium values in the concentrate to produce titanium tetrachloride. These reactions take place in a divided reactor. U.S. Patent 3,376,112 to Dunn et al relates to a process for flowing a molten metal salt complex of the formula XFeCl4 where X is an alkali metal as a thin film over a moving bed of particulate inert material concurrently with an oxygen containing gas and recovering chlorine as a product. U.S. Patent 3,495,936 to Jones discloses a dilute phase chlorination process for titaniferous ores. Here the ores reacted with chlorine and a carbonaceous reducing agent in a dilute phase reactor system to yield metal chloride products, chiefly titanium tetrachloride. U.S. Patent 3,683,590 to Dunn teaches a process for condensing iron chlorides from a gaseous stream in two steps, the first step being the cooling of the gases to about 6750C. to condense ferrous chloride as a liquid and leaving a gaseous ferrous residual and then in a second step of adding chlorine gas and sodium chloride salt separately wherein the remaining FeC12 is oxidized to FeC13 which with the initial FeC13 is converted to NaFeC14 and cooling that product to a temperature above 1590C. This process is useful for recovering iron chlorides from gaseous effluent to minimize air pollution. U.S. Patent 3,865,920 to Dunn teaches that chlorine and iron oxide are produced by the oxidation of iron chlorides and mixtures thereof, produced in the chloride process for beneficiating titaniferous ores, by injecting oxygen in the gas space above the fluidized bed. U.S. Patent 3,925,057 to Fukushima et al teaches a process for recycling chlorine gas in the selective chlorination treatment of iron oxide ores containing titanium for the purpose of obtaining ores enriched with TiO2. Here the chlorine gas introduced into the chlorination reaction is converted to ferric chloride by reaction with the iron oxide. The ferric chloride is reconverted to free chlorine by reaction with oxygen in an oxidation process, and the isolated chlorine returned to the chlorination step. U.S. Patent 3,926,614 to Glaeser teaches a process for the selective chlorination of the iron constituent of titaniferous ores using FeC13 as the chlorinating agent and using a solid carbonaceous reductant. The FeC13 can be produced by oxidizing the FeC12 resulting from the selective chlorination thereby providing for a recycled operation. U.S. Patent 4,046,853 to Robinson teaches the simultaneous chlorination of the iron and titanium values in an iron-containing titaniferous ores such as ilmenite. Here, the ilmenite is converted to ferrous chloride, but the resulting gaseous effluent is difficult to process to recover the titanium tetrachloride. The iron values in the effluent are partially oxidized to Fe203 and FeC13 thereby reducing the partial pressure of the ferrous chloride while maintaining the presence of some ferrous chloride to scavenge any chlorine emitted from the chlorination stage. The residual gaseous iron chlorides are condensed and chlorine free titanium tetrachloride may be recovered from the remaining gases. U.S. Patent 4,055,621 to Okudaira teaches a process for obtaining chlorine from iron chloride by adding iron oxide to iron chloride prepared by chlorinating iron-containing titanium ore, in an amount above 10% by weight of the resulting mixture, charging the mixture in solid phase into a fluidizing roasting furnace for oxidation, any overflow being oxidized in a second reactor. The iron oxide thus obtained is recycled to the primary reactor for controlling the reaction temperature in the furnace. U.S. Patent 4,140,746 to Turner et al relates to the recovery of chlorine values from iron chloride produced from the chlorination of titaniferous material containing iron and particularly from the carbochlorination of ilmenite which, for example, can be the first stage in the so-called chloride route to form titanium dioxide pigment. The iron chloride which may be ferric chloride or ferrous chloride is subjected to a combination of reduction and oxidation reactions. In the reduction reaction, ferric chloride is dechlorinated to ferrous chloride by a reducing agent suitable for producing a chloride compound for recycle to the chlorination process. In the oxidation reaction ferrous chloride is oxidized to ferric oxide and ferric chloride, ferric chloride being recycled to the reduction reaction. By this method the chlorine values are recovered from the by-product iron chloride by a route which avoids the difficult reaction between ferric chloride and oxygen to produce chlorine and ferric oxide. U.S. Patent 4,174,381 to Reeves et al teaches an improved process and an apparatus for producing chlorine and iron oxide in a multistage recirculating fluidized bed reactor wherein ferric chloride in the vapor phase is reacted with an excess of oxygen at temperatures of from 550 to 8000C. The improvement comprises utilizing a reactor that includes an initial "dense" zone and a downstream "dilute zone". In the dense zone, a fuel is burned, reactants and recirculated iron oxide particles are heated, ferric chloride is vaporized and at least 50% of the ferric chloride is converted to chlorine and iron oxide. In the downstream dilute zone, the conversion of ferric chloride is continued to greater than 95% completion. European Patent publication 5054 discloses a process for the preparation of micaceous iron oxide which comprises reacting ferrous chloride substantially free from disruptive impurities, such as carbon, with oxygen at a temperature of 300 to 12000C. The process can be carried out in a fluidized bed and it can form a part of a process for the recovery of chlorine values from iron chloride. The presence of carbon gives a nonmicaceous iron oxide. Also a fluid bed reactor has disadvantages in that Fe2O3 cannot be discharged continuously as in a packed bed system, without entraining unreacted FeC12. This is because a fluid bed regime is a perfectly mixed reactor which makes separation of fresh feed and product impossible. The product of the present invention is nonmicaceous iron oxide. As can be seen from the prior art above, in various methods for chlorinating titaniferous materials, e.g., ilmenite rutile, and titaniferous slags, to produce TiC14 and iron chlorides, chlorine is generally the chlorinating agent, and chlorine is recovered from iron chlorides by oxidation to C12 and Fe203. In the TiC14 process where the partial oxidation reaction of the present case is especially advantageous, the charge of titaniferous material is divided into two portions, each of which is treated differently. The first is chlorinated by any conventional process using chlorine or a chlorine rich gas as the chlorinating agent to yield Fed2 or Fecal3 or a mixture thereof, and TiC14. A second smaller portion is chlorinated to TiC14 and Fecal2 in an entrained flow reactor with FeCl3 from the partial oxidation step as described herein, where by-product Fed4 is oxidized to FeC13 and Fe2O3. In such process, all chlorine values are utilized in the production of TiC14 or a valuable chlorinating agent, FeC13, and easily disposed of Fe2O3. The present invention provides, therefore, an improved process for producing FeCl3 by partial oxidation of Fecal2 to yield Fe203 and FeC13. Problems attendant disposal of by-products such as FeC12 or FeC13 are avoided. BRIEF STATEMENT OF THE INVENTION Briefly stated, the present invention is a process for the partial oxidation of ferrous chloride to ferric chloride and ferric oxide (Fe2O3, hematite) with oxygen which comprises: (a) establishing and maintaining at a temperature of 3500C. to 6750C. in a vertical tubular reaction zone, a downwardly moving packed bed containing solid ferrous chloride and carbon; (b) flowing a molecular oxygen-containing gas upwardly through said bed at a rate sufficient provide a contact time of at least one second; (c) feeding to the upper end of said bed particulate ferrous chloride and carbon; (d) the oxygen in passing upwardly through the bed being completely reacted such that, for example, one mole of oxygen reacts with four moles of FeC12 to yield 0.667 mole of Fe203 and 2.667 moles of FeC13 vapor, and one additional mole of oxygen reacts with each mole of carbon present to form gaseous carbon oxides; (e) collecting and removing ferric oxide from the lower end of the bed, and (f) recovering ferric chloride vapor and carbon oxides from the upper end of said tubular reaction zone. Better results are obtained when a reactive or porous carbon is used. BRIEF DESCRIPTION OF THE DRAWINGS The invention may be understood by having reference to the annexed drawing wherein: Figure 1 shows in diagrammatic and schematic form an apparatus in which the partial oxidation reaction of the present invention may be carried out. Figure 2 is a drawing illustrating in diagrammatic form an integrated TiCl4 process, which incorporates the oxidation process hereof where Fecal2 is produced in both the primary and secondary chlorinators as a part thereof. DETAILED DESCRIPTION OF THE INVENTION The present invention is illustrated in Figure,2 as a part of a two stage process for producing TiC14. It is convenient, therefore, to discuss such a process wherein the present process may be used. Although a common method in the art of making TiC14 involves chlorination of an iron-containing titaniferous material in a single reactor (fluid bed, entrained flow, or other type) with C12 or a mixture of gases including C12, the illustrated process is distinguished from prior efforts in that chlorination of a predetermined amount of ore is done in two stages: (a) 60-90% of the ore necessary by stoichiometry being chlorinated by a conventional process with C12 as the sole or primary chlorinating agent; and (b) 10-40% of the ore being chlorinated in a second isolated entrained flow reactor with FeC13 vapor as the chlorination agent. The exact amounts of ore chlorinated in the primary and secondary chlorinators are dependent on the Fe/Ti ratio in the feed stock as shown in Figure 4 in copending application Serial No.: filed (Docket No.: 30,023-1 entitled "Two Stage Chlorination of Titaniferous Ore with FeC13 Reclamation"). The FeC13 which is the chlorinating agent in the secondary chlorinator is produced by partial oxidation of FeC12 to FeC13 and Fe2O3. The iron in the iron-containing titaniferous material is recovered as readily disposable material (Fe203). Representative equations are: First Stage Chlorination (I) 2FeTiO3 + 6C12 + 3C+2TiC14 + 3CO2 + 2FeC12 (II) 2FeTiO3 + 6C12 + 6C+2TiC14 + 6CO + 2FeC12 Second Stage Chlorination (III) 2FeTiO3 + 12FeC13 + 3C > 2TiC14 + 3CO2 + 14 FeCl2 (IV) FeTiO3 + 6FeCl3 + 3C)TiC14 + 3CO + 7FeCl2 Ferrous Chloride Oxidation (V) 12FeC12 + 302- > 2Fe2O3 + 8FeCl3 Figure 1 shows in diagrammatic and schematic form a reactor in which the partial oxidation of <RTI ID=9.21> FeC12 is carried out in the presence of carbon. Thus, there is provided a tubular reactor 10 having suitable refractory insulation 11 and a gas outlet 12 from the upper end and a solid Fe203 outlet 14 fitted with a suitable valve 16. Spaced upwardly from the valve 16 and near the lower end of the reactor 10 is an oxygen distribution inlet ring 18 for admitting oxygen in counter-current relation to downwardly moving FeC12. Solid Fecal2 is introduced into the side of reactor 10 at an inlet port 20 near the upper end of the reactor 10 where it is allowed to fall to the upper end of the bed of solids. In the embodiment illustrated in Figure 1, the Fecal2 and carbon are derived from a TiC14 stream containing solid Fecal2 dust and carbon dust blow-over, which enters a solid-gas separator 22, e.g., a cyclone separator. The solid FeC12 and carbon enter the reactor 10 at the inlet port 20. The interior of the reactor contains three ill-defined zones (a) an upper zone composed mainly of fresh FeC12 and carbon; (b) an intermediate zone of mixed Fecal2 and Fe2O3 and carbon and (c) a lower zone composed mainly of Fe203 settling into the lower end 19 of the reactor 10. In the reactor 10, it is preferable to maintain a large excess of Fecal2 solids relative to the oxygen gas. The gas velocity is such that it fails to generate a fluidized bed regime for the particle diameter of the FeCl2, which is generally smaller than about 100 microns as recovered from a TiC14 process. The bed of mixed gas and solid particles can be described as a loose assembly of particles which are not fluidized and which flow by gravity in response to opening valve 16. The final Fe203 particle is smaller than the original FeC12 particle, being for the most part less than 30 microns in diameter. Some accumulation of Fe203 in the lower section of the reactor 10 is beneficial to preheat the oxygen. Desirably the temperature in the reactor is in the range of 3500C. to 6750C. and preferably 5250C. to 6000C. The partial oxidation of FeCl2 is desirably carried out in the presence of carbon particles. This carbon can be chlorinator blow-over dust which accompanys FeC12, or it can be separately added, or a combination of the two. In the oxygen atmosphere, the carbon burns to CO2 or a mixture of CO2 and CO to provide an internal source of heat in the reaction zone as illustrated below. This becomes essential in commercial scale apparatus where it is difficult to provide heat to this endothermic reaction from an external heater. The amount of carbon is that which maintains the reaction temperature within the desired temperature range and will vary, of course, with the scale of the equipment. Referring more particularly to Figure 2, there is here shown in diagrammatic and schematic form a process flow sheet for one mode of utilizing the present invention. The numerical values associated with the compounds are in moles. Australian ilmenite ore is the iron-containing titaniferous ore used in the illustrated process. Typically, it has an analysis corresponding to the empirical formula FeO 56TiO2 8. This Australian ore, which is obtained as a sand size material (-40 +140 mesh as mined) is divided into two parts. A 0.78 mole portion is introduced into a conventional fluidized bed reactor 30 from the top along with -6 +40 mesh, U.S. Standard petroleum coke (coal, preferably anthracite or brown coal may be used as well). A two mole portion of chlorine gas is introduced at the bottom of the reactor 30 and the rate adjusted for fluidization and complete nonselective chlorination of the metal values in the ore. The reaction temperature is 800-11000C., e.g., 10000C. The vaporous reaction products are discharged through line 32 and contain 0.78 mole of TiC14 vapor, 0.44 mole of Fecal2 vapor, and 1.1 moles of carbon oxides (as CO2) from primary chlorinator 30. The balance of the ore (0.22 mole portion) is ground to an average particle size of from 10 microns to 40 microns and along with powdered carbon of similar size is introduced into a downwardly directed entrained flow reactor 44 as a secondary reactor for chlorination with FeCl3 vapor from the following oxidation step. Advantageously, the added carbon here is a reactive (porous) carbon added in slight excess over stoichiometric. (See U.S. Patent 4,329,322 for discussion of useful porous carbons, particularly these having a particle size less than 100 microns and a specific surface area of greater than 10 m2/g.). This entrained flow (EFC) operation results in the production of a 0.22 mole portion of TiC14, a 1.24 mole portion of FeC12 vapor and carbon oxides. The gaseous efflux 46 from chlorinator 44 is combined with gaseous efflux 32 from chlorinator 30 at point 34 and quenched with a spray of liquid TiC14 36 to a temperature of about 500-6000C. which causes the FeC12 to "snow out" of the gas stream. The solid Fed2 and carbon dust blow-over from chlorinator 30 plus excess carbon used in chlorinator 44 and gaseous phases, which contain one mole of newly formed TiC14 and 1.4 moles of carbon oxides as CO2 are separated in a suitable cyclone separator 38. The FeC12, 0.44 mole from primary chlorinator 30 and 1.24 mole from secondary chlorinator 44 is then introduced into an oxidizer 40 where it is partially oxidized ("partial" in that the oxygen is limited so that complete oxidation to C12 is not accomplished). An apparatus suitable for use in partially oxidizing FeC12 and FeCl3 and Fe2O3 is shown in Figure 1. This partial oxidation yields a 0.28 mole portion of Fe2O3 and a 1.12 mole portion of FeC13. Molecular oxygen or air is introduced into the bottom of a suitable reactor 40, to effect the oxidation according to the equation: 12FeC12 + 30, / 8FeCl3 + 2Fe203 In this oxidation step, only that amount of O, 2 is used to yield Fe203 and FeCl3 vapor plus that required to burn carbon to CO2 and CO. This is in contrast to most prior art processes which attempt to force the oxidation to completion to yield C12 and Fe2O3. FeCl2 oxidation is relatively fast around 6000C. whereas FeCl3 and Fe2C16 oxidation is slow. From the data below it was calculated that the reaction of oxygen with FeCl2 goes essentially to completion at 6000C. in as little as 2.4 seconds. Thermodynamic calculations indicate that FeC12 oxidation is quite favorable in the 350-6500C. range; that is, the reaction goes essentially to completion in this range. Thermodynamic calculations also indicate that the ferric chloride vapor produced by the oxidation reaction is mainly dimeric (Fe2C16) rather than monomeric (FeCl3). At 6000C., 80 mole percent of the Fe(III) exists as dimer; at 4000 it is about 98%. So the more correctly written oxidation equation should be: l2Fecl2(s) + 30 EMI13.1 4Fe2C16(v) + 2Fe2O3 with only a minor contribution from: l2Fecl2(s) + 302 EMI13.2 8FeCl3(v) + 2Fe2O3. Exemplary oxidation reactions were carried-out in a vertical quartz reactor tube 122 mm in length, about 20 mm ID, with a gas inlet at the bottom and a gas outlet at the top. The reactor tube was held at the desired temperature along 60 mm of its length by an electrical resistance heater. A bed of coarse silica sand was placed in the bottom of the reactor tube to support a bed of FeC12 powder in the 60 mm hot zone. FeCl2 powder (175 um av. dia.) was poured into the reactor tube, while flowing 1000 cm3/min. of N2 up through the tube, to give an FeCl2 bed about 28 mm in height containing from 2.0 to 2.3 grams FeC12 per mm of height. The reactor was heated to the desired temperature with the N2 flow on. After reaching the desired temperature, the N2 flow was stopped, a Teflon gas collection bag was attached to the top reactor gas outlet, and O2 was emitted. After the amount of O2 needed to react with 15 to 17 grams of FeCl2 (equivalent to about 7.6 mm of bed height) was added, the O2 flow was stopped and N2 at the same flow rate as O2 was started. The N2 flow was stopped after a sufficient amount was added to purge unreacted O2 and any C12 into the gas collection bag. The contents of the gas collection bag were analyzed for percent N2, 02, and C12 (and CO and CO2 when carbon was present) by gas chromatography. From these results and the volume of N2 metered to the Teflon bag, the volumes of O2 and C12 (and CO and CO2 when carbon was present) were calculated. After calculating the actual amount of Fecal2 reacted, this quantity of fresh FeC12 powder was added to the top of the Fecal2 bed with N2 flowing as before. Another 15 to 17 g Fecal2 was reacted and the procedure was repeated. As Fe203 built-up in the lower section of the FeC12 bed, the reactor tube was lowered through the heater to keep the bed of unreacted FeCl2 in the heated zone. Fe2C16 vapor condensed in the cool section of the reactor tube between the heater and the gas collection bag. This was removed occasionally to prevent pluggage of the tube. After 2 to 3 bed displacements (120 to 200 g FeCl2) had been reacted (and added) the experiment was stopped. The results from each added portion of FeC12 was then averaged. The average FeC12 bed height was 24 mm. The average superficial O2 contact time was 2.4 seconds in Examples 1-3 and 4.8 seconds in Examples 4 and 5. EXAMPLE 1 In this run, the reaction was carried out at 4900C. Conditions and results are given in Table I. EXAMPLE 2 In this run, the reaction was carried-out at 5250C. Conditions and results are given in Table I. EXAMPLE 3 In this run, the reaction was carried-out at 6000C. Conditions and results are given in Table I. EXAMPLE 4 In this run, which is the best mode presently known to me for carrying out my invention, carbon is added to the charge of Fecal2 and the reaction carried out at 6000C. One mole of carbon was mixed with each eight moles of FeC12. Conditions and results are given in Table I. The carbon used in this Example 4 was a porous brown coal (lignite) char having a particle size less than 75 microns and a specific surface area of 370 m2/g. (See U.S. Patent 4,329,322). EXAMPLE 5 In this run, the conditions were the same as in Example 4 except that carbon was omitted. The Examples illustrate a packed bed of FeC12 particles that move downwardly against a countercurrent flow of 02. In a practical operating system, Fe203 powder is continuously discharged at the bottom of the oxidizer, as by a star valve. The average particle size of a dull, dark gray, nonlusterous Foe203 powder was approximately 10 microns. Fecal3 flows out of the oxidizer as a vapor. If examples 1, 2 and 3 are compared, it is seen that the reaction of O2 with FeC12 is essentially complete at the higher temperatures. Comparing Examples 4 and 5 in Table I, it is seen that the presence of carbon in Example 4 reduced the amount of oxygen reacting with Fe2C16 from 2.4 to 0.16% and reduced the amount of unreacted oxygen from 0.5 to 0.02%. These results show that the O2/FeC12 reaction is fast and that the reaction of oxygen is selective for FeC12 rather than FeC13. The oxidation step of Fecal2 to Fecal3 of the ilmenite chlorination process of application Serial No.: 638,977 is not limited to downwardly moving packed bed type reactors. Other reactor types are also useful. The use of a packed bed type system in the Examples serves to illustrate the present invention and the achievable efficiency of the O2/FeC12 reaction when a large excess of FeC12 over O2 is present in the oxidation reactor. While this process has been described in conjunction with a dual stage process for making TiC14, it will be understood that the process may be used independently, if desired, to make FeCl3 from FeC12, or to make finely divided Fe203 or nonmicaceous hematite. TABLE I Example No. 1 2 3 4 5 Temperature OC. 490 525 600 600 600 Reactor ID cm 2.25 2.25 1.93 2.25 2.25 3 O Flow cm Rate per min. 920 882 598 404 404 Flow Time seods 53 53 72 202 135 Total Volume O2 cm 810 787 712 1350 911 3 N2 Flow cm Rate per min. 920 882 598 404 404 Flow Time second 211 214 179 309 310 Total Volume N cm 3239 3146 1779 2082 2087 AV. Vol. % N2 94.6 98.2 99.0 81.5 97.7 AV. Vol. % 2 3.9 0.61 0.11 0.01 0.21 AV. Vol. % C12 0.34 0.51 0.84 0.17 2.1 AV. Vol. % CO 3.6 AV. Vol. % CO2 14.6 AV. Volume O2 cm 134.0 19.9 2.2 0.3 4.5 AV. Volume C12 om 11.3 16.3 15.1 4.4 43.8 3 AV. Volume CO cm 90.0 3 AV. Volume CO2 cm 380.0 TABLE I con't Example No. 1 2 3 4 5 % 2 Reacting with Fe2Cl6 a 0.7 1.0 1.1 0.16 2.4 % O2 Not Reacting 16.5 2.5 0.30 0.02 0.5 % 2 Reacting with FeCl2 b 82.8 96.5 98.6 68.3 97.1 % 2 Reacting with Carbon 31.5 a Each 2 moles C12 found required one mole of O2 according to 2Fe2C16 + 302-- > 6C12 + 2Fe203 b By difference.

Claims: CLAIMS 1. A process for the partial oxidation of solid ferrous chloride to ferric chloride and ferric oxide with oxygen in a gas/solid reaction characterized by: (a) establishing and maintaining at a temperature of from 3500C. to 6750C. in a reaction zone, a downwardly moving packed bed containing solid ferrous chloride and carbon; (b) flowing a molecular oxygen-containing gas upwardly through said bed at a rate sufficient to provide a contact time of at least one second; (c) feeding the upper portion of said bed with particulate ferrous chloride in a proportion to provide 4 moles of ferrous chloride for each mole of molecular oxygen to be reacted therewith, the molecular oxygen being in an amount such that the amount over the stoichiometric amount for partial oxidation of FeC12 is consumed in the oxidation of a solid carbonaceous material; (d) collecting and removing a ferric oxide from the lower end of the reaction zone; and (e) recovering ferric chloride vapor and carbon oxides from the upper end of the reaction zone. 2. A process as defined in claim 1, wherein the carbon is a reactive porous carbon with a specific surface area greater than 10 m2/g.

Inventors: BONSACK, JAMES P.
Applicants: SCM CORPORATION
Application year: 1985
Main classification: C01G49
IPC codes: C22B34, C01G49