JPS62252301A - Production of aqueous solution of titanium hydroperoxide of high purity - Google Patents

Abstract

PURPOSE:A titanium alkoxide is dissolved in an aqueous hydrogen peroxide and treated with reduced pressure to covert the alkoxy groups in the alkoxide into a volatile organic compound and remove it whereby an aqueous solution of titanium hydroperoxide of high purity is readily obtained. CONSTITUTION:A titanium alkoxide such as titanium methoxide or ethoxide is dissolved in an aqueous hydrogen peroxide under cooling with ice water. Then, the aqueous solution is subjected to vacuum-distillation to remove the alcohol liberated by substitution with hydrogen peroxide and a small amount of the oxidation products of the alcohol such as ketone or aldehyde whereby an aqueous solution of titanium hydroperoxide of high purity is obtained. The aqueous solution is suitably used for making titanium dioxide powder, film or fiber of high purity.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing an aqueous titanium peroxide solution useful for producing high-purity titanium oxide powder, membranes, and fibrous structures.

Prior Art Conventional methods for producing titanium hydroxide or titanium oxide include:
It is known to use a titanium salt such as titanium chloride, titanium sulfate, or alkoxytitanium as a raw material and to hydrolyze it, oxidize it, or use both together. According to these methods, in the production of titanium hydroxide or titanium oxide, components that cause impurities, such as sulfuric acid, hydrochloric acid, chlorine, or alcohol, are present. Therefore, these substances were incorporated into the product and made the titanium hydroxide or titanium oxide impure.

In addition, as titanium hydrogen peroxide aqueous solutions, titanium chloride aqueous solutions or titanium sulfate aqueous solutions with hydrogen peroxide added are known, but even if these are decomposed, impure products are obtained for the same reason as mentioned above. It will be done.

Purpose of the Invention The present invention was carried out to eliminate the drawbacks of conventional methods, and the first purpose is to provide a highly pure aqueous titanium peroxide solution as a raw material that does not contain components that cause impurities in the product. An object of the present invention is to provide a manufacturing method for easily obtaining titanium hydroxide and titanium oxide with extremely high purity. The second purpose is to provide a method for producing a high-purity titanium hydrogen peroxide aqueous solution, by slowly forming solids from the raw material liquid, and by converting the solids into fibers or films, and producing titanium oxide with high purity. It's about trying to get it easier.

Structure of the Invention As a result of research to achieve the above object, the present inventors have found that
It has been found that by dissolving alkoxytitanium in an aqueous hydrogen peroxide solution and distilling the solution under reduced pressure, a highly pure aqueous titanium peroxide solution suitable as a raw material for producing high-purity titanium hydroxide and titanium oxide can be obtained. . It has been found that highly pure titanium oxide can be easily obtained in the form of fibers or films from an aqueous solution of titanium hydrogen peroxide. −
1. The present invention was completed based on these findings.

The gist of the present invention is a method for producing a high-purity titanium hydrogen peroxide aqueous solution, which comprises dissolving alkoxy titanium in a hydrogen peroxide aqueous solution and distilling the obtained aqueous solution under reduced pressure to remove organic components.

It is preferable that the alkoxy titanium used in the present invention is substituted with a hydrogen peroxide solution, and the alcohol produced is enriched in first instar. For example, methoxy titanium, ethoxy titanium,
There is propoxy titanium.

However, in some cases, alkoxy titanium having a larger number of carbon atoms may be used. When alkoxy titanium is dissolved in hydrogen peroxide, water in the hydrogen peroxide causes
In order to avoid hydrolysis of alkoxy titanium, it is desirable that the concentration of hydrogen peroxide be as high as possible;
% to about 30%, and the higher the concentration, the lower the solubility. In addition, at high temperatures, hydrogen peroxide and alkoxy titanium peroxide decompose, which is inconvenient.
Hereinafter, it is necessary to mix and dissolve pure hydrogen peroxide solution, preferably while cooling with ice water. When the aqueous alkoxy titanium peroxide solution obtained in this manner is reduced in pressure to 10-2 to 10-'' torr using, for example, an oil rotary pump, hydrogen peroxide is substituted, liberating alcohol and some alcohol oxidation products. Ketones or aldehydes, etc., are distilled off together with water and free hydrogen peroxide to produce a pure aqueous titanium peroxide solution.

The obtained aqueous alkoxy titanium peroxide solution and titanium hydrogen peroxide solution are metastable at cold temperatures;
First, free hydrogen peroxide is decomposed to release a large amount of oxygen gas. At the same time, high hydrogen peroxide titanium changes to low hydrogen peroxide titanium, and the orange color tone becomes lighter over time, followed by condensation of low hydrogen peroxide titanium, gradually increasing the degree of condensation, and increasing the viscosity. The consistency increases and becomes jelly-like. Generally, this state continues for several hours to several days at room temperature, or for several minutes to several hours at 100°C. Finally, the condensed low hydrogen peroxide titanium is precipitated. Eventually it turns into a precipitate, titanium hydroxide. Colloidal particles in the jelly aggregate by drying or freezing.

It also becomes hydrophobic.

When a gel solution with a low concentration and degree of condensation is applied onto a solid and air-dried at room temperature, the solution becomes a uniform solid film.

When a gel is rapidly frozen, it becomes a frozen solid that is a fine mixture of colloid particles and solid water. When it is dried under reduced pressure, the portion occupied by solid water becomes voids, and the shape of the voids indicates the growth of solid water. The remainder forms a three-dimensional structure (honeycomb-like, fibrous-like). When the gel is gradually frozen, it becomes coarse particles or coarse pieces.

When the temperature of dry condensed low hydrogen peroxide titanium is gradually raised, dehydration and endotherm occur at about 100°C, and the temperature rises to about 250-320°C.
Dehydration, deoxidation, and heat generation occur, resulting in titanium oxide that maintains its shape at 450°C or higher. When heated rapidly, degassing causes the former shape to collapse and become powder-like.

Effects of the Invention The method of the present invention has the following excellent effects. 1
) Titanium, hydrogen,
Since it does not contain any elements other than oxygen, it does not generate impurities from the raw material itself, and there is no need to add additives to the raw material, it only needs to be thermally decomposed, so contamination with impurities can be avoided and extremely A highly pure titanium hydrogen peroxide aqueous solution is obtained.

2) By gradually forming a solid from a raw material liquid, titanium oxide can be more easily obtained in the form of a fiber or film with high purity.

Example 1) Put 0.522 grams of titanium tetraisopropoxy into a beaker, and while cooling the beaker by immersing it in ice water, add 5 ml of 30% high-purity hydrogen peroxide solution and gradually While stirring, a homogeneous tangerine-colored aqueous solution of isopropoxytitanium hydrogen peroxide was obtained. This aqueous solution was depressurized to remove isopropanol to obtain a titanium hydrogen peroxide aqueous solution.

Written amendment to the procedure Mr. Kunio Ogawa, Commissioner of the Patent Office■, Indication of the case, Patent Application No. 93583 of 1988 2, Name of the invention, Process for producing a high-purity titanium hydrogen peroxide aqueous solution 3, Person making the amendment Relationship with the case Patent applicant Takanobu Nise i ノ□l j, )j, -,
1"I++ ・11・" -・ A 1) I, ・ 4. Date of amendment order Voluntary amendment --1.

5゜Number of inventions increased by amendment None 6. Subject of amendment Separate sheets of claims and detailed description of the invention (1) The scope of claims is amended as follows.

"A method for producing a high-purity titanium hydrogen peroxide aqueous solution, which is characterized by dissolving alkoxy titanium in a hydrogen peroxide aqueous solution and removing it." High purity”
join.

(3) On page 2, line 1, “sulfuric acid, hydrochloric acid,” was replaced with “sulfate.”

Chloride,” he corrected.

(4) On page 2, line 7, "hydrogen water" is corrected to "hydrogen aqueous solution."

(5) On page 2, line 11, "resolution" is corrected to "improvement."

(6) Page 2, line 12, “monode,” is replaced with “mono de.”
I am corrected.

(7) On page 3, line 3, "the present inventors" is corrected to "the present inventors."

(8) On page 3, line 4, “hydrogenated aqueous solution” is changed to “hydrogen aqueous solution”.
I am corrected.

(9) On page 3, line 11, "based on" is corrected to "based on".

(10) On page 3, line 13, "hydrogenated aqueous solution" is corrected to "hydrogen aqueous solution."

(11) Delete 3 lines “water” from the bottom of the 3rd line.

(12) On the third page, 3 lines from the bottom, ``alcohol wa'' is corrected to ``alcohol ga''.

(13) On page 4, line 1, ``large'' is corrected to ``large''.

(14) Add the following sentence after ``No problem.'' on page 4, line 2.

``The aqueous hydrogen peroxide solution used in the present invention may be a commercially available product, but there are various purity products, and the most preferred is the highest purity product that does not contain stabilizers, but it is not limited to this. ” (15) Page 4, line 3 “Peroxidation...
・Correct "When mixing with hydrogen peroxide solution" to "When mixing with hydrogen peroxide solution."

(16) On page 4, lines 3-4, "hydrogen peroxide solution" is corrected to "hydrogen peroxide solution."

(17) On page 4, line 9, "decomposition occurs" is corrected to "decomposition occurs violently."

(18) Delete "pure" on page 4, line 11.

(19) On page 4, line 12, "with hydrogen oxide water" is corrected to "with hydrogen oxide aqueous solution."

(20) Add "no" next to "alcohol" in the fourth line from the bottom of the same page.

(21) Correct “pure” in the second line from the bottom of No. 4 to “high purity”.

(22) Add "high purity" next to "and" on page 5, line 2.

(23) On page 5, line 3, add ``at room temperature or above'' before ``first''.

(24) Add "ha" next to "sediment" on page 5, line 12.

(25) Correct the 8th line from the bottom of No. 6 to the last line as follows.

``The method of the present invention has the following excellent effects.

■) High purity titanium oxide can be obtained as a raw material for producing high purity titanium oxide. Since the raw material does not contain any elements other than titanium, hydrogen and oxygen, no impurities are generated from the raw material itself. Further, since there is no need to add a decomposing agent to the raw material and only thermal decomposition is required, contamination with impurities can be avoided and a highly pure product can be obtained. (26) On page 7, line 8, ``Hydrogen oxide water'' is corrected to ``Hydrogen oxide aqueous solution.''

(27) Add "high purity" before "peroxide" on page 7, line 11.

Claims (1)

[Claims] A method for producing a high-purity titanium hydrogen peroxide aqueous solution, which comprises dissolving alkoxy titanium in an aqueous hydrogen peroxide solution and distilling the solution under reduced pressure to remove organic components.