KR810002046B1 - Production of titanium metal values - Google Patents

Abstract

Ti is recovered by the wet smelting of Ti-contg. ore(e.g. Ilmenite). Thus, the ore is reduction-calcined at 650-1000≰C, 0.5-2 hr and dipped out with HCl at 85-105≰C. The dipped ore is pptd. catalytically with metal oxide(e.g.Fe2O3, V2O5, VO2) and separated to recover TiO2. Whil, HCl and metal oxide is regenerated and recycled from waste soln.

Description

Recovery method of titanium metal

The accompanying drawings are process diagrams of the present invention.

The present invention relates to a method for recovering titanium from a titanium containing source, and more particularly, to a method for recovering titanium so that a large amount of titanium is obtained from a titanium containing source such as ilmenite.

Titanium as a metal form or compound is an important element in the chemical field. For example, titanium dioxide is used in paints, pigments, white rubber and plastics, floor coverings, glassware and ceramics, paint inks, paper opacifiers and the like. Other titanium compounds are used in the electronic field as flame retardants, waterproofing agents, and the like. The metal may be used as a structural material such as an aircraft, a jet engine, a steamer, a loom, a medical device, an exercise machine, a kitchenware or the like as the metal itself or in the form of an alloy. Until now, in recovering titanium from titanium containing sources such as ilminite and rutile, titanium has undergone a separation step in which titanium is formed as a compound having a valence of +4 (these compounds are mainly titanium oxide). . However, when titanium dioxide is to be separated from impurities contained in ore such as iron, a relatively large amount of iron is obtained together with titanium when hydrolyzed titanium dioxide at high temperature.

Various methods of recovering titanium from a titanium containing source are known. For example, U.S. Patent No. 3,236,596 discloses leaching uncalcined ilminite ore with hydrogen chloride at elevated temperatures, and then reducing the dissolved saliva with iron or other reducing agents to convert the solution into hydrogen chloride gas. Precipitate with ferrous chloride while saturating. Hydrogen chloride is then extracted from the liquid by vacuum distillation and then titanium is recovered by conventional methods. Similarly, U.S. Patent No. 3,825,419 obtains ferrous oxide by reducing ilminite ore. Iron is dissolved in acid with about 15% titanium because the reduced ore is usually leached for 4 hours under input. Iron is recovered as ferric oxide containing impurities in the spray calciner, and insoluble products containing all silica present in the ore, consisting mainly of titanium dioxide, are recovered separately. US Pat. No. 3,859,077 relates to a method for recovering titanium, wherein titanium tetrahalide is mixed with iron oxide or titaniferose ore in slag at about 1000 ° C. to produce volatile chloride impurities and titanium dioxide. As a similar patent, U.S. Patent No. 3,929,962 can facilitate the separation of titanium and iron by treating titanium-containing ores at high temperatures to produce oxides of titanium hemp. In other literature, U.S. Patent No. 3,903,239 suggests a method of leaching uncalcined ilminite for at least one day at room temperature to recover 80% of titanium. The solution is diluted and heated to recover titanium dioxide and then Sulfur dioxide should be added to the first sedimentation treatment.

The inventors have demonstrated that the present invention exhibits many features by reacting with ferric oxide to produce titanium dioxide as compared to the prior art described above. By the method of the present invention, the reaction is carried out for a relatively short time, for example, leaching of reduced titanium ore for 0.25-0.5 hours, and the precipitation of the desired titanium dioxide is carried out for about 0.1 hours. In addition, it has been demonstrated that the process of the present invention allows the reaction to be carried out under normal pressure, thereby eliminating a relatively expensive and complicated device. In addition, the present invention is characterized in that titanium oxide having a desired yield can be obtained by using a relatively low grade ore as a starting material. Another feature of the present invention is that the solution used has a strong reducing power, so it has excellent stability even at relatively high temperatures, and titanium dioxide such as rutile is recovered with high purity below the boiling point of the solution, and the acid is diluted to precipitate titanium dioxide. This is because there is no need for industrial water.

It is therefore an object of the present invention to provide an improved method for producing titanium metal.

It is still another object of the present invention to provide a wet smelting method for obtaining titanium metal from a titanium containing source in high yield.

According to one embodiment of the present invention, the present invention reduces and calcinates a titanium-containing source and then leaches the reduced titanium-containing source with hydrogen chloride in the leaching zone, and contacts the leached titanium-containing source with a metal oxide present in a highly oxidized state. Titanium, consisting of sedimentation in the settling zone and separation and recovery of the precipitated titanium dioxide, followed by treatment of the waste liquor to produce hydrogen chloride to recycle to the aforementioned leaching zone and at the same time to produce metal oxides for recycling to the aforementioned settling zone. It is to provide a method for recovering titanium from the source.

According to another embodiment of the present invention, the present invention is reduced calcining a titanium-containing source such as ilminite at a temperature of 650-1000 ℃ and then hydrochloric acid in the leaching zone in which the reduced titanium containing source is maintained at a temperature of 85-105 ℃ Leached, the leached titanium-containing source was contacted with ferric oxide at a temperature of 75-105 ° C. to precipitate in the precipitation zone, and the thus-obtained titanium dioxide was separated and recovered, and the waste solution was treated to produce hydrochloric acid, thereby leaching the aforementioned leaching. It is to provide a method for recovering titanium from a titanium containing source, such as ilminite, which consists of producing ferric oxide for recycling to the above-described precipitation zone while simultaneously recycling to the zone.

As described above, the present invention relates to an improved method for obtaining titanium metal from titanium containing sources such as ilminite, rutile, and the like. By using the method of the present invention, a relatively inexpensive facility and low grade raw materials are used. The desired product can be obtained in high yield. The process of the present invention is achieved by reducing calcination of a titanium containing source containing, for example, iron, vanadium, chromium, manganese and the like at a temperature of 650-1000 ° C. or higher, wherein the above-mentioned reducing calcination is carried out by hydrogen, carbon monoxide and hydrogen In the presence of a reducing agent such as a mixture, or other suitable reducing agent. According to a preferred embodiment of the present invention, reducing calcination is carried out on a metal containing source such as ore that has been ground into particles of about 100 mesh or less for about 0.5-2 hours or longer. The reducing atmosphere used to achieve the purpose of calcination consists of a mixture of 50% carbon monoxide and 50% hydrogen, using an excess of reducing agent to completely reduce the iron present in the system to the metal. Reducing calcination of the titanium containing source, followed by leaching with aqueous hydrochloric acid solution, in this case is carried out for about 0.25-1 hour at a high temperature of 85-105 占 폚.

At this time, the aqueous solution of hydrogen chloride contains about 20% -37% hydrogen chloride. At the end of the leaching process, the leached solution is treated with a metal oxide in which the metal part of the oxide is highly oxidized. Examples of metal oxides that can be used to precipitate titanium are ferric oxide, vanadium pentoxide, vanadium dioxide, chromium oxide, manganese dioxide, oxidant transfer, and the like. The precipitated titanium dioxide is then recovered and recovered from the waste liquor and the waste liquor described above is treated to form hydrogen oxide that is recycled to the leaching zone and to form metal oxide to be recycled or recovered to the precipitation zone. According to a preferred embodiment of the present invention, the metal oxide can be recycled to the precipitation zone in an amount of 50% -100% by weight of the titanium containing source, and the rest is recovered for commercial use as the metal oxide. According to a preferred embodiment of the invention, the treatment of the waste liquid is carried out in a spray drying apparatus, wherein the waste liquid is heated to 300-950 ° C. in an oxidizing atmosphere provided by air, oxygen or one of the compounds of air and oxygen.

Referring to the present invention in detail based on the accompanying drawings as follows.

According to this process, a titanium containing source, such as illite, which is crushed to a predetermined size, is charged into the reducing calcining zone 2 through the conduit 1. In this apparatus, ore is calcined to the above-mentioned range temperature in the presence of a reducing agent composed of a mixture of hydrogen and carbon monoxide, which is charged through the conduit 3 into the reducing calcining zone 2. After reduced calcination for a predetermined period of time, a titanium containing source, i.e., ore, is discharged from the reduced calcination zone 2 through the conduit 4 and passed through to the leaching zone 5. In the leaching zone, the ore is subjected to the action of a hydrogen chloride source, and some of the hydrogen chloride is introduced through the conduit. The leaching step is carried out at a high temperature of 85 ° -105 ° C. for a predetermined time sufficient to convert the metal to the corresponding chloride. Thereafter, the leached solution is discharged from the leaching zone (5) through the conduit (7) and then introduced into the settling zone (8), while the mother rock formed in the leaching step is separated and discharged through the conduit (20). do. In the precipitation zone 8, the solution is treated at a temperature of 75 ° -105 ° C. in contact with a metal oxide in which a metal part of the compound is present in a highly oxidized state. A portion of the metal oxide used to precipitate titanium is charged through the conduit 9 into the precipitation zone 8. When titanium is precipitated as titanium dioxide, the leachate is discharged from the settling zone (8) through the conduit (10) and introduced into the liquid / solid separation zone (11). In this zone, solid titanium dioxide is separated from the waste leaching liquor and discharged through the conduit 12 to the reservoir while the waste leaching liquor described above is discharged through the conduit 13 and introduced into the treatment zone 14. In the treatment zone 14, the waste leaching liquor is treated in a similar manner to the above-described method, and an aqueous hydrogen chloride solution and a metal oxide are simultaneously produced. The aqueous hydrogen chloride solution described above is discharged from treatment zone 14 through conduit 15 and recycled to leaching zone 5 to act as part of the leaching compound, while the solid metal oxide is treated with treatment zone 14 through conduit 16. Discharge into the metal oxide recovery zone (17). In this zone, the metal part of the compound separates the metal oxide that is present in the highly oxidized state, and a portion of the oxide is returned to the precipitation zone 8 through the conduit 18 for recycling while the metal is not used as a precipitant. The oxide is introduced into the reservoir via a conduit 19.

Although the above description shows a batch type operation, the feedstock consisting of crushed ore is continuously fed to the reducing calcining zone, where a reducing agent consisting of a small number, carbon monoxide or a mixture thereof is continuously loaded into this zone. When calcining the raw materials, the method of the present invention can be carried out using a continuous operation method. After passing through the band for a predetermined time, the reduced charged feedstock is continuously discharged and sent to the leaching zone, where it is treated with a hydrogen chloride source such as hydrochloric acid. After keeping the leaching zone at a high temperature and passing this zone, the leaching solution containing dissolved metal chlorides is continuously discharged and sent to the settling zone, where the leaching solution is treated with a metal oxide, the metal part of the compound being highly oxidized. Is in a state of being. The solution containing the precipitated titanium dioxide after treatment in the precipitation zone for a predetermined time is continuously discharged from the zone and introduced into the liquid / solid separation zone. Since the liquid / solid separation zone consists of a centrifugal or filtration device, the waste leachate is continuously discharged and sent to the treatment zone while the soot titanium dioxide is continuously removed therefrom and introduced into the reservoir. After the treatment in the oxidizing atmosphere, hydrogen chloride and metal oxide in the form of an aqueous solution are simultaneously formed. The metal compound is continuously recycled to the precipitation zone and the hydrogen chloride is continuously recycled to the leaching zone.

Hereinafter, the present invention will be described in detail with reference to Examples.

Example 1

The millite ore is crushed to a size of 0-100 mesh and 200 g of the sample is heated in a rotary quartz furnace at a temperature of 750 ° C. under a nitrogen atmosphere, followed by hydrogen and carbon monoxide at 640 cm 3 / min. The temperature of the quartz tube is maintained at 750 ° C. while each is introduced through the quartz tube at a rate. By the end of almost one hour, the quartz glass containing the sample was cooled to room temperature in the presence of nitrogen. 50 g of reduced ilminite ore is then mixed with 300 ml of concentrated hydrochloric acid and warmed to a temperature of 100 ° C. The solid is leached at reflux for 120 minutes and then filtered. Washing and drying the leached solid yielded 2.18 g which was 8.9% titanium and 5.2% iron. Analysis of 280 mL of the leached liquor revealed that it contained 40 g of titanium per liter of solution, 55 g of iron per liter of solution, and 0.45 g of vanadium per liter of solution. 100 ml of the treatment solution is taken and cooled to room temperature to recover most of the iron in the form of ferric chloride. Then 90 ml of the remaining solution is warmed to 100 ° C. and 13.0 g of ferric oxide powder is added. The reaction was allowed to proceed for 1 hour, and then the solid was filtered off, washed, and dried to obtain 7 g of rutile, which contained 0.7% of iron but was not completely impregnated with vanadium. Analysis of 79 ml of these solutions revealed that 0.48 g of titanium was contained per liter of solution. This amount converts 99% of the titanium in the + trivalent state to titanium dioxide.

Example 2

This is an experiment to explain that a solution of dilute hydrochloric acid can be used. 50 g of reductively calcined one minite was mixed with 220 ml of concentrated hydrochloric acid and 80 ml of water in the same manner as described in Example 1. The mixture was warmed to 100 ° C. and leached at reflux for 15 minutes. Filtration of the slurry yielded 285 ml of a leaching solution, which was analyzed and found to contain 33 g of titanium, 53 g of iron, and 0.37 g of vanadium in one liter of the solution. An analysis of 5.24 g of solid revealed that it contained 19% titanium, 25% iron and 0.04% vanadium. 100 ml of the liquid was warmed to 100 ° C. and then 12.3 g of ferric oxide powder was added. These reagents were stirred at 100 ° C. for about 1 hour and then filtered. The waste liquid produced in the reaction was 87 ml, and the analysis showed that 0.21 g of titanium, 165 g of iron, and 0.34 g of vanadium were contained per liter of the solution. The solid consisted of 6.38 g of titanium dioxide containing 2.0% iron and 0% vanadium. This amount is 91% of titanium extracted by converting 99% of titanium in the + 3-valent state into titanium dioxide.

Example 3

In this example, Norka Kraka telemaric acid ilminite was heated to 750 ° C., and hydrogen and carbon monoxide per 100 g of ilminite were reduced for 1 hour using 320 mg / min each. After the reduction, the solids were analyzed and found to contain 31% titanium. 50 g of the reduced ilminaite was mixed with 300 ml of concentrated hydrochloric acid and then heated to a temperature of 100 ° C. The solid was leached at 100 ° C. for 15 minutes and then filtered and washed and dried. Analysis of the dried solid (14.2 g basis weight) yielded 27% titanium and analysis of the solution (243 mL weighed) showed 34 g of titanium per liter of solution. 100 mL of the solution was heated to 85 ° C. and 10.3 g of ferric oxide powder was added. The reaction was allowed to proceed for 5 minutes and then the powder was filtered off. After washing and drying, the solid was flattened and found to be 5.36 g. The remaining solution of 88 ml was found to contain 6.2 g of titanium per liter of the solution. This means that about 70% of the titanium is extracted, meaning 84% conversion of dissolved titanium to titanium dioxide.

Claims (1)

As described above and shown in the drawings, the titanium-containing source is reduced and calcined, and then the reduced titanium-containing source is leached from the leaching zone to the hydrogen chloride source, and the leached titanium-containing source is highly oxidized in the precipitation zone. Contact with the metal oxide present in the precipitated state to precipitate, and the precipitated titanium dioxide is separated and recovered, and the waste liquid is treated to generate hydrogen chloride, recycled to the above-mentioned leaching zone, and at the same time to form a metal oxide to form the above-mentioned precipitation zone. A method for recovering titanium from a titanium containing source, characterized in that for recycling.

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