CN102762298B - Method for oxidizing organic compound - Google Patents

Abstract

An object of the present invention is to provide a method for oxidizing an organic compound in a mixed gas containing an organic compound, hydrogen chloride, and oxygen at a good conversion rate. The present invention is a method for oxidizing an organic compound in a mixed gas containing an organic compound, hydrogen chloride and oxygen by oxygen, characterized in that the reaction is carried out in the presence of a catalyst containing titanium oxide having a ruthenium content of 0.1% by mass or less. Titanium oxide preferably contains anatase crystal form titanium oxide. This method can be advantageously applied when the organic compound is at least one selected from the group consisting of aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, and phosgene.

Description

Oxidation Methods of Organic Compounds

technical field

This patent application claims priority under the Paris Convention based on Japanese Patent Application No. 2010-028641 (filed on February 12, 2010), and all the contents described in the above application are incorporated herein by reference.

The invention relates to an oxidation method, which uses oxygen to oxidize organic compounds in a mixed gas containing organic compounds, hydrogen chloride and oxygen in the presence of a catalyst.

Background technique

A method of supplying a hydrogen chloride-containing gas and an oxygen-containing gas in the presence of a catalyst to oxidize hydrogen chloride to obtain chlorine gas is known. As the catalyst, for example, a Ru-based catalyst can be used (for example, refer to Patent Document 1).

In the above-mentioned hydrogen chloride-containing gas, oxygen-containing gas, or inert gas that can be supplied together with them, an organic compound may be contained as an impurity due to its production method, generation source, and the like. When an organic compound is contained as an impurity in these gases, there are following problems: the presence of the organic compound itself or a chlorinated derivative of the organic compound causes a reduction in the conversion rate of hydrogen chloride; the above-mentioned organic compound or the above-mentioned derivative is carried After entering the reaction process, it will cause clogging of pipes, etc. In response to these problems, a method of decomposing the above-mentioned organic compound and a method of reducing the content of the organic compound in the raw material gas are urgently desired so that the above-mentioned organic compound is not contained and the above-mentioned derivative is not formed. As this method, a method has been proposed in which hydrogen chloride in a mixed gas containing an organic compound, hydrogen chloride, and oxygen is oxidized to chlorine gas in the presence of a catalyst in which ruthenium and/or a ruthenium compound are supported on titanium oxide, and A method of oxidatively decomposing an organic compound into carbon dioxide (Patent Document 2); a method of reducing the content of an organic compound by treating the gas containing hydrogen chloride and an organic compound used in the oxidation reaction with activated carbon (Patent Document 3).

prior art literature

patent documents

Patent Document 1: Japanese Patent Application Laid-Open No. 9-67103

Patent Document 2: Japanese Patent Laid-Open No. 2005-289800

Patent Document 3: Japanese Patent Publication No. 6-17203

Contents of the invention

The problem to be solved by the invention

However, the conventional methods described above are not necessarily sufficient for the purpose of oxidizing an organic compound in a mixed gas containing an organic compound, hydrogen chloride, and oxygen at a good conversion rate. Therefore, an object of the present invention is to provide a method for oxidizing an organic compound in a mixed gas containing an organic compound, hydrogen chloride, and oxygen at a good conversion rate.

means to solve the problem

As a result of intensive studies, the inventors of the present invention found the following new findings and completed the present invention. That is, by carrying out the above-mentioned oxidation reaction in the presence of a catalyst containing titanium oxide in which the content of ruthenium is 0.1% by mass or less, the organic compound in the mixed gas containing the organic compound, hydrogen chloride, and oxygen can be treated with a good conversion rate by oxygen. to oxidize.

That is, the present invention includes the following preferred aspects.

[1] An oxidation method for oxidizing an organic compound in a mixed gas containing an organic compound, hydrogen chloride, and oxygen with oxygen in the presence of a catalyst containing titanium oxide having a ruthenium content of 0.1% by mass or less.

[2] The method according to the above [1], wherein the titanium oxide contains anatase crystal form titanium oxide.

[3] The method according to [2] above, wherein the ratio of the anatase crystal-form titanium oxide in the titanium oxide measured by X-ray diffraction method to the sum of the anatase crystal-form titanium oxide and the rutile crystal-form titanium oxide is 20% or more.

[4] The method according to any one of the above [1] to [3], wherein the organic compound is at least one selected from the group consisting of aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons and phosgene.

[5] The method according to the above [4], wherein the aliphatic hydrocarbon is ethylene.

[6] The method according to the above [4], wherein the chlorinated aliphatic hydrocarbon is at least one selected from the group consisting of 2-chloropropane, methyl chloride and carbon tetrachloride.

[7] The method according to any one of the above [1] to [6], wherein the oxidation temperature is 250 to 450°C.

Invention effect

According to the present invention, an organic compound in a mixed gas containing an organic compound, hydrogen chloride, and oxygen can be oxygenated with oxygen at a good conversion rate. Furthermore, according to the oxidation method of the present invention, it is possible to selectively oxidize organic compounds while suppressing the oxidation of hydrogen chloride, and as a result, it is possible to obtain a hydrogen chloride mixed gas which is preferable as a raw material gas for producing chlorine gas. In addition, since the oxidation of hydrogen chloride can be suppressed and the organic compound can be selectively oxidized, the content of the organic compound can be reduced, and the production of chlorinated derivatives of the organic compound can be suppressed, thereby preventing clogging of the pipes which is a concern. Furthermore, by suppressing the oxidation of hydrogen chloride, heat generation due to generation of chlorine gas can be suppressed, the temperature of the reactor can be easily adjusted, and the oxidation reaction of the organic compound can be continued satisfactorily.

Detailed ways

The present invention relates to an oxidation method for oxidizing an organic compound in a mixed gas containing an organic compound, hydrogen chloride, and oxygen with oxygen in the presence of a catalyst containing titanium oxide having a ruthenium content of 0.1% by mass or less. The catalyst containing titania mentioned here includes, in addition to titania itself, composite oxides of titania and other metal oxides, titania and other metals such as alumina, zirconia, silica, niobium oxide, etc. mixture of oxides. Among them, titanium oxide itself is preferable.

In addition, the above-mentioned titanium oxide includes amorphous titanium oxide, titanium oxide in anatase crystal form (anatase titanium oxide), and titanium oxide in rutile crystal form (rutile titanium oxide). Among them, titanium oxide composed of anatase-type titanium oxide and/or rutile-type titanium oxide is preferable. Titanium oxide containing anatase-type titanium oxide is particularly preferred, and the ratio of anatase-type titanium oxide to the sum of anatase-type titanium oxide and rutile-type titanium oxide (hereinafter sometimes referred to as "anatase-type titanium oxide") is preferred. Ratio".) is 20% or more of titanium oxide, more preferably 50% or more of titanium oxide, and even more preferably 90% or more of titanium oxide. The higher the ratio of anatase-type titanium oxide, the better the activity of the resulting catalyst.

The ratio of the above-mentioned anatase-type titanium oxide is measured by an X-ray diffraction method (hereinafter referred to as "XRD method"), and is a value calculated from the following formula (I).

Anatase titanium oxide ratio [%] = [ _IA / ( _IA + I _R )] × 100 (I)

I _A : Represents the intensity of the diffraction line of the (101) plane of anatase titanium oxide

I _R : Represents the intensity of the diffraction line of the rutile-type titanium oxide (110) plane

As the above-mentioned catalyst, commercially available titanium oxide, commercially available titanium oxide shaped, or powdered or sol-shaped titanium oxide kneaded and shaped can be used, and fired as necessary. The firing may be performed before forming or after forming, and the strength of the titanium oxide can be improved by performing forming and firing in this order.

The firing temperature is usually 200 to 1200°C, preferably 300 to 800°C, more preferably 500 to 700°C. Firing is performed, for example, under a gas atmosphere such as an inert gas, an oxidizing gas, or a reducing gas. Examples of the inert gas include nitrogen, helium, etc. Examples of the oxidizing gas include air, oxygen, a mixed gas of nitrogen and oxygen, etc. Examples of the reducing gas include hydrogen, hydrogen A mixed gas such as nitrogen and nitrogen can be used alone or in combination of two or more. In addition, about 1 to 5 hours is generally suitable as the firing time, and about 60 to 1000° C./hour is suitable as the rate of temperature increase up to the firing temperature.

The shape of the above-mentioned catalyst can be used in the form of spherical particles, cylindrical particles, extruded shapes, ring shapes, honeycomb shapes, or particles of appropriate sizes that have been pulverized and classified after molding. In this case, the diameter of the catalyst is preferably 5 mm or less. When the diameter of the catalyst is too large, the conversion rate of the oxidation reaction of the organic compound becomes low. The lower limit of the diameter of the catalyst is not particularly limited, but if it becomes too small, the pressure loss on the catalyst layer increases, so a diameter of 0.5 mm or more is generally used. In addition, the diameter of the catalyst referred to here means the diameter of a sphere in the case of spherical particles, the diameter of a circular cross-section in the case of cylindrical particles, and the maximum diameter of the cross-section in other shapes.

In this way, a catalyst containing titanium oxide having a ruthenium content of 0.1% by mass or less can be obtained. The content of ruthenium in the titanium oxide is usually 0.1% by mass or less, preferably 0.05% by mass or less, more preferably 0.01% by mass or less. In addition, elements such as rhodium, palladium, copper, chromium, silver, osmium, iridium, platinum, and gold may be contained, and the total content of these elements in the titanium oxide is usually 0.1% by mass or less.

Sodium, potassium, magnesium, calcium, zirconium, niobium, iron, zinc, aluminum, silicon, cobalt, nickel, phosphorus, sulfur, chlorine, etc. may be contained in the said titanium oxide. In the above-mentioned titanium oxide, each content of these elements is usually 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.2% by mass or less.

The content of each element in the catalyst can be quantified, for example, by inductively coupled plasma emission spectrometry (hereinafter referred to as "ICP analysis").

In addition, when the above-mentioned catalyst is used in the oxidation reaction, it may be diluted with a substance inert to the reaction, such as alumina, zirconia, or silica, before use.

In the present invention, an organic compound, hydrogen chloride, and oxygen are supplied in the presence of the above-mentioned catalyst to form a mixed gas. Also, in such a reaction system in which an organic compound and hydrogen chloride coexist, the organic compound can be oxidized with little hydrogen chloride oxidized.

The mixed gas containing organic compound, hydrogen chloride and oxygen can be obtained by the following method. For example, a method of mixing a gas containing an organic compound and hydrogen chloride with a gas containing oxygen; a method of mixing a gas containing hydrogen chloride with a gas containing an organic compound and oxygen; mixing a gas containing an organic compound, a gas containing hydrogen chloride, and a gas containing oxygen The method of gas mixing, etc. The mixed gas may be brought into contact with the above-mentioned catalyst after being contacted with activated carbon.

The gas containing an organic compound and hydrogen chloride is not particularly limited as long as it contains an organic compound and hydrogen chloride. In addition, the gas containing hydrogen chloride is not particularly limited as long as it is a gas containing hydrogen chloride. Examples of the above-mentioned organic compound and hydrogen chloride-containing gas or the above-mentioned hydrogen chloride-containing gas include reactions between hydrogen and chlorine, thermal decomposition or combustion of chlorides, phosgenation or chlorination of organic compounds, chlorine Production of fluoroalkanes, hydrolysis of chlorinated hydrocarbons, heating of hydrochloric acid, gases generated during combustion in incinerators, oxidation of hydrogen chloride to chlorine, production of 1,2-dichloroethane from hydrogen chloride and ethylene, etc. Gases recovered from etc. In addition, oxygen and an inert gas that can be recovered in each of the above reactions may also be contained in the above-mentioned mixed gas.

Examples of the thermal decomposition reaction of the chlorides include the production of vinyl chloride from 1,2-dichloroethane, the production of tetrafluoroethylene from chlorodifluoromethane, and the like.

Examples of the phosgenation reaction of the organic compound include production of isocyanate by reaction of amine and phosgene, production of carbonate by reaction of alcohol and/or aromatic alcohol and phosgene, and the like.

As the chlorination reaction of the above-mentioned organic compound, the production of chloropropene by the reaction of propylene and chlorine gas, the production of chloroethane by the reaction of ethane and chlorine gas, the production of chloroethane from the reaction of 1,2-dichloroethane Manufacture of trichlorethylene and tetrachlorethylene by reaction with chlorine gas, manufacture of chlorobenzene by reaction of benzene and chlorine gas, etc.

Examples of the production of the above-mentioned chlorofluoroalkanes include the production of dichlorodifluoromethane and trichloromonofluoromethane by the reaction of carbon tetrachloride and hydrogen fluoride, and the production of dichlorodifluoromethane by the reaction of methane, chlorine and hydrogen fluoride. Manufacture of methane and trichlorofluoromethane, etc.

Examples of the hydrolysis reaction of the above-mentioned chlorinated hydrocarbons include production of phenol by the reaction of chlorobenzene and water, and the like.

The oxygen-containing gas may be pure oxygen, a gas obtained by diluting pure oxygen with a gas inert to the oxidation reaction, such as nitrogen or argon, or air. The gas containing an organic compound and oxygen may be a gas composed only of an organic compound and oxygen, or may be a gas in which an organic compound and oxygen are diluted with a gas inert to an oxidation reaction such as nitrogen or argon. Can be a gas composed of organic compounds and air. Pure oxygen can be obtained by common industrial methods such as air pressure swing adsorption and cryogenic separation. The amount of oxygen used is not particularly limited, but is preferably 1 times the mole or more, more preferably 10 times the mole or more, based on the organic compound. When the amount of oxygen used is less than 1 mole of the organic compound, the conversion rate of the organic compound may be low.

The organic compounds in the above-mentioned mixed gas containing organic compounds, hydrogen chloride and oxygen can be appropriately selected, and preferably include aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, phosgene, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated aromatic At least one selected from the group consisting of aliphatic hydrocarbons, alcohols, and phenols, among which at least one selected from the group consisting of aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, and phosgene is preferred.

Examples of the aliphatic hydrocarbons include saturated aliphatic hydrocarbons such as methane, ethane, propane, butane, and hexane, and unsaturated aliphatic hydrocarbons such as ethylene, propylene, butene, butadiene, hexene, and acetylene. Among them, methane, ethane, ethylene, propylene, and acetylene are preferable, and ethylene is particularly preferable.

Examples of chlorinated aliphatic hydrocarbons include methyl chloride, methylene chloride, chloroform, carbon tetrachloride, ethyl chloride, dichloroethane such as 1,2-dichloroethane, trichloromethane, Chloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, chloropropanes like 2-chloropropane, dichloropropanes like 1,2-dichloropropane, vinyl chloride, dichloroethylene , trichloroethylene, vinyl chloride such as tetrachloroethylene, chloropropene, dichloropropene such as 1,3-dichloro-1-propene, and the like. Among them, methyl chloride, dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, vinyl chloride, ethylene dichloride, chloropropane, dichloropropane, chloropropene, and dichloropropene are preferred, and chloropropene is particularly preferred. Methane, carbon tetrachloride, 2-chloropropane.

The content of the organic compound contained in the mixed gas is usually 20% by volume or less, preferably 1% by volume or less, more preferably 0.1% by volume or less, based on hydrogen chloride. When the content of the organic compound exceeds 20% by volume, the conversion rate of the organic compound may decrease. In addition, the content of the organic compound contained in the above-mentioned mixed gas depends on the source of the gas, but usually contains the organic compound in an amount of 0.1 volume ppm or more relative to hydrogen chloride, and the present invention can be advantageously employed in this case.

Chlorine gas and/or moisture may be contained in the above-mentioned mixed gas. When chlorine gas is contained, the conversion rate of the oxidation reaction of the organic compound increases. When water is contained, the catalyst layer may be effectively used by smoothing the temperature distribution in the catalyst layer, thereby maintaining stable activity of the catalyst. The contents of chlorine gas and moisture in the mixed gas are usually not more than 50% by volume, preferably not more than 30% by volume, and more preferably not more than 10% by volume.

In addition, reducing agents such as hydrogen and carbon monoxide may be contained in the above-mentioned mixed gas. The reducing agent can be oxidized using the oxidation method of the present invention.

Gases inert to oxidation reactions, such as nitrogen and argon, may be contained in the above-mentioned mixed gas.

The concentration of hydrogen chloride in the mixed gas is usually at least 5% by volume, preferably at least 30% by volume, and more preferably at least 50% by volume.

The amount of the catalyst used is usually 10 to 50000 h ^-1 when represented by the ratio (GHSV) of the supply rate of the mixed gas containing the organic compound, hydrogen chloride and oxygen to the catalyst volume under the standard state.

The reaction temperature in the oxidation reaction of the present invention is usually 200 to 500°C, preferably 250 to 450°C, more preferably 300 to 400°C. When the reaction temperature is too low, the conversion rate of the organic compound may decrease. On the other hand, when the reaction temperature is too high, the conversion rate of the organic compound may decrease due to thermal degradation of the catalyst.

The pressure of the oxidation reaction is usually 0.1 to 5 MPa, preferably 0.1 to 1 MPa.

The gas linear velocity of the superficial tower reference is usually 0.1-20m/s. In addition, the gas linear velocity of the superficial tower reference in the present invention refers to the total amount of the supply velocity and the cross-sectional area of the reactor ( The ratio of the area of the section perpendicular to the gas supply direction).

As the reaction method, reaction methods such as a fluidized bed, a fixed bed, and a moving bed can be used, and a fixed bed reactor of an adiabatic method or a heat exchange method is preferable. When using an adiabatic fixed-bed reactor, any of a single-tubular fixed-bed reactor and a multi-tubular fixed-bed reactor can be used, and a single-tubular fixed-bed reactor is preferably used. When using a fixed-bed reactor of a heat exchange system, any of a single-tubular fixed-bed reactor and a multi-tubular fixed-bed reactor can be used, and a multi-tubular fixed-bed reactor is preferably used.

The oxidation reaction of the present invention selectively oxidizes organic compounds while suppressing oxidation of hydrogen chloride. According to the present invention, the ratio of the conversion rate of hydrogen chloride to the conversion rate of organic compounds (conversion rate (%) of hydrogen chloride/conversion rate (%) of organic compounds) is generally 0.5 or less, preferably 0.2 or less, more preferably 0.1 React in the following manner. When the ratio of the conversion rate of hydrogen chloride to the conversion rate of the organic compound becomes high, the heat generated by the oxidation reaction of hydrochloric acid becomes large, and it may be difficult to control the temperature of the reactor.

The hydrogen chloride obtained in the present invention can be used for production of chlorine gas by reaction with oxygen, production of chlorine gas by electrolysis of hydrogen chloride, and production of 1,2-dichloroethane by reaction with ethylene.

Example

Hereinafter, although an Example demonstrates this invention, this invention is not limited to the following Example. In addition, the ruthenium content of the catalysts obtained in each of the following examples was analyzed using an ICP emission spectrometer (manufactured by Shimadzu Corporation, ICPS-8100).

Example 1

(Preparation of Catalyst A)

Titanium oxide powder [SSP-M manufactured by Sakai Chemical Co., Ltd., titanium oxide > 95% by mass, X-ray particle size: 15nm] is tableted and then pulverized to make a 1-2mm granular catalyst to obtain an oxidized Titanium catalyst A (the ratio of anatase type titanium dioxide is 100%). The ruthenium content of catalyst A is less than 50 mass ppm.

(oxidation reaction)

Fill the catalyst A of 1.1g (0.9cm ³ ) in the upright quartz reaction tube (inner diameter 14mm), from this reaction tube top, respectively 100ml/min, 50ml/min and 10.0ml/min (both at an absolute pressure of 0.1MPa at a flow rate of 0°C conversion) to continuously supply hydrogen chloride gas, oxygen, and ethylene gas diluted to 2.0% by volume with nitrogen, and start the reaction at a reaction temperature of 380°C and a reaction pressure of 0.1 MPa (the amount of ethylene relative to hydrogen chloride: 0.2 volume %). The ratio (GHSV) of the supply rate of the raw material gas (hydrogen chloride gas, oxygen gas, and ethylene gas diluted to 2.0% by volume with nitrogen) to the catalyst volume was 10667 h ^-1 .

When 2 hours had elapsed from the start of the reaction, the conversion rate of hydrogen chloride and the respective yields of carbon monoxide and carbon dioxide relative to ethylene were determined. The measurement methods of conversion rate and yield are as follows, and the results are shown in Table 1.

(conversion rate of hydrogen chloride)

The gas at the outlet of the reaction tube was circulated in a 30% by mass potassium iodide aqueous solution, sampling was performed for 20 minutes, and the amount of chlorine gas produced was measured by iodometric titration to obtain the chlorine gas production rate (mol/hour). The production rate of chlorine gas and the supply rate of hydrogen chloride gas were substituted into the following formula (I) to calculate the conversion rate of hydrogen chloride.

The conversion rate (%) of hydrogen chloride=[(a×2)/b]×100 (I)

a: Chlorine generation rate (mol/hour)

b: Supply rate of hydrogen chloride gas (mol/hour)

(yield of carbon monoxide and carbon dioxide)

The residual gas not absorbed by the potassium iodide aqueous solution in the above sample was analyzed for carbon monoxide and carbon dioxide by gas chromatography using a TCD detector. The yields of carbon monoxide and carbon dioxide were calculated by substituting the amount of carbon monoxide and the production rate (mol/hour) of carbon dioxide thus obtained into the following formula (II).

Carbon monoxide or carbon dioxide yield (%) = c/(d×e)×100 (II)

c: production rate of carbon monoxide or carbon dioxide (mol/hour)

d: Supply rate of organic compound gas (mol/hour)

e: carbon number of organic compound molecule

Example 2

(Preparation of Catalyst B)

Titanium oxide powder [MC-50 manufactured by Ishihara Sangyo Co., Ltd., titanium oxide = 97%, particle size: 24nm] is tabletted, crushed, and made into a granular catalyst of 1 to 2 mm to obtain titanium oxide catalyst B (The ratio of anatase type titanium dioxide is 100%). The ruthenium content of catalyst B is less than 50 mass ppm.

(oxidation reaction)

The oxidation reaction was carried out in the same manner as in Example 1, except that 1.2 g (1.1 cm ³ ) of catalyst B (GHSV: 8727h ^-1 ) was used instead of catalyst A. Table 1 shows the conversion rate of hydrogen chloride and the respective yields of carbon monoxide and carbon dioxide relative to ethylene.

Example 3

(Preparation of Catalyst C)

Under air circulation, heat up titanium oxide balls [CS-300S-12 manufactured by Sakai Chemical Co., Ltd., 1-2mm particle size] from room temperature to 200°C in 15 minutes, and from 200°C to 600°C in 1.3 hours. Then, it was kept at this temperature for 2 hours and fired to obtain a titanium oxide catalyst C (ratio of anatase-type titanium dioxide: 100%). Catalyst C has a ruthenium content of less than 50 ppm by mass.

(oxidation reaction)

The oxidation reaction was carried out in the same manner as in Example 1, except that 1.4 g (1.1 cm ³ ) of catalyst C (GHSV: 8727h ^-1 ) was used instead of catalyst A. Table 1 shows the conversion rate of hydrogen chloride and the respective yields of carbon monoxide and carbon dioxide relative to ethylene.

Example 4

(Preparation of Catalyst D)

Under air circulation, heat up titanium oxide balls [CS-300S-12 manufactured by Sakai Chemical Co., Ltd., 1-2mm particle size] from room temperature to 200°C in 15 minutes, and from 200°C to 700°C in 1.7 hours. Then, it was kept at this temperature for 2 hours and fired to obtain a titanium oxide catalyst D (ratio of anatase-type titanium dioxide: 100%). Catalyst D has a ruthenium content of less than 50 ppm by mass.

(reaction)

The oxidation reaction was carried out in the same manner as in Example 1, except that 1.4 g (1.1 cm ³ ) of catalyst D (GHSV: 8727h ^-1 ) was used instead of catalyst A. Table 1 shows the conversion rate of hydrogen chloride and the respective yields of carbon monoxide and carbon dioxide relative to ethylene.

Example 5

In addition to supplying 2-chloropropane gas diluted to 1.0% by volume with nitrogen gas at a flow rate of 5.0ml/min (absolute pressure 0.1MPa, 0°C conversion) instead of ethylene gas diluted to 2.0% by volume with nitrogen, and carried out. Example 4 is the same operation. 2-Chloropropane was calculated to be 0.05% by volume based on the amount of hydrogen chloride in the raw material. Table 2 shows the conversion rate of hydrogen chloride and the respective yields of carbon monoxide and carbon dioxide relative to 2-chloropropane.

Example 6

Except that instead of ethylene gas diluted to 2.0% by volume with nitrogen, methyl chloride gas diluted to 2.6% by volume with nitrogen was supplied at a flow rate of 3.9ml/min (absolute pressure 0.1MPa, 0°C conversion), and the same procedure as in Example was carried out. 4 the same operation. Methyl chloride was calculated to be 0.1% by volume relative to the amount of hydrogen chloride in the raw material. Table 2 shows the conversion rate of hydrogen chloride and the respective yields of carbon monoxide and carbon dioxide relative to methyl chloride.

Example 7

Except that instead of ethylene gas diluted to 2.0% by volume with nitrogen, carbon tetrachloride diluted to 15.0% by volume with nitrogen was supplied at a flow rate of 3.8ml/min (absolute pressure 0.1MPa, 0°C conversion), and the same procedure as in Example was carried out. 4 the same operation. Carbon tetrachloride was calculated to be 0.6% by volume based on the amount of hydrogen chloride in the raw material. Table 2 shows the conversion rate of hydrogen chloride and the respective yields of carbon monoxide and carbon dioxide relative to carbon tetrachloride.

Comparative example 1

(Preparation of Catalyst E)

An aqueous solution prepared by dissolving 4.2 g of cerium nitrate hydrate [manufactured by Kosun Chemical Co., Ltd.] in 91.7 g of pure water, and 0.64 g of zirconium nitrate hydrate [manufactured by Taiyo Mining Co., Ltd.] in 91.7 g of pure water were prepared. The prepared aqueous solution and an aqueous solution prepared by dissolving 5.1 g of citric acid (manufactured by Wako Pure Chemical Industries, Ltd.) in 21.4 g of pure water were mixed, stirred at 80°C for 2 hours, and then stirred at room temperature for 1 hour . After stirring, water was distilled off at 80°C under reduced pressure, and the obtained solid was dried at 80°C. After drying, it pulverized with a mortar, and then baked at 500 degreeC for 2 hours in air. The calcined product was pulverized in a mortar, and the powder was pelletized and pulverized to obtain a 1 to 2 mm granular catalyst, whereby a ceria-zirconia composite oxide catalyst E was obtained.

(reaction)

The same operation as in Example 1 was carried out except that 1.1 g (0.9 cm ³ ) of catalyst E was used instead of catalyst A. Table 1 shows the conversion rate of hydrogen chloride and the respective yields of carbon monoxide and carbon dioxide relative to ethylene.

Comparative example 2

(Preparation of Catalyst F)

Pulverize silica and alumina [JRC-SAH-1 manufactured by Nikki Catalyst Chemicals Co., Ltd.] with a mortar, press the powder into tablets, and then pulverize it to make a granular catalyst of 1 to 2 mm. Silica-alumina catalyst F.

(reaction)

The same operation as in Example 1 was carried out except that 1.3 g (0.9 cm ³ ) of catalyst F was used instead of catalyst A. Table 1 shows the conversion rate of hydrogen chloride and the respective yields of carbon monoxide and carbon dioxide relative to ethylene.

Comparative example 3

(Preparation of Catalyst G)

A commercially available titanium oxide catalyst containing ruthenium oxide [manufactured by N.E. Chemcat Corporation, with a ruthenium oxide content of 6.6% by mass (a ruthenium content of 5.0% by mass), an anatase-type titanium dioxide ratio of 100%, and 1 to 2 mm balls] was pulverized The powder was classified into 75 to 150 μm, and this powder was referred to as catalyst G.

(reaction)

The same operation as in Example 1 was carried out except that 0.9 g (0.9 cm ³ ) of catalyst G was used instead of catalyst A. Table 1 shows the conversion rate of hydrogen chloride and the respective yields of carbon monoxide and carbon dioxide relative to ethylene.

Comparative example 4

(Preparation of Catalyst H)

Titanium oxide powder [F-1R manufactured by Showa Titanium Co., Ltd., rutile-type titanium oxide ratio of 93%] 100 parts, Cerander [YB-152A manufactured by Yuken Industry Co., Ltd.] 0.5 parts and sugar ester [Mitsubishi Chemical Foods Co., Ltd. S-1570] 2 parts were mixed, then, 25.5 parts of pure water were added, 12.5 parts of titanium oxide sol [CSB manufactured by Sakai Chemical Co., Ltd., titanium oxide content was 40%] were added, and mixed refining. This mixture was extruded into a noodle shape with a diameter of 3.0 mmφ, dried at 110° C. for 2 hours, and crushed into a length of about 3 to 5 mm. The obtained molded body was heated from room temperature to 600° C. in air over 1.7 hours, and then kept at this temperature for 3 hours to perform firing. Further, a solution prepared by dissolving 31.9 g of tetraethyl orthosilicate [Si(OC ₂ H ₅ ) ₄ manufactured by Wako Pure Chemical Industries, Ltd.] in 137.7 g of ethanol was impregnated into 900 g of the obtained fired product, It was left to stand at 22° C. for 3.3 hours in an air atmosphere. Under air circulation, 900 g of the obtained solid was heated from room temperature to 300° C. in 2 hours, then kept at this temperature for 2 hours, and fired to obtain 898 g of a white titanium oxide carrier with a silicon dioxide content of 1.0%. The titanium dioxide ratio is 90% or more, the sodium content is 12 mass ppm, and the calcium content is 8 mass ppm]. An aqueous solution prepared by dissolving 2.16 g of ruthenium chloride hydrate [RuCl ₃ nH ₂ O manufactured by NEChemcat Corporation, with a Ru content of 40.0% by mass] in 20.5 g of pure water was impregnated into 90.0 g of the titanium oxide carrier, and the Under air atmosphere, it was left to stand at 35° C. for 6.2 hours. Under air flow, 18.2 g of the obtained solid was heated from room temperature to 250° C. over 1.3 hours, then kept at this temperature for 2 hours, and fired to obtain a ruthenium oxide content of 1.25% by mass (ruthenium content: 0.95% by mass). TiO catalyst H.

(reaction)

The same operation as in Example 1 was carried out except that 1.1 g (0.9 cm ³ ) of catalyst H was used instead of catalyst A. Table 1 shows the conversion rate of hydrogen chloride in the raw material and the respective yields of carbon monoxide and carbon dioxide relative to ethylene.

【Table 1】

【Table 1】

Claims (7)

1. a method for oxidation, its content at ruthenium is under the existence of the catalyst that comprises titanium oxide below 0.1 quality %, utilizes oxygen to be oxidized the organic compound including in the mist of organic compounds, hydrogen chloride and oxygen,

The conversion ratio of hydrogen chloride is below 0.1 with the conversion ratio % that the ratio of the conversion ratio of organic compound is the conversion ratio %/organic compound of hydrogen chloride.

2. method according to claim 1, wherein, described titanium oxide contains anatase crystalline form titanium oxide.

3. method according to claim 2, wherein, utilizing the ratio of anatase crystalline form titanium oxide in the described titanium oxide that X-ray diffraction method measures is more than 20% with respect to the summation of anatase crystalline form titanium oxide and rutile crystal form titanium oxide.

4. method according to claim 1, wherein, described organic compound is at least a kind that selects in the group of free aliphatic hydrocarbon, chloro fat family hydrocarbon and phosgene composition.

5. method according to claim 4, wherein, described aliphatic hydrocarbon is ethene.

6. method according to claim 4, wherein, described chloro fat family hydrocarbon is at least a kind that selects in the group of free 2 cbloropropane isopropyl chloride, chloromethane and carbon tetrachloride composition.

7. according to the method described in any one in claim 1～6, wherein, oxidizing temperature is 250～450 DEG C.