JPH10194705A - Method for producing chlorine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chlorine production method capable of producing chlorine at a lower reaction temperature with a smaller amount of a catalyst when oxidizing hydrogen chloride to produce chlorine. SOLUTION: A method for producing chlorine in which hydrogen chloride is oxidized with oxygen in the presence of at least one catalyst selected from the following (A) to (D). (A): a carrier containing at least one compound of titanium oxide and zirconium oxide, wherein the supported ruthenium chloride catalyst has a weight ratio of ruthenium to the carrier of 0.5 to 20% by weight; (B) a ruthenium complex On a carrier. (C) a ruthenium oxide catalyst obtained by oxidizing a catalyst supporting a ruthenium compound (halide or complex) on a carrier; (D) a ruthenium chloride catalyst supported on a carrier;
A catalyst obtained by calcining at a temperature of 0 ° C or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing chlorine. More specifically, the present invention provides a process for producing chlorine by oxidizing hydrogen chloride using a highly active catalyst having a high activity per contained ruthenium, and using a smaller amount of a catalyst at a lower reaction temperature. And a method for producing chlorine which can produce

[0002]

2. Description of the Related Art It is well known that chlorine is useful as a raw material for vinyl chloride, phosgene and the like, and is obtained by oxidation of hydrogen chloride. For example, D using a Cu-based catalyst
The eacon reaction is well known. Also, for example, West German Patent No. 1,567,788 describes a method of oxidizing hydrogen chloride using a catalyst containing a ruthenium compound. Further, among the ruthenium compounds,
In particular, it is described that ruthenium (III) chloride is effective. Also described is a method in which a ruthenium compound is supported on a carrier and used, and examples of the carrier include silica gel, alumina, pumice, and ceramic materials. As an example, a ruthenium chloride catalyst supported on silica is mentioned. However, an experiment was conducted using a catalyst prepared by following the method for preparing a silica-supported ruthenium (III) chloride catalyst described in the patent,
The volatilization of the ruthenium compound as a catalyst component was intense, which was inconvenient for industrial use. For example, European Patent EP 0 844 413 A2 describes a method for oxidizing hydrogen chloride using a chromium oxide catalyst. However, the activity of the catalyst is insufficient with the conventionally known methods,
There was a problem that a high reaction temperature was required.

When the activity of the catalyst is low, it is necessary to raise the reaction temperature. However, the reaction of oxidizing hydrogen chloride with oxygen to produce chlorine is an equilibrium reaction. And the equilibrium conversion of hydrogen chloride is reduced. Therefore, if the catalyst has high activity, the reaction temperature can be lowered, and the reaction becomes equilibrium advantageous,
Higher hydrogen chloride conversions can be obtained. Also,
When the temperature is high, there is a fear that the activity may be reduced due to the volatilization of the catalyst component.

[0004] Industrially, both high activity of the catalyst and high activity per unit weight of ruthenium contained in the catalyst are required. Since the activity per unit weight of ruthenium contained in the catalyst is high, the amount of ruthenium contained in the catalyst can be reduced, which is advantageous in terms of catalyst cost. By using a highly active catalyst and conducting the reaction at a lower temperature, more favorable reaction conditions can be selected equilibrium. It is also preferable to carry out the reaction at a lower temperature in terms of catalyst stability.

[0005] In view of these points, the development of a catalyst having high activity and usable at a low temperature has been desired.

[0006]

Under these circumstances, the problem to be solved by the present invention is to have a high activity in oxidizing hydrogen chloride to produce chlorine and a high activity per ruthenium contained. It is an object of the present invention to provide a method for producing chlorine by using a catalyst and producing chlorine at a lower reaction temperature with a smaller amount of catalyst.

[0007]

The present inventors have conducted intensive studies on a method for producing chlorine using a catalyst that does not have the above-mentioned problems, and as a result, have found that a specific catalyst containing ruthenium has been converted to chlorine. It has been found that when used for the production of, the catalyst activity is high and the activity per contained ruthenium is high, and it is possible to produce chlorine at a lower reaction temperature with a smaller amount of catalyst, thereby completing the present invention.

That is, the present invention relates to a method for producing chlorine by oxidizing hydrogen chloride with oxygen in the presence of at least one catalyst selected from the following (A) to (D). (A): a supported ruthenium chloride catalyst in which the carrier contains at least one compound of titanium oxide and zirconium oxide, wherein the weight ratio of ruthenium to the carrier is 0.5 to 20% by weight. (B): ruthenium carbonyl Complex, ruthenium organic acid salt, ruthenium nitrosyl complex, ruthenium ammine complex, ruthenium ammine complex chloride, ruthenium organic amine complex, ruthenium acetylacetonate complex at least one ruthenium compound selected from the group consisting of a ruthenium compound supported on a carrier. And a catalyst in which the weight ratio of ruthenium to the carrier is 0.5 to 20% by weight (C): chlororuthenate, chlororuthenate hydrate, ruthenate salt, ruthenium oxychloride salt, ruthenium ammine Complex, chloride or bromide of ruthenium ammine complex, Ruthenium bromide, ruthenium organic amine complex, ruthenium acetylacetonato complex,
A ruthenium oxide catalyst obtained by oxidizing a catalyst having at least one ruthenium compound selected from the group consisting of a ruthenium carbonyl complex, a ruthenium organic acid salt, a ruthenium nitrosyl complex, and a ruthenium phosphine complex, wherein the ruthenium and the carrier Has a weight ratio of 0.
5 to 20% by weight of a catalyst (D): a ruthenium chloride catalyst supported on a carrier was treated with 28
Catalyst obtained by calcination at a temperature of 0 ° C or higher

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The ruthenium catalyst used in the present invention is a supported catalyst containing ruthenium chloride or a ruthenium compound, which comprises (A), (B), (C),
(D) at least one catalyst selected from the group consisting of:

In the present invention, the supported ruthenium chloride catalyst in the catalyst (A) is a catalyst in which ruthenium chloride is supported on a carrier.

As ruthenium chloride, ruthenium (III) chloride hydrate is usually used. When ruthenium (IV) chloride hydrate is used, it may be decomposed during catalyst preparation due to instability. That is, in the present invention, the ruthenium chloride supported on the carrier includes ruthenium chloride.
(III), ruthenium (III) chloride hydrate, ruthenium chloride (I
II) Compounds obtained by hydrolyzing hydrates, ruthenium (IV) chloride hydrate, and ruthenium compounds formed by decomposition of ruthenium (IV) hydrate.

In the catalyst (A) of the present invention, it is important to use a carrier containing at least one of titanium oxide and zirconium oxide as the carrier of the supported ruthenium chloride catalyst. Titanium oxide, at least one carrier among zirconium oxides is a titanium oxide carrier, a zirconium oxide carrier, or a mixture of these carriers, or a mixture of these carriers with other carriers such as alumina and silica. . By using the above carrier, a highly active supported ruthenium chloride catalyst can be obtained. A preferred carrier is a carrier containing titanium oxide, and a more preferred carrier is titanium oxide. The weight ratio of ruthenium to the carrier is 0.5-20% by weight, preferably 1-8% by weight, more preferably 1-6% by weight.

If the ratio of ruthenium is too high, the price of the catalyst increases, and if the ratio of ruthenium is too low, the activity of the catalyst decreases.

As a preparation method, for example, RuCl _3.
After impregnating the carrier with an aqueous solution of nH ₂ O or a hydrochloric acid solution, the carrier is dried under reduced pressure, under a nitrogen stream or in air.

The catalytic activity can be improved by adding a third component other than ruthenium. Titanium compounds, zirconium compounds, noble metal compounds other than ruthenium such as palladium compounds, rare earth compounds, copper compounds, chromium compounds, nickel compounds, alkali metal compounds, alkaline earth metal compounds, manganese compounds, tantalum compounds, tin as the third component And vanadium compounds.

As the third component, noble metal chlorides other than ruthenium such as titanium chloride, zirconium chloride and palladium chloride, copper chloride, chromium chloride, manganese chloride, tantalum chloride, tin chloride, nickel chloride and the like are preferable, and more preferably. It is titanium chloride.

The addition amount of the third component is usually 0.1 to 10% by weight as a ratio to the carrier. As a method for adding the third component, for example, a solution obtained by mixing an aqueous solution of TiCl ₄ or an aqueous solution of hydrochloric acid with an aqueous solution of RuCl ₃ .nH ₂ O or an aqueous solution of hydrochloric acid is impregnated into the carrier, and then the pressure is reduced or the flow of nitrogen gas is increased. There is a method of drying under the air or in the air. The mixing ratio of ruthenium chloride and titanium chloride is preferably 100 as a molar ratio of titanium to ruthenium.
One to one hundred to ten.

If the temperature of the supported catalyst is too high, volatilization of ruthenium chloride occurs.
The temperature is preferably about 60 ° C to 400 ° C in 00 ° C and nitrogen.
In air, the temperature is preferably about 60 ° C to 250 ° C. The drying time is preferably about 30 minutes to 5 hours.

The catalyst (B) in the present invention is Ru (CO)
_5, Ru ₃ (CO) ₁₂ ruthenium carbonyl complexes, such as,
_{[Ru 3 O (OCOCH 3)} 6 (H 2 O) 3] OCOCH 3
Hydrate, ruthenium organic acid salt such as Ru ₂ (RCOO) ₄ Cl (R = alkyl group having 1-3 carbon atoms), K ₂ [RuC
l ₅ NO)], _{[Ru (NH 3) 5 (NO} ) ] Cl _3, [R
u (OH) (NH ₃ ) ₄ (NO)] (NO ₃ ) ₂ , Ru
Ruthenium nitrosyl complexes such as (NO) (NO ₃ ) ₃ ,
[Ru (NH ₃ ) ₆ ] ²⁺ , [Ru (NH ₃ ) ₆ ] ³⁺ , [Ru
(NH _{3) 5} H ₂ O] ²⁺ ruthenium ammine complexes, such as,
[Ru (NH ₃ ) ₅ Cl] ²⁺ , [Ru (NH ₃ ) ₆ ] C
at least one ruthenium compound selected from the group consisting of a chloride of a ruthenium ammine complex such as l ₂ and [Ru (NH ₃ ) ₆ ] Cl ₃ , a ruthenium organic amine complex, and a ruthenium acetylacetonate complex; Examples include catalysts prepared by being supported on a carrier such as alumina, zeolite, diatomaceous earth, oxides of elements such as titanium oxide, zirconium oxide, and vanadium oxide and composite oxides. These carriers may be used as a mixture of two or more kinds. The ruthenium compound is preferably a ruthenium carbonyl complex, ruthenium acetate, or ruthenium nitrosyl complex, more preferably a ruthenium carbonyl complex or ruthenium acetate. As the carrier, titanium oxide, zirconium oxide,
Alumina, silica, titanium composite oxide, zirconium composite oxide, and aluminum composite oxide are preferably used, and titanium oxide is more preferably used.

The weight ratio of ruthenium to the carrier is 0.5 to 20.
%, Preferably 1 to 8% by weight, more preferably 1 to 6% by weight.

Examples of the supporting method include an impregnation method, an ion exchange method, a precipitation supporting method, a coprecipitation method, and a mixing method.
Preferably, the impregnation method and the ion exchange method are used.

The impregnation method includes, for example, a method in which a carrier is suspended in a solution in which a ruthenium compound is dissolved, the solvent is evaporated, and the carrier is dried.
Examples of the solvent include water, methanol, an organic solvent and the like.

When the temperature of the supported catalyst is too high, the ruthenium compound volatilizes if the temperature is too high.
A temperature of about 200C to about 400C in nitrogen is preferable. Further, in the air, a temperature at which the ruthenium compound is not oxidatively decomposed by oxygen is generally used. The drying time is preferably about 30 minutes to 5 hours.

The catalyst (C) used in the present invention comprises:
For example, K_ThreeRuCl₆, [RuCl ₆]^3-, K_TwoRuCl
₆Chlororuthenate, such as [RuCl_FiveH_TwoO)]
^2-, K_Two[RuCl_Five(H_TwoO)], (NH_Four)_Two[RuC
l_Five(H_TwoO)], [RuCl_Two(H_TwoO)_Four]⁺Such as black
Lorthenate hydrate, K_TwoRuO_FourSuch as ruthenium
Acid salt, Ru_TwoOCI_Four, Ru_TwoOCI_Five, Ru_TwoOCI₆What
Which ruthenium oxychloride, 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 complexes, such as
[Ru (NH_Three)_FiveCl]²⁺, [Ru (NH _Three)₆] C
l_Two, [Ru (NH_Three)₆] Cl_Three, [Ru (NH_Three)₆] B
r_ThreeChloride, bromide, etc. of ruthenium ammine complex
RuBr_Three, RuBr_ThreeRuthenium bromide such as hydrate,
Other ruthenium organic amine complexes, ruthenium acetyl
Ruacetonate complex, Ru (CO)_Five, Ru_Three(CO)₁₂
Ruthenium carbonyl complexes such as [Ru_ThreeO (OCO
CH_Three)₆(H_TwoO)_ThreeOCOCH_ThreeHydrate, Ru_Two(R
COO)_FourCl (R = alkyl group having 1-3 carbon atoms)
Ruthenium organic acid salt, K_Two[RuCl_FiveNO)], [R
u (NH_Three)_Five(NO)] Cl_Three, [Ru (OH) (N
H _Three)_Four(NO)] (NO_Three)_Two, Ru (NO) (NO_Three)
_ThreeRuthenium nitrosyl complex, ruthenium phosph
Compounds such as alumina complex, alumina, silica, silica
Lumina, zeolite, diatomaceous earth or titanium oxide,
Oxides of elements such as zirconium oxide and vanadium oxide
And a catalyst prepared on a carrier such as a composite oxide
This is a ruthenium oxide catalyst obtained by the conversion treatment.

The ruthenium compound supported on the carrier includes ruthenic acid salt, ruthenium ammine complex, chloride of ruthenium ammine complex, ruthenium bromide, ruthenium organic amine complex, ruthenium acetylacetonate complex, ruthenium carbonyl complex, ruthenium organic acid salt And a ruthenium nitrosyl complex are preferable, a ruthenium ammine complex, a chloride of a ruthenium ammine complex, ruthenium acetate, a ruthenium carbonyl complex and a ruthenium nitrosyl complex are more preferable, and a chloride of a ruthenium ammine complex and ruthenium nitrosyl nitrate are more preferably used.

As the carrier, silica and titanium oxide are preferably used.

The weight ratio of ruthenium to the carrier is 0.5 to 20.
%, Preferably 1 to 8% by weight, more preferably 1 to 6% by weight, and still more preferably 2 to 6% by weight.

As a preparation method, for example, a method in which a catalyst in which the above-mentioned ruthenium compound is supported on a carrier is calcined in a gas containing oxygen is mentioned. Air is usually used as the gas containing oxygen. Firing temperature is 28
0 ° C. or higher is preferable, and more preferably 280 to 500 ° C.
It is. If the calcination temperature is too low, the ruthenium compound may remain without being sufficiently oxidized and decomposed, resulting in insufficient catalytic activity and volatilization of the ruthenium compound during the chlorine production reaction. On the other hand, if the firing temperature is too high, agglomeration of ruthenium oxide particles may occur, and the catalytic activity may decrease.

By the calcination, the ruthenium compound supported on the carrier is converted into a ruthenium oxide catalyst. The firing time is usually 30 minutes to 5 hours. The conversion of the ruthenium compound to ruthenium oxide was confirmed by X-ray diffraction and XPS.
(X-ray photoelectron spectroscopy) or the like.

A third component other than ruthenium chloride and a ruthenium compound may be added. As the third component, a palladium compound, a copper compound, a chromium compound, a vanadium compound, a nickel compound, an alkali metal compound,
Rare earth compounds, manganese compounds, alkaline earth compounds and the like can be mentioned. The amount of the third component added is preferably 0.1 to 10% by weight relative to the carrier.

The catalyst (D) in the present invention is obtained by calcining ruthenium chloride supported on a carrier at a temperature of 280 ° C. or higher.

Examples of the carrier include oxides or composite oxides such as titanium oxide, alumina, zirconium oxide, silica, titanium composite oxide, zirconium composite oxide, aluminum composite oxide, and silicon composite oxide. Are titanium oxide, alumina, zirconium oxide and silica, and more preferred carriers are titanium oxide and zirconium oxide.

The supported ruthenium chloride in the present invention can be prepared by being supported on a carrier which has been previously shaped in accordance with the use of the catalyst, and the catalyst can be easily prepared. Has advantages.

The weight ratio of ruthenium to the carrier is 0.5 to 2
It is preferably 0% by weight, more preferably 1 to 8% by weight, and still more preferably 1 to 6% by weight.

If the amount of ruthenium is too small, the activity may decrease. On the other hand, if the amount of ruthenium is excessive, the price of the catalyst may increase.

The method for producing the ruthenium chloride catalyst supported on a carrier includes, for example, the above-mentioned titanium oxide, alumina, zirconium oxide, silica, titanium composite oxide, zirconium composite oxide, aluminum composite oxide, silicon composite oxide, and the like. The carrier is impregnated with an aqueous solution of ruthenium chloride or a solution of ruthenium chloride in hydrochloric acid, and then dried in nitrogen or air to carry ruthenium chloride. In addition, a commercial item can also be used for a carrier. Also, the carrier can be used in powder form,
What is molded can also be used.

As the firing atmosphere, various atmospheres can be mentioned, and a gas containing oxygen, for example, air is preferable. The firing temperature is 280 ° C or higher, preferably 280-500 ° C. More preferably 300 ° C
~ 450 ° C. If the calcination temperature is too low, the catalytic activity becomes insufficient, and the ruthenium compound may volatilize during the chlorine production reaction. On the other hand, if the firing temperature is too high, the catalytic activity may decrease. The firing time is usually 30 minutes to 5 hours.

Further, a preparation method in which a compound other than ruthenium chloride is added in addition to ruthenium chloride and calcined can be mentioned as a preferable preparation method because the catalyst can be highly activated. The compound to be added is preferably an alkali metal salt such as potassium chloride, sodium chloride, potassium nitrate, and cesium nitrate. Firing in the presence of an alkali metal salt is preferable because ruthenium chloride can be oxidized and decomposed into finer ruthenium oxide particles, and a highly active catalyst can be obtained. As a specific method of firing in the presence of an alkali metal, for example, a method of impregnating ruthenium chloride supported on a carrier with an aqueous solution of an alkali metal salt, drying in nitrogen or air, and firing in air is used. be able to. Here, the amount of the alkali metal salt used is 0.01 to 10 in a molar ratio to ruthenium.
Is preferred. If the amount of the alkali metal is too small, the effect of improving the catalytic activity may be reduced, while if the amount of the alkali metal is too large, the price of the catalyst may be increased.
Usually, the added alkali metal is removed by washing with water or the like, but it is acceptable that the alkali metal remains as long as the effect of the present invention is not impaired.

A third component other than ruthenium chloride and a ruthenium compound may be added. As the third component, a palladium compound, a copper compound, a chromium compound, a vanadium compound, a nickel compound, an alkali metal compound,
Rare earth compounds, manganese compounds, alkaline earth compounds and the like can be mentioned. The amount of the third component added is preferably 0.1 to 10% by weight relative to the carrier.

The present invention discloses a method for producing chlorine by oxidizing hydrogen chloride with oxygen in a gas phase flow reaction using the above catalyst.

When a catalyst is used in a fixed bed, the catalyst is usually formed into a large-sized industrial apparatus, and the reaction is carried out. The above catalyst can also be used in a fluidized bed. The catalyst of the present invention can be used in a reactor such as a fixed-bed reactor, a fluidized-bed reactor, and a column reactor.

The present invention is to produce chlorine by oxidizing hydrogen chloride with oxygen using the above catalyst. In producing chlorine, examples of a reaction system include a flow system such as a fixed bed or a fluidized bed, 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 in a highly oxidized state is volatilized, so that the reaction is preferably performed at a lower temperature, but is preferably 100 to 500 ° C, more preferably 200 to 380 ° C. Reaction pressure is atmospheric pressure ~
A pressure of about 50 atm is preferred. As the oxygen source, air may be used as it is, or pure oxygen may be used,
More preferably, when the inert nitrogen gas is discharged outside the apparatus, other components are also released at the same time, and thus pure oxygen containing no inert gas can be used. The theoretical molar amount of oxygen to hydrogen chloride is 1/4 mole, but it is preferable to supply 0.1 to 10 times the theoretical amount. The amount of the catalyst used is usually 10 to 20,000 h ^{-1 in} the case of a fixed bed gas phase flow system, expressed as a ratio GHSV to the feed rate of the raw material hydrogen chloride under atmospheric pressure.
It is preferred that it is about.

[0044]

Next, the present invention will be described with reference to examples.

Example 1 A catalyst was prepared by the following method. That is, 1.41 g of commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) was dissolved in 3.2 g of water, and stirred well to obtain an aqueous ruthenium chloride solution. The obtained aqueous solution was added dropwise to 5.0 g of a titanium oxide carrier (CS-300S, manufactured by Sakai Chemical Industry Co., Ltd.), which was adjusted to 12 to 18.5 mesh and dried in air at 500 ° C. for 1 hour, and ruthenium chloride was added. Impregnated and supported. The supported material was cooled to room temperature under nitrogen flow of 100 ml / min.
The temperature was raised to about 00 ° C. in about 0.5 hour and dried at the same temperature for 2 hours, and then 100 ° C. under a nitrogen stream of 100 ml / min.
The temperature was raised from 50 ° C. to 250 ° C. in 50 minutes, and dried by heating at the same temperature for 3 hours to obtain 10.5 g of a black solid. The obtained black solid was adjusted to 12 to 18.5 mesh to obtain a titanium oxide-supported ruthenium chloride catalyst. The calculated value of the ruthenium chloride content was RuCl
₃ / (RuCl ₃ + TiO ₂ ) × 100 = 9.3% by weight. The calculated value of the ruthenium content is Ru / (RuCl
₃ + TiO ₂ ) × 100 = 4.5% by weight. 2.5 g of the thus obtained titanium oxide-supported ruthenium chloride catalyst was charged into a quartz reaction tube (inner diameter: 12 mm). 190 ml / min of hydrogen chloride gas, 200 m of oxygen gas
1 / min (all at 0 ° C., 1 atm) 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. 1.7 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 potassium iodide solution, and the amount of chlorine produced and the amount of unreacted chloride were determined by iodine titration and neutralization titration, respectively. The amount of hydrogen was measured. The chlorine generation activity per unit catalyst weight determined by the following equation is 2.97 × 10 ⁻⁴ mol / m.
ing-catalyst. Chlorine production activity per unit catalyst weight (mol / min · g
−catalyst) = the amount of outlet 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 65.6 × 10 ⁻⁴ mol / min · g-Ru. Chlorine-forming activity per unit Ru weight (mol / min · g
−Ru) = amount of chlorine produced at the outlet per unit time (mol / m)
in) / Ru weight (g)

Example 2 A catalyst was prepared by the following method. That is, 1.41 g of commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) was dissolved in 2.8 g of water, and the mixture was stirred well to obtain an aqueous ruthenium chloride solution. The obtained aqueous solution was adjusted to 12 to 18.5 mesh and dried in air at 500 ° C. for 1 hour. 10.0 g of a zirconium oxide support (Nikki Chemical Co., Ltd. E26H6)
Into the pores of the zirconium oxide carrier until it is almost immersed in the aqueous solution, vacuum-dry at 40 ° C. for 1 hour, and again add the ruthenium chloride aqueous solution again. I got The obtained black-brown solid was cooled to room temperature under nitrogen flow of 100 ml / min.
The temperature was raised to about 00 ° C. in about 0.5 hour and dried at the same temperature for 2 hours, and then 100 ° C. under a nitrogen stream of 100 ml / min.
The temperature was raised from 50 ° C. to 250 ° C. in 50 minutes, and dried by heating at the same temperature for 3 hours to obtain 10.5 g of a black solid. The obtained black solid was adjusted to 12 to 18.5 mesh to obtain a zirconium oxide-supported ruthenium chloride catalyst. The calculated value of the ruthenium chloride content is R
uCl ₃ / (RuCl ₃ + ZrO ₂ ) × 100 = 9.3% by weight. The calculated value of the ruthenium content is Ru / (R
uCl ₃ + ZrO ₂ ) × 100 = 4.5% by weight.
2.5 g of the thus obtained zirconium oxide-supported ruthenium chloride catalyst was placed in a quartz reaction tube in the same manner as in Example 1.
Filled. The reaction was carried out according to the reaction method of Example 1. At 1.6 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 1.11 × 10 ⁻⁴ mol / min ·
g-catalyst. The production activity of chlorine per unit Ru catalyst weight was 24.5 × 10 ⁻⁴ mol / min · g-Ru.

Example 3 A catalyst was prepared by the following method. That is, 0.69 g of a commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) was dissolved in 3.6 g of water and stirred well to obtain an aqueous ruthenium chloride solution. 9.5 g of a titanium oxide carrier (CS-300S, Sakai Chemical Industry Co., Ltd.) obtained by adjusting the obtained aqueous solution to 12 to 18.5 mesh and drying in air at 500 ° C. for 1 hour.
Was added dropwise, and ruthenium chloride was impregnated and supported. The loaded material was heated from room temperature to 100 ° C. for 1 hour under a nitrogen flow of 100 ml / min, dried at the same temperature for 2 hours, and then dried at 100 ° C. under a nitrogen flow of 100 ml / min.
To 250 ° C. in 50 minutes, and dried by heating at the same temperature for 3 hours to obtain 9.6 g of a black solid. The obtained black solid was adjusted to 12 to 18.5 mesh to obtain a titanium oxide-supported ruthenium chloride catalyst.
The calculated value of the ruthenium chloride content was calculated as RuCl ₃ /
(RuCl ₃ + TiO ₂ ) × 100 = 5.0% by weight. The calculated value of the ruthenium content is Ru / (RuCl ₃ +
TiO ₂ ) × 100 = 2.4% by weight. 1. Ruthenium chloride catalyst supporting titanium oxide thus obtained
5 g was charged into a quartz reaction tube in the same manner as in Example 1, and hydrogen chloride gas was supplied at 187 ml / min and oxygen gas was supplied at 200 ml / min.
The reaction was carried out in accordance with the reaction method of Example 1 except that the reaction mixture was flowed in min. 2.4 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 2.79 × 10 ⁻⁴ mo.
1 / min · g-catalyst. The activity of forming chlorine per unit Ru catalyst weight is 114.1 × 10 ⁻⁴ mol / min.
-It was g-Ru.

Example 4 A catalyst was prepared by the following method. That is, 0.28 g of a commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) was dissolved in 4.1 g of water and stirred well to obtain an aqueous ruthenium chloride solution. 9.8 g of a titanium oxide carrier (CS-300S, Sakai Chemical Industry Co., Ltd.) obtained by adjusting the obtained aqueous solution to 12 to 18.5 mesh and drying in air at 500 ° C. for 1 hour.
Was added dropwise, and ruthenium chloride was impregnated and supported. The loaded material was heated from room temperature to 100 ° C. for 1 hour under a nitrogen flow of 100 ml / min, dried at the same temperature for 2 hours, and then dried at 100 ° C. under a nitrogen flow of 100 ml / min.
To 250 ° C. in 1 hour, and dried by heating at the same temperature for 3 hours to obtain 9.8 g of a black solid. The obtained black solid was adjusted to 12 to 18.5 mesh to obtain a titanium oxide-supported ruthenium chloride catalyst.
The calculated value of the ruthenium chloride content was calculated as RuCl ₃ /
(RuCl ₃ + TiO ₂ ) × 100 = 2.0% by weight. The calculated value of the ruthenium content is Ru / (RuCl ₃ +
TiO ₂ ) × 100 = 1.0% by weight. 1. Ruthenium chloride catalyst supporting titanium oxide thus obtained
5 g was charged into a quartz reaction tube in the same manner as in Example 1, and hydrogen chloride gas was supplied at 187 ml / min and oxygen gas was supplied at 200 ml / min.
The reaction was carried out in accordance with the reaction method of Example 1 except that the reaction mixture was flowed in min. 2.2 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 2.29 × 10 ⁻⁴ mo.
1 / min · g-catalyst. The activity of forming chlorine per unit Ru catalyst weight is 232 × 10 ⁻⁴ mol / min · g.
-Ru.

Example 5 A catalyst was prepared by the following method. That is, 2.10 g of commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) was dissolved in 3.7 g of water, and stirred well to obtain an aqueous ruthenium chloride solution. Next, add 7.5 g of water to an ice-cooled beaker,
While stirring, 0.044 g of commercially available titanium tetrachloride was added dropwise, and the mixture was thoroughly stirred to prepare an aqueous solution of titanium tetrachloride. An aqueous solution was obtained. The obtained aqueous solution was dried in air at 500 ° C. for 1 hour, and the titanium oxide carrier powder (Sakai Chemical Co., Ltd. SSP-20) 15.0
g was added dropwise and ruthenium chloride was impregnated and supported. The support was dried at 60 ° C. for 1 hour to obtain a green solid. The obtained solid was heated from room temperature to 200 ° C. for about 1 hour under a nitrogen stream of 100 ml / min and dried at the same temperature for 2 hours to obtain 10.5 g of a black solid. The obtained black solid was adjusted to 12 to 18.5 mesh to obtain a titanium oxide-supported titanium chloride ruthenium chloride catalyst. Incidentally, the calculated value of the ruthenium chloride content is RuCl ₃ / (R
uCl ₃ + TiCl ₄ + TiO ₂ ) = 9.2% by weight. The calculated value of the ruthenium content is Ru / (RuCl ₃ +
TiCl ₄ + TiO ₂ ) × 100 = 4.5% by weight. In the same manner as in Example 1, 2.5 g of the titanium oxide-supported titanium chloride ruthenium chloride catalyst thus obtained was charged into a quartz reaction tube. The reaction was carried out according to the reaction method of Example 1. 1.7 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 3.6 × 10 ⁻⁴ mol / mi.
ng-catalyst. The activity of forming chlorine per unit Ru catalyst weight is 80.2 × 10 ⁻⁴ mol / min · g-Ru.
Met.

Example 6 A catalyst was prepared by the following method. That is, commercially available dodecacarbonyl triruthenium (Ru ₃ (CO) ₁₂ ) 1.
05 g was dissolved in 190 ml of tetrahydrofuran (THF). Next, commercially available titanium oxide (Sakai Chemical CS300)
10 g of the pulverized product was placed in a glass flask, a THF solution of dodecacarbonyltriruthenium was added to the extent that the titanium oxide was moistened, and dried at 60 ° C. with a rotary evaporator. This operation was repeated, and the entire amount of dodecacarbonyltriruthenium was supported on titanium oxide to obtain 11.0 g of a supported catalyst. The obtained catalyst was adjusted to 12 to 18.5 mesh to obtain a titanium oxide-supported dodecacarbonyl triruthenium catalyst. The calculated value of the content of dodecacarbonyltriruthenium was calculated as Ru ₃ (CO) ₁₂ /
(Ru ₃ (CO) ₁₂ + TiO ₂ ) × 100 = 9.5% by weight
Met. The calculated value of the ruthenium content is Ru / (Ru ₃
(CO) ₁₂ + TiO ₂ ) × 100 = 5.0% by weight. 2.5 g of the titanium oxide-supported dodecacarbonyltriruthenium catalyst thus obtained was charged into a quartz reaction tube in the same manner as in Example 1, and hydrogen chloride gas was charged at 202 ml / m2.
The reaction was carried out according to the reaction method of Example 1 except that in and oxygen gas were passed at 213 ml / min. 2.3 hours after the start of the reaction, the chlorine generation activity per unit catalyst weight was 1.14 × 10 ⁻⁴ mol / min · g-catalyst. The activity of producing chlorine per unit Ru catalyst weight is 2
It was 2.9 × 10 ⁻⁴ mol / min · g-Ru.

Example 7 A catalyst was prepared by the following method. That is, commercially available dodecacarbonyl triruthenium (Ru ₃ (CO) ₁₂ ) 0.1.
32 g was dissolved in 119 ml of tetrahydrofuran (THF). Next, commercially available titanium oxide (Sakai Chemical CS300)
6 g of the pulverized product of S) was placed in a glass flask, a THF solution of dodecacarbonyltriruthenium was added to such an extent that the titanium oxide became wet, and dried at 60 ° C. with a rotary evaporator. The THF solution of dodecacarbonyltriruthenium was used in the preparation of the catalyst under light shielding since the color of the solution may be changed if left in air. This operation was repeated, and the whole amount of dodecacarbonyltriruthenium was supported on titanium oxide to obtain 5.89 g of a supported catalyst. The obtained catalyst was adjusted to 12 to 18.5 mesh to obtain a titanium oxide-supported dodecacarbonyl triruthenium catalyst. The calculated value of the content of dodecacarbonyltriruthenium is calculated as Ru ₃ (CO) ₁₂ / (Ru ₃ (CO) ₁₂ + Ti
O ₂ ) × 100 = 5.0% by weight. The calculated value of the ruthenium content is Ru / (Ru ₃ (CO) ₁₂ + TiO ₂ ) ×
100 = 2.5% by weight. 1. Dodecacarbonyl ruthenium catalyst supported on titanium oxide thus obtained
5 g was charged into a quartz reaction tube in the same manner as in Example 1, and hydrogen chloride gas was supplied at 187 ml / min and oxygen gas was supplied at 200 ml / min.
The reaction was carried out in accordance with the reaction method of Example 1 except that the mixture was circulated for 1 min and the internal temperature was changed to 301 ° C. Start of reaction 2.0
After a lapse of time, the activity of forming chlorine per unit weight of the catalyst was 2.41 × 10 ⁻⁴ mol / min · g-catalyst.
The activity of forming chlorine per unit Ru catalyst weight is 96.2 × 1.
It was 0 ^-4 mol / min.g-Ru.

Example 8 A catalyst was prepared by the following method. That is, commercially available dodecacarbonyl triruthenium (Ru ₃ (CO) ₁₂ ) 0.1.
2 g was dissolved in 74 ml of tetrahydrofuran (THF). Next, 9.8 g of a crushed product of commercially available titanium oxide (Sakai Chemical CS300S) was placed in a glass flask, a THF solution of dodecacarbonyltriruthenium was added to such an extent that the titanium oxide became wet, and dried at 60 ° C. with a rotary evaporator. . The THF solution of dodecacarbonyltriruthenium was used in the preparation of the catalyst under light shielding since the color of the solution may be changed if left in air. Repeat this operation,
The whole amount of ruthenium dodecacarbonyl was supported on titanium oxide to obtain 9.2 g of a supported catalyst. The obtained catalyst is 12-
By adjusting the size to 18.5 mesh, a titanium oxide-supported dodecacarbonyl triruthenium catalyst was obtained. In addition,
The calculated value of the dodecacarbonyltriruthenium content is Ru
₃ (CO) ₁₂ / (Ru ₃ (CO) ₁₂ + TiO ₂ ) × 100
= 2.0% by weight. The calculated value of the ruthenium content is
Ru / (Ru ₃ (CO) ₁₂ + TiO ₂ ) × 100 = 1.0
% By weight. 2.5 g of the titanium oxide-supported dodecacarbonyltriruthenium catalyst thus obtained was filled in a quartz reaction tube in the same manner as in Example 1, and hydrogen chloride gas was added to the reaction tube.
The reaction was performed according to the reaction method of Example 1 except that 87 ml / min and oxygen gas were passed at 184 ml / min. 2.0 hours after the start of the reaction, the chlorine generation activity per unit catalyst weight was 1.61 × 10 ⁻⁴ mol / min.
G-catalyst. The chlorine generation activity per unit Ru catalyst weight was 161 × 10 ⁻⁴ mol / min · g-Ru.

Example 9 A catalyst was prepared by the following method. That is, 12 to 1
Titanium oxide carrier (Sakai Chemical Co., Ltd. CS300S) 1 prepared in 8.5 mesh and dried in air at 500 ° C for 1 hour
0.0 g was placed in a glass beaker and a commercially available trinitranitrosyl ruthenium solution (Ru (NO) (NO ₃ ) ₃ , Ru)
5% by weight) to the extent that the titanium oxide becomes wet.
And dried under an air stream on an oil bath. This operation was repeated to prepare a trinitrate nitrosyl ruthenium solution (Ru
10.0 g of (NO) (NO ₃ ) ₃ , containing 5% by weight of Ru was impregnated and supported. The loaded material was heated from room temperature to 100 ° C. for about 1.5 hours under a nitrogen stream of 100 ml / min and dried at the same temperature for 2 hours. .5 hours,
By drying by heating at the same temperature for 3 hours, 10.6 g of a black solid was obtained. The obtained black solid was 12 to 18.
By adjusting the mesh size to 5 mesh, a trinitrate nitrosyl ruthenium catalyst supported on titanium oxide was obtained. Note that the calculated value of the trinitranitrosylruthenium content is Ru (N
O) (NO ₃ ) ₃ / (Ru (NO) (NO ₃ ) ₃ + Ti
O ₂ ) × 100 = 13.6% by weight. The calculated value of the ruthenium content is Ru / (Ru (NO) (NO ₃ ) ₃ + T
iO ₂ ) × 100 = 4.32% by weight. 2.5 g of the thus-obtained trinitranitrosylruthenium catalyst supporting titanium oxide was charged into a quartz reaction tube in the same manner as in Example 1, and hydrogen chloride gas was passed at 180 ml / min and oxygen gas was passed at 180 ml / min. The reaction was performed according to the reaction method of Example 1 except for the above. 1.8 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 1.
It was 02 × 10 ⁻⁴ mol / min · g-catalyst. The activity of forming chlorine per unit Ru catalyst weight is 23.6 × 10 ^-4.
mol / min.g-Ru.

Example 10 A catalyst was prepared by the following method. That is, commercially available μ ₃
-Oxo-hexa-μ-acetatrichlorotriruthenium (1+) acetate hydrate ([Ru ₃ O (OCOCH ₃ )
_{3 (H 2 O) 3] OCOCH} 3 · nH 2 O) 1.3g were dissolved in pure water 3.6 g. The obtained aqueous solution is 12 to 18.
Titanium oxide carrier prepared in 5 mesh and dried in air at 500 ° C for 1 hour (Sakai Chemical Industry Co., Ltd. CS-300S)
The solution was added dropwise to 10 g, and impregnated with μ ₃ -oxo-hexa-μ-acetatrichlorotriruthenium (1+) acetate. After drying the supported material at 60 ° C. for 1 hour, 10
The temperature was raised from room temperature to 60 ° C. for 1 hour under a nitrogen stream of 0 ml / min, and dried by heating at the same temperature for 4 hours to obtain 10.9 g of a black solid. The obtained solid was 12
By adjusting the size to 〜18.5 mesh, a titanium oxide-supported μ ₃ -oxo-hexa-μ-acetatrichlorotriruthenium (1+) acetate catalyst was obtained. It should be noted that μ ₃ -oxo-hexa-μ-acetatrichlorotriruthenium (1
+) The calculated acetate content is [Ru ₃ O (OCOCH ₃ )
₃ (H ₂ O) ₃ ] OCOCH ₃ / ([Ru ₃ O (OCOC
_{H 3) 3 (H 2 O} ) 3] OCOCH 3 + TiO 2) × 100 =
9.3% by weight. The calculated value of the ruthenium content is
Ru / ([Ru ₃ O (OCOCH ₃ ) ₃ (H ₂ O) ₃ ] OC
OCH ₃ + TiO ₂ ) × 100 = 4.6% by weight.
The thus-obtained titanium oxide-supporting μ ₃ -oxo-
2.5 g of hexa-μ-acetatrichlorotriruthenium (1+) acetate catalyst was charged into a quartz reaction tube in the same manner as in Example 1, and hydrogen chloride gas was passed at 180 ml / min and oxygen gas was passed at 180 ml / min. The reaction was performed according to the reaction method of Example 1 except for the above. 1.8 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 3.30.
× 10 ⁻⁴ mol / min · g-catalyst. Unit Ru
The activity of forming chlorine per catalyst weight is 71.6 × 10 ⁻⁴ mo.
1 / min · g-Ru.

Example 11 A catalyst was prepared by the following method. First, the carrier silica was subjected to ion exchange. 20 g of commercially available aerosil silica (Aerosil-300, Nippon Aerosil Co., Ltd.) was placed in a glass flask, and then 300 ml of water was placed therein, heated and refluxed for 1 hour. Cool to room temperature and add 2
5.4 g of 5% by weight aqueous ammonia was added and left for 4 days. Next, the aerosil silica was filtered off, washed well with water, and sufficiently dried at room temperature to obtain 15.1 g of an NH ⁴⁺ -type silica carrier. 6 g of this silica carrier and 6.15 g of water were placed in a glass flask, and 0.92 g of [Ru (NH ₃ ) ₆ ] Cl ₃ was dissolved in 297 ml of water with stirring while heating to 60 ° C. in an oil bath. , And then stirred at the same temperature for 2 hours. After completion of the stirring, the mixture was evaporated to dryness while heating to 60 ° C. using a rotary evaporator to obtain 5.68 g of a pale yellow powder. Put this powder in air stream 4
Calcination at 56 ° C. for 3 hours gave a black solid. By aligning the obtained black solid to 12-18.5 mesh,
A silica-supported ruthenium oxide catalyst was obtained. The calculated value of the ruthenium oxide content is calculated as RuO ₂ / (RuO ₂ + Si
O ₂ ) × 100 = 6.2% by weight. The calculated value of the ruthenium content is Ru / (RuO ₂ + SiO ₂ ) × 100 =
It was 4.7% by weight. A reaction tube was prepared in the same manner as in Example 1 except that 1.21 g of the thus-obtained silica-supported ruthenium oxide catalyst was thoroughly mixed with 5 g of a titanium oxide carrier prepared in 12 to 18.5 mesh to dilute the catalyst. The reaction was carried out according to the reaction method of Example 1 except that hydrogen gas was supplied at 200 ml / min and oxygen gas was supplied at 200 ml / min. 1.8 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 2.
The catalyst was 23 × 10 ⁻⁴ mol / min · g-catalyst. The activity of forming chlorine per unit Ru catalyst weight is 47.5 × 10 ^-4.
mol / min.g-Ru. At the outlet of the reaction tube, volatilization of the ruthenium compound as a catalyst component was not observed.

Example 12 A catalyst was prepared by the following method. 10 g of a commercially available titanium oxide powder (SSP-20, Sakai Chemical Co., Ltd.) is placed in a glass flask, and then 1.36 g of [Ru (NH ₃ ) ₆ ] Cl _2.
Was dissolved in 35.6 g of water, and then 2
10 ml of 5% by weight aqueous ammonia was added, and the mixture was stirred in a nitrogen atmosphere. After completion of the stirring, the mixture was left at room temperature for 2 days. Then
The mixture was evaporated to dryness while heating to 60 ° C. with a rotary evaporator to obtain 10.7 g of a pale yellow powder. This powder was heated to 355 ° C. for 4.5 hours in an air stream, calcined at the same temperature for 3 hours, and further calcined at 390 ° C. for 2 hours to obtain 9.56 g of a black solid. The obtained black solid was 12 to 1
By adjusting the size to 8.5 mesh, a ruthenium oxide catalyst supporting titanium oxide was obtained. The calculated value of the ruthenium oxide content is calculated as follows: 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. A reaction tube was prepared in the same manner as in Example 1 except that the catalyst was diluted by sufficiently mixing 2.5 g of the titanium oxide-supported ruthenium oxide catalyst obtained in this way with 5 g of a titanium oxide carrier having a size of 12 to 18.5 mesh. Was filled.
200 ml / min of hydrogen chloride gas and 200 ml of oxygen gas
The reaction was carried out in accordance with the reaction method of Example 1 except that the reaction was conducted at a flow rate of ml / min and the internal temperature during the reaction was set at 299 ° C. 1.5 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 1.62 × 10 ⁻⁴ mol / min ·
g-catalyst. The chlorine generation activity per unit Ru catalyst weight was 34.5 × 10 ⁻⁴ mol / min · g-Ru. At the outlet of the reaction tube, volatilization of the ruthenium compound as a catalyst component was not observed.

Example 13 A catalyst was prepared by the following method. First, the carrier silica was subjected to ion exchange. 30 g of commercially available aerosil silica (Aerosil-300, Nippon Aerosil Co., Ltd.) was placed in a glass flask, and then 450 ml of water was placed therein, heated and refluxed for 1 hour. Cool to room temperature and add 2
8.1 g of 5% by weight aqueous ammonia was added and left for 2 days. Next, the aerosil silica was separated by filtration, washed well with water, and sufficiently dried in air at 60 ° C. to obtain 27.0 g of an NH ⁴⁺ type silica carrier. 6 g of this silica carrier and 20.1 of water
g (Ru (NH ₃ ) ₆ ] Cl ₃ 0/09 while stirring at 60 ° C. in an oil bath.
A solution obtained by dissolving 5 g in 30 ml of water was gradually added dropwise, and then stirred at the same temperature for 2 hours. After completion of the stirring, the mixture was evaporated to dryness while heating to 60 ° C. with a rotary evaporator to obtain a light yellow powder. This powder is placed in an air stream 45
Calcination at 6 ° C. for 3 hours gave 5.47 g of a gray solid. The obtained gray solid was adjusted to 12 to 18.5 mesh to obtain a silica-supported ruthenium oxide catalyst. In addition,
The calculated value of the ruthenium oxide content is RuO ₂ / (RuO ₂ +
SiO ₂ ) × 100 = 0.65% by weight. The calculated value of the ruthenium content is Ru / (RuO ₂ + SiO ₂ ) × 1
00 = 0.5% by weight. 2.5 g of the silica-supported ruthenium oxide catalyst thus obtained was charged into a quartz reaction tube in the same manner as in Example 1, and 187 ml of hydrogen chloride gas was added.
The reaction was carried out according to the reaction method of Example 1 except that oxygen gas was passed at 184 ml / min. 2.0 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 0.54 × 10 ⁻⁴ mol / min · g-catalyst. The activity of forming chlorine per unit weight of the Ru catalyst was 108 × 10 ⁻⁴ mol / min · g-Ru. At the outlet of the reaction tube, volatilization of the ruthenium compound as a catalyst component was not observed.

Example 14 A catalyst was prepared by the following method. First, the carrier silica was subjected to ion exchange. 10 g of commercially available aerosil silica (Aerosil-300, Nippon Aerosil Co., Ltd.) was placed in a glass flask, and then 450 ml of water was placed therein, heated and refluxed for 1 hour. Cool to room temperature and add 2
8.1 g of 5% by weight aqueous ammonia was added and left for 2 days. Next, the aerosil silica was separated by filtration, washed well with water, and sufficiently dried in air at 60 ° C. to obtain 27.0 g of an NH ⁴⁺ type silica carrier. 6 g of this silica carrier and 20.1 of water
g in a glass flask and, while heating to 60 ° C in an oil bath, with stirring, [Ru (NH ₃ ) ₆ ] Cl ₃ 0.19
g in 59 ml of water was gradually added dropwise, and then stirred at the same temperature for 2 hours. After completion of the stirring, the mixture was evaporated to dryness while heating to 60 ° C. with a rotary evaporator to obtain a light yellow powder. This powder is placed in an air stream 45
The mixture was calcined at 6 ° C. for 3 hours to obtain 5.53 g of a bluish gray solid. The obtained black solid was adjusted to 12 to 18.5 mesh to obtain a silica-supported ruthenium oxide catalyst. The calculated value of the ruthenium oxide content is calculated as RuO ₂ / (Ru
O ₂ + SiO ₂ ) × 100 = 1.3% by weight. The calculated value of the ruthenium content is Ru / (RuO ₂ + SiO ₂ ) ×
100 = 1.0% by weight. The silica-supported ruthenium oxide catalyst (2.5 g) thus obtained was charged into a quartz reaction tube in the same manner as in Example 1, and hydrogen chloride gas was supplied at 187 m2.
The reaction was carried out according to the reaction method of Example 1 except that oxygen gas was passed at 1 ml / min and 202 ml / min.
2.0 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst is 0.81 × 10 ⁻⁴ mol / min · g-
It was a catalyst. The chlorine generation activity per unit Ru catalyst weight was 82.0 × 10 ⁻⁴ mol / min · g-Ru. At the outlet of the reaction tube, volatilization of the ruthenium compound as a catalyst component was not observed.

Example 15 A catalyst was prepared by the following method. First, the carrier silica was subjected to ion exchange. 10 g of commercially available aerosil silica (Aerosil-300, Nippon Aerosil Co., Ltd.) was placed in a glass flask, and then 200 ml of water was placed therein, heated and refluxed for 1 hour. Cool to room temperature and add 2
10.8 g of 5% by weight aqueous ammonia and 400 ml of water were added and left for 2 days. Next, the aerosil silica was separated by filtration, washed well with water, and sufficiently dried at 60 ° C. in the air to obtain 8.4 g of an NH ⁴⁺ type silica carrier. 6 g of this silica carrier and 20 g of water are put into a glass flask, and [Ru (NH ₃ ) ₆ ] is stirred and heated to 60 ° C. in an oil bath.
A solution prepared by dissolving 1.8 g of Cl ₃ in 564 ml of water was gradually added dropwise, and then stirred at the same temperature for 2 hours. After completion of the stirring, the mixture was evaporated to dryness while heating to 60 ° C. with a rotary evaporator to obtain a pale yellow powder. This powder was calcined at 456 ° C. for 3 hours in an air stream to obtain 6.3 g of a black solid.
I got The obtained black solid was adjusted to 12 to 18.5 mesh to obtain a silica-supported ruthenium oxide catalyst. Incidentally, the calculated value of the ruthenium oxide content is RuO ₂
/ (RuO ₂ + SiO ₂ ) × 100 = 11.2% by weight. The calculated value of the ruthenium content is Ru / (RuO ₂ +
SiO ₂ ) × 100 = 8.5% by weight. 2.5 g of the silica-supported ruthenium oxide catalyst thus obtained
Oxide carrier 5 in which 12 to 18.5 mesh is prepared
The reaction tube was filled in the same manner as in Example 1 except that the catalyst was diluted by mixing well with g. 180 hydrogen chloride gas
The reaction was carried out according to the reaction method of Example 1 except that oxygen gas was flowed at 180 ml / min at a flow rate of 180 ml / min. 1.8 hours after the start of the reaction, the chlorine generation activity per unit catalyst weight was 2.41 × 10 ⁻⁴ mol / min ·
g-catalyst. The activity of forming chlorine per unit weight of the Ru catalyst was 28.5 × 10 ⁻⁴ mol / min · g-Ru. At the outlet of the reaction tube, volatilization of the ruthenium compound as a catalyst component was not observed.

Example 16 A catalyst was prepared by the following method. That is, 12 to 1
10 g of a titanium oxide carrier (Sakai Chemical CS300S), which was adjusted to 8.5 mesh and dried in air at 500 ° C. for 1 hour, was placed in a glass beaker, and a commercially available trinitranitrosylruthenium solution (Ru (NO) (NO ₃ ) ₃ , Ru5 weight was used. %) Was added to such an extent that the titanium oxide became wet, and dried on a 60 ° C. oil bath under an air stream. This operation was repeated to prepare a trinitrate nitrosyl ruthenium solution (Ru (NO) (N
10.0 g of O ₃ ) ₃ , containing 5% by weight of Ru). After drying the supported material in air at 60 ° C. for 2 hours,
The temperature was raised from room temperature to 350 ° C. in about 2 hours under an air flow of 100 ml / min, and oxidized by heating at the same temperature for 3 hours to obtain 9.3 g of a blue-black solid. The obtained black solid was adjusted to 12 to 18.5 mesh to obtain a titanium oxide-supported ruthenium oxide catalyst. In addition,
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 / (RuO ₂ + TiO ₂ ) × 10
0 = 4.7% by weight. 2.5 g of the thus-obtained titanium oxide-supported ruthenium oxide catalyst was 12 to 1
A reaction tube was filled in the same manner as in Example 1 except that the catalyst was diluted by thoroughly mixing with 5 g of a titanium oxide carrier prepared in 8.5 mesh, and hydrogen chloride gas was supplied at 180 ml / mi.
The reaction was carried out in accordance with the reaction method of Example 1 except that n and oxygen gas were passed at 180 ml / min. 1.8 hours after the start of the reaction, the chlorine generation activity per unit catalyst weight was 2.39 × 10 ⁻⁴ mol / min · g-catalyst. The chlorine generation activity per unit Ru catalyst weight was 51.0 × 10 ⁻⁴ mol / min · g-Ru.
At the outlet of the reaction tube, volatilization of the ruthenium compound as a catalyst component was not observed.

Example 17 A catalyst was prepared by the following method. That is, a commercially available trinitranitrosyl ruthenium solution (Ru (NO) (NO
₃ ) ₃ , 2 g of Ru (containing 5% by weight) were dissolved in 2 g of water to obtain 4 g of a trinitranitrosylruthenium solution. Next 1
Titanium oxide carrier (Sakai Chemical CS300S) 10 which was adjusted to 2-18.5 mesh and dried in air at 500 ° C for 1 hour.
g in a glass beaker and impregnated with 4 g of the trinitranitrosylruthenium solution, and then dried in an air stream at 60 ° C. in an oil bath to impregnate and support the entire amount of trinitranitrosylruthenium in titanium oxide. After drying the supported material in air at 60 ° C. for 2 hours, 100 ml
/ Min. From room temperature to 350 ° C.
The mixture was heated for 3 hours, and calcined by heating at the same temperature for 3 hours to obtain 10.0 g of a blue-grey solid. The obtained blue-gray solid was adjusted to 12 to 18.5 mesh to obtain a ruthenium oxide catalyst supporting titanium oxide. The calculated value of the ruthenium oxide content is calculated as RuO ₂ / (RuO ₂ + TiO _2
2 ) × 100 = 1.3% by weight. The calculated value of the ruthenium content is Ru / (RuO ₂ + TiO ₂ ) × 100 =
0.99% by weight. 2.5 g of the titanium oxide-supported ruthenium oxide catalyst thus obtained was charged into a quartz reaction tube in the same manner as in Example 1, and 180 ml of hydrogen chloride gas was charged.
The reaction was carried out according to the reaction method of Example 1 except that oxygen gas was flowed at 180 ml / min. 1.8 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 0.67 × 10 ⁻⁴ mol / min · g-catalyst. The chlorine generation activity per unit Ru catalyst weight was 67.4 × 10 ⁻⁴ mol / min · g-Ru. At the outlet of the reaction tube, volatilization of the ruthenium compound as a catalyst component was not observed.

Example 18 A catalyst was prepared by the following method. That is, commercially available chloride
Ruthenium hydrate (RuCl_Three・ NH_TwoO, Ru content 3
(5.5%) 0.89 g was dissolved in 3.2 g of water. Aqueous solution
After stirring well, zirconium oxide powder (JGC
Crushed zirconium oxide tablet manufactured by
) Was added dropwise to 6.0 g and impregnated with ruthenium chloride.
I carried it. The support was dried at 60 ° C. for 4 hours to obtain 6.9.
g of a black powder was obtained. This powder is dried in air at room temperature to 3
Raise the temperature to 50 ° C in 3.5 hours and bake at the same temperature for 3 hours.
As a result, 6.4 g of a black catalyst was obtained. In addition, oxidation
The calculated value of the ruthenium content is RuO_Two/ (RuO_Two+ Zr
O_Two) × 100 = 6.5% by weight. Ruthenium included
The calculated value of the quantity is Ru / (RuO_Two+ ZrO_Two) × 100 =
It was 4.9% by weight. This powder is molded and 12 to 1
8.5 mesh makes it possible to carry zirconium oxide.
A ruthenium oxide catalyst was obtained. Obtained in this way
2.75 g of ruthenium oxide catalyst supported on zirconium oxide
5 g of titanium oxide carrier aligned to 12-18.5 mesh
The catalyst was diluted by mixing well with
Into a quartz reaction tube and add 200 ml of hydrogen chloride gas
/ Min, oxygen gas was passed at 200 ml / min.
Except for the above, the reaction was carried out according to the reaction method of Example 1. Anti
1.3 hours after the start of the reaction, chlorine per unit catalyst weight
Has a production activity of 4.04 × 10 ^-Fourmol / min-g-contact
Medium. The activity of chlorine production per unit Ru catalyst weight is
82.4 × 10^-Fourmol / min.g-Ru.
At the outlet of the reaction tube, the catalyst component ruthenium compound
No volatilization of the object was observed.

Example 19 A catalyst was prepared by the following method. That is, 0.70 g of a commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) was dissolved in 4.0 g of water, and stirred well to obtain an aqueous ruthenium chloride solution. The obtained aqueous solution was adjusted to 12 to 18.5 mesh, and dried in air at 500 ° C. for 1 hour. Silica gel carrier (Carry Act G-1 by Fuji Silysia Ltd.)
0) Added dropwise to 5.0 g, and impregnated with ruthenium chloride. The temperature of the loaded material was raised from room temperature to 100 ° C. in about 0.5 hour under a nitrogen stream at 100 ml / min and dried at the same temperature for 2 hours, and then from room temperature to 350 ° C. in a 100 ml / min air stream for about 2 hours. , And calcined by heating at the same temperature for 3 hours to obtain 5.4 g of a black solid. The obtained black solid was adjusted to 12 to 18.5 mesh to obtain a silica-supported ruthenium oxide catalyst. The calculated value of the ruthenium oxide content was calculated as RuO ₂ /
(RuO ₂ + SiO ₂ ) × 100 = 6.2% by weight. The calculated value of the ruthenium content is Ru / (RuO ₂ + S
iO ₂ ) × 100 = 4.7% by weight. The silica-supported ruthenium oxide catalyst (2.5 g) thus obtained was charged into a quartz reaction tube in the same manner as in Example 1, and hydrogen chloride gas was added at 202 ml / min and oxygen gas was added at 213 ml / mi.
The reaction was carried out in accordance with the reaction method of Example 1 except that the reaction was conducted with n. At 1.7 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 2.04 × 10 ⁻⁴ mol /.
min.g-catalyst. The activity of forming chlorine per unit Ru catalyst weight is 43.5 × 10 ⁻⁴ mol / min · g-
Ru. At the outlet of the reaction tube, volatilization of the ruthenium compound as a catalyst component was not observed.

Example 20 A catalyst was prepared by the following method. That is, 0.70 g of a commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) was dissolved in 4.0 g of water, and stirred well to obtain an aqueous ruthenium chloride solution. The obtained aqueous solution was adjusted to 12 to 18.5 mesh, and dried in air at 500 ° C. for 1 hour. Silica gel carrier (Carry Act G-1 by Fuji Silysia Ltd.)
0) Added dropwise to 5.0 g, and impregnated with ruthenium chloride. The temperature of the loaded material was raised from room temperature to 100 ° C. in about 0.5 hour under a nitrogen stream at 100 ml / min and dried at the same temperature for 2 hours, and then from room temperature to 300 ° C. in an air stream at 100 ml / min for about 1 hour. The temperature was raised in 30 minutes and calcined by heating at the same temperature for 3 hours to obtain a black solid 5.3.
g was obtained. The obtained black solid was adjusted to 12 to 18.5 mesh to obtain a silica-supported ruthenium oxide catalyst. The calculated value of the ruthenium oxide content was 6.2.
% By weight. The calculated value of the ruthenium content was 4.7% by weight. 1. The silica-supported ruthenium oxide catalyst thus obtained was placed in a quartz reaction tube in the same manner as in Example 1.
5 g were filled. The reaction was carried out according to the reaction method of Example 1 except that hydrogen chloride gas was passed at 202 ml / min and oxygen gas was passed at 213 ml / min. Reaction start 2.4
After a lapse of time, the activity of forming chlorine per unit catalyst weight was 1.9 × 10 ⁻⁴ mol / min · g-catalyst. The activity of forming chlorine per unit Ru catalyst weight is 41.2 × 10
^-4 mol / min.g-Ru. At the outlet of the reaction tube, volatilization of the ruthenium compound as a catalyst component was not observed.

Example 21 A catalyst was prepared by the following method. That is, 0.70 g of a commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) was dissolved in 4.0 g of water, and stirred well to obtain an aqueous ruthenium chloride solution. The obtained aqueous solution was adjusted to 12 to 18.5 mesh, and dried in air at 500 ° C. for 1 hour. Silica gel carrier (Carry Act G-1 by Fuji Silysia Ltd.)
0) Added dropwise to 5.0 g, and impregnated with ruthenium chloride. The supported product was dried at 60 ° C. for 4 hours to obtain a black-brown solid. 100 ml / mi of the obtained black-brown solid
The temperature was raised from room temperature to 450 ° C. for about 2 hours and 30 minutes in an air stream of n, and calcined by heating at the same temperature for 3 hours to obtain 5.3 g of a black solid. The obtained black solid was 12 to 1
By adjusting to 8.5 mesh, a silica-supported ruthenium oxide catalyst was obtained. The calculated value of the ruthenium oxide content was 6.2% by weight. The calculated value of the ruthenium content was 4.7% by weight. The silica-supported ruthenium oxide catalyst thus obtained was filled in a quartz reaction tube in the same manner as in Example 1, and a reaction was carried out in accordance with the reaction method of Example 1. 1.8 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 2.0 × 10 ⁻⁴ mol / mi.
ng-catalyst. The activity of forming chlorine per unit Ru catalyst weight is 41.8 × 10 ⁻⁴ mol / min · g-Ru.
Met. At the outlet of the reaction tube, volatilization of the ruthenium compound as a catalyst component was not observed.

Example 22 A catalyst was prepared by the following method. That is, commercially available chloride
Ruthenium hydrate (RuCl_Three・ NH_TwoO) 0.70g
Dissolve in 3.0 g of water, stir well, and dissolve in ruthenium chloride
A liquid was obtained. The obtained aqueous solution is 12 to 18.5 mesh
Alumina dried in air at 500 ° C for 1 hour
Drops on 5.0 g of carrier (Sumitomo Aluminum Co., Ltd. NKHD)
In addition, ruthenium chloride was impregnated and supported. What was carried
Was dried at 60 ° C. for 4 hours to obtain a black-brown solid. Obtained
Black brown solid at room temperature under a nitrogen stream of 100 ml / min.
To 100 ° C in about 0.5 hour and at the same temperature for 2 hours
After drying, from room temperature under an air flow of 100 ml / min
Raise the temperature to 350 ° C in about 2 hours and heat at the same temperature for 3 hours
As a result, 5.2 g of a black solid was obtained. Get
Aligning the black solid to 12-18.5 mesh
As a result, an alumina-supported ruthenium oxide catalyst was obtained. What
The calculated value of the ruthenium oxide content is RuO_Two/ (Ru
O_Two+ Al_TwoO_Three) × 100 = 6.2% by weight. Le
The calculated value of the ruthenium content was 4.7% by weight. this
The alumina-supported ruthenium oxide catalyst thus obtained is
Filled into a quartz reaction tube as in Example 1,
200 ml / min and oxygen gas at 200 ml / min
The reaction was performed in accordance with the reaction method of Example 1 except that
Was. 1.7 hours after the start of the reaction, per unit catalyst weight
Has a chlorine generation activity of 1.55 × 10 ^-Fourmol / min.
g-catalyst. Chlorine formation activity per unit Ru weight
Is 33.0 × 10^-Fourmol / min-g-Ru
Was. At the outlet of the reaction tube, ruthenium, a catalyst component,
No volatilization of the compound was observed.

Example 23 A catalyst was prepared by the following method. That is, 0.70 g of commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) was dissolved in 1.4 g of water, and the mixture was stirred well to obtain a ruthenium chloride aqueous solution. The obtained aqueous solution was adjusted to 12 to 18.5 mesh, and dried in air at 500 ° C. for 1 hour, 5.0 g of a zirconium oxide carrier (Nikki Chemical Co., Ltd. E26H6).
Into the pores of the zirconium oxide carrier until it is almost immersed in the aqueous solution, vacuum-dry at 40 ° C. for 1 hour, and again add the ruthenium chloride aqueous solution again. I got The obtained black-brown solid was cooled to room temperature under nitrogen flow of 100 ml / min.
The temperature was raised to 00 ° C. in about 0.5 hour, and dried at the same temperature for 2 hours.
The temperature was raised to about 2 hours in about 2 hours, and calcined by heating at the same temperature for 3 hours to obtain 5.2 g of a black solid. The obtained black solid was adjusted to 12 to 18.5 mesh to obtain a zirconium oxide-supported ruthenium oxide catalyst.
The calculated value of the ruthenium oxide content is calculated as RuO ₂ / (R
uO ₂ + ZrO ₂ ) × 100 = 6.2% by weight. The calculated value of the ruthenium content is Ru / (RuO ₂ + ZrO ₂ )
× 100 = 4.7% by weight. The zirconium oxide-supported ruthenium oxide catalyst thus obtained was charged into a quartz reaction tube in the same manner as in Example 1, and hydrogen chloride gas was added to the reaction tube.
The reaction was carried out in accordance with the reaction method of Example 1 except that oxygen gas was passed at 213 ml / min at 02 ml / min. 2.5 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 4.0 × 10 ⁻⁴ mol / min ·
g-catalyst. The chlorine generation activity per unit Ru weight was 85 × 10 ⁻⁴ mol / min · g-Ru. At the outlet of the reaction tube, volatilization of the ruthenium compound as a catalyst component was not observed.

Example 24 A catalyst was prepared by the following method. That is, 0.70 g of commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) was dissolved in 1.4 g of water, and the mixture was stirred well to obtain a ruthenium chloride aqueous solution. The obtained aqueous solution was adjusted to 12 to 18.5 mesh, and dried in air at 500 ° C. for 1 hour. 5.0 g of a titanium oxide carrier (CS-300S, Sakai Chemical Industry Co., Ltd.).
Was added dropwise, and ruthenium chloride was impregnated and supported. The supported material was heated from room temperature to 100 ° C. in about 0.5 hour under a nitrogen stream of 100 ml / min and dried at the same temperature for 2 hours.
The temperature was raised to 0 ° C. in about 2 hours, and calcined by heating at the same temperature for 3 hours to obtain 5.2 g of a black solid. The obtained black solid was adjusted to 12 to 18.5 mesh to obtain a titanium oxide-supported ruthenium oxide catalyst. In addition,
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 / (RuO ₂ + TiO ₂ ) × 10
0 = 4.7% by weight. The titanium oxide-supported ruthenium oxide catalyst thus obtained was filled in a quartz reaction tube in the same manner as in Example 1 except that the catalyst was not diluted with titanium oxide, and hydrogen chloride gas was added at 200 ml / min and oxygen gas was added at 200 ml / min.
The reaction was carried out in accordance with the reaction method of Example 1 except that the mixture was distributed in a minimum. 1.8 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 2.37 × 10 ⁻⁴ mol / mi.
ng-catalyst. The production activity of chlorine per unit weight of Ru was 50.4 × 10 ⁻⁴ mol / min · g-Ru. At the outlet of the reaction tube, volatilization of the ruthenium compound as a catalyst component was not observed.

Example 25 A catalyst was prepared by the following method. That is, 0.84 g of a commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) was dissolved in 2.2 g of water and stirred well to obtain an aqueous ruthenium chloride solution. The obtained aqueous solution was adjusted to 200 mesh or less, added dropwise to 6.0 g of a titanium oxide carrier (CS-300, Sakai Chemical Industry Co., Ltd.) calcined at 350 ° C. for 1 hour in the air, and impregnated with ruthenium chloride. . The support was dried in air at 60 ° C. for 1 hour to obtain a black powder. To this powder, about 2.5 g of an aqueous solution of 2.1 g of commercially available cesium nitrate dissolved in 9.6 g of water was dropped until the pores of the powder were almost saturated, and then dried at 60 ° C. in air for 0.5 hour. did. By repeating this operation five times, the whole amount is dropped,
2.1 g of cesium nitrate was impregnated and supported. The support was dried in air at 60 ° C. for 4 hours, and then dried in air at room temperature for 3 hours.
The temperature was raised to 50 ° C. in 3 hours and calcined at the same temperature for 3 hours to obtain 7.94 g of powder. After washing the obtained powder three times with 0.5 l of water using a glass filter,
5.88 g of green-black powder after drying in air at 60 ° C. for 4 hours
I got This powder was molded to have a mesh size of 12 to 18.5 to obtain a ruthenium oxide catalyst supporting titanium oxide. The calculated value of the ruthenium oxide content was 6.2% by weight. The calculated value of the ruthenium content was 4.7% by weight. The titanium oxide-supported ruthenium oxide catalyst thus obtained, 2.50 g, was thoroughly mixed with 5 g of a titanium oxide carrier having a size of 12 to 18.5 mesh to dilute the catalyst. The reaction was carried out in accordance with the reaction method of Example 1 except for filling and setting the internal temperature to 299 ° C. 1.3 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 4.58 × 10 ⁻⁴ mol / m.
ing-catalyst. The chlorine generation activity per unit Ru weight was 97.4 × 10 ⁻⁴ mol / min · g-Ru. At the outlet of the reaction tube, volatilization of the ruthenium compound as a catalyst component was not observed.

Comparative Example 1 A catalyst was prepared by the following method. That is, 0.70 g of commercially available ruthenium chloride hydrate (RuCl ₃ .3H ₂ O) was dissolved in 4.0 g of water, and a well-stirred ruthenium chloride aqueous solution was obtained. The obtained aqueous solution was adjusted to 12 to 18.5 mesh, and dried in air at 500 ° C. for 1 hour. A silica gel carrier (Carry Act G-Fuji Silysia Ltd.)
10) Added dropwise to 5.0 g, and impregnated with ruthenium chloride. The supported product was dried at 60 ° C. for 4 hours to obtain a black-brown solid. 100 ml / m of the obtained black-brown solid
The temperature was raised from room temperature to 120 ° C. in about 0.5 hour under a nitrogen stream of in, and dried at the same temperature for 2 hours, then 100 ml / mi.
The temperature was raised from room temperature to 250 ° C. in about 1.5 hours under an air stream of n, and dried by heating at the same temperature for 3 hours to obtain 5.4 g of a black solid. The obtained black solid was 12 to 1
By adjusting the size to 8.5 mesh, a ruthenium chloride catalyst supported on silica was obtained. The calculated value of the content of ruthenium chloride is calculated as follows: RuCl ₃ / (RuCl ₃ + SiO ₂ ) × 100
= 9.3% by weight. The calculated value of the ruthenium content is
Ru / (RuCl ₃ + SiO ₂ ) × 100 = 4.5% by weight
Met. 2.5 g of the silica-supported ruthenium chloride catalyst thus obtained was placed in a quartz reaction tube in the same manner as in Example 1.
Filled. Example 1 except that hydrogen chloride gas was passed at 202 ml / min and oxygen gas was passed at 213 ml / min.
The reaction was carried out according to the reaction method described above. 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.
The activity of forming chlorine per unit weight of Ru is 10.8 × 10 ^−4.
mol / min.g-Ru. Further, the volatilization of the ruthenium compound as a catalyst component was observed at the outlet of the reaction tube as a brown compound, and the generated water was also colored orange.

Comparative Example 2 A catalyst was prepared by the following method. That is, 0.84 g of commercially available ruthenium chloride hydrate (RuCl ₃ .3H ₂ O) was dissolved in 6.0 g of water, and a well-stirred ruthenium chloride aqueous solution was obtained. The obtained aqueous solution was adjusted to 12 to 18.5 mesh, and dried in air at 500 ° C. for 1 hour. A silica gel carrier (Carry Act G-Fuji Silysia Ltd.)
10) It was added dropwise to 6.0 g, and ruthenium chloride was impregnated and supported. The temperature of the loaded material was increased from room temperature to 100 ° C. in about 1 hour under a nitrogen stream of 100 ml / min, and dried at the same temperature for 2 hours. Dried by heating for 3 hours,
6.48 g of a black solid were obtained. The obtained black solid was 12
By adjusting the size to １８18.5 mesh, a silica-supported ruthenium chloride catalyst was obtained. The calculated value of the ruthenium chloride content was calculated as RuCl ₃ / (RuCl ₃ + SiO ₂ ) × 1.
00 = 9.4% by weight. The calculated value of the ruthenium content was Ru / (RuCl ₃ + SiO ₂ ) × 100 = 4.6% by weight. 1. The silica-supported ruthenium chloride catalyst thus obtained was placed in a quartz reaction tube in the same manner as in Example 1.
5 g were filled. 187 ml / min of hydrogen chloride gas,
The reaction was carried out according to the reaction method of Example 1 except that oxygen gas was passed at 200 ml / min. 1. Start of reaction
After 6 hours, the activity of forming chlorine per unit weight of the catalyst was 0.17 × 10 ⁻⁴ mol / min · g-catalyst. The activity of forming chlorine per unit Ru weight is 3.8 × 10
^-4 mol / min.g-Ru. Further, volatilization of the ruthenium compound as a catalyst component was observed as a brown compound at the outlet of the reaction tube.

Comparative Example 3 A catalyst was prepared by the following method. That is, 0.70 g of commercially available ruthenium chloride hydrate (RuCl ₃ .3H ₂ O) was dissolved in 3.0 g of water, and a well-stirred ruthenium chloride aqueous solution was obtained. The obtained aqueous solution was adjusted to 12 to 18.5 mesh and dried in air at 500 ° C. for 1 hour, 5.0 g of alumina carrier (NKHD-24, Sumitomo Aluminum Co., Ltd.).
Was added dropwise, and ruthenium chloride was impregnated and supported. The supported product was dried at 60 ° C. for 4 hours to obtain a black-brown solid. The resulting black-brown solid was heated from room temperature to 100 ° C. for about 0.5 hours under a nitrogen stream at 100 ml / min and dried at the same temperature for 2 hours, and then dried from room temperature to 250 ° C. under a 100 ml / min air stream. The temperature was raised in 1.5 hours and dried by heating at the same temperature for 3 hours to obtain a black solid 5.2.
g was obtained. The obtained black solid was adjusted to 12 to 18.5 mesh to obtain a ruthenium chloride catalyst supported on alumina. The alumina-supported ruthenium chloride catalyst thus obtained was placed in a quartz reaction tube in the same manner as in Example 1 for 2.5 times.
g. The reaction was carried out according to the reaction method of Example 1 except that hydrogen chloride gas was passed at 200 ml / min and oxygen gas was passed at 200 ml / min. Reaction start 1.8
After a lapse of time, the activity of forming chlorine per unit weight of the catalyst was 0.45 × 10 ⁻⁴ mol / min · g-catalyst.
The activity of forming chlorine per unit Ru weight is 10.0 × 10 ^-4.
mol / min.g-Ru.

Comparative Example 4 A catalyst was prepared by the following method. That is, 60.3 g of chromium nitrate nonahydrate was dissolved in 600 ml of water,
The temperature was raised to 5 ° C. and 25% by weight of aqueous ammonia 6 was stirred.
4.9 g was added dropwise over 1.5 hours, and stirring was continued at the same temperature for 30 minutes. To the generated precipitate, 3.3 l of water was added, and the mixture was allowed to stand overnight. After settling, the supernatant was removed by decantation. Next, 2.7 l of water was added, and the mixture was stirred well for 30 minutes. This operation was repeated 5 times to wash the precipitate, the supernatant was removed by decantation, 49 g of 20% by weight silica sol was added, and the mixture was stirred and evaporated to dryness at 60 ° C. using a rotary evaporator. Next, at 60 ° C., 8
After drying for an hour, and further drying at 120 ° C. for 6 hours, a green solid was obtained. The solid was dried in a nitrogen stream at 120 ° C. for 6 hours, and then cooled to room temperature to obtain a green solid. Next, this was baked at 600 ° C. for 3 hours in the air and formed into a mesh of 12 to 18.5 to obtain a Cr ₂ O ₃ —SiO ₂ catalyst. 2.5 g of the Cr ₂ O ₃ —SiO ₂ catalyst 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 192 ml / min of hydrogen chloride gas. And the internal temperature is 3
The procedure was performed according to Example 2 except that the temperature was set to 01 ° C.
3.7 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 0.19 × 10 ⁻⁴ mol / min · g.
It was a catalyst.

Comparative Example 5 A catalyst was prepared by the following method. That is, 41.9 g of commercially available tetraethyl orthosilicate was dissolved in 93 ml of ethanol, and 56.8 g of titanium tetraisopropoxide was added while stirring at room temperature. After stirring at room temperature for 1 hour, a solution obtained by thoroughly mixing 93 ml of ethanol 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 added dropwise. A white precipitate formed as the solution was added. After completion of the dropwise addition, the mixture was stirred at room temperature for 0.5 hour, and then heated with stirring.
The mixture was refluxed for 1 hour on an oil bath at ℃. The liquid temperature at this time was 80 ° C. Next, the solution was allowed to cool, filtered through a glass filter, and washed with 500 ml of pure water.
Filtered again. After repeating this operation twice,
It was dried at 0 ° C for 1 hour, heated from room temperature to 550 ° C for 1.5 hours, and calcined at the same temperature for 3 hours to obtain 27.4 g.
A white solid was obtained. The obtained solid was pulverized to obtain titania silica powder. 8.0 g of the obtained titania silica powder
Commercially available ruthenium chloride hydrate (Ru content 35.5%)
After impregnating a liquid in which 1.13 g is dissolved in 8.2 g of water,
After drying in air at 60 ° C. for 1 hour, ruthenium chloride was supported. Next, the supported material was heated from room temperature to 300 ° C. for 1 hour and 30 minutes under a mixed gas flow of 50 ml / min of hydrogen and 100 ml / min of nitrogen, and reduced at the same temperature for 1 hour.
The mixture was allowed to cool to room temperature to obtain 8.4 g of black metal ruthenium-supported titania silica powder. 8.4 g of the titania silica-supported metal ruthenium powder was heated from room temperature to 6 g under an air atmosphere.
The temperature was raised to 00 ° C. in 3 hours and 20 minutes and calcined at the same temperature for 3 hours to obtain 8.5 g of a black powder. The obtained powder was molded and made into a mesh of 12 to 18.5 to obtain a ruthenium oxide catalyst supported on titania silica. The calculated value of the ruthenium oxide content is calculated as RuO ₂ / (Ru
O ₂ + TiO ₂ + SiO ₂ ) × 100 = 6.2% by weight. The calculated value of the ruthenium content is Ru / (RuO ₂ +
TiO ₂ + SiO ₂ ) × 100 = 4.7% by weight.
2.5 g of the titania silica-supported ruthenium oxide catalyst thus obtained was charged into a reaction tube in the same manner as in Example 1,
The reaction was performed according to the reaction method of Example 1. 2 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 0.1.
It was 46 × 10 ⁻⁴ mol / min · g-catalyst. The activity of forming chlorine per unit Ru weight is 9.77 × 10 ⁻⁴ mo.
1 / min · g-Ru.

Comparative Example 6 A catalyst was prepared by the following method. First, the carrier silica was subjected to ion exchange. 10 g of commercially available aerosil silica (Aerosil 300, Nippon Aerosil Co., Ltd.) was placed in a glass flask, and then 200 ml of water was placed therein, heated and refluxed for 1 hour. Cool to room temperature and add 2
16.2 g of 5% by weight aqueous ammonia and 700 ml of water were added and left for 2 days. Next, the aerosil silica was separated by filtration, washed well with water, and sufficiently dried in air at 60 ° C. to obtain 8.07 g of an NH ⁴⁺ -type silica carrier. 3.7 g of this silica carrier and 120 ml of water are placed in a glass flask,
While heating to 60 ° C. in an oil bath, with stirring, [Ru
A solution obtained by dissolving 5.0 g of (NH ₃ ) ₆ ] Cl _{3 in} 1500 ml of water was gradually added dropwise, and then stirred at the same temperature for 2 hours. After completion of stirring, use a rotary evaporator.
The mixture was evaporated to dryness while heating to 60 ° C. to obtain a yellow powder. This powder was calcined in an air stream at 456 ° C. for 3 hours to obtain 5.5 g of a black solid. The obtained black solid was 12 to 1
By adjusting to 8.5 mesh, a silica-supported ruthenium oxide catalyst was obtained. The calculated value of the content of ruthenium oxide is calculated as RuO ₂ / (RuO ₂ + SiO ₂ ) × 100 = 3.
It was 6% by weight. The calculated value of the ruthenium content is Ru /
(RuO ₂ + SiO ₂ ) × 100 = 27% by weight.
A reaction tube was prepared in the same manner as in Example 1 except that the catalyst was diluted by thoroughly mixing 2.5 g of the silica-supported ruthenium oxide catalyst obtained in this way with 5 g of a titanium oxide carrier prepared in 12 to 18.5 mesh. Filled. Hydrogen chloride gas at 194 ml / min, oxygen gas at 198 ml / min
The reaction was carried out in accordance with the reaction method of Example 1 except that the reaction was conducted as described above. 1.8 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 3.86 × 10 ⁻⁴ mol / m.
ing-catalyst. The activity of forming chlorine per unit Ru catalyst weight is 14.1 × 10 ⁻⁴ mol / min · g-R.
u.

[0076]

As described above, according to the present invention, when oxidizing hydrogen chloride to produce chlorine, a catalyst having a high activity and a high activity per contained ruthenium is used, and a smaller amount of the catalyst is used. A method for producing chlorine capable of producing chlorine at a lower reaction temperature can be provided.

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[Submission date] April 7, 1998

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 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 8-302655 (32) Priority date Hei 8 (November 14, 1996) (33) Priority claim country Japan (JP)

Claims (16)

[Claims] 1. A method for producing chlorine, wherein hydrogen chloride is oxidized by oxygen in the presence of at least one catalyst selected from the following (A) to (D). (A): a supported ruthenium chloride catalyst in which the carrier contains at least one compound of titanium oxide and zirconium oxide, wherein the weight ratio of ruthenium to the carrier is 0.5 to 20% by weight. (B): ruthenium carbonyl Complex, ruthenium organic acid salt, ruthenium nitrosyl complex, ruthenium ammine complex, ruthenium ammine complex chloride, ruthenium organic amine complex, ruthenium acetylacetonate complex at least one ruthenium compound selected from the group consisting of a ruthenium compound supported on a carrier. And a catalyst in which the weight ratio of ruthenium to the carrier is 0.5 to 20% by weight (C): chlororuthenate, chlororuthenate hydrate, ruthenate salt, ruthenium oxychloride salt, ruthenium ammine Complex, chloride or bromide of ruthenium ammine complex, Ruthenium bromide, ruthenium organic amine complex, ruthenium acetylacetonato complex,
A ruthenium oxide catalyst obtained by oxidizing a catalyst having at least one ruthenium compound selected from the group consisting of a ruthenium carbonyl complex, a ruthenium organic acid salt, a ruthenium nitrosyl complex, and a ruthenium phosphine complex, wherein the ruthenium and the carrier Has a weight ratio of 0.
5 to 20% by weight of a catalyst (D): a ruthenium chloride catalyst supported on a carrier was treated with 28
Catalyst obtained by calcination at a temperature of 0 ° C or higher 2. The process according to claim 1, wherein the weight ratio of ruthenium to the carrier of the catalyst (A) according to claim 1 is 1 to 8% by weight. 3. The process according to claim 1, wherein the support of the catalyst (A) according to claim 1 is titanium oxide. 4. The method according to claim 1, wherein the catalyst (A) according to claim 1 is a catalyst further containing titanium chloride. 5. The process according to claim 1, wherein the weight ratio of ruthenium to the carrier of the catalyst (B) according to claim 1 is 1 to 8% by weight. 6. The catalyst according to claim 1, wherein the catalyst (B) has at least one ruthenium compound selected from the group consisting of ruthenium carbonyl complex, ruthenium acetate and ruthenium nitrosyl complex supported on a carrier. Manufacturing method. 7. The process according to claim 1, wherein the weight ratio of ruthenium to the carrier of the catalyst (C) according to claim 1 is 1 to 8% by weight. 8. The catalyst (C) according to claim 1, wherein the ruthenium compound is a salt of ruthenic acid, a ruthenium ammine complex, a chloride of a ruthenium ammine complex, ruthenium bromide, a ruthenium organic amine complex, a ruthenium acetylacetonate complex, ruthenium. The production method according to claim 1, wherein the production method is at least one ruthenium compound selected from the group consisting of a carbonyl complex, a ruthenium organic acid salt, and a ruthenium nitrosyl complex. 9. The catalyst (C) according to claim 1, wherein the ruthenium compound is at least one selected from the group consisting of a ruthenium ammine complex, a chloride of a ruthenium ammine complex, a ruthenium carbonyl complex, a ruthenium acetate, and a ruthenium nitrosyl complex. The production method according to claim 1, wherein the production method is a ruthenium compound. 10. The process according to claim 1, wherein the ruthenium compound of the catalyst (C) according to claim 1 is at least one ruthenium compound selected from the group consisting of ruthenium ammine complex chloride and ruthenium nitrosyl nitrate. 11. The production method according to claim 1, wherein the oxidation treatment of the catalyst (C) according to claim 1 is performed at 280 to 500 ° C. 12. The process according to claim 1, wherein the catalyst (D) according to claim 1 is a catalyst obtained by calcining ruthenium chloride supported on a carrier at a temperature of 280 to 500 ° C. 13. The method according to claim 1, wherein the calcination temperature of the catalyst (D) according to claim 1 is 300 to 450 ° C. 14. The support of the catalyst (D) according to claim 1,
2. The production method according to claim 1, wherein the production method is titanium oxide or zirconium oxide. 15. The catalyst (D) according to claim 1, wherein the weight ratio of ruthenium to the carrier is 0.5 to 20% by weight.
The manufacturing method as described. 16. The reaction temperature for oxidizing hydrogen chloride with oxygen is 200 to 380 ° C., the reaction pressure is atmospheric pressure to 50 atm,
2. The method according to claim 1, wherein pure oxygen is used as oxygen, and the molar ratio of hydrogen chloride to oxygen is 0.1 / 4 to 10/4.