JPH032936B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is applicable to metal titanium (Ti), metal zirconium (Zr), metal hafnium (Hf), metal niobium (Nb).
and a method for producing metal tantalum (Ta). [Prior art] Conventionally, as a method for manufacturing titanium metal, materials with low impurities such as natural rutile and synthetic rutile have been used.
There is a method of adding carbon to TiO ₂ and producing titanium chloride at high temperature as shown in the following formula. TiO ₂ +2C+2Cl ₂ →TiCl ₄ +2CO The raw material contains impurities such as V in addition to Fe, so the TiCl ₄ produced is purified by distillation, and then metal magnesium and metal sodium are brought into contact. Many methods are used to do this. TiCl ₄ +2Mg→Ti+2MgCl ₂ TiCl ₄ +4Na→Ti+4NaCl The MgCl ₂ and NaCl by-produced at this time are recycled to the molten salt electrolysis process, and metal Mg, Na and Cl ₂
This method turns it into a gas and cycles it. Next, the conventional method for producing metallic zirconium is to first process zircon sand in an arc furnace,
Zircon carbide is obtained at the same time as SiO ₂ is vaporized and separated, and then the zircon carbide is chlorinated as shown in the following formula. ZrC + 2Cl ₂ →ZrCl ₄ Alternatively, a method of separating SiO ₂ and creating zircon oxide, which is then chlorinated, has also been adopted. ZrO ₂ +2C+2Cl ₂ →ZrCl ₄ +2CO The ZrCl ₄ thus obtained is dissolved in acid and impurities and hafnium are separated using a solvent extraction device.
Next, this is crystallized and precipitated, and then thermally decomposed.
The obtained oxide is further chlorinated to produce purified ZrCl ₄ ,
There is a method of reducing this with metallic Mg. In addition, zircon sand is mixed and reacted with K ₂ SiF ₆ to form a soluble fluoride, which is then leached and further processed.
Perform crystallization to separate impurities. obtained
Mixed crystals of K ₂ ZrF ₆ and K ₂ HfF ₆ were obtained by fractional crystallization.
Purified K ₂ ZrF ₆ is obtained by separating Hf. Next, there is a method of producing metal Zr from this K ₂ ZrF ₆ through a molten salt electrolysis process. All of these processes are extremely long and are separated into a separation and purification process, a halogenation process, and a reduction process to produce metals. The manufacturing process for metal hafnium is exactly the same as that for metal zirconium, as it is manufactured from natural resources in which Hf coexists with Zr, and is manufactured using a complicated manufacturing method. In addition, the conventional method for producing niobium metal is to dissolve concentrated natural raw materials in hydrofluoric acid and sulfuric acid, then separate impurities and tantalum in a solvent extraction process, neutralize this solution with NH ₃ , and extract the tantalum. The precipitate is passed through _a high temperature oxidative decomposition process to obtain purified _Nb2O5 . Purified Nb ₂ O ₅ is mixed with Al powder and the thermite reaction is used to obtain crude niobium metal. next,
The crude metal niobium is introduced into an electron beam furnace,
A method has been adopted in which impurities are separated and purified by raising the temperature to high temperatures. The manufacturing method for tantalum metal involves the coexistence of natural raw materials with niobium, so impurities and niobium are separated in a solvent extraction process, KOH is added to obtain purified K ₂ TaF ₇ crystals, and this is then extracted with metal Mg, metal Reduced with Na,
Either obtain crude tantalum metal, or obtain crude tantalum metal by subjecting K ₂ TaF ₇ to a molten salt electrolysis process, and wash the obtained crude tantalum metal with a strong acid such as aqua regia to remove impurities. The common method is to create. [Problems to be solved by the invention] In the conventional method as described above, the process to produce the purified metal halide intermediate is long and complicated, resulting in low yield and high cost. There were flaws. When purified oxides such as niobium metal are reduced with Al etc., the content of impurities is high, and
Because it has a high oxygen content, it has to be melted and refined many times in an electrobeam furnace to refine it, resulting in high costs. As halides such as zirconium and hafnium are first created, they are redissolved to separate hafnium and zirconium to create purified oxides, and purification is required to convert this into halides, which increases costs. The drawback was that not only was the amount bulky, but the yield was also reduced. [Means for solving the problems] The present invention provides an oxygen-containing organic solvent containing and extracting one type of metal halide complex selected from the group consisting of Ti, Zr, Hf, Nb, and Ti. ,
A desiccant selected from the group consisting of anhydrous calcium chloride, anhydrous magnesium sulfate, anhydrous magnesium chloride, anhydrous potassium chloride, phosphorus pentoxide, activated alumina, magnesium perchlorate, anhydrous potassium carbonate, quicklime, barium oxide, zeolite, etc. After contacting, the oxygen-containing organic solvent is heated and distilled under reduced pressure or normal pressure to generate a metal halide and regenerate the oxygen-containing organic solvent; , metal Ti, metal Zr, metal Hf, characterized in that metal Ti, Zr, Hf, Nb and Ta are obtained by contacting with single metals of calcium, magnesium and sodium and alloys mainly composed of these metals.
The present invention provides a method for producing metal Nb and metal Ta. [Operation] The present invention does not use high-quality raw materials or expensive raw materials, nor does it require the production of halides over and over again. This method creates highly pure metal halides at once from natural resources and reduces them to metals.Refined metal halides are obtained through a long process of repeating the separation process several times as in conventional methods. This method overcomes the drawbacks of complex steps and low yields that occur when reducing oxidation with metallic Na or metallic Mg. That is, the present invention uses Ti, Zr, Hf, Nb and Ti.
An oxygen-containing organic solvent containing one type of metal halide complex selected from the group consisting of anhydrous sodium sulfate, anhydrous calcium chloride, anhydrous magnesium sulfate, anhydrous magnesium chloride, anhydrous potassium chloride,
Water physically contained in an oxygen-containing organic solvent or Dehydrate the H ₂ O contained in the extraction, dry the oxygen-containing organic solvent, and then fill the device with inert gas to expel the atmosphere inside the device or fill it with inert gas. While letting
By performing thermal evaporation or thermal distillation at normal pressure or reduced pressure, the organic solvent is regenerated and recovered, and a metal halide is produced as shown in the following formula using the vapor pressure difference between the organic solvent and the metal halide. H ₂ TiF ₆・nOrg heating---→ nOrg+TiF ₄ +2HF H ₂ TiCl ₆・nOrg heating---→ nOrg+TiCl ₄ +2HCl HNbF ₆・nOrg heating---→ nOrg+NbF ₅ +HF HNbCl ₆・nOrg heating---→ nOrg+NbCl ₅ +HCl HTaF ₆・nOrg heating---→ nOrg+TaF ₅ +HF HTaCl ₆・nOrg heating---→ nOrg+TaCl ₅ +HF HZrCl ₅・nOrg heating---→ nOrg+ZrCl ₄ +HCl HHfCl ₅・nOrg heating---→ nOrg+HfCl ₀ +HCl In the formula, Org is an oxygen-containing organic One or more solvents selected from the group of ethers, esters, ketones, amides, and alcohols can be used. In addition, the above-mentioned metal extraction species are merely examples, and the halogen ion concentration and H + ion concentration, which greatly affect the chemical species of the metal complex compound when extracted and contained in an oxygen-containing organic solvent, are ^not fixed. It should be understood that the extraction species of the metal halide complex is not limited by the above formula, as it is a matter of course that it varies depending on the concentration. Furthermore, the extracted species of metal halide complexes include chloride complexes, fluoride complexes, bromide complexes, and iodide complexes. Depending on the oxygen-containing organic solvent, the amount of H ₂ O extracted together with the metal halide complex ions is also not constant. One or two halides of the above-mentioned metals ((Ti, Zr, Hi, Nb and Ta) obtained in the evaporation and distillation process are selected from the group of metals Na, Mg, Zn, Pb, Ca and Al. By contacting with the above gaseous metals and liquid metals, metal Ti, Zr, Hf,
This is a method of building Nb and Ta. In this way, the present invention dissolves raw materials in an acid, separates and refines the coexisting metals in a solvent extraction process, creates high-purity metal halides all at once, and reduces them to produce metal Ti,
It manufactures metals Zr, Hf, Nb and Ta. The halides of the above metals (Ti, Zr, Hf, Nb and Ta) are mixed with one or more gases selected from the group consisting of sodium metal, magnesium metal, aluminum metal, zinc metal, calcium metal and lead metal. By contacting a liquid metal with a liquid metal, a metal can be obtained as shown in the following formula. TiCl ₄ +4Na→Ti+4NaCl TiF ₄ +2Mg→Ti+2MgF ₂ ZrCl ₄ +4Na→Zr+4NaCl ZrF ₄ +2Mg→Zr+2MgF ₂ HfCl ₄ +4Na→Hf+4NaCl HfF ₄ +2Mg→Hf+2MgF ₂ NbF ₅ +2.5Zn→Nb+2.5Z nF ₂ NbCl ₅ +5Na→Nb+5NaCl TaF ₅ +2.5Zn→Ta+2.5ZnF ₂ TaCl ₅ +2.5Mg→Ta+2.5MgCl ₂ NbF ₅ +2.5Pb→Nb+2.5PbF _2The above equation shows an example of a method for producing metals, including chlorides and fluorides. A single reducing agent or an alloy of multiple reducing agents can be used. Regarding the reduction process, there are methods such as dropping a reduced metal liquid into the molten metal halide, blowing the reduced metal gas, and blowing the reduced metal gas onto the molten reducing metal. You can use it to create the desired metal. Furthermore, it should be understood that various combinations are possible, such as introducing a metal halide gas and a reduced metal gas into a reactor to produce a desired gas through a gas-to-gas reaction. The reduction reactor is usually filled with an inert gas to carry out the reduction reaction, but a reducing gas such as H ₂ gas may also be mixed therein. In the present invention, various metals (Ti, Zr, Hf, Nb and
The metal halide complex of Ta) can be produced, for example, as follows. An extractant selected from the group of ethers, ketones, esters, amides and alcohols is prepared by contacting the metal halide complex present in an aqueous solution. HTiF ₆ ^- +H ⁺ +nOrg→H ₂ TiF ₆・nOrg (Aqueous phase) (Aqueous phase) (Organic phase) (Organic phase) NbF ₆ ^- +H ⁺ +nOrg→ HNbF ₆・nOrg TaF ₆ ^- +H ⁺ +nOrg→ HTaF ₆・nOrg ZrCl ₅ ^- +H ⁺ +nOrg→ HZrCl ₅・nOrg HfCl ₅ ^- +H ⁺ +nOrg→ HHfCl ₅・nOrg The chemical species of the halogenated complex ions of each metal listed above are just examples; It is well known that the chemical species of complexes also differ depending on the concentration of halogen ions and H ⁺ ions present. The oxygen-containing organic solvent used in the present invention is selected from the following group. (a) Group of ethers: Includes diisoamyl ether, diethyl ether, diisopropyl ether, dichloroethyl ether and ethers exhibiting forms similar to these. (b) Group of Ketones: Includes methyl isobutyl ketone, methyl propyl ketone, methyl amyl ketone, cyclohexanone, methyl cyclohexanone and similar ketones. (c) Group of esters: Of course, extractants such as phosphoric esters, acetic esters and TOPO (trioctylphosphine oxide) are also included. (d) Group of amides: acetamides, amides of _C4 - _C15 aliphatic carboxylic acids. (e) Group of alcohols: Various (n-, secondary, tertiary) alcohols having 4 to 18 carbon atoms. The desiccant used in the present invention is used to remove physically mixed water and water extracted together with the metal halide complex before distillation, and includes anhydrous sodium sulfate, anhydrous calcium chloride, anhydrous magnesium sulfate, Anhydrous magnesium chloride, anhydrous potassium chloride,
Molecular sieves such as phosphorus pentoxide, activated alumina, magnesium perchlorate, anhydrous potassium carbonate, quicklime, barium oxide, and synthetic zeolites can be used. The inert gas used in the present invention is _N2 gas and
Ar gas is Ar gas, which can be introduced as appropriate in the drying process to expel the atmosphere in the oxygen-containing organic solvent and prevent deterioration of the desiccant due to moisture absorption. Furthermore, in the heating evaporation and heating distillation steps, it can also be used to prevent oxidation of the oxygen-containing organic solvent or to prevent deterioration of each metal halide produced. Further, an inert gas can be introduced into the process as appropriate depending on the conditions of thermal evaporation and thermal distillation. The metals used as reducing agents in the present invention are Na,
Single or dual metals of Mg, Ca, Al, Pb and Zn
It is an alloy of more than one species and can be used in gaseous, liquid and red-hot solid forms. In addition, the target metal halide can also be used in gaseous, liquid, or solid forms for reduction, and the reducing atmosphere is usually an inert gas alone or a mixture of _H2 gas to prevent deterioration. You can also use The present invention will be described below based on the drawings, but it should be understood that the present invention is not limited thereto. The flow sheet in Figure 1 is a diagram showing the basic type of operation of the present invention.
The oxygen-containing organic solvent A that extracts and contains the metal halide complex of Ta) is led to the drying step B, and is brought into contact with a desiccant, thereby removing the water physically present in the oxygen-containing organic solvent or extracting it. The water is dehydrated and the oxygen-containing organic solvent is dried. In this case, an inert gas can be introduced as appropriate to expel the atmosphere existing in the oxygen-containing organic solvent. Next, the water-containing desiccant D is removed, and in a heating/evaporation or heating/distillation step C, an inert gas is introduced and heating/evaporation or heating/distillation is performed under normal pressure conditions filled with inert gas. Or, by heating and distilling under reduced pressure, halides of each metal E can be obtained.
and the regenerated oxygen-containing organic solvent F is recovered. Next, the halides E of each metal are converted into reducing metals (Na, Mg, Ca, Al, Pb and
Each metal (Ti, Zr,
Hf, Nb and Ta)H are produced. The reducing metal is separated as halide J. The flow sheet in Figure 2 is for each metal (Ti, Zr, Hf,
A solution containing a metal halide complex of Nb and Ta),
By contacting the regenerated oxygen-containing organic solvent F in the extraction step K, the halogenated metal complexes of each metal (Ti, Zr, Hf, Nb, and Ta), which are the starting materials of the present invention, are extracted and contained. 3 illustrates another embodiment of the invention that incorporates a process for making an oxy-organic solvent. [Example] The present invention will be further explained with reference to Examples below. Examples Table 1 shows the details of experiments to produce metal halides for each metal. The amount of sample is approximately 0.2% of the metal halide produced.
The amount of oxygen-containing organic solvent that extracted the metal was determined in moles. In each experiment, Ar gas was injected in advance to replace the air and water in the apparatus before heating and distillation and drying.

【table】

[Table] The halides of each metal obtained in the experimental examples in Table 1 were placed in a sealed crucible in a circular electric furnace, and reduction tests using various reducing metals were conducted. The results are shown in Table 2 below. show.

【table】

〔Effect of the invention〕

According to the present invention, each metal (Ti,
Compared to the production of Zr, Hf, Nb, and Ta), the process is simplified, there are no restrictions on raw materials, various raw materials can be used, and the production method has a high yield and is energy-saving.

[Brief explanation of the drawing]

FIG. 1 is a flow sheet showing the basic type of operation of the invention, and FIG. 2 is a flow sheet of another embodiment of the invention incorporating extraction step K. In the figure: A...Each metal (Ti, Zr, Hf, Nb and
Oxygen-containing organic solvent extracting and containing the metal halide complex of Ta), B...Drying step, C...Heating/evaporation or heating/distillation step, D...Water-containing desiccant, E
...Halides of each metal (Ti, Zr, Hf, Nb and Ta), F ... Regenerated oxygen-containing organic solvent, G
...Reduction process, H...Each metal (Ti, Zr, Hf, Nb
and Ta), J...halide, K...extraction step.

Claims (1)

[Scope of Claims] 1. An oxygen-containing organic solvent extracted and containing one type of metal halide complex selected from the group consisting of Ti, Zr, Hf, Nb, and Ti, anhydrous mirabilite, anhydrous calcium chloride, anhydrous After contacting with a desiccant selected from the group consisting of magnesium sulfate, anhydrous magnesium chloride, anhydrous potassium chloride, phosphorus pentoxide, activated alumina, magnesium perchlorate, anhydrous potassium carbonate, quicklime, barium oxide and zeolite,
The oxygen-containing organic solvent is heated and distilled under reduced pressure or normal pressure to generate metal halides and regenerate the oxygen-containing organic solvent; Metals Ti, Zr, Hf,
Metal Ti, metal characterized by obtaining Nb and Ta
Method for manufacturing Zr, metal Hf, metal Nb and metal Ta. 2. The manufacturing method according to claim 1, wherein water in the oxygen-containing organic solvent is removed by bringing it into contact with a desiccant, and then distillation is carried out at normal pressure while being filled with an inert gas. 3. The oxygen-containing organic solvent containing the halogenated metal complex contains one or more selected from the group consisting of hydrochloric acid, sulfuric acid, hydrobromic acid, hydroiodic acid, nitric acid, phosphoric acid, and hydrofluoric acid. A patent claim obtained by contacting a halide metal complex ion of one of Ti, Zr, Hf, Nb, and Ta generated in an aqueous solution with an oxygen-containing organic solvent and extracting the complex ion. The manufacturing method according to item 1 or 2.