WO2008041407A1

WO2008041407A1 - METHOD FOR PRODUCTION OF Ti GRANULE OR Ti ALLOY GRANULE, METHOD FOR PRODUCTION OF METAL Ti OR Ti ALLOY, AND PRODUCTION APPARATUS

Info

Publication number: WO2008041407A1
Application number: PCT/JP2007/064635
Authority: WO
Inventors: Tadashi Ogasawara; Makoto Yamaguchi; Masahiko Hori; Katsunori Dakeshita; Satomi Kawaguchi
Original assignee: Osaka Titanium Technologies Co., Ltd.
Priority date: 2006-10-03
Filing date: 2007-07-26
Publication date: 2008-04-10
Also published as: JP2008088513A

Abstract

Disclosed is a method for producing a Ti granule or a Ti alloy granule, which comprises the step of contacting Ti particles or Ti alloy particles produced by the reduction in a molten salt with one another to produce the Ti granule or Ti alloy granule. The method may further comprise the step of condensing the Ti granule or the Ti alloy granule in the molten salt that contains the Ti granule or the Ti alloy granule produced by the method. The method for producing a Ti granule or a Ti alloy granule in a molten salt may be applied to a step for separating the produced Ti granule or the Ti alloy granule from the molten salt in the process forthe production of metal Ti or a Ti alloy by Ca reduction. In this case, the productivity rate can be improved and it becomes possible to produce metal Ti or a Ti alloy at low cost.

Description

Specification

Ti grain or Ti alloy grain manufacturing method, metal Ti or Ti alloy manufacturing method and manufacturing apparatus

Technical field

[0001] The present invention relates to a method for producing Ti grains or Ti alloy grains, characterized by granulating Ti grains or Ti alloy grains produced by reduction in molten salt, and the Ti grains or Ti alloy grains. The present invention relates to a manufacturing method of metal Ti or Ti alloy to which the manufacturing method is applied and a manufacturing apparatus used therefor. Background art

[0002] As an industrial production method of metal Ti, a crawl method in which TiCl is reduced with Mg is common.

Four

Yes, it is possible to produce high-purity products. However, since the generated Ti powder settles in an aggregated state and is difficult to recover outside the reaction vessel, the operation must be carried out batchwise.

[0003] Further, TiCl is supplied in a liquid form from above to the molten Mg liquid surface in the reaction vessel, and melted.

Four

Since the reaction takes place only near the surface of the Mg solution, avoiding a decrease in the efficiency of TiCl use,

Four

TiCl supply rate is limited to avoid local heat generation due to reaction. as a result,

Four

Manufacturing costs are high and product prices are very high.

[0004] For this reason, much research and development has been conducted on methods for producing metallic Ti other than the crawl method. For example, US Pat. No. 4,820,339 describes the melting of CaCl in a reaction vessel.

2 Hold the salt, supply metal Ca powder from above into the molten salt, dissolve Ca in the molten salt, and supply downward force TiCl gas to dissolve in the molten salt of CaCl And Ti

4 2

A method of reacting C1 is described. However, metal Ca powder is extremely expensive.

Four

In addition, since the highly reactive Ca is very difficult to handle, this method cannot be established as an industrial Ti production method.

[0005] Therefore, in order to industrially establish a method for producing metal Ti by reduction of Ca, the present inventors need to reduce TiCl with Ca, and Ca contained in molten salt consumed in the reduction reaction.

Four

Therefore, it is necessary to replenish the Ca produced by the electrolysis of molten CaCl.

2

In addition to using it, we propose a method of recycling this Ca, that is, the “OYIK method”. (See JP-A-2005-133195 and JP-A-2005-133196).

[0006] In Japanese Patent Laid-Open No. 2005-133195, Ca is generated and replenished by electrolysis, and Ca-rich molten CaCl is introduced into a reaction vessel and used to generate Ti particles by Ca reduction.

2

JP-A-2005-133196 further discloses a method for effectively suppressing back reaction due to electrolysis by using an alloy electrode (for example, Mg—Ca alloy electrode) as a cathode. Yes.

[0007] In the methods described in JP-A-2005-133195 and JP-A-2005-133196, both Ti grains or Ti alloys formed by the reaction of TiCl and Ca

Four

A step of separating the grains from the molten salt is included. That is, C by electrolysis of molten CaCl

2

When the generation of a and the reduction of TiCl by Ca (generation of Ti grains or Ti alloy grains) are performed continuously,

Four

At the same time, the separation of the produced Ti grains or Ti alloy grains from the molten CaCl is performed continuously and rapidly.

2

This is extremely important when continuously producing metallic Ti by the OYIK method.

[0008] In the manufacturing process of metallic Ti or Ti alloy by Ca reduction using the OYIK method, the separation step is performed by sedimentation separation using gravity. The Ti grains immediately after being generated by Ca reduction are submicron fine particles. The heat generated during the force generation (reduction heat) promotes the bonding between the grains and coalesces. Sediment separation is possible.

[0009] However, even if such coalescence and agglomeration of grains occur, the recovery rate of Ti grains or Ti alloy grains is very fine, and the recovery rate decreases. In addition, Ti grains or Ti alloy grains are formed in a mixed state with bath salt, and its strength and strength are low. For example, Ti grains or Ti alloy grains are dissolved to form a liquid phase, and the upper layer bath salt is dissolved. If a method such as dissolution separation is used, a large amount of energy is required, and an increase in manufacturing cost is inevitable!

[0010] If the particle size of the generated Ti particles can be increased (the operation or treatment for increasing the particle size is referred to as “granulation” in this case), the particles settle and immediately become large in order to solve the above problems. This is thought to lead to improvement. However, no such attempt has been made in the past.

[0011] The operation of granulation has long been performed by various methods for various purposes. For example, to obtain pharmaceutical granules and tablets, granular products such as pesticides and chemical fertilizers, In order to obtain good pellets such as non-ringed and sintered raw materials, and briquettes, etc., granulation operations are performed from powders (fine particles) to molded products having various shapes. It is.

[0012] In addition, as a granulation method, generally, a moistened powdery substance is separated from granules and granular substances by utilizing an agglomeration phenomenon by an action such as rolling, stirring, and vibration using a rotary pan or a rotary drum. The dry powder (or moistened) is made into a granular material by compression between rolls or other mechanical forming.

[0013] However, the purpose and method of these granulation operations are all to form a powdery product (fine particles) into a molded product having a predetermined shape in the air. The fine particles are aggregated in a liquid such as a molten salt. It is not granulated.

Disclosure of the invention

[0014] As described above, in the OYIK method proposed by the present inventors, it is extremely important to continuously and rapidly separate the produced Ti grains or Ti alloy grains from the bath salt. However, it is difficult to increase the recovery rate of Ti grains or Ti alloy grains before the separation operation is very fine, resulting in a decrease in production speed and an increase in manufacturing cost.

[0015] Ti grains or Ti alloy grains are formed in a state of being mixed with a bath salt and have low strength and / or low concentration.

For this reason, if the method for removing bath salt by the above-described dissolution separation or the method for removing bath salt by washing with water is used, a large amount of energy is required, so an increase in production cost is inevitable.

[0016] Further, when producing powdered metal Ti or Ti alloy, there is a problem that the size of the obtained metal Ti or Ti alloy is small, and it is difficult to adjust the particle size and quality.

These problems can be solved by granulating the produced Ti grains or Ti alloy grains before separating them from the molten salt and promoting the sedimentation of the particles to increase the separation efficiency.

[0017] An object of the present invention is to produce Ti grains or Ti alloy grains by granulating Ti grains or Ti alloy grains produced by reduction in a molten salt in the molten salt, as well as the Ti grains or The production method of Ti alloy grains is applied in the process of separating the Ti grains or Ti alloy grains from the molten salt in the production process of metallic Ti or Ti alloys by Ca reduction, and the productivity is improved. Another object is to provide a method for producing a Ti alloy at a low cost and a production apparatus used for carrying out the method.

[0018] In order to solve the above problem, the present inventors reduced Ca in molten salt (molten CaCl 2).

2

We examined the granulation of Ti grains produced by the above method in the molten salt. As a result, TiCl was added to the molten CaCl, and the molten salt flow at the time when Ti grains formed (hereinafter referred to as the molten salt).

twenty four

By changing the state of molten salt to “bath salt” or “bath”, and changing the flow of molten salt to “bath flow” to make contact between grains easy to occur, It was found that they can be combined and granulated in bath salt. To change the bath flow, methods such as stirring the bath and providing a guide plate (baffle plate) in the bath are effective.

[0019] Further, the bath salt containing the Ti particles granulated in this way is concentrated using, for example, a liquid cyclone,

It was confirmed that the concentration (content rate) of Ti grains could be increased.

[0020] Then, if the granulation in the molten salt is applied to the production process of metal Ti or Ti alloy by Ca reduction in the process of separating the Ti grain or Ti alloy grain from the molten salt, Productivity can be improved and metal Ti or Ti alloys can be manufactured at low cost. In that case, the productivity improvement effect is further increased by applying the granulation accompanied by the concentration.

[0021] The present invention has been made on the basis of these findings. The gist of the present invention is the following (1) or (2) Ti grain or Ti alloy grain production method, and (3) metal Ti or Ti alloy. The manufacturing method of (4) and the manufacturing apparatus of (4) used for the implementation of the method are.

[0022] (1) A method for producing Ti grains or Ti alloy grains, characterized in that granulation is performed by bringing Ti grains or Ti alloy grains produced by reduction in molten salt into contact with each other.

(2) Concentration of Ti grains or Ti alloy grains in molten salt containing Ti grains or Ti alloy grains granulated by the production method described in (1) above. It is a manufacturing method.

Here, the “molten salt” refers to a substance obtained by heating and melting a solid salt or oxide at room temperature into a liquid state, or a mixture thereof. For example, molten salt consisting only of molten CaCl, molten

2

Examples thereof include molten salts containing CaCl, such as CaF added to CaCl.

2 2 2

[0024] Here,! /, "Contact" includes impingement in addition to the original meaning of! /, U.

[0025] In the method for producing Ti grains or Ti alloy grains described in (1) above, by contact between grains. If granulation is carried out by changing the bath flow, it is possible to significantly accelerate the granulation.

“Changing the bath flow” means changing the state of the bath salt flow (including the resting state here) at the time when Ti grains or Ti alloy grains are formed. For the purpose of granulation by contact, the premise is to change the movement of the bath salt so that contact between the grains is likely to occur. For example, if the bath is stationary when Ti grains or Ti alloy grains are formed, the bath is in a fluid state, and if the bath flow is in a laminar flow or a state close thereto, the bath is in a turbulent state. It means changing.

[0027] This "changing the bath flow" is to change the bath from a stationary state to a fluid state, or to make the bath flow turbulent. In addition to stirring the bath, a guide plate (baffle plate) is provided in the bath. It is also possible to change the speed of the bath flow or to rotate the bath flow.

[0028] In the method for producing Ti grains or Ti alloy grains described in (1) above, if the average grain size of the granulated grains is 1 μm or more, the sedimentation of the grains is promoted. The separation efficiency can be increased. In addition, if the average particle size after granulation is 100 m or more, it is desirable because the separation efficiency of the particles is remarkably improved. The “average particle size” means the particle size (D) at which the particle on the sieve or under the sieve is 50% in the particle size distribution (integrated distribution) expressed on a mass basis.

50

[0029] Furthermore, if the particle size of the Ti particles or Ti alloy particles granulated so that the average particle size is 1 am or more is 0.05 m or more and 10 m or less, the Ti particles or Ti The alloy grains can be regarded as Ti grains or Ti alloy grains produced by the method for producing Ti grains or Ti alloy grains described in (1) or (2) above.

[0030] Here,! /, “Particle size of the constituent particles” means that the major axis and minor axis of a particle are measured in an image observed with a SEM (scanning electron microscope), and the particle is regarded as an ellipse. This is an average value of the diameters of the circles obtained by performing the operation of obtaining the area and obtaining the diameter of the circle of the same area on the grains having 50 or more samples.

[0031] In the method for producing Ti grains or Ti alloy grains as described in (2) above, "/ Ti grains or Ti alloy grains in molten salt containing Ti grains or Ti alloy grains after granulation" "Concentration" can be done by hydrocyclone, centrifugation, filtration separation, or mechanical compression.

[0032] (3) A method for producing metal Ti or Ti alloy by Ca reduction in molten salt, A metal chloride containing TiCl is continuously fed into a molten salt containing Ca and dissolved therein to dissolve it.

Four

A reduction process for generating Ti grains or Ti alloy grains in the molten salt, a granulation process for granulating the Ti grains or Ti alloy grains immediately after the formation by coalescence by Brownian motion and then bringing the grains into contact with each other A separation step of separating the granulated Ti particles or Ti alloy particles from the molten salt, and melting to separate the Ti particles or Ti alloy particles after the separation into metal Ti or Ti alloy ingots. It is a manufacturing method of metal Ti or Ti alloy including a process.

[0033] If the production method described in (3) above further includes a concentration step of concentrating the granulated Ti particles or Ti alloy particles, the separation efficiency can be further increased. Can do.

[0034] (4) A molten salt containing CaCl and dissolving Ca is retained, and continuously in the molten salt.

2

The supplied metal chloride containing TiCl reacts with Ca to produce Ti grains or Ti alloy grains.

Four

A granulation means for bringing together Ti particles or Ti alloy particles produced in the molten salt by Brownian motion and then bringing the particles into contact with each other, and the granulation means Separation means for separating the granulated Ti grains or Ti alloy grains from the molten salt, and the Ti grains or Ti alloy grains separated by the separation means are continuously melted to form metal Ti or Ti alloy. It is the manufacturing apparatus of metal _Ti or _Ti alloy which has a melt | dissolution means used as an ingot.

[0035] If the production method according to (4) above has a concentration means for concentrating Ti particles or Ti alloy particles after granulation by the granulation means! The power S is used to further increase the efficiency of separation.

[0036] According to the method for producing Ti grains or Ti alloy grains of the present invention, Ti grains or Ti alloy grains produced by reduction in molten salt are granulated, and the sedimentation of the grains is promoted to significantly increase the efficiency of separation. You can increase your power. If it concentrates after granulation, the improvement effect of a separation efficiency can be heightened further.

[0037] Further, if this method for producing Ti grains or Ti alloy grains is applied in the process of separating the Ti grains or Ti alloy grains from the molten salt in the production process of metallic Ti or Ti alloys by Ca reduction, the productivity will be improved. This makes it possible to produce metal Ti or Ti alloys at low cost. In that case, the productivity improvement effect can be further enhanced by applying the method for producing Ti grains or Ti alloy grains which are concentrated after granulation.

Brief Description of Drawings

[0038] Figure 1 shows the separation from the formation of Ti grains or Ti alloy grains produced by Ca reduction through granulation. It is a figure which shows typically the process until.

Fig. 2 is an explanatory diagram of a method for stirring molten salt containing Ti grains or Ti alloy grains using a static mixer. (A) is the structure of the main part of the static mixer, and (b) is a melt using this mixer. It is a figure which shows typically the stirring condition of a salt, respectively.

Fig. 3 is a diagram schematically showing an example of the configuration of an apparatus for concentrating Ti grains or Ti alloy grains by using a liquid cyclone and a filter separator together.

FIG. 4 is a diagram showing a schematic configuration example of an apparatus used for carrying out the Ti or Ti alloy manufacturing method of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

[0039] Hereinafter, the method for producing Ti particles or Ti alloy particles of the present invention, the method for producing metal Ti or Ti alloy of the present invention, and the apparatus for producing the same will be described.

[0040] 1. Method for producing Ti grain or Ti alloy grain of the present invention

The method for producing Ti grains or Ti alloy grains of the present invention contains CaCl as a molten salt and

2 When Ca is dissolved! /, When the target is molten salt!

The method for producing Ti grains or Ti alloy grains of the present invention is a method of producing Ti grains or Ti alloy grains by granulating Ti grains or Ti alloy grains produced by reduction in molten salt by bringing them into contact with each other. is there.

[0041] When TiCl is added to CaCl-containing molten salt in which Ca is dissolved, TiCl force is reduced by Ca.

2 4 4

Ti particles are generated. Metal chlorides containing TiCl (V, Al, Cr, etc.

Four

The resulting metal chlorides are reduced by Ti simultaneously with the reduction of TiCl.

Four

Ti alloy grains are generated.

[0042] Ti grains or Ti alloy grains formed by reduction in molten salt in this way are fine particles of submicron (for example, particle size of 150 nm or less), force S, and heat generated during the reduction reaction ( Combine with heat of reduction. Furthermore, these fine particles are brought into contact (collision) with each other due to Brownian motion resulting from collision of molten salt constituents (molecules) with the particles, and aggregate. As the particle size increases due to agglomeration, the Brownian motion becomes slow, and no further increase in particle size can be expected.

[0043] If the molten salt (bath) is in a static state or a gentle fluid state, Ti grains or Ti alloy grains The increase in diameter is limited to the particle size that can be achieved by agglomeration due to Brownian motion (up to about 1 to 3 m). In addition, the particle size is increased.

FIG. 1 is a diagram schematically showing a process from generation of Ti grains or Ti alloy grains to separation through granulation in the method for producing Ti grains or Ti alloy grains of the present invention. The particle size indicated in the figure is a rough guide for the particle size in the middle stage.

[0045] As shown in FIG. 1, the produced Ti particles coalesce and aggregate due to reduction heat or Brownian motion, and then coalesce due to collision during the movement of the aggregated particles along with the bath flow (this , “Inertial force coalescence” proceeds, and granulation is performed to a particle size (desirably 20 to; ίθθπι) necessary for separation. In particular, in the granulation process, sintering due to the heat possessed by the bath salt occurs between the collided particles, so that inertial force coalescence easily proceeds.

[0046] In the method for producing Ti grains or Ti alloy grains of the present invention, the granulation by bringing the Ti grains or Ti alloy grains into contact with each other is performed by coalescence by the reduction heat, collision / aggregation by Brownian motion, and This is to create a condition where coalescence due to inertial force is likely to occur, and to promote inertial force coalescence that has a particularly large granulation effect.

[0047] Factors affecting the granulation process in the bath salt (influencing factors) and their controllability will be discussed below.

Usually, “granulation” refers to the operation of producing granules and other granular products, pellets, briquettes, and other specific forms of granulated products. This means that fine particles are combined (fixed) to increase the particle size. When fine particles are aggregated to increase the size of the grains, there is no difference between the two points. Therefore, the term “granulation” is also used in the present invention.

[0048] Granulation in bath salt is simplified,

“Granulation” = “Fixing particles” “Separation of fixed particles”

It is expressed. That is, among the fixed particles, the remainder obtained by subtracting the amount of particles that have separated and collapsed remains as fixed particles. “Separation of fixed particles” is mainly caused by the collapse due to the shearing force acting on the fixed particles.

[0049] As factors affecting the "adhesion between particles", the cohesive force of particles and the sensible heat of bath salt There is a sintering action. The cohesive force here is mainly a force caused by van der Waals force acting between particles and an electric double layer formed on the particle surface. The former acts as attractive force, the latter acts as repulsive force, and the sum of these forces is expressed as cohesive force. In granulation in molten salt, it is necessary to consider the effect of bath wettability.

The effect is negligible in the case of a molten salt of 2.

[0050] The sintering action described above is performed when the Ti grains or Ti alloy grains are granulated in a molten salt containing CaCl.

2

When the temperature is 850 ° C or higher, the sintering effect is obtained. The higher the temperature, the greater the sintering effect. However, if the temperature is too high, a large amount of energy is required and the durability of the equipment is impaired, so the upper limit temperature is desirably 1050 ° C.

[0051] This cohesive force and sintering action are considered to work synergistically with "adhesion between particles", that is, "granulation", but when expressed in a simplified manner, the following equation (1) is obtained. . In addition, (A)-(D) in (1) Formula is the code | symbol attached | subjected for convenience of explanation.

"Granulation" = (A) "Van der Waals force, cohesive force due to electric double layer force"

+ (B) "Particle collision (contact)"

+ (C) "Merge after collision (contact)"

1 (D) "Disruption due to shear force" (1)

[0052] (C) “Merging after collision (contact)” in the equation (1) is mainly due to a sintering action of the bath salt by sensible heat. By controlling these influencing factors, it is possible to increase the fixed particle size and improve the granulation rate in the granulation of Ti grains or Ti alloy grains in the molten salt.

[0053] From the viewpoint of the controllability of the factors affecting the granulation process and! /, In the above formula (1), (A) is because the system is determined (explained above) In the case of molten salt containing CaCl),

2

It is difficult to control. In addition, (C) is a sintering action, which is a function of the temperature of the molten salt and the time during which granulation is performed, but the granulation time is high enough to extend the time! / Controllability cannot be expected. (D) is a force related to the strength of the shearing force acting on each particle and the strength of each particle. In granulation in molten salt where the sintering action works, it is not considered to be a significant influence factor. .

[0054] In the end, it is possible to control the force and the effect is great! / (B) “Particle Collision (Contact)”. Increasing the granulation (increasing the fixed particle size) It is speculated that it will greatly contribute to the improvement of granulation speed.

[0055] Regarding the collision of particles in the molten salt (that is, the liquid phase), it is difficult to theoretically consider the influence of the medium. However, the collision of solid particles in the gas-solid model is handled theoretically, and referring to it, the main factors that affect the granulation in molten salt (granulation factor) ) May be the relative speed of each particle, the particle density (the proportion of particles in the system), the residence time (granulation time), and the impact particle size.

[0056] Of these influencing factors (granulation factors), the relative speed, particle density, and residence time (granulation time) of each particle were changed, and as a result of the granulation test, these factors were also generated. It was confirmed that there was an effect of advancing the grains.

[0057] In the method for producing Ti grains or Ti alloy grains of the present invention, it is desirable to perform granulation by contacting Ti grains or Ti alloy grains by changing the bath flow. By changing the bath flow, the probability of particle collision (contact) in the bath salt (B) can be increased, and granulation can be promoted remarkably.

[0058] As a specific method for changing the bath flow, there is a method of stirring the bath. Usually, stirring methods using various types of stirring blades used for solid-liquid stirring and the like can be applied. This increases the collision (contact) frequency of Ti grains or Ti alloy grains in the bath salt and promotes granulation. The stirring conditions such as the shape of the stirring blade and the stirring speed may be appropriately selected so that granulation is suitably performed.

[0059] The stirring of the bath can also be performed by using a specific mixer. The application of this mixer is particularly effective for the purpose of use of Ti grains or Ti alloy grains obtained by the method for producing Ti grains or Ti alloy grains of the present invention.

[0060] Fig. 2 is an explanatory diagram of a method of stirring a bath with a static mixer. (A) is a structure of the main part of the static mixer, and (b) is a schematic diagram of the stirring state of the bath using this mixer. FIG.

[0061] The static mixer 1 is used by being inserted into a cylindrical tube. As shown in Fig. 2 (a), the main parts are sequentially placed with the right element 2 that rotates the fluid in the right direction and the left element 3 that rotates the fluid in the left direction shifted by 90 ° around the axis of the mixer 1. Connected structures Have.

[0062] When the molten salt containing fine particles of Ti or Ti alloy is supplied to the static mixer 1 inserted in the pipe in the state shown in Fig. 2 (a), the molten salt is moved to the front side by the right element 2. And the other side (indicated as the back side). The molten salt on the near side moves along the twisted surface in the right element 2 from the central part of the pipe to the wall side while rotating rightward, and the molten salt on the far side also rotates rightward. Move to the front side.

[0063] Next, the molten salt is divided into two parts up and down by the left element 3 and moves while rotating counterclockwise, and the up and down positions are reversed. The next right element 2 is divided into two parts, the front side and the back side.

As described above, the molten salt containing fine particles of Ti or Ti alloy changes its rotation direction every time it passes through each element, so that it is vigorously stirred by abrupt reversal action and remarkably promotes granulation.

[0064] Fig. 2 (b) shows a stirring state when the static mixer 1 is attached in the middle of the pipe 4 through which the molten salt containing fine particles of Ti or Ti alloy passes. In this example, a hydrocyclone 5 for concentrating and separating the granulated particles is attached to the exit side of the static mixer 1, and the particle diameter is 3 to 100 after passing through the static mixer 1. The molten salt containing Ti grains or Ti alloy grains, which has reached about m, is subject to particle collision (contact) during the treatment with hydrocyclone 5, so that granulation proceeds further, and the particle size of the whole particle is reduced. It is about 100〃 m. That is, the liquid cyclone is used to concentrate the granulated particles as will be described later, but also has a granulating function.

[0065] In order to change the bath flow, a method of providing a guide plate (baffle plate) in the pipe through which the bath salt passes is simple and effective. By appropriately selecting the baffle shape and location, granulation can be promoted by changing the bath flow.

[0066] Changing the speed of the bath flow is also effective in changing the bath flow. For example, by intermittently increasing or decreasing the speed of the bath salt that passes through the pipe, the flow becomes turbulent, increasing the probability of particle collision (contact) and granulation. Is promoted.

[0067] An effective way to change the bath flow is to make the bath flow turbulent. There are various ways to do this, such as stirring the bath, installing baffles, and changing the bath flow rate. Misalignment also causes turbulent flow.

[0068] Rotating the bath flow is also effective in changing the bath flow. Granulation is promoted because the particles collide violently due to the turbulence caused by the rotation.

[0069] In the method for producing Ti grains or Ti alloy grains of the present invention, if the average grain size of the granulated grains is 1 μm or more, the sedimentation of the grains is promoted and the separation efficiency is increased. Can be increased. The larger the particle size, the easier the separation, so it is desirable that the average particle size be 20 m or more and the particle size range 20-100 111.

[0070] If the average particle size of the granulated particles is 100 m or more, the particle separation efficiency is remarkably improved, which is more desirable. The particle size after granulation is either Ti grains in molten salt containing CaCl or

2

In the case of granulation of Ti alloy grains, the average grain size is usually set to 100 m or more by applying the force S with an average grain size of about 100 m, and the Ti grain or Ti alloy grain production method described in detail later. It is possible to do.

[0071] If the particle size of the constituent particles of Ti particles or Ti alloy particles granulated so that the average particle size is 1 am or more is from 0 · 05 m to 10 m, as described below, These Ti grains or Ti alloy grains can be regarded as Ti grains or Ti alloy grains produced by the method for producing Ti grains or Ti alloy grains of the present invention.

[0072] In the method for producing Ti grains or Ti alloy grains of the present invention, in order for the granulation to proceed in the molten salt, the Ti grains or Ti alloy grains must be brought into contact with each other and coalesced. That is, the granulated particles obtained by granulation are Ti particles or Ti alloy particles (which are called “constituting particles” in the sense of particles constituting the granulated particles) in contact with each other. The particle diameter of the constituent particles that have been combined and can be combined by the Ti grain or Ti alloy grain manufacturing method of the present invention is about 10 am or less. Particles exceeding this particle size are not likely to be constituent particles that are easily present as independent granulated particles.

[0073] On the other hand, in order to granulate particles having a small particle size (in this case, particles having a small particle size exist as constituent particles in the granulated particles), a particle size of 1 am or more is required. It is necessary to increase the number of (collisions) extremely in a short time. In the method for producing Ti grains or Ti alloy grains of the present invention, such an extreme increase in the number of collisions cannot be expected. Therefore, particles less than 0.05 111 are granulated and less than 0.05 m in the granulated particles. It is difficult to exist as a constituent particle of is there.

[0074] Therefore, if the particle size of the Ti particles or Ti alloy particles granulated to have an average particle size of 1 m or more is 0.05 to 10 am, the Ti particles or Ti alloy The grain can be regarded as Ti grain or Ti alloy grain produced by the method for producing Ti grain or Ti alloy grain of the present invention. From the viewpoint of granulation, the desirable particle size range of the constituent particles is 0.115 111 to 3.O ^ m, and granulation with a particle size of this level enables granulation relatively easily.

[0075] The Ti grain or Ti alloy grain production method of the present invention is obtained by concentrating the Ti grain or Ti alloy grain granulated by the production method of the present invention (described in (1) above). It can be a manufacturing method.

[0076] Concentration can increase the particle density (the ratio of particles in the system) as a main factor (granulation factor) that affects the granulation in the molten salt described above. It is possible to promote the granulation by increasing the probability of collision (contact) with each other and to facilitate the separation of the granulated Ti grains or Ti alloy grains.

[0077] In the method for producing Ti grains or Ti alloy grains of the present invention, it is desirable to concentrate the Ti grains or Ti alloy grains after granulation by a liquid cyclone. Since the hydrocyclone also has a granulating function as described above, it can be effectively granulated and concentrated by using it together with other concentrating means.

[0078] The concentration of Ti particles or Ti alloy particles after granulation can also be performed by centrifugation. In centrifugation, molten particles containing Ti grains or Ti alloy grains are placed in a high-speed rotating field, and the granulated particles are concentrated and separated by applying centrifugal force. Since each particle moves uniformly toward the outer periphery of the separator, a granulation effect as in the case of using a hydrocyclone cannot be expected! /, But efficient concentration can be achieved.

[0079] It is also effective to concentrate Ti particles or Ti alloy particles after granulation by filtration separation. Since the average particle size of the particles is increased by granulation! /, It is possible to use fine mesh! / And a wire mesh, and filtration separation can be performed easily. It is also possible to perform effective concentration by using in combination with other concentration means.

[0080] Fig. 3 is a diagram schematically showing an example of the configuration of an apparatus in the case where the granulated Ti grains or Ti alloy grains are concentrated by using a liquid cyclone and a filter separator together. As hydrocyclone A cyclone of the same type as shown in Fig. 2 (b) is used, and a filter separator using a wire mesh is used for filtration.

[0081] The filter separator 7 has a cylindrical shape, and a helical fin 8 is attached to the inner wall of the tube (tube), and a fine wire mesh (not shown) is stretched near the inside of the inner wall. . The filter separator 7 is configured such that the outlet side is inclined slightly upward with respect to the inlet side and is rotatable about the axis C.

[0082] When the molten salt containing Ti particles or Ti alloy particles after granulation is supplied to the hydrocyclone 6, the granulation of particles further proceeds due to the collision (contact) of the particles, and part of the molten salt. Is separated and discharged from the fluid outlet 6a, and the Ti particles or Ti alloy particles after granulation are concentrated. On the other hand, the Ti particles or Ti alloy particles after concentration are discharged from the solid outlet 6b together with the remaining molten salt and supplied to the filter separator 7.

[0083] Most of the supplied molten salt containing the concentrated Ti particles or Ti alloy particles passes through the wire mesh while being processed in the filter separator 7 and moves to the inlet side of the filter separator 7, The Ti particles or Ti alloy particles on the wire mesh are pushed up by the spiral fin 8 as the filter separator 7 rotates, and discharged from the outlet side. The Ti grains or Ti alloy grains after discharge are only accompanied by the adhering molten salt, and extremely effective concentration can be achieved.

[0084] Concentration by mechanical compression is also effective depending on the method of use. Since it is mechanically dehydrated (ie, pressed), it is effective when it is desired to eliminate molten salt as much as possible and to separate only Ti grains or Ti alloy grains.

[0085] 2. Metal Ti or Ti alloy production method and production apparatus of the present invention

Next, the manufacturing method of the metal Ti or Ti alloy of the present invention and the manufacturing apparatus thereof will be described with reference to the drawings.

[0086] Fig. 4 is a diagram showing a schematic configuration example of a manufacturing apparatus used when the Ti or Ti alloy manufacturing method of the present invention is carried out. The basic construction of the manufacturing equipment shown in Fig. 4 is based on the OYIK method, and the method developed by the present inventors is implemented as a manufacturing process that can perform stable and efficient operation on an industrial scale. It is an example of a device that can be used.

[0087] As shown in FIG. 4, the production apparatus of the present invention includes a melt containing CaCl and dissolving Ca.

2

The salt is retained and TiCl supplied in this molten salt reacts with the Ca to produce Ti grains. And a separation means 10 for granulating and separating Ti particles produced in the molten salt, and continuously dissolving the separated Ti particles to form metal Ti A melting means 11 as an ingot, an electrolytic cell 12 for electrolyzing the molten salt after the Ti grains are separated to produce Ca, and a concentration of Ca produced by electrolysis to be constant And a Ca concentration removal device 14 for removing and recovering Ca dissolved in the molten salt separated by the separation means 10 and sent to the electrolytic cell 12.

In this production apparatus, the separation means 10 includes a granulation means and a separation means, and includes all of the reaction vessel, granulation means, separation means, and dissolution means of the production apparatus of the present invention. Yes.

The above-described method for producing Ti grains or Ti alloy grains of the present invention is applied to the separation step performed using the separation means 10 of this production apparatus, and the liquid cyclone 6 shown in FIG. 3 is granulated. For concentration and filtration, a filter separator 7 using a wire mesh is used for concentration and separation.

In order to produce metal Ti using the production apparatus shown in FIG. 4, first, molten salt continuously supplied from the electrolytic cell 12 through the adjustment vessel 13 is introduced into the reaction vessel 9. The TiCl supplied from the TiCl supply port 15 is allowed to react with Ca in the molten salt, and Ti particles are added to the molten salt.

4 4

Generate (reduction step).

[0091] The fine Ti particles generated in the molten salt in the reduction step are granulated by the liquid cyclone 6 in the separation step, and at the same time, part of the molten salt is separated upward and concentrated. . The granulated Ti grains are discharged from the bottom of the hydrocyclone 6 together with the remaining molten salt. The discharged Ti particles are concentrated and separated after the molten salt is removed by the filter separator 7.

The separated Ti grains are continuously heated and melted by the plasma irradiated from the plasma torch 24 in the separation tank 23, and poured into the vertical mold 25 to become a Ti ingot 26.

[0093] In the separation process, the molten salt separated by the liquid cyclone 6, the molten salt removed by the filter separator 7, and the molten salt separated as an upper layer by heating and melting with the plasma torch 24 are: Then, they are sent to the Ca recovery process using the Ca concentration removal device 14 via the routes La, Lb and Lc, respectively. The Ca concentration removal device 14 holds the molten salt separated by a partition wall 16 into a Ca concentration region 17 and a Ca removal region 18, and uses a molten Mg-Ca alloy electrode 19 held on the molten salt. To remove Ca in molten salt or high concentration It has a function to convert.

[0094] The molten salt from which Ca that has an adverse effect on electrolysis in the Ca recovery process is removed and recovered is sent to the electrolysis process, where it is electrolyzed to produce Ca, and the Ca concentration of the molten salt is increased. The electrolytic cell 12 includes a cylindrical electrolytic cell container 12a that holds molten salt, and a cylindrical anode 2

0 and a cylindrical cathode 21 with a diaphragm 22 therebetween, and the anode 2 from the lower end of the electrolytic cell 12

The molten salt continuously supplied between 0 and the cathode 21 can be electrolyzed to extract the molten salt enriched with Ca! /.

[0095] Ca produced by electrolysis in the electrolysis step is introduced together with the molten salt into the adjustment tank 13 having a Ca supply source, and after the Ca concentration of the molten salt is made constant, the Ca is introduced into the reaction vessel 9. The production of metal Ti is carried out continuously.

Thus, in the manufacturing apparatus illustrated in FIG. 4, the hydrocyclone 6 is used as the granulating means,

Then, a filtration separator 7 using a wire mesh is used as a concentration and separation means, and Ti particles are granulated, concentrated and separated.

[0097] Conventionally, when Ti grains formed in molten salt are granulated or further concentrated, no technology has been developed. Therefore, as described above, Ti before the separation operation is performed. The grains are very fine, and it is difficult to increase the recovery rate, resulting in a problem that the production speed is reduced and the production cost is increased.

[0098] In contrast, according to the method for producing metal Ti or Ti alloy of the present invention, separation and recovery of metal Ti can be performed efficiently, so that productivity can be improved and metal Ti can be produced at low cost. it can . In addition, this manufacturing method can be easily performed by the manufacturing apparatus described in (4) above.

In the apparatus illustrated in FIG. 4, the produced Ti particles are granulated with a hydrocyclone, and further concentrated and separated with a filter separator 7. That is, a manufacturing apparatus incorporating the apparatus for carrying out the manufacturing method of Ti particles or Ti alloy particles accompanied by the concentration of the granulated Ti particles or Ti alloy particles described in (2) above, Even when only the equipment that implements the manufacturing method of Ti grains or Ti alloy grains is applied, the separation efficiency of Ti grains is improved, so that the productivity improvement effect is recognized.

Industrial applicability [0100] The Ti grain or Ti alloy grain production method of the present invention is a method in which Ti grains or Ti alloy grains produced by reduction in molten salt are brought into contact with each other or further concentrated to reduce the sedimentation of the particles. It can be promoted to significantly increase the efficiency of separation. Concentration after granulation can further enhance the effect of improving the separation efficiency of Ti grains or Ti alloy grains.

[0101] Further, if this method for producing Ti grains or Ti alloy grains is applied in the process of separating the produced Ti grains or Ti alloy grains from the molten salt in the production process of metallic Ti or Ti alloys by Ca reduction, the productivity This makes it possible to produce metal Ti or Ti alloys at low cost.

[0102] Therefore, the Ti grain or Ti alloy grain production method, metal Ti or Ti alloy production method and production apparatus of the present invention can be effectively used in the production of metal Ti or Ti alloy by Ca reduction. it can.

Claims

The scope of the claims

[I] A method for producing Ti grains or Ti alloy grains, characterized by granulating Ti grains or Ti alloy grains produced by reduction in molten salt.

[2] The production of Ti grains or Ti alloy grains according to claim 1, further comprising concentrating Ti grains or Ti alloy grains in a molten salt containing the granulated Ti grains or Ti alloy grains. Method.

[3] The method for producing Ti grains or Ti alloy grains according to claim 1, wherein granulation by contact between the grains is performed by changing a bath flow.

4. The method for producing Ti grains or Ti alloy grains according to claim 3, wherein the bath is stirred to change the bath flow.

5. The method for producing Ti grains or Ti alloy grains according to claim 3, wherein a guide plate is provided in the bath to change the bath flow.

6. The method for producing Ti grains or Ti alloy grains according to claim 3, wherein the bath flow speed is changed in order to change the bath flow.

7. The bath flow according to claim 3, wherein the bath flow is turbulent to change the bath flow.

Manufacturing method of Ti grain or Ti alloy grain.

8. The bath flow according to claim 3, wherein the bath flow is rotated to change the bath flow.

Manufacturing method of Ti grain or Ti alloy grain.

[9] The method for producing Ti particles or Ti alloy particles according to [1], wherein the average particle size of the particles after granulation is 1 am or more when granulating by contact between the particles.

[10] The method for producing Ti particles or Ti alloy particles according to [1], wherein an average particle size of the particles after granulation is set to 10011 m or more when granulating by contact between the particles.

[II] The constituent particles of Ti particles or Ti alloy particles granulated to have an average particle size of 1 am or more have a particle size of 0 · 05, 1 m or more and 10 m or less. 9. The method for producing Ti grains or Ti alloy grains according to 9.

12. The method for producing Ti particles or Ti alloy particles according to claim 2, wherein concentration of the granulated Ti particles or Ti alloy particles is performed by a liquid cyclone.

13. The method for producing Ti particles or Ti alloy particles according to claim 2, wherein the granulated Ti particles or Ti alloy particles are concentrated by centrifugation.

14. The method for producing Ti particles or Ti alloy particles according to claim 2, wherein the granulated Ti particles or Ti alloy particles are concentrated by filtration separation.

[15] The method for producing Ti grains or Ti alloy grains according to claim 2, wherein the granulated Ti grains or Ti alloy grains are concentrated by mechanical compression.

[16] A method for producing metal Ti or Ti alloy by reducing Ca in molten salt,

Metal chloride containing TiCl is continuously added to the molten salt containing CaCl and dissolved in Ca.

twenty four

A reduction step of supplying Ti to produce Ti grains or Ti alloy grains in the molten salt;

A granulation process in which Ti grains or Ti alloy grains immediately after formation are combined by Brownian motion and then granulated by bringing the grains into contact with each other;

A separation step of separating the granulated Ti particles or Ti alloy particles from the molten salt;

A method for producing a metal Ti or Ti alloy, comprising a melting step of continuously melting the separated Ti particles or Ti alloy particles to form an ingot of metal Ti or Ti alloy.

17. The method for producing metal Ti or Ti alloy according to claim 16, further comprising a concentration step of concentrating the granulated Ti particles or Ti alloy particles.

[18] Hold molten salt containing CaCl and dissolved in Ca, and supply continuously into the molten salt

2

To react Ti with TiCl containing metal chloride with Ca to produce Ti grains or Ti alloy grains

Four

A reaction vessel,

After coalescence of Ti grains or Ti alloy grains formed in the molten salt by Brownian motion

A granulating means for granulating the particles by bringing them into contact with each other;

Separating means for separating Ti particles or Ti alloy particles after granulation by the granulating means from molten salt;

A manufacturing apparatus for metal Ti or Ti alloy, comprising: melting means for continuously melting Ti grains or Ti alloy grains after being separated by the separating means to form an ingot of metal Ti or Ti alloy.

[19] The apparatus for producing a metal Ti or Ti alloy according to claim 18, further comprising a concentration means for concentrating the Ti grains or Ti alloy grains after granulation by the granulation means. .