WO1998055660A1 - Method for purifyting titanium and apparatus for purifyting titanium - Google Patents

Abstract

A method for purifying titanium by reacting crude titanium as a starting material with TiC14 to prepare purified titamium, comprising: (a) step 1 of reacting crude titanium as a starting material with TiC14 to produce vapor of lower titanium chloride TiC1x; (b) step 2 of precipitating a solid TiC1x from the vapor of TiC1x evolved in the step 1; and (c) step 3 of heat-decomposing the solid TiC1x to prepare purified titanium, wherein TiC1x is lower titanium chloride with x being 2 or 3. The temperature t1 (°C) and the pressure pl (Torr) at which the step 1 is carried out are 750 °C ≤ tl and log(p1) < 20.158-(21859/(t1+273)), respectively. The pressure (p2) and the temperature (t2) at which the step 2 is carried out are 0.001 Torr < p2 < 1520 Torr and 150 °C < t2 < (21859/(20.158 - log(p2)) - 273 °C, respectively. The temperature t3 (°C) and the pressure p3 (Torr) at which the step 3 is carried out are 750 °C ≤ t3 and log(p3) < 20.158-(21859/(t3+273)), respectively.

Description

 Specification

 Titanium purification method and titanium purification device

 Technical field to which the invention belongs

 The present invention relates to a titanium purification method and a titanium purification apparatus, and more particularly to a titanium purification method and a titanium purification apparatus for producing a high-purity titanium material suitable for forming a semiconductor thin film or for medical use from crude titanium. Background art

 In the titanium manufacturing industry, various manufacturing methods have been developed to meet the recent quality requirements for high-purity titanium materials in the semiconductor field. On the other hand, in the medical field, demand for fine wires made of high-purity titanium materials is expected in the future because of their excellent properties.

 Normally, titanium ingots are produced by further dissolving titanium sponge produced by the Kroll method. As a high-purification technique, a molten salt electrolysis method using titanium sponge as a raw material is suitable for producing 5N-6N-level high-purity titanium.

The titanium sponge into a Ti or Ti 1 ₂ with iodine as another means, ® one blade method to the Ti or Ti 1 ₂ producing by re high purity titanium to thermal decomposition are known. These techniques are disclosed in JP-A-8-165566 and JP-A-3-215633. However, the method has a drawback that it is difficult to select a material for the manufacturing equipment because the method is performed under a high temperature of about 1100 to 1300 ° C and a high vacuum of about 0.001 to 0.1 ITorr. As a result, there is a drawback that the equipment structure and operation are complicated, resulting in high costs.

According to the research of the present inventor, it has been found that the above-mentioned prior art has the following disadvantages. That is, since the productivity of the molten salt electrolysis method is low, Has the disadvantage of low cost. In addition, the eod method is carried out under conditions of high temperature of about 1100 to 1300 ° C and high vacuum of about 0.001 to 0.1 Torr, which makes it difficult to select materials for manufacturing equipment. However, there is a disadvantage in that the cost is high and the cost is high.

 Disclosure of the invention

 An object of the present invention is to provide a method for producing crude titanium at a relatively mild condition, specifically, at a pressure of 0.0 CH to 520 Torr and a temperature range of 5 ° to 100 ° C. An object of the present invention is to provide a titanium purification method for producing high-purity titanium.

 Another object of the present invention is to provide a titanium purification method that can produce high-purity titanium from crude titanium at a lower cost and is more efficient than conventional methods for producing purified titanium.

 Still another object of the present invention is to provide an apparatus for purifying titanium consistently to obtain high-purity titanium from crude titanium metal.

The present inventors have repeatedly studied a method for purifying titanium for obtaining high-purity titanium from crude metal titanium with the aim of providing an inexpensive production method. As a result, the TiC vapor is reacted with the crude titanium metal to generate TiGlx vapor, and then the TiGlx vapor is precipitated as a solid, and after the TiCI ₄ vapor is separated, at a certain temperature and pressure, In thermal decomposition of the TiGlx solid, a part of the TiGlx solid is converted to TiGlx vapor without being thermally decomposed, so that the TiGlx vapor is deposited again as a solid, and the thermal decomposition is repeated again. As a result, they have found that purified titanium can be efficiently produced, and have completed the present invention. The lower titanium chloride vapor is represented by TiClx, X is an integer of 2-3, and includes a mixture of 2 and 3.

The object of the present invention is to provide a method for purifying titanium according to the present invention, wherein (a) reacting crude titanium raw material with TiGI ₄ to generate low-grade titanium chloride vapor. Step 1; (b) Step 2 of depositing solid TiClx from the TiClx vapor generated in Step 1; (c) Step 3 of pyrolyzing the solid TiGlx to obtain purified titanium; and Step 2 Depositing TiGlx vapor generated as a result of the thermal decomposition reaction in Step 3 as a solid together with the TiGlx vapor generated in Step 1 to obtain purified titanium by reacting crude titanium raw material with TiGI _4. Is achieved. The temperature tl (° C) and the pressure pi (Torr) for performing the step 1 are respectively 750. C≤t1 and log (p1) 20.158-(21859 / (t1 + 273)), and the pressure (p2) and temperature (t2) for performing the step 2 are 0.001 Torr <p2 and 1520 To, 150 ° C <t2 <(21859 / (20.158-I og (p2)))-273 ° C, and the temperature t3 (° C) and pressure p3 (Torr) at which Step 3 is performed are 750 ° C≤ t3 and log (p3) <20.158-(21859 / (t3 + 273)) Note that, in the present specification, logP is log _| P, and unless otherwise specified, the unit of temperature is ° C and the unit of pressure is ° C. The unit is Torr.

 The method for purifying titanium according to the present invention specifically provides three methods: a stationary method, a transfer method, and a composite method.

Hereinafter, the stationary method will be described. Performing step 1 in zone 1 located adjacent to zone 2 adjacent to zone 3 in a single vessel to generate TiClx vapor, and converting the TiClx vapor generated in step 1 to Move to zone 2 located between zone 1 and zone 3 in a single container and zone 3 located adjacent to zone 2 adjacent to zone 1 in said single container. Step 2 is carried out, and solid TiClx is deposited in the zone 2 and the zone 3 .Then, the zone 2 is depressurized and / or raised, and the step 3 is carried out in the zone 2 to generate TiGlx vapor. At the same time, purified titanium is deposited, then the zone 2 is brought to the initial pressure and the initial temperature, the step 1 is performed in the zone 1, and solid TiClx is deposited in the zone 2 and the zone 3, and the zone 2 and the zone are deposited. 3 above Step 3 and the step of depositing the solid TiGlx are alternately repeated to produce purified titanium.

 Further, the above step 1 is performed in zone 1 arranged adjacent to zone 2 adjacent to zone 3 in a single container to generate TiGlx vapor, and the TiGlx vapor generated in step 1 is Moving to zone 2 located between zone I and zone 3 in a single container and zone 3 located adjacent to zone 2 adjacent to zone I in the single container Step 2 is performed, and solid T i GIX is precipitated in the zone 2 and the zone 3.Then, the zone 3 is depressurized and / or heated, and the step 3 is performed in the zone 3, and TiGlx vapor is discharged. Simultaneously with the generation, the purified titanium is precipitated, then the zone 3 is brought to the initial pressure and the initial temperature, and the step 1 is performed in the zone 1 to precipitate solid TiClx in the zone 2 and the zone 3. Said zone 2 and said zone 3 produce purified titanium By repeating alternately the precipitation process of the step 3 and the solid TiGlx.

Hereinafter, the transfer method will be described. The above-described step (1) is performed in zone (1) disposed adjacent to zone (2) adjacent to zone (3) in a single container to generate TiClx vapor, and the single TiGlx vapor generated in step (1) is generated. Moved to Zone 3 adjacent to Zone 2 adjacent to Zone 1 in the container of Step 1 and carried out Step 2, and deposited solid TiGlx in Zone 3 and continued simultaneously with Step 2 Either intermittently or intermittently, the solid TiGlx deposited in the zone 3 is transferred to the zone 2 provided between the zone 1 and the zone 3 by mechanical means. And generating purified titanium at the same time as generating TiGlx vapor, moving the TiClx vapor generated in the zone 2 to the zone 3, depositing solid TiClx in the zone 3, and performing the process in the zone 2. 3 and said zone 3 And the step of depositing the solid TiGlx, which is carried out in the above, is alternately and repeatedly performed to produce refined titanium.

 Hereinafter, the combined method will be described. Performing step 1 in zone 1 disposed adjacent to zone 2 adjacent to zone 3 in a single vessel to generate TiGlx vapor; and converting the TiClx vapor generated in step 1 to Move to zone 2 located between zone 1 and zone 3 in a single container, and zone 2 located adjacent to zone 1 and zone 3 adjacent to zone 1 in a single container. Is carried out, and solid TiGlx is precipitated in the zones 2 and 3; then, the solid TiClx deposited in the zone 3 is moved to the zone 2 by mechanical means, and at the same time, the zone 2 is depressurized and / or raised. Step 3 is performed in Zone 2 where the pressure has been reduced and / or increased to generate TiGlx vapor, and at the same time, purified titanium is deposited.Then, Zone 2 and Zone 3 are brought to the initial pressure and initial temperature. The preceding Solid Ti GIX is deposited in zone 2 and zone 3, and purified titanium is produced by repeating step 3 and the solid TiG deposition step in zone 2 and zone 3. I do.

Further, the temperature t1 (° C) and the pressure p1 (Torr) at which the step 1 is performed are 850 ° C <t1 and 1000, respectively. C and 5 Torr <p1 <970 Torr, and the temperature t2 (° C.) and the pressure p2 (Torr) for performing the step 2 and the step of depositing the solid TiGlx are 200, respectively. C <t2 <900 ° C and 5 Torr and p2 <970 Torr, and the temperature t3 (° C) and the pressure p3 (Torr) at which the step 3 is performed are 850 ° C <t3 <1000 ° C and 5 Torr, respectively. <p3 <970Tor condition. Further, the TiGI ₄ vapor supplied from the outside of the vessel in the step 1 passes through the packed bed of the raw crude titanium solid in the zone 1, passes through the step 1 and is subjected to the steps 2 and 3, The TiCI ₄ vapor is separated from other gases present in the container and discharged out of the container, and the separated TiCI ₄ vapor is supplied again into the container. It is preferable to be configured so as to be supplied and used in the step 2 and the step of depositing the solid TiGlx and the step 3.

 It is more preferable that step 3 be performed by introducing an inert gas into the container.

 In order to achieve the above object, the apparatus for purifying titanium by the above-mentioned stationary method includes a left zone 1 and a right zone for performing the generation process at positions near the left and right ends of a single tubular reaction tube. 1 are provided, and the space between these two zones 1

2 and a right zone 2, comprising two gas inlet / outlet pipes connected to the left and right ends of the reaction tube, and a movable heating device arranged on the outer periphery of the reaction tube, and flowing in the reaction tube. The airflow is reversed every fixed period. Further, as another titanium purification apparatus by a static method, zone 1 for performing step 1; zone 2 for performing steps 2 and 3; and step 2 in a single reaction vessel. An opening is formed between the zone 2 and the zone 3 so that the mixed vapor of TiGlx vapor and TiG vapor generated in the zone 2 and solid TiClx can be transferred to each other between the zone 2 and the zone 3. It is configured to include two connected gas inlet / outlet pipes and a movable heating device arranged on the outer periphery of the reaction tube.

Further, the apparatus for purifying titanium by the transfer method includes a zone 1 for performing the step 1, a zone 2 for performing the step 3, and a zone 3 for performing the step 2 in a single reaction vessel. A communication path for transferring the mixed steam generated in zone 1 from zone 1 to zone 3 between zone 1 and zone 3; and a zone between zone 2 and zone 3 An opening through which the mixed vapor of TiGlx vapor and TiCI ₄ vapor generated in 2 and solid TiClx can be transferred to each other is formed, and has two gas inlet / outlet pipes connected to the TiCI ₄ reaction tube. Solid solidified and deposited in zone 3 It is configured to have mechanical means for scraping and transferring TiClx to the zone 2 side.

 Further, as the titanium purification apparatus by the combined method, zone 1 for performing the step 1, zone 2 for performing the steps 2 and 3, and zone 3 for performing the step 2 in a single reaction vessel. An opening is formed between the zone 2 and the zone 3 so that the mixed vapor of the TiGlx vapor and the TiG vapor generated in the zone 2 and the solid TiGlx can be transferred to each other. A gas inlet / outlet pipe is provided, and the zone 3 is provided with mechanical means for transferring solid TiGlx solidified and deposited in the zone 3 to the zone 2 side.

 As the raw titanium material used in the present invention, a titanium material having relatively low purity, specifically, sponge titanium or ingot having a purity level of 2N5-4N is used. However, the raw titanium raw material is not limited to these forms and purity, and those having other forms and purity can be used according to the purity of the target purified titanium.

 For example, when the present invention is carried out for the purpose of obtaining high-purity titanium of 4N5-5N level, about 2N5-4N titanium material may be used as raw titanium. The high-purity titanium produced in the present invention is 4N—6N (99.99) whose impurity concentration is reduced to about 110 to 1Z100 in comparison with crude titanium in view of the purpose and use of titanium. (99 to 99.99%), but not limited to.

The basic chemical equilibrium reaction, which is the principle of the titanium purification method according to the present invention, is shown. _(In the following reaction formula or the description in the text, a substance in a gaseous state is represented by (G) attached to a molecular formula, and a solid state is shown. A substance is represented by (S) attached to the molecular formula, so for example, TiGI ₄ vapor is represented as TiGI ₄ (G) Figure 1 shows the equilibrium diagram of the Ti (S) -TiGI ₂ (S) system, That is, gaseous TiCI ₂ FIG. 2 is an equilibrium diagram of (G), TiCI ₃ (G), and TiCI ₄ (G) with solid TiGI ₂ (S) and metallic titanium Ti (S). Curve S in the figure. ₂ represents the temperature t and the pressure p at which Ti (S) and TiGI ₂ (S) equilibrate with the gas phase.

 I o g p = 20.158—21859 (t + 273).

This curve s. _{When the} temperature is higher or lower than ₂ , that is, on the lower right side of the curve s _{() 2} , only titanium Ti (S) can be present in the solid phase, and TiCI ₂ (S) is present in the solid phase. Or that TiGI ₃ (S) cannot exist. The curve S ₀₂ O Li also low temperature side or high pressure side, i.e. the curve s. _If it is located on the upper left side, it means that titanium Ti (S) cannot exist in the solid phase.

 Here, steps 1 to 3 will be described. In step 1, the raw titanium raw material and TiG vapor supplied from outside the process

-TiCI ₄ (G) + Ti (S) ——> TiClx (G) + (1- a) TiCI, (G) ―

-CD

 (a indicates the reaction rate)

 To produce lower titanium chloride TiGlx (G).

 Then, in step 2, the mixed vapor of TiClx (G) and TiC (G) generated in step 1 is led to the low temperature section, and TiGlx (G) is precipitated as solid TiGlx (S). In other words, in step 2, the condition where only TiClx (S) can be stably present as a solid is obtained by the following equation (2).

TiClx (G) + TiCI ₄ (G)-1-> TiClx (S) + TiC and (G)--(2) separates TiC (G) and TiClx (S).

 Next, in step 3, the TiGlx (S) precipitated in equation (2) is heated or Z and decompressed to obtain equation (3).

TiGlx (S)> T i ( S) + T i C 1 4 (G) (3) by the re obtain solid Ti a (S). With the reaction of equation (3), TiClx (G) and TiG An equilibrium mixed vapor consisting of (G) is generated.

The temperature tl (° C.) and the pressure _P 1 (Torr) at which the step 1 is performed are 750 ° C. ≦ t1 and log (p1), respectively, and 20.158− (21859 / (t1 + 273)). By performing the above-mentioned step 1 at a temperature t1 and a pressure p1 (Torr) within the range of the above values, the reaction of the step 1 can proceed at a realistic rate.

Within the above range, the temperature tl (° C) is in the range of 800 ° C to 10000 ”C, the pressure pi (Torr) is 1.0 and log PI (20. 158—21859 / (ΐ I + 2 7 3 ))) From the viewpoints of TiClx (S) yield, production efficiency and purification effect, etc., it is considered that the higher the reaction temperature and pressure in step 1, the better, but the strength of equipment and heat resistance Considering the properties and durability, the upper limit of the temperature is preferably about 100 ° C. In order to obtain only Ti (S), the pressure (P1) must be determined by changing the pressure (P1) to the equilibrium curve s in FIG. The low pressure side of ₂ , ie

 Log P <20.158 ― (21859 / (t + 273))

 This is because it is essential to be within the range.

In addition, the temperature tl in step 1 is 850 ° C ≤ t1 ≤ 1000 ° C, and the pressure _P1 is 1. Otorr or more in Fig. 1 and the equilibrium curve S. Setting the value on the low pressure side of ₂ is more advantageous in terms of reaction speed.

 In addition, as long as it is on the high temperature / low pressure side of the equilibrium curve shown in FIG. 1 even outside the above range, in step 1, TiGlx (G) can be generated according to the reaction of equation (1). .

The step 2 pressure to carry out (p2) between the temperature (t2), respectively 0.001 Torr is <p2 ° 1520 Tor 150 ° C <t2 < (21859 (20.158- I og (P 2)) -. And 273.C temperature The reason for limiting (t2) to 150 ° C or higher is that when the temperature (1: 2) becomes 150 ° C or lower, TiGI ₄ (G) may liquefy and TiCI ₄ may not be separated from TiGlx (S). The reason why the temperature (t2) is limited to (21859 ° (20.158-Iog (p2))-273 ° C or lower) is that when the temperature (t2) exceeds the upper limit, the pressure ( _P2 ), Temperature (t2) Is the equilibrium curve S. _This is because TiClx cannot be present as a solid.

The reason why the pressure (p2) is limited to 0.001 Torr or more is that if the pressure (p2) becomes 0.001 Torr or less, the reaction in Step 2 does not proceed. In addition, the reason for limiting the pressure (ρ2) to 1520 Torr or less is that when the pressure ( _P2 ) exceeds I 520 Torr, TiG (G) is easily condensed, and 0 (6) is reduced to TiClx (S ) May not be able to be separated. Furthermore, when a normally used pressure vessel is used, if the pressure (P2) becomes 1520 Torr or more, the load on the equipment increases.

 Within the above range, the pressure (p2) is preferably 0.01 to 60 Torr, and the temperature (t2) is preferably 20 ° C. or more.

 This is because practical productivity can be ensured by performing the step 2 at a pressure (p2) and a temperature (t2) within such ranges.

Further, the pressure (p2) is 0.1 Torr to 500 Torr, the temperature (t2) is 200 ° C or more, and the equilibrium curve S in FIG. It is preferable that the temperature of ₂ be equal to or lower than the temperature at the point of intersection with the straight line indicating 500 Tor. The reason why the pressure (p2) is limited to 0.1 Torr or more is that when (p2) is less than 0.1 I Torr, the concentration of the reacting TiClx (G) gas is low, so that the practical reaction speed is reduced. Because you cannot get it.

The reason why the pressure (p2) is limited to 500 Torr or less is as follows. That is, the production reaction in step 1 can obtain a high reaction rate under relatively low temperature and low pressure conditions, and the separation reaction in step 2 can obtain a high reaction rate under relatively high temperature and high pressure conditions. There is a property that can be. In the present invention, since the production reaction in step 1 and the separation reaction in step 2 are performed simultaneously in a single reaction vessel, the pressure (p2) is limited to 500 Torr or less in consideration of suitable conditions for the production reaction and the separation reaction. This is because it is necessary to increase the overall yield of the titanium purification reaction. The temperature (t2) is shown in the equilibrium curve S in Fig. 1. _The reason for limiting the temperature below the point where ₂ intersects the 500 Torr line is that TiCI ₄ (G) present in the gas phase condenses in TiClx (S) when the temperature (t2) rises above this temperature. It is.

₀ to; the temperature t3 to performing step 3 (° C) Pressure p3 (Torr), respectively 750 ° C ≤t3 and iog is (p3) Ku 20.158 _ (2 I 859 / ( I 3 + 273))

The reason why the temperature t3 (° C) and the pressure p3 (Torr) were limited to the above ranges was that the atmosphere in which the step 3 was performed was S from the left side of the _SOT curve shown in FIG. _The reason is that purified Ti (S) is deposited according to the above equation (3) by moving to the right side of the _two curves, that is, to the high-temperature / low-pressure side. In other words, the temperature and pressure at which only Ti (S) precipitates (exists) in the solid phase are represented by curve S shown in Fig. 1. _This is because the side ₂ is high temperature and low pressure. The preferable conditions regarding the temperature and the pressure in the step 3 are the same as those in the step 1 described above.

In the stationary method, the transfer method, and the combined method, the temperature t 1 (° C) and the pressure p 1 (Torr) at which the above step 1 is performed are 850 ° C. t 1 and 1000 ° C. and 5 Tor r p 1 <970 Torr. Further, the temperature t2 (° C) and the pressure _P2 (Torr) at which the step 2 and the step of depositing the solid TiGIx are performed are 200 ° C <t2 <900 ° C and 30 Torr < _P2 <970 Torr, respectively. is there. Further, the temperature t 3 (° C.) and the pressure p 3 (Torr) at which the step 3 is performed are 850 ″ C <t 3 and I000 ° C. and 5 Torr <p3 <970 Torr, respectively.

When the static method is performed, the pressure P 1 for performing the step 1, the pressure p 2 for performing the step of depositing the solid TiGlx and the pressure p 2 for performing the precipitation step of the solid TiGlx are selected from the range of 10 OTorr to 50 OTo. Good to do. Further, the pressure ρ1 and the pressure ρ2 are preferably in the range of 200 to 40 OTorr. By selecting the values of the pressure p1 and the pressure p2 from within such a range, a practical reaction speed can be obtained. In addition, the precipitation of TiGlx (S) can be promoted, and the condensation of TiG (G) can be suppressed. Within the above range, the temperature ΐ1 at which the step 1 is performed, the temperature t2 at which the step 2 and the step of depositing the solid TiClx are performed have a temperature gradient such that the temperature decreases from the zone 1 toward the zone 3; It is preferable that the zone 1 has a temperature of 950 ° C. to 105 ° C. and the zone 3 has a temperature of 200 ° C. to 9 ° C. 0 ° C. With this configuration, a practical reaction speed can be obtained. Further, the precipitation of TiClx (S) can be promoted, and the condensation of TiG (G) can be suppressed.

 Furthermore, it is most preferable that the temperature at the lower end of zone 1 be about 1000 ° C. and the temperature at the upper end of zone 3 be about 150 ° C. to 250 ° C. from the viewpoint of the yield of purified titanium and the reaction efficiency.

 In the stationary method, when TiClx (s) precipitated and solidified in zone 3 is heated to obtain Ti (s), the temperature of zone 2 in which step 3 is performed is 800 to 970 °. C is good.

The vessel was depressurized while the vessel was kept at a constant temperature Place the zone 3 to the high temperature and low pressure side under the S ₀₂ curve, in the case of performing the step 3, the pressure _P 3 1 ~ 4 0 0Torr ( 850 ° C <t3 1000 ° C)

 In the transfer method, the temperature range of the zone 2 in which the step 3 is further performed is preferably set to 950 to 100 ° C. Further, in the combined method, the conditions for performing the step 3 may be a temperature of 800 ° C. to 100 ° C. and a pressure of 1 to 5 OTorr.

The TiG vapor supplied from the outside of the vessel in the step 1 is passed through the packed bed of the raw crude titanium solid in the zone 1 and then separated from other gases present in the vessel and separated from the outside of the vessel. Is discharged. By passing TiGI ₄ through the packed layer of coarse metal titanium, impurities such as Fe, Ni and Cr in the coarse metal titanium can be removed.

Titanium sponge, chips and the like can be used as the coarse titanium metal to be filled in zone 1. In addition, the form of the metal coarse titanium is such a form. However, the present invention is not limited to this, and one having another form can be used.

The bulk specific gravity of the packed layer made of metal coarse titanium is preferably 0.2 to 0.5. If the bulk specific gravity is larger than the upper limit, the flow resistance of the gas such as TiCI ₄ vapor is increased, and the operation becomes difficult. Conversely, when the bulk specific gravity is smaller than the lower limit, the reaction efficiency in step 1 is reduced.

 The length of the packed bed of raw titanium solid material should be selected so that the average residence time of the gas such as TiG vapor is 0.5 seconds or more. Further, the ratio of the length to the diameter of the packed bed is preferably set to 3 or more. If the ratio of the length to the diameter of the packed bed is 3 or less, uneven distribution of the gas flow in the radial direction of the packed bed is likely to occur, and a uniform reaction becomes difficult to progress.

 With reference to FIG. 2, an example of the method of titanium purification according to the present invention will be described. In this example, zone 1, zone 2, and zone 3 are provided in order from the bottom inside a tubular reaction vessel extending vertically. In the initial state, the bottom of Zone 1 is 100 ° C, the boundary between Zone 1 and Zone 2 is 963 ° C, the boundary between Zone 2 and Zone 3 is 850 ° C, and the top of Zone 3 Temperature gradient so that the temperature becomes 200 ° C. The pressure is 30 OTorr.

In Zone 1, Step 1 is performed, and the generated TiGlx (G) is led to Zone 2 and Zone 3 where it is cooled and deposited as a solid (Figure 2 (a)). After that, the boundary temperature between Zone 1 and Zone 2 was 980 ° C, and the boundary temperature between Zone 2 and Zone 3 was 963. The temperature is raised to C (Fig. 2 (b)). With this configuration, Zone 2 has the equilibrium curve S. The conditions of ₂ are high temperature and low pressure side, and zone 2 is a system in which only Ti (S) can exist as a solid phase. As a result, Ti (S) precipitates in zone 2. Note that TiClx (G) is generated simultaneously with the precipitation of Ti (S). Thereafter, the entire reaction vessel is set to the initial temperature, and TiClx (G) generated in zone 2 is deposited in zones 2 and 3 (Fig. 2 (a)) o As described above, the process in the initial state (FIG. 2 (a)) and the process of pyrolysis in zone 2 (FIG. 2 (b)) are repeated while introducing TiCI ₄ (G) from the bottom of the reaction vessel. By repeating this operation, dense titanium having a bulk density of about 2.1 g m ³ can be purified.

The pressure in the reaction vessel may be reduced to 5 Torr while maintaining the temperature in the initial state in order to set the inside of zone 2 to the high temperature and low pressure side of the equilibrium curve S _Q2 (see FIG. 2 (c)).

 FIG. 6 shows an example of an apparatus for purifying titanium for performing the stationary method. The tubular reaction tubes 3 1 are arranged horizontally, and from the left end of the reaction tubes 3 1, in order, left zone 133, left zone 236 (right zone 3), right zone 2 3 7 (left zone 3) ), Right zone 134 is formed. When the left zone 236 is heated, Step 3 is performed in the left zone 236, and Step 2 is performed in the right zone 237. When the temperature of the right zone 237 is increased, the left zone 236 becomes the right zone 3, the process 2 is performed in the left zone 236, and the process 3 is performed in the right zone 23.

The interior of each zone 133, 34 is pre-filled with crude titanium metal as a raw material. Zone 1 is set to a temperature suitable for the production reaction by heating furnace 38 installed outside reaction tube 31. When the TiGI ₄ (G) supplied from the left end of the reaction tube 31 reaches the left zone 134, it reacts with the crude titanium metal filled in the left zone 134 to generate TiGlx (G). The generated TiGlx (G) is guided to the left zone 3 (right zone 2) 37 in the direction of gas flow, and cooled and condensed in the left zone 337 ■. The TiClx (S) precipitated upon cooling is separated from gaseous TiGI ₄ (G).

Then, after the supply of TiGI ₄ (G) from the left end of the reaction tube 3 1 was stopped, the heating furnace 38 was moved from the left zone 133 and the left zone 236 to the right zone 134 and the right zone 237. And the right zone 1 34 And right zone 2 37 are heated and heated. Reaction tube 3 1 TiGI ₄ (G) is supplied to the left from the right end, and the reaction in step 1 between crude titanium metal and TiG (G) is performed in right zone 1 3 4 to generate TiGlx (G). . The TiGlx (G) generated in the right zone 1 34 is cooled and precipitated in the right zone 3 (left zone 2) 36 and separated from TiC (G).

Reaction tube 3 1 TiClx (S) precipitated in left zone 3 (right zone 2) when TiG (G) was supplied from the left end, reversed the supply of TiG (G) and shifted the heating area to the right. Purified titanium is deposited at the site in the thermal decomposition reaction when the titanium is moved to the zones 136 and 237. The TiGlx (G) generated at this time is condensed and solidified in the right zone 336 along with the TiClx (G) generated in the right zone 334 and separated from TiGI ₄ (G).

 Next, the heating furnace 38 is moved to the left, and a reaction is performed by airflow from left to right. By repeating such an operation, Τί (S) can be precipitated in almost all regions of the left zone 236 and the right zone 237, and the inside of the reaction vessel can be effectively used. it can. In addition, highly pure metallic titanium can be obtained.

Incidentally, TiCI ₄ (G) by-produced in the production reaction and the thermal decomposition reaction passes through the left production chamber, is guided to the outside of the reaction tube 31, is condensed, and is reused.

FIG. 3 illustrates an example of the transfer method in the titanium purification method according to the present invention. Set the tubular reaction vessel extending vertically to zone 1, zone 2, and zone 3. The pressure inside the reactor is 300 Torr. Zone 1 Bottom 1 000 ° C, Zone 1-Zone 2 interface 980 ° C, Zone 2-Zone 3 interface 96 3 ° C, Zone 3 Top 2 Set a temperature gradient to reach 0 ° C (Fig. 3 (a)). With this configuration, the interface between zone 2 and zone 3 is the equilibrium curve S. _The above condition is satisfied.In Zone 2, only Ti (S) can be present as solid phase, and in Zone 3, only TiGl _x (S) can be present as solid phase. Becomes

The TiGlx (G) produced in zone 1 is deposited as a solid in zone 3. Next, the TiGlx (S) deposited in Zone 3 was forcibly transferred to Zone 2 by mechanical means, and the TiClx (S) was thermally decomposed in Zone 2 to deposit purified titanium and TiGlx (G (Fig. 3 (b)) ₍ , TiGlx (G) generated at this time is also deposited as a solid in zone 3. Means for transferring TiGlx (s) to zone 2 include, for example, moving vertically The means of transporting TiGlx (s) is not limited to scrapers that can move upward and downward, but can be achieved by rotating scrapers. A double screw may be used, etc. By these means of transport, the TiGlx (s) solidified and precipitated in the separation step is continuously supplied to the pyrolysis step, thereby continuously and efficiently performing the pyrolysis reaction. This makes it possible to run the entire process simultaneously and continuously.

Referring to FIG. 4, an example of the combined method of the method for purifying titanium according to the present invention will be described. Set the tubular reaction vessels extending vertically to Zone 1, Zone 2 and Zone 3. Initially, the bottom of Zone 1 is 100 "", the boundary between Zone 1 and Zone 2 is 963 ° C, the boundary between Zone 2 and Zone 3 is 850 ° C, and the top of Zone 3 is 200 °. a temperature gradient such that the C. the pressure in the reaction vessel is a 3 0 OTorr (Fig 4 (a)) ₀

The TiGlx (G) generated in zone 1 is deposited as a solid in zones 2 and 3. Next, the TiGlx (S) precipitated in zone 3 is forcibly transferred to zone 2. The pressure in the entire reaction vessel is gradually reduced from 30 OTorr to 5 Torr (Fig. 4 (b)). TiGlx (S) is gradually decomposed from the bottom of Zone 2 where the temperature is high. Equilibrium curve S gradually from high temperature part. _This is because the system moves to the condition on the lower right side of ₂ . When the pressure reaches 5 Torr, thermal decomposition of TiClx (S) occurs in the entire zone 2. In other words, in this condition, There is no solution.

 Thereafter, the pressure is alternately set to 300 Torr (FIG. 4 (a)) and 5 Torr (FIG. 4 (b)), and the above operation is repeated.

In any of the stationary method, the transfer method, and the compound method, the TiCI ₄ gas discharged from the reaction vessel to the outside of the system is cooled and liquefied. With such a configuration, almost all of the TiG supplied to the reaction vessel can be recovered. The recovered TiG can be recycled as a raw material for the reaction. In addition, purified titanium, which is a result of the present invention, refers to a 4N-6N-level titanium material whose impurity concentration is about 1/10 to 1/100 of that of crude titanium, depending on its use and application. As expected, it is not limited to this.

 As described above, according to the purification method of the present invention, purified titanium having a high bulk density and a high yield can be obtained. That is, the titanium purification method according to the present invention is a titanium purification method with high productivity. Further, according to the titanium refining method according to the present invention, titanium can be purified at a lower price as compared with the conventional method, and material loss is small. Such effects can be obtained with a simpler device. Other advantages of the present invention will become more apparent from the following description. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is an equilibrium diagram of the Ti (S) -TiGI ₂ (S) system. FIG. 2 is an explanatory diagram of a purification method by a stationary method. FIG. 3 is an explanatory view of the purification method by the transfer method. FIG. 4 is an explanatory diagram of the purification method by the hybrid method. FIG. 5 is a schematic configuration diagram showing an example of a preferred apparatus for carrying out the transfer method. FIG. 6 is a schematic diagram showing an example of a preferred apparatus for performing the stationary method. Figure f is an enlarged view of the main part of Figure 6. FIG. 8 is a schematic configuration diagram showing an example of a preferred apparatus for performing the combined method. Figure 9 shows another device for carrying out the transfer method. It is a schematic structure figure showing an example.

BEST MODE FOR CARRYING OUT THE INVENTION

 Next, an example of the manufacturing method of the present invention will be described with reference to FIG.

 In this example, as shown in FIG. 5, a reaction vessel 1 as a single vessel is disposed in an electric furnace 8 as a heating device, and a reaction vessel lid 5 is provided on an upper surface of the reaction vessel 1. Is provided. A tubular section is provided so as to rise from the bottom of the reaction vessel lid 5, and this tubular section is used as a separation chamber 6 as a zone 3. The separation chamber 6 is equipped with a scraper 7 as a mechanical means for scraping low-grade titanium chloride deposited on the inner wall surface of the separation chamber 6. The lower half of the reaction vessel 1 of this example is used as a production chamber 2 as a zone 1. Then, coarse titanium particles 16 are filled in layers in the generation chamber 2, and the upper half is used as a pyrolysis chamber 3 as a zone 2. The pyrolysis chamber 3 is provided with a pyrolysis vessel 4.

 General-purpose iron, stainless steel, etc. are used as the structural material of the above-mentioned apparatus, and the surface of these structural materials is lined with titanium or titanium itself is used at the part that comes into contact with the reaction-related substances. Also, the titanium tetrachloride supply pipe 9, the production chamber 2, and the part where only the vapor of the reaction-participants are in contact are replaced with titanium, and titanium is also made of a material having low affinity with chlorine, such as nickel lining or nickel. It itself can be used.

The heating wire of the electric furnace 8 surrounding the reaction vessel 1 is divided into several parts in the vertical direction, and a heating wire is also provided at the bottom of the reaction vessel lid 5. Then, the production chamber 2 and the thermal decomposition chamber 3 are maintained at a predetermined temperature by the heating wire of the electric furnace 8. The outer wall of the separation chamber 6 is cooled to an appropriate temperature by a heat medium. Also, in this example, titanium tetrachloride vapor does not condense at each part of the manufacturing equipment, especially at the local area such as the flange. I keep it warm.

 Titanium tetrachloride vapor is continuously supplied at a constant flow rate to the production chamber 2 from the titanium tetrachloride supply pipe 9 attached to the bottom of the reaction vessel 1, and discharged from the separation chamber 6 through the titanium tetrachloride discharge pipe 10. By adjusting the flow rate of titanium tetrachloride vapor to be maintained, the inside of the apparatus is maintained at a predetermined pressure.

 The titanium tetrachloride vapor supplied to the generation chamber 2 reacts with the coarse titanium while passing through the gap between the coarse titanium pieces 16 and becomes a mixed vapor that reaches equilibrium before reaching the upper surface of the coarse titanium particle packed bed. This mixed vapor is supplied to the separation chamber 6 through the gap 11 between the inner wall of the reaction vessel 1 and the outer wall of the pyrolysis vessel 4 and the many small holes 12 at the bottom of the pyrolysis vessel 4 as flow paths. The lower titanium chloride contained therein is cooled on the inside to precipitate out on the inner wall surface, and the titanium tetrachloride remaining as a vapor is discharged outside through a titanium tetrachloride discharge pipe 10.

 The lower titanium chloride deposited on the inner wall of the separation chamber 6 is continuously scraped off by the scraper 17 and falls into the lower pyrolysis chamber 3.

 In the pyrolysis chamber 3, the lower chloride continuously falling from the separation chamber 6 is thermally decomposed to produce purified titanium 17 and the lower titanium chloride unavoidably generated accompanying this reaction. Mixed steam consisting of steam and titanium tetrachloride steam is continuously generated. This mixed vapor is supplied to the separation chamber 6 together with the mixed vapor generated in the generation step, and continuously deposits lower titanium chloride, and the residual titanium tetrachloride vapor is continuously discharged outside the vessel.

 In the continuous operation described above, in the process in which the exchange of low-grade titanium chloride between the separation chamber 6 and the thermal decomposition chamber 3 is repeatedly and continuously performed, the generation process is performed at a rate corresponding to the rate at which the low-grade chloride is consumed by thermal decomposition. It is stabilized by replenishing low-grade titanium chloride.

This is achieved by supplying titanium tetrachloride to production chamber 2 at a flow rate equal to the flow rate of titanium tetrachloride discharged out of the process from separation chamber 6, In this case, for example, if the lower titanium chloride has a composition of 0.2 mol of titanium trichloride to 1 mol of titanium dichloride, the purified titanium is about 0.5 mol per 1 mol of the supply or discharge of titanium tetrachloride. Molar strength is generated and accumulated in the pyrolysis chamber 3.

 (Specific examples)

 【Example 1 】

 Example 1 shows an example of a preferable apparatus for carrying out the transfer method.In FIG. 5, a stainless steel reaction vessel 1 as a single vessel has an inner diameter of about 16 cm and a zone 1 is used. Approximately 4 Ocm in height of the generation chamber 2 of the furnace, Approximately 6 Ocm in height of the pyrolysis chamber 3 as Zone 2, Approximately 14 cm in outer diameter of the pyrolysis vessel 4 made of titanium, 5.5 cm in height, Zone 3 The inner diameter of the reaction chamber 1 (excluding the bottom), the inner wall of the reaction chamber 1 (excluding the bottom), the inner wall of the reaction chamber 1 and the inner wall of the separation chamber 6 and the inner wall of the separation chamber 6 For this, a device lined with a titanium plate was used.

 In this example, a scraper 7 as a mechanical means in the separation chamber 6 has a titanium shaft having a diameter of about 2 cm, and a diameter of about 1 cm 8.5 which is attached at a right angle to a tip of the shaft. Consists of a rod-shaped inner wall scraper made of titanium with a diameter of less than 1 cm and a wing blade 14. By moving it, the lower titanium chloride deposited on the inner wall of the separation chamber 6 is completely scraped.

At the same time, just above the position of the inner wall scraper and the wing at the upper limit of the spiral movement of the scraper 7, two titanium chips, about 1 cm in diameter and slightly more than 3 cm in diameter, attached to the inner wall in the diametric direction of the inner wall, i.e., shaft scraper A mechanism is used to scrape the low-grade titanium chloride that precipitates on the shaft by the tip of the blade 15 sliding on the shaft surface as the scraper spirals. In the production chamber 2, 1 Okg of commercially available titanium titanium sponge was inserted. The interior of the reaction vessel 1 was evacuated to about 1 0- ³ T orr vacuum pump through an exhaust pipe 1 3 as the gas inflow and outflow pipes, generation chamber outer wall temperature of the second bottom surface to the upper 3 OCM about 9 6 0 ° C, heat medium wound around the outer wall of the separation chamber 6 while maintaining the outer wall temperature from 1 Ocm above the bottom of the pyrolysis chamber 3 to the upper end and the bottom temperature of the reaction vessel lid 5 at about 940 "C A heating medium of 150 mm was flowed through the pipe, and the entire area of the apparatus was kept at 150 ° C or higher.

A titanium tetrachloride liquid was supplied from the titanium tetrachloride supply pipe 9 as a gas inlet / outlet pipe to the production chamber 2 at a constant flow rate of 40 Og / hr. (Liquid is easier to supply titanium tetrachloride quantitatively. However, since the supplied liquid is vaporized before reacting in the production chamber 2, it is essentially the same as that supplied by steam.) The internal pressure of the reaction vessel 1 was maintained at 20 Torr by adjusting the flow rate of steam discharged from the titanium tetrachloride discharge pipe, and the scraper 17 was operated continuously. The reaction was carried out for 60 hours under the above conditions, then the supply of titanium tetrachloride was stopped, the operation of the scraper 7 was continued for about one hour thereafter, and it was confirmed that the discharge of titanium tetrachloride was stopped. the while holding temperature at the time of the reaction, carried out for approximately 1 hour evacuated by a vacuum pump, the vacuum degree in the reaction chamber 1 as follows 1 0- ³ T orr, the reaction vessel 1 was sealed, further purification obtained After keeping each part of the equipment warm for about three hours to stabilize the crystal state of titanium, the equipment was cooled to room temperature.

Then, 2.91 kg of purified titanium accumulated in the pyrolysis chamber 3 was collected. The total supply amount of titanium tetrachloride was 24.6 kg. The discharged titanium tetrachloride vapor was cooled and liquefied and measured, and 24.2 kg was recovered. Theoretically, the same amount as the supply should be recovered, and the loss of titanium tetrachloride is 24.6 kg-24.2 kg = 0.4 kg, or about 1.6% of the supply. However, when the equipment was disassembled, the gap between reaction vessel 1 and reaction vessel lid 5, separation chamber 6 Since the lower titanium chloride had adhered to the head and the tip of the shaft of the scraper 17, it is estimated that the loss of titanium tetrachloride was lost in the form of lower titanium chloride. Chart 10 shows the analytical values of raw titanium crude and purified titanium.

 [Example 2]

 An example of a preferred apparatus for performing the stationary method of the present invention will be described with reference to FIGS. FIG. 6 shows the overall configuration of the apparatus, and FIG. 6 is an enlarged view of a main part of FIG.

 As shown in Fig. 6, a transparent quartz reaction tube 31 (outer diameter 24, inner diameter 21, length 5 O O mm) as a single vessel is installed horizontally. When purifying with this apparatus, the airflow flowing in the reaction tube 31 is reversed from left to right or right to left in FIG. 6 at regular intervals.

 Therefore, two production chambers are required as zone 1 for the reaction between titanium and titanium tetrachloride, and they are located near the left and right ends of the reaction tube 31 and at the axial center plane 32 of the reaction tube 31. On the other hand, a left generation chamber 33 and a right generation chamber 34 (each of which has a position of 70 13 O mm from the center) are provided at the same positions.

 As shown in Fig. 7, in the left and right production chambers 33 and 34, approximately 14 g of cutting chips obtained by cutting a titanium pre-gut with a lathe as raw titanium was densely packed per chamber. Fill and stuff quartz wool 35 into a plug at each end. This quartz wool 35 can pass airflow if there is a slight pressure difference between both ends of the left and right generation chambers 3334, but if there is no pressure difference but convection occurs, the convection is left. It functions to block the gas from entering and exiting the inside and outside of the right and left generation chambers 3 3 3 4. That is, it functions to confine the gas in the room unless there is an airflow passing through the left and right generation chambers 3 3 3 4.

The space inside the reaction tube 31 sandwiched between the left and right production chambers 3 3 3 4 is a mixture of lower titanium chloride and titanium tetrachloride discharged from the left and right production chambers 3 3 3 4. The combined steam is cooled, the lower titanium chloride solid is deposited on the inner wall of the reaction tube 31, and the function of the separation chamber as zone 3 is separated from the titanium tetrachloride vapor, and the lower titanium chloride deposited on the inner wall of the reaction tube 31. It is used as a refining chamber that also functions as a pyrolysis chamber as zone 2 for heating and pyrolysis, and is divided into left and right, and the left refining chamber 36 and the right refining chamber 3 mm).

 In Fig. 6 and Fig. F, in the case of airflow from the left, the left purification chamber 36 functions as a pyrolysis chamber, the right purification chamber 37 functions as a separation chamber, and in the case of airflow from right to left, the right purification chamber 3 Is a pyrolysis chamber, and the left purification chamber 36 functions as a separation chamber.

 A tubular electric furnace 38 (with an inner diameter of 34 mm and a length of 22 O mm) is installed on the outer periphery of the reaction tube 31 as a heating device that can move to the right and left. In the leftward position shown in Fig. 6 (the right end face is 4 Omm to the right from the center, the left end face is 180 圆 to the left from the center). In the case of airflow from right to left, with respect to the center of the reaction tube 31, Move to the right position symmetrical to the above.

The electric furnace 3 8, by a special arrangement of the heat generating element, 9 5 0 ⁿ portions furnace temperature within a range of ± 5 ° C when heated to about C equals, i.e. the length of the isothermal section 3 9 1 2 O mm, for example, when placed at the left side position, most of the left generation chamber 33 and the left purification chamber 36 can be covered by the temperature equalizing section 39, and in the opposite case, the reverse chamber is forced. You.

 In the gap between the inner wall of the electric furnace 38 and the outer wall of the reaction tube 31, there are 7 pairs of hot-melt and alumel thermoelectric heaters with hot contacts placed at the center of the electric furnace 38 and at right and left intervals of 3 O mm. Insert pairs 40, 41, 42, 43, 44, 45, 46 and connect to the meters respectively. Figure 6 shows only the hot junction position. Insulating materials 47 are inserted at both ends of the gap to keep the temperature.

The left and right ends of the reaction tube 31 are connected to a left gas inlet / outlet tube 48 and a right gas outlet / inlet tube 49, respectively, and the connection is sealed with a fluoro rubber stopper. Titanium tetrachloride solution is stored via the valves 50 and 51, respectively, and the left and right reservoirs 52 and 53 where vaporization and liquefaction are to be performed are performed (each having an inner diameter of 21 mm). It has a total length of 250 mm and a storage capacity of about 60 g).

 The left and right liquid reservoirs 52, 53 are connected to the line 56 via valves 54, 55, respectively, and the liquid trap 5 7 (inner diameter 3 O itiiru total length 300 nim, approx. 120 g), and further through a cold trap 57, through a valve 58, through an exhaust pipe 59 to a vacuum pump 60. The left liquid reservoir 52 is provided with a titanium tetrachloride injection port 62 having a valve 61, and the right gas inlet / outlet pipe 49 is provided with a U-tube pressure gauge 64 and a device via a valve 63. A gas supply port 66 having a valve 65 for introducing argon, air, etc. into the inside is connected. The left and right reservoirs 52 and 53 are immersed in water bath pots 6 and 68, respectively, with a temperature control function, and the cold trap 5 is in a coolant port 69 with cooling function. Soaked in

 Next, the purification reaction will be described.

At temperature t = 900 ° C, pressure P = 37 Torr, but system S. _{Since this is} the upper limit of ₂ , even if there are slight errors and fluctuations in the temperature and pressure during the operation, the system S. Therefore, for example, the temperature t = 950 ° C, the pressure P = 27 Torr (the temperature of the titanium tetrachloride liquid showing this vapor pressure is about 40 ° C), the titanium and titanium tetrachloride Set the conditions for the reaction of steam and the thermal decomposition reaction of lower titanium chloride.c Temperature of left reservoir 52 is 0 L at 45 ° C, temperature of right reservoir 53 is 0 R at 0 to 10 ° C, electric furnace 3 8 is set to the left position, the temperature of the soaking section is 900 ° C, the valve 50 is fully opened, the pressure gauge reading P is adjusted to 27 Torr, and the air flow is adjusted to 3 1 Start the reaction with the flow from left to right.

The reason why 0 L was raised to 45 ° C instead of the theoretical value of 40 ° C was that the evaporation area of the liquid pool was not enough and there was a pressure loss in the reaction tube 31, so P of This is because the value cannot be increased to 27 Torr, and in order to keep P constant and obtain the specified titanium tetrachloride supply rate, it is necessary to increase the level to 0 L while observing the rate of decrease in the liquid level h of the liquid reservoir. The opening of valve 51 must be adjusted. It is appropriate that the feed rate of titanium tetrachloride is about 0.1 g / tn in on this scale. If the operation is continued in this state, the titanium tetrachloride vapor supplied into the reaction tube 31 reacts from the left end of the crude titanium filled in the left generation chamber 33, passes through the packed bed, and is discharged from the right end. By the balance equation

(Equation 1) Ti (solid phase) + Ti CI ₄ (gas phase) << ₂ Ti CI ₂ (gas phase) (Formula 2) Ti CI ₂ (gas phase) + Ti CI ₄ (gas phase) 《2 T i CI ₃ (vapor phase), which becomes a mixed vapor of lower titanium chloride vapor and titanium tetrachloride vapor. The lower titanium chloride solid is placed in the reaction tube 3 near the center in the lengthwise direction of the right reaction chamber. 1 On the inner wall, the radial center is deposited in the shape of a hollow ring, and its axial section is deposited in the shape of a lens. When the supply amount of titanium tetrachloride reaches about 5 g in the airflow direction from left to right, the valves 50 and 51 are closed once, the temperature of the right reservoir 53 is 45 ° C, and the left reservoir 5 2 After setting the temperature of the furnace to 0 to 10 ° C and once opening the valve 50, the electric furnace 38 is gradually moved to the right side position. While the electric furnace 38 is moving, when the right purification chamber 37 enters the heating section of the electric furnace 38, the thermal decomposition reaction of the lower titanium chloride starts as soon as possible.

 After moving the electric furnace 38, adjust the temperature of the soaking zone t to 900 ° C, adjust the opening of the valve 50, open the valve 51, and set the pressure P = 17 Torr, tetrachloride. Adjust the operation conditions to a titanium supply flow rate of 0.1 g / min and start operation with a right-to-left airflow.

The reaction in the right generation chamber 34, solidification and deposition of lower titanium chloride in the left purification chamber 36, separation from titanium tetrachloride vapor, etc. are the same as in the case of airflow from left to right. In parallel with the reaction separation, the lower titanium chloride is thermally decomposed in the right purification chamber 37. Since the pyrolysis reaction proceeds rapidly, it ends at the beginning of this stage, and the reaction proceeds in the right production chamber 3 4 with the purified titanium in the right purification chamber 3, and the right production chamber 3 4 The mixed vapor flowing out of the tank passes through the purified titanium in the right purification chamber 37, and this mixed vapor has already reached equilibrium with the crude titanium in the right generation chamber 34, and the right purification chamber 3 in which purified titanium exists Since it is under the same temperature and pressure conditions as the heat pump, there is no reverse reaction or contamination.

 When the supply of about 5 g of titanium tetrachloride is completed in the right-to-left airflow direction, the operation is switched to the left-to-right airflow again. The switching procedure and operating conditions are the same as above, except that in this operation, solidification and deposition of lower titanium chloride in the right purification chamber 31 occurs on the purified titanium that has already been formed. However, the cavity at the center of the reaction tube 31 in this part, that is, the passage of the air flow is narrowed.

 Changing the leftward or rightward position of the electric furnace 38 by about 1 Omm each time has a certain degree of blockage prevention effect, but the airflow passage is blocked after several operations. This means that the operation has been performed up to the capacity of the refining room, so the clogged low-grade titanium chloride is thermally decomposed and the operation is terminated.

 First, close the valves 50 and 51 once, and then close the left and right water bath

6 Add ice to 9 and cool the left and right reservoirs 52 and 53 to around 0 ° C, then open the valves 50 and 51. This is because the titanium tetrachloride in the reaction tube 31 and the piping is absorbed as much as possible into the left and right liquid reservoirs 52, 53, and the pressure is reduced to complete the final pyrolysis.

Next, the electric furnace 38 was gradually moved to the center of the reaction tube 31 at a temperature of the soaking temperature of t = 950 ° C, and the left and right refining chambers 36 and 37 were almost uniformly heated. Cover the lower part and pyrolyze the low-grade titanium tetrachloride into the left and right liquid reservoirs 52, 53 until the distilling of the titanium tetrachloride stops, and then perform valves 50, 51 And then maintain the temperature in the soaking zone at t = 95 ° C for another 3 hours. 8 Turn off the power and end the operation.

 As far as the last, the electric furnace 38 is placed in the center of the reaction tube 31 because, for example, low-grade titanium chloride clogged in the left purification chamber 36 is pyrolyzed at the electric furnace 38 position on the left side. This is because the lower titanium chloride generated along with the solidification deposits on the purified titanium in the right purification chamber 37, and if the electric furnace 38 is placed at the center of the reaction tube 3 3, this lower titanium chloride will be located at both ends of the furnace. Solidified around the left and right production chambers 33, 34, and the purified titanium in the left and right purification chambers 36, 37 is protected from contamination with low-grade titanium chloride.

 When the reaction tube 31 has cooled down to room temperature, real gas or air is gradually introduced into the reaction tube 31 from the gas supply port 66, and the reaction tube 31 is cut to collect purified titanium.

 The collected purified titanium is in the form of a fine-grained sponge and may adhere to traces of lower chlorides.Therefore, it is recommended to wash with about 0.5N diluted hydrochloric acid, then wash with pure water, and dry before use. preferable.

 [Example 3]

 With reference to FIG. 8, an example of a preferable manufacturing apparatus for performing the combined method of the present invention will be described. In this example, the reaction vessel 1 is used as a single vessel, and the reaction vessel 1 includes a production chamber 2 as a zone 1, a separation chamber 6 as a zone 3, a pyrolysis chamber 91 as a zone 2, The main components are a scraper shaft 84 and a scraping blade 85 as mechanical means.

The reaction vessel 1 in this example is made of stainless steel, and is a hollow cylindrical vessel as shown in Fig. 8, having a body length of about 17.5 cm and an outer diameter of about 22 cm. . A reaction vessel lid 5 is attached to the head of the reaction vessel 1, and can be hermetically sealed. A titanium tetrachloride supply pipe 5 inserted up to the inner cylinder bottom plate 4 is attached to the bottom of the reaction vessel 1, and a titanium tetrachloride discharge pipe 10 is attached to a side surface of the reaction vessel lid 2. Inside the reaction vessel 1 of this example, a hollow cylindrical inner cylinder 3 suspended from the reaction vessel lid 2 is provided. The inner cylinder 3 is made of titanium and has a length of about 1 cm and an inner diameter of 18 cm.

 The generation chamber 2 of the present example is a part of the inner cylinder 3, a hollow cylindrical part divided by the partition plate 8 and the inner cylinder bottom plate 4, and has a height of 60 cm. The partition plate 8 is attached at a position approximately 110 cm below the upper surface of the reaction vessel head flange 82 to be joined to the reaction vessel lid 2. Although gas can flow through the partition plate 83, granules cannot flow and are supported by the partition plate 83. The production chamber 2 is filled with crude titanium. In the production chamber 2, the filled crude titanium and the titanium tetrachloride vapor supplied from below react in the first step to produce a produced mixed vapor.

 The scraper shaft 84 penetrates through the center of the head of the reaction vessel lid 2 and is inserted into the center of the inner cylinder 3. The scraper shaft 84 is made of titanium. At the tip of the scraper shaft 84, a scraping blade 85 is attached in an inverted T-shape with respect to the shaft 84. The scraper shaft 84 is configured to perform a spiral motion, that is, a combined motion of a rotational motion and a vertical motion. Along with the spiral movement of the scraper shaft 84, the tip of the scraping blade 85 slides on the inner wall of the inner cylinder 3 to scrape the lower titanium chloride deposited on the inner wall downward.

 FIG. 8 shows the lower limit position of the scraping blade 85, that is, the lower limit position of the spiral movement of the scraper shaft 84 in the vertical direction. The lower limit position of the scraping blade 85 shown in FIG. 8 is about 6 O cm below the upper surface of the reaction vessel head flange 82. Accordingly, the scraping range of the scraping blade 85 is from the position of the scraping blade 85 shown in FIG.

The separation chamber 6 in this example is a part of the inner cylinder 91, and is a hollow cylindrical part partitioned by the lower limit position of the scraping blade 85 and the partition plate 83, and has a height of 60 c. m. In the separation chamber 6, the lower titanium chloride vapor is cooled, and a lower titanium chloride solid precipitates and is scraped downward.

 The pyrolysis chamber 3 of this example is a part of the inner cylinder 91, and is a hollow cylindrical part partitioned at the lower limit position of the partition plate 83 and the scraping blade 85, and has a height of about 5 O. cm range. In the thermal decomposition chamber 3, a part of the lower titanium chloride precipitates from the mixed gas generated in the first step. In the second step, the deposited lower titanium chloride and the lower titanium chloride scraped off from the separation chamber are thermally decomposed.

 The electric furnace 8 of this example is a temperature control mechanism, and is configured to surround the reaction vessel 1. In the electric furnace 8, the temperature and the temperature distribution of the production chamber 2, the separation chamber 6, and the thermal decomposition chamber 3 are adjusted. The electric furnace 8 is divided into at least three upper and lower stages, and each section can independently adjust the temperature and the temperature distribution arbitrarily.

 The titanium tetrachloride supply pipe 9 of this example is connected to a titanium tetrachloride supply facility (not shown) via a titanium tetrachloride supply valve 86. The titanium tetrachloride supply equipment is equipment for supplying titanium tetrachloride vapor into the reaction vessel and adjusting the pressure in the reaction vessel to a pressure of about 60 T rr (abs.) Or less. A measuring instrument is attached to the titanium tetrachloride supply facility. A pressure gauge 87 is installed between the reaction vessel 1 and the titanium tetrachloride supply valve 86, and the pressure gauge 87 measures the pressure in the reaction vessel.

The titanium tetrachloride discharge pipe 10 of this example is connected to a titanium tetrachloride condenser (not shown) via a titanium tetrachloride discharge valve 88. The titanium tetrachloride condenser is a device for cooling and liquefying the discharged titanium tetrachloride vapor to 120 ° C. or less. The titanium tetrachloride condenser is provided with a collection receiver for storing the collected titanium tetrachloride. The titanium tetrachloride discharge pipe 10 is further connected to exhaust equipment (not shown) via an exhaust valve 89. You. When titanium tetrachloride emissions from the reaction vessel 1 is small opens the exhaust valve 8 9, the pressure in the reaction vessel can be evacuated until 1 0- ² (T orr) below.

 Exhaust equipment (not shown) to which a titanium tetrachloride discharge pipe 10 is connected via an exhaust valve 89 is further provided with a pipe and connected to the titanium tetrachloride condenser. Since the vapor pressure of titanium tetrachloride at 120 ° C is about 0.9 (Torr), when there is no non-condensable gas in the condenser, the condenser removes the exhausted titanium tetrachloride from the condenser. It can be evacuated until the pressure is close to 0.9 (Torr). However, when non-condensable gas accumulates in the condenser, the discharge capacity decreases. Therefore, the gas in the condenser can be temporarily exhausted by the exhaust equipment through the pipe.

 The scraper shaft 84 is connected to the screwing drive mechanism above the shaft 90. To protect the seal from contamination due to the attachment of low-grade titanium chloride in the lower half of the shaft inserted into the reactor and high temperatures, the shaft seal 90 is positioned approximately 6 Ocm above the top of the reactor lid 5. Is provided. The length of about 6 O cm corresponds to the vertical stroke distance of the scraper shaft 84.

Using the apparatus used in this example, a titanium purification experiment of the pyrolysis zone transfer method under reduced pressure conditions described in the section of the embodiment was performed. The principle of the thermal decomposition zone transfer method under reduced pressure conditions will be described. In this experiment, a temperature gradient was set so that the lower end of the reactor was hot and the upper end was cold, and the temperature of each part was kept constant. The pressure inside the reaction vessel is gradually reduced, and the range in which thermal decomposition occurs increases from the lower end to the upper end. Since the lower titanium chloride present in the reaction vessel is thermally decomposed in order from the lower end, the generated pyrolysis mixed steam starts the pyrolysis reaction at a lower temperature than the part under pyrolysis above and near it. Is guided to the part that is not. The pyrolysis mixed vapor deposits a lower titanium chloride solid in a portion where the pyrolysis reaction has not yet started at a lower temperature than the portion under the pyrolysis. In the process where the position of this thermal decomposition and precipitation gradually moves upward with a decrease in pressure, thermal decomposition is repeated. By doing so, the rate of thermal decomposition per operation of thermal decomposition can be increased.

 Hereinafter, the operation of the titanium purification experiment will be described. A commercially available sponge titanium 19 (kg) having a particle size of about 1 (mm;) to 17 (mm) as crude titanium is filled in the production chamber 2 so as to have a layer height of 55 (cm). Assemble. Then, the inside of the reaction vessel 1 is evacuated to 10— (T rr) by the exhaust system.

 Next, the temperature of the reaction vessel 1 is increased. The temperature at the lower end of the production chamber 2 is 100 000 (° C). The temperature at the boundary between the production chamber 2 and the pyrolysis chamber 3 is 966 (° C). Here, if the solid-phase titanium dichloride equilibrium system is defined as an equilibrium system in which only titanium dichloride can stably exist as the solid phase, 963 (° C) is the solid phase at 300 (Torr). This is the boundary temperature between the titanium equilibrium system and the solid phase titanium dichloride equilibrium system. The temperature at the boundary between the pyrolysis chamber 3 and the separation chamber 6 is set to 850 (° C). 850 (° C) is the boundary temperature between the solid titanium equilibrium system and the solid titanium dichloride equilibrium system at 5 (T rr). The temperature at the upper end of the separation chamber 6 is set to 200 (° C). After raising the temperature of each part of the reaction vessel 1 to the above-mentioned temperature, these temperatures are maintained until the entire purification reaction is completed.

 Next, the titanium tetrachloride supply valve 15 is opened, and titanium tetrachloride vapor is supplied into the reaction vessel 1 at a flow rate of 30 (moIr.), That is, 5.69 (KgZHr.). The first generation reaction is performed for about 2 hours.

The production reaction is performed with the pressure in the reaction vessel 1 set to 300 (Torr). Since the production chamber 2 is in a solid-phase titanium equilibrium system, lower titanium chloride does not precipitate in the production chamber 2. In contrast, pyrolysis chamber 3 is in the equilibrium system of solid titanium dichloride. Therefore, when the produced mixed vapor flows into the pyrolysis chamber 3, titanium dichloride is immediately deposited at the bottom of the pyrolysis chamber 3. From the bottom to the upper end of the pyrolysis chamber 3, lower titanium chloride rich in titanium trichloride is gradually deposited as the temperature decreases.

 Immediately before the end of the first production reaction, the scraper shaft 84 is operated two reciprocations to scrape the lower titanium chloride deposited in the separation chamber 6 into the thermal decomposition chamber. When the scraper shaft 84 is stopped to prevent the temperature of the scraper from rising, the scraper shaft 84 is stopped at the upper limit position shown in FIG. The titanium tetrachloride supply valve 86 is closed to stop the supply of titanium tetrachloride, and the first generation reaction is completed. Then, in order to start the first thermal decomposition reaction, immediately open the titanium tetrachloride discharge valve 88, and raise the pressure in the reaction vessel 1 to about 300 (Torr) at a rate of about 10 (Torr). Reduce the pressure to 5 (Torr) or less.

 When the pressure in the reaction vessel 1 is gradually decreased from 300 (Torr), the thermal decomposition chamber 3 enters the conditions of the solid phase titanium equilibrium system from the bottom and starts thermal decomposition, and the range in which thermal decomposition occurs first Is expanded upward. When the pressure drops to 5 (Torr), the range in which pyrolysis occurs reaches the upper end of the pyrolysis chamber 3. Due to the decrease in pressure, thermal decomposition and precipitation of lower titanium chloride are repeatedly performed, and by repeating such thermal decomposition and precipitation, a high yield of purified titanium can be obtained.

At the end of the first thermal decomposition reaction, when the pressure in the reaction vessel 1 becomes 5 (Torr) or less and the discharge of titanium tetrachloride becomes small, the titanium tetrachloride discharge valve 88 is closed once, and the titanium tetrachloride is discharged. Open supply valve 15. Titanium tetrachloride is supplied at a flow rate of 30 (mol ZH r.). The titanium tetrachloride discharge valve 88 is adjusted so that the pressure in the reaction vessel 1 becomes 300 (Torr). The second production reaction is performed by the same operation as the first production reaction. After the completion of the second generation reaction, the second pyrolysis reaction is performed in the same manner as the first pyrolysis reaction. In the same manner, the third, fourth, and fifth production reactions and thermal decomposition reactions are performed.

 After the completion of the fifth pyrolysis, the titanium tetrachloride supply valve 86 was closed. The titanium tetrachloride discharge valve 88 was also closed once, and the continuous operation of the scraper 84 was started. This is because the residual low-grade titanium chloride precipitated in the separation chamber 6 from the pyrolysis mixed vapor generated during this pyrolysis is completely pyrolyzed. Immediately, the pressure in the reaction vessel 1 rises due to the thermal decomposition of the lower titanium chloride, so the titanium tetrachloride discharge valve 88 is adjusted so that it does not exceed 300 (Torr). Reduce pressure. When the pressure in the reaction vessel 1 becomes 5 (T rr) or less, close the valve 88 and allow the reaction vessel 1 to cool. When the temperature of the reaction vessel 1 is cooled to room temperature, the reaction vessel 1 is disassembled and the purified titanium generated in the pyrolysis chamber 3 is collected. Immediately wash the purified titanium successively with 1N hydrochloric acid, pure water, and methanol, and perform vacuum drying.

 Hereinafter, the results of an experiment performed by the above operation using the above apparatus will be described. The supply amount of titanium tetrachloride in the first production reaction was 60.0 (moI), that is, 11.4 (Kg). This is because titanium tetrachloride vapor at a flow rate of 30 (moI / Hr.) Was supplied for about 2 hours. On the other hand, the emission amount of titanium tetrachloride was 23.8 (moI), that is, 4.52 (Kg). After the discharged titanium tetrachloride vapor is liquefied by the condenser, it is stored as liquid titanium tetrachloride in the recovery receiver. This is a numerical value obtained by measuring the amount of liquid stored in this recovery receiver. From the above, the titanium tetrachloride emission was 39.7% of the titanium tetrachloride supply. It is probable that the difference between the supply and the discharge, 6 ◦ 30/0, was consumed in the production of lower titanium chloride.

Immediately before the end of the first production reaction, the scraper 8 was operated two reciprocations, and the lower titanium chloride deposited in the separation chamber 6 was scraped off to the pyrolysis chamber 3. An increase in titanium tetrachloride discharge flow was observed. It is presumed that titanium trichloride in lower titanium chloride was thermally decomposed and changed to titanium dichloride.

 After the completion of the first generation reaction, adjust the titanium tetrachloride discharge valve 88 to start the first thermal decomposition reaction, and adjust the pressure inside the reaction vessel 1 to 300 (Torr). When the pressure was reduced at a rate of about 10 (Tor Zmin.) To less than (T orr), it took about 30 minutes to reach about 3 (T orr).

 The emission amount of titanium tetrachloride in the first thermal decomposition reaction was 27.9 (moI) or 5.29 (g), and the ratio to the titanium tetrachloride supply amount during the production reaction was (2F. 9 (mo I) 60 (mo I)] 100 = 46.5%. This discharged titanium tetrachloride is probably generated by thermal decomposition of lower titanium chloride.

 If a method is used in which only one thermal decomposition occurs during one thermal decomposition operation without using the thermal decomposition zone transfer method of this example, the amount of titanium tetrachloride supplied during the production The ratio of titanium chloride emissions is usually around 20%. Compared to this, the value of 46.5% in this experimental result is very large. This result suggests that in this experiment, pyrolysis was performed repeatedly in one pyrolysis process, and the pyrolysis rate was high.

 The supply amount of titanium tetrachloride in the second production reaction was 60.0 (moI) or 11.4 (Kg), and the discharge amount of titanium tetrachloride was 24.2 (moI) or 4.59 (g) was 40.3% of the supplied amount.

The emission of titanium tetrachloride in the second pyrolysis reaction was 33.9 (moI) or 6.43 (Kg). The ratio of titanium tetrachloride emissions from the decomposition reaction was 56.5%. The reason that this ratio is higher than the similar ratio in the first stage is that the first stage pyrolysis reaction does not pyrolyze but forms a pyrolysis mixed vapor and precipitates in separation chamber 6. It is estimated that the undecomposed lower titanium chloride was thermally decomposed together with the lower titanium chloride from the second generation reaction.

 The total supply amount of titanium tetrachloride in the first to fifth production reactions was 300 (moI), that is, 56.9 (Kg). The total titanium tetrachloride emission was 123 (moI) or 23.3 (Kg), 41.7% of the titanium tetrachloride supply.

 100-41.7 = 58.3% of the supplied titanium tetrachloride is estimated to have contributed to the production of lower titanium chloride.

On the other hand, the total amount of titanium tetrachloride supplied in the first to fifth pyrolysis reactions was 164 (m ₀ I) or 31.1 (K g), indicating that the titanium tetrachloride supply in the production reaction was 54.7% of the total amount. This value is also significantly higher than when a method is used in which only one pyrolysis occurs during one pyrolysis operation without using the pyrolysis zone transfer method of this example.

 After the completion of the fifth pyrolysis, the scraper 84 was continuously operated to completely pyrolyze the residual lower titanium chloride deposited in the separation chamber 6 from the pyrolysis mixed vapor generated during the fifth pyrolysis. (moI), that is, 0.6 (Kg) of titanium tetrachloride was discharged.

 From the above results, the total amount of titanium tetrachloride emitted through all the reactions was 123 + 164 + 3 = 290 (moI), that is, 55.0 (Kg). The ratio of titanium tetrachloride emission to titanium tetrachloride supply was (290/300) X 100 = 96.7%. This value should be 100% if there is no physical loss. Equivalent to the loss of material quantity 100-96% = 3.3% is mainly due to non-condensation when exhausting low-grade titanium chloride accumulated in the non-scratchable part of the reaction vessel 1 and non-condensable gas accumulated in the condenser 1 It is highly probable that titanium tetrachloride was exhausted along with the volatile gas.

The purified titanium finally collected has a weight of 5.5 1 (K g) or 11.5 (moI). The specific gravity of the bulk was about 0.2 when the particle size was adjusted to about 25 (mm).

The analytical values of the crude titanium used as the raw material in this example and the purified titanium collected are as shown in Table 11.

 [Example 4]

 FIG. 9 shows an example of another manufacturing apparatus for performing the transfer method of the present invention. In this example, as shown in FIG. 9, an inert gas supply pipe 21 for introducing an inert gas into the bottom of the pyrolysis chamber 3 as the zone 2 was provided to penetrate the bottom of the reaction vessel lid 5. The tip was formed in a horizontal loop along the bottom of pyrolysis chamber 3. A large number of pores 22 were drilled in the lower surface of the loop-shaped tube, and the inert gas was uniformly dispersed and jetted. There is no hole in the bottom of the pyrolysis chamber 3, and the chloride mixed vapor is guided to the separation chamber 6 as zone 3 through the gap between the outer wall of the pyrolysis chamber 3 and the inner wall of the reaction vessel 1 as a single vessel It was configured as follows. The rest of the configuration is the same as in FIG.

 Next, a method of operating the apparatus of this example will be described.

 First, (a) argon was used as an inert gas, and a supply flow rate of 2.1 Mol / hr (titanium tetrachloride supply flow rate: 400 g / hr = 2.1 1 Mol / hr).

(B) an outer wall temperature and the bottom temperature of the reaction vessel lid 5 to the upper end from above 1 Oc _m at the bottom of the pyrolysis chamber 3 and 8 8 0 ° C, the reaction vessel pressure is the same as in Example 1 <2 0 T Adjusted to orr.

 (c) The operation method of the other devices is the same as that of the first embodiment.

 The temperature of the pyrolysis chamber at 880 ° C;

(Equation 8) Substituting into the right-hand side of I og P <20. 1 5 8— {2 1 8 5 9 / (t + 2 7 3)] I og P <20. 1 5 8-{2 1 8 5 9 (t + 2 7 3)}

 = 2 0. 1 5 8— (2 1 8 5 9 (8 8 0 + 27 3) 1

 = 1.200

 That is, P <15.8 T or r

 This indicates that if argon is not introduced, thermal decomposition will not occur unless the sum of the partial pressures of the reaction-related substances, that is, the total pressure, becomes 15.8 T rr or less. However, in this example, as a result of introducing argon into the pyrolysis chamber, the pyrolysis reaction proceeded smoothly even though the total pressure, that is, the sum of the partial pressures of the reaction participants and the partial pressure of argon was set to 20 Torr. In this way, purified titanium was obtained.

 This is a value obtained by subtracting the partial pressure of argon in the pyrolysis chamber from this value, even if the total pressure is 20 T or “, as a result of introducing argon into the pyrolysis chamber, that is, the sum of the partial pressures of the substances participating in the reaction. This indicates that the thermal decomposition reaction had progressed because it fell below 15.8 Torr.

 The result in the above example is

 Titanium tetrachloride supply = 23.8 kg

 Titanium tetrachloride recovery = 23.3 kg

 Titanium tetrachloride loss = 0.5kg (2.1%)

 Refined titanium collection = 2.87 kg

 Met. Industrial applicability

As described above, according to the present invention, titanium purification with high purification effect can be easily performed, the entire process can be performed in a single vessel having a simple structure, and there is no restriction on the expansion of equipment, so that once Thus, large-capacity refining is possible, and equipment costs per production volume are low. For example, the Kro II method By slightly modifying the reduction or separation equipment for one-chart titanium, it can be diverted to the practice of the present invention. Thus, the production volume per facility area or volume, that is, facility productivity is extremely high.

 Furthermore, operating conditions such as temperature and pressure are within easy-to-implement ranges, and there are no strict restrictions on equipment materials, etc., and there is little material loss due to the operation of the manufacturing process equipment, and the operation is simple and labor hours are low. Due to the above advantages, high-purity titanium can be refined at high productivity and at low cost.

Claims

The scope of the claims

 1. In an atmosphere from which all gases except the reaction-related substances, ie, titanium tetrachloride, titanium trichloride, titanium dichloride, and titanium, have been excluded, or all gases except the reaction-related substances and the inert gas have been excluded. A method for producing purified titanium by reacting crude titanium raw material and titanium tetrachloride supplied from outside the process in an atmosphere at a high temperature to obtain lower titanium chloride, and then thermally decomposing the lower titanium chloride. ,

 In the hermetic reaction vessel, a process comprising a production step of producing lower titanium chloride, a separation step of separating titanium tetrachloride from the lower titanium chloride, and a pyrolysis step of thermally decomposing the lower titanium chloride is constituted.

 In the production step, among various heterogeneous gas phase equilibrium systems formed as a result of the reaction between titanium and titanium tetrachloride, an equilibrium system in which only titanium can stably exist as a solid phase, that is, the following two equilibria:

T i (solid phase) + T i CI ₄ (gas phase) << ₂ T i CI ₂ (gas phase)

T i CI ₂ (gas phase) + T i CI ₄ (gas phase) << 2 T i CI, (gas phase)

Below the temperature and pressure selected from within the range of pressures defined as the sum of the temperature at which the equilibrium system represented by

 Producing a mixed vapor comprising lower titanium chloride vapor and titanium tetrachloride vapor obtained by sufficiently reacting until the equilibrium is substantially reached;

 In the separation step, by cooling the mixed vapor, the lower titanium chloride in the mixed vapor is separated from solid as titanium tetrachloride as vapor, and the titanium tetrachloride vapor is discharged out of the process,

In the pyrolysis step, the temperature and pressure are selected from within a temperature and pressure range in which an equilibrium system in which only titanium can be stably present is formed using the lower titanium chloride solid obtained in the separation step as the solid phase. Put under By

The following pyrolysis reaction:

Ί ί CI ₂ (solid phase) → Ti (solid phase) + Ti CI ₄ (gas phase)

4 T i CI 3 (solid phase) — D i (solid phase) + 3 T i CI ₄ (solid phase)

To obtain purified titanium, and the two equilibriums inevitably formed in association with this reaction;

T i (solid phase) + T i CI ₄ (gas phase) << ₂ T i CI ₂ (gas phase)

T i CI ₂ (gas phase) + Τ ί CI ₄ (gas phase) A mixed vapor composed of lower titanium chloride vapor and titanium tetrachloride vapor generated by T i CI, (gas phase) is produced in the above-mentioned production step. In the same manner as the mixed vapor, the mixture is cooled again in the separation step to separate the lower titanium chloride solid and the titanium tetrachloride vapor.The titanium tetrachloride is discharged out of the process, and the lower titanium chloride solid is pyrolyzed again in the pyrolysis step. By repeating the operation, almost all of the lower titanium chloride supplied from the production process was obtained as the total mass balance of both processes by the following two reactions;

2 T i CI ₂ → T i + T i CI ₄

4 T i CI ₃ → T i +3 T i CI ₄

According to, quantitatively converted to purified titanium and titanium tetrachloride,

 The overall physical balance of the entire process is as follows: titanium tetrachloride in an amount equivalent to titanium tetrachloride supplied to the production process from outside the process is discharged from the separation process, and crude titanium reacted and consumed in the production process within the process. A method for purifying titanium, characterized in that an amount of purified titanium equivalent to the above is obtained in a pyrolysis step.

 2. (a) Step 1 of reacting raw crude titanium with TiG to produce lower titanium chloride TiGlx vapor;

(b) Step 2 of depositing solid TiClx from TiGlx vapor generated in step 1 (c) a step 3 of thermally decomposing the solid TiClx to obtain purified titanium;

Hints process for purifying titanium obtaining a purified titanium is reacted with the raw material crude titanium and Tigi _4.

However, lower titanium chloride is represented by TiGlx, X is an integer of 2-3, and it is assumed that a mixture of 2 and 3 is included.The temperature tl (° C) and the pressure pi (Torr) at which the step 1 is performed are respectively 750. C≤t1 and I og (p I) 20.158-(21859 / (t1 +273)), and the pressure (p2) and temperature (t2) for performing the step 2 are 0.001 Torr <p2 <1520, respectively. To, 150 ° C <t2 <(21859 (20.158-log ( _P 2))-273 ° C, and the temperature t3 (° C) and pressure p3 (Torr) for performing the step 3 are 750 ° C ≤ t3, respectively. And I og (p3) <20.158-(21859 / (t3 + 273)).

 3. Perform Step 1 in Zone 1 located adjacent to Zone 2 adjacent to Zone 3 in a single vessel to generate TiClx vapor,

 The TiGlx vapor generated in Step 1 is transferred to Zone 2 located between Zone 1 and Zone 3 in the single container and to Zone 2 adjacent to Zone 1 in the single container. To the zone 3 arranged in the above-mentioned manner, the above-mentioned step 2 is carried out, and solid TiGlx is deposited in the zones 2 and 3; then, the inside of the vessel is depressurized and / or heated, and Step 3 is performed to precipitate purified titanium, and at the same time, Ti CIX vapor by-produced in step 3 is transferred to zone 3 to precipitate solid TiClx,

 Then, the zone 2 is brought to the initial pressure and the initial temperature, the step 1 is performed in the zone 1, and the solid TiGlx is deposited in the zone 2 and the zone 3,

Producing purified titanium by alternately repeating the step 3 and the solid TiClx precipitation step in the zone 2 and the zone 3; 2. The method for purifying titanium according to claim 1, wherein:

 4. Performing step 1 above in zone 1 located adjacent to zone 2 adjacent to zone 3 in a single vessel to generate TiGlx vapor,

 The TiClx vapor generated in the step 1 is transferred to the zone 2 disposed between the zone 1 and the zone 3 in the single container and to the zone 2 in the single container adjacent to the zone 1. Moved to the zone 3 arranged in the above-mentioned manner, and performed the step 2, and deposited solid TiGlx in the zones 2 and 3;

 Then, the zone 3 was depressurized and Z or heated, and the step 3 was performed in the zone 3 to generate TiGlx vapor and precipitate purified titanium at the same time.

 Then, the zone 3 is brought to the initial pressure and the initial temperature, and the step 1 is performed in the zone 1 to deposit solid TiGlx in the zones 2 and 3.

 The method for purifying titanium according to claim 1, wherein the step 3 and the step of depositing the solid TiClx are alternately and repeatedly performed in the zone 2 and the zone 3, thereby producing purified titanium.

 5. Performing step 1 above in zone 1 located adjacent to zone 2 adjacent to zone 3 in a single vessel to generate TiC Ix vapor,

 The TiGlx vapor generated in the step 1 is moved to the zone 3 arranged adjacent to the zone 2 adjacent to the zone 1 in a single container, and the step 2 is performed. Is precipitated,

 Simultaneously or intermittently with the step 2, the solid TiGlx deposited in the zone 3 is moved by mechanical means to the zone 2 provided between the zone 1 and the zone 3,

Next, Step 3 is performed in Zone 2 to generate TiGlx vapor. Sometimes precipitated titanium is deposited,

 The TiGlx vapor generated in the zone 2 is moved to the zone 3, and solid TiClx is deposited in the zone 3,

 The refinement of titanium according to claim 1, wherein the refined titanium is produced by alternately repeating the step 3 performed in the zone 2 and the solid TiGlx precipitation step performed in the zone 3. Method.

 6. Perform Step 1 above in Zone 1 located adjacent to Zone 3 and Zone 1 in a single vessel to generate TiGlx vapor,

 The TiGlx vapor generated in Step 1 is placed in Zone 2 between Zone 1 and Zone 3 in the single vessel and Zone 2 adjacent to Zone 1 in a single vessel. The zone 2 is moved to the zone 3, and the step 2 is performed.Solid TiG is deposited in the zones 2 and 3.The solid TiGlx deposited in the zone 3 is moved to the zone 2 by mechanical means. At the same time, the zone 2 is depressurized and heated or heated, and the step 3 is performed in the depressurized and / or heated zone 2 to generate TiClx vapor and precipitate purified titanium at the same time.

Then, the zone 2 and the zone 3 were brought to the initial pressure and the initial temperature, the step 1 was performed in the zone 1, and solid TiGlx was deposited in the zone 2 and the zone ³ ,

 The method for purifying titanium according to claim 1, wherein the step 3 and the step of depositing the solid TiGlx are repeatedly performed in the zone 2 and the zone 3 to produce purified titanium.

7. The temperature tl (C) and the pressure pi (Torr) at which the step 1 is performed are 850 ° C / tl / 1000 ° C and 5 Torr / p1 <970 Torr, respectively, and the temperature of the step 2 and the solid TiGlx The temperature t2 (° C) and the pressure _P 2 (Torr) for performing the deposition process are 200, respectively. C <t2 less 900. C and 5Torr <p2 <970Torr And the temperature t3 (° C) and the pressure p3 (Torr) at which the step 3 is performed are 850 ° 〇 <3 <1000 ° ぴ 5 ”1” 0 <nit3 <9701 ”0, respectively. The method for purifying titanium according to any one of claims 2, 3, and 4, wherein:

 8. The TiC vapor supplied from outside the vessel in the step 1 passes through the packed bed of the raw titanium solid material in the zone I and passes through the step I to be subjected to the steps 2 and 3 After being separated from other gases present in the container and discharged out of the container,

The separated TiGI ₄ vapor is supplied again into the vessel and used in the step 2, the step of depositing the solid TiClx, and the step 3. Method for refining titanium.

 9. The method for purifying titanium according to claim 1, wherein the step 3 is performed by introducing an inert gas into the container.

10 0. Left zone 1 and right where step 1 is performed to produce low-grade titanium chloride TiC Ix vapor by reacting crude titanium raw material and TiGI _{4 at} positions near the left and right ends of a single tubular reaction tube Zone 1 is provided, and left and right zones 2 are provided at the left and right portions of the longitudinal center of the reaction tube, respectively, in the space sandwiched between both zones 1, and the left and right ends of the reaction tube are provided. And a movable heating device arranged on the outer periphery of the reaction tube, wherein a gas flow flowing in the reaction tube is reversed at regular intervals. Titanium refining equipment.

 1 1. In a single reaction vessel, zone 1 in which step 1 is performed, step 2 in which solid TiGlx is precipitated from the TiGlx vapor generated in step 1, and solid titanium chloride is thermally decomposed to produce purified titanium. Zone 2 for performing the step 3 for obtaining, and zone 3 for performing the step 2

An opening is formed between the zone 2 and the zone 3 so that a mixed vapor of TiClx vapor and TiC vapor generated in the zone 2 and solid TiGlx can be transferred to each other. Is formed,

A titanium purifying apparatus _c comprising: two gas inlet / outlet pipes connected to a reaction tube; and a movable heating device disposed on an outer periphery of the reaction tube.

1 2. Within a single reaction vessel, there is a zone 1 for performing the step 1, a zone 2 for performing the step 3, and a zone 3 for performing the step 2.

 Forming a communication path between the zone 1 and the zone 3 for transferring the mixed steam generated in the zone 1 from the zone 1 to the zone 3;

 An opening is formed between the zone 2 and the zone 3 so that a mixed vapor of TiGlx vapor and TiC vapor generated in the zone 2 and solid TiGlx can be transferred to each other,

 It has two gas inlet / outlet pipes connected to the reaction tube, and the zone 3 is provided with mechanical means for transferring solid TiC Ix solidified and deposited in the zone 3 to the zone 2 side. An apparatus for refining titanium.

1 3. In a single reaction vessel, zone 1 for performing step 1 above, zone 2 for performing steps 2 and 3 above, and zone for performing step 2 above

Has 3,

An opening is formed between the zone 2 and the zone 3 so that the mixed vapor of the TiG vapor and the TiCI ₄ vapor generated in the zone 2 and the solid TiClx can be transferred to each other,

 It has two gas inlet / outlet pipes connected to a reaction tube, and the zone 3 is provided with mechanical means for scraping solid TiGlx solidified and precipitated in the zone 3 and transferring it to the zone 2 side. Titanium refining equipment.