JPH10338502A - Production of chlorine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain chlorine with a smaller quantity of a catalyst at a lower temp. by oxidizing hydrogen chlorine with oxygen in the presence of a specific carried ruthenium oxide catalyst or ruthenium multiple oxide catalyst. SOLUTION: The carried ruthenium oxide catalyst is obtained by carrying 0.1-20 wt.% ruthenium oxide having 1.0-10.0 nm central particle diameter on 99.9-80 wt.% carrier such as titanium oxide, alumina and zirconium oxide or the ruthenium oxide multiple oxide type catalyst containing 0.1-20 wt.% ruthenium oxide having 1.0-10 nm central particle diameter is obtained by hydrolyzing an (oxy) chloride of titanium or the like dissolved in water, adding an alkali hydrolyzed material of a ruthenium compound dissolved in water and firing in the air at 300-500 deg.C. Chlorine is obtained by supplying hydrogen chloride and a quantity of oxygen 0.1-10 times, preferably 0.2-5 times the theoretical quantity to hydrogen chloride and oxidizing in the presence of the catalyst at 90-150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD OF THE INVENTION

[0001] The present invention relates to a method for producing chlorine. More specifically, the present invention relates to a method for producing chlorine by oxidizing hydrogen chloride, which is characterized by using a highly active catalyst and producing chlorine at a lower reaction temperature with a smaller amount of catalyst. And a method for producing the same.

[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, a Deacon reaction using a Cu-based catalyst is well known. Further, for example, British Patent No. 1,046,313 describes a method of oxidizing hydrogen chloride using a catalyst containing a ruthenium compound, and further, among the ruthenium compounds, particularly, ruthenium (III) chloride Is also stated to be effective. Further, a method in which a ruthenium compound is used by being supported on a carrier is also described.
Alumina, pumice, and ceramic materials are exemplified. As an example, a ruthenium chloride catalyst supported on silica is mentioned. However, when an experiment was conducted using a catalyst prepared by following the method for preparing a silica-supported ruthenium chloride (III) catalyst described in the patent, the volatilization of the ruthenium compound as a catalyst component was intense,
It was found to be inconvenient for industrial use. Also,
For example, European Patent EP 0 844 413 A2 describes a method for oxidizing hydrogen chloride using a chromium oxide catalyst. However, the conventionally known method has a problem that the activity of the catalyst is insufficient and a high reaction temperature is required.

[0003] When the activity of the catalyst is low, a higher reaction temperature is required. However, the reaction of oxidizing hydrogen chloride with oxygen to produce chlorine is an equilibrium reaction. And the equilibrium conversion of hydrogen chloride decreases. Therefore, if the catalyst has high activity, the reaction temperature can be lowered, and the reaction becomes equilibrium advantageous, and a higher conversion of hydrogen chloride can be obtained. In addition, when the reaction temperature is high, there is a possibility that the activity may be reduced due to volatilization of the catalyst component, and from this point, development of a catalyst having high activity and usable at low temperature has been desired.

[0004] Industrially, both high catalytic activity and high catalytic 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 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]

Under such circumstances, an object of the present invention is to provide a method for producing chlorine by oxidizing hydrogen chloride, using a highly active catalyst and using a smaller amount of chlorine. It is an object of the present invention to provide a method for producing chlorine which can produce chlorine at a lower reaction temperature with a catalyst.

[0006]

The first aspect of the present invention is a method for producing chlorine by oxidizing hydrogen chloride with oxygen, wherein the content of ruthenium oxide is 0.1%.
-20% by weight, and the central particle size of ruthenium oxide is 1.
The present invention relates to a method for producing chlorine using a supported ruthenium oxide catalyst or ruthenium oxide composite oxide type catalyst having a particle size of 0 to 10.0 nanometers.

A second aspect of the present invention is a method for producing chlorine by oxidizing hydrogen chloride with oxygen, wherein the supported ruthenium oxide catalyst has a ruthenium oxide content of 0.5 to 20% by weight. The present invention relates to a method for producing chlorine using

[0008] A third aspect of the present invention is a method for producing chlorine by oxidizing hydrogen chloride with oxygen, which comprises converting a supported metal ruthenium catalyst into a gas containing oxygen.
The present invention relates to a method for producing chlorine using a supported ruthenium oxide catalyst oxidized at 0 ° C. or lower.

A fourth aspect of the present invention is a method for producing chlorine by oxidizing hydrogen chloride with oxygen, wherein a supported metal ruthenium catalyst is prepared in a gas containing oxygen in the presence of an alkali metal salt. The present invention relates to a method for producing chlorine using a supported ruthenium oxide catalyst obtained by calcination.

A fifth aspect of the present invention is a method for producing chlorine by oxidizing hydrogen chloride with oxygen, comprising a supported ruthenium oxide catalyst supported on a spherical carrier having a particle size of 10 to 500 μm. The present invention relates to a method for producing chlorine using

A sixth aspect of the present invention is a method for producing chlorine by oxidizing hydrogen chloride with oxygen, comprising extruding a ruthenium oxide catalyst or a catalyst in which an inert carrier is coated with a ruthenium oxide catalyst. And a method for producing chlorine using the catalyst.

A seventh aspect of the present invention relates to a method for producing chlorine by oxidizing hydrogen chloride with oxygen, and relates to a method for producing chlorine using a ruthenium catalyst in an aqueous phase.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The ruthenium oxide catalyst having a center particle size of 1.0 to 10.0 nanometers used in the present invention has a ruthenium oxide content of 0.1 to 20% by weight, The catalyst is a composite oxide of ruthenium and another metal, and contains a supported ruthenium oxide catalyst using ruthenium oxide as a carrier. Generally, industrially, it is used in a form supported on a carrier.

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.
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 15.0.0. 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.

A third component other than ruthenium can be added. As the third component, a noble metal compound other than ruthenium such as a palladium compound, a rare earth compound, a copper compound, a chromium compound, a nickel compound, an alkali metal compound, an alkali metal compound, Examples include earth metal compounds, manganese compounds, tantalum compounds, tin compounds, vanadium compounds and the like. The addition amount of the third component is usually 0.1 to 10% by weight as a ratio to the carrier.

As the ruthenium oxide composite oxide type catalyst, one of oxides such as titanium oxide, zirconium oxide, alumina, silica, vanadium oxide, boron oxide, chromium oxide, niobium oxide, hafnium oxide, tantalum oxide, and tungsten oxide is used. The compound obtained by compounding the above with ruthenium oxide is obtained, but the compound forming ruthenium oxide is not limited to the above compounds.

The center particle size of ruthenium oxide is 1.0 to 1
An example of a method for preparing a composite oxide type catalyst comprising 0.0 nm of ruthenium and another metal will be described below. As a method of compounding ruthenium oxide, chlorides such as titanium dissolved in water, oxychlorides, nitrates, oxynitrates, alkali salts of oxyacids and sulfates are converted to alkali metals such as alkali metal hydroxides and aqueous ammonia. In addition, to a product obtained by hydrolyzing an alkoxide or the like with an acid, a product obtained by hydrolyzing a ruthenium compound such as ruthenium chloride dissolved in water with an alkali such as an alkali metal hydroxide or ammonia water is added, and mixed well. Examples of the method include filtration, washing, and calcination in air. The firing temperature is usually 300 to 5
00 ° C. Preferable examples of the oxide that forms ruthenium oxide include titanium oxide, zirconium oxide, alumina, silica, a titanium composite oxide, a zirconium composite oxide, an aluminum composite oxide, and a silicon composite oxide.

Further, the ruthenium oxide composite oxide may be supported on a carrier. Examples of a method of supporting the ruthenium oxide composite oxide on a carrier include a method of impregnating the carrier with a chloride such as titanium, a nitrate or the like, and a ruthenium compound such as ruthenium chloride, and then calcining in air. As the carrier, the carrier described in the section of the supported ruthenium oxide catalyst can be used similarly. The content of ruthenium oxide contained in the ruthenium composite oxide is usually 0.1 to 20% by weight,
Preferably it is 0.5 to 15% by weight, more preferably 1 to 15% by weight. In addition, a third component can be added, and as the third component, the third component described in the section of the supported ruthenium oxide catalyst can be similarly used.

The center particle size of ruthenium oxide is 1.0 to 1
An example of a method for preparing a 0.0 nm ruthenium oxide catalyst is described below. Ruthenium chloride (RuCl ₃・ n
H ₂ O) is dissolved in a dilute hydrochloric acid aqueous solution to prepare a ruthenium chloride aqueous solution. After allowing the aqueous solution to stand for one day, a carrier powder such as titanium oxide is suspended in the aqueous solution, and an aqueous alkali metal hydroxide solution is added dropwise with stirring, and a predetermined p.
While controlling to H, hydrolysis is carried out while ruthenium chloride is precipitated and supported on the carrier. Further, the suspension is heated while controlling to a predetermined pH to promote hydrolysis.
The pH is usually from 3 to 7, and the heating temperature is from 5 to 7.
0-70 ° C is normal. The heating time is usually 1 to 10 hours. The suspension is then heated and evaporated to dryness. The temperature for evaporation to dryness is usually 40 to 150 ° C. at the external temperature, and drying under reduced pressure is also possible. Also, after allowing the suspension to stand, remove the supernatant by decantation,
It can also be evaporated to dryness. Next, primary baking is performed at 100 to 200 ° C. for 2 hours to 24 hours.
Secondary firing for 24 hours. Next, a method of removing the alkali metal chloride contained in the catalyst by washing with water and drying at about 100 ° C. is exemplified. The atmosphere for the above preparation is air.

In addition to the above-mentioned preparation method, the following method may be mentioned as an example of a method for preparing a ruthenium oxide catalyst in which the center particle size of ruthenium oxide is 1.0 to 10.0 nanometers.

That is, the supported metal ruthenium catalyst is impregnated with an aqueous solution of an alkali metal salt, dried, calcined in a gas containing oxygen, washed with water, and dried. As the supported metal ruthenium catalyst, a catalyst having a small metal ruthenium particle diameter is preferable. As a method for preparing the supported metal ruthenium catalyst, for example, a method in which ruthenium chloride is supported on the above-described carrier and then reduced with hydrogen, after supporting ruthenium chloride on the above-described carrier, ruthenium hydroxide is applied on the carrier by alkali hydrolysis. And reducing it with hydrogen or the like. A commercially available supported metal ruthenium catalyst having a small metal ruthenium particle diameter may be used. Commercially available supported metal ruthenium catalysts having a small metal ruthenium particle size include commercially available spherical 2% by weight supported metal ruthenium titanium oxide catalyst and spherical 5% by weight.
And a supported metal ruthenium titanium oxide catalyst (manufactured by NE Chemcat). The alkali metal salt / ruthenium molar ratio is preferably 0.01 to 10,
0.1-5 is more preferable. The firing temperature is 280-4
50 ° C. is preferred. The firing time is usually 30 minutes to 10 hours. The added alkali metal salt is removed by washing with water, but may remain as long as the catalytic activity of the present catalyst is not impaired.

The above ruthenium oxide has a center particle diameter of 1.0.
A ruthenium oxide catalyst, 〜10.0 nanometers,
It can be prepared later by the preparation method described in the section of precipitated supported ruthenium oxide catalyst, or the supported oxide obtained by calcining the supported metal ruthenium in the presence of an alkali metal salt in a gas containing oxygen later. It can also be prepared by the preparation method described in the section of the ruthenium catalyst.

In the supported ruthenium oxide catalyst prepared in the above example, ruthenium oxide having a center particle size of 1.0 to 10.0 nanometers is supported on a carrier, and the particle size of the ruthenium oxide is a transmission type It can be measured with a microscope or the like. The central particle size is a statistical average value of the observed particle size of ruthenium oxide, but can be substituted by an arithmetic mean of the particle sizes occupying a large number of the observed particles.

Generally, the particle size of metal ruthenium can be measured by adsorbing carbon monoxide after hydrogen reduction of a supported ruthenium oxide catalyst, and the measured value is as follows:
As long as there is no large error as compared with the value measured by the transmission electron microscope, it can be substituted.

If the center particle size exceeds 10.0 nanometers, the catalytic activity decreases, so the range of 1.0 to 10.0 nanometers is appropriate, and the range of 1.0 to 6.0 nanometers is more preferable. preferable. In addition, 1.0 to 1 within the above range.
The percentage of 0.0 nanometer ruthenium oxide particles is 80
% Is preferable. Further, a catalyst having a smaller central particle diameter in the above range is preferable because of high activity.

Whether the ruthenium compound contained in the catalyst is ruthenium oxide can be confirmed by analysis such as X-ray diffraction or XPS (X-ray photoelectron spectroscopy).

According to the present invention, the content of ruthenium oxide is set to 0.1.
Supported ruthenium oxide catalysts that are from 5 to 20% by weight can also be used. If the content of ruthenium oxide is more than 20% by weight, the activity per unit ruthenium contained decreases, but if it is less than 0.5% by weight, the activity per unit ruthenium decreases. The supported ruthenium oxide includes ruthenium oxide such as ruthenium dioxide and ruthenium hydroxide.

There are various supporting methods. For example, a preferred example is a method for preparing a precipitation-supported ruthenium oxide catalyst. That is, a method in which a carrier is suspended in a solution in which a ruthenium compound such as ruthenium chloride is dissolved, an alkali is added, and the carrier is hydrolyzed to be precipitated and supported on the carrier as ruthenium hydroxide, and this is oxidized to ruthenium oxide. Is raised. The preferred ruthenium compound is ruthenium chloride. In this case, the oxidation may be performed using a hydrogen peroxide solution or oxygen.
When calcination is performed using air, the calcination temperature is preferably 300 to 400 ° C.

As a support for the supported ruthenium oxide catalyst,
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 are preferable. , Alumina, zirconium oxide and silica, and a more preferred carrier is titanium oxide. The ratio of ruthenium oxide to the support is usually between 0.5 / 99.5 and 20/80, preferably between 1.0 / 99.0 and 15/85.

If the ratio of ruthenium is too low, the activity may decrease, and if the ratio of ruthenium is too high, the price of the catalyst may increase. In addition, a third component other than ruthenium can be added, and as the third component, palladium, a copper compound, a chromium compound, a vanadium compound,
Nickel compounds, alkali metal compounds, rare earth compounds,
Manganese compounds, alkaline earth compounds and the like can be mentioned. The addition amount of the third component is usually 0.1 to 10% by weight as a ratio to the carrier.

An example of a method for preparing the catalyst is described below. That is,
Ruthenium chloride (RuCl ₃ .nH ₂ O) is dissolved in a dilute hydrochloric acid aqueous solution to prepare a ruthenium chloride aqueous solution. After allowing the aqueous solution to stand for one day, a carrier powder such as titanium oxide is suspended in the aqueous solution, and an alkaline aqueous solution of an alkali metal hydroxide is added dropwise with stirring, and ruthenium chloride is precipitated and supported on the carrier while controlling to a predetermined pH. And hydrolyze. Further, the suspension is heated while controlling to a predetermined pH to promote hydrolysis. The pH is usually 3 to 7, and the heating temperature is usually 50 to 70C. The heating time is usually 1 to 10 hours. Next, the suspension is heated to evaporate to dryness. The suspension may be directly heated to evaporate to dryness, or may be filtered, washed with water and evaporated to dryness. When evaporated to dryness as it is, it is possible to obtain a ruthenium oxide catalyst having a smaller particle size. The temperature for evaporation to dryness is usually 40 to 150 ° C. at the external temperature, and drying under reduced pressure is also possible. Alternatively, after the suspension is allowed to stand, the supernatant may be removed by decantation and then evaporated to dryness. Next, 100-200
C. for 2 to 24 hours at 300 ° C. for 2 to 24 hours.
Secondary firing for 24 hours. Next, a method of removing the alkali metal chloride contained in the catalyst by washing with water and drying at about 100 ° C. is exemplified. The atmosphere for the above preparation is air.

In the present invention, a catalyst obtained by oxidizing a supported metal ruthenium catalyst in a gas containing oxygen at 500 ° C. or lower can also be used. Note that a catalyst obtained by oxidizing a supported metal ruthenium catalyst in a gas containing oxygen at 280 to 450 ° C. is preferable because of high activity. By the oxidation treatment, high activation of the catalyst can be easily achieved.

The supported ruthenium catalyst which is used industrially and is commercially available is generally a supported metal ruthenium catalyst. Therefore, the catalyst in the present invention may be prepared by using an existing catalyst or a catalyst prepared for industrial use. It has the advantage that the technology can be easily diverted and the catalyst can be obtained more cheaply and more easily.

The catalyst obtained by oxidizing the supported metal ruthenium catalyst can also be prepared by putting the supported metal ruthenium catalyst into a reactor and calcining the same in a gas containing oxygen. Further, a catalyst obtained by oxidizing a supported metal ruthenium catalyst in advance can be used in a reactor. Air is usually used as the gas containing oxygen.

As the carrier of the catalyst used by oxidizing the supported metal ruthenium, alumina, silica, silica-alumina, zeolite, diatomaceous earth, vanadium oxide, zirconium oxide, or titanium oxide may be used as in the case of the supported metal ruthenium catalyst. Oxides and composite oxides of such elements, and metal sulfates, and the like, and preferred carriers are titanium oxide, zirconium oxide, alumina, zeolite, silica, titanium composite oxides other than titania silica, zirconium composite oxide, Aluminum composite oxides, and more preferred carriers are titanium oxide, zirconium oxide, and alumina. An even more preferred carrier is titanium oxide.

The weight ratio of ruthenium oxide to the carrier in the catalyst obtained by oxidizing the supported metal ruthenium catalyst is usually 0.1 / 99.9 to 20/80, and 0.5 / 9 to 20/80.
It is preferably from 9.5 to 15/85, more preferably 1.
0 / 99.0 to 15/85. If the amount of ruthenium is too small, the catalytic activity may decrease, and if the amount of ruthenium is excessive, the catalyst price may increase.

As a method for producing a catalyst obtained by oxidizing a supported metal ruthenium catalyst, for example, a method in which ruthenium chloride is supported on the above-described carrier and then reduced with hydrogen, or a method in which ruthenium chloride is supported on the above-described carrier and then alkali hydrolysis is performed. A method of generating a ruthenium hydroxide on a carrier and calcining a supported metal ruthenium catalyst produced by a method of reducing the same with hydrogen or the like or a commercially available supported metal ruthenium catalyst in a gas containing oxygen is exemplified.

The firing temperature is generally 500 ° C. or lower, preferably 280-450 ° C. If the calcination temperature is too low, a large amount of metal ruthenium particles will remain, and the catalytic activity may be insufficient as compared with the case where the oxidization is sufficiently oxidized. Also,
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 5 hours. 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).

As a third component other than ruthenium, a noble metal compound other than ruthenium such as a palladium compound;
Rare earth compounds, copper compounds, chromium compounds, nickel compounds, alkaline earth metal compounds, manganese compounds, tantalum compounds, tin compounds, vanadium compounds and the like can be mentioned. The addition amount of the third component is usually 0.1 to 10% by weight as a ratio to the carrier.

According to the present invention, a supported metal ruthenium in which metal ruthenium is supported on a carrier is mixed with a gas containing oxygen,
A supported ruthenium oxide catalyst obtained by calcining in the presence of an alkali metal salt can also be used.

The present catalyst is common to the catalyst described in the section of the catalyst in which the supported metal ruthenium catalyst is oxidized in an oxygen-containing gas, in that the supported metal ruthenium catalyst is oxidized in an oxygen-containing gas. However, it is characterized by firing in the presence of an alkali metal salt.

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

The weight ratio of metal ruthenium / carrier is preferably 0.1 / 99.9 to 20/80, more preferably 0.5 / 99.5 to 15/85, and further preferably 1/9. 99 to 10/90. If the amount of metal ruthenium is too small, the catalytic activity may be reduced, while
If the amount of metal ruthenium is excessive, the catalyst price may increase. Examples of the method for producing the metal ruthenium supported on the carrier include a method in which ruthenium chloride is supported on the carrier and then reduced with hydrogen. Note that commercially available supported metal ruthenium may be used.

By calcining the metal ruthenium in the presence of an alkali metal salt in a gas containing oxygen, it can be oxidized to highly active ruthenium oxide. Air is usually used as the gas containing oxygen.

The firing temperature is usually 100 to 600 ° C., preferably 280 to 450 ° C. If the firing temperature is too low, a large amount of metal ruthenium particles may remain, resulting in insufficient catalytic activity. 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, 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. Examples of the alkali metal salt include potassium chloride, sodium chloride, cesium nitrate and the like, preferably potassium chloride, sodium chloride, and 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.

An example of a method for preparing the catalyst is described below. That is, the supported metal ruthenium catalyst is impregnated with an aqueous solution of an alkali metal salt, dried, and fired in a gas containing oxygen.
Examples of the method include washing with water and drying. As the supported metal ruthenium catalyst, a catalyst having a small metal ruthenium particle diameter is preferable. As a method for preparing the supported metal ruthenium catalyst, for example, a method in which ruthenium chloride is supported on the above-described carrier and then reduced with hydrogen, after supporting ruthenium chloride on the above-described carrier, ruthenium hydroxide is applied on the carrier by alkali hydrolysis. And reducing it with hydrogen or the like. A commercially available supported metal ruthenium catalyst having a small metal ruthenium particle diameter may be used.
Examples of commercially available supported metal ruthenium catalysts having a small metal ruthenium particle size include commercially available spherical 2% by weight supported metal ruthenium titanium oxide catalysts and spherical 5% by weight supported metal ruthenium titanium oxide catalysts (manufactured by NE Chemcat). Can be given. The molar ratio of the alkali metal salt / ruthenium in the used amount of the alkali metal salt is 0.01 to 1
0 is preferable, and 0.1 to 5 is more preferable. The firing temperature is preferably from 280 to 450 ° C. Baking time is usually 30
Minutes to 10 hours. The added alkali metal salt is removed by washing with water, but may remain as long as the catalytic activity of the present catalyst is not impaired.

In the present invention, a supported ruthenium oxide catalyst supported on a spherical carrier having a particle size of 10 to 500 μm can also be used. Examples of the supported ruthenium oxide catalyst include a catalyst in which ruthenium oxide such as ruthenium dioxide and ruthenium hydroxide is supported on a carrier. As the carrier of the supported ruthenium oxide catalyst, 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 are given. can give.

The supported ruthenium oxide catalyst is usually 10 to
Spherical catalysts in the range of 500 μm are used. When used in a fluidized bed reactor, it is preferred to use a catalyst of the above form. In a fluidized bed reactor, a particle size having a certain particle size distribution is selected in the above range depending on the physical properties and amount of a fluid to be circulated.

As an example of the method for preparing the above-mentioned ruthenium oxide catalyst, the following method can be mentioned. First, oxides or composite oxides of elements such as titanium oxide and alumina,
Preferably, a fine powder slurry and / or a hydrogel slurry of titanium oxide, alumina, and titanium oxide / silica composite oxide are sprayed and dried by a spray drier,
By baking, a spherical carrier of 10 to 500 μm is prepared. Next, ruthenium oxide is supported on the carrier by the supporting method described in the section of supported ruthenium oxide catalyst. For example, the carrier is impregnated with an aqueous solution of ruthenium chloride, and after drying, the carrier is impregnated with an aqueous solution of an alkali metal hydroxide. You can also. According to the above preparation examples, the above ruthenium oxide catalyst can be prepared.

Since the catalyst has a small particle size as described above, a highly active catalyst can be prepared relatively easily. As a result, generally, the catalytic activity per supported ruthenium can also be increased.

The weight ratio of ruthenium oxide / carrier is usually
0.1 / 99.9-20 / 80 is preferable, and 0.5 / 99.5-15 / 85 is more preferable. If the amount of ruthenium oxide is too small, the catalytic activity may decrease, while if the amount of ruthenium oxide is excessive, the catalyst price may increase.

A third component other than ruthenium can be added. Examples of the third component include palladium, copper compounds, chromium compounds, nickel compounds, vanadium compounds, alkali metal compounds, rare earth compounds, manganese compounds, and alkaline compounds. Earth compounds and the like. The addition amount of the third component is usually 0.1 to 10% by weight as a ratio to the carrier.

The firing temperature of ruthenium chloride hydrolyzed and supported on a carrier is generally 100 to 500 ° C., and is preferably used. The sintering time of the supported material is usually about 30 minutes to 10 hours. Particularly preferred firing temperature is 300 to 4
00 ° C. If the firing temperature is too low, ruthenium does not sufficiently turn into ruthenium oxide, and high activity may not be obtained. On the other hand, if the firing temperature is too high, the activity may be reduced due to aggregation of ruthenium oxide or the like.

In the present invention, a catalyst obtained by coating a ruthenium oxide catalyst on an inert carrier or a catalyst obtained by extruding a ruthenium oxide catalyst can be used.

The present invention relates to a method for oxidizing hydrogen chloride with oxygen in a gas-phase flow reaction using the above-mentioned catalyst. When the catalyst is used in a fixed bed, it is usually used in an industrial large-scale apparatus. And reacting. When the filling length is long, a catalyst having a certain particle size or more is used to reduce the pressure difference between the inlet and the outlet of the reactor. Particles of various sizes are used depending on the gas flow rate and the filling length.
m or more are used. The present invention is characterized in that a ruthenium oxide catalyst is used.However, in order to increase the particle size of the catalyst, the activity of the catalyst is reduced to an inert carrier such as alumina, silica or titanium oxide. A method for coating ruthenium oxide catalyst without any problems could be developed. In other words, there are various coating methods, but as an example, an α-alumina carrier is rolled, and a ruthenium oxide catalyst is added thereto, and an aqueous titanium oxide sol solution is sprayed to convert the ruthenium oxide catalyst to α-alumina. Coating method. By this method, a catalyst having a particle size of 3 mm or more could be prepared without reducing the activity of the catalyst.

Examples of the ruthenium oxide catalyst include the above-described supported ruthenium oxide catalyst and composite oxide type ruthenium oxide catalyst. Examples of the carrier to be coated include metal oxides such as α-alumina, silica, titanium oxide, γ-alumina, and zirconium oxide.

The ratio of the supported ruthenium oxide catalyst to the carrier to be coated is usually between 5/95 and 40/60.

Examples of the binder used for coating include water, titanium oxide sol, silica sol, and alumina sol. Titanium oxide sol is preferably used.
The binder may be used after being diluted with a solvent. As the solvent, water or an organic solvent such as methanol is used. As the content, based on the ruthenium oxide catalyst,
Usually, it is about 1 to 10% by weight. The coated product may be fired if necessary, and the firing temperature is usually about 300 to 400 ° C.

As a method for preparing a catalyst having a particle diameter of 1 mm or more, there is also a method of extruding a ruthenium oxide catalyst. For example, a method in which a titanium oxide sol and potassium chloride are mixed with a ruthenium oxide catalyst, kneaded, extruded, dried, calcined, washed with water to remove potassium chloride, and dried to prepare a catalyst is also given as an example.

Examples of the ruthenium oxide catalyst include the above-mentioned supported ruthenium oxide catalyst and composite oxide type ruthenium oxide catalyst. Examples of the binder include water, titanium oxide sol, silica sol, and alumina sol. The content is usually about 5 to 30% by weight based on the ruthenium oxide catalyst. It is not necessary to use potassium chloride, but it is preferable to use potassium chloride.
It is about 20% by weight. The drying temperature after extrusion is usually preferably 150 to 250 ° C., and the firing temperature is usually
300-400 ° C is preferred. The firing time is usually 5 to
It is about 24 hours. The firing atmosphere is preferably air. Next, water washing and drying are usually performed.

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. In general, the preferred catalyst particle size and shape differ depending on the reactor used. For example, a catalyst to be charged into a fixed bed reactor is usually formed into a spherical, cylindrical, or extruded catalyst having a diameter of 1 mm or more in order to reduce a pressure difference due to fluid flow.
Further, in a fluidized bed reactor, a spherical catalyst having a particle size in the range of 10 to 500 μm is usually used, and a particle size having a certain particle size distribution is selected depending on the physical properties and quantity of a fluid to be circulated.

The present invention is to obtain chlorine by oxidizing hydrogen chloride with oxygen using the above catalyst. In obtaining chlorine, examples of the 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 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 380 ° C. Can be 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 not preferable 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 10 to 20,000 in terms of the ratio GHSV to the feed rate of the raw material hydrogen chloride under atmospheric pressure in the case of the fixed bed gas phase flow system.
h ^-1 .

The present invention also includes a process for producing chlorine which reacts in an aqueous phase using a ruthenium catalyst. Examples of the ruthenium catalyst used in the reaction in the aqueous phase include ruthenium chloride, ruthenium chloride and titanium chloride, supported metal ruthenium, ruthenium oxide, and supported ruthenium oxide.

As the ruthenium chloride catalyst, commercially available ruthenium trichloride (RuCl ₃ .nH ₂ O) or the like can be used.
In addition, ruthenium compounds such as ruthenium ammine complex hydrochloride, ruthenium bromide, ruthenium acetylacetonate complex, ruthenium carbonyl complex, ruthenium organic acid salt, and ruthenium nitrosyl complex also change to ruthenium chloride in an aqueous hydrogen chloride solution. it can. These ruthenium chloride compounds are dissolved in an aqueous hydrogen chloride solution and used for the reaction.

Examples of the mixture catalyst of ruthenium chloride and titanium chloride include an aqueous hydrogen chloride solution of a mixture of a ruthenium chloride compound and titanium chloride described in the ruthenium chloride catalyst. As titanium chloride, titanium tetrachloride, titanium trichloride and the like can be used. The mixing ratio of ruthenium chloride to titanium chloride is usually from 100: 1 to 100: 10 as a molar ratio of titanium to ruthenium.

As the supported metal ruthenium catalyst, either a commercially available supported metal ruthenium catalyst or a prepared supported metal ruthenium catalyst can be used. Further, since ruthenium is expensive, it is generally preferable to use it in a form supported on a carrier industrially. Furthermore, supported ruthenium catalysts used industrially and commercially available are generally supported metal ruthenium catalysts. That is, when the supported metal ruthenium catalyst is used industrially, an existing catalyst or a catalyst preparation technique can be easily diverted, and thus has an advantage that the catalyst can be obtained at lower cost and more easily.

The supported metal ruthenium catalyst will be described below.

As a support for the supported metal ruthenium catalyst,
Examples thereof include oxides and composite oxides of elements such as alumina, silica, silica alumina, zeolite, diatomaceous earth, vanadium oxide, zirconium oxide, and titanium oxide, and metal sulfates. Preferred carriers are titanium oxide, zirconium oxide, alumina, zeolite, silica, titanium composite oxide, zirconium composite oxide, and aluminum composite oxide. More preferred carriers are titanium oxide, zirconium oxide, and alumina. An even more preferred carrier is titanium oxide. The ratio of metal ruthenium / carrier is usually from 0.1 / 99.9 to 20/80, preferably from 1/99 to 10/90. If the amount of the metal ruthenium is too small, the catalytic activity may decrease, while if the amount of the metal ruthenium is excessive, the catalyst price may increase.

As a method for producing the metal ruthenium supported on the carrier, for example, a method in which ruthenium chloride is supported on the above-described carrier and then reduced with hydrogen, a method in which ruthenium chloride is supported on the above-described carrier, and a ruthenium aqueous solution obtained by alkali hydrolysis are used. There is a method in which an oxide is formed on a carrier and this is reduced with hydrogen or the like. Note that a commercially available supported metal ruthenium catalyst may be used.

A third component other than ruthenium can be added. Examples of the third component include noble metal compounds other than ruthenium such as palladium compounds, rare earth compounds, copper compounds, chromium compounds, nickel compounds, alkali metal compounds, and alkali metals. Examples include earth metal compounds, manganese compounds, tantalum compounds, tin compounds, vanadium compounds and the like. The addition amount of the third component is usually 0.1 to 10% by weight as a ratio to the carrier.

The ruthenium oxide catalyst and the supported ruthenium oxide catalyst include the following catalysts.

As the ruthenium oxide catalyst, ruthenium oxide such as ruthenium dioxide and ruthenium hydroxide, or a known method (for example, Catalyst Handbook by Element, 1978)
Ruthenium dioxide catalyst, ruthenium hydroxide catalyst, ruthenium oxide composite oxide, and supported ruthenium oxide catalyst prepared by Jinjinkan, p. 544, but may be commercially available ruthenium dioxide. Further, a compound in which another element is bonded to ruthenium oxide such as a halogenated oxide may also be used. Among these, a ruthenium oxide composite oxide and a supported ruthenium oxide catalyst have high activity and are preferred. In addition, a supported ruthenium oxide catalyst is industrially preferable because it is inexpensive. As a method for preparing an industrially preferable ruthenium oxide catalyst for obtaining a highly active ruthenium oxide catalyst, a method of hydrolyzing ruthenium chloride with an alkali to form ruthenium hydroxide, and calcinating this in the air to form ruthenium dioxide. Is raised. In this case, the firing temperature is 30
0-400 degreeC is preferable. As a carrier of the supported ruthenium oxide, titanium oxide, alumina, zirconium oxide,
Silica, titanium composite oxide, zirconium composite oxide,
Examples thereof include oxides of elements such as an aluminum composite oxide and a silicon composite oxide, and composite oxides. Preferred carriers are titanium oxide, alumina, zirconium oxide, and silica, and more preferred carriers are titanium oxide. The ratio of ruthenium oxide to the carrier is usually 0.1 / 99.9 to 70.
/ 30, preferably 0.1 / 99.9 to 2
0/80.

If the ratio of ruthenium is too low, the activity decreases, and if the ratio of ruthenium is too high, the price of the catalyst increases. Incidentally, a third component other than ruthenium can also be added, and as the third component, a noble metal compound other than ruthenium such as a palladium compound, a rare earth compound, a copper compound,
Chromium compounds, nickel compounds, alkali metal compounds,
Examples include alkaline earth metal compounds, manganese compounds, tantalum compounds, tin compounds, vanadium compounds and the like. The addition amount of the third component is usually 0.1 to 10% by weight as a ratio to the carrier.

As the compound to be supported, ruthenium oxide,
Examples thereof include ruthenium hydroxide and ruthenium oxide halide. An example of an industrially inexpensive and preferable supporting method is a method of oxidizing a supported metal ruthenium in a gas containing oxygen. As an example, a catalyst obtained by oxidizing a supported metal ruthenium catalyst in a gas containing oxygen will be described. The catalyst obtained by oxidizing the supported metal ruthenium catalyst in the present invention is a catalyst obtained by oxidizing a supported metal ruthenium catalyst by calcination in a gas containing oxygen.

Examples of the catalyst obtained by oxidizing a supported metal ruthenium catalyst include a catalyst obtained by calcining a supported metal ruthenium catalyst in a gas containing oxygen and oxidizing the same. Air is usually used as the gas containing oxygen. As the carrier of the catalyst used by oxidizing the supported metal ruthenium, as in the case of the supported metal ruthenium catalyst, an element such as alumina, silica, silica alumina, zeolite, diatomaceous earth, vanadium oxide, zirconium oxide, or titanium oxide is used. Oxides and composite oxides, or metal sulfates, and the like, preferred carriers are titanium oxide, zirconium oxide, alumina, zeolite, silica, titanium composite oxide, zirconium composite oxide, aluminum composite oxide, More preferred carriers are titanium oxide, zirconium oxide, and alumina. An even more preferred carrier is titanium oxide.

The ruthenium / support ratio is usually 0.1 / 99.9, as in the case of the supported metal ruthenium catalyst described above.
２０20/80, preferably 1/99 to 10/9
0. If the amount of ruthenium is too small, the catalytic activity decreases, and if the amount of ruthenium is too large, the price of the catalyst increases.

As a method for producing a catalyst obtained by oxidizing a supported metal ruthenium catalyst, a catalyst produced by the above-described method for producing a supported metal ruthenium catalyst or a commercially available supported metal ruthenium catalyst is calcined in a gas containing oxygen. There is a way to do it.

The firing temperature is preferably from 100 to 600 ° C.
More preferably, it is 280-450 ° C. If the firing temperature is too low, many ruthenium metal particles remain. 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 5 hours. 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).

The third component other than ruthenium can be added in the same manner as in the case of the above-mentioned supported metal ruthenium catalyst. As the third component, a noble metal compound other than ruthenium such as a palladium compound, a rare earth compound, a copper compound , Chromium compounds, nickel compounds, alkali metal compounds, alkaline earth metal compounds, manganese compounds, tantalum compounds, tin compounds, vanadium compounds and the like. 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 supporting the supported ruthenium oxide, an aqueous solution of RuCl ₃ was impregnated into the carrier, and then alkali was added to precipitate ruthenium hydroxide on the carrier.
Firing in the air to carry ruthenium oxide,
An example is a method of impregnating a carrier with an aqueous solution of RuCl ₃ , drying, and then firing in air to oxidatively decompose to carry ruthenium oxide. The calcination of the supported material is usually performed at 100 to 500 ° C. for about 30 minutes to 5 hours. A particularly preferred firing temperature is 300 to 400 ° C. If the firing temperature is too low, ruthenium does not sufficiently turn into ruthenium oxide, and high activity may not be obtained. On the other hand, if the firing temperature is too high, low activity may be caused due to aggregation of ruthenium oxide.

The ruthenium oxide catalyst includes a ruthenium oxide composite oxidation catalyst. Examples of the ruthenium oxide composite oxidation catalyst include one or more oxides such as titanium oxide, zirconium oxide, alumina, silica, vanadium oxide, boron oxide, chromium oxide, niobium oxide, hafnium oxide, tantalum oxide, and tungsten oxide. And ruthenium oxide. Preferred compounds for forming ruthenium oxide include titanium oxide, zirconium oxide and titanium oxide composite oxide.

As a method for complexing ruthenium oxide, a method of hydrolyzing a chloride such as titanium, an oxychloride, a nitrate, an oxynitrate, an alkali salt of an oxyacid, a sulfate, an alkoxide, or the like, and a ruthenium chloride or the like are used. A method in which a ruthenium compound is hydrolyzed, filtered, washed, and calcined in the air is used. The content of ruthenium oxide contained in the ruthenium composite oxide is usually 0.1 to 80% by weight. In addition, a third component can be added, and examples of the third component include a palladium compound, a copper compound, a chromium compound, a vanadium compound, an alkali metal compound, a rare earth compound, a manganese compound, and an alkaline earth compound. The amount of the third component is usually 0.1 to 1 as a ratio to the weight of the ruthenium composite oxide.
0% by weight. Examples of the method for preparing the ruthenium oxide composite oxide include a coprecipitation method, a method by mixing precipitation, and an impregnation method. Examples of a method for supporting the ruthenium oxide composite oxide on a carrier include an impregnation method and a precipitation supporting method. Conditions for baking and preparing these ruthenium oxide composite oxides are usually 100 ° C. to 500 ° C. for about 30 minutes to 5 hours. Examples of the firing atmosphere include nitrogen and air.

If the ratio of ruthenium is too low, the activity may decrease. If the ratio of ruthenium is too high, the price of the catalyst may increase. In addition, a third component can be added, and examples of the third component include a palladium compound, a copper compound, a chromium compound, a vanadium compound, an alkali metal compound, a rare earth compound, a manganese compound, and an alkaline earth compound. The amount of the third component is usually 0.1 to 1 as a ratio to the weight of the ruthenium composite oxide.
0% by weight.

The present invention is to produce chlorine by oxidizing hydrogen chloride with oxygen in a water phase using a ruthenium chloride catalyst, ruthenium chloride and titanium chloride catalyst, a supported ruthenium catalyst, and a ruthenium oxide catalyst. The reaction system in the production of chlorine is not particularly limited, but a circulation system is preferable, and a liquid phase circulation system is more preferable. In the case of ruthenium chloride, a tank-type uniform aqueous phase reaction method is used, and in the case of a solid catalyst, a tank-type slurry aqueous phase reaction method is used. In any case, a reactive distillation method is preferably employed. The temperature is suitably around the boiling point of the aqueous hydrogen chloride solution,
Although it depends on the pressure, it is usually 90 to 150 ° C.
The reaction pressure is also not particularly limited, but is preferably about atmospheric pressure to about 10 atm. As the oxygen raw material, air may be used as it is, or pure oxygen may be used, but preferably, when the inert nitrogen gas is discharged outside the apparatus, other components are also released at the same time. Pure oxygen containing no inert gas can be used. The theoretical molar amount of oxygen with respect to hydrogen chloride is 1/4 mol, but it is preferably supplied 0.1 to 10 times the theoretical amount, and more preferably 0.2 to 5 times the theoretical amount. When ruthenium chloride is used, the amount of the catalyst used is usually 1 to 30% as a value expressed as a percentage by weight in an aqueous hydrogen chloride solution. When a solid catalyst is used, it is usually 1 to 20% as a value expressed as a percentage by weight in an aqueous hydrogen chloride solution.

[0089]

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, 0.1 mo
1.66 g of commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) was dissolved in 1580 ml of a 1 / l aqueous hydrochloric acid solution and left overnight. Next, 12.0 g of titanium oxide powder (Catalyst Chemical Industry Co., Ltd. No. 1) was suspended in this solution, and a 0.1 mol / l aqueous solution of potassium hydroxide was added with stirring to adjust the pH to 4.5. The ruthenium was adjusted and deposited on titanium oxide. The addition amount of the aqueous potassium hydroxide solution was 2,200 ml. Next, the suspension is brought to pH
While adjusting to 4.5, the mixture was heated to 60 ° C. and stirred for 5 hours. The amount of the aqueous potassium hydroxide solution added was 22 ml. After completion of the stirring, the mixture was allowed to cool to room temperature and left overnight. Next, 3000 ml of the supernatant was removed and the remaining suspension was
Evaporate to dryness on an oil bath heated to 0 ° C. to obtain a green-grey powder. This green-gray powder is heated from room temperature to 170 ° C in air.
Until 1 hour, and calcined at the same temperature for 8 hours. next,
Similarly, the temperature is raised from room temperature to 375 ° C in the air in one hour,
It was baked at the same temperature for 8 hours. After cooling, 14.3 g of the obtained green-gray powder was washed with 3.4 l of water for 1 day using a glass filter. Next, this powder was dried under reduced pressure at 60 ° C. using a rotary evaporator to obtain 12.1 g of a green-gray powder. This powder was molded to have a mesh size of 12 to 18.5 to obtain a ruthenium oxide catalyst supporting titanium oxide. An additional 36.0 g of the same catalyst was obtained in the same manner as described above. The calculated value of the content of ruthenium oxide is calculated as follows: RuO ₂ / (RuO ₂ + TiO ₂ +) × 100 = 6.
It was 0% by weight. The calculated value of the ruthenium content is Ru /
(RuO ₂ + TiO ₂ ) × 100 = 4.6% by weight. 15.0 g of the thus-obtained titanium oxide-supported ruthenium oxide catalyst was charged into a quartz reaction tube (26 mm inner diameter). Hydrogen chloride gas was supplied at a normal pressure of 41 ml / min, and oxygen gas was supplied at a normal pressure of 18 ml / min (both at 0 ° C. and 1 atm). The quartz reaction tube was heated in an electric furnace, and the internal temperature (hot spot) was set to 325 ° C. At 11.2 hours after the start of the reaction, sampling was performed by flowing the gas at the outlet of the reaction tube through a 30% aqueous potassium iodide solution.
The amount of generated chlorine and the amount of unreacted hydrogen chloride were measured by an iodine titration method and a neutralization titration method. The conversion of hydrogen chloride was 91.9%.

Example 2 A catalyst was prepared by the following method. That is, 0.1 mo
Dissolve 0.84 g of commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) in 790 ml of 1 / l hydrochloric acid aqueous solution,
Left overnight. Next, 6.0 g of titanium oxide powder (Catalyst Chemical Co., Ltd. No. 1) was suspended in this solution, and a 0.1 mol / l aqueous solution of potassium hydroxide was added with stirring to adjust the pH to 4.5. Then, ruthenium was precipitated and supported on titanium oxide. Addition amount of aqueous solution of potassium hydroxide is 980m
l. Next, while adjusting the pH of the suspension to 4.5, the suspension was heated to 60 ° C. and stirred for 5 hours. The amount of the aqueous potassium hydroxide solution added was 5 ml. After completion of the stirring, the mixture was allowed to cool to room temperature and left overnight. Next, the supernatant liquid 1100m
and the remaining suspension was evaporated to dryness on an oil bath heated to 130 ° C. to give a gray powder. This gray powder was heated in the air from room temperature to 180 ° C. in 1 hour and calcined at the same temperature for 8 hours. Next, from room temperature to 3
The temperature was raised to 78 ° C. in 1 hour, and baked at the same temperature for 8 hours.
After cooling, 8.09 g of the obtained black-green powder was washed with 3.2 l of water for 1 day using a glass filter. Next, this powder was dried under reduced pressure at 60 ° C. using a rotary evaporator to obtain 5.86 g of a black-green powder. By molding this powder and making it 12 to 18.5 mesh,
A ruthenium oxide catalyst supported on titanium oxide was obtained. The calculated value of the ruthenium oxide content is calculated as RuO ₂ / (RuO ₂ + Ti
O ₂ ) × 100 = 6.0% by weight. The calculated value of the ruthenium content is Ru / (RuO ₂ + TiO ₂ ) × 100 =
It was 4.6% by weight. X-ray diffraction and XPS analysis of this catalyst confirmed that the supported catalyst was ruthenium oxide. As a result of measurement under the following conditions using the following transmission electron microscope, the particle size of ruthenium oxide on the carrier was as follows. Apparatus: Hitachi H-9000 NAR type Acceleration voltage: 300 kv Observation magnification: 300,000 times Photo magnification 1.5 million times Sampling: RuO ₂ dispersed on a Cu mesh with a microgrid is identified by RuO ₂ (110). d
Is 0.318 nanometers, which was determined by measuring the spacing between the lattice fringes of the high-resolution image. As a result of measuring the particle size of 61 RuO ₂ particles, the RuO ₂ particle size was 0.8 nm to 7.2 nm, and the central particle size was 2.73 nm. 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, and the mixture was placed in a quartz reaction tube (12 mm inner diameter). Filled.
200 ml / min of hydrogen chloride gas and 200 ml of oxygen gas
The solution was supplied at a normal pressure of ml / min (both at 0 ° C. and 1 atm). The quartz reaction tube was heated in an electric furnace, and the internal temperature (hot spot) was set to 300 ° C. At 1.4 hours after the start of the reaction, sampling was performed 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 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 4.90 × 10 ⁻⁴ m
ol / min · g-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)

Example 3 A catalyst was prepared by the following method. That is, 1-2 mm
2 mol per 50.02 g (manufactured by NE Chemcat) of 5 wt% supported metal ruthenium titanium oxide catalyst of φ spherical shape
/ L of a potassium chloride aqueous solution (specific gravity 1.09 measured with a hydrometer) was impregnated until water floated on the surface of the catalyst, and then dried at 60 ° C in air for 10 minutes to 1 hour. This operation was repeated three times. The impregnation amount of the aqueous potassium chloride solution was 21.5 g for the first time, 17.5 g for the second time, and 5.7 g for the third time.
And the total was 44.6 g. The calculated value of the molar ratio of potassium chloride to ruthenium was 3.4. Next, this catalyst was dried in air at 60 ° C. for 4 hours, further heated from room temperature to 350 ° C. in air for about 1 hour, and calcined at the same temperature for 3 hours to obtain a spherical solid. 1 l of pure water was added to the obtained solid,
After stirring at room temperature for 1 minute, the catalyst was filtered. This operation was repeated 10 times, and then dried in air at 60 ° C. for 4 hours to obtain 49.85 g of a blue-black spherical catalyst. This spherical solid was crushed and sized to 12 to 18.5 mesh to obtain a titanium oxide-supported ruthenium oxide catalyst. The calculated value of the ruthenium oxide content was 6.5% by weight. The calculated value of the ruthenium content is 4.9% by weight
Met. As a result of analyzing this catalyst by X-ray diffraction, it was confirmed that the supported substance was ruthenium oxide. As a result of measurement with the same transmission electron microscope as in Example 2 under the same conditions, ruthenium oxide on the carrier was identified by the same method as in Example 2, and the particle size of ruthenium oxide was measured. As a result of measuring the particle size of 67 RuO ₂ particles, the RuO ₂ particle size was 0.8 to 6.0 nm, and the central particle size was 1.79 nm. 2.50 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 is passed at a flow rate of 202 ml / min, oxygen gas is passed at 213 ml / min, and the internal temperature is 300 ° C.
The procedure was performed in the same manner as in Example 2 except for the above. Reaction start
After 3 hours, the activity of forming chlorine per unit weight of the catalyst was 5.34 × 10 ⁻⁴ mol / min · g-catalyst.

Example 4 A catalyst was prepared by the following method. That is, 0.1 mo
Dissolve 0.85 g of commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) in 790 ml of 1 / l hydrochloric acid aqueous solution,
Left overnight. Next, silica gel powder (AEROSIL-300, Nippon Aerosil Co., Ltd.) 6.00 was added to this solution.
g of the resulting solution was suspended, and while stirring, a 0.1 mol / l aqueous solution of potassium hydroxide was added thereto, and further a 1 mol / l aqueous solution of hydrochloric acid was added to adjust the pH to 4.5, and ruthenium was precipitated and supported on silica. The addition amount of the aqueous potassium hydroxide solution is 10
00 ml, 1 mol / l aqueous solution of hydrochloric acid was added at 0.5
ml. Next, the suspension was heated to 60 ° C. and stirred for 5 hours while adjusting the pH to 4.5. The amount of the added potassium hydroxide aqueous solution was 2 ml. After stirring,
It was allowed to cool to room temperature and left overnight. Next, the supernatant liquid 1200
The remaining suspension was evaporated to dryness on an oil bath heated to 130 ° C. to obtain a black powder. The temperature of the black powder was raised from room temperature to 170 ° C. in the air in 1 hour, and calcined at the same temperature for 8 hours. Next, the temperature was raised from room temperature to 375 ° C. for 1 hour in the same air, and baked at the same temperature for 8 hours. After cooling, 7.27 g of the obtained black powder was washed with 3.4 L of water for 4 hours using a glass filter.
Next, the powder was heated to 60 ° C. using a rotary evaporator.
And dried under reduced pressure to obtain 5.71 g of a black powder. This powder was molded to have a mesh of 12 to 18.5 to obtain a silica-supported ruthenium oxide catalyst. The calculated value of the content of ruthenium oxide was 6.1% by weight. The calculated value of the ruthenium content was 4.7% by weight. The silica-supported ruthenium oxide catalyst 2.5 thus obtained
The catalyst was diluted by thoroughly mixing 0 g with 5 g of a titanium oxide support having a mesh size of 12 to 18.5 mesh, and filled in a quartz reaction tube (inner diameter: 12 mm). Hydrogen chloride gas 2
The reaction was performed in accordance with the reaction method of Example 2 except that the flow rate of oxygen gas was 200 ml / min and the internal temperature was 300 ° C. 1.6 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 3.36 × 10 ^−4.
mol / min.g-catalyst.

Example 5 A catalyst was prepared by the following method. That is, 0.1 mo
Dissolve 0.85 g of commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) in 790 ml of 1 / l hydrochloric acid aqueous solution,
Left overnight. Next, 6.00 g of alumina powder (pulverized NKHD, Sumitomo Chemical Co., Ltd.) was suspended in this solution, and a 0.1 mol / l aqueous solution of potassium hydroxide was added with stirring to adjust the pH to 4.5. The ruthenium was adjusted and precipitated on alumina. The added amount of the aqueous potassium hydroxide solution was 855 ml. Next, the suspension was adjusted to pH 4.
While adjusting to 5, the mixture was heated to 60 ° C. and stirred for 5 hours. The amount of the added potassium hydroxide aqueous solution was 10 ml.
After completion of the stirring, the mixture was allowed to cool to room temperature and left overnight. Next, 1200 ml of the supernatant was removed, and the remaining suspension was evaporated to dryness on an oil bath heated to 130 ° C. to obtain a black powder. The temperature of the black powder was raised from room temperature to 170 ° C. in the air in 1 hour, and calcined at the same temperature for 8 hours. Next, the temperature was raised from room temperature to 375 ° C. for 1 hour in the same air, and baked at the same temperature for 8 hours. After cooling, the resulting black-green powder 6.32.
g was washed with 3.4 l of water for 4 hours using a glass filter. Next, this powder was dried under reduced pressure at 60 ° C. using a rotary evaporator to obtain 5.71 g of a black-green powder. This powder was molded to have a mesh size of 12 to 18.5 to obtain a ruthenium oxide catalyst supported on alumina. The calculated value of the content of ruthenium oxide was 6.1% by weight. The calculated value of the ruthenium content was 4.7% by weight. 2.50 g of the alumina-supported ruthenium oxide catalyst thus obtained was charged into a reaction tube in the same manner as in Example 2, the internal temperature was set to 300 ° C., and the reaction was carried out in accordance with the reaction method of Example 2. 1.3 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 2.74 × 10 ⁻⁴ mol.
/ Min · g-catalyst.

Example 6 A catalyst was prepared by the following method. That is, 0.1 mo
Dissolve 0.85 g of commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) in 790 ml of 1 / l hydrochloric acid aqueous solution,
Left overnight. Next, zirconium oxide powder (pulverized from JGC Chemicals E-26H1) was added to this solution.
0.1 g of a 0.1 mol / l aqueous solution of potassium hydroxide was added to the suspension, and the mixture was adjusted to pH 4.5 with stirring.
Ruthenium was precipitated and supported on zirconium oxide. The added amount of the aqueous potassium hydroxide solution was 460 ml. next,
The suspension was heated to 60 ° C. and stirred for 5 hours while adjusting the pH to 4.5. The amount of the aqueous potassium hydroxide solution added was 11.5 ml. After completion of the stirring, the mixture was allowed to cool to room temperature and left overnight. Next, 1200 ml of the supernatant was removed, and the remaining suspension was evaporated to dryness on an oil bath heated to 130 ° C. to obtain a black powder. The temperature of the black powder was raised from room temperature to 170 ° C. in the air in 1 hour, and calcined at the same temperature for 8 hours. Next, the temperature was raised from room temperature to 375 ° C. for 1 hour in the same air, and baked at the same temperature for 8 hours. After cooling,
Using a glass filter, 6.9 g of the obtained black-green powder was washed with 3.4 l of water for 4 hours. Next, this powder was dried under reduced pressure at 60 ° C. using a rotary evaporator to obtain 5.83 g of a black-green powder. This powder was molded to have a mesh size of 12 to 18.5 to obtain a ruthenium oxide catalyst supporting zirconium oxide. The calculated value of the ruthenium oxide content was 6.1% by weight. The calculated value of the ruthenium content was 4.7% by weight. 2.50 g of the thus obtained zirconium oxide-supported ruthenium oxide catalyst was charged into a reaction tube in the same manner as in Example 2, the internal temperature was set to 300 ° C., and the reaction was carried out in accordance with the reaction method of Example 2.
1.5 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 2.93 × 10 ⁻⁴ mol / min · g.
-A catalyst.

Example 7 A catalyst was prepared by the following method. That is, 2 mol /
0.37 g of commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) was dissolved in 457 ml of 1 aqueous hydrochloric acid solution and left for 1 hour. Next, 34.7 g of titanium oxide powder (Catalyst Chemical Industry Co., Ltd. No. 1) was suspended in this solution, and a 2 mol / l aqueous solution of potassium hydroxide was added thereto while stirring to adjust the pH to 4.5. Then, ruthenium was precipitated and supported on titanium oxide. Addition amount of potassium hydroxide solution is 604g
Met. Next, the suspension was heated to 60 ° C. and stirred for 3 hours while adjusting the pH to 4.5. 2mol added
The amount of 1 / l hydrochloric acid aqueous solution was 1 g. After completion of the stirring, the mixture was allowed to cool, and the precipitate was filtered. The filtered product was dried at 60 ° C. to obtain a yellow powder. The yellow powder was heated in the air from room temperature to 170 ° C. in 1 hour and calcined at the same temperature for 8 hours. Next, the temperature was raised from room temperature to 375 ° C. for 1 hour in the same air, and baked at the same temperature for 8 hours. After cooling, a gray powder was obtained. Using a glass filter, the obtained powder,
Washed with 3.5 l of water for 7 hours. Next, this powder was dried at 60 ° C. for 4 hours to obtain 33.5 g of a gray powder. 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 0.50% by weight. The calculated value of the ruthenium content was 0.38% by weight. 2.50 g of the thus-obtained titanium oxide-supported ruthenium oxide catalyst was charged into a reaction tube in the same manner as in Example 2, the internal temperature was set to 300 ° C., and hydrogen chloride gas was added to the reaction tube.
The reaction was performed in accordance with the reaction method of Example 2, except that 2 ml / min and oxygen gas were passed at 184 ml / min.
Two hours after the start of the reaction, the activity of forming chlorine per unit catalyst weight was 0.35 × 10 ⁻⁴ mol / min · g-
It was a catalyst.

Example 8 A catalyst was prepared by the following method. That is, 2 mol /
0.74 g of commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) was dissolved in 1
Let stand for minutes. Next, 34.7 g of titanium oxide powder (Catalyst Chemical Industry Co., Ltd. No. 1) was suspended in this solution, and a 2 mol / l aqueous solution of potassium hydroxide was added thereto while stirring to adjust the pH to 4.5. Then, ruthenium was precipitated and supported on titanium oxide. Addition amount of potassium hydroxide solution is 463m
l. Next, the suspension was heated to 60 ° C. and stirred for 3 hours while adjusting the pH to 4.5. The amount of potassium hydroxide added was 0.5 ml. After completion of the stirring, the mixture was allowed to cool, and the precipitate was filtered. The filtered product was dried at 60 ° C. to obtain a powder. This powder is heated from room temperature to 170 ° C in air.
Until 1 hour, and calcined at the same temperature for 8 hours. next,
Similarly, the temperature is raised from room temperature to 375 ° C in the air in one hour,
It was baked at the same temperature for 8 hours. After cooling, a gray powder was obtained. Using a glass filter, 3 l of the obtained gray powder
Of water for 3 hours. Next, this powder was dried at 60 ° C. for 4 hours to obtain 33.6 g of a gray powder. This powder was molded to have a mesh size of 12 to 18.5 to obtain a ruthenium oxide catalyst supporting titanium oxide. In addition,
The calculated value of the ruthenium oxide content was 1.0% by weight. The calculated value of the ruthenium content was 0.75% by weight. 2.50 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, the internal temperature was set to 300 ° C., and hydrogen chloride gas was supplied at 192 ml / hour.
The reaction was carried out in accordance with the reaction method of Example 2 except that oxygen gas was passed at 184 ml / min. Two hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 0.85 × 10 ⁻⁴ mol / min · g-catalyst.

Example 9 A catalyst was prepared by the following method. That is, 2 mol /
Dissolve 4.23 g of commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) in 228 ml of 1 aqueous hydrochloric acid solution.
Let stand for minutes. Next, 30.0 g of titanium oxide powder (Catalyst Chemical Industry Co., Ltd. No. 1) was suspended in this solution, and a 2 mol / l aqueous solution of potassium hydroxide was added thereto while stirring to adjust the pH to 4.5. Then, ruthenium was precipitated and supported on titanium oxide. The amount of the 2 mol / l aqueous solution of potassium hydroxide added was 206 ml. Next, the suspension was adjusted to pH 4.
While adjusting to 5, the mixture was heated to 60 ° C. and stirred for 5 hours. The amount of added 0.1 mol / l potassium hydroxide is 125 m
l. 0.1 mol / l potassium hydroxide aqueous solution 1
After addition of 02 ml, the pH was adjusted to 7.0, and after completion of stirring, the mixture was allowed to cool and the precipitate was filtered. The filtered product was dried at 60 ° C. for 8 hours to obtain 33.4 g of a greenish gray powder. 6.67 g of this green-gray powder is taken out, and is heated from room temperature to 170 ° C. in air.
Until 1 hour, and calcined at the same temperature for 8 hours. next,
Similarly, the temperature is raised from room temperature to 375 ° C in the air in one hour,
It was baked at the same temperature for 8 hours. After cooling, a green-grey powder was obtained. Next, it was washed with 3 l of water for 3 hours using a glass filter. Next, this powder was dried at 60 ° C. with a rotary evaporator to obtain 6.01 g of a black powder. 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 is 4.7% by weight
Met. 2.50 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, the internal temperature was set at 301 ° C., and hydrogen chloride gas was supplied at 190 m2.
The reaction was carried out in accordance with the reaction method of Example 2 except that the mixture was passed at 1 / min. 2.1 hours after the start of the reaction,
The activity of forming chlorine per unit catalyst weight is 4.90 × 10
^-4 mol / min.g-catalyst.

Example 10 A catalyst was prepared by the following method. That is, 2 mol /
13.0 g of a commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) was dissolved in
Let stand for minutes. Next, 34.7 g of titanium oxide powder (Catalyst Chemical Industry Co., Ltd. No. 1) was suspended in this solution, and a 2 mol / l aqueous solution of potassium hydroxide was added thereto while stirring to adjust the pH to 4.5. Then, ruthenium was precipitated and supported on titanium oxide. Addition amount of potassium hydroxide solution is 675m
l. Next, the suspension was heated to 60 ° C. and stirred for 3 hours while adjusting the pH to 4.5. The amount of potassium hydroxide added was 3 ml. After completion of stirring, allow to cool,
The precipitate was filtered. The filtered product was dried at 60 ° C. to obtain a green-gray powder. The green-gray powder was heated in the air from room temperature to 170 ° C. in 1 hour and calcined at the same temperature for 8 hours. Next, the temperature was raised from room temperature to 375 ° C. for 1 hour in the same air, and baked at the same temperature for 8 hours. After cooling, 44.0 g of a green-grey powder were obtained. 8.0 g of this was collected and washed with 3 l of water for 3 hours using a glass filter. Next, the powder is dried at 60 ° C. for 8 hours.
8 g of a green-grey powder were obtained. This powder is molded and 12 ~
By setting the mesh size to 18.5, a ruthenium oxide catalyst supporting titanium oxide was obtained. The calculated value of the content of ruthenium oxide was 14.9% by weight. The calculated value of the ruthenium content was 11.3% by weight. Except that 2.50 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, the internal temperature was set to 300 ° C., and hydrogen chloride gas was passed at 190 ml / min, The reaction was performed according to the reaction method of Example 2. 2.0 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 6.1 × 10 ⁻⁴ mol / min · g-catalyst.

Example 11 A catalyst was prepared by the following method. That is, 2 mol /
18.4 g of commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O) was dissolved in
Let stand for minutes. Next, 34.7 g of titanium oxide powder (Catalyst Chemical Industry Co., Ltd. No. 1) was suspended in this solution, and a 2 mol / l aqueous solution of potassium hydroxide was added thereto while stirring to adjust the pH to 4.5. Then, ruthenium was precipitated and supported on titanium oxide. Addition amount of potassium hydroxide aqueous solution is 990m
l. Next, the suspension was heated to 60 ° C. and stirred for 3 hours while adjusting the pH to 4.5. The amount of potassium hydroxide added was 7 ml. After completion of stirring, allow to cool,
The precipitate was filtered. The filtered product was dried at 60 ° C. to obtain a green-gray powder. The green-gray powder was heated in the air from room temperature to 170 ° C. in 1 hour and calcined at the same temperature for 8 hours. Next, the temperature was raised from room temperature to 375 ° C. for 1 hour in the same air, and baked at the same temperature for 8 hours. After cooling, 47.2 g of a green-grey powder were obtained. 8.2 g of this was collected and washed with 3 l of water for 3 hours using a glass filter. Next, the powder is dried at 60 ° C. for 8 hours.
8 g of a green-grey powder were obtained. This powder is molded and 12 ~
By setting the mesh size to 18.5, a ruthenium oxide catalyst supporting titanium oxide was obtained. The calculated value of the ruthenium oxide content was 19.9% by weight. The calculated value of the ruthenium content was 15.0% by weight. Except that 2.50 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, the internal temperature was set to 300 ° C., and hydrogen chloride gas was passed at 190 ml / min, The reaction was performed according to the reaction method of Example 2. 1.9 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 7.1 × 10 ⁻⁴ mol / min · g-catalyst.

Example 12 A catalyst was prepared by the following method. That is, 1-2 mm
A spherical 5% by weight metal ruthenium titanium oxide catalyst (manufactured by NE Chemcat) having a diameter of 35 mm in air from room temperature to 35%
4. Raise the temperature to 0 ° C in about 1 hour, bake at the same temperature for 3 hours,
08 g of a blue-black spherical solid were obtained. The obtained solid was crushed, and the resulting solid was sized to 12 to 18.5 mesh to obtain a catalyst obtained by oxidizing a titanium oxide-supporting metal ruthenium catalyst. When the obtained catalyst was analyzed by X-ray diffraction and XPS (X-ray photoelectron spectroscopy), the presence of ruthenium oxide particles was confirmed by X-ray diffraction, and no metal ruthenium particles were detected. In XPS, the presence of ruthenium oxide was confirmed, and no metallic ruthenium was detected. The calculated value of the content of ruthenium oxide was 6.5% by weight. The calculated value of the ruthenium content was 4.9% by weight. The thus-obtained titanium oxide-supported ruthenium oxide catalyst (2.50 g) was mixed well with a titanium oxide carrier (5 g) having a mesh size of 12 to 18.5 mesh to dilute the catalyst. Filled. The reaction was carried out in accordance with the reaction method of Example 2 except that hydrogen chloride gas was passed at 190 ml / min and oxygen gas was passed at 200 ml / min, and the internal temperature was set at 300 ° C. 2.3 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 13 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, 56.7 g of titanium tetraisopropoxide was added while stirring at room temperature, and the mixture was stirred at room temperature for 1 hour. 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 1 hour, heated with stirring, and refluxed for 1 hour on a 110 ° C. oil bath. The liquid temperature at this time was 80 ° C. Next, the solution was allowed to cool, filtered through a glass filter, washed with 500 ml of pure water, and filtered again. After repeating this operation twice, it was dried in air at 60 ° C. for 1 hour, heated from room temperature to 550 ° C. in 1 hour, and calcined at the same temperature for 3 hours to obtain 1
9.8 g of a white solid was obtained. Crush the resulting solid,
A titania silica powder was obtained. A commercially available ruthenium chloride hydrate (RuCl) was added to 12.0 g of the obtained titania silica powder.
_(3. nH ₂ O, Ru content: 35.5%)
After impregnating with a solution dissolved in 5 g, it was dried in air at 60 ° C. for 1 hour to carry ruthenium chloride. 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 for 1 hour and 30 minutes. 12.5 g of titania silica-supported metal ruthenium powder was obtained. 6.2 g of the obtained titania silica-supported metal ruthenium powder was heated from room temperature to 350 ° C. in 2 hours under an air current of 100 ml / min, and calcined at the same temperature for 3 hours to obtain 5.8 g of black color. A powder was obtained. By molding the obtained powder and setting it to 12 to 18.5 mesh,
A ruthenium oxide catalyst supported on titania silica was obtained. In addition,
The calculated value of the ruthenium oxide content is RuO ₂ / (RuO ₂ +
TiO ₂ + SiO ₂ ) × 100 = 6.1% by weight.
The calculated value of the ruthenium content is Ru / (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 charged at 202 ml / mi.
n and oxygen gas were passed at 213 ml / min, and the reaction was carried out in accordance with the reaction method of Example 2 except that the internal temperature was set at 301 ° C. 2.4 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst is 1.44 × 10 ⁻⁴ mol / min.
G-catalyst.

Example 14 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 completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes, then heated while 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.
Then, the temperature was raised in 1 hour and 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 (Ru) was added to 7.0 g of the obtained titania silica powder.
After impregnating a solution obtained by dissolving 0.97 g of Cl ₃ .nH ₂ O with a Ru content of 35.5% in 7.2 g of 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 / mi of nitrogen.
Under a mixed air stream of n, the temperature was raised from room temperature to 300 ° C. for 1 hour and 30 minutes, reduced at the same temperature for 1 hour, and allowed to cool to room temperature.
A gray-brown titania silica-supported metal ruthenium powder was obtained. The obtained titania silica-supported metal ruthenium powder was heated from room temperature to 300 ° C. under an air flow of 100 ml / min.
The temperature was raised in 1 hour until the temperature was raised, and the mixture was calcined at the same temperature for 3 hours to obtain 7.5 g of a gray 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 / (RuO ₂ + TiO ₂ +
SiO ₂ ) × 100 = 6.1% by weight. The calculated value of the ruthenium content is Ru / (RuO ₂ + TiO ₂ + SiO
₂ ) × 100 = 4.6% 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 2, and hydrogen chloride gas was
The reaction was carried out in accordance with the reaction method of Example 2 except that 80 ml / min and oxygen gas were passed at 180 ml / min and the internal temperature was set to 300 ° C. The activity of forming chlorine per unit weight of the catalyst at the point of time 1.8 hours after the start of the reaction is 2.00 × 10 ^−4.
mol / min.g-catalyst.

Example 15 A catalyst was prepared by the following method. That is, Example 14
The titania-silica-supported metal ruthenium powder obtained by the same preparation method as that described above was used under air atmosphere from room temperature to 450 ° C. for 2 hours.
The temperature was raised for 30 minutes and calcined at the same temperature for 3 hours to obtain 7.6 g of a gray 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 / (RuO ₂ + TiO ₂ +
SiO ₂ ) × 100 = 6.1% by weight. The calculated value of the ruthenium content is Ru / (RuO ₂ + TiO ₂ + SiO
₂ ) × 100 = 4.6% 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 2, and hydrogen chloride gas was
The reaction was carried out in accordance with the reaction method of Example 2 except that 80 ml / min and oxygen gas were passed at 180 ml / min and the internal temperature was set to 300 ° C. 1.8 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 1.14 × 10 ^−4.
mol / min.g-catalyst.

Example 16 A catalyst was prepared by the following method. That is, 1-2 mm
0.5 mo to 6.02 g (manufactured by NE Chemcat) of a 5% by weight metal ruthenium titanium oxide catalyst having a spherical shape of φ
l / l of an aqueous potassium chloride solution was impregnated until water appeared on the surface of the catalyst, and then in air at 60 ° C for 10 minutes to 1 hour.
Dried for hours. This operation was repeated twice. The impregnation amount of the aqueous potassium chloride solution was 3.04 g for the first time and 2.89 for the second time.
g and the total was 5.93 g. The calculated value of the molar ratio between potassium chloride and ruthenium was 1.0. Next, this catalyst was dried in air at 60 ° C. for 4 hours, further heated from room temperature to 350 ° C. in air for about 1 hour, and calcined at the same temperature for 3 hours to obtain a spherical solid. After adding 500 ml of pure water to the obtained solid and stirring at room temperature for 1 minute, the catalyst was filtered. After repeating this operation four times, the resultant was dried in air at 60 ° C. for 4 hours to obtain 5.89 g of a blue-black spherical catalyst.
This spherical solid was crushed and sized to 12 to 18.5 mesh to obtain a titanium oxide-supported ruthenium oxide catalyst. The calculated value of the ruthenium oxide content was 6.5% by weight. The calculated value of the ruthenium content was 4.9% by weight. 2.50 g of the titanium oxide-supported ruthenium oxide catalyst thus obtained was filled in a quartz reaction tube in the same manner as in Example 2. Hydrogen chloride gas was supplied at a normal pressure of 202 ml / min, and oxygen gas was supplied at a pressure of 213 ml / min. The procedure was performed according to Example 2 except that the internal temperature (hot spot) was set to 301 ° C. 1.5 hours after the start of the reaction, the chlorine generation activity per unit catalyst weight was 4.19 × 10 ⁻⁴ mol /.
min.g-catalyst.

Example 17 A catalyst was prepared by the following method. That is, 1-2 mm
4 mol / l to 6.0 g of 5% by weight metal ruthenium titanium oxide catalyst (manufactured by NE Chemcat) having a spherical shape of φ
Was impregnated with water until the water surfaced on the surface of the catalyst, and dried in air at 60 ° C. for 10 minutes to 1 hour. This operation was repeated twice. The impregnation amount of the aqueous potassium chloride solution was 2.95 g in the first time and 3.72 g in the second time, and the total amount was 6.67 g. The calculated value of the molar ratio between potassium chloride and ruthenium was 10.0. Next, the catalyst is dried in air at 60 ° C. for 4 hours, and further dried in air at room temperature for 3 hours.
When the temperature was raised to 50 ° C. in about 1 hour and calcined at the same temperature for 3 hours, the powder was powdered, so that a powder was obtained. 50 on the resulting solid
After adding 0 ml of pure water and stirring at room temperature for 1 minute, the catalyst was filtered. After repeating this operation four times, the air
And dried for 4 hours to obtain 5.37 g of a blue-black powdery catalyst. This powder was molded, and the particles were adjusted to 12 to 18.5 mesh to obtain a titanium oxide-supported ruthenium catalyst.
The calculated value of the ruthenium oxide content was 6.5% by weight.
The calculated value of the ruthenium content was 4.9% by weight. 2.46 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 2. 190 ml / min of hydrogen chloride gas, 200 ml of oxygen gas
The procedure was performed in the same manner as in Example 2 except that the internal temperature was set to 301 ° C. while supplying the mixture at normal pressure / min. At 1.4 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 4.14 × 10 4
^-4 mol / min.g-catalyst.

Example 18 A catalyst was prepared by the following method. That is, 1-2 mm
2 mol / to 5.00 g (manufactured by NE Chemcat) of a 5 wt% supported metal ruthenium titanium oxide catalyst having a spherical shape of φ
The resulting solution was impregnated with an aqueous solution of sodium chloride prepared to a volume of 1 l until water appeared on the surface of the catalyst, and then dried in air at 60 ° C for 30 minutes to 1 hour. This operation was repeated twice. The impregnation amount of the aqueous sodium chloride solution was 2.28 g in the first time and 2.12 in the second time.
g and the total was 4.40 g. This was dried in air at 60 ° C. for 4 hours. The calculated value of the molar ratio between sodium chloride and ruthenium was NaCl / Ru = 3.3 (molar ratio). Next, the catalyst is heated in air at room temperature to 350 ° C. for about 1 hour.
The temperature was raised over a period of time and calcined at the same temperature for 3 hours to obtain a spherical solid.
After adding 500 ml of pure water to the obtained solid and stirring at room temperature for 1 minute, the catalyst was filtered. After repeating this operation three times, the resultant was dried in air at 60 ° C. for 4 hours to obtain 4.80 g of a blue-black spherical catalyst. The obtained solid is crushed and 12 to 1
A titanium oxide-supported ruthenium catalyst was obtained by adjusting the size to 8.5 mesh. The calculated value of the ruthenium oxide content was 6.5% by weight. The calculated value of ruthenium content is 4.
It was 9% by weight. 2.51 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 190 ml / min, and the internal temperature was changed to 301 ° C. Performed according to the reaction method of Example 2. 1.3 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 4.28 × 10 ⁻⁴ mo.
1 / min · g-catalyst.

Example 19 A catalyst was prepared by the following method. That is, 6.8 g of water
Ruthenium chloride RuCl ₃ .nH ₂ O (Ru content 35.
5%) was dissolved. Next, titanium oxide 60
%, Silica 40%, a particle size in the range of 10 to 90 μm, a statistical average of 41.2 μm, and 15.0 g of a spherical catalyst support for fluidized bed reaction manufactured by a manufacturer were impregnated with the entire amount of the previously prepared ruthenium chloride aqueous solution, Dry at 60 ° C. for 30 minutes. Next, 1.12 g of 96% sodium hydroxide was added to 20.6 g of water.
The carrier impregnated with ruthenium chloride was added to the aqueous solution dissolved in, stirred, and allowed to stand for 10 minutes. Then, a mixed aqueous solution of 0.46 g of 61% nitric acid and 20.8 g of water was added to adjust the pH to 7. The completed black catalyst is filtered off and 500 ml
Was washed four times with deionized water. After drying the catalyst at 60 ° C. for 4 hours, the temperature was raised to 350 ° C. in 3 hours and 30 minutes, and
By calcining for an hour, 15.1 g of a black catalyst was obtained.
The calculated value of the ruthenium oxide content is calculated as RuO ₂ / (R
uO ₂ + TiO ₂ ) × 100 = 6.2% by weight. The calculated value of the ruthenium content was 4.7% by weight. The thus obtained catalyst for a ruthenium oxide-supported fluidized bed 0.2
Example 2 except that no titanium oxide carrier for diluting g was used.
Into the reaction tube in the same manner as in
The reaction was carried out in accordance with the reaction method of Example 2 except that the mixture was circulated at a minimum temperature of 300 ° C. 1.7 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 7.65 × 10 ⁻⁴ mol / min · g-catalyst.

Example 20 A catalyst was prepared by the following method. That is, 2.0 mo
Commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O, Ru content 35.5%) in 861 ml of 1 / l hydrochloric acid aqueous solution
8.4 g was dissolved and left for 30 minutes. Next, 34.7 g of a titanium oxide powder (Catalyst Chemical Industry Co., Ltd. No. 1) was suspended in an aqueous solution of ruthenium chloride in hydrochloric acid, and the suspension was stirred.
A 2.0 mol / l aqueous solution of potassium hydroxide is added, and p
H was adjusted to 4.5, and ruthenium was precipitated and supported on titanium oxide. The added amount of the aqueous potassium hydroxide solution was 983 ml. Next, the suspension was heated to 60 ° C. while adjusting the pH to 4.5, and stirred for 3 hours. 2.0mo added
The amount of 1 / l aqueous potassium hydroxide solution was 15 ml. After completion of the stirring, the mixture was allowed to cool to room temperature, and the black-green powder was filtered. Next, the filtrate was dried at 60 ° C. for 4 hours. The gray powder was heated to 170 ° C. in air for 1 hour and heated at 170 ° C. for 8 hours. Next, also in air, to 375 ° C.
The temperature was raised over time and heated at 375 ° C. for 8 hours. After cooling, 48.7 g of a gray powder were obtained. Next, the above-mentioned ruthenium oxide catalyst was coated on an α-alumina carrier by the following method. That is, 8 g of α-alumina (3 mm sphere, manufactured by Fujimi Incorporated) was placed in an evaporating dish having a diameter of 12 cm, and 3.43 g of the catalyst powder was taken out while rolling, and gradually added. Occasionally, water containing 5% by weight of titanium oxide sol was sprayed for coating. The added aqueous solution was 3.8 g. The water containing the titanium oxide sol was prepared by previously diluting 38% by weight of a titanium oxide sol (manufactured by Sakai Chemical Co., Ltd., CSB) with water. The coated product was dried at 60 ° C., heated to 350 ° C. for 2.7 hours, and fired at the same temperature for 3 hours. Then, after cooling, 6 L with 2.0 L water using a glass filter.
Washed over time. Using an aqueous silver nitrate solution, it was confirmed that chlorine ions were not contained in the washing water. Next, it was dried at 60 ° C. for 8 hours with a dryer to obtain 11.1 g of a titanium oxide-supported ruthenium oxide catalyst coated on an α-alumina carrier. The content of ruthenium oxide in the coating catalyst was analyzed. The content as ruthenium by ICP (inductively coupled plasma) emission analysis was 2.9% by weight. 2.5 g of the coating catalyst thus obtained
Is mixed well with a titanium oxide carrier having a diameter of 2 to 4 mm to dilute the catalyst and fill the reaction tube made of quartz.
n, 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 weight of the catalyst was 3.86.
× 10 ⁻⁴ mol / min · g-catalyst.

Example 21 A catalyst was prepared by the following method. That is, 2.0 mo
Commercially available ruthenium chloride in 960 ml of 1 / l hydrochloric acid aqueous solution
Hydrate (RuCl_Three・ NH_TwoO, Ru content 35.5%) 2
0.5 g was dissolved and left for 30 minutes. Next, the titanium oxide
Powder (Catalyst Chemical Co., Ltd.) 22.4 g
Suspended in aqueous hydrochloric acid and stirred for 2.0 m
ol / l aqueous potassium hydroxide solution to adjust the pH to 4.
5, and ruthenium was precipitated and supported on titanium oxide.
The amount of aqueous potassium hydroxide added was 1070 ml.
Was. The suspension is then adjusted to pH 4.5 while adjusting the pH to 4.5.
C. and stirred for 3 hours. 2.0mol /
The aqueous solution of potassium hydroxide was 8 ml. End of stirring
Thereafter, the mixture was allowed to cool to room temperature, and the blackish green powder was filtered. Next,
Was dried at 60 ° C. for 4 hours. Empty this gray powder
Raise the temperature to 170 ° C in the air in 1 hour, and 8 hours at 170 ° C
Heated. Next, also in air, to 375 ° C in one hour
The temperature was raised and heated at 375 ° C. for 8 hours. Gray powder after cooling
48.6 g were obtained. Next, the ruthenium oxide contact
The medium is coated on an α-alumina carrier by the following method.
Was. That is, α-alumina (Fujimi Incorporated)
8 g of a rated evaporator dish with a diameter of 12 cm
And while rolling, 2.0
g, and gradually added, occasionally 5 wt.
% Methanol solution by spraying
Was. The amount of the added methanol solution was 6.7 g. Oxidation
The methanol solution containing the tansol is 38
Weight percent titanium oxide sol (CSB, manufactured by Sakai Chemical Co., Ltd.)
It was prepared by diluting with ethanol. What was coated
After drying at 60 ° C, the temperature is raised to 350 ° C in 2.7 hours
Then, firing was performed at the same temperature for 3 hours. Then, after cooling, the glass
Wash with 3.0 L of water for 6 hours using a filter
Was. Using silver nitrate aqueous solution, cleaning water contains chlorine ions
Confirmed that it was not. Then, at 60 ° C in a dryer, 8
Dry for 10 hours and coat on 10.1 g α-alumina carrier
To obtain a ruthenium oxide catalyst supported on titanium oxide. This
8.0 g of the coating catalyst obtained in
To mix well with 24g titanium oxide carrier of 4mm sphere
After diluting the catalyst into a quartz reaction tube,
700 ml / min, oxygen gas 700 ml / mi
n and the internal temperature was set to 300 ° C.
Performed according to the reaction method. 2.2 hours after the start of the reaction
The activity of chlorine production per unit catalyst weight was 4.13.
× 10 ^-Fourmol / min.g-catalyst.

Example 22 A catalyst was prepared by the following method. That is, 2.0 mo
Commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O, Ru content 35.5%) in 195 ml of 1 / l hydrochloric acid aqueous solution
4.23 g was dissolved and left for 30 minutes. Next, 30.0 g of titanium oxide powder (manufactured by Catalysis Kasei Co., Ltd.) was suspended in an aqueous solution of ruthenium chloride in hydrochloric acid, and stirred for 2.0 m.
ol / l aqueous potassium hydroxide solution to adjust the pH to 4.
5, and ruthenium was precipitated and supported on titanium oxide.
The added amount of the aqueous potassium hydroxide solution was 230 ml.
Next, the suspension was heated to 60 ° C. while adjusting the pH to 4.5, and stirred for 5 hours. The added 0.1 mol / l aqueous potassium hydroxide solution was 28 ml. After stirring,
After cooling to room temperature, 88 ml of a 0.1 mol / l aqueous potassium hydroxide solution was added to adjust the pH to 7, and then the blackish green powder was filtered. The amount of the filtrate (cake) was 63.3 g. 12.6 g of this was fractionated, and 1.57 g of a 38% by weight titanium oxide sol (manufactured by Sakai Chemical Co., Ltd., CSB) and 0.1% of potassium chloride.
6 g was added, kneaded well and extruded into a 4 mm clay.
The extruded product was dried at 60 ° C. for 4 hours. Then
The temperature was raised to 170 ° C. in the air in 1 hour, and heated at 170 ° C. for 8 hours. Next, the temperature was raised to 375 ° C. for 1 hour in the same air and heated at 375 ° C. for 8 hours. After cooling, 6.83 g of the obtained extruded product was washed with 6.0 L of water for 8 hours using a glass filter. Next, the extruded product was dried at 60 ° C. for 8 hours with a dryer, and then dried.
g of a ruthenium oxide catalyst supported on gray-green titanium oxide. The calculated value of the ruthenium oxide content was 6.3% by weight. The calculated value of the ruthenium content was 4.7% by weight.
By arranging this catalyst to a particle size of 2 to 4 mm,
A catalyst to be used for the reaction was obtained. The catalyst thus obtained was diluted by mixing 2.5 g of the shaped catalyst thus obtained with a titanium oxide carrier having a sphere diameter of 2 to 4 mm and charged into a quartz reaction tube. Hydrogen chloride gas was added at a rate of 202 ml / min. 2
The reaction was carried out in accordance with the reaction method of Example 2 except that the solution was circulated at 13 ml / min and the internal temperature was set to 300 ° C. 1.4 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 4.27 × 10 ⁻⁴ mol / min · g-catalyst.

Example 23 100 g of 16% by weight hydrochloric acid was placed in an ice-cooled flask, and 0.87 g of commercially available titanium tetrachloride was added dropwise with stirring in a nitrogen atmosphere. After stirring well, commercially available ruthenium chloride hydrate ( 28.24 g of RuCl ₃ .nH ₂ O) was dissolved. While stirring this aqueous solution, heat in an oil bath at 120 ° C.
Reflux. 200 ml / mi of oxygen in this aqueous solution
n was supplied under normal pressure to start the reaction. The liquid temperature at the start of the reaction was 104 ° C. At 30 minutes after the start of the reaction, the gas at the outlet of the reactor was passed through a 30% aqueous solution of potassium iodide to sample for 20 minutes, and the amount of chlorine produced was measured by an iodine titration method. The generated chlorine was 0.04 mmol.

Example 24 10.2 g of a spherical 5 wt% supported metal ruthenium titanium oxide catalyst having a diameter of 1 to 2 mmφ (manufactured by NE Chemcat)
Was ground and suspended in 98 g of 20% by weight hydrochloric acid in a glass flask with stirring. While stirring this aqueous solution, 1
The mixture was heated in an oil bath at 20 ° C. and refluxed. 200 ml / min of oxygen was supplied to this aqueous solution under normal pressure to start the reaction. The liquid temperature at the start of the reaction was 109 ° C.
Immediately after the start of the reaction, the gas at the outlet of the reactor was passed through a 30% aqueous potassium iodide solution for sampling for 60 minutes, and the amount of chlorine produced was measured by an iodine titration method. The generated chlorine was 2.87 mmol.

Comparative Example 1 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%) 0.70 g was dissolved in 4.0 g of water. After stirring the aqueous solution well, it is adjusted to 12-18.5 mesh,
It was added dropwise to 5.0 g of silica (Caractact G-10, manufactured by Fuji Silysia K.K.) dried at 500 ° C. for 1 hour in the air, and ruthenium chloride was impregnated thereon. The supported material was heated from room temperature to 100 ° C. for 30 minutes under a nitrogen stream of 100 ml / min, dried at the same temperature for 2 hours, and allowed to cool to room temperature to obtain a black solid. 100 ml of the obtained solid
1 hour 3 from room temperature to 250 ° C under an air flow of / min3
The temperature was raised in 0 minutes, dried at the same temperature for 3 hours, and 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 Ru /
(RuCl ₃ .3H ₂ O + SiO ₂ ) × 100 = 4.5% 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, and hydrogen chloride was added to a gas containing 20 g of hydrogen.
Circulated at 2 ml / min and oxygen gas at 213 ml / m
Example 2 except that the temperature was 300 ° C.
Performed according to. 1.7 hours after the start of the reaction, the activity of forming chlorine per unit catalyst weight was 0.49 × 10 ⁻⁴ m.
ol / min · g-catalyst.

Comparative Example 2 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. Then, it is fired in air at 600 ° C. for 3 hours, formed into a mesh of 12 to 18.5 mesh, and formed into Cr ₂ O ₃ —Si.
O ₂ catalyst was obtained. Cr ₂ O ₃ -Si obtained in this way
Without diluting 2.5 g of the O ₂ catalyst with the titanium oxide carrier, the reaction tube was filled in the same manner as in Example 2, and 192 ml of hydrogen chloride gas /
min. And carried out in accordance with Example 2 except that the internal temperature was 301 ° 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 catalyst.

Comparative Example 3 A catalyst was prepared by the following method. That is, spherical titanium oxide (manufactured by Sakai Chemical Industry Co., Ltd., CS-300) was pulverized in a mortar and powdered, and 8.0 g of ruthenium dioxide powder (NE Chemcat (manufactured by Co., Ltd.)) of 0.53 g were added. After mixing well while grinding in a mortar, the mixture was molded into a mesh of 12 to 18.5 mesh to obtain a mixed catalyst of ruthenium oxide and titanium oxide, and the calculated value of ruthenium oxide content was 6.2% by weight. Was calculated to be 4.7% by weight. A reaction tube was charged with 2.5 g of the thus obtained mixed catalyst of ruthenium oxide and titanium oxide in the same manner as in Example 2, and hydrogen chloride gas was supplied at 199 ml / min. 1 oxygen gas
The flow was carried out in accordance with Example 2 except that the solution was circulated at 94 ml / min and the internal temperature was set at 299 ° C. 2.3 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 0.3.
The catalyst was 83 × 10 ⁻⁴ mol / min · g.

Comparative Example 4 Titania silica powder was obtained in the same manner as in Example 14. A commercially available ruthenium chloride hydrate (RuCl ₃ .nH ₂ O, Ru content 3) was added to 8.0 g of the obtained titania silica powder.
(5.5%) After impregnating a solution in which 1.13 g of 1.13 g was dissolved in 8.2 g of water, the resultant was dried at 60 ° C. for 1 hour in the air to carry ruthenium chloride. Next, the supported substance was hydrogen 50 ml / mi.
n, from room temperature to 3 in a mixed gas flow of 100 ml / min of nitrogen
The temperature was raised to 00 ° C. in 1 hour and 30 minutes, reduced at the same temperature for 1 hour, and allowed to cool to room temperature to obtain 8.4 g of a gray-brown titania silica-supported metal ruthenium powder. 8.4 g of the obtained titania silica-supported metal ruthenium powder was added to 100 ml /
3 hours from room temperature to 600 ° C under a stream of air
By raising the temperature in 0 minutes and firing at the same temperature for 3 hours,
8.5 g of a gray powder were obtained. Molding the resulting powder,
By setting the mesh size to 12 to 18.5, a ruthenium oxide catalyst supported on titania silica was obtained. Note that the calculated value of the ruthenium oxide content is RuO ₂ / (RuO ₂ + TiO ₂ + Si
O 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 thus obtained ruthenium oxide catalyst supported on titania silica was charged into a reaction tube in the same manner as in Example 2, and the mixture was not diluted with a titanium oxide carrier, but was supplied with 180 ml / min of hydrogen chloride gas and 180 ml / min of oxygen gas. The reaction was carried out in accordance with the reaction method of Example 2 except that the reaction mixture was passed in min. 1.8 hours after the start of the reaction, the activity of forming chlorine per unit weight of the catalyst was 0.46 × 10 6
^-4 mol / min.g-catalyst.

[0118]

As described above, according to the present invention, there is provided a method for producing chlorine by oxidizing hydrogen chloride, wherein chlorine is produced at a lower reaction temperature with a smaller amount of catalyst using a highly active catalyst. A possible method for producing chlorine could be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application Hei 8-296305 (32) Priority date Hei 8 (1996) November 8 (33) Priority claim country Japan (JP) (31) Priority Claim number Japanese Patent Application No. 8-302656 (32) Priority Date Hei 8 (1996) November 14, (33) Priority claiming country Japan (JP) (31) Priority claim number Patent Application No. 9-10608 (32) Priority Japan, Japan (JP) (31) Priority claim number Japanese Patent Application No. 9-92042 (32) Priority day Hei 9 (1997) April 10, (33) ) Priority claiming country Japan (JP) (72) Inventor Masaru Ishino 5-1, Anesaki Beach, Ichihara City, Chiba Prefecture Within Sumitomo Chemical Co., Ltd. (72) Inventor Toshio Nakayama 5-1, Anesaki Beach, Ichihara City, Chiba Prefecture Sumitomo Chemical Industrial Co., Ltd.

Claims (7)

[Claims] 1. A method for producing chlorine by oxidizing hydrogen chloride with oxygen, wherein the content of ruthenium oxide is 0.1%.
-20% by weight, and the central particle size of ruthenium oxide is 1.
A method for producing chlorine using a supported ruthenium oxide catalyst or a ruthenium oxide composite oxide type catalyst having a particle size of 0 to 10.0 nanometers. 2. A method for producing chlorine by oxidizing hydrogen chloride with oxygen, wherein the content of ruthenium oxide is 0.5%.
A method for producing chlorine using a supported ruthenium oxide catalyst of up to 20% by weight. 3. A method for producing chlorine by oxidizing hydrogen chloride with oxygen, comprising using a supported ruthenium oxide catalyst obtained by oxidizing a supported metal ruthenium catalyst in a gas containing oxygen at 500 ° C. or lower. . 4. A method for producing chlorine by oxidizing hydrogen chloride with oxygen, wherein the supported ruthenium oxide catalyst is obtained by calcining a supported metal ruthenium catalyst in a gas containing oxygen in the presence of an alkali metal salt. Method for producing chlorine using 5. A method for producing chlorine by oxidizing hydrogen chloride with oxygen, comprising using a supported ruthenium oxide catalyst supported on a spherical carrier having a particle size of 10 to 500 μm. 6. A method for producing chlorine by oxidizing hydrogen chloride with oxygen, the method comprising using a catalyst obtained by coating a ruthenium oxide catalyst on an inert carrier or a catalyst obtained by extruding a ruthenium oxide catalyst. 7. A method for producing chlorine by oxidizing hydrogen chloride with oxygen, comprising using a ruthenium catalyst in an aqueous phase.