DE1592408B2 - PROCESS FOR THE PREPARATION OF TITANIUM TRACHLORIDE AND FERRIOXYDE - Google Patents

Description

The invention relates to a method for producing an oven which is provided with a perforated base plate

of titanium tetrachloride and ferric oxide by chlorine, being the metallic constituents of ilmenite

tion of titanium iron ore in the presence of coke in to be chlorinated and after which the titanium tetrachloride

a fluidized bed, which is separated from the ferric chloride by the chlorination gas, is from the German forms, and subsequent separation of the received 5 Auslegeschrift 1 023 024 and the associated

NEN titanium tetrachloride from iron trichloride by se- additional patent 1 032 727 known. The fractional

selective condensation. ned condensation of the chlorides formed is there

The chlorination of titanium iron ores for formation is described. Cold titanium is used as the coolant.

of titanium tetrachloride is known and often described chloride or ferric chloride. For the production of ferrules been. An important process for chlorinating io oxide would then have to be based on the known process

of titanium iron ores is that chlorination gas special step are added, namely the one

through a fluidized bed of titanium iron ores - the oxidation of ferric chloride.

is directed. The reaction proceeds in a very general way. This known process is only practical

according to the following formula: in question for high quality titanium ore.
Tc.n τ; η _l-j / 1'-L'7ί-Ί. οτ, τι i_ λρ-, γί j_? pa ¹ S The fractional condensation of the flowing

The hot chlorination gases produced in the bed oven

Often the metal chlorides are then removed from rutile for the purpose of separating the chlorides from iron,

separated and the titanium tetrachloride with a gas zirconium and other metallic impurities

oxidized, which contains free oxygen, to titanium dioxide by washing with condensed titanium tetrachloride

to manufacture pigments. In general, this ao is also described in German patent 1 080 989

Oxidation can be represented as follows: ben. A clean separation of the metals from each other

τ'π _i_ η rn _u on cannot be achieved with this method because

HCi ₄ -t- υ ₂ -> HU ₂ -τ- / Ci ₂ as a direct coolant a titanium compound (. (

British patent specification 992 317 describes an application.

Process for the selective chlorination of the iron constituents present in the Ti- 25 Also from the German patent 879 546 betane iron ores, it is known to prepare the titanium iron ores during the chlorination of titanium iron ore, ie to oxidize on chemical ferrous chloride and thereby remove the To remove the chlorine contained in the iron components in the ore to chlorinate the titanium ore component and thus to replace the titanium concentration in the ore, but there is heights in the dust separator. For this purpose, a two-stage chlorination process is not pure Fe ₂ O ₃ , because this is required together with the one to remove both titanium tetrachloride and the fine dust from the fluidized bed.

To obtain ferric chloride. Also, those are general will. ■■■ · - - ■ ·

My invention for the treatment of low grade titanium iron is one for the economy and ores used chemical substances, for example 'the trade interesting process for manufacturing Chlorine, hydrochloric acid, and sulfuric acid, compared with titanium tetrachloride and ferric oxide, are relatively low in value expensive and increase the overall cost of creating titanium iron ores, with a significant amount. Since this process also produces a second valuable ferric oxide and chlorine is efficiently chlorinated necessary for the formation of titanium tetrachloride. ;

The object of the invention is the precautions described at the beginning, such as emptying, collecting and 4 ° bene processes for the production of titanium tetrachloride, storage of the processed ore and additional and ferric oxide by chlorination, which is thereby made-heated will. Therefore one draws is that the ferric chloride at about 330 ⁰ C such selective chlorination for the production of host fractionated re-evaporated and at temperatures economic quantities and commercial qualities of over about 600 ° C with a gas that is free (; ■ of titanium tetrachloride and Iron oxide is expensive and contains oxygen, is oxidized to ferric oxide and the troublesome process, when chlorine is released, is returned to the initial stage.

British patent specification 978 998 discloses a run.

continuous process for the production of titanium. A utilizable one is advantageously obtained tetrachloride and iron oxide from titanium iron ores, with by-products, namely pure ferric oxide. aside from that which the chlorination and oxidation of the ore in 50 is favorably obtained in the oxidation carried out a single reaction vessel and recycled iron-chlorine and under in the embodiment is won. In this process, however, the reaction conditions described in more detail in game independent and precise regulation and chlorination plant containing ilmenite and coke troll the temperature and speed of each re-initiated. ■ action limited. Such a control is, however, for 55 As titanium iron ore are ilmenite, titanium iron magnetite, Formation of very pure products with corresponding titanium and iron slag or mixtures of this machine speed important. In addition, this includes materials that can be used. Phosgene, iron oxide obtained by this process is generally chlorine, carbon tetrachloride or mixtures thereof substantial amounts of impurities such as zirconium are used.

oxide, silicon dioxide, aluminum oxides, chromium oxides, 60 The invention is described below with reference to the;

Vanadium oxide, entrained pieces of ore and coke, and drawing depicting a diagram showing the main j

therefore shows only an inferior quality of loading process in the production of titanium tetrachloride, I

limited commercial value. Consequently, this method is shown in more detail. ^: j

ren from an economic point of view for the production. In a typical procedure, a j

treatment of titanium tetrachloride and ferric oxide from the chlorination plant 1, mixed with coke

valuable titanium iron ores are of no importance. Bed of titanium iron ore through an oxygen-containing - |

The chlorination of ilmenite and coal after the gas is whirled up and preheated. The reacts

Fluidized bed process in an isolated shaft - oxygen contained in the gas with the coke. To ;

3 4

Sufficient preheating will determine the supply of acidic gases and the degree of heating required

Substantial gas is reduced. Then we will depend.

then through the chlorination system 1 a chlorination gas, such as The method according to the invention is particularly suitable

Chlorine, passed through, whereby a mixture of titanium - special for ores, such as ilmenite, titanium iron magnetite,

tetrachloride, ferric chloride, other metal chlorides, 5 slags and the like. Also already processed titanium iron

such as silicon tetrachloride, aluminum trichloride, Vana-, ores, d. H. Ores, some but not all of which are ferrous

dium pentachloride, chromium trichloride, zirconium tetrachloride components have been removed by chemical substances

rid and chlorinated by-product gases are formed. There are can with the method according to the invention

it should be noted that the total amount of further processed, provided that this

In the chlorination plant 1 introduced gases and the io ores contain sufficient amounts of iron so

The way in which they are supplied has been carefully selected and the advantages of the process have also been properly exploited

is monitored so that a fluidized bed is maintained. will. However, the procedure is particularly

From the chlorination plant 1, the mixture then flows in part when untreated titanium iron ores, such as Ilme-

a selective condensation device known per se, which should contain at least about 5%

device 3, in which the ferric, chromium, zirconium and aluminum contain iron.

mmiumchloride from the mixture in a first stage The particle size of the titanium iron ores and coke in the condensed out and the titanium tetrachloride and the fluidized bed fluctuates considerably. In general, the remaining metal oxides in a second stage depend on the particle size but are collected on the execution of the predensation. The titanium tetrachloride condensed in this second direction, the composition of the chlorination gases and stage, is removed from the others of the ore, etc. Typical particle sizes for known processes, such as reflux and / or chemical titanium ores, which are normally suitable for the metal chlorides according to the invention by any process per se, range from about 250 to 90 μ (60 to treatment, 160 US. Standard mesh freed from the other metal chlorides) . The particle sizes of the coke that are customarily invented and are made available as a commercial product or that are used in accordance with the invention are treated with a gas containing free oxygen, 25 ranging from about 840 to 149 μ (20 to 100 mesh! Which lasts to produce titanium dioxide pigments. The amount of coke maintained in the fluidized bed can vary in a mixture of ferric chlorides and the other metal-wide ranges essentially only up to about 30 percent by weight of coke,
the ferric chloride evaporates again and is thus separated from the preheating of the fluidized bed and / or the heat of other metal chlorides. The received mezufuhr can be done in various ways. Thus ferric chloride vapor is free from impurities and can be externally used by heating elements, heat exchange is then oxidized in the reaction vessel 7 with a gas which contains shear and the like as well as by chemical means, e.g. oxygen. The hereby usually reaction of coke and / or carbon monoxide nenen products are cooled and separated and an oxygen-containing gas within the gas in the reaction vessel 7 will be heated in the air bed. The last titanium iron ore chlorination plant is preferably recycled. called working method. · '■:

^It: it is noted that the many by the erfinduhgs- are as Chloriergase, gases; so contemporary method achieved economic advantages are advantageous z. B. chlorine, phosgene, tetra-chlorine are at least partly due to the fact that carbon and mixtures of these gases are used to remove the iron content of the titanium iron the large amounts of oxygen must be easily obtained and the reaction conditions, such as temperatures, and partial comparison to the costs of the aforementioned, to the size, must be coordinated so that a processing of the ores required chemical substances 45 satisfactory performance is achieved. Therefore, the process is relatively cheap, for the sake of simplicity, the most important chlorination gas is to name the chlorine according to the invention compared to the state of the art.

nik a significant advantage. In addition, the In the same way it is possible to use any gas that contains oxygen released by the pyrogenic oxidation of ferric chloride. Preferred Iron oxide pigments of such a pure 5 ° are, however, oxygen, air and / or with acidity and goodness that they are high-quality commercial products of substance-enriched air. These gases are easy to use can be. As a result, they are accessible and therefore cheap, so that they are dated economically the total cost of the procedure even further, as the point of view borne out for the procedure is paramount two important commercial products are obtained. Meaning are. Besides, it can do the free one

The oxygen-containing gas used for the process according to the invention, alone or together with apparatus, corresponds essentially to known and to each of the other gases used in the process in customary designs and constructions. So the reaction zone are to be introduced
For example, the burners, ovens, heating devices, for a more detailed explanation, the following is used for heat exchangers and the like, which are used to form the metal game:

chlorides and oxides are known. From 60 the reaction was carried out in a chlorinator Basically, the execution, the size and led, which consisted of a steel boiler, its other features of the device for carrying out outer diameter was 61 cm and that with a of the method is not the subject of the invention. It becomes a 15.24 cm thick refractory lining However, it is particularly noted that the special ones are made of bricks that are resistant to chlorine the explanations of how the figure and the body were dressed. The kettle contained 106 kg of ilmenite, power of the device, the used Ma- average particle size 177 μ, mixed with material and the like to a certain extent of the 29.50 kg coke, average particle size 250 μ. special titanium iron ores and the ChIo- The ilmenite coke batch was about 91 cm deep and

was fluidized and heated by bubbling oxygen through it at a rate of about 91 kg / h. The coke reacted with the oxygen and the temperature rose to around 1000 ° C. The oxygen flow was then reduced to about 4.54 kg / h and coke was added to the kettle charge to replace the coke consumed during the warm-up period. Chlorine was then passed into the fluidized bed at a rate of 75 kg / h. In order to maintain an approximately constant feed composition and volume, ilmenite and coke were added continuously and at an appropriate rate. The gas stream supplied by the chlorination plant consisted of a mixture of titanium tetrachloride, ferric chloride, relatively small amounts of impurities such as chlorides of zirconium, aluminum, vanadium and chromium, as well as carbon monoxide and carbon dioxide and other by-products. This mixture was continuously fed to a selective condensation unit 3 of known embodiment, in which approximately 57 kg / h of a mixture of ferric chloride and other metal chlorides, such as chromium chloride and tin tetrachloride, with a boiling point above about 25O ⁰ C, at a temperature of about 220 ⁰ C condensed. The condensed solid ferric chloride was then simply and essentially completely separated from the other metal chlorides by selective re-evaporation at about 330 ° C. The gaseous ferric chloride, which contained essentially no metal chloride impurities, was then placed in a furnace and oxidized at about 800 ° C. with oxygen which was introduced at a rate of about 6.40 m ³ / h. Approximately 27 kg / h of ferric oxide was formed and separated and collected by a cyclone and bag filter collection system. About 36 kg / h of the chlorine obtained as a by-product of the oxidation was returned to the chlorination plant.

The substances that do not condense with the mixture of ferric chloride and the other metal chlorides were led to a second condensation stage, in which a liquid mixture of titanium tetrachloride, and other chlorides such as tin tetrachloride, vanadium pentachloride and silicon tetrachloride, was won. Commercially available titanium tetrachloride can be recovered by any conventional purification process.

Instead of ilmenite, other titanium iron ores, such as titanium iron magnetite, slag and the like, can also be used. or mixtures of these materials are treated by the process according to the invention, provided that that there are sufficient amounts of iron in the ore.

Claims (3)

Patent claims: 1. A process for the production of titanium tetrachloride and ferric oxide by chlorination of titanium iron ore in the presence of coke in a fluidized bed formed by the chlorination gas , and subsequent separation of the resulting titanium (tetrachloride of iron trichloride by selective condensation, characterized in that the ferric chloride at about 330 ° C fractionally evaporated again and in a known manner at temperatures above about 600 ° C by a gas containing free oxygen, oxidized to ferric oxide and the chlorine released in this way is returned to the initial stage. 2. The method according to claim 1, characterized in that the titanium iron ore ilmenite, titanium iron magnetite, Slags or mixtures of these materials are used. 3. The method according to claim 1 or 2, characterized in that phosgene, chlorine, Carbon tetrachloride or mixtures thereof are used. 1 sheet of drawings