JPH06336448A - Production of chlorinated hydrocarbon - Google Patents

Abstract

PURPOSE:To provide a method for efficiently producing a chlorinated hydrocarbon from a hydrocarbon or a partially chlorinated hydrocarbon in a high yield. CONSTITUTION:This method for producing a chlorinated hydrocarbon comprises chlorinating a hydrocarbon and/or a partially chlorinated hydrocarbon in the presence of a zirconium oxide catalyst containing a copper chloride. A zirconium oxide containing the copper chloride, an alkali metal or alkaline earth metal chloride and a rare earth metal chloride can also be used.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a process for producing chlorinated hydrocarbons.

[0002]

2. Description of the Related Art Conventionally, the following methods are known as methods for producing chlorinated hydrocarbons. (1) A method of reacting a hydrocarbon and / or a partially chlorinated hydrocarbon with chlorine in a gas phase. (2) A method of oxychlorinating a hydrocarbon and / or a partially chlorinated hydrocarbon, hydrogen chloride and oxygen by bringing them into contact with a molten salt containing copper chloride. (3) A method of oxychlorinating a hydrocarbon and / or a partially chlorinated hydrocarbon, hydrogen chloride and oxygen by bringing them into contact with a catalyst in which copper chloride is supported on a carrier containing alumina or silica.

[0003]

Each of the above conventional methods has various disadvantages.

The method (1) requires large-scale equipment, and the reaction requires extremely complicated operation. Furthermore, since the reaction temperature is high, side reactions such as carbon formation are likely to occur and there is a risk of explosion.

The method (2) requires a difficult operation of circulating a molten salt, which is highly corrosive at high temperature, between two tanks.

In the method (3), since the raw material hydrocarbon or partially chlorinated hydrocarbon is polymerized and oxidized, the yield of chlorinated hydrocarbon becomes low. Furthermore, when hydrogen chloride is contained in hydrogen chloride, the specific surface area of the carrier is reduced, fluorination occurs, the crystalline state is changed, etc., and the yield of chlorinated hydrocarbons and catalyst life are greatly reduced. There was a problem.

[0007]

SUMMARY OF THE INVENTION The present invention seeks to solve the above-mentioned problems, in which hydrocarbons and / or partially chlorinated hydrocarbons are oxidised in the presence of a copper chloride added zirconium oxide catalyst. It is a process for producing chlorinated hydrocarbons characterized by chlorination.

The hydrocarbon of the present invention is selected from known or well known aliphatic or aromatic hydrocarbons.
The aliphatic hydrocarbon may be either saturated aliphatic hydrocarbon or unsaturated aliphatic hydrocarbon, but saturated aliphatic hydrocarbon is preferred. The number of carbon atoms of the aliphatic hydrocarbon is preferably 1-6, particularly preferably 1-4. As the aromatic hydrocarbon, those having a structure containing a benzene ring are preferable, and those having an alkyl group bonded to the benzene ring are particularly preferable.

The hydrocarbons of the present invention will be exemplified below, but the hydrocarbons are not limited to these. The isomers in the following examples are also included. Methane, ethane, propane, butane, pentane,
Ethylene, propylene, butene, butadiene, benzene, toluene, ethylbenzene, styrene, α-methylstyrene and the like.

The partially chlorinated hydrocarbon has a structure in which a part of hydrogen atoms of the above hydrocarbon is replaced with chlorine atoms. Further, the partially chlorinated hydrocarbon of the present invention may have a structure containing a chlorine atom and a halogen atom other than the chlorine atom. Examples of halogen atoms other than chlorine include fluorine, iodine, bromine and the like.

Of the partially chlorinated hydrocarbons, the partially chlorinated hydrocarbons of the present invention are preferably those containing only chlorine atoms as halogen atoms. Particularly preferred is a saturated aliphatic hydrocarbon having 4 or less carbon atoms in which 1 to 2 hydrogen atoms are replaced with chlorine atoms.

The partially chlorinated hydrocarbons of the present invention will be exemplified below, but the invention is not limited thereto. The isomers in the following examples are also included.

Chloromethane, dichloromethane, trichloromethane, monochloroethane, dichloroethane, trichloroethane, monochloroethylene, dichloroethylene,
Monofluoromethane, difluoromethane, trifluoromethane, monofluoroethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, trifluoroethylene, bromodifluoroethane, etc.

The hydrocarbon and / or the partially chlorinated hydrocarbon which is the raw material of the present invention may be one kind or may contain two or more kinds. In addition, the respective proportions when two or more kinds are contained may be appropriately changed depending on the proportion at the time of obtaining raw materials, the proportion of expected products, and the like.

In the present invention, it is important that a zirconium oxide catalyst containing copper chloride be present.
As the copper chloride, any of CuCl, CuCl ₂ , and copper oxychloride can be adopted.

The amount of copper chloride to the zirconium oxide catalyst can be appropriately changed depending on the specific surface area of zirconium oxide. Usually, 1 to 30 parts by weight of copper chloride, preferably 3 to 100 parts by weight of zirconium oxide is used.
It is preferable to add about 25 parts by weight.

In the present invention, it is also possible to oxychlorinate a zirconium oxide catalyst obtained by adding at least one selected from an alkali metal chloride and an alcal earth metal chloride to copper chloride.

The alkali metal chloride is not particularly limited. For example, lithium chloride, sodium chloride, potassium chloride and the like can be exemplified. Also, the alkaline earth metal chloride is not particularly limited. For example, calcium chloride, magnesium chloride, strontium chloride, barium chloride and the like can be exemplified.

The amount of the above-mentioned alkali metal chloride or alkaline earth metal chloride with respect to zirconium oxide can also be appropriately changed depending on the specific surface area of zirconium oxide. In the usual case, with respect to 100 parts by weight of zirconium oxide, in any case where one kind or two or more kinds selected from an alkali metal chloride and an alkaline earth metal chloride is added to 100 parts by weight of zirconium oxide. 1 to
20 parts by weight, preferably 3 to 15 parts by weight.

In the present invention, it is also possible to oxychlorinate a zirconium oxide catalyst prepared by adding a rare earth metal chloride to copper chloride. As the rare earth metal chloride, any of the rare earth metal chlorides having atomic numbers of 57 to 71 can be adopted, and these can be used alone or in combination of two or more. Examples thereof include cerium chloride, lanthanum chloride, yttrium chloride, scandium chloride and the like.

The amount of the above-mentioned rare earth metal chloride based on zirconium oxide can also be appropriately changed depending on the specific surface area of zirconium oxide. Usually, the amount of rare earth metal chloride is about 0.1 to 20 parts by weight, preferably about 1 to 15 parts by weight, based on 100 parts by weight of zirconium oxide.

Further, the copper chloride, the alkali metal chloride and / or the alkaline earth metal chloride, and the rare earth metal chloride can be added to zirconium oxide.

The amount of these metal chlorides with respect to zirconium oxide is the amount in the case of adding one or more kinds of alkali metal chlorides and / or alkaline earth metal chloride metal chlorides and rare earth metal chlorides. Also, the above amount is preferable.

The copper chloride of the present invention acts as the active site of the catalyst, increasing the yield of chlorinated hydrocarbons. Further, rare earth metal chlorides, alkali metal chlorides, and alkaline earth metal chlorides increase the yield of chlorinated hydrocarbons by suppressing the loss due to polymerization or oxidation of the raw materials.

As zirconium oxide of the present invention, an oxide of tetravalent zirconium (hereinafter referred to as zirconia) is preferably used. The specific surface area of zirconia is preferably 150 m ² / g or less, particularly preferably 50 m ² / g.
The following is preferable.

The method of adding the above metal chloride to zirconium oxide is not particularly limited, and the impregnation method, the deposition method,
Known methods used for ordinary catalyst preparation such as coprecipitation method and kneading method can be applied.

For example, the following methods can be adopted, but are not limited to these.

Copper chloride, rare earth metal chlorides, alkali metal chlorides, alkaline earth metal chlorides are dissolved in water or an organic solvent such as methanol, ethanol, or acetone, and supported by a method such as impregnation, adsorption or deposition on zirconia. After letting
A method of preparing by drying.

Copper, rare earth metal, alkali metal, alkaline earth metal nitrate, acetate, hydroxide, carbonate, complex salt and the like are dissolved in water or an organic solvent such as methanol, ethanol or acetone, preferably water. , Impregnated with zirconia,
A method in which it is converted into a chloride by supporting it by a method such as adsorption or deposition, drying it, and then baking it in a gas containing hydrogen chloride.

A zirconium source such as zirconium oxynitrate and a salt of copper, a rare earth metal, an alkali metal or an alkaline earth metal are dissolved in an organic solvent such as water or alcohol and coprecipitated with a neutralizing agent such as sodium carbonate, A method of converting to chloride by washing, filtering, drying, and baking in the presence of a gas containing hydrogen chloride.

The catalyst of the present invention is used in a known or known shape. For example, it is used after being pelletized into various shapes.

The oxychlorination of the present invention is carried out by chlorinating the above hydrocarbon and / or chlorinated hydrocarbon with oxygen and hydrogen chloride in the presence of the above zirconium oxide catalyst. Oxychlorination can usually be carried out in a gas phase reaction.

Air can also be used as oxygen for oxychlorination. The amount of oxygen is 0.1 to 5.0 mol, preferably 0.3 to 1. mol per mol of hydrogen chloride.
5 mol is good.

As the hydrogen chloride for oxychlorination, not only synthetic hydrogen chloride but also hydrogen chloride produced as a by-product in another reaction can be used. Further, as the hydrogen chloride of the present invention,
Hydrogen chloride containing hydrogen fluoride can be used. In this case, the concentration of hydrogen fluoride in hydrogen chloride is preferably less than 10%. For example, a large amount of hydrogen chloride produced as a by-product when fluorinating a chlorinated hydrocarbon to produce a fluorinated hydrocarbon or a fluorinated chlorinated hydrocarbon can be exemplified.
Such by-product hydrogen chloride generally contains 10 ppm to several% of hydrogen fluoride.

The amount of hydrogen chloride is 0.1 to 10 with respect to 1 mol of the raw material regardless of whether the raw material hydrocarbon and / or the partially chlorinated hydrocarbon is contained in one kind or in two or more kinds. The molar amount is preferably 0.3 to 3.5.

The reaction apparatus, reaction system, reaction conditions, etc. are not particularly limited as long as the reaction can be carried out in the gas phase using a catalyst, but when hydrogen chloride is contained in hydrogen chloride, an acid-resistant material is used. It is preferable to employ a reactor consisting of For example, a reactor made of a material made of Inconel, Hastelloy, or stainless can be exemplified. As the reaction system, a usual fixed bed system, fluidized bed system or the like can be adopted.

As the reaction pressure, not only atmospheric pressure but also pressurizing conditions can be adopted. In the case of pressurizing conditions, about 2 to 5 atm is preferable.

The reaction temperature is not particularly limited, but in the usual case, a temperature in the range of 200 to 450 ° C. is suitable. If the temperature is too high, the raw material may be rapidly oxidized to generate carbon monoxide or carbon dioxide, which may reduce the yield of the target chlorinated hydrocarbon. In addition, the catalyst component volatilizes,
The activity and the life are likely to decrease. further,
It is also disadvantageous in terms of durability of the reactor.

The space velocity (SV) in the reactor is 100.
About 10000 h ^-1 , preferably 300 to 5000 h
^-1 is preferable.

Examples of the chlorinated hydrocarbon which is the product of the present invention include various compounds having a structure in which hydrogen atoms in the raw material are replaced by chlorine atoms. The chemical structure of the products, the degree of chlorination, and the selectivity of each product can vary depending on the raw materials or reaction conditions.

Examples of the chlorinated hydrocarbon which is the product of the present invention will be given below, but the invention is not limited thereto. The isomers in the following examples are also included.

Monochloromethane, dichloromethane, trichloromethane, tetrachloromethane, monochloroethane, dichloroethane, trichloroethane, monochloropropane, dichloropropane, monochloroethylene, dichloroethylene, trichloroethylene, tetrachloroethylene, monochloropropene, dichloropropene, dichlorobutene, chloroprene, trichlorofluoro methane,
Dichlorodifluoromethane, monochlorotrifluoromethane, monochlorodifluoromethane, monochlorofluoromethane, monochloropentafluoroethane, dichlorofluoroethane, monochlorodifluoroethane, trichlorotrifluoroethane, dichlorotetrafluoroethane, monochlorobenzene, dichlorobenzene, benzyl chloride, dichlorobenzal Chloride, chloroethylbenzene, chlorostyrene, chloromethylstyrene, chlorobromodifluoroethane, bromochlorotrifluoroethane, etc.

The reaction product is separated from the unreacted product and collected by a known method.

Since the zirconium oxide catalyst of the present invention has a longer catalyst life than conventional catalysts containing alumina, silica, etc., a high chlorinated hydrocarbon yield can be achieved. Particularly, when hydrogen chloride containing hydrogen fluoride is adopted, a remarkable effect is exhibited. Further, in the present invention, the production of carbon monoxide and carbon dioxide produced by the polymerization or oxidation of the raw material is suppressed. That is, the yield is increased by suppressing the loss of raw materials. Further, since the catalyst can be used as spherical particles, the pressure difference before and after the catalyst bed is reduced during continuous operation, and the power for passing the gas through the catalyst bed can be saved.

[0045]

EXAMPLES The present invention will be described more specifically below with reference to examples. The reaction rate and selectivity in the table are expressed in mol%.

Example 1 Commercially available zirconia powder (specific surface area 100 m ² / g) was dipped in an aqueous solution of copper chloride and then dried at 250 ° C. for 10 hours to obtain 10% by weight of copper chloride.
It was supported. This was press-molded with a gauge pressure of 150 kg / cm ² , crushed, and then classified with a sieve to obtain a catalyst having a particle size of 7 to 15 mesh. 20 ml of catalyst with an inner diameter of 14
mm reactor made of Inconel and heated to a predetermined temperature. Methyl chloride, hydrogen chloride and air are added to this with CH ₃ Cl
/ HCl / O ₂ = 1.0 / 1.6 / 0.6 (molar ratio),
The reaction was carried out by flowing at a space velocity SV = 1000 h ⁻¹ .
The results are shown in Table 1.

[0047]

[Table 1]

Example 2 A reaction was conducted in the same manner as in Example 1 except that hydrogen chloride containing hydrogen fluoride (HF = 300 ppm) was used instead of hydrogen chloride. The results are shown in Table 2.

[0049]

[Table 2]

Example 3 Commercially available zirconia powder (specific surface area: 85 m ² / g) was dipped in a mixed aqueous solution of copper chloride and potassium chloride and then dried at 250 ° C. for 10 hours to give 10% by weight of copper chloride. 5% by weight of potassium chloride was supported. This was press-molded at a gauge pressure of 200 kg / cm ² , then crushed and classified with a sieve to obtain a catalyst having a particle size of 10 to 20 mesh. 20 ml of the catalyst was filled in an Inconel reactor having an inner diameter of 14 mm and heated to a predetermined temperature. Methyl chloride, hydrogen chloride and air are added to this and CH ₃ Cl / HCl.
/ O ₂ = 1.0 / 1.2 / 0.6 (molar ratio), and space velocity SV = 800 h ⁻¹ was allowed to flow to react. The results are shown in Table 3.
Shown in.

[0051]

[Table 3]

Example 4 Commercially available zirconia powder (specific surface area 100 m ² / g) was immersed in a mixed aqueous solution of copper chloride and calcium chloride, and then dried at 250 ° C. for 12 hours,
12% by weight of copper chloride and 8% by weight of calcium chloride were carried. This was press-molded at a gauge pressure of 160 kg / cm ² , then crushed and classified with a sieve to obtain a catalyst having a particle size of 10 to 20 mesh. 20 ml of catalyst with an inner diameter of 14 m
m Inconel reactor was charged and heated to a predetermined temperature. Methyl chloride, hydrogen chloride and air are added to this with CH ₃ Cl /
HCl / O ₂ = 1.0 / 1.5 / 0.8 (molar ratio) and a space velocity SV = 1200 h ⁻¹ were flowed to react. The results are shown in Table 4.

[0053]

[Table 4]

Example 5 A mixed aqueous solution of zirconium oxynitrate, copper nitrate and magnesium nitrate was prepared. The mixed aqueous solution and a 10% aqueous sodium carbonate solution were gradually added dropwise to stirred water so as to maintain pH = 8, thereby forming a coprecipitated gel. This was left standing for 1 day, washed with water and filtered, and dried at 110 ° C. for 20 hours. further,
After crushing this, calcination is performed at 500 ° C. for 10 hours, and C
to obtain a composite oxide of uO-MgO-ZrO _2. CuO in the composite oxide was 10% by weight, MgO was 6% by weight, and the specific surface area was 95 m ² / g. The composite oxide was treated in hydrogen chloride at 400 ° C. for 20 hours to be converted into chloride. This was press-molded with a gauge pressure of 140 kg / cm ² , then crushed and classified with a sieve to obtain a test catalyst having a particle size of 10 to 20 mesh. 20 ml of the catalyst was filled in an Inconel reactor having an inner diameter of 14 mm, and hydrogen chloride containing methyl chloride and hydrogen fluoride (HF = 300 pp
m) and air to CH ₃ Cl / HCl / O ₂ = 1.0 / 1.
5 / 0.9 (molar ratio) and space velocity SV = 700 h ⁻¹ were circulated and reacted. The results are shown in Table 5.

[0055]

[Table 5]

Example 6 Commercially available zirconia powder (specific surface area 100 m ² / g) was immersed in a mixed aqueous solution of copper chloride, potassium chloride and magnesium chloride, and then at 250 ° C. for 1 hour.
After drying for 2 hours, 10% by weight of copper chloride, 5% by weight of potassium chloride and 5% by weight of magnesium chloride were supported.
This was press-molded at a gauge pressure of 160 kg / cm ² , then crushed and classified with a sieve to obtain a catalyst having a particle size of 10 to 20 mesh. 20 ml of the catalyst was filled in an Inconel reactor having an inner diameter of 14 mm and heated to a predetermined temperature. Methyl chloride, hydrogen chloride and air were added to this and CH ₃ Cl / HCl / O.
₂ = 1.0 / 1.5 / 0.8 (molar ratio), space velocity SV
= 1200 h ⁻¹ for circulation and reaction. The results are shown in Table 6.

[0057]

[Table 6]

Example 7 Commercially available zirconia powder (specific surface area: 95 m ² / g) was dipped in a mixed aqueous solution of copper chloride and cerium chloride and then dried at 250 ° C. for 10 hours to obtain 12% by weight of copper chloride. 4% by weight of cerium chloride was supported. This was press-molded at a gauge pressure of 160 kg / cm ² , then crushed and classified by a sieve to obtain a catalyst having a particle size of 10 to 15 mesh. 20 ml of the catalyst was filled in an Inconel reactor having an inner diameter of 14 mm and heated to a predetermined temperature. Methyl chloride, hydrogen chloride and air are added to this and CH ₃ Cl / HCl.
/ O ₂ = 1.0 / 1.6 / 0.6 (molar ratio), and space velocity SV = 1300 h ⁻¹ was flowed to react. The results are shown in Table 7.

[0059]

[Table 7]

Example 8 Commercially available zirconia powder (specific surface area 90 m ² / g) was dipped in a mixed aqueous solution of copper chloride, potassium chloride and cerium chloride and then dried at 250 ° C. for 18 hours to give 10 parts of copper chloride. %, Potassium chloride 5%, and cerium chloride 2% by weight. Next, after press molding with a gauge pressure of 150 kg / cm ^2, it was crushed,
A catalyst having a particle size of 10 to 20 mesh was classified by sieving. 20 ml of the catalyst was filled in an Inconel reactor having an inner diameter of 14 mm and heated to a predetermined temperature. CH ₄ / HCl / O ₂ = 1.0 / 1.5 with methane, hydrogen chloride and air.
/1.0 (molar ratio) and the space velocity SV = 1100 h ^-1 for reaction. The results are shown in Table 8.

[0061]

[Table 8]

Example 9 Using zirconium oxynitrate as the zirconium source and cerium nitrate as the cerium source, a mixed aqueous solution of these was prepared. This mixed aqueous solution and 10% aqueous sodium carbonate solution were added to stirred water to adjust the pH.
= 8 was gradually added dropwise to form a coprecipitated gel. This was left standing for 1 day, washed with water, filtered, and dried at 110 ° C. for 24 hours. Further, this was crushed and baked at 500 ° C. for 12 hours to obtain CeO ₂ -Zr.
A composite oxide of O ₂ was obtained. CeO ₂ in the composite oxide is 1
0% by weight, and the specific surface area was 100 m ² / g. The composite oxide was immersed in a mixed aqueous solution of copper chloride and potassium chloride, and then allowed to stand in hydrogen chloride at 250 ° C. for 10 hours to support 10% by weight of copper chloride and 6% by weight of potassium chloride.
This was press-molded with a gauge pressure of 180 kg / cm ² , then crushed and classified with a sieve to obtain a test catalyst having a particle size of 10 to 15 mesh. 20 ml of this catalyst is 14m in inside diameter
m of Inconel reactor and hydrogen chloride (HF = 300 ppm) containing methyl chloride and hydrogen fluoride and air were added to CH ₃ Cl / HCl / O ₂ = 1.0 / 1.4 / 1.
Table 9 shows the results obtained by causing the reaction to flow at 0 (molar ratio) and space velocity SV = 900 h ⁻¹ .

[0063]

[Table 9]

Example 10 Commercially available zirconia powder (specific surface area 110 m ² / g) was immersed in a mixed aqueous solution of copper nitrate, magnesium nitrate and cerium nitrate, and then dried at 120 ° C. for 24 hours. Next, it was baked in air at 500 ° C. for 6 hours to carry 10% by weight of copper oxide, 5% by weight of magnesium oxide and 2% by weight of cerium oxide. Further, it was left in hydrogen chloride at 400 ° C. for 15 hours to convert copper oxide, magnesium oxide and cerium oxide into copper chloride, magnesium chloride and cerium chloride, respectively. Next, it was press-molded with a gauge pressure of 150 kg / cm ² , crushed, and then classified with a sieve to obtain a catalyst having a particle size of 10-20 mesh. 20 ml of the catalyst was filled in an Inconel reactor having an inner diameter of 14 mm and heated to a predetermined temperature. Methyl chloride, hydrogen chloride and air were added to this, CH ₃ Cl / HCl / O ₂ = 1.0 /
1.3 / 0.9 (molar ratio), space velocity SV = 1100h
^It was circulated at ^-1 and reacted. The results are shown in Table 10.

[0065]

[Table 10]

Example 11 Commercially available zirconia powder (specific surface area 95 m ² / g) was dipped in a mixed aqueous solution of copper chloride, potassium chloride, magnesium chloride and cerium chloride, dried at 250 ° C. for 10 hours, and chlorinated. Copper was loaded 10% by weight, potassium chloride was loaded 5% by weight, magnesium chloride was loaded 5% by weight, and cerium chloride was loaded 5% by weight. This was press-molded at a gauge pressure of 160 kg / cm ² , then crushed and classified by a sieve to obtain a catalyst having a particle size of 10 to 15 mesh. 20 ml of the catalyst was filled in an Inconel reactor having an inner diameter of 14 mm and heated to a predetermined temperature. Methyl chloride, hydrogen chloride and air were added to this, and CH ₃ Cl / HCl / O ₂ =
1.0 / 1.6 / 0.6 (molar ratio), space velocity SV = 1
The reaction was carried out by circulating at 300 h ^-1 . The results are shown in Table 11.

[0067]

[Table 11]

Comparative Example 1 Commercially available γ-alumina powder (specific surface area 140 m ² / g) was immersed in an aqueous solution of copper chloride and then dried at 250 ° C. for 12 hours to give 10% by weight of copper chloride.
It was supported. This was press-molded with a gauge pressure of 150 kg / cm ² , crushed, and then classified with a sieve to obtain a catalyst having a particle size of 7 to 15 mesh. 20 ml of catalyst with an inner diameter of 14
mm reactor made of Inconel and heated to a predetermined temperature. Methyl chloride, hydrogen chloride and air are added to this with CH ₃ Cl
/ HCl / O ₂ = 1.0 / 1.5 / 0.7 (molar ratio),
The reaction was carried out by flowing at a space velocity SV = 1000 h ⁻¹ .
The results are shown in Table 12.

[0069]

[Table 12]

[Comparative Example 2] The reaction was carried out in the same manner as in Comparative Example 1 except that hydrogen chloride containing hydrogen fluoride (HF = 300 ppm) was used instead of hydrogen chloride. The results are shown in Table 13.

[0071]

[Table 13]

[0072]

【The invention's effect】

(1) Addition of copper chloride, alkali metal chlorides, alkaline earth metal chlorides, and rare earth metal chlorides to the zirconium oxide catalyst to cause loss of hydrocarbons and / or partially chlorinated hydrocarbons as raw materials due to polymerization or oxidation. Suppresses
The yield of chlorinated hydrocarbons can be increased. (2) Even when hydrogen chloride containing hydrogen fluoride is used, a high chlorinated hydrocarbon yield can be achieved because the zirconium oxide catalyst has a long catalyst life. (3) Since the catalyst can be used as spherical particles, the pressure difference before and after the catalyst bed becomes small during continuous operation, and the power for passing the gas to the catalyst bed can be saved.

Claims (6)

[Claims] 1. A process for producing a chlorinated hydrocarbon, characterized in that a hydrocarbon and / or a partially chlorinated hydrocarbon is oxychlorinated in the presence of a zirconium oxide catalyst to which copper chloride is added. 2. The process according to claim 1, wherein a zirconium oxide catalyst to which copper chloride and an alkali metal chloride and / or an alkaline earth metal chloride are added is used. 3. The method according to claim 1, wherein a zirconium oxide catalyst to which copper chloride and a rare earth metal chloride are added is used. 4. The method according to claim 1, wherein a zirconium oxide catalyst to which copper chloride and an alkali metal chloride and / or an alkaline earth metal chloride and a rare earth metal chloride are added is used. 5. The method according to claim 1, wherein the zirconium oxide is an oxide of tetravalent zirconium. 6. The method according to any one of claims 1 to 5, wherein oxychlorination is carried out using hydrogen chloride containing hydrogen fluoride.