JP5365540B2 - Method for oxidizing organic compounds - Google Patents

Description

  The present invention relates to a 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.

  A method is known in which a hydrogen chloride-containing gas and an oxygen-containing gas are supplied in the presence of a catalyst to oxidize hydrogen chloride to obtain chlorine. Examples of the catalyst include a Ru-based catalyst (for example, Patent Document 1). Etc.) are used.

  An organic compound may be contained as an impurity in the hydrogen chloride-containing gas, the oxygen-containing gas, or an inert gas that can be supplied in combination with the hydrogen chloride-containing gas, the oxygen-containing gas, or the like. If an organic compound is contained as an impurity in these gases, the organic compound itself or the presence of a chlorinated derivative of the organic compound may cause problems such as a decrease in the conversion rate of hydrogen chloride, and the organic compound or the derivative may react. There is a problem of blockage of piping due to being brought in after the process. In order to prevent these organic compounds from being included in the above-described problem and to prevent the formation of the derivatives, a method of decomposing the organic compound or a method of reducing the content of the organic compound in the raw material gas Is desired. As the method, in the presence of a catalyst in which ruthenium and / or a ruthenium compound is supported on titanium oxide, hydrogen chloride in a mixed gas containing an organic compound, hydrogen chloride and oxygen is oxidized to chlorine, and the organic compound is oxidized with oxygen. A method of oxidizing and decomposing into carbon dioxide (Patent Document 2), or a method of reducing the content of an organic compound by treating a gas containing hydrogen chloride and an organic compound used for the oxidation reaction with activated carbon (Patent Document 3). ) Has been proposed.

JP-A-9-67103 JP-A-2005-289800 Japanese Examined Patent Publication No. 6-17203

  However, the above-described conventional methods are not necessarily sufficient in that the organic compound in the mixed gas containing the organic compound, hydrogen chloride and oxygen is oxidized 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.

  As a result of intensive studies, the present inventors have conducted a mixture reaction including an organic compound, hydrogen chloride, and oxygen by performing the oxidation reaction in the presence of a catalyst containing titanium oxide having a ruthenium content of 0.1% by weight or less. The inventors have found a new finding that an organic compound in a gas can be oxidized with oxygen at a good conversion rate, and have completed the present invention.

  That is, the present invention provides a 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 weight or less. To do.

  According to the present invention, an organic compound in a mixed gas containing an organic compound, hydrogen chloride, and oxygen can be oxidized with oxygen at a good conversion rate. In addition, according to the oxidation method of the present invention, an organic compound can be selectively oxidized while suppressing oxidation of hydrogen chloride, and as a result, a hydrogen chloride mixed gas suitable as a raw material gas for producing chlorine can be obtained. . In addition, since the organic compound can be selectively oxidized while suppressing the oxidation of hydrogen chloride, the content of the organic compound can be reduced and the production of chlorinated derivatives of the organic compound can also be suppressed, and the blockage of the piping concerned is prevented. Can do. Furthermore, by suppressing the oxidation of hydrogen chloride, heat generation due to the generation of chlorine can be suppressed, the temperature of the reactor can be easily adjusted, and the oxidation reaction of the organic compound can be favorably continued.

  The present invention is capable of 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 weight or less. Is. As the catalyst containing titanium oxide here, in addition to titanium oxide itself, composite oxides of titanium oxide and other metal oxides, other metal oxides such as titanium oxide and alumina, zirconium oxide, silica, niobium oxide, etc. Mixtures with products are also included. Among these, titanium oxide itself is preferable.

  Examples of the titanium oxide include amorphous ones, anatase crystal form (anatase type titanium oxide), and rutile crystal form (rutile type titanium oxide). Especially, what consists of anatase type titanium oxide and / or a rutile type titanium oxide is preferable. In particular, titanium oxide containing anatase-type titanium oxide is preferable, and the ratio of anatase-type titanium oxide to the total of anatase-type titanium oxide and rutile-type titanium oxide (hereinafter sometimes referred to as “anatase-type titanium oxide ratio”) is 20. % Or more of titanium oxide is preferable, 50% or more of titanium oxide is more preferable, and 90% or more of titanium oxide is even more preferable. The higher the anatase titanium oxide ratio, the better the activity of the resulting catalyst.

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

Anatase-type titanium oxide ratio [%] = [I _A / (I _A + I _R )] × 100 (I)
I _A : Intensity of diffraction line showing anatase type titanium oxide (101) plane I _R : Intensity of diffraction line showing rutile type titanium oxide (110) plane

  As the catalyst, commercially available titanium oxide, a product obtained by molding a commercially available titanium oxide, or a product obtained by kneading and molding a powdered or sol-like titanium oxide can be used, and calcined as necessary. The firing may be performed before molding or after molding, but the strength of the titanium oxide can be improved by performing the molding and firing in this order.

  The firing temperature is usually 200 to 1200 ° C, preferably 300 to 800 ° C, and more preferably 500 to 700 ° C. Firing is performed in a gas atmosphere such as an inert gas, an oxidizing gas, or a reducing gas. Examples of the inert gas include nitrogen and helium. Examples of the oxidizing gas include air, oxygen, and a mixed gas of nitrogen and oxygen. Examples of the reducing gas include hydrogen, Examples thereof include a mixed gas of hydrogen and nitrogen, and these may be used alone or in combination. The firing time is usually about 1 to 5 hours, and the heating rate up to the firing temperature is about 60 to 1000 ° C./hour.

  The catalyst may be used in the form of a spherical granule, a cylindrical pellet, an extruded shape, a ring shape, a honeycomb shape, or an appropriately sized granule that has been pulverized and classified after molding. At this time, the diameter of the catalyst is preferably 5 mm or less. If the diameter of the catalyst is too large, the conversion rate of the oxidation reaction of the organic compound may be low. The lower limit of the diameter of the catalyst is not particularly limited, but if it becomes excessively small, pressure loss in the catalyst layer increases, and therefore, a catalyst having a diameter of 0.5 mm or more is usually used. The diameter of the catalyst here means the diameter of a sphere in the case of spherical particles, the diameter of a circular cross section in the case of a cylindrical pellet, and the maximum diameter of the cross section in other shapes.

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

  The titanium oxide may include sodium, potassium, magnesium, calcium, zirconium, niobium, iron, zinc, aluminum, silicon, cobalt, nickel, phosphorus, sulfur, chlorine and the like. Each content of these elements is usually 1% by weight or less, preferably 0.5% by weight or less, and more preferably 0.2% by weight or less in the titanium oxide.

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

  In addition, when using the said catalyst for an oxidation reaction, it can also be used by diluting with a substance inactive to reaction, such as an alumina, a zirconium oxide, and a silica.

  In the present invention, an organic compound, hydrogen chloride, and oxygen are supplied in the presence of the catalyst to form a mixed gas. In a reaction system in which such an organic compound and hydrogen chloride coexist, the organic compound can be oxidized with almost no oxidation of hydrogen chloride.

  The mixed gas containing an organic compound, hydrogen chloride and oxygen contains, for example, a method of mixing a gas containing an organic compound and hydrogen chloride and a gas containing oxygen, a gas containing a hydrogen chloride, an organic compound and oxygen. It can be obtained by a method of mixing with a gas, a gas containing an organic compound, a gas containing hydrogen chloride and a gas containing oxygen, or the like. The mixed gas may be brought into contact with the catalyst after being brought into contact with activated carbon.

  The gas containing the organic compound and hydrogen chloride is not particularly limited as long as the gas contains the organic compound and hydrogen chloride. Further, the gas containing hydrogen chloride is not particularly limited as long as it contains hydrogen chloride. Examples of the gas containing the organic compound and hydrogen chloride or the gas containing hydrogen chloride include, for example, a reaction between hydrogen and chlorine, a pyrolysis reaction or combustion reaction of a chlorine compound, a phosgenation reaction or chlorination reaction of an organic compound, Production of chlorofluoroalkanes, hydrolysis reaction of chlorinated hydrocarbons, heating of hydrochloric acid, gas generated in combustion of incinerators, oxidation reaction of hydrogen chloride to chlorine, 1,2-dichloroethane from hydrogen chloride and ethylene Examples include gas recovered in the reaction to be produced. Further, oxygen and inert gas that can be recovered in each of these reactions may be contained in the mixed gas.

  Examples of the thermal decomposition reaction of the chlorine compound include production of vinyl chloride from 1,2-dichloroethane, 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 ester by reaction of alcohol and / or aromatic alcohol and phosgene, and the like.

  As the chlorination reaction of the organic compound, production of allyl chloride by reaction of propylene and chlorine, production of chloroethane by reaction of ethane and chlorine, production of trichloroethylene and tetrachloroethylene by reaction of 1,2-dichloroethane and chlorine, Examples include production of chlorobenzene by reaction of benzene with chlorine.

  Production of the chlorofluoroalkane includes production of dichlorodifluoromethane and trichloromonofluoromethane by reaction of carbon tetrachloride and hydrogen fluoride, and dichlorodifluoromethane and trichloromonofluoromethane by reaction of methane, chlorine and hydrogen fluoride. And the like.

  Examples of the hydrolysis reaction of the chlorinated hydrocarbon include production of phenol by a reaction of chlorobenzene and water.

  The oxygen-containing gas may be pure oxygen, pure oxygen diluted with an inert gas such as nitrogen gas or argon gas, 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 obtained by diluting an organic compound and oxygen with a gas inert to an oxidation reaction such as nitrogen gas or argon gas. It may be a gas composed of a compound and air. Pure oxygen can be obtained by ordinary industrial methods such as air pressure swing method or cryogenic separation. Although there is no restriction | limiting in particular in the usage-amount of oxygen, It is preferable to set it as 1 mol times or more with respect to an organic compound, and it is more preferable to set it as 10 mol times or more. When the amount of oxygen used is less than 1 mole times the organic compound, the conversion rate of the organic compound may be low.

  The organic compound in the mixed gas containing the organic compound, hydrogen chloride, and oxygen can be selected as appropriate, but is preferably an aliphatic hydrocarbon, a chlorinated aliphatic hydrocarbon, phosgene, an alicyclic hydrocarbon, an aromatic hydrocarbon. And at least one selected from the group consisting of chlorinated aromatic hydrocarbons, alcohols and phenols, and among them, at least one selected from the group consisting of aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons and phosgene. Is preferred.

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

  Examples of chlorinated aliphatic hydrocarbons include dichloroethane such as chloromethane, dichloromethane, trichloromethane, carbon tetrachloride, chloroethane, and 1,2-dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, and 2-chloropropane. Examples include chloropropane, dichloropropane such as 1,2-dichloropropane, vinyl chloride, dichloroethylene, trichloroethylene, chloroethylene such as tetrachloroethylene, allyl chloride, dichloropropene such as 1,3-dichloro-1-propene, and the like. Of these, chloromethane, dichloromethane, trichloromethane, carbon tetrachloride, chloroethane, vinyl chloride, dichloroethane, chloropropane, dichloropropane, allyl chloride, and dichloropropene are preferable, and chloromethane, carbon tetrachloride, and 2-chloropropane are particularly preferable.

  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 with respect to hydrogen chloride. When the content of the organic compound exceeds 20% by volume, the conversion rate of the organic compound may be lowered. In addition, although the content of the organic compound contained in the mixed gas depends on the origin of the gas, it is usually contained by 0.1 volume ppm or more with respect to hydrogen chloride, and in this case, the present invention is advantageously employed. Is done.

  Chlorine and / or moisture may be contained in the mixed gas. When chlorine is contained, the conversion rate of the oxidation reaction of the organic compound may be improved. When moisture is contained, the catalyst layer may be effectively utilized and the stable activity of the catalyst may be maintained by smoothing the temperature distribution in the catalyst layer. The contents of chlorine and moisture in the mixed gas are each usually 50% by volume or less, preferably 30% by volume or less, more preferably 10% by volume or less.

  Further, the mixed gas may contain a reducing agent such as hydrogen or carbon monoxide. The reducing agent can be oxidized by the oxidation method of the present invention.

  The mixed gas may contain a gas inert to the oxidation reaction, such as nitrogen gas or argon gas.

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

The amount of the catalyst used is usually 10 to 50000 h ⁻¹ in terms of the ratio (GHSV) to the supply rate of the mixed gas containing the organic compound, hydrogen chloride and oxygen in 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. If the reaction temperature is too low, the conversion of the organic compound may be low. On the other hand, if the reaction temperature is too high, the conversion rate of the organic compound may be lowered due to thermal degradation of the catalyst.

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

  The gas linear velocity based on the empty column is usually 0.1 to 20 m / s. The superficial gas linear velocity of the present invention refers to the total amount of supply rates and the cross-sectional area of the reactor in the standard state (absolute pressure 0.1 MPa, converted to 0 ° C.) of all gases supplied to the reactor. It means the ratio of (area of the cross section perpendicular to the gas supply direction).

  As the reaction method, a reaction method such as a fluidized bed, a fixed bed, or a moving bed can be adopted, and an adiabatic or heat exchange type fixed bed reactor is preferable. When an adiabatic fixed bed reactor is used, either a single tube fixed bed reactor or a multitubular fixed bed reactor can be used, but a single tube fixed bed reactor is preferably used. Can do. When a heat exchange type fixed bed reactor is used, either a single-tube fixed bed reactor or a multi-tube fixed bed reactor can be used, but a multi-tube fixed bed reactor is preferably used. be able to.

  The oxidation reaction of the present invention selectively oxidizes an organic compound while suppressing oxidation of hydrogen chloride. Ratio of hydrogen chloride conversion to organic compound conversion (hydrogen chloride conversion (%) / organic compound conversion (%)) is usually 0.5 or less, preferably 0.2 or less, more preferably The reaction is performed so that it becomes 0.1 or less. When the ratio of the conversion rate of hydrogen chloride to the conversion rate of the organic compound is increased, heat generation due to the hydrochloric acid oxidation reaction increases, 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 by reaction with oxygen, production of chlorine by electrolysis of hydrogen chloride, and production of 1,2-dichloroethane by reaction with ethylene.

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

Example 1
(Preparation of catalyst A)
Titanium oxide powder [SSP-M manufactured by Sakai Chemical Co., Ltd., titanium oxide> 95 wt%, X-ray particle diameter 15 nm] is tableted and then pulverized to form a granular catalyst of 1 to 2 mm, and titanium oxide catalyst A (Anatase type titania ratio 100%) was obtained. The ruthenium content of Catalyst A was less than 50 ppm by weight.

(Oxidation reaction)
An upright quartz reaction tube (inner diameter: 14 mm) was filled with 1.1 g (0.9 cm ³ ) of catalyst A. From the top of the reaction tube, hydrogen chloride gas was 100 ml / min, oxygen gas was 50 ml / min, nitrogen Ethylene gas diluted to 2.0% by volume with gas was continuously supplied at a flow rate of 10.0 ml / min (both absolute pressure 0.1 MPa, converted to 0 ° C.), reaction temperature 380 ° C., reaction pressure 0. The reaction was started at 1 MPa (ethylene content relative to hydrogen chloride: 0.2% by volume). The ratio (GHSV) of the feed rate of the source gas (ethylene gas diluted to 2.0% by volume with hydrogen chloride gas, oxygen gas, nitrogen gas) with respect to the catalyst volume was 10667 h ⁻¹ .

  At the time when 2 hours passed from the start of the reaction, the conversion rate of hydrogen chloride and the yields of carbon monoxide and carbon dioxide with respect to ethylene were determined. The conversion rate and yield measurement methods are shown below, and the results are shown in Table 1.

(Hydrogen chloride conversion)
Sampling was performed for 20 minutes by flowing the gas at the outlet of the reaction tube through a 30% by mass potassium iodide aqueous solution, the amount of chlorine produced was measured by the iodometric titration method, and the chlorine production rate (mol / hour) was determined. The conversion rate of hydrogen chloride was calculated by applying the chlorine generation rate and the hydrogen chloride gas supply rate to the following formula (I).

Conversion rate of hydrogen chloride (%) = [(a × 2) / b] × 100 (I)
a: Chlorine production rate (mole / hour)
b: Supply rate of hydrogen chloride gas (mol / hour)

(Yield of carbon monoxide and carbon dioxide)
With respect to the residual gas that was not absorbed by the potassium iodide aqueous solution in the above sampling, carbon monoxide and carbon dioxide were analyzed by gas chromatography using a TCD detector. The yield of carbon monoxide and carbon dioxide was calculated by applying the carbon monoxide amount and carbon dioxide production rate (mole / hour) thus determined to the following formula (II).

Yield of carbon monoxide or carbon dioxide (%) = c / (d × e) × 100 (II)
c: Carbon monoxide or carbon dioxide production rate (mole / 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 24 nm] was tableted and then pulverized to obtain a granular catalyst of 1 to 2 mm to obtain titanium oxide catalyst B. (Anatase titania ratio 100%). The ruthenium content of catalyst B was less than 50 ppm by weight.

(Oxidation reaction)
The oxidation reaction was performed in the same manner as in Example 1 except that 1.2 g (1.1 cm ³ ) of catalyst B was used in place of catalyst A (GHSV: 8727 h ⁻¹ ). Table 1 shows the conversion rate of hydrogen chloride and the yields of carbon monoxide and carbon dioxide with respect to ethylene.

Example 3
(Preparation of catalyst C)
Titanium oxide spheres (CS-300S-12 manufactured by Sakai Chemical Co., Ltd., 1-2 mm particle size) were heated from room temperature to 200 ° C. over 15 minutes under air flow, and from 200 ° C. to 600 ° C. for 1.3 hours. And heated for 2 hours at the same temperature and calcined to obtain a titanium oxide catalyst C (anatase-type titania ratio 100%). The ruthenium content of catalyst C was less than 50 ppm by weight.

(Oxidation reaction)
The oxidation reaction was performed in the same manner as in Example 1 except that 1.4 g (1.1 cm ³ ) of catalyst C was used instead of catalyst A (GHSV: 8727h ⁻¹ ). Table 1 shows the conversion rate of hydrogen chloride and the yields of carbon monoxide and carbon dioxide with respect to ethylene.

Example 4
(Preparation of catalyst D)
Titanium oxide spheres [CS-300S-12 manufactured by Sakai Chemical Co., Ltd., 1-2 mm particle size] were heated from room temperature to 200 ° C. over 15 minutes under air flow, and from 200 ° C. to 700 ° C. for 1.7 hours. And heated at the same temperature for 2 hours and calcined to obtain titanium oxide catalyst D (anatase-type titania ratio 100%). The ruthenium content of catalyst D was less than 50 ppm by weight.

(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 was used instead of catalyst A (GHSV: 8727h ⁻¹ ). Table 1 shows the conversion rate of hydrogen chloride and the yields of carbon monoxide and carbon dioxide with respect to ethylene.

Example 5
Instead of ethylene gas diluted to 2.0% by volume with nitrogen gas, 2-chloropropane gas diluted to 1.0% by volume with nitrogen gas is 5.0 ml / min (absolute pressure 0.1 MPa, converted to 0 ° C.) The same operation as in Example 4 was performed except that the flow rate was supplied. The amount of 2-chloropropane relative to hydrogen chloride in the raw material is calculated to be 0.05% by volume. Table 2 shows the conversion rate of hydrogen chloride and the yields of carbon monoxide and carbon dioxide with respect to 2-chloropropane.

Example 6
Instead of ethylene gas diluted to 2.0% by volume with nitrogen gas, the flow rate of 3.9 ml / min (converted to absolute pressure 0.1 MPa, 0 ° C.) of chloromethane gas diluted to 2.6% by volume with nitrogen gas The same operation as in Example 4 was performed except that the above was supplied. The amount of chloromethane relative to hydrogen chloride in the feed is calculated to be 0.1% by volume. Table 2 shows the conversion rate of hydrogen chloride and the yields of carbon monoxide and carbon dioxide with respect to chloromethane.

Example 7
Instead of ethylene gas diluted to 2.0% by volume with nitrogen gas, carbon tetrachloride diluted to 15.0% by volume with nitrogen gas was 3.8 ml / min (absolute pressure 0.1 MPa, converted to 0 ° C.). The same operation as in Example 4 was performed except that it was supplied at a flow rate. The amount of carbon tetrachloride relative to hydrogen chloride in the raw material is calculated to be 0.6% by volume. Table 2 shows the conversion rate of hydrogen chloride and the yields of carbon monoxide and carbon dioxide with respect 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 High Purity Chemical Co., Ltd.] in 91.7 g of pure water, 0.64 g of zirconyl nitrate hydrate [manufactured by Taiyo Mining Co., Ltd.] An aqueous solution prepared by dissolving in 91.7 g of water 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, and then mixed at 80 ° C. Stir for hours and then at room temperature for 1 hour. After stirring, water was distilled off at 80 ° C. under reduced pressure, and the resulting solid was dried at 80 ° C. After drying, it was pulverized in a mortar and then baked in air at 500 ° C. for 2 hours. The fired product was pulverized in a mortar, and the powder was tableted and then pulverized to obtain a ceria / zirconia composite oxide catalyst E as a granular catalyst of 1 to 2 mm.

(reaction)
The same operation as in Example 1 was performed 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 yields of carbon monoxide and carbon dioxide with respect to ethylene.

Comparative Example 2
(Preparation of catalyst F)
Silica-alumina [JRC-SAH-1 manufactured by JGC Catalysts & Chemicals Co., Ltd.] is pulverized in a mortar, and the powder is tableted and then pulverized to obtain a 1-2 mm granular catalyst to obtain silica-alumina catalyst F. It was.

(reaction)
The same operation as in Example 1 was performed 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 yields of carbon monoxide and carbon dioxide with respect to ethylene.

Comparative Example 3
(Preparation of catalyst G)
75 commercially available ruthenium oxide-containing titanium oxide catalyst (manufactured by NE Chemcat Co., Ltd., ruthenium oxide content 6.6 wt% (ruthenium content 5.0 wt%), anatase titania ratio 100%, 1-2 mm sphere) After pulverization and classification to ˜150 μm, this powder was used as catalyst G.

(reaction)
The same operation as in Example 1 was performed 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 yields of carbon monoxide and carbon dioxide with respect 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 93%] 100 parts, Serander [YB-152A manufactured by Yuken Industry Co., Ltd.] 0.5 parts and sugar ester [Mitsubishi Chemical Foods S-1570] 2 parts were mixed, and then 25.5 parts of pure water and 12.5 parts of titanium oxide sol [CSB manufactured by Sakai Chemical Co., Ltd., titanium oxide content 40%] were added and kneaded. This mixture was extruded into a noodle shape having a diameter of 3.0 mmφ, dried at 110 ° C. for 2 hours, and then crushed to a length of about 3 to 5 mm. The obtained molded body was heated in air from room temperature to 600 ° C. over 1.7 hours and then calcined by holding at the same temperature for 3 hours. Further, 900 g of the obtained fired product was impregnated with 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. And allowed to stand at 22 ° C. for 3.3 hours in an air atmosphere. 900 g of the obtained solid was heated from room temperature to 300 ° C. over 2 hours under air flow, then held at the same temperature for 2 hours and calcined, and white oxidation with a silica content of 1.0% As a result, 898 g of a titanium carrier (rutile-type titania ratio of 90% or more, sodium content of 12 ppm by weight, calcium content of 8 ppm by weight) was obtained. In 90.0 g of this titanium oxide carrier, 2.16 g of ruthenium chloride hydrate (RuCl ₃ · nH ₂ O manufactured by NE Chemcat Co., Ltd., Ru content 40.0 wt%) was dissolved in 20.5 g of pure water. The resulting aqueous solution was impregnated and allowed to stand at 35 ° C. for 6.2 hours in an air atmosphere. 18.2 g of the obtained solid was heated from room temperature to 250 ° C. over 1.3 hours under air flow, and then calcined by holding at the same temperature for 2 hours. The ruthenium oxide content was 1.25 wt. % (Ruthenium content 0.95% by weight) of titanium oxide catalyst H was obtained.

(reaction)
The same operation as in Example 1 was performed 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 yields of carbon monoxide and carbon dioxide with respect to ethylene.

Claims (7)

  A method of 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 weight or less.   The method according to claim 1, wherein the titanium oxide contains anatase crystalline titanium oxide.   The method according to claim 2, wherein a ratio of the anatase crystalline titanium oxide in the titanium oxide measured by X-ray diffraction method is 20% or more based on the total of the anatase crystalline titanium oxide and the rutile crystalline titanium oxide.   The method according to claim 1, wherein the organic compound is at least one selected from the group consisting of aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, and phosgene.   The method of claim 4, wherein the aliphatic hydrocarbon is ethylene.   The method according to claim 4, wherein the chlorinated aliphatic hydrocarbon is at least one selected from the group consisting of 2-chloropropane, chloromethane, and carbon tetrachloride.   The method according to any one of claims 1 to 6, wherein the oxidation temperature is 250 to 450 ° C.