JP2000254502A - Production of carried ruthenium oxide catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a high activity catalyst which can produce an aimed compound at a lower temperature by a small amount of the catalyst by including a process in which a ruthenium compound is carried by a carrier and treating with a basic compound and a process in which it is treated with a reduceable compound and in which it is treated in an oxidation process. SOLUTION: In a method for producing a catalyst, a ruthenium compound such ruthenium chloride hydrate is carried by a carrier such as titanium oxide. An impregnation method, an equilibrium adsorption method, and others are used as the method. In an alkali treatment process, preferably an alkali metal hydroxide, carbonate, and others the used. Moreover, in a reduceable compound treatment process, hydrazine, a hydrazine solution, and others are used. In a next oxidation process, it is important to be burned in air preferably at about 100-600 deg.C in the presence of an alkali metal salt. By this method, ruthenium oxide of finer particles is produced, and higher catalytic activity can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a supported ruthenium oxide catalyst. More specifically, the present invention provides:
It is a method for producing a supported ruthenium oxide catalyst, which is a method for producing a highly active catalyst, and has the feature that it has become possible to produce a highly active catalyst that can produce the target compound at a lower reaction temperature with a smaller amount of catalyst. The present invention relates to a method for producing a supported ruthenium oxide catalyst.

[0002]

2. Description of the Related Art A method for producing a supported ruthenium oxide catalyst will be described. The ruthenium oxide catalyst is useful as a catalyst in a method for producing chlorine by an oxidation reaction of hydrogen chloride, and hydrolyzes ruthenium chloride, oxidizes it, and calcinates it. It is known that it can be obtained. For example, Japanese Patent Application Laid-Open No. 9-67103 describes that a ruthenium compound supported on titanium oxide can be obtained by hydrolyzing a ruthenium compound with an alkali metal hydroxide, and then supporting it on titanium hydroxide and calcining with air. ing. We have also found that a supported ruthenium oxide catalyst can be obtained by oxidizing a supported metal ruthenium catalyst. As a supported metal ruthenium catalyst, for example, a method is known in which ruthenium chloride is supported on a carrier, dried, and then heated in a hydrogen stream to prepare a supported metal ruthenium catalyst. However, when ruthenium chloride is reduced with hydrogen, ruthenium sintering occurs, and there is a problem that a supported ruthenium oxide catalyst prepared by oxidizing a hydrogen reduction catalyst has low activity.

[0003] A method for preparing ruthenium oxide supported on a carrier without causing sintering in the catalyst preparation process is desirable, but first, it is not a method of reducing at high temperature with hydrogen, but a reducing compound. A method has been desired in which a ruthenium compound is treated with a mixed solution of a basic compound or a mixture of an alkali and a reducing compound and then oxidized to form ruthenium oxide on a carrier while preventing sintering. Second, instead of completely reducing the ruthenium compound to a zero-valent oxidation number, it oxidizes after passing through a state of one or more valences to less than four valences to prevent oxidation on the carrier while preventing sintering. There has been a desire for a method of converting ruthenium. In general, ruthenium compounds are unlikely to be reduced by reducing compounds unlike platinum and palladium. For example, it is known that hydrazine is added to ruthenium chloride to form a complex, and there is a problem in that a supported ruthenium oxide catalyst prepared by adding hydrazine to ruthenium chloride and then oxidizing it has low activity. Next, conventionally, a supported ruthenium oxide catalyst using an anatase crystal system or amorphous titanium oxide as a carrier has been highly active in oxidizing hydrogen chloride, but the development of a catalyst having higher activity has been desired. .

Conventionally, the surface OH of titanium oxide as a carrier is
With a carrier having too much or too little group content, a catalyst having high activity could not be obtained, and there was a problem that the catalyst activity was lowered in some of them. In addition, since the supported catalyst is generally prepared by being supported on a carrier having pores of 30 to 200 angstroms, the rate of reaction is determined by diffusion in the catalyst pores. Are known. As a result, the reaction proceeds near the outer surface of the catalyst particles, so that ruthenium oxide supported on the outer surface of the catalyst carrier is used for the reaction, but ruthenium oxide supported inside the catalyst particles is not used for the reaction. it is conceivable that. Therefore, development of a technique for supporting ruthenium oxide on the outer surface of the catalyst has been desired.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a method for producing a supported ruthenium oxide catalyst, which is a method for producing a catalyst having a high activity, and which is capable of producing a target compound with a smaller amount of a catalyst at a lower reaction temperature. Another object of the present invention is to provide a method for producing a supported ruthenium oxide catalyst which enables production of a catalyst having a high level of resistance.

[0006]

The present invention relates to a method for producing one supported ruthenium oxide catalyst selected from the following (1) to (5). (1) A method for producing a supported ruthenium oxide catalyst comprising a step of supporting a ruthenium compound on a carrier and treating with a basic compound and a step of treating with a reducing compound, and then oxidizing. (2) A method for producing a supported ruthenium oxide catalyst which comprises a step of supporting a ruthenium compound on a carrier and treating it with a reducing agent to once convert the ruthenium into a monovalent oxide having a valence of 1 to less than 4, and then oxidize. (3) A method for producing a supported ruthenium oxide catalyst in which a ruthenium compound is supported on a titanium oxide carrier containing rutile crystalline titanium oxide, which is treated with a reducing agent, and then oxidized. (4) The amount of OH groups is 0.1 × 10 ⁻⁴ per unit weight of the carrier.
A method for producing a supported ruthenium oxide catalyst in which a ruthenium compound is supported on a titanium oxide carrier containing ３０30 × 10 ⁻⁴ (mol / g-support) and then reduced in a liquid phase, followed by oxidation. (5) supporting an alkali on the carrier, and then supporting at least one ruthenium compound selected from the group consisting of ruthenium halide, ruthenium oxychloride, ruthenium acetylacetonate complex, ruthenium organic acid salt and ruthenium nitrosyl complex; Next, the catalyst is treated with a reducing agent and further oxidized.
And a method for producing a supported ruthenium oxide catalyst comprising ruthenium oxide only in the outer surface shell layer of the support. S / L <0.35 (1) L: A catalyst which is perpendicular to the catalyst surface at an arbitrary point (A) on the surface of the catalyst and which goes down to the inside of the catalyst at the opposite side of the point (A) from the catalyst to the outside. The distance between the point (A) and the point (B) when the point on the surface is the point (B) S: the distance measured on the perpendicular from the point (A) and the point (A) From the point (C) at which ruthenium oxide disappears

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The supported ruthenium oxide catalyst produced in the catalyst (1) of the present invention includes a ruthenium compound supporting step, an alkali treatment step, a reducing compound treatment step,
A supported ruthenium oxide catalyst prepared in the oxidation step, more preferably a supported ruthenium oxide catalyst prepared in a ruthenium halide supporting step, an alkali treatment step, a reducing compound treatment step, and an oxidation step. Even more preferably,
It is a supported ruthenium oxide catalyst prepared in a ruthenium halide supporting step, an alkali treatment step, a reducing compound treatment step, an alkali metal chloride addition step, and an oxidation step.

[0008] The supported ruthenium oxide catalyst produced in the catalyst (2) of the present invention includes a step of supporting a ruthenium compound on a carrier and treating the same with a reducing agent. This is a method for producing a supported ruthenium oxide catalyst prepared by oxidizing after converting it to ruthenium.

There are various methods for preparing a supported ruthenium oxide catalyst. For example, after ruthenium chloride is supported on a carrier and hydrolyzed by an alkali, a catalyst in which ruthenium oxide having a valence of 4 is supported on the carrier can be prepared by calcining with air, or after supporting ruthenium chloride on the carrier. It is also possible to prepare a catalyst supported by ruthenium oxide having a tetravalent oxidation number by reducing it with various reducing agents to form zero-valent ruthenium, followed by calcining with air. Further, for example, after ruthenium chloride is supported on a carrier, it is treated with a mixed solution of various reducing compounds and a basic compound, treated with an aqueous alkali solution of the reducing compound, or treated with various reducing agents. There is also a preparation example in which a ruthenium compound having an oxidation number of at least 1 and less than tetravalent is prepared and then calcined in air to obtain a supported ruthenium oxide supporting ruthenium oxide having a valence of four. Is an example of a preparation which is most active in the oxidation reaction of hydrogen chloride. There are various methods for making the ruthenium compound supported on the carrier an oxidation number of from 1 to less than 4, and there are various methods. And a method of treating with an organic lithium compound, an organic sodium compound, and an organic potassium compound, a method of treating with an organic aluminum compound, a method of treating with an organic magnesium compound, and a method of treating with hydrogen. When these reducing agents are used, if used in excess, the ruthenium compound will be reduced to zero valence, so it is necessary to use an appropriate amount.

There are various methods for measuring the oxidation number of the supported ruthenium. For example, when hydrazine is used as a reducing agent, nitrogen is mainly generated, and the valence of ruthenium is determined from the amount of generated nitrogen. be able to.

The reaction formula is shown below. 4RuCl ₃ + 3N ₂ H ₄ + 12OH ⁻ → 4Ru ⁰ + 12Cl ⁻ + 12H ₂ O + 3N ₂ (1) or 4RuCl ₃ + 3N ₂ H ₄ → 4Ru ⁰ + 12Cl ⁻ + 12H ⁺
+ 3N _{2 Further} , for example, when a ruthenium compound is reduced with hydrazine under alkaline aqueous solution conditions, a hydroxide of ruthenium is generated. Therefore, after dehydration in vacuum, elemental analysis is performed, and oxygen and chlorine bonded to ruthenium and ruthenium are analyzed. By measuring such ratios, the oxidation number of ruthenium can also be determined. Here, the oxidation number of ruthenium was determined from the amount of generated nitrogen using the equation (1).

The parts common to the catalyst production methods (1) and (2) will be described below. Examples of the carrier include oxides of elements such as titanium oxide, alumina, zirconium oxide, silica, titanium composite oxide, zirconium composite oxide, aluminum composite oxide, and silicon composite oxide, and composite oxides. Is titanium oxide, alumina, zirconium oxide and silica, and a more preferred carrier is titanium oxide.

As a ruthenium compound supported on a carrier
Is RuCl_Three, RuCl_ThreeRuthenium chloride such as hydrate
Thing, K_ThreeRuCl₆, [RuCl₆]^3-, K_TwoRuCl₆What
Which chlororuthenate, [RuCl_Five(H_TwoO)_Four]
^2-, [RuCl_Two(H_TwoO)_Four]⁺Such as chlororuthenium
Acid salt hydrate, K_TwoRuO_FourRuthenic acid salts such as Ru
_TwoOCI_Four, Ru_TwoOCI_Five, Ru_TwoOCI₆Such as Ruteniu
Moxy chloride, K_TwoRu_TwoOCI_Ten, Cs_TwoRu_TwoOCI
_FourRuthenium oxychloride salts such as [Ru (NH_Three)
₆]²⁺, [Ru (NH_Three)₆]³⁺, [Ru (NH_Three)_FiveH
_TwoO]²⁺Ruthenium ammine complex such as [Ru (N
H_Three)_FiveCl]²⁺, [Ru (NH_Three)₆] Cl_Two, [Ru
(NH_Three)₆] Cl_Three, [Ru (NH_Three)₆] Br_ThreeSuch as le
Chloride, bromide, RuBr of ruthenium ammine complex_Three,
RuBr_ThreeRuthenium bromide such as hydrates, other ruthenium
Ruthenium organic amine complex, ruthenium acetylacetona
Complex, Ru (CO)_Five, Ru_Three(CO)₁₂Such as lute
Carbonyl complex, [Ru_ThreeO (OCOCH_Three)
₆(H_TwoO)_Three] OCOCH_ThreeHydrate, Ru_Two(RCOO)_Four
Ruthenium such as Cl (R = alkyl group having 1-3 carbon atoms)
Organic acid salt, K_Two[RuCl_FiveNO)], [Ru (N
H_Three)_Five(NO)] Cl_Three, [Ru (OH) (NH_Three)
_Four(NO)] (NO_Three)_Two, Ru (NO) (NO_Three)_ThreeSuch
Ruthenium nitrosyl complex, ruthenium phosphine complex
Compounds such as the body. Preferred ruthenium
As the compound, RuCl_Three, RuCl_ThreeHydrates
Ruthenium chloride, RuBr_Three, RuBr_ThreeHydrates
Ruthenium halide compounds such as ruthenium bromide
I can do it. Preferred ruthenium halides include
RuCl_Three, RuCl_ThreeRuthenium chlorides such as hydrates,
 RuBr_Three, RuBr_ThreeRuthenium bromide such as hydrate
Is raised. More preferably, ruthenium chloride hydrate
Is raised.

As a method for supporting a ruthenium compound on a carrier, there are an impregnation method, an equilibrium adsorption method and the like. Examples of the alkali used in the alkali treatment step include hydroxides, carbonates, and hydrogen carbonates of alkali metals, aqueous solutions of ammonia, ammonium carbonate, ammonium hydrogen carbonate, and the like, and solutions of organic solvents such as alcohols. As the alkali, hydroxides, carbonates and bicarbonates of alkali metals are preferably used. Water is preferably used as the solvent. It is also a preferable method to dissolve and use the reducing compound in an alkaline solution.

The reducing compound used in the reducing compound treatment step is hydrazine, methanol, ethanol,
Formaldehyde, hydroxylamine or formic acid. Or, an aqueous solution of hydrazine, methanol, ethanol, formaldehyde, hydroxylamine or formic acid or a solution of an organic solvent such as alcohol,
Preferably, hydrazine, methanol, ethanol, formaldehyde and hydrazine, methanol, ethanol,
A formaldehyde solution, more preferably,
Hydrazine and solutions of hydrazine. Also,
Examples of the reducing compound for treating a ruthenium compound supported on a carrier include compounds having an oxidation-reduction potential of -0.8 to 0.5 V, and an aqueous solution thereof and a solution of an organic solvent such as alcohol. Here, the standard electrode potential is used instead of the oxidation-reduction potential. Among the compounds exemplified above, when the standard electrode potential is shown, hydrazine is -0.23 V, formaldehyde is 0.056 V, and formic acid is -0.199.
V. It is also a preferable method to use an aqueous alkali solution of a reducing compound. Examples of the basic compound mentioned in the catalyst (2) include ammonia and amines such as alkylamine, pyridine, aniline, trimethylamine and hydroxylamine; alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide;
Examples thereof include alkali metal carbonates such as potassium carbonate, sodium carbonate, and lithium carbonate; hydroxides of quaternary ammonium salts; and alkylaluminums such as triethylaluminum.

As a method of treating with a reducing compound, the product obtained in the alkali treatment step is treated with a reducing compound or
Examples of the method include immersion in a solution of a reducing compound or impregnation with a solution of a reducing compound or a solution of a reducing compound. It is also a preferable method to use an aqueous alkali solution of a reducing compound.

It is also a preferable method to add a alkali metal chloride after treating with a reducing compound or an aqueous alkali solution of the reducing compound.

Next, as a method of oxidizing, a method of firing in air is exemplified.

The weight ratio of ruthenium oxide to the carrier is preferably from 0.1 / 99.9 to 20.0 / 80.0,
More preferably, 0.5 / 99.5 to 15.0 / 85.
0, still more preferably 1.0 / 99.0-1.
5.0 / 85.0. If the ratio of ruthenium oxide is too low, the activity may decrease, and if the ratio of ruthenium oxide is too high, the price of the catalyst may increase. Examples of supported ruthenium oxide include ruthenium dioxide and ruthenium hydroxide.

As a specific example of preparing the supported ruthenium oxide catalyst produced in the production methods (1) and (2) of the catalyst of the present invention, a preparation method including the following steps can be mentioned. Ruthenium compound supporting step: a step of supporting a ruthenium compound on a catalyst carrier Alkali treatment step: a step of adding an alkali to the one obtained in the ruthenium compound supporting step Reducing compound treatment step: The one obtained in the alkali treatment step is a reducing compound Treatment Step Oxidation step: Step of oxidizing the product obtained in the reducing compound treatment step In order to simultaneously perform the alkali treatment step and the reducing compound treatment step in the above steps, it is also a preferable method to use an aqueous alkali solution of the reducing compound. is there.

Further, as a preferred specific example of preparing the supported ruthenium oxide catalyst produced in the production methods (1) and (2) of the catalyst of the present invention, a preparation method including the following steps can be mentioned. Ruthenium halide compound supporting step: Step of supporting ruthenium halide on a catalyst carrier Alkali treatment step: Step of adding an alkali to the one obtained in the ruthenium compound supporting step Reducing compound treatment step: Hydrazine obtained by the alkali treatment step , A process of treating with methanol, ethanol or formaldehyde Oxidation process: a process of oxidizing the product obtained in the reducing compound treatment process In order to simultaneously perform the alkali treatment process and the reducing compound treatment process in the above process, an alkaline aqueous solution of the reducing compound is used. Is also a preferred method. Further, as a more preferable specific example of preparing the supported ruthenium oxide catalyst produced in the production methods (1) and (2) of the catalyst of the present invention, a preparation method including the following steps can be mentioned. Ruthenium halide supporting step: Step of supporting ruthenium halide on the catalyst carrier Alkali treatment step: Step of adding an alkali to the one obtained in the ruthenium halide supporting step Hydrazine treatment step: Treating the one obtained in the alkali treatment step with hydrazine Oxidation step: Oxidation step of the hydrazine treatment step obtained by the hydrazine treatment step In order to simultaneously perform the alkali treatment step and the hydrazine treatment step in the above steps, it is also a preferable method to use an aqueous solution of hydrazine in alkali.

Further, as a more preferred specific example of preparing the supported ruthenium oxide catalyst produced in the production methods (1) and (2) of the catalyst of the present invention, a preparation method including the following steps can be mentioned. Ruthenium halide supporting step: Step of supporting ruthenium halide on a catalyst carrier Alkali treatment step: Step of adding an alkali to the one obtained in the ruthenium halide supporting step Hydrazine treatment step: Treating the one obtained in the alkali treatment step with hydrazine Step of adding an alkali metal chloride: Step of adding an alkali metal chloride to the one obtained in the hydrazine treatment step Oxidation Step: Step of oxidizing the one obtained in the alkali metal chloride addition step It is also a preferable method to use an aqueous solution of hydrazine in an alkaline solution in order to simultaneously perform the hydrazine treatment step.

The ruthenium halide supporting step is a step of supporting ruthenium halide on a catalyst carrier. Examples of the ruthenium compound to be supported on the carrier include various ruthenium compounds described above.
ruthenium chlorides such as uCl ₃ , RuCl ₃ hydrate,
Preferred examples include ruthenium halides such as ruthenium bromide such as RuBr ₃ and RuBr ₃ hydrate. Preferred ruthenium halides are RuC
l ₃ , ruthenium chloride such as RuCl ₃ hydrate, RuB
and ruthenium bromide such as r ₃ and RuBr ₃ hydrate. More preferably, hydrated ruthenium chloride is used.

The amount of ruthenium halide used in the ruthenium halide supporting step is usually an amount corresponding to a preferable weight ratio of ruthenium oxide to the carrier. That is, the catalyst carrier is supported on the catalyst carrier exemplified above by impregnating a solution of ruthenium halide or by equilibrium adsorption. As the solvent, an organic solvent such as water or alcohol is used, and preferably, water is used. Next, the impregnated material can be dried, or can be subjected to an alkali treatment without drying, but a method of drying is a preferred example. Conditions for drying the impregnated material are preferably 50 to 200 ° C, preferably 1 to 200 ° C.
10 hours.

The alkali treatment step is a step of adding an alkali to the one obtained in the ruthenium halide supporting step.
The alkali used in the alkali treatment step is an aqueous solution of an alkali metal hydroxide, carbonate, hydrogen carbonate, and ammonia, ammonium carbonate, ammonium hydrogen carbonate, and the like.
Examples thereof include a solution of an organic solvent such as alcohol. As the alkali, preferably an alkali metal hydroxide,
Carbonates and bicarbonates are used. Water is preferably used as the solvent. The concentration of the alkali varies depending on the alkali used, but is preferably 0.1 to 10 mol / l.
Is raised. The molar ratio of ruthenium halide to alkali is, for example, 3 moles equivalent to 1 mole of ruthenium halide in the case of sodium hydroxide, but preferably 0.1 to 20 times the equivalent of ruthenium halide is used. You. Examples of a method of adding an alkali include a method of impregnating with an alkali solution and a method of immersing in an alkali solution. The time for impregnation with the alkali solution is usually within 60 minutes, but if the impregnation time is long, the activity of the catalyst is reduced.
The temperature is preferably 0 to 100 ° C, more preferably 10 to 60 ° C.

The hydrazine treatment step is a step of treating the substance obtained in the alkali treatment step with hydrazine. As a method of treating with hydrazine, there is a method of impregnating with a hydrazine solution, dipping in a hydrazine solution, or the like. The supported ruthenium halide and the alkali solution which have been subjected to the alkali treatment in the previous step may be added to the hydrazine solution in a mixed state, or the alkali solution may be filtered and then added to the hydrazine solution. A preferred method is to impregnate the supported ruthenium halide with an alkali and then immediately add it to the hydrazine solution.
The concentration of hydrazine used in the hydrazine treatment step is:
Preferably, it is 0.1 mol / l or more, but hydrazine hydrate such as hydrazine monohydrate may be used as it is. Alternatively, it is used as a solution of an organic solvent such as alcohol. Preferably, an aqueous solution or hydrazine hydrate is used. Hydrazine can be an anhydride or a monohydrate. The molar ratio of ruthenium halide to hydrazine is preferably 0.1 to 2 of ruthenium halide.
0-fold molar is used. The time for immersion in the hydrazine solution is preferably 5 minutes to 5 hours, and more preferably 10 minutes to 2 hours. The temperature is preferably 0 to 100 ° C, more preferably 1 to 100 ° C.
0 to 60 ° C. After immersion in the hydrazine solution, the solids are preferably filtered off from the solution. In order to simultaneously perform the alkali treatment step and the hydrazine treatment step in the above steps, it is also a preferable method to use an aqueous solution of hydrazine in an alkaline solution. As a method, there is a method in which a mixture obtained by mixing a preferable amount of a used alkali and a preferable amount of a hydrazine in the form of an aqueous solution, the one obtained in a ruthenium halide supporting step is gradually added, and the mixture is treated for 5 minutes to 5 hours. It is mentioned as a preferred method.

As a more preferred method, the solid produced in the alkali treatment and hydrazine treatment steps is washed to remove alkali and hydrazine, dried, and alkali metal chloride is added in the next alkali metal chloride addition step. After that, a method of drying and oxidizing can be given.

A more preferred method is a method in which the solid produced in the alkali treatment and hydrazine treatment steps is washed with an aqueous solution of an alkali metal chloride, dried and oxidized. This method is preferable because the removal of alkali and hydrazine and the addition of alkali metal chloride can be performed in the same step.

The alkali metal chloride adding step is a step of adding an alkali metal chloride to the product obtained in the alkali treatment and hydrazine treatment. Although this step is not an essential step for preparing a supported ruthenium oxide catalyst, the activity of the catalyst is further improved by performing this step. That is, the solid is oxidized in the next oxidation step, and in this case, it is preferable to convert the solid which has been subjected to the alkali treatment and the hydrazine treatment in the presence of an alkali metal salt into a highly active ruthenium oxide by oxidation. It is.

Examples of the alkali metal chloride include alkali metal chlorides such as potassium chloride and sodium chloride, preferably potassium chloride and sodium chloride, and more preferably potassium chloride. Here, the molar ratio of alkali metal salt / ruthenium is preferably 0.01 to 10, more preferably 0.1 to 5.0. If the amount of the alkali metal salt is too small, a sufficiently high activity catalyst cannot be obtained.

As an impregnation method of the alkali metal chloride aqueous solution, there is a method of impregnating the washed and dried hydrazine-treated ruthenium carrier. A more preferable method is a method of washing with an alkali metal chloride aqueous solution for impregnation.

Hydrochloric acid can be added to an aqueous solution of an alkali metal chloride for the purpose of adjusting the pH during washing of the obtained solid. The concentration of the aqueous solution of the alkali metal chloride is preferably from 0.01 to 10 mol / l, more preferably from 0.1 to 5 mol / l.

The purpose of the washing is to remove the alkali and hydrazine, but the alkali and hydrazine can be left as long as the effects of the present invention are not impaired.

After impregnation with the alkali metal chloride, the solid is usually dried. Drying conditions are preferably 50-200.
° C, preferably for 1 to 10 hours.

The oxidation step is a step of oxidizing the product obtained in the alkali treatment and hydrazine treatment steps (when the alkali metal chloride addition step is not used), or oxidizing the product obtained in the alkali metal chloride addition step. (When an alkali metal chloride addition step is used). As the oxidation step, a method of firing in air can be mentioned.
It is a preferable preparation example to oxidize to a highly active supported ruthenium oxide by calcining an alkali-treated and hydrazine-treated product in the presence of an alkali metal salt in a gas containing oxygen. The gas containing oxygen usually includes air.

The firing temperature is preferably 100 to 600 ° C.
And more preferably 280 to 450 ° C. If the firing temperature is too low, a large amount of particles generated by the alkali treatment and the hydrazine treatment remain as the ruthenium oxide precursor, and the catalytic activity may be insufficient. On the other hand, if the firing temperature is too high, agglomeration of the ruthenium oxide particles occurs, and the catalytic activity decreases. The firing time is preferably 30 minutes to 1
0 hours.

In this case, it is important to perform calcination in the presence of an alkali metal salt. By this method, finer particles of ruthenium oxide are produced, and higher catalytic activity can be obtained as compared with calcining in the substantial absence of an alkali metal salt.

By the calcination, the particles formed by the alkali treatment and hydrazine treatment carried on the carrier are converted into a supported ruthenium oxide catalyst. The conversion of the particles generated by the alkali treatment and the hydrazine treatment to ruthenium oxide can be confirmed by analysis such as X-ray diffraction or XPS (X-ray photoelectron spectroscopy). The particles generated by the alkali treatment and the hydrazine treatment are preferably substantially all converted to ruthenium oxide. May be allowed to remain.

A preferred preparation method is to subject the alkali-treated and hydrazine-treated ones to an oxidation treatment, and then wash and dry the remaining alkali metal chloride with water.
It is preferable that the alkali metal chloride contained at the time of firing is sufficiently washed with water. As a method of measuring the residual amount of the alkali metal chloride after washing, there is a method of adding an aqueous solution of silver nitrate to the filtrate and examining the presence or absence of cloudiness. However, alkali metal chlorides may remain as long as the catalytic activity of the present catalyst is not impaired.

The preferred method of preparation is to dry the washed solids next. Drying conditions are preferably 50 to 2
00 ° C., preferably for 1 to 10 hours.

The supported ruthenium oxide catalyst produced in the above steps was highly active, and was more active than the catalyst prepared by oxidizing a catalyst obtained by reducing ruthenium chloride with hydrogen.
In addition, a catalyst obtained by subjecting ruthenium chloride to hydrazine treatment with alkali pretreatment or oxidizing a product obtained by treating with alkali and hydrazine was higher in activity than a catalyst obtained by subjecting ruthenium chloride to hydrazine treatment and oxidation treatment.

The supported ruthenium oxide catalyst produced by the catalyst production method (3) of the present invention is a supported ruthenium oxide catalyst using titanium oxide containing rutile crystal titanium oxide as a carrier. Is a rutile crystal system,
Anatase crystal systems, amorphous and the like are known. The titanium oxide containing rutile crystal-based titanium oxide used in the present invention refers to a substance containing rutile crystal among which the ratio of rutile crystal and anatase crystal in titanium oxide is measured by X-ray diffraction analysis. . The measuring method will be described later in detail. When the chemical composition of the carrier used in the present invention is titanium oxide alone, the ratio of rutile crystals is determined from the ratio of rutile crystals and anatase crystals in titanium oxide by X-ray diffraction analysis. In this case, the ratio of rutile crystals is determined by the following method. Examples of oxides to be complexed with titanium oxide include elemental oxides.
Zirconium oxide, silica and the like can be mentioned. The ratio of the rutile crystal in the composite oxide is determined from the ratio of the rutile crystal and the anatase crystal in the titanium oxide by X-ray diffraction analysis, but it is necessary to include the rutile crystal. At this time, the content of the oxide other than titanium oxide in the composite oxide is in the range of 0 to 60% by weight. Preferred carriers include titanium oxide containing no metal oxide other than titanium oxide.

It is necessary that the titanium oxide contains rutile crystals. Preferably, the ratio of rutile crystals is at least 10%, more preferably at least 30%. Still more preferably, it is 80% or more.

There are various methods for preparing titanium oxide containing rutile crystals, and the following preparation examples are generally given. For example, when titanium tetrachloride is used as a raw material, titanium tetrachloride is dropped and dissolved in ice-cooled water and neutralized with an aqueous ammonia solution to generate titanium hydroxide (ortho titanic acid). Thereafter, the generated precipitate is washed with water to remove chlorine ions. At this time, when the temperature at the time of neutralization becomes a high temperature of 20 ° C. or more, or when chlorine ions remain in the titanium oxide after washing, a stable transition to rutile crystal system at the time of firing occurs. More likely to happen. Also, the firing temperature is 600
C. or higher causes rutile formation (catalyst preparation chemistry, 19
1989, p. 211, Kodansha). Further, for example, a reaction gas is prepared by passing an oxygen-nitrogen mixed gas into a titanium tetrachloride evaporator, and is introduced into the reactor. The reaction between titanium tetrachloride and oxygen starts at around 400 ° C., and titanium dioxide produced by the reaction of the TiCl ₄ —O ₂ system is mainly of anatase type, but when the reaction temperature exceeds 900 ° C., the formation of rutile type occurs. (Catalyst preparation chemistry, 1989, page 89, Kodansha). Further, for example, a method in which titanium tetrachloride is hydrolyzed in the presence of ammonium sulfate and then calcined (for example, Catalyst Engineering Lecture 10 Handbook of Catalysts by Element, 1978, 2
Page 54, Jinjinshokan), a method of calcining anatase crystalline titanium oxide (for example, metal oxide and composite oxide,
980, p. 107, Kodansha). Further, rutile crystalline titanium oxide can be obtained by a method of heating and hydrolyzing an aqueous solution of titanium tetrachloride.
Furthermore, a titanium compound aqueous solution such as titanium sulfate or titanium chloride and rutile crystal titanium oxide powder are mixed in advance, and then subjected to thermal hydrolysis or alkaline hydrolysis,
By firing at a low temperature of about 500 ° C., rutile crystal titanium oxide is also generated.

The method of determining the proportion of rutile crystals in titanium oxide is X-ray diffraction analysis, and various X-ray sources are used. For example, Kα radiation of copper is used. When copper Kα radiation is used, the ratio of rutile crystals and the ratio of anatase crystals are (110)
The intensity of the diffraction peak at 2θ = 27.5 degrees of the plane and (10
1) Determined using the intensity of the diffraction peak at 2θ = 25.3 degrees on the plane. The carrier used in the present invention has a peak intensity of rutile crystal and a peak intensity of anatase crystal. Alternatively, it has a peak intensity of rutile crystal.
That is, it has both the diffraction peak of the rutile crystal and the diffraction peak of the anatase crystal, or has only the diffraction peak of the rutile crystal. Preferably, the ratio of the peak intensity of the rutile crystal to the sum of the peak intensity of the rutile crystal and the peak intensity of the anatase crystal is 1
0% or more. In the supported ruthenium oxide catalyst used for the titanium oxide carrier containing rutile crystal titanium oxide, the amount of the OH group contained in the carrier is preferably the same as in the production method (4) of the catalyst of the present invention. For details, see the method for producing the catalyst of the present invention (4).
As described above, the amount of OH groups in the titanium oxide of the carrier used for the catalyst is usually 0.1 × 10 ⁻⁴ to 30 × 10 ⁻⁴ (mol
/ G-carrier), preferably from 0.2 × 10 ⁻⁴ to
20 × 10 ⁻⁴ (mol / g-carrier), more preferably 3.0 × 10 ⁻⁴ to 15 × 10 ⁻⁴ (mol / g-carrier).
Carrier).

The supported ruthenium oxide catalyst produced by the catalyst production method (4) of the present invention is defined as OH per unit weight of the carrier.
Next to the step including the step of supporting a ruthenium compound on a titanium oxide carrier having a base amount of 0.1 × 10 ⁻⁴ to 30 × 10 ⁻⁴ (mol / g-carrier) and subjecting the ruthenium compound to reduction in a liquid phase, The oxidized supported ruthenium oxide catalyst. Examples of the carrier include rutile crystal system, anatase crystal system, and amorphous. Preferably, a rutile crystal system and an anatase crystal system are used, and more preferably, a rutile crystal system is used. Generally, the surface of titanium oxide has O 2 bonded to Ti.
It is known that a hydroxyl group represented by H exists. The titanium oxide used in the present invention contains an OH group, and a method for measuring the content will be described later in detail. When the chemical composition of the carrier used in the present invention is titanium oxide alone, it is determined from the OH group content in the titanium oxide. In the present invention, a composite oxide of titanium oxide and another metal oxide is also included. Oxides that are complexed with titanium oxide include elemental oxides.
Preferably, alumina, zirconium oxide, silica and the like are used. At this time, the content of the oxide other than titanium oxide in the composite oxide is in the range of 0 to 60% by weight.
Also in this case, O per unit weight of the carrier contained in the carrier is used.
The H group content is also determined by a measuring method which will be described in detail later. Preferred carriers include titanium oxide containing no metal oxide other than titanium oxide. When the OH group content of the carrier is large, the carrier and the supported ruthenium oxide react,
May be inactivated. On the other hand, when the OH group content of the carrier is small, the activity of the catalyst may be reduced due to sintering of the supported ruthenium oxide and other phenomena.

There are various methods for determining the OH group content of titanium oxide. For example, there is a method using a thermogravimetric method (TG). When using the thermogravimetric method, keep the temperature constant, remove excess moisture in the sample, then raise the temperature,
The OH group content is determined from the weight loss. In this method, the amount of the sample is small and accurate measurement is difficult. Further, when a thermally decomposable impurity is present in the carrier, there is a disadvantage that the actual OH group content cannot be determined accurately. Similarly, in the case of using the ignition loss measurement (Igloss) for measuring the OH group content from the weight loss of the sample, a high-precision measurement can be performed by increasing the amount of the sample. Affected by pyrolytic impurities. Furthermore, the weight loss obtained by the thermogravimetric method or the measurement of loss on ignition has a drawback that it includes up to the bulk OH group content which is not effective during catalyst preparation. Another example is a method using sodium naphthalene. In this method, an OH group in a sample is reacted with sodium naphthalene as a reagent, and the OH group content is measured from an appropriate amount of sodium naphthalene. In this case, a change in the concentration of the appropriate reagent or a small amount of water greatly affects the result, and the measurement result is affected by the storage state of the reagent, so that it is extremely difficult to obtain an accurate value. Further, an appropriate method using an alkyl alkali metal may be used. As an appropriate method using an alkyl alkali metal, a titanium oxide carrier or a titanium oxide carrier powder is suspended in a dehydrated solvent, and the alkyl alkali metal is dropped in a nitrogen atmosphere. A preferred method is a method for determining the amount of OH groups contained in the polymer. At this time, the water contained in the dehydrated solvent and the alkyl alkali metal react with each other to generate hydrocarbons, and the amount thereof is subtracted from the measured value to calculate the OH in the titanium oxide.
The group content must be determined. As the most preferable method, a titanium oxide carrier or a titanium oxide carrier powder is suspended in dehydrated toluene, methyllithium is dropped in a nitrogen atmosphere, and an OH group content contained in the titanium oxide is determined based on an amount of generated methane. The OH group content in the titanium oxide carrier defined in the claims of the present invention is a value determined by this method.

The following procedure can be mentioned as a measuring procedure, for example. First, the sample was previously placed in air at 150 ° C.
After drying for 2 hours, the mixture is cooled in a desiccator. Thereafter, a predetermined amount of the sample is transferred into a flask purged with nitrogen,
Suspend in an organic solvent such as dehydrated toluene. The flask is cooled with ice to suppress heat generation, methyl lithium is dropped from the dropping funnel, the generated gas is collected, and the volume at the measured temperature is measured. The OH group content of the carrier titanium oxide used for the catalyst thus determined is usually 0.1 × 10 ^−4.
３０30 × 10 ^-4 (mol / g-carrier), but preferably 0.2 × 10 ^-4 -20 × 10 ^-4
-4 (mol / g-carrier), more preferably 3.0 × 10 ^-4 to 15 × 10 ^-4 (mol / g-carrier).

There are various methods for adjusting the content of the OH group contained in the titanium oxide carrier to a predetermined amount. For example, the firing temperature and firing time of the carrier can be mentioned. The OH groups in the titanium oxide carrier are eliminated by applying heat, but the OH group content can be controlled by changing the firing temperature and the firing time. The firing temperature of the carrier is usually 100 to 1000 ° C, preferably 150 to 800 ° C.
Is raised. The sintering time of the carrier is usually 30 minutes to 1
2 hours. In this case, it should be noted that the surface area of the support decreases as the firing temperature increases and the firing time increases. In addition, when the titanium oxide is produced in a gas phase, one having a small OH group content can be produced, and when the titanium oxide is produced from an aqueous phase such as an aqueous solution, one having a large OH group content can be produced. Further, there are a method of treating the OH group of the carrier with an alkali, and a method of reacting the OH group with an OH group using 1,1,1-3,3,3-hexamethyldisilazane or the like.

The present invention relates to a method for producing a supported ruthenium oxide catalyst using the above-mentioned carrier. The weight ratio of ruthenium oxide to the carrier is usually 0.1 / 99.9 to 20.0 / 8.
0.0, preferably 0.5 / 99.5 to 15.
0 / 85.0, more preferably 1.0 / 99.0.
１５15.0 / 85.0. If the ratio of ruthenium oxide is too low, the activity may decrease, and if the ratio of ruthenium oxide is too high, the price of the catalyst may increase.
Examples of the ruthenium oxide to be supported include ruthenium dioxide, ruthenium hydroxide, and the like.

The method of preparing a supported ruthenium oxide catalyst using the above-mentioned carrier includes a process of supporting a ruthenium compound on a carrier, reducing this in a liquid phase, and then oxidizing the catalyst. However, as a step of performing a reduction treatment in a liquid phase, a method of performing a reduction treatment in a liquid phase performed in the catalysts (1), (2) and (3) of the present invention, or a reductive hydride compound such as sodium borohydride How to reduce with
And a method exemplified below. That is, a method in which a ruthenium compound already supported on a carrier is suspended in an aqueous phase or an organic solvent and hydrogen is blown therein, an organic lithium compound such as butyllithium in an organic solvent, or an organic sodium compound or an organic potassium Examples of the method include a method of treating with a compound, a method of treating with an organoaluminum compound such as a trialkylaluminum, and a method of treating with an organomagnesium compound such as a Grignard reagent.
In addition, various organic metal compounds can be used, such as alkali metal alkoxides such as sodium methoxide, alkali metal naphthalene compounds such as sodium naphthalene, azide compounds such as sodium azide, alkali metal amide compounds such as sodium amide, and organic calcium compounds. And organic aluminum alkoxides such as organic zinc compounds and alkylaluminum alkoxides, organic tin compounds, organic copper compounds, organic boron compounds, borane such as borane and diborane, sodium ammonia solution, and carbon monoxide. Also, various organic compounds can be used, and examples thereof include diazomethane, hydroquinone, and oxalic acid. As a preferred method for producing a supported ruthenium oxide catalyst, the catalysts (1) and (2) of claim 1 are supported ruthenium oxide catalysts using titanium oxide containing 10% or more of rutile crystal titanium oxide as a carrier. A method for producing a supported ruthenium oxide catalyst may be mentioned. More preferably,
A method for producing a supported ruthenium oxide catalyst, wherein the catalyst (1) or (2) of claim 1 is a supported ruthenium oxide catalyst using a titanium oxide containing 30% or more of rutile crystalline titanium oxide as a carrier. Further, preferably, the ruthenium compound is supported on a carrier, this is reduced with a reducing hydrogenation compound, and this is oxidized.
For producing a supported ruthenium oxide catalyst. Further, preferably, the method for producing a supported ruthenium oxide catalyst according to claim 1 (3) or (4), wherein the ruthenium compound is supported on a carrier, treated with a reducing compound and then oxidized. More preferably, the method for producing a supported ruthenium oxide catalyst according to claim 1 (3) or (4), wherein the ruthenium compound is supported on a carrier, treated with an alkaline solution of a reducing compound, and then oxidized. Further, preferably, it is obtained by supporting a ruthenium halide on a carrier, treating this with a reducing compound, and then oxidizing it.
(3) or (4), a method for producing a supported ruthenium oxide catalyst. More preferably, the method for producing a supported ruthenium oxide catalyst according to (1) or (2) is obtained by supporting a ruthenium halide on a carrier, treating this with an alkaline solution of a reducing compound, and oxidizing the same. Is raised.

The catalyst produced by the catalyst production method (5) of the present invention satisfies the following formula (1) for at least 80% of the entire outer surface of the catalyst and oxidizes only the outer surface shell layer of the carrier. It is a supported ruthenium oxide catalyst containing ruthenium. S / L <0.35 (1) Here, L is a perpendicular to the inside of the catalyst perpendicular to the surface of the catalyst at an arbitrary point (A) on the surface of the catalyst. This is the distance between point (A) and point (B) when the point on the catalyst surface that exits is point (B). Also S
Is the distance measured from the point (A) on the perpendicular, and is the distance from the point (A) to the point (C) at which ruthenium oxide disappears. Preferably, S /
L <0.30. That is, the catalyst of the present invention contains ruthenium oxide substantially only in the outer surface shell layer of the carrier and does not contain ruthenium oxide inside the catalyst, as defined by the above formula (1). is there. With such a structure, the activity per unit weight of ruthenium contained in the catalyst can be increased.

The structure of the catalyst of the present invention will be specifically described with reference to a sectional view of the catalyst. If the catalyst is spherical,
As shown in FIG. L corresponds to the diameter passing through the center of the sphere, and S corresponds to the thickness of the outer shell layer of the sphere containing ruthenium oxide. When the catalyst has a columnar shape, it is as shown in FIG. In the case where the catalyst has a columnar shape having a cavity therein, it is as shown in FIG. The catalyst of the present invention
It may have a shape other than the above. In order for the catalyst to meet the above conditions, the method for producing the catalyst described below is used, in particular, pre-supporting an alkali on a carrier to be used, then supporting a specific ruthenium compound,
Adjustment is made so as to satisfy the above formula (1) by forming a precipitate of the ruthenium compound on the outer surface of the carrier by an acid-base reaction.

As a method for confirming that the above formula (1) is satisfied, there is a method of cutting a plane passing through the center of the particles of the supported ruthenium oxide catalyst and measuring with a graduated loupe. (EPMA). Further, the ruthenium component is immobilized on the carrier by drying the precipitate in which the ruthenium compound has formed on the carrier, so that the ruthenium component does not significantly move in the catalyst preparation step. Therefore, the thickness of the layer on which the ruthenium compound is supported is measured at the stage when the precipitate in which the ruthenium compound is formed is dried, and can be used as the thickness of the ruthenium oxide layer.

The catalyst of the present invention comprises an alkali supported on a carrier, and then at least one selected from the group consisting of ruthenium halide, ruthenium oxychloride, ruthenium acetylacetonate complex, ruthenium organic acid salt and ruthenium nitrosyl complex. Carrying a ruthenium compound,
Next, it is manufactured by treating with a reducing agent and further oxidizing. By using such a step, the activity of the catalyst can be increased.

Examples of the carrier include oxides of elements such as titanium oxide, alumina, zirconium oxide, silica, titanium composite oxide, zirconium composite oxide, aluminum composite oxide, and silicon composite oxide, and composite oxides. ,
Preferred carriers are titanium oxide, alumina, zirconium oxide and silica, and more preferred carriers are titanium oxide. The weight ratio of ruthenium oxide to the carrier is usually 0.1 /
99.9 to 20.0 / 80.0, preferably
0.5 / 99.5 to 15.0 / 85.0, more preferably 1.0 / 99.0 to 15.0 / 85.0. If the ratio of ruthenium oxide is too low, the activity may decrease, and if the ratio of ruthenium oxide is too high, the price of the catalyst may increase. Examples of the ruthenium oxide to be supported include ruthenium dioxide, ruthenium hydroxide, and the like.

The method for supporting ruthenium oxide of the present invention on the surface of a carrier will be described below. That is, it has been found that ruthenium oxide can be favorably supported on the outer surface of a carrier such as titanium oxide by the alkali impregnation supporting method described below, and a preparation example will be described. That is, first, a carrier such as titanium oxide having an appropriate particle size is impregnated with an aqueous solution of an alkali metal hydroxide such as potassium hydroxide or an alkali such as ammonium carbonate or ammonium hydrogen carbonate. At this time, the type of alkali and the concentration of alkali,
The thickness of the ruthenium compound layer on the surface supported on the carrier is determined by changing the amount of the supported ruthenium compound and the time from the impregnation of the ruthenium compound to the drying. For example, when potassium hydroxide is used, the thickness of the layer impregnated with the ruthenium compound can be changed by changing the concentration of the aqueous solution to be impregnated from 0.1 normal to 2.0 normal. Next, the carrier is dried after impregnating the carrier with an aqueous alkali solution. Next, the carrier is impregnated with a solution of a ruthenium compound. As the solution, an aqueous solution, a solution of an organic solvent such as alcohol, or a mixed solution of water and an organic solvent can be used.
A solution of an organic solvent such as ethanol is preferred. Then
A method in which a carrier impregnated with a ruthenium compound is dried and hydrolyzed with an alkali to form ruthenium hydroxide to form ruthenium oxide, or a method in which a supported ruthenium compound is reduced to once metal ruthenium, and oxidized to form ruthenium oxide. And so on.

The type of alkali preferably used in the step of impregnating the carrier with an aqueous alkali solution includes potassium hydroxide, sodium hydroxide, ammonium carbonate and ammonium hydrogen carbonate. The concentration of the alkali to be impregnated in the carrier is usually 0.01 to 4.0 normal, preferably 0.1 to 3.0 normal. If the time between the impregnation of the ruthenium compound and the carrier impregnated with the alkali-impregnated carrier to the drying is long, the ruthenium compound is impregnated into the interior of the carrier. It does not have to be dried immediately after impregnation, or it is dried after standing for up to 120 minutes. Preferably, it is dried immediately after impregnation or dried after standing for up to 30 minutes.

The ruthenium compounds supported on the carrier include ruthenium chlorides such as RuCl ₃ and RuCl ₃ hydrate, ruthenium halides such as ruthenium bromide such as RuBr ₃ and RuBr ₃ hydrate, Ru ₂ OCl ₄ , R
u ₂ OCl _5, ruthenium oxychlorides such as _{Ru 2 OCl 6, [Ru (} CH 3 COCHCOCH 3) 3] ruthenium acetylacetonate _{complex, [Ru 3 O (OCOCH 3} )
_{6 (H 2 O) 3]} OCOCH 3 hydrate, Ru ₂ (RCOO)
Ruthenium organic acid salts such as ₄ Cl (R = alkyl group having 1 to 3 carbon atoms), [Ru (NH ₃ ) ₅ (NO)] Cl ₃ ,
[Ru (OH) (NH ₃ ) ₄ (NO)] (NO ₃ ) ₂ , Ru
Ruthenium nitrosyl complexes such as (NO) (NO ₃ ) ₃ . Preferred ruthenium compounds include Ru
Ruthenium chloride such as Cl ₃ , RuCl ₃ hydrate, Ru
Ruthenium halides such as ruthenium bromide such as Br ₃ and RuBr ₃ hydrate; More preferably,
Ruthenium chloride hydrate.

Next, a method for preparing a supported ruthenium oxide catalyst will be described.
An example is described. That is, the supported ruthenium compound
The product with an alkali such as an aqueous solution of an alkali metal hydroxide.
Hydrolyze to ruthenium hydroxide and oxidize to ruthenium oxide
Method to reduce the amount of ruthenium compound supported
And then temporarily convert it to metallic ruthenium and oxidize it to ruthenium oxide.
The method used here is, for example,
An example of a method for reducing a ruthenium compound will be described. ruthenium
The method of reducing the compound is a method of heating under a stream of hydrogen
And hydrazine, formaldehyde and borohydride
Method for wet reduction using lithium, lithium borohydride
Potassium borohydride, trisec butyl hydride
Lithium iodide, trisec butyl boron sodium hydride
System, potassium trisecbutyl borohydride, lithium
Aluminum hydride, diisobutyl aluminum hydride
Uses Lido, sodium hydride, potassium hydride, etc.
And reduction methods.
Sodium boron (NaBH) _FourExample)
You. That is, a ruthenium compound is supported on the above carrier.
After drying, soak in a solution of sodium borohydride.
Solutions include aqueous solutions and solutions of organic solvents such as alcohol
But a mixed solution of water and an organic solvent can also be used.
Wear. After wet reduction with the above solution, wash with water and dry.
You. Next, the solid carrying ruthenium is oxidized by oxidation.
Ruthenium, but using an oxidizing agent or in air
There is a firing method. Ruthenium bearing
An alkaline metal chloride aqueous solution such as potassium chloride
After impregnation, drying and baking in air, ruthenium oxide
Is also a preferable method. In that case it remains
Wash and remove the alkali metal chlorides
Of supported ruthenium oxide catalyst by preparing
Can be.

The amount of the ruthenium compound to be impregnated in the carrier is usually the amount of the ruthenium compound corresponding to the above-mentioned preferable amount of the supported ruthenium oxide.

Various reducing agents can be used for reducing the supported ruthenium compound. When sodium borohydride (NaBH ₄ ) is used, it is preferably used as a solution, and the concentration is usually 0.05 to 20. % By weight, preferably 0.1 to 10% by weight. The molar ratio of sodium borohydride to the supported ruthenium compound is usually from 1.0 to 30, preferably from 2.0 to 15.

Next, a method of oxidizing a metal ruthenium carrier obtained by reduction to obtain a supported ruthenium oxide catalyst will be exemplified. Here, an example of a method of calcining in air is described. It is a preferable preparation example that the supported metal ruthenium is oxidized to highly active supported ruthenium oxide by calcining the supported metal ruthenium in the presence of an alkali metal salt in a gas containing oxygen. Air is usually used as the gas containing oxygen.

The firing temperature is usually from 100 to 600 ° C., preferably from 280 to 450 ° C. If the firing temperature is too low, a large amount of metal ruthenium particles may remain, and the catalytic activity may be insufficient. On the other hand, if the firing temperature is too high, agglomeration of the ruthenium oxide particles occurs, and the catalytic activity decreases. The firing time is usually 30 minutes to 10 hours.

In this case, the calcination is preferably performed in the presence of an alkali metal salt. By this method, finer particles of ruthenium oxide are produced, and higher catalytic activity can be obtained as compared with calcining in the substantial absence of an alkali metal salt. Examples of the alkali metal salt include potassium chloride, sodium chloride and the like, preferably potassium chloride and sodium chloride, more preferably potassium chloride. Here, the molar ratio of alkali metal salt / ruthenium is preferably from 0.01 to 10, more preferably from 0.1 to 5. If the amount of the alkali metal salt is too small, a sufficiently high activity catalyst cannot be obtained.

By the calcination, the metal ruthenium supported on the carrier is converted into a supported ruthenium oxide catalyst. The conversion of metal ruthenium to ruthenium oxide can be confirmed by analysis such as X-ray diffraction or XPS (X-ray photoelectron spectroscopy). It is preferable that substantially all of the metal ruthenium is converted into ruthenium oxide, but it is acceptable that the metal ruthenium remains as long as the effect of the present invention is not impaired.

Using the catalyst of the present invention, chlorine can also be obtained by oxidizing hydrogen chloride with oxygen. In obtaining chlorine, a reaction system such as a fixed bed or a fluidized bed is used as a reaction system, and a gas phase reaction such as a fixed bed gas phase flow system or a gas phase fluidized bed flow system is preferably employed.
The fixed-bed type does not require the separation of the reaction gas and the catalyst, and has an advantage that a high conversion can be achieved because the contact between the raw material gas and the catalyst can be sufficiently performed. Further, the fluidized bed method has an advantage that the heat in the reactor can be sufficiently removed and the width of the temperature distribution in the reactor can be reduced.

When the reaction temperature is high, ruthenium oxide in a highly oxidized state is volatilized, so that it is desirable to carry out the reaction at a lower temperature, preferably 100 to 500 ° C, more preferably 200 to 400 ° C. And more preferably 200 to 380 ° C. The reaction pressure is usually about atmospheric pressure to about 50 atm. As the oxygen source, air may be used as it is, or pure oxygen may be used. However, it is preferable to use inert nitrogen gas because other components are simultaneously released when the inert nitrogen gas is released outside the apparatus. Pure oxygen containing no active gas can be used. The theoretical molar amount of oxygen with respect to hydrogen chloride is 1/4 mole, but usually 0.1 to 10 times the theoretical amount is supplied. The amount of the catalyst used is usually about 10 to 20,000 h ^{-1 in} the case of the fixed bed gas phase flow system, expressed as a ratio GHSV to the feed rate of the raw material hydrogen chloride under atmospheric pressure.

[0069]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 A catalyst was prepared by the following method. That is, 0.81 g of commercially available ruthenium chloride (RuCl ₃ .nH ₂ O, Ru content 37.3% by weight) is dissolved in 6.4 g of pure water to prepare an aqueous solution, and titanium oxide powder (manufactured by Nippon Aerosil Co., Ltd.) , P25) 20.0 g. Next, the impregnated product was dried at 60 ° C. for 2 hours. The dried powder was thoroughly ground in a mortar to obtain 20.3 g of a dark green powder.
This operation was repeated 9 times to obtain 183.8 g of a dark green powder. Next, 10.4 g of this powder was immersed in a mixed solution of 2.1 g of potassium hydroxide solution adjusted to 2N at room temperature and 30.1 g of pure water in an ultrasonic cleaner for 1 minute. Next, a solution consisting of 0.61 g of a hydrazine monohydrate solution and 5.0 g of pure water was poured into the suspension of the immersed solution and the solution at room temperature while applying ultrasonic waves in nitrogen. Foaming was observed in the solution upon pouring.
After standing for 15 minutes until the firing disappeared, the supernatant was removed by filtration. Next, 500 ml of pure water was added, and 30
After washing for minutes, it was filtered off. This operation was repeated five times. At this time, the pH of the first cleaning solution was 9.1, and the pH of the fifth cleaning solution was 7.4. 2mo on the filtered powder
After the addition of 1 / l potassium chloride solution and stirring, the powder was filtered off again. This operation was repeated three times. The amount of the potassium chloride solution added was 54.4 g for the first time and 52.1 g for the second time.
g, the third time was 52.9 g. The procedure from the operation of dipping in the potassium hydroxide solution was similarly repeated six times to obtain 107 g of a cake. 53.1 g of the obtained cake was heated to 60 ° C.
For 4 hours to obtain 34.1 g of a gray powder. Then
The obtained powder was heated in the air from room temperature to 350 ° C. in 1 hour and calcined at the same temperature for 3 hours. After firing, 500m
After adding 1 l of pure water and stirring, the catalyst was filtered off. This operation was repeated 21 times, and an aqueous solution of silver nitrate was dropped into the washing solution, and it was confirmed that potassium chloride did not remain. Then
The catalyst was dried at 60 ° C. for 4 hours to obtain 28.
0 g of a blue-gray powder was obtained. 7. molding the resulting powder;
By setting the mesh size to 6 to 16.0, a ruthenium oxide catalyst supporting titanium oxide was obtained. The calculated value of the content of ruthenium oxide is calculated as follows: RuO ₂ / (RuO ₂ + TiO ₂ ) × 100 =
It was 1.9% by weight. The calculated value of the ruthenium content is R
u / (RuO ₂ + TiO ₂ ) × 100 = 1.5% by weight. The titanium oxide powder used was subjected to X-ray diffraction analysis under the following conditions. Apparatus Rotorflex RU200B (manufactured by Rigaku Corporation) X-ray Cu Kα-ray X-ray output 40 kV-40 mA Divergence slit 1 ° Scattering slit 1 ° Light receiving slit 0.15 mm Scanning speed 1 ° / min Scanning range 5.0 to 75.0 ° Counter Monochromator Using curved crystal monochromator Peak intensity of rutile crystal at 2θ = 27.4 ° 381 cp
s and peak intensity 1 of anatase crystal at 2θ = 25.3 °
Rutile peak intensity relative to the total value of 914 cps (2
θ = 27.4 °, 381 cps) was 17%. From this, the content of rutile crystals was 17%. The same glass reaction tube was charged with 17.8 g of the thus obtained ruthenium oxide catalyst supporting titanium oxide in two divided zones. The inside diameter of the glass reaction tube was 15 mm, and a thermocouple protection tube having an outside diameter of 6 mm was placed inside. The upper zone is composed of 5.9 g of a ruthenium oxide catalyst supported on titanium oxide and a commercially available α-alumina carrier having 2 mm spheres (manufactured by Nikkato Corporation, SSA9).
95) The catalyst was diluted and charged by thoroughly mixing 23.6 g. The lower zone was charged undiluted with 11.9 g of ruthenium oxide catalyst supported on titanium oxide. 96 ml / min of hydrogen chloride gas and 53 ml / min of oxygen gas
(All converted to 0 ° C., 1 atm.) The mixture was supplied from the upper part to the lower part under normal pressure. The upper zone of the glass reaction tube was heated with an electric furnace, and the internal temperature (hot spot) was set to 361 ° C. Similarly, set the lower zone to 2 internal temperatures (hot spots).
95 ° C. 4.5 hours after the start of the reaction, sampling was carried out by flowing the gas at the outlet of the reaction tube through a 30% aqueous solution of potassium iodide, and the amount of chlorine produced and the unreacted chloride were measured by iodine titration and neutralization titration, respectively. The amount of hydrogen was measured. As a result, the conversion of hydrogen chloride was 93.0.
%Met. 146 ml / mi of hydrogen chloride gas
n, oxygen gas is supplied under normal pressure of 74 ml / min (both at 0 ° C. and 1 atm), and the internal temperature of the upper zone is set to 360.
° C, and the reaction was carried out in accordance with the above-mentioned reaction method except that the internal temperature of the lower zone was 300 ° C.
At the end of the hour, the conversion of hydrogen chloride was 91.6%.

Example 2 A catalyst was prepared by the following method. That is, commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O, Ru content 3
(5.5 wt%) 3.52 g was dissolved in 7.6 g of pure water and stirred well to obtain an aqueous ruthenium chloride solution. The obtained aqueous solution is coated with a spherical titanium oxide carrier having a diameter of 1 to 2 mm (Sakai Chemical Industry Co., Ltd. CS-300S-12, anatase crystal form).
Ruthenium chloride was impregnated and supported by dropwise addition to 25.0 g. The supported product was left in the air at 60 ° C. for 4 hours to obtain 28.0 g of ruthenium chloride supported on titanium oxide. 4.0 g of 28.0 g of the obtained titanium oxide-supported ruthenium chloride
Was immersed in a mixed solution of 2.4 g of an aqueous potassium hydroxide solution adjusted to 2 mol / l at room temperature and 1.2 g of pure water for 1 minute.
Next, the immersed product was poured into 0.67 g of hydrazine monohydrate together with the solution at room temperature under a nitrogen atmosphere. Foaming was observed in the solution upon pouring. After standing for about 15 minutes until the bubbling disappeared, 4.0 g of pure water was poured and stirred. Next, the supernatant was removed by decantation. Then 2mol
Then, 30 ml of an aqueous solution of potassium chloride adjusted to 1 / l was added, the mixture was stirred after stirring, and the supernatant was removed by decantation. This operation was repeated six times to wash the aqueous potassium chloride solution. Next, the washed product was dried in air at 60 ° C. for 4 hours to obtain a gray spherical solid containing potassium chloride. Next, the obtained solid was heated from room temperature to 350 ° C. in the air in about 1 hour and calcined at the same temperature for 3 hours to obtain a spherical solid. 0.5 l of pure water was added to the obtained solid, stirred, left standing for 30 minutes, and filtered to wash with water.
This operation was repeated four times. The washing time was about 4 hours. The washed product was dried in the air at 60 ° C. for 4 hours to obtain 3.73 g of a ruthenium oxide catalyst carrying black spherical titanium oxide. The calculated value of the ruthenium oxide content was RuO ₂ / (RuO ₂ + TiO ₂ ) × 100 = 6.1% by weight. The calculated value of the ruthenium content is Ru / (R
uO ₂ + TiO ₂ ) × 100 = 4.7% by weight. The titanium oxide-supported ruthenium oxide catalyst (2.5 g) thus obtained was mixed with a spherical titanium oxide (CS-3) having a diameter of 1 to 2 mmφ.
The catalyst was diluted by thoroughly mixing 5 g of 00S-12 Sakai Chemical Industry Co., Ltd., and filled in a quartz reaction tube (inner diameter: 12 mm). 192 ml / min of hydrogen chloride gas and 184 ml / min of oxygen gas (both at 0 ° C. and 1 atm)
It was supplied under normal pressure. The quartz reaction tube was heated in an electric furnace, and the internal temperature (hot spot) was set to 300 ° C. Reaction start 1.8
At the time after the sampling, the gas at the outlet of the reaction tube is sampled by passing the gas through a 30% by weight aqueous solution of potassium iodide, and the amount of chlorine produced and the amount of unreacted hydrogen chloride are measured by an iodine titration method and a neutralization titration method, respectively. did. The chlorine generation activity per unit catalyst weight determined by the following equation is 3.68 ×
It was 10 ⁻⁴ mol / min · g-catalyst. Chlorine formation activity per unit catalyst weight (mol / min · g
−catalyst) = amount of exit chlorine produced per unit time (mol / m
in) / Catalyst weight (g) The chlorine generation activity per unit Ru weight determined by the following formula was 78.4 × 10 ⁻⁴ mol / min · g-Ru. Chlorine-forming activity per unit Ru weight (mol / min · g
-Ru) = amount of outlet chlorine produced per unit time (mol / m)
in) / Ru weight (g)

Example 3 A catalyst was prepared by the following method.
That is, commercially available ruthenium chloride hydrate (RuCl_Three・
nH_Two3.52 g of O, Ru content 35.5% by weight)
Dissolve in 7.6g, stir well and add ruthenium chloride aqueous solution
I got The resulting aqueous solution is oxidized in a spherical shape of 1-2 mmφ.
Titanium carrier (Sakai Chemical Industry Co., Ltd. CS-300S-1
2) Add dropwise to 25.0 g and impregnate with ruthenium chloride
Carried. The supported material is kept in air at 60 ° C. for 4 hours,
28.1 g of ruthenium chloride supported on titanium oxide was obtained. Obtained
Out of 28.1 g of ruthenium chloride supported on titanium oxide.
0 g of potassium hydroxide solution adjusted to 2 mol / l at room temperature
Dipped in a mixed solution of 2.4 g of solution and 1.2 g of pure water for 1 minute
Was. Next, the immersed material is mixed with the solution at room temperature in a nitrogen atmosphere.
Was added to 0.67 g of hydrazine monohydrate. Added
At this time, foaming was observed in the solution. Approximately 1 until foam disappears
After standing for 5 minutes, 30 ml of pure water was added, and the mixture was stirred after adding,
The supernatant was removed by decantation. This operation
Was repeated six times to wash with water. Next washed
Was dried in air at 60 ° C. for 4 hours. To a dry solid,
Aqueous potassium chloride solution 1.3 adjusted to 1.4 mol / l
g, impregnated in air at 60 ° C. for 0.5 hours,
A gray spherical solid containing potassium iodide was obtained. Potassium chloride
The calculated value of the molar ratio of metal to ruthenium was 1.0. Next
Temperature from room temperature to 350 ° C in air in about 1 hour
The mixture was calcined for 3 hours to obtain a spherical solid. To the resulting solid
0.5 l of pure water was added and the mixture was washed with water by filtration.
Was. This operation was repeated four times. Washing time is about 4 hours
there were. After washing with water, dry in air at 60 ° C for 4 hours
3.65 g of black spherical titanium oxide supported oxidation
A ruthenium catalyst was obtained. The ruthenium oxide content
The calculated value is RuO_Two/ (RuO_Two+ TiO_Two) × 100 = 6.
It was 1% by weight. The calculated value of the ruthenium content is Ru /
(RuO_Two+ TiO_Two) × 100 = 4.7% by weight
Was. Ruthenium oxide supported on titanium oxide thus obtained
The reaction tube was charged with 2.5 g of the catalyst in the same manner as in Example 2.
The reaction was carried out according to the reaction method of Example 2. Start reaction
1.8 hours later, formation of chlorine per unit weight of catalyst
The activity is 3.63 × 10 ^-Fourmol / min.g-catalyst
Was. The activity of forming chlorine per unit Ru catalyst weight is 77.
3 × 10^-Fourmol / min.g-Ru.

Example 4 A catalyst was prepared by the following method. That is, 33.4 g of pure water and titanium oxide sol (CSB, TiO ₂ content 38% by weight) were added to 50.0 g of titanium oxide powder (Sakai Chemical Co., STR-60N, 100% rutile crystal system). .6
g was added and kneaded. The kneaded material was blown with dry air at room temperature, and dried until the carrier had an appropriate viscosity. At this time, the amount of water reduced by drying was 0.2 g. This mixture was extruded into a 1.5 mmφ noodle shape. Next, it was dried in the air at 60 ° C. for 4 hours to obtain 46.3 g of white noodle-like titanium oxide. Next, the temperature was raised in the air from room temperature to 500 ° C. in 1.3 hours, and baked at the same temperature for 3 hours. After firing, noodle-like solid is 5m
By trimming the length to about m, 45.3 g of a white extruded titanium oxide carrier was obtained. Then, the carrier 4
0.0 g of commercially available ruthenium chloride (RuCl ₃ .nH
₂ O, Ru content 37.3 wt%) 3.23 g and 21.9
g of pure water was impregnated with an aqueous solution prepared and dried at 60 ° C. for 2 hours. Next, the obtained solid was immersed in a solution composed of 16.7 g of a 2N potassium hydroxide solution, 241 g of pure water, and 4.1 g of hydrazine monohydrate at room temperature. Foaming occurred upon soaking. After 80 minutes, the supernatant was removed by filtration. Then, 500 ml of pure water was added to the obtained solid, washed for 30 minutes, and filtered. This operation was repeated five times. At this time, the pH of the first washing solution was 9.2,
The pH of the fifth washing was 7.2. 50 g of a 0.5 mol / l potassium chloride solution was added to the filtered solid and stirred, and then the solid was filtered again. This operation was repeated three times. The obtained solid was dried at 60 ° C. for 4 hours to obtain a gray solid. Next, the temperature was raised from room temperature to 350 ° C. in air for 1 hour, and baked at the same temperature for 3 hours. After firing, 500
After adding and stirring the pure water of ml, the solid was separated by filtration. This operation was repeated 10 times, and an aqueous solution of silver nitrate was added dropwise to the washing solution.
It was confirmed that potassium chloride did not remain. Then, the solid is dried at 60 ° C. for 4 hours to obtain 4
1.1 g of a blue-gray extruded ruthenium oxide catalyst supported on titanium oxide was obtained. The calculated value of the ruthenium oxide content is:
RuO ₂ / (RuO ₂ + TiO ₂ ) × 100 = 3.8% by weight. The calculated value of the ruthenium content is Ru / (Ru
O ₂ + TiO ₂ ) × 100 = 2.9% by weight. The prepared titanium oxide support was subjected to X-ray diffraction analysis under the same conditions as in Example 1. The ratio of the rutile peak intensity (2θ = 27.4 °, 1389 cps) to the sum of the peak intensity of 1389 cps of the rutile crystal at 2θ = 27.4 ° and the peak intensity of 40 cps of the anatase crystal at 2θ = 25.3 ° is 97%. From this, the content of the rutile crystal form was 97%. 2.5 g of the thus-obtained titanium oxide-supported ruthenium oxide catalyst was added to a commercially available α-
Alumina carrier (manufactured by Nikkato Corporation, SSA995) 10
g, the catalyst was diluted and filled into a quartz reaction tube (12 mm inner diameter), and oxygen gas was added at 192 ml /
The reaction was carried out in accordance with the reaction method of Example 2 except that the temperature was set at 298 ° C. 2.3 hours after the start of the reaction, the chlorine generation activity per unit catalyst weight was 8.8.
It was 8 × 10 ⁻⁴ mol / min · g-catalyst.

Example 5 A catalyst was prepared by the following method. That is, 15.0 g of titanium oxide powder (STR-60N, 100% rutile crystal system) from commercially available ruthenium chloride (RuCl) was used.
₃ · nH ₂ O, Ru content 37.3 wt%) 2.01 g and 2
It was immersed in an aqueous solution consisting of 6.7 g of pure water, and then evaporated under reduced pressure at 50 ° C. for 4 hours. Next, at 60 ° C
For 2 hours. After drying, the catalyst was pulverized well to obtain a black powder. This powder was immersed in a solution consisting of 10.4 g of 2N potassium hydroxide solution, 69.9 g of pure water and 2.53 g of hydrazine monohydrate at room temperature under a nitrogen atmosphere. Foaming occurred upon soaking. During the treatment for 1 hour, the foamed gas was collected and the volume was measured.
Met. Next, the supernatant was removed by filtration. Next, 500 ml of pure water was added to the obtained powder, washed for 30 minutes, and filtered. This operation was repeated five times. At this time, the pH of the first cleaning solution was 9.4, and the pH of the fifth cleaning solution was 7.1. 2mo on the filtered powder
After adding 50 g of a 1 / l potassium chloride solution and stirring, the powder was filtered off again. This operation was repeated three times. The obtained cake was dried at 60 ° C. for 4 hours to obtain a black-brown powder.
Next, the obtained powder was heated in the air from room temperature to 350 ° C. in 1 hour, and calcined at the same temperature for 3 hours. After firing,
After adding 500 ml of pure water and stirring, the powder was separated by filtration. This operation was repeated five times, and an aqueous solution of silver nitrate was added dropwise to the washing solution, and it was confirmed that potassium chloride did not remain.
Next, this powder was dried at 60 ° C. for 4 hours to obtain 14.5 g of a black powder. The obtained powder was molded and made into a 8.6 to 16.0 mesh to obtain a titanium oxide-supported ruthenium oxide catalyst. The calculated value of the ruthenium oxide content is calculated as RuO ₂ / (RuO ₂ + TiO ₂ ) ×
100 = 6.2% by weight. The calculated value of the ruthenium content was Ru / (RuO ₂ + TiO ₂ ) × 100 = 4.7% by weight. Used titanium oxide powder (STR-60
N) was subjected to X-ray diffraction analysis under the same conditions as in Example 1. As a result, the peak intensity 101 of the rutile crystal at 2θ = 27.4 ° was 101.
It was 5 cps. No peak intensity of anatase crystal at 2θ = 25.3 ° was observed. Therefore, the content of the rutile crystal form was 100%. Further, the OH group content of the carrier was measured as follows. That is, the sample was previously dried in air at 150 ° C. for 2 hours, and then cooled in a desiccator. Thereafter, 1.06 g of the sample was transferred into a nitrogen-purged flask, and suspended in 40 ml of a dehydrated toluene solvent. The flask was cooled with ice to suppress heat generation, and 5 ml of methyllithium was dropped from the dropping funnel. As a result, 52 ml of methane gas was generated. When the same operation was carried out with 40 ml of toluene without the sample, 30 ml of methane gas was generated. The temperature at this time was 24 ° C. Using the following formula (1), the OH group content Q (mol / g-
When the carrier was calculated, Q = (V−V ₀ ) / (22400 × (273 + T) / 273) / W (1) V: amount of generated gas (ml) Volume of methane gas generated during measurement at temperature T V ₀ : blank generated gas amount (ml) Amount of methane gas at temperature T generated from residual moisture in the measurement system when measurement was performed without inserting a measurement sample T: measured temperature (° C) W: sample amount (g) 8 0.5 × 10 ^-4 (mol / g-carrier). Furthermore,
R reduced from the amount of nitrogen generated by the hydrazine treatment
The valence of u was determined by the following equation (2). ４N ₂ H ₄ → e ⁻ + H ⁺ + ／ N ₂ ↑ (1) In the present invention, the valence of ruthenium is determined by the equation (1). The valence of Ru when reaction (1) proceeds is as follows: Ru valence = 3-((V / 22400 × 4) / N) (2) V: amount of generated gas (ml) N: content of Ru (mol) And the Ru valence was 1.22. Ru is 1.2
Had been reduced to divalent. On the other hand, besides the reaction of the above formula, 9 / 2N ₂ H ₄ → e ⁻ + 5NH ₃ + 3H ⁺ + 2N ₂の (3) Reaction (3) is also known. 2.5 g of the titanium oxide-supported ruthenium oxide catalyst thus obtained was placed on a commercially available α-alumina carrier having a diameter of 2 mm (manufactured by Nikkato Corp., SSA9
95) The catalyst was diluted by thoroughly mixing with 10 g, and filled in a quartz reaction tube (inner diameter: 12 mm).
The reaction was performed in accordance with the reaction method of Example 2 except that the solution was flowed at 92 ml / min. 2.2 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 5.1 × 10 ⁻⁴ m.
ol / min.g-catalyst.

Example 6 A catalyst was prepared by the following method. That is, 1-2 mm
Spherical titanium oxide carrier (CS-30, Sakai Chemical Industry Co., Ltd.)
0S-12, anatase crystal system) 5.0 g
Ruthenium chloride (RuCl_Three・ NH_TwoO, Ru content 3
(5.5%) Solution of 0.71 g dissolved in 1.7 g of pure water
And dried at 60 ° C. for 2 hours. Next, hydrogenation
Sodium iodine (NaBH_Four) 0.84 g and pure water 4.1
and a solution consisting of 22.1 g of ethanol and an ice bath.
After cooling sufficiently, the ruthenium chloride already prepared
Add supported titanium oxide to reduce ruthenium chloride
Was. At this time, foaming of the solution was observed. Foaming subsides
, The reduced solid was filtered off. Next, 500ml
Was washed with pure water for 30 minutes, and the solid was filtered off again. This operation
The crop was repeated five times. Next, the solid is placed at 60 ° C. for 4 hours.
Dried. 5.2 g of a black solid were obtained. Then,
0.19 g of potassium chloride in 3.05 g of pure water
The dissolved solution was impregnated twice. Potassium chloride water
The impregnation amount of the solution was 1.72 g of the first time. 1 at 60 ° C
After drying for an hour, the second time, 1.52 g was impregnated. Obtained solid
The body was dried at 60 ° C. for 4 hours. Dry things in the air
Raise the temperature to 350 ° C in 1 hour and bake at the same temperature for 3 hours
Was. Next, the obtained solid was washed with 500 ml of pure water for 30 minutes.
Washed and filtered off. This operation was repeated five times. Nitrate in filtrate
Aqueous silver salt solution is added dropwise, no potassium chloride remains
It was confirmed. After washing, the solid is dried at 60 ° C. for 4 hours.
After drying, a spherical black titanium oxide-supported ruthenium oxide
5.1 g of medium were obtained. The ruthenium oxide content
The calculated value is RuO_Two/ (RuO_Two+ TiO_Two) × 100 =
It was 6.2% by weight. The calculated value of the ruthenium content is R
u / (RuO_Two+ TiO_Two) × 100 = 4.7% by weight
Was. The used titanium oxide powder was the same as in Example 1.
As a result of X-ray diffraction analysis under the following condition, 2θ = 25.3 °
For the peak intensity of anatase crystal of 1824 cps,
No peak of rutile crystal at 2θ = 27.4 ° is observed
Was. From this, the content of rutile crystals was 0%. Ma
The same as in Example 5 except that the sample amount was 2.56 g.
When the OH group content of the carrier was measured under the conditions, 86 ml
Methane gas was generated. The OH group content of the carrier is 9.0 ×
10^-Four(Mol / g-carrier). Like this
2.5 g of the obtained titanium oxide-supported ruthenium oxide catalyst was
The reaction tube was filled in the same manner as in Example 2, and hydrogen chloride gas was added to the reaction tube.
7ml / min, oxygen gas flow at 199ml / min
The reaction was carried out in the same manner as in Example 2 except that the reaction was performed. Reaction opening
2.0 hours after the start of production of chlorine per unit catalyst weight
The active activity is 3.92 × 10 ^-Fourmol / min-g-catalyst
there were.

Example 7 A catalyst was prepared by the following method. That is, titanium oxide
To 10.1 g of powder (Nippon Aerosil, P25)
Ruthenium chloride (RuCl)_Three・ NH_TwoO,
(Ru content: 37.3% by weight) 0.41 g to 3.5 g of pure water
And then impregnated with an aqueous solution prepared by dissolving
Dried for hours. Grind the dried powder well in a mortar,
A greenish powder was obtained. This powder is
Sodium borohydride for reduction with thorium.
Prepare a solution of 50 g dissolved in 100 g of ethanol,
Cooled in an ice bath. In this sodium borohydride solution,
While stirring the entire amount of ruthenium chloride-supported titanium oxide,
Added. Foaming occurred upon addition. One hour later, on
The supernatant was removed by decantation. Then obtained
500 ml of pure water was added to the powder and washed for 30 minutes.
Then, it was separated by filtration. This operation was repeated five times. At this time
The pH of the first washing solution is 9.3, the pH of the fifth washing solution
Was 4.2. 2 mol / l potassium chloride is added to the filtered powder.
After adding a lithium solution and stirring, the powder was filtered off again.
This operation was repeated three times. Of the added potassium chloride solution
The amount was 48.1 g for the first time, 52.9 g for the second time, and 4 for the third time.
7.2 g. Dry the obtained cake at 60 ° C for 4 hours
Drying gave a gray powder. Then, the obtained powder is in air
Then, the temperature is raised from room temperature to 350 ° C. in one hour.
Fired for hours. After firing, add 500 ml of pure water and stir
After that, the powder was filtered off. Repeat this operation 5 times and wash
An aqueous solution of silver nitrate is added dropwise to the solution, and potassium chloride remains.
Confirmed that there is no. Then, the cake was heated at 60 ° C for 4 hours.
After drying for an hour, 9.2 g of blue-gray powder was obtained.
Was. The obtained powder is molded and 8.6 to 16.0 mesh
To obtain a ruthenium oxide catalyst supporting titanium oxide.
Was. The calculated value of the ruthenium oxide content is RuO_Two/
(RuO_Two+ TiO_Two) × 100 = 1.9% by weight
Was. The calculated value of the ruthenium content is Ru / (RuO_Two+ T
iO_Two) × 100 = 1.5% by weight. in this way
Oxide-supported ruthenium oxide catalyst 2.5 obtained by
g into a reaction tube in the same manner as in Example 2, and hydrogen chloride gas was added.
195 ml / min, oxygen gas at 198 ml / min
The reaction was carried out in the same manner as in Example 2 except that the reaction was carried out. Anti
2.0 hours after the start of the reaction, chlorine per unit catalyst weight
Has a production activity of 5.56 × 10 ^-Fourmol / min-g-contact
Medium.

Example 8 A catalyst was prepared by the following method. That is, commercially available ruthenium chloride (RuCl ₃ .nH ₂ O,
An aqueous solution prepared by dissolving 0.40 g of Ru content (37.3% by weight) in 3.4 g of pure water was impregnated, and then the obtained powder was dried at 60 ° C. for 2 hours. The dried powder was pulverized well in a mortar to obtain a dark green powder. At room temperature, 2.1 g of a 2N potassium hydroxide solution and 30.2
g of the solution and stirred while placing the flask in an ultrasonic cleaner. One minute later, a solution consisting of 0.59 g of hydrazine monohydrate and 5.1 g of pure water was added to the suspension stirred at room temperature under nitrogen, and treated with hydrazine. Foaming occurred upon addition. After 15 minutes, the supernatant was filtered off. next,
500 ml of pure water was added to the obtained powder, washed for 30 minutes, and filtered. This operation was repeated five times. At this time, the pH of the first cleaning solution was 7.8, and the pH of the fifth cleaning solution was 6.0. 2mol / l to the filtered powder
After adding a potassium chloride solution and stirring, the powder was filtered off again. This operation was repeated three times. The amount of the potassium chloride solution added was 53.6 g for the first time, 62.4 g for the second time, and 39.4 g for the third time. The obtained cake was dried at 60 ° C. for 4 hours to obtain a beige powder. Then, the temperature of the dried powder is raised from room temperature to 350 ° C. in the air in one hour,
It baked at the same temperature for 3 hours. After baking, 500 ml of pure water was added and stirred, and then the powder was separated by filtration. This operation was repeated five times, and an aqueous solution of silver nitrate was added dropwise to the washing solution, and it was confirmed that potassium chloride did not remain. The catalyst was then added to 6
By drying at 0 ° C. for 4 hours, 8.4 g of a blue-gray powder was obtained. The obtained powder was molded and made into a 8.6 to 16.0 mesh to obtain a titanium oxide-supported ruthenium oxide catalyst. The calculated value of the ruthenium oxide content is Ru
_{O 2 / (RuO 2 + TiO} 2) was × 100 = 1.9% by weight. The calculated value of the ruthenium content is Ru / (RuO ₂
+ TiO ₂ ) × 100 = 1.4% by weight. X-ray diffraction analysis of the used titanium oxide powder under the same conditions as in Example 1 showed a rutile crystal content of 17%. . The sample amount was 4.08 g and the toluene amount was 80 m.
When the OH group content of the carrier was measured under the same conditions as in Example 5 except that the amount was changed to 1, 88 ml of methane gas was generated. The OH group content of the carrier was 2.8 × 10 ⁻⁴ (mol / g)
-Carrier). 2.5 g of the titanium oxide-supported ruthenium oxide catalyst thus obtained was charged into a reaction tube in the same manner as in Example 2, hydrogen chloride gas was passed at 187 ml / min, oxygen gas was passed at 199 ml / min, and the internal temperature was lowered. 301
The reaction was performed according to the reaction method of Example 2 except that the temperature was changed to ° C.
2.0 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 5.33 × 10 ⁻⁴ mol / min · g-
It was a catalyst.

Example 9 A catalyst was prepared by the following method. That is, commercially available ruthenium chloride (RuCl ₃ .nH ₂ O, P25) was previously added to 19.7 g of titanium oxide powder (P25, manufactured by Nippon Aerosil Co., Ltd.).
(Ru content: 37.3% by weight) was impregnated with an aqueous solution prepared by dissolving 0.81 g of pure water in 6.0 g of pure water.
Dried for hours. The dried powder was pulverized well in a mortar to obtain a dark green powder. To reduce this powder with sodium borohydride sodium borohydride 1.
A solution prepared by dissolving 00 g in ethanol 200 g was prepared.
Cooled in an ice bath. In this sodium borohydride solution,
The total amount of titanium oxide supporting ruthenium chloride was added with stirring. Foaming occurred upon addition. After 1 hour, the supernatant was removed by decantation. Next, 500 ml of pure water was added to the obtained powder, washed for 30 minutes, and filtered. This operation was repeated five times. At this time, the pH of the first cleaning solution was 9.8, and the pH of the fifth cleaning solution was
Was 6.6. The obtained cake was dried at 60 ° C. for 4 hours. 18.0 g of a blue-gray powder were obtained. Next, the obtained powder was impregnated with an aqueous solution consisting of 0.66 g of potassium chloride and 9.0 g of pure water, and dried at 60 ° C. for 4 hours. Then
In air, the temperature was raised from room temperature to 350 ° C. in 1 hour, and baked at the same temperature for 3 hours. After baking, 500 ml of pure water was added and stirred, and then the powder was separated by filtration. This operation was repeated five times, and an aqueous solution of silver nitrate was added dropwise to the washing solution, and it was confirmed that potassium chloride did not remain. Then, the powder was cooled to 60 ° C.
For 4 hours to obtain 17.3 g of a blue-gray powder. The obtained powder was molded and made into a 8.6 to 16.0 mesh to obtain a titanium oxide-supported ruthenium oxide catalyst. The calculated value of the ruthenium oxide content is RuO
₂ / (RuO ₂ + TiO ₂ ) × 100 = 2.0% by weight. The calculated value of the ruthenium content is Ru / (RuO ₂ +
TiO ₂ ) × 100 = 1.5% by weight. X-ray diffraction analysis of the used titanium oxide powder under the same conditions as in Example 1 showed a rutile crystal content of 17%. .
2.5 g of the titanium oxide-supported ruthenium oxide catalyst thus obtained was charged into a reaction tube in the same manner as in Example 2, and 195 ml / min of hydrogen chloride gas and 198 ml of oxygen gas were used.
/ Min, and carried out in accordance with the reaction method of Example 2 except that the internal temperature was set to 299 ° C. 2.0 hours after the start of the reaction, the activity of forming chlorine per unit catalyst weight was 4.
It was 41 × 10 ⁻⁴ mol / min · g-catalyst.

Example 10 A catalyst was prepared by the following method. That is, titanium oxide powder (Sakai Chemical Co., Ltd., STR-60N, 100% rutile crystal system) was heated in advance from room temperature to 500 ° C. in air for 1.4 hours, and calcined at the same temperature for 3 hours. Then, 15.1 g of the calcined product was added to commercially available ruthenium chloride (RuCl ₃ .nH ₂ O, Ru content 37.3% by weight).
It was immersed in an aqueous solution composed of 61 g and 26.7 g of pure water, and then evaporated under reduced pressure at 50 ° C. for 4 hours. Next, it dried at 60 degreeC for 2 hours. The dried powder was pulverized well to obtain a dark green powder. At room temperature,
It was immersed in a solution consisting of 3.2 g of a 2N potassium hydroxide solution, 52.6 g of pure water, and 0.77 g of hydrazine monohydrate in a nitrogen atmosphere for treatment. Foaming occurred upon addition.
After 1 hour, the supernatant was filtered off. Then 5
After adding 00 ml of pure water and washing for 30 minutes, the mixture was filtered off. This operation was repeated seven times. At this time, the pH of the first cleaning solution was 9.9, and the pH of the seventh cleaning solution was 7.5. After adding 50 g of a 2.0 mol / l potassium chloride solution to the filtered powder and stirring, the powder was filtered again.
This operation was repeated three times. The obtained cake was dried at 60 ° C. for 4 hours to obtain a red-gray powder. Then in the air,
The temperature was raised from room temperature to 350 ° C. in 1 hour, and baked at the same temperature for 3 hours. After baking, 500 ml of pure water was added and stirred, and then the powder was separated by filtration. This operation was repeated five times, and an aqueous solution of silver nitrate was added dropwise to the washing solution, and it was confirmed that potassium chloride did not remain. Next, this powder was dried at 60 ° C. for 4 hours to obtain 13.9 g of a blue-gray powder. The obtained powder was molded and made into a 8.6 to 16.0 mesh to obtain a titanium oxide-supported ruthenium oxide catalyst. The calculated value of the ruthenium oxide content is calculated as RuO ₂ / (Ru
O ₂ + TiO ₂ ) × 100 = 1.9% by weight. The calculated value of the ruthenium content is Ru / (RuO ₂ + TiO ₂ ) ×
100 = 1.5% by weight. In addition, the sample amount was set to 1.3.
When the OH group content of the carrier was measured under the same conditions as in Example 5 except that the amount was changed to 1 g, 48 ml of methane gas was generated. The OH group content of the carrier was 5.6 × 10 ⁻⁴ (mol / g)
-Carrier). 2.5 g of the titanium oxide-supported ruthenium oxide catalyst thus obtained was added to a commercially available α
-Alumina carrier (Nikkato Co., Ltd., SSA995) 1
The catalyst was diluted by thoroughly mixing with 0 g, and filled in a quartz reaction tube (inner diameter: 12 mm).
/ Min. 2.0 hours after the start of the reaction, the formation activity of chlorine per unit catalyst weight was 4.27 × 10 ⁻⁴ mol /.
min.g-catalyst.

Example 11 A catalyst was prepared by the following method. That is, the titanium oxide powder (Sakai Chemical Co., Ltd., STR-60N, 100% rutile crystal system) was heated in advance from room temperature to 700 ° C. in air for 1.9 hours and calcined at the same temperature for 3 hours. Then, 15.0 g of the calcined product was added to a commercially available ruthenium chloride (RuCl ₃ .nH ₂ O, Ru content 37.3% by weight).
It was immersed in an aqueous solution composed of 61 g and 26.7 g of pure water, and then evaporated under reduced pressure at 50 ° C. for 4 hours. Next, it dried at 60 degreeC for 2 hours. The dried powder was pulverized well to obtain a dark green powder. At room temperature,
Under a nitrogen atmosphere, it was immersed in a solution consisting of 3.2 g of 2N potassium hydroxide solution, 52.7 g of pure water, and 0.77 g of hydrazine monohydrate. Foaming occurred upon soaking. One hour later,
The supernatant was filtered off. Then, 500 ml of pure water was added to the obtained powder, washed for 30 minutes, and filtered. This operation was repeated seven times. PH of the first cleaning solution at this time
Was 9.9, and the pH of the seventh washing was 7.5. 50 g of a 2.0 mol / l potassium chloride solution was added to the filtered powder.
Was added and stirred, and the powder was filtered off again. This operation was repeated three times. The obtained cake was dried at 60 ° C. for 4 hours to obtain a gray powder. Next, the temperature of the obtained powder is raised from room temperature to 350 ° C. in air for one hour,
Fired for hours. After baking, 500 ml of pure water was added and stirred, and then the powder was separated by filtration. This operation was repeated five times, and an aqueous solution of silver nitrate was added dropwise to the washing solution, and it was confirmed that potassium chloride did not remain. Next, this powder was dried at 60 ° C. for 4 hours to obtain 13.5 g of a blue-gray powder. The obtained powder was molded and made into a 8.6 to 16.0 mesh to obtain a titanium oxide-supported ruthenium oxide catalyst. The calculated value of the ruthenium oxide content was calculated as RuO ₂ /
(RuO ₂ + TiO ₂ ) × 100 = 2.0% by weight. The calculated value of the ruthenium content is Ru / (RuO ₂ + T
iO ₂ ) × 100 = 1.5% by weight. The OH group content of the carrier was measured under the same conditions as in Example 5 except that the sample amount was changed to 2.02 g. As a result, 46 ml of methane gas was generated. The OH group content of the carrier is 3.3 × 10
^-4 (mol / g-carrier). 2.5 g of the thus-obtained ruthenium oxide catalyst supporting titanium oxide was added to 2 m
m-sphere commercially available α-alumina carrier (manufactured by Nikkato Corporation, S
SA995) The reaction was carried out in accordance with the reaction method of Example 2 except that the catalyst was diluted by thoroughly mixing with 10 g, filled in a quartz reaction tube (inner diameter: 12 mm), and oxygen gas was passed at 192 ml / min. . 2.0 hours after the start of the reaction, the activity of forming chlorine per unit catalyst weight was 4.32 ×
It was 10 ⁻⁴ mol / min · g-catalyst.

Example 12 A catalyst was prepared by the following method. That is, 76.3 g of pure water and 15.8 g of titanium oxide sol (Sakai Chemical Co., Ltd., CSB, TiO2 content 38% by weight) were added to 120 g of titanium oxide powder (Sakai Chemical Co., STR-60N, 100% rutile crystal system).
Was added and kneaded. The kneaded material was blown with dry air at room temperature, and dried until the carrier had an appropriate viscosity. The reduction in water due to drying was 10.5 g. This mixture was extruded into a 1.5 mmφ noodle shape. Next, it was dried in air at 60 ° C. for 4 hours to obtain 119 g of white noodle-like titanium oxide. Next, in air, the temperature was raised from room temperature to 500 ° C. for 1.4 hours, and baked at the same temperature for 3 hours. After firing, the white extruded titanium oxide carrier 1 is cut by cutting the noodle-like solid to a length of about 5 mm.
15 g were obtained. Then, commercially available ruthenium chloride (RuCl ₃ .nH ₂ O, Ru content 3) was added to 50.0 g of the obtained carrier.
(7.3% by weight) was impregnated with an aqueous solution prepared by dissolving in 2.04 g and 27.0 g of pure water, and dried at 60 ° C. for 2 hours.
Next, 10.5 g of a 2N potassium hydroxide solution, 300 g of pure water, and 2.5 g of hydrazine monohydrate were added to the obtained solid at room temperature.
It was immersed in a solution consisting of 7 g, stirred every 15 minutes, and immersed for 1 hour. Foaming occurred upon soaking. After reduction, the supernatant was removed by filtration. Next, 500 ml of pure water was added to the obtained solid, washed for 30 minutes, and then filtered. This operation was repeated five times. At this time, the pH of the first cleaning solution was 8.8, and the pH of the fifth cleaning solution was 6.8.
Met. 100 g of a 0.5 mol / l potassium chloride solution was added to the filtered extruded solid and stirred, and then the extruded solid was filtered again. This operation was repeated three times. The obtained solid was dried at 60 ° C. for 4 hours to obtain a gray solid. Next, in air, the temperature is raised from room temperature to 350 ° C. in one hour,
It baked at the same temperature for 3 hours. After calcination, 500 ml of pure water was added and stirred, and then the solid was separated by filtration. This operation was repeated five times, and an aqueous solution of silver nitrate was added dropwise to the washing solution, and it was confirmed that potassium chloride did not remain. Next, this extruded solid was dried at 60 ° C. for 4 hours to obtain 50.7 g of a blue-gray extruded ruthenium oxide catalyst supported on titanium oxide. Further, the operation from the impregnation step is similarly repeated.
0.8 g of a blue-gray extruded titanium oxide-supported ruthenium oxide catalyst was obtained, and these were mixed to obtain 101.5 g of a blue-gray extruded ruthenium oxide-supported titanium oxide catalyst. The calculated value of the ruthenium oxide content is calculated as RuO ₂ / (RuO ₂ + T
iO ₂ ) × 100 = 2.0% by weight. The calculated value of the ruthenium content is Ru / (RuO ₂ + TiO ₂ ) × 10
0 = 1.5% by weight. X-ray diffraction analysis of the used titanium oxide support under the same conditions as in Example 1 showed a rutile crystal content of 97%. 2.5 g of the thus-obtained ruthenium oxide catalyst supporting titanium oxide was added to 2 m
m-sphere commercially available α-alumina carrier (manufactured by Nikkato Corporation, S
SA995) The reaction was carried out in accordance with the reaction method of Example 2 except that the catalyst was diluted by well mixing with 10 g, filled into a quartz reaction tube (inner diameter: 12 mm), and oxygen gas was passed at 206 ml / min. . 2.0 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 4.83 ×
It was 10 ⁻⁴ mol / min · g-catalyst.

Example 13 A catalyst was prepared by the following method. That is, titanium oxide powder (Taika Co., Ltd., MT-600B, rutile crystal system) 1
0.0 g of commercially available ruthenium chloride (RuCl ₃ .nH
₂ O, Ru content 37.3 wt%) 0.41 g and 17.8
g of pure water and then immersed in
Evaporate at 0 ° C. for 2 hours. Next, it dried at 60 degreeC for 2 hours. After drying, the catalyst was pulverized well to obtain a dark green powder. This powder was immersed in a solution consisting of 2.1 g of 2N potassium hydroxide solution and 30.0 g of pure water at room temperature and stirred. One minute later, a solution consisting of 0.59 g of hydrazine monohydrate and 5.0 g of pure water was added to the suspension under stirring at room temperature under a nitrogen atmosphere, and treated with hydrazine. Foaming occurred upon addition. After 1 hour, the supernatant was filtered off. Then, 500 ml of pure water was added to the obtained powder, washed for 30 minutes, and filtered. This operation was repeated five times. At this time, the pH of the first cleaning solution was 8.8, and the pH of the fifth cleaning solution was 7.4. 2mo on the filtered powder
After adding 50 g of a 1 / l potassium chloride solution and stirring, the powder was filtered off again. This operation was repeated three times. The obtained cake was dried at 60 ° C. for 4 hours to obtain a beige powder. Next, the temperature was raised from room temperature to 350 ° C. in air for 1 hour, and baked at the same temperature for 3 hours. After firing, 500ml
After adding pure water and stirring, the powder was separated by filtration. This operation was repeated five times, and an aqueous solution of silver nitrate was added dropwise to the washing solution, and it was confirmed that potassium chloride did not remain. Next, this powder was dried at 60 ° C. for 4 hours to obtain 9.23 g.
A blue-grey powder was obtained. The obtained powder is molded, and 8.6-
By setting the mesh size to 16.0, a ruthenium oxide catalyst supporting titanium oxide was obtained. The calculated value of the ruthenium oxide content was calculated as RuO ₂ / (RuO ₂ + TiO ₂ ) × 100 = 2.
It was 0% by weight. The calculated value of the ruthenium content is Ru /
(RuO ₂ + TiO ₂ ) × 100 = 1.5% by weight. The titanium oxide-supported ruthenium oxide catalyst (2.5 g) thus obtained was mixed well with 5 g of a commercially available α-alumina carrier (manufactured by Nikkato Co., Ltd., SSA995) having a diameter of 1 mm to dilute the catalyst. Tube (12m inside diameter
m), and the reaction was carried out in accordance with the reaction method of Example 2 except that hydrogen chloride gas was passed at 211 ml / min and oxygen gas was passed at 211 ml / min. 1.8 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 4.4.
It was 0 × 10 ⁻⁴ mol / min · g-catalyst.

Example 14 A catalyst was prepared by the following method. That is, pure water 270
g and 30% by weight titanium sulfate solution (manufactured by Wako Pure Chemical Industries) 134
g was mixed at room temperature. 10.0 g of titanium oxide powder (PT-101, rutile crystal system, manufactured by Ishihara Sangyo Co., Ltd.) was added to the obtained solution.
Was mixed at room temperature. Next, the obtained suspension was heated to 102 ° C. with stirring using an oil bath, and heated and hydrolyzed for 7 hours. After hydrolysis, the reaction solution is cooled to room temperature,
After standing overnight, it was filtered off. 0.5 to the resulting white precipitate
L of pure water was added, washed for 30 minutes, and filtered. This operation was repeated eight times. Next, the obtained precipitate was dried at 60 ° C. for 4 hours to obtain 25.0 g of a white powder. This powder is heated in air to 300 ° C. in one hour,
By calcining for 2 hours, 23.2 g of a white solid was obtained. Further, 20.2 g of this powder was fractionated, heated to 500 ° C. in air for 1.4 hours, and calcined at the same temperature for 3 hours to obtain 19.5 g of a white solid. .
The obtained solid was pulverized to obtain a titanium oxide powder. An aqueous solution prepared from 1.27 g of commercially available ruthenium chloride (RuCl ₃ .nH ₂ O, Ru content 37.3% by weight) and 9.5 g of pure water was impregnated into 9.5 g of the obtained titanium oxide powder, and then Under reduced pressure, evaporation was performed at 40 ° C. for 2 hours. Next, it dried at 60 degreeC for 2 hours. The dried powder was pulverized well in a mortar to obtain a black powder. This powder,
At room temperature, 6.6 g of 2N potassium hydroxide solution and 28.5 pure water
g of solution and stirred. One minute later, hydrazine monohydrate 1.8 was added to the suspension under stirring at room temperature under a nitrogen atmosphere.
A solution consisting of 3 g and 4.8 g of pure water was added and treated with hydrazine. Foaming occurred upon addition. After 1 hour, the supernatant was filtered off. Then, 500 ml of pure water was added to the obtained powder, washed for 30 minutes, and filtered. This operation was repeated five times. At this time, the pH of the first cleaning solution was 8.2, and the pH of the fifth cleaning solution was 6.6. 48 g of a 2 mol / l potassium chloride solution was added to the filtered powder, and the mixture was stirred and then filtered again. This operation was repeated three times. The obtained cake was dried at 60 ° C. for 4 hours to obtain 10.2 g of a black powder. Next, the temperature was raised from room temperature to 350 ° C. in air for 1 hour, and baked at the same temperature for 3 hours. After baking, 500 ml of pure water was added and stirred, and then the powder was separated by filtration. This operation was repeated five times, and an aqueous solution of silver nitrate was added dropwise to the washing solution, and it was confirmed that potassium chloride did not remain. Next, this powder was dried at 60 ° C. for 4 hours to obtain 8.9 g of a black powder. The obtained powder was molded and made into a 8.6 to 16.0 mesh to obtain a titanium oxide-supported ruthenium oxide catalyst. The calculated value of the ruthenium oxide content is calculated as RuO ₂ / (RuO ₂ + TiO _2
2 ) × 100 = 6.2% by weight. The calculated value of the ruthenium content is Ru / (RuO ₂ + TiO ₂ ) × 100 =
It was 4.7% by weight. X-ray diffraction analysis of the used titanium oxide powder under the same conditions as in Example 1 showed that 2θ =
The peak intensity of the rutile crystal at 27.4 ° is 1497 cps.
Met. The peak intensity of the anatase crystal at 2θ = 25.3 ° was not observed. Rutile crystal content is 100%
Met. The OH group content of the carrier was measured under the same conditions as in Example 5 except that the sample amount was changed to 2.36 g. As a result, 51 ml of methane gas was generated. The OH group content of the carrier was 3.7 × 10 ⁻⁴ (mol / g-carrier).
The titanium oxide-supported ruthenium oxide catalyst (2.5 g) thus obtained was thoroughly mixed with 10 g of a commercially available α-alumina carrier (manufactured by Nikkato Co., Ltd., SSA995) having a diameter of 2 mm to dilute the catalyst to make a quartz reaction. Tube (12m inside diameter
m), hydrogen chloride was passed at a rate of 211 ml / min, and oxygen gas was passed at a rate of 211 ml / min. 2.3 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 8.18 × 10 ⁻⁴ mol / min · g-catalyst.

Example 15 A catalyst was prepared by the following method. That is, a titanium oxide powder (Sakai Chemical Co., Ltd., 100% rutile crystal form) was previously heated in air from room temperature to 500 ° C. for 1.4 hours, and calcined at the same temperature for 3 hours. Then fired 1
0.0 g of commercially available ruthenium chloride (RuCl ₃ .nH
₂ O, Ru content 37.3 wt%) 1.34 g and 17.8
g of pure water and then immersed in
Evaporate at 0 ° C. for 2 hours. Next, it dried at 60 degreeC for 2 hours. The dried powder was pulverized well to obtain a black-brown powder. This powder was immersed in a solution consisting of 6.9 g of a 2N potassium hydroxide solution and 30.0 g of pure water at room temperature and stirred. One minute later, a solution consisting of 1.93 g of hydrazine monohydrate and 5.0 g of pure water was added to the suspension under stirring at room temperature under a nitrogen atmosphere, and treated with hydrazine. Foaming occurred upon addition. After 1 hour, the supernatant was removed by filtration. Then, 500 ml of pure water was added to the obtained powder,
After washing for minutes, it was filtered off. This operation was repeated five times. At this time, the pH of the first cleaning solution was 8.7, and the pH of the fifth cleaning solution was 7.4. 2mo on the filtered powder
After adding 50 g of a 1 / l potassium chloride solution and stirring, the powder was filtered off again. This operation was repeated three times. The obtained cake was dried at 60 ° C. for 4 hours to obtain a black powder. Next, the temperature was raised from room temperature to 350 ° C. in air for 1 hour, and baked at the same temperature for 3 hours. After baking, 500 ml of pure water was added and stirred, and then the powder was separated by filtration. This operation 5
Repeated twice, an aqueous solution of silver nitrate was added dropwise to the washing solution, and it was confirmed that potassium chloride did not remain. Next, this powder was dried at 60 ° C. for 4 hours to obtain 9.7 g of a black powder. The obtained powder was molded and 8.6 to 16.0
By forming a mesh, a ruthenium oxide catalyst supporting titanium oxide was obtained. The calculated value of the ruthenium oxide content is R
uO ₂ / (RuO ₂ + TiO ₂ ) × 100 = 6.2% by weight
Met. The calculated value of the ruthenium content is Ru / (RuO
₂ + TiO ₂ ) × 100 = 4.7% by weight. X-ray diffraction analysis of the used titanium oxide powder under the same conditions as in Example 1 showed that the peak intensity of the rutile crystal at 2θ = 27.4 ° was 907 cps. The peak intensity of the anatase crystal at 2θ = 25.3 ° was not observed. The content of rutile crystals was 100%. In addition, the sample amount was 1.64.
The OH group content of the carrier was measured under the same conditions as in Example 5 except that the amount was changed to g. As a result, 54 ml of methane gas was generated. The OH group content of the carrier was 6.0 × 10 ⁻⁴ (mol / g)
-Carrier). 2.5 g of the titanium oxide-supported ruthenium oxide catalyst thus obtained was added to a commercially available α
-Alumina carrier (Nikkato Co., Ltd., SSA995) 1
The catalyst was diluted by thoroughly mixing with 0 g, and filled in a quartz reaction tube (inner diameter: 12 mm).
The reaction was performed in accordance with the reaction method of Example 2 except that the flow rate of oxygen gas was 211 ml / min. 1.8 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 7.85 × 10 ⁻⁴ mol / min · g-catalyst.

Example 16 A catalyst was prepared by the following method. That is, commercially available ruthenium chloride (RuCl ₃ .nH ₂ O, Ru content 37.3% by weight) was added to 10.1 g of titanium oxide powder (SSP-HJ, anatase crystal system, manufactured by Sakai Chemical Industry Co., Ltd.) in advance.
An aqueous solution prepared by dissolving 35 g in 4.5 g of pure water was impregnated, and the impregnated product was dried at 60 ° C. for 2 hours.
The dried powder was pulverized well in a mortar to obtain a black powder.
To reduce this powder with sodium borohydride, 1.65 g of sodium borohydride and 330 g of ethanol
Was prepared and cooled in an ice bath. To this sodium borohydride solution, the total amount of titanium oxide supporting ruthenium chloride was added with stirring. Foaming occurred upon addition. After 1 hour, the supernatant was removed by decantation. Next, 500 ml of pure water was added to the obtained powder, washed for 30 minutes, and filtered. This operation was repeated five times. At this time, the pH of the first washing solution was 9.
The pH of the third and fifth washings was 5.3. The obtained cake was dried at 60 ° C. for 4 hours. 9.8 g of black powder
I got Next, 1.21 g of potassium chloride was added to the obtained powder.
And an aqueous solution consisting of 4.2 g of pure water. Next, the impregnated product was dried at 60 ° C. for 4 hours. Next, the obtained powder was heated in the air from room temperature to 350 ° C. in 1 hour, and calcined at the same temperature for 3 hours. After baking, 500 ml of pure water was added and stirred, and then the powder was separated by filtration. This operation 5
Repeated twice, an aqueous solution of silver nitrate was added dropwise to the washing solution, and it was confirmed that potassium chloride did not remain. Next, this powder was dried at 60 ° C. for 4 hours to obtain 9.3 g of a black powder. The obtained powder was molded and 8.6 to 16.0
By forming a mesh, a ruthenium oxide catalyst supporting titanium oxide was obtained. The calculated value of the ruthenium oxide content is R
uO ₂ / (RuO ₂ + TiO ₂ ) × 100 = 6.1% by weight
Met. The calculated value of the ruthenium content is Ru / (RuO
₂ + TiO ₂ ) × 100 = 4.7% by weight. Also,
When the OH group content of the carrier was measured under the same conditions as in Example 5 except that the sample amount was 1.79 g, 111 ml of methane gas was generated. The OH group content of the carrier was 18.6 ×
It was 10 ^-4 (mol / g-carrier). 2.5 g of the titanium oxide-supported ruthenium oxide catalyst thus obtained was filled in a reaction tube in the same manner as in Example 2, and hydrogen chloride gas was added to the reaction tube.
The reaction was carried out according to the reaction method of Example 2 except that oxygen gas was passed at 7 ml / min and 199 ml / min. 2.0 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 3.59 × 10 ⁻⁴ mol / min · g-catalyst.

Example 17 A catalyst was prepared by the following method. That is, commercially available ruthenium chloride (RuCl ₃ .nH ₂ O, 10.0 g of titanium oxide powder (P25, manufactured by Nippon Aerosil Co., Ltd.)
(Ru content: 37.3% by weight) was impregnated with an aqueous solution prepared by dissolving 1.34 g in 4.8 g of pure water.
Dried for hours. The dried powder was pulverized well in a mortar to obtain a black powder. In order to reduce this powder with sodium borohydride, a solution in which 1.66 g of sodium borohydride was dissolved in 330 g of ethanol was prepared, and cooled in an ice bath. To this sodium borohydride solution, the total amount of titanium oxide supporting ruthenium chloride was added with stirring. Foaming occurred upon addition. After 1 hour, the supernatant was removed by decantation. Next, 5 was added to the obtained powder.
After adding 00 ml of pure water and washing for 30 minutes, the mixture was filtered off. This operation was repeated nine times. At this time, the pH of the first cleaning solution was 9.6, and the pH of the ninth cleaning solution was 7.7. The obtained cake was dried at 60 ° C. for 4 hours to obtain a black powder. Next, potassium chloride was added to the obtained powder.
An aqueous solution consisting of 22 g and 4.7 g of pure water was impregnated. Next, the impregnated product was dried at 60 ° C. for 4 hours. Next, the obtained powder was heated in the air from room temperature to 350 ° C. in 1 hour, and calcined at the same temperature for 3 hours. After baking, 500 ml of pure water was added and stirred, and then the powder was separated by filtration. This operation was repeated five times, and an aqueous solution of silver nitrate was added dropwise to the washing solution, and it was confirmed that potassium chloride did not remain. Next, this powder was dried at 60 ° C. for 4 hours to obtain 9.5 g of a black powder. The obtained powder is molded, and 8.6 to 16.
By setting the mesh to 0 mesh, a ruthenium oxide catalyst supporting titanium oxide was obtained. The calculated value of the ruthenium oxide content is:
RuO ₂ / (RuO ₂ + TiO ₂ ) × 100 = 6.2% by weight. The calculated value of the ruthenium content is Ru / (Ru
O ₂ + TiO ₂ ) × 100 = 4.7% by weight. X-ray diffraction analysis of the used titanium oxide powder under the same conditions as in Example 1 showed a rutile crystal content of 17%. 2.5 g of the titanium oxide-supported ruthenium oxide catalyst thus obtained was charged into a reaction tube in the same manner as in Example 2,
195 ml / min of hydrogen chloride gas and 198 ml of oxygen gas
The flow was carried out in accordance with Example 2 except that the solution was circulated at a rate of ml / min and the internal temperature was set at 299 ° C. 2.0 hours after the start of the reaction, the activity of forming chlorine per unit catalyst weight was 4.31 ×
It was 10 ⁻⁴ mol / min · g-catalyst.

Example 18 A catalyst was prepared by the following method. That is, 10.3 g of fibrous cellulose (manufactured by Toyo Roshi Kabushiki Kaisha, filter paper 5B) dispersed in pure water was mixed with 40.3 g of titanium oxide powder (Catalyst Chemical Co., Ltd. No. 1), and titanium oxide sol (Sakai Chemical Co., Ltd.) was mixed. (Ltd.) CSB, was kneaded added TiO ₂ content of 38 wt%) 31.5 g and pure water. The kneaded product was dried at 60 ° C. to obtain an appropriate viscosity and molded into a rod shape. Next, the rod-shaped solid was dried at 60 ° C. for 4 hours to obtain 64.3 g of a white solid. The obtained solid was heated to 500 ° C. in the air for 3 hours, and then calcined at the same temperature for 5 hours to obtain 48.5 g of a white rod-shaped titanium oxide carrier. Next, the obtained solid was crushed to obtain 28.0 g of a solid having 8.6 to 16 mesh.
5.1 g of the titanium oxide carrier thus obtained was taken, impregnated with 0.5 N potassium hydroxide solution until water appeared on the surface of the carrier, and dried in air at 60 ° C. for 2 hours. At this time, the impregnation amount of the added potassium hydroxide solution was 3.6 g. A commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O, Ru content 35.5%) was added to the obtained carrier.
After impregnating with a solution prepared by dissolving 0.71 g in 3.0 g of ethanol, it was immediately dried in air at 60 ° C. for 2 hours to carry ruthenium chloride. Next, a solution composed of 0.55 g of sodium borohydride (NaBH ₄ ), 2.0 g of pure water and 42.3 g of ethanol was prepared, cooled sufficiently in an ice bath, and then ruthenium chloride supported on titanium oxide which had already been prepared was added. , To reduce ruthenium chloride. At this time, foaming was observed in the solution. After the bubbling subsided, the supernatant was removed by decantation. 200 ml for the reduced solid
And decanted. This operation was repeated five times. Then, after adding 200 ml of pure water, the pH was 9.2. 3.6 g of 0.1N HCl was added to this solution.
The mixture was poured to adjust the pH to 6.7 and decanted. Next, the solid was washed with 500 ml of pure water for 30 minutes, and the solid was filtered off again. This operation was repeated five times. Next, this solid was dried at 60 ° C. for 4 hours to obtain 5.2 g of a blue-black solid.
Next, this solid was impregnated with a solution of 0.63 g of potassium chloride dissolved in 3.2 g of pure water, and dried at 60 ° C. for 4 hours. The dried product was heated in the air to 350 ° C. in 1 hour and fired at the same temperature for 3 hours. Next, the calcined solid was washed with 500 ml of pure water for 30 minutes and filtered. This operation was repeated five times. An aqueous solution of silver nitrate is added dropwise to the filtrate,
It was confirmed that potassium chloride did not remain. After washing, the solid was dried at 60 ° C. for 4 hours to obtain 5.1 g of a blue-black titanium oxide-supported ruthenium oxide catalyst of 8.6 to 16 mesh. When the thickness of the RuO ₂ layer of the obtained catalyst was measured with a graduated loupe, ruthenium oxide was supported at 0.3 mm from the outer surface. The measured particle size of the catalyst was 1.5 mm. L and S were determined as described above for the range S / L in which ruthenium oxide was supported on the catalyst surface in the catalyst. As a result, the calculated value of S / L was 0.2. The calculated value of the content of ruthenium oxide was calculated as RuO ₂ / (RuO ₂ + TiO ₂ ) × 100.
= 6.2% by weight. The calculated value of the ruthenium content is
Ru / (RuO ₂ + TiO ₂ ) × 100 = 4.7% by weight. 2.5 g of the titanium oxide-supported ruthenium oxide catalyst thus obtained was charged into a reaction tube in the same manner as in Example 2, and 195 ml / min of hydrogen chloride gas and 1 g of oxygen gas were added.
The procedure was performed in the same manner as in Example 2 except that the flow rate was 98 ml / min. 2.0 hours after the start of the reaction, the formation activity of chlorine per unit weight of the catalyst was 4.30 × 10 ⁻⁴ mol / mi.
ng-catalyst.

Example 19 A catalyst was prepared by the following method. That is, 1-2 mm
φ spherical titanium oxide carrier (Sakai Chemical CS300S-1
2) 5.1 g of a 2 mol / l ammonium bicarbonate solution was impregnated with water until water appeared on the surface of the catalyst,
Dry at 0 ° C. for 2 hours. A commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O, Ru content 35.5) was added to the obtained carrier.
%) After impregnating a solution prepared by dissolving 0.71 g in 2.2 g of ethanol, immediately dried in air at 60 ° C. for 2 hours to carry ruthenium chloride. After drying, then
A solution composed of 0.50 g of sodium borohydride (NaBH ₄ ) and 60.9 g of ethanol was prepared, and after sufficiently cooling in an ice bath, ruthenium chloride already supported on titanium oxide was added to reduce ruthenium chloride. At this time, foaming was observed in the solution. After the bubbling subsided, the supernatant was removed by decantation. 200 ml of pure water was added to the reduced solid and decanted. This operation was repeated five times. Next, the pH after adding 200 ml of pure water was 4.5. The added pure water was removed by decantation. Next, the solid was washed with 500 ml of pure water for 30 minutes, and the solid was filtered off again. This operation was repeated five times. The pH of the fifth washing was 5.2. Next, this solid was dried at 60 ° C. for 4 hours to obtain 5.4 g of a blue-black solid. Next, 0.19 g of potassium chloride was added to this solid.
Is dissolved in 1.9 g of pure water,
Dried for hours. Dry the product up to 350 ° C in air.
The temperature was raised over a period of time and calcined at the same temperature for 3 hours. Next, the calcined solid was washed with 500 ml of pure water for 30 minutes and filtered.
This operation was repeated five times. An aqueous solution of silver nitrate was added dropwise to the filtrate, and it was confirmed that potassium chloride did not remain.
After washing, the solid was dried at 60 ° C. for 4 hours to obtain 5.4 g of a black spherical titanium oxide-supported ruthenium oxide catalyst. When the thickness of the RuO ₂ layer was measured by EPMA, ruthenium oxide was carried in a range of 0.15 to 0.25 mm from the outer surface. The measured particle size of the catalyst is 1.4 to
1.6 mm. The calculated value of the range S / L in which ruthenium oxide is supported on the catalyst surface is 0.09 to 0.1
It was 8. The calculated value of the ruthenium oxide content is R
uO ₂ / (RuO ₂ + TiO ₂ ) × 100 = 6.1% by weight
Met. The calculated value of the ruthenium content is Ru / (RuO
₂ + TiO ₂ ) × 100 = 4.6% by weight. 2.5 g of the titanium oxide-supported ruthenium oxide catalyst thus obtained was charged into a reaction tube in the same manner as in Example 2, and 187 ml / min of hydrogen chloride gas and 199 ml / m2 of oxygen gas were used.
Example 2 except that the temperature was 302 ° C.
Performed according to. 2.0 hours after the start of the reaction, the activity of forming chlorine per unit catalyst weight was 4.47 × 10 ⁻⁴ m
ol / min.g-catalyst.

Example 20 A catalyst was prepared by the following method. That is, 1-2 mm
φ spherical titanium oxide carrier (Sakai Chemical CS300S-1
2) 5.0 g of a 2 mol / l ammonium carbonate solution was impregnated with water until the water surfaced on the surface of the catalyst, and then in air at 60 ° C.
For 2 hours. A commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O, Ru content 35.5%) was added to the obtained carrier.
After impregnating with a solution prepared by dissolving 0.70 g in 1.5 g of ethanol, it was immediately dried in air at 60 ° C. for 2 hours to carry ruthenium chloride. Next, a solution consisting of 0.50 g of sodium borohydride (NaBH ₄ ), 2.1 g of pure water and 41.1 g of ethanol was prepared, and after sufficiently cooling in an ice bath, ruthenium chloride supported on titanium oxide already added was added. , To reduce ruthenium chloride. At this time, foaming was observed in the solution. After the bubbling subsided, the supernatant was removed by decantation. 200 ml of pure water was added to the reduced solid and decanted. This operation was repeated five times. Next, the pH after adding 200 ml of pure water was 3.9. The added pure water was removed by decantation. Next, the solid was washed with 500 ml of pure water for 30 minutes, and the solid was filtered off again. This operation was repeated five times. The pH of the fifth washing was 5.6. Next, this solid was dried at 60 ° C. for 4 hours to obtain 5.3 g of a black solid. Next, the solid was impregnated with a solution of 0.19 g of potassium chloride dissolved in 1.9 g of pure water, and dried at 60 ° C. for 4 hours. The dried product was heated in the air to 350 ° C. in 1 hour and fired at the same temperature for 3 hours. Next, the calcined solid was washed with 500 ml of pure water for 30 minutes and filtered. This operation was repeated five times. An aqueous solution of silver nitrate was added dropwise to the filtrate, and it was confirmed that potassium chloride did not remain. After washing, the solid was dried at 60 ° C. for 4 hours. 5.2 g of a black spherical titanium oxide-supported ruthenium oxide catalyst were obtained. When the thickness of the RuO ₂ layer was measured by EPMA, ruthenium oxide was carried in a range of 0.19 to 0.30 mm from the outer surface. The measured catalyst particle size is 1.5 ~
1.6 mm. The calculated value of the range S / L in which ruthenium oxide is supported on the catalyst surface is 0.13 to 0.1.
Nine. The calculated value of the ruthenium oxide content is R
uO ₂ / (RuO ₂ + TiO ₂ ) × 100 = 6.2% by weight
Met. The calculated value of the ruthenium content is Ru / (RuO
₂ + TiO ₂ ) × 100 = 4.7% by weight. 2.5 g of the titanium oxide-supported ruthenium oxide catalyst thus obtained was charged into a reaction tube in the same manner as in Example 2, and 187 ml / min of hydrogen chloride gas and 199 ml / m2 of oxygen gas were used.
The procedure was carried out in accordance with Example 2, except that it was distributed in. 2.0 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 4.34 × 10 ⁻⁴ mol / min · g-catalyst.

Example 21 A catalyst was prepared by the following method. That is, 1-2 mm
φ spherical titanium oxide carrier (Sakai Chemical CS300S-1
2) 5.0 g of a 2.0 N potassium hydroxide solution was impregnated with water until water appeared on the surface of the carrier, followed by drying in air at 60 ° C. for 2 hours. A commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O, Ru content 35.5%) 0.7 was added to the obtained carrier.
After impregnating with a solution prepared by dissolving 1 g in 3.0 g of ethanol, it was immediately dried in air at 60 ° C. for 2 hours to carry ruthenium chloride. Next, a solution composed of 0.57 g of sodium borohydride (NaBH ₄ ), 2.0 g of pure water and 42.5 g of ethanol was prepared, and after sufficiently cooling in an ice bath, ruthenium chloride supported on titanium oxide which had already been prepared was added. , To reduce ruthenium chloride. At this time, foaming was observed in the solution. After the bubbling subsided, the supernatant was removed by decantation. 20 for reduced solids
0 ml of pure water was added and decanted. This operation 5
Repeated times. Next, the solid was washed with 500 ml of pure water for 30 minutes, and the solid was filtered off again. This operation was repeated five times.
Then, the solid was dried at 60 ° C. for 4 hours to obtain 5.1 g of a black solid. Next, this solid was impregnated with a solution of 0.19 g of potassium chloride dissolved in 1.8 g of pure water,
Dry at 60 ° C. for 4 hours. Dry in air 35
The temperature was raised to 0 ° C. in 1 hour and calcined at the same temperature for 3 hours. Next, the calcined solid was washed with 500 ml of pure water for 30 minutes and filtered. This operation was repeated five times. An aqueous solution of silver nitrate was added dropwise to the filtrate, and it was confirmed that potassium chloride did not remain. After washing, the solid was dried at 60 ° C. for 4 hours. 4. Ruthenium oxide catalyst supported on black spherical titanium oxide
1 g was obtained. When the thickness of the RuO ₂ layer was measured by EPMA, ruthenium oxide was 0.11 to 0.1 from the outer surface.
It was carried in a range of 8 mm. The measured particle size of the catalyst was 1.5 to 1.7 mm. The calculated value of the range S / L in which ruthenium oxide is supported on the catalyst surface is 0.06
０．１0.11. The calculated value of the content of ruthenium oxide is calculated as follows: RuO ₂ / (RuO ₂ + TiO ₂ ) × 100 = 6.
It was 2% by weight. The calculated value of the ruthenium content is Ru /
(RuO ₂ + TiO ₂ ) × 100 = 4.7% by weight. 2.5 g of the titanium oxide-supported ruthenium oxide catalyst thus obtained was charged into a reaction tube in the same manner as in Example 2,
187 ml / min of hydrogen chloride gas and 199 of oxygen gas
The procedure was performed according to Example 2 except that the solution was distributed at a rate of ml / min. 2.0 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 4.29 × 10 ⁻⁴ mol / min.
G-catalyst.

Comparative Example 1 A catalyst was prepared by the following method. That is, commercially available ruthenium chloride hydrate (RuCl ₃ .3H ₂ O, Ru content 3
(5.5% by weight) 0.70 g was dissolved in 4.0 g of pure water.
After well stirring the aqueous solution, the mixture was adjusted to 12 to 18.5 mesh, added dropwise to 5.0 g of silica (Carrierct G-10, manufactured by Fuji Silysia K.K.) in air at 500 ° C. for 1 hour, and added dropwise to ruthenium chloride. Was impregnated. The supported product was cooled to room temperature under nitrogen flow of 100 ml / min.
After heating to 0 ° C in 30 minutes and drying at the same temperature for 2 hours,
The mixture was allowed to cool to room temperature to obtain a black solid. The solid obtained is 10
From room temperature to 250 ° C under an air flow of 0 ml / min.
After heating for 30 minutes and drying at the same temperature for 3 hours, the mixture was allowed to cool to room temperature to obtain 5.37 g of a black silica-supported ruthenium chloride catalyst. The calculated value of the ruthenium content is R
u / (RuCl ₃ .3H ₂ O + SiO ₂ ) × 100 = 4.
It was 5% by weight. The silica-supported ruthenium chloride catalyst (2.5 g) thus obtained was not diluted with a titanium oxide carrier, but was charged into a reaction tube in the same manner as in Example 2. Hydrogen chloride was supplied at a rate of 202 ml / min, and oxygen gas at 213 ml / min. min
And the reaction was carried out in accordance with Example 2, except that the internal temperature was 300 ° C. 1.7 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 0.49 × 10 ^−4.
mol / min · g-catalyst.

Comparative Example 2 A catalyst was prepared by the following method. That is, 8.0 g of spherical titanium oxide (manufactured by Sakai Chemical Industry Co., Ltd., CS-300) pulverized in a mortar and powdered, and 0.53 g of ruthenium dioxide powder (manufactured by NE Chemcat Co., Ltd.) were mortared. After mixing well with grinding, the mixture was formed into a mesh of 12 to 18.5 mesh to obtain a mixed catalyst of ruthenium oxide and titanium oxide. The calculated value of the ruthenium oxide content was 6.2% by weight.
Met. The calculated value of the ruthenium content was 4.7% by weight. The catalyst thus obtained was diluted well by mixing 2.5 g of the thus-obtained ruthenium oxide titanium oxide mixed catalyst with 5 g of a titanium oxide carrier having a size of 12 to 18.5 mesh to dilute the catalyst into a quartz reaction tube (inner diameter 12 mm). 199 ml / min of hydrogen chloride gas and 194 ml /
min, and carried out in accordance with Example 2, except that the internal temperature was 299 ° C. 2.3 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 0.83 × 10 3
^-4 mol / min.g-catalyst.

Comparative Example 3 A catalyst was prepared by the following method. That is, 41.7 g of commercially available tetraethyl orthosilicate was dissolved in 186 ml of ethanol, and 56.8 g of titanium tetraisopropoxide was added while stirring at room temperature, followed by stirring at room temperature for 30 minutes. Next, an aqueous solution in which 93 ml of ethanol was well mixed with a 0.01 mol / l acetic acid aqueous solution prepared by dissolving 0.14 g of acetic acid in 233 ml of pure water was dropped into the above solution. A white precipitate formed as the solution was added. After the completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes, heated with stirring, and refluxed for 1 hour on a 102 ° C. oil bath. The liquid temperature at this time was 80 ° C. Next, the solution was allowed to cool, and then filtered through a glass filter.
, And filtered again. After repeating this operation twice, it is dried in air at 60 ° C. for 4 hours, and is dried at room temperature to 550 ° C.
The temperature was raised in 1 hour until the temperature was increased, and the mixture was calcined at the same temperature for 3 hours to obtain 27.4 g of a white solid. The obtained solid was pulverized to obtain titania silica powder. A commercially available ruthenium chloride hydrate (R) was added to 8.0 g of the obtained titania silica powder.
uCl ₃ .3H ₂ O, Ru content 35.5% by weight) 1.1
After impregnating with a solution prepared by dissolving 3 g in 8.2 g of pure water, the solution was dried in air at 60 ° C. for 1 hour to carry ruthenium chloride.
Next, the carrier was loaded with 50 ml / min of hydrogen and 100 ml of nitrogen.
The mixture was heated from room temperature to 300 ° C. for 1 hour and 30 minutes under a mixed air flow of ml / min, reduced at the same temperature for 1 hour, and allowed to cool to room temperature, and 8.4 g of grey-brown titania silica-supported metal ruthenium powder was added. Obtained. 8.4 g of the obtained titania silica-supported metal ruthenium powder was heated from room temperature to 600 ° C. for 3 hours and 20 minutes under an air stream of 100 ml / min,
By calcining at the same temperature for 3 hours, 8.5 g of a gray powder was obtained. The obtained powder was molded and made to have a mesh size of 12 to 18.5 to obtain a ruthenium oxide catalyst supported on titania silica. The calculated value of the ruthenium oxide content is:
RuO ₂ / (RuO ₂ + TiO ₂ + SiO ₂ ) × 100 =
It was 6.2% by weight. The calculated value of the ruthenium content is R
u / (RuO ₂ + TiO ₂ + SiO ₂ ) × 100 = 4.7
% By weight. The titania-silica-supported ruthenium oxide catalyst (2.5 g) thus obtained was not diluted with a titanium oxide carrier, but charged into a reaction tube in the same manner as in Example 2, and hydrogen chloride gas was supplied at 180 ml / min and oxygen gas was supplied at 180 ml / min. mi
The reaction was carried out in accordance with the reaction method of Example 2 except that the mixture was passed through n. 1.8 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst is 0.46 × 10 ⁻⁴ mol / min.
G-catalyst.

Comparative Example 4 A catalyst was prepared by the following method. That is, 1-2 mm
φ spherical titanium oxide carrier (manufactured by Sakai Chemical Industry, CS-30
OSS-12) 10.1 g of an aqueous solution previously prepared by dissolving 1.34 g of commercially available ruthenium chloride (RuCl ₃ .nH ₂ O, Ru content 37.3% by weight) in 3.7 g of pure water was impregnated. Then, it was dried in air at 60 ° C. for 4 hours.
A dark brown solid was obtained. In order to reduce this solid by hydrogen, hydrogen (20 ml / min) and nitrogen (200 ml / m
The mixture was heated from room temperature to 250 ° C. for 2 hours under a mixed gas stream of (in), and reduced at the same temperature for 8 hours. After reduction, 10.3 g of a black solid was obtained. Next, the obtained solid is subjected to 35
The temperature was raised to 0 ° C. in 1 hour and calcined at the same temperature for 3 hours. 1
0.6 g of a black ruthenium oxide catalyst supported on titanium oxide was obtained. The calculated value of the ruthenium oxide content is Ru
O ₂ / (RuO ₂ + TiO ₂ ) × 100 = 6.1% by weight. The calculated value of the ruthenium content is Ru / (RuO ₂
+ TiO ₂ ) × 100 = 4.7% by weight. X-ray diffraction analysis of the used titanium oxide powder under the same conditions as in Example 1 showed a rutile crystal content of 0%. The reaction tube was filled with 2.5 g of the titanium oxide-supported ruthenium oxide catalyst thus obtained in the same manner as in Example 2, and 187 ml / min of hydrogen chloride gas and 199 ml / m2 of oxygen gas.
The procedure was carried out in accordance with Example 2, except that it was distributed in. 2.0 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 2.89 × 10 ⁻⁴ mol / min · g-catalyst.

Comparative Example 5 A catalyst was prepared by the following method. That is, 1-2 mm
0.5 g of 10.0 g of a 5 wt% supported metal ruthenium titanium oxide catalyst (manufactured by NE Chemcat Co., Ltd.)
The catalyst was impregnated with an aqueous ol / l potassium chloride solution until water appeared on the surface of the catalyst, and dried in air at 60 ° C. for 1 hour.
This operation was repeated twice. The impregnation amount of the aqueous potassium chloride solution was 3.31 g for the first time and 3.24 g for the second time, and the total was 6.
55 g. The calculated value of the molar ratio of potassium chloride to ruthenium was 0.66. Dry in air 3
The temperature was raised to 50 ° C. in 1 hour and calcined at the same temperature for 3 hours.
Next, the obtained solid was washed with 500 ml of pure water for 30 minutes and filtered. This operation was repeated five times. An aqueous solution of silver nitrate was added dropwise to the filtrate, and it was confirmed that potassium chloride did not remain. After washing, the solid was dried at 60 ° C. for 4 hours to obtain a ruthenium oxide catalyst supporting black spherical titanium oxide.
9 g were obtained. The calculated value of the ruthenium oxide content was calculated as RuO ₂ / (RuO ₂ + TiO ₂ ) × 100 = 6.6.
% By weight. The calculated value of the ruthenium content is Ru /
(RuO ₂ + TiO ₂ ) × 100 = 5.0% by weight. A reaction tube was filled with 2.5 g of the titanium oxide-supported ruthenium oxide catalyst thus obtained in the same manner as in Example 2,
187 ml / min of hydrogen chloride gas and 199 of oxygen gas
The reaction was performed in accordance with the reaction method of Example 2 except that the solution was flowed at a rate of ml / min. 2.0 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 4.03 × 10 ⁻⁴ mo.
1 / min · g-catalyst.

[0095]

As described above, according to the present invention, there is provided a method for producing a supported ruthenium oxide catalyst, which has a high activity and can produce a target compound at a lower reaction temperature with a smaller amount of catalyst. Could be provided.

[Brief description of the drawings]

FIG. 1 is a diagram showing a cross section of a catalyst when the shape is spherical. In the figure, the hatched portion is a portion containing ruthenium oxide.

FIG. 2 is a diagram showing a cross section of a catalyst when the shape is a columnar shape. In the figure, the hatched portion is a portion containing ruthenium oxide.

FIG. 3 is a view showing a cross section of a catalyst in a case where the shape is a columnar shape having a cavity therein. In the figure, the hatched portion is a portion containing ruthenium oxide.

 ──────────────────────────────────────────────────続 き Continuation of the front page (31) Priority claim number Japanese Patent Application No. 10-350272 (32) Priority date December 9, 1998 (12.9 December 1998) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 11-1028 (32) Priority date January 6, 1999 (Jan. 6, 1999) (33) Priority claim country Japan (JP) 5-1, Anesaki Beach, Ichihara City, Chiba Pref. Within Sumitomo Chemical Co., Ltd. (72) Inventor Tatsuya Suzuki 5-1 Sokaicho, Niihama-shi, Ehime Sumitomo Chemical Co., Ltd. (72) Inventor Takahiro Oizumi Tsukuba, Ibaraki 6 Ichikitahara Sumitomo Chemical Co., Ltd. F-term (reference) 4G069 AA03 AA08 BA04A BA04B BA27C BB04A BB04B BB08C BC70A BC70B BD02C BD12C CB81 EC22X EC22Y FA02 FA03 FB39 FB43 FB45

Claims (26)

[Claims] 1. A method for producing a supported ruthenium oxide catalyst selected from the following (1) to (5): (1) A method for producing a supported ruthenium oxide catalyst comprising a step of supporting a ruthenium compound on a carrier and treating with a basic compound and a step of treating with a reducing compound, and then oxidizing. (2) A method for producing a supported ruthenium oxide catalyst, which comprises a step of supporting a ruthenium compound on a carrier and treating with a reducing agent, converting the ruthenium into an oxide having a valence of 1 to less than 4 and then oxidizing the same. (3) A method for producing a supported ruthenium oxide catalyst in which a ruthenium compound is supported on a titanium oxide carrier containing rutile crystalline titanium oxide, which is treated with a reducing agent, and then oxidized. (4) The amount of OH groups is 0.1 × 10 ⁻⁴ per unit weight of the carrier.
A method for producing a supported ruthenium oxide catalyst in which a ruthenium compound is supported on a titanium oxide carrier containing ３０30 × 10 ⁻⁴ (mol / g-support) and then reduced in a liquid phase, followed by oxidation. (5) supporting an alkali on the carrier, and then supporting at least one ruthenium compound selected from the group consisting of ruthenium halide, ruthenium oxychloride, ruthenium acetylacetonate complex, ruthenium organic acid salt and ruthenium nitrosyl complex; Next, the catalyst is treated with a reducing agent and further oxidized.
And a method for producing a supported ruthenium oxide catalyst comprising ruthenium oxide only in the outer surface shell layer of the support. S / L <0.35 (1) L: A catalyst which is perpendicular to the catalyst surface at an arbitrary point (A) on the surface of the catalyst and which goes down to the inside of the catalyst at the opposite side of the point (A) from the catalyst to the outside. The distance between the point (A) and the point (B) when the point on the surface is the point (B) S: the distance measured on the perpendicular from the point (A) and the point (A) From the point (C) at which ruthenium oxide disappears 2. Ruthenium halide, chlororuthenate, oxyruthenate, ruthenium oxychloride, ruthenium ammine complex, ruthenium ammine complex chloride, acetylacetonate complex, ruthenium organic acid salt, ruthenium nitrosyl complex Carrying on the carrier at least one ruthenium compound selected from the group,
2. The method according to claim 1, further comprising the step of: treating with a reducing agent, converting the ruthenium having an oxidation number of from 1 to less than 4 and then oxidizing it.
Manufacturing method. 3. Ruthenium halide, chlororuthenate, oxyruthenate, ruthenium oxychloride, ruthenium ammine complex, chloride of ruthenium ammine complex, acetylacetonate complex, ruthenium organic acid salt, ruthenium nitrosyl complex Supporting at least one ruthenium compound selected from the group on a carrier,
The method according to claim 1, comprising a step of treating with a basic compound and a step of treating with a reducing agent, followed by oxidation. 4. The method according to claim 1, wherein the reducing agent is a reducing compound.
(2). 5. The method according to claim 1, wherein the ruthenium halide is supported on a carrier, an alkali is added thereto, the resultant is treated with a reducing compound, and then oxidized. 6. The method according to claim 1, wherein the ruthenium halide is supported on a carrier, and the ruthenium is treated with an alkaline solution of a reducing compound and then oxidized. 7. The method according to claim 1, wherein the ruthenium halide is supported on a carrier, an alkali is added thereto, the resultant is treated with a reducing compound, an alkali metal chloride is added thereto, and the resultant is oxidized. ) Or (2). 8. The method according to claim 1, wherein the ruthenium halide is carried on a carrier, which is treated with an alkaline solution of a reducing compound, and alkali metal chloride is added thereto, followed by oxidation. Manufacturing method. 9. The method according to claim 1, wherein the ruthenium halide is supported on a carrier, an alkali is added to the carrier, and the alkali is treated with hydrazine and then oxidized. 10. The method according to claim 1, wherein the ruthenium halide is carried on a carrier, and the ruthenium is treated with an alkali solution of hydrazine and then oxidized. 11. The method according to claim 1, wherein the ruthenium halide is supported on a carrier, an alkali is added thereto, the resultant is treated with hydrazine, an alkali metal chloride is further added thereto, and the resultant is oxidized. The manufacturing method of (2). 12. The process according to claim 1, wherein the ruthenium halide is supported on a carrier, which is treated with an alkali solution of hydrazine, to which alkali metal chloride is added and then oxidized. Method. 13. The method according to claim 1, wherein the catalysts (1) and (2) are supported ruthenium oxide catalysts using a titanium oxide containing 10% or more of rutile crystalline titanium oxide as a carrier. 14. The method according to claim 1, wherein the catalysts (1) and (2) are supported ruthenium oxide catalysts using titanium oxide containing at least 30% of rutile crystal titanium oxide as a carrier. 15. The method according to claim 1, wherein the titanium oxide contains 10% or more of rutile crystalline titanium oxide. 16. The method according to claim 1, wherein the titanium oxide contains at least 30% of rutile crystal titanium oxide. 17. The method according to claim 1, wherein the ruthenium compound is supported on a carrier, reduced with a reducing hydrogenation compound, and oxidized. 18. The method according to claim 1, wherein the ruthenium compound is supported on a carrier, treated with a reducing compound, and then oxidized. 19. The method according to claim 1, wherein the ruthenium compound is supported on a carrier, treated with an alkaline solution of a reducing compound, and then oxidized. 20. A supported ruthenium oxide obtained by supporting a ruthenium compound on a carrier and subjecting the ruthenium compound to a reduction treatment in a liquid phase and then oxidizing the ruthenium compound, wherein the amount of OH groups per unit weight of the carrier is 0%. 1 × 10 ⁻⁴ to 30 × 10 ⁻⁴ (mol
/ G-carrier), wherein the titanium oxide contained in the carrier is used as the carrier. 21. A supported ruthenium oxide obtained by supporting a ruthenium compound on a carrier and subjecting it to a reduction treatment in a liquid phase, and then oxidizing the ruthenium compound, wherein the amount of OH groups per unit weight of the carrier is 0%. 2 × 10 ^{−4 to} 20 × 10 ⁻⁴ (mol
/ G-carrier), wherein the titanium oxide contained in the carrier is used as the carrier. 22. A supported ruthenium oxide obtained by supporting a ruthenium compound on a carrier and subjecting the ruthenium compound to reduction in a liquid phase, followed by oxidation, wherein the amount of OH groups per unit weight of the carrier is 3%. × 10 ^-4 to 15 × 10 ^-4 (mol / g
2. The carrier according to claim 1, wherein the carrier comprises titanium oxide.
(3). 23. The method according to claim 1, wherein the ruthenium halide is supported on a carrier, treated with a reducing compound, and then oxidized. 24. The process according to claim 1, wherein the ruthenium halide is supported on a carrier, treated with an alkaline solution of a reducing compound, and then oxidized. 25. A supported ruthenium oxide obtained by supporting a ruthenium compound on a carrier and subjecting the ruthenium compound to reduction treatment in a liquid phase, and then oxidizing the ruthenium compound. 2 × 10 ^{−4 to} 20 × 10 ⁻⁴ (mol
/ G-carrier), wherein the titanium oxide contained in the carrier is used as the carrier. 26. A supported ruthenium oxide obtained by supporting a ruthenium compound on a carrier and reducing it in a liquid phase, and then oxidizing the ruthenium compound, wherein the amount of OH groups per unit weight of the carrier is 3 × 10 ^-4 to 15 × 10 ^-4 (mol / g
2. The carrier according to claim 1, wherein the carrier comprises titanium oxide.
(4).