JPH07206727A - Production of chloribated hydrocarbon - Google Patents

Abstract

PURPOSE:To produce a chlorinated hydrocarbon from a hydrocarbon or a partially chlorinated hydrocarbon in high yield and efficiency. CONSTITUTION:A chlorinated hydrocarbon is produced by the oxychlorination of a hydrocarbon and/or a partially chlorinatad hydrocarbon in the presence of a catalyst obtained by adding a copper chloride to an inorganic porous carrier having an average pore diameter of >=100Angstrom . The catalyst may further contain an alkali metal chloride, an alkaline earth metal chloride or a rare earth metal chloride in addition to the copper chloride.

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, as a method for producing chlorinated hydrocarbons, a catalyst in which copper chloride is supported on a carrier containing alumina or silica is used to chlorinate hydrocarbons and / or partially chlorinated hydrocarbons with oxygen. A method of oxychlorination with hydrogen is known.

[0003]

However, when it is carried out by the conventional method, there is a disadvantage that the raw material hydrocarbon or partially chlorinated hydrocarbon is polymerized and oxidized, and the yield of chlorinated hydrocarbon is lowered. . A closer examination reveals that the catalyst of this method has an average pore size of less than 100Å, which is too small, so that the reaction gas stays in the micropores in the catalyst and oxygen and hydrogen chloride do not react efficiently. Turned out to be a problem.

[0004]

The present invention is intended to solve the above-mentioned problems. That is, when producing chlorinated hydrocarbons by oxychlorination of hydrocarbons and / or partially chlorinated hydrocarbons, a catalyst in which (A) copper chloride is supported on an inorganic porous carrier having an average pore size of 100Å or more is used. A method for producing a chlorinated hydrocarbon characterized by being present.

The hydrocarbon in the present invention is selected from known or known aliphatic or aromatic hydrocarbons. The aliphatic hydrocarbon may be either saturated aliphatic hydrocarbon or unsaturated aliphatic hydrocarbon,
Saturated aliphatic hydrocarbons are 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 in the present invention are exemplified below, but the hydrocarbons are not limited to these. Methane, ethane, propane,
Examples are butane, pentane, ethylene, propylene, butene, butadiene, benzene, toluene, ethylbenzene, styrene, α-methylstyrene and the like. Note that the above examples of chlorinated hydrocarbons include isomers.

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

The partially chlorinated hydrocarbons in the present invention will be exemplified below, but the invention is not limited thereto. Chloromethane, dichloromethane, trichloromethane, monochloroethane, dichloroethane, trichloroethane, monochloroethylene, dichloroethylene, monofluoromethane, difluoromethane, trifluoromethane, monofluoroethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, trifluoroethane Examples include ethylene and bromodifluoroethane. The examples of the above-mentioned partially chlorinated hydrocarbons include isomers.

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

Oxychlorination in the present invention is carried out by chlorinating the above hydrocarbon and / or the above chlorinated hydrocarbon with oxygen and hydrogen chloride. In general, oxychlorination is preferably carried out by 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 oxychlorinated hydrogen chloride, not only synthetic hydrogen chloride but also hydrogen chloride produced as a by-product in another reaction can be used. Alternatively, hydrogen chloride containing hydrogen fluoride can be used as the hydrogen chloride. In this case, the concentration of hydrogen fluoride in hydrogen chloride is preferably less than 10% by weight. For example, fluorinated hydrocarbons may be fluorinated to produce fluorinated hydrocarbons, or hydrogen chloride produced as a by-product in a large amount when producing fluorinated chlorinated hydrocarbons. Such by-produced hydrogen chloride is generally contained in hydrogen chloride at 10 p
It contains pm to several wt% 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. The molar amount is preferably 0.3 to 3.5.

In the present invention, during oxychlorination,
As the catalyst, it is important to use a catalyst in which copper chloride (A) is supported on an inorganic porous carrier having an average pore size of 100 Å or more.

That is, since the average pore size of the conventional catalyst is less than 100Å, the present inventor has found that the reaction gas stays in the micropores in the catalyst and most of the supplied oxygen effectively acts with hydrogen chloride. It was found that the cause is that the yield of the desired chlorinated hydrocarbon is lowered, because it is used for the combustion reaction of the raw material without doing so. Therefore, as a result of detailed examination of the average pore diameter and reactivity of the catalyst, in the present invention, by adopting a catalyst in which copper chloride (A) is supported on an inorganic porous carrier having an average pore diameter of 100 Å or more, We have found that chlorinated hydrocarbons can be obtained with very good results.

The average pore diameter value is a value measured by the nitrogen adsorption method. The nitrogen adsorption method is a method in which after degassing the inorganic porous carrier, nitrogen is adsorbed at the liquid nitrogen temperature, and the average pore diameter is calculated from the amount of nitrogen desorbed when the temperature is returned to room temperature.

The value of the average pore diameter is not particularly limited as long as it is 100 liters or more, but if the average pore diameter is too large, the surface area of the catalyst becomes small and the amount of (A) copper chloride carried becomes small. Therefore, in the normal case, 100 to 10
It is about 000Å, preferably 100 to 8000Å,
Particularly, 100 to 1000Å is preferable, and further 100 to 5
00Å is preferred.

The specific surface area of the inorganic porous carrier is 0.5 to 20.
0 m ² / g, preferably from those which are 1~150m ² / g. If the specific surface area is smaller than the above range, the activity of the catalyst decreases and the reaction rate decreases. If the specific surface area is too large, the proportion of micropores of 100 Å or less may increase. Therefore, in the present invention, it is preferable that the inorganic porous carrier has an average pore diameter of 100 to 500 Å and a specific surface area of 1 to 150 m ² / g.

The inorganic porous carrier has an average pore size of 1
There is no particular limitation as long as it is an inorganic porous material having a diameter of 00Å or more.
Examples of the inorganic porous material include zirconium oxide, aluminum oxide, titanium oxide, silica, silica alumina, diatomaceous earth, zeolite, composite oxide, layered compounds such as montmorillonite and saponite, and the like, but zirconium oxide, Titanium oxide and aluminum oxide are preferred. In particular, when adopting hydrogen chloride containing hydrogen fluoride as hydrogen chloride for oxychlorination, an inorganic porous body containing zirconium oxide is preferable, and particularly an inorganic body containing tetravalent zirconium oxide (zirconia). The porous body of is preferable.

As (A) copper chloride, CuCl, CuC
Either l ₂ or copper oxychloride can be employed. The amount of (A) copper chloride to the inorganic porous carrier can be appropriately changed depending on the specific surface area of the inorganic porous carrier. Usually, 1 to 30 parts by weight of copper chloride is added to 100 parts by weight of the inorganic porous carrier.
About 3 parts by weight, preferably about 3 to 25 parts by weight, should be supported.

Further, in the present invention, the average pore diameter is 1
It is also possible to oxychlorinate a catalyst having (A) copper chloride and (B) an alkali metal chloride and / or an alcal earth metal chloride supported on an inorganic porous carrier having a volume of 00 Å or more.

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 copper chloride (A) and the alkali metal chloride and / or the alcal earth metal chloride (B) may each be one kind or two or more kinds.

The amounts of the above-mentioned (A) copper chloride and (B) alkali metal chloride and / or alkaline earth metal chloride with respect to the inorganic porous carrier can be appropriately changed depending on the specific surface area of the inorganic porous carrier. In the usual case, (A) copper chloride is in the same amount as described above, and (B) alkali metal chloride and / or alkaline earth metal chloride is either one kind or two or more kinds respectively. Also, 1 to 20 parts by weight, and preferably 3 to 15 parts by weight, relative to 100 parts by weight of the inorganic porous carrier.

In the present invention, the average pore size is 1
It is also possible to oxychlorinate a catalyst having (A) copper chloride and (C) a rare earth metal chloride supported on an inorganic porous carrier having a volume of 00Å or more. As the rare earth metal chloride (C), any of the rare earth metal chlorides having atomic numbers of 57 to 71 can be adopted. Examples thereof include cerium chloride, lanthanum chloride, yttrium chloride, scandium chloride and the like. The (A) copper chloride and (C) rare earth metal chloride may be one kind or two or more kinds of each.

The amounts of the above-mentioned (A) copper chloride and (C) rare earth metal chloride with respect to the inorganic porous carrier can be appropriately changed depending on the specific surface area of the inorganic porous carrier. Usually, (A) copper chloride is in the same amount as described above, and (C) rare earth metal chloride is about 0.1 to 20 parts by weight, preferably 100 parts by weight of the inorganic porous carrier. About 1 to 15 parts by weight is preferable.

Further, in the present invention, the average pore diameter is 1
Presence of a catalyst in which (A) copper chloride, (B) alkali metal chloride and / or alkaline earth metal chloride, and (C) rare earth metal chloride are supported on an inorganic porous carrier of 00 Å or more It can also be oxychlorinated. Each of (A) copper chloride, (B) alkali metal chloride and / or alkaline earth metal chloride, and (C) rare earth metal chloride may be one kind or two or more kinds. Also, the amount to be carried is preferably the same amount as described above.

In the following, (A) copper chloride and (B)
One or more selected from the group consisting of alkali metal chlorides and / or alkaline earth metal chlorides and (C) rare earth metal chlorides is referred to as the metal chloride in the present invention,
(A) Copper chloride is essential.

Among the metal chlorides in the present invention, (A)
It is believed that copper chloride acts as the active site of the catalyst and increases the yield of chlorinated hydrocarbons. Further, (C) rare earth metal chloride, (B) alkali metal chloride and / or alkaline earth metal chloride are considered to increase the yield of chlorinated hydrocarbons by suppressing the loss due to polymerization or oxidation of the raw materials. To be

The method for supporting the metal chloride in the present invention on the inorganic porous carrier is not particularly limited, and it is used for ordinary catalyst preparation such as impregnation method, deposition method, coprecipitation method, or kneading method. A known 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 and / or alkaline earth metal chlorides are dissolved in water or an organic solvent such as methanol, ethanol or acetone, and impregnated, adsorbed or deposited on an inorganic porous carrier. A method of preparing by carrying after carrying by a method such as.

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. A method of converting into a chloride by carrying it on an inorganic porous carrier by a method such as impregnation, adsorption, and deposition, then drying and firing in a gas containing hydrogen chloride.

A raw material salt of an inorganic porous carrier such as zirconium oxynitrate, titanium chloride, or aluminum nitrate and a salt of copper, a rare earth metal, an alkali metal or an alkaline earth metal are dissolved in water or an organic solvent such as alcohol to obtain carbonic acid. Examples thereof include a method of converting into a chloride by coprecipitation with a neutralizing agent such as sodium, 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 well-known shape. For example, it is used after being pelletized into various shapes.

The reaction apparatus, reaction system, reaction conditions, etc. are not particularly limited as long as they can carry out the reaction 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.

The reaction pressure may be any of reduced pressure, normal pressure, and increased pressure, and normal pressure or increased pressure is preferable, and increased pressure is particularly preferable. 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 ° C. 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. Further, the catalyst component is volatilized, and 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 that is the product of the present invention include various compounds having a structure in which a hydrogen atom of a raw material is replaced with a chlorine atom. 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 chlorinated hydrocarbons which are the products of the present invention will be given below, but the invention is not limited thereto. Monochloromethane, dichloromethane, trichloromethane, tetrachloromethane, monochloroethane, dichloroethane, trichloroethane, monochloropropane, dichloropropane, monochloroethylene, dichloroethylene, trichloroethylene, tetrachloroethylene, monochloropropene, dichloropropene, dichlorobutene, chloroprene, trichlorofluoromethane, dichloro Difluoromethane, monochlorotrifluoromethane, monochlorodifluoromethane, monochlorofluoromethane, monochloropentafluoroethane, dichlorofluoroethane, monochlorodifluoroethane, trichlorotrifluoroethane, dichlorotetrafluoroethane, monochlorobenzene, dichlorobenzene, benzyl chloride, dichlorobenzalk Ride, chloroethylbenzene, chlorostyrene, chloromethylstyrene, chloro bromo-difluoroethane, and the like bromochloromethane trifluoroethane. The above examples of chlorinated hydrocarbons include isomers.

The reaction product is separated from the unreacted product and collected by a known method. For example, the reaction product may be brought into contact with water to remove unreacted hydrogen chloride and the like, and then distilled.

According to the method of the present invention, by using a catalyst having an average pore size of 100 Å or more as a catalyst, compared with the conventional catalyst using a carrier of less than 100 Å, the raw material hydrocarbon and / or partial chlorination can be obtained. The combustion reaction of hydrocarbons can be suppressed and a high yield of chlorinated hydrocarbons can be achieved. In particular, when an inorganic porous carrier containing zirconium oxide is used as a carrier, even when hydrogen chloride containing hydrogen fluoride is adopted, not only a remarkable combustion suppressing effect is exhibited but also high durability is achieved. Can be expressed. 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.

[0042]

EXAMPLES The present invention will be specifically described below with reference to examples.

The value of the average pore diameter was measured by the following method. Further, the reaction rate and selectivity in the table are expressed in mol%.

[Measurement Method of Average Pore Diameter] The inorganic porous carrier was placed in nitrogen and left at 300 ° C. for 20 minutes. As a result, the inorganic porous carrier was degassed and the adsorbed water was removed. Then cooled to liquid nitrogen temperature. A mixed gas of nitrogen and helium was flowed here at 15 cc / min to adsorb nitrogen. Next, the temperature was returned to room temperature, the desorbed nitrogen was detected by a thermal conductivity detector, and the desorbed nitrogen amount (V) was obtained. Similarly, a mixed gas having different ratios of nitrogen and helium was adsorbed on the inorganic porous carrier, and the amount of desorbed nitrogen was measured.

A graph was obtained in which the vertical axis represents the amount of desorbed nitrogen (V) and the horizontal axis represents the partial pressure of nitrogen in the mixed gas, and the curve of the graph was calculated to determine the average pore diameter. In addition, the measurement was performed using a cantasorb manufactured by Cantachrome (US), and the average pore diameter was measured in the range of 10 to 1000Å.

Example 1 Commercially available zirconia powder (average pore size 150Å, specific surface area 12 m ² / g) was dipped in an aqueous solution of copper chloride and then dried at 250 ° C. for 10 hours to give 10% by weight of copper chloride. It was supported. This is 160 gauge pressure
After press-molding at kg / cm ^2, it was crushed and classified with a sieve to obtain a catalyst having a particle size of 10-20 mesh. 20 cc of catalyst was filled in an Inconel reactor having an inner diameter of 14 mm and heated to a required temperature. Methyl chloride, hydrogen chloride and air were added to this, CH ₃ Cl / HCl / O ₂ = 1.0 / 1.5 /
The reaction was carried out at 1.1 (molar ratio) and a space velocity SV = 1200 h ⁻¹ . The results are shown in Table 1.

Example 2 Commercially available zirconia powder (average pore size 120Å, specific surface area 20 m ² / g) was dipped in an aqueous solution of copper chloride and then dried at 250 ° C. for 10 hours to give 10% by weight of copper chloride. It was supported. This is the gauge pressure 180
After press-molding at kg / cm ^2, it was crushed and classified with a sieve to obtain a catalyst having a particle size of 10-20 mesh. 20 cc of catalyst was filled in an Inconel reactor having an inner diameter of 14 mm and heated to a required temperature. To this, hydrogen chloride containing hydrogen chloride and hydrogen fluoride (HF = 300 ppm) and air were added CH ₃ Cl / HCl / O ₂ = 1.0 / 1.7 / 1.2
(Mole ratio) and space velocity SV = 1300 h ⁻¹ to allow reaction. The results are shown in Table 1.

Example 3 Commercially available zirconia powder (average pore size 130 Å, specific surface area 15 m ² / g) was immersed in a mixed aqueous solution of copper nitrate and potassium nitrate, and then at 120 ° C. for 2 hours.
It was dried for 4 hours. Then, it was baked in air at 500 ° C. for 6 hours to carry 10% by weight of copper oxide and 6% by weight of potassium oxide. Further, the mixture was allowed to stand in hydrogen chloride at 400 ° C. for 15 hours to convert copper oxide and potassium oxide into copper chloride and cerium chloride, respectively. Gauge pressure 190kg / cm
After press molding at ² , crush and classify with a sieve to 7-15
A catalyst having a mesh particle size was used. 20 cc of catalyst was filled in an Inconel reactor having an inner diameter of 14 mm and heated to a required temperature. Add methyl chloride, hydrogen chloride and air to this
₃ Cl / HCl / O ₂ = 1.0 / 1.1 / 0.9 (molar ratio) and a space velocity SV = 1100 h ⁻¹ were flowed to react. The results are shown in Table 2.

Example 4 Commercially available zirconia powder (average pore size 160 Å, specific surface area 8 m ² / g) was immersed in a mixed aqueous solution of copper chloride and calcium chloride, and then at 250 ° C. for 1 hour.
After drying for 2 hours, copper chloride was carried by 11% by weight and calcium chloride was carried by 9% by weight. This is a gauge pressure of 200 kg
/ Cm ² and then crush and sieving
A catalyst having a particle size of -15 mesh was used. Catalyst 20c
c was charged into an Inconel reactor having an inner diameter of 14 mm and heated to a required temperature. Methyl chloride, hydrogen chloride and air were added to this, CH ₃ Cl / HCl / O ₂ = 1.0 / 1.2 / 0.9
(Mole ratio) and space velocity SV = 1000 h ⁻¹ to allow the reaction to proceed. The results are shown in Table 2.

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 to stand for one day, washed with water, filtered, and dried at 110 ° C. for 20 hours. further,
After crushing this, baking at 900 ° C. for 10 hours
to obtain a composite oxide of uO-MgO-ZrO _2. CuO in the composite oxide was 10% by weight, MgO was 5% by weight, the average pore diameter was 150Å, and the specific surface area was 10 m ² / g. The composite oxide was treated in hydrogen chloride at 400 ° C. for 20 hours to be converted into chloride. This is gauge pressure 2
After press-molding at 00 kg / cm ^2, it was crushed and classified with a sieve to obtain a test catalyst having a particle size of 10 to 15 mesh. A catalyst made of Inconel having an inner diameter of 14 mm was filled with 20 cc of the catalyst, and hydrogen chloride (HF = 300 ppm) containing methyl chloride and hydrogen fluoride and air were mixed with CH ₃ Cl / HC.
1 / O ₂ = 1.0 / 1.6 / 0.9 (molar ratio) and a space velocity SV = 1500 h ⁻¹ were flowed to react. The results are shown in Table 3.

Example 6 Commercially available zirconia powder (average pore diameter 180Å, specific surface area 4 m ² / g) was immersed in a mixed aqueous solution of copper chloride, potassium chloride and magnesium chloride, and then dried at 250 ° C. for 12 hours. Copper chloride was loaded at 11% by weight, potassium chloride was loaded at 5% by weight, and magnesium chloride was loaded at 6% by weight. This is a gauge pressure of 140 kg / cm ²
After press molding with, crush and classify with a sieve for 10 to 20
A catalyst having a mesh particle size was used. 20 cc of catalyst was filled in an Inconel reactor having an inner diameter of 14 mm and heated to a required temperature. Add methyl chloride, hydrogen chloride and air to this
₃ Cl / HCl / O ₂ = 1.0 / 1.3 / 0.8 (molar ratio) and space velocity SV = 1200 h ⁻¹ were allowed to flow for reaction. The results are shown in Table 3.

Example 7 Commercially available zirconia powder (average pore size 130 Å, specific surface area 25 m ² / g) was immersed in a mixed aqueous solution of copper chloride and cerium chloride, and then at 250 ° C. for 1 hour.
After drying for 0 hour, 11% by weight of copper chloride and 5% by weight of cerium chloride were supported. Gauge pressure 180kg / c
After press molding at m ² , crush and sieving to 7-1
A catalyst having a particle size of 5 mesh was used. 20 cc of catalyst was filled in an Inconel reactor having an inner diameter of 14 mm and heated to a required temperature. Add methyl chloride, hydrogen chloride and air to this.
H ₃ Cl / HCl / O ₂ = 1.0 / 1.3 / 0.8 (molar ratio) and space velocity SV = 1100 h ⁻¹ were flowed to react. The results are shown in Table 4.

Example 8 Commercially available zirconia powder (average pore size 140Å, specific surface area 12 m ² / g) was dipped in a mixed aqueous solution of copper chloride, potassium chloride and cerium chloride, and dried at 250 ° C. for 18 hours. , Copper chloride 12% by weight, potassium chloride 6% by weight, cerium chloride 2% by weight
It was supported. Next, it was press-molded at a gauge pressure of 200 kg / cm ² , crushed, and then classified with a sieve to obtain a catalyst having a particle size of 10 to 15 mesh. Catalyst 20cc with inner diameter 1
A 4 mm Inconel reactor was charged and heated to the required temperature. This methane with hydrogen chloride and air CH ₄ / HC
1 / O ₂ = 1.0 / 1.4 / 1.0 (molar ratio) and a space velocity SV = 1300 h ⁻¹ were flowed to react. The results are shown in Table 4.

Example 9 Commercially available zirconia powder (average pore size 140Å, specific surface area 15 m ² / g) was immersed in a mixed aqueous solution of copper chloride, potassium chloride, magnesium chloride and cerium chloride, and then at 10 ° C at 250 ° C. After drying for an hour, 10% by weight of copper chloride, 6% by weight of potassium chloride, 5% by weight of magnesium chloride and 6% by weight of cerium chloride were carried. This was press-molded at a gauge pressure of 180 kg / cm ² , then crushed and classified with a sieve to obtain a catalyst having a particle size of 10 to 20 mesh. 20 cc of catalyst was filled in an Inconel reactor having an inner diameter of 14 mm and heated to a required temperature.
Methyl chloride, hydrogen chloride and air are added to this and CH ₃ Cl / HC
The reaction was carried out at a flow rate of 1 / O ₂ = 1.0 / 1.6 / 1.2 (molar ratio) and a space velocity SV = 1200 h ⁻¹ . The results are shown in Table 5.

Example 10 Commercially available silica-alumina powder (Al ₂ O ₃ content 30% by weight, average pore diameter 110 Å,
The specific surface area (110 m ² / g) was immersed in a mixed aqueous solution of copper chloride and potassium chloride, and then dried at 250 ° C. for 10 hours to carry 10% by weight of copper chloride and 6% by weight of potassium chloride. 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. Catalyst 20cc inside diameter 14m
m Inconel reactor was charged and heated to the required temperature. To this, add methyl chloride, hydrogen chloride and air to CH ₃ Cl.
/ HCl / O ₂ = 1.0 / 1.5 / 1.0 (molar ratio),
The reaction was carried out by flowing at a space velocity SV = 1300 h ⁻¹ .
The results are shown in Table 5.

Example 11 A mixed aqueous solution of zirconium oxynitrate and aluminum nitrate and 10% ammonia water were gradually added dropwise to stirred water so as to maintain pH = 8, to form a coprecipitated gel. . After leaving it to stand for one day, it was washed with water, filtered, and dried at 120 ° C. for 24 hours. Furthermore, after crushing, it is baked at 800 ° C. for 12 hours, and Al ₂
O ₃ to obtain a composite oxide of -ZrO _2. Al ₂ O ₃ in the composite oxide was 21% by weight, the average pore diameter was 130 Å, and the specific surface area was 18 m ² / g. The composite oxide is dipped in a copper chloride aqueous solution and then dried at 250 ° C. for 10 hours,
12% by weight of copper chloride was supported. This is gauge pressure 17
After press molding at 0 kg / cm ^2, it was crushed and classified by a sieve to obtain a catalyst having a particle size of 10 to 20 mesh. 20 ml of the catalyst was charged into an Inconel reactor having an inner diameter of 14 mm and heated to a required temperature. Methyl chloride, hydrogen chloride and air were added to this, CH ₃ Cl / HCl / O ₂ = 1.
0 / 1.2 / 0.8 (molar ratio), space velocity SV = 110
Table 6 shows the results of reaction at ⁰ h ^-1 for circulation.

[Example 12] A mixed aqueous solution of zirconium oxynitrate and aluminum nitrate and 10% ammonia water were gradually added dropwise to stirred water so as to maintain pH = 8 to form a coprecipitated gel. . After leaving it to stand for one day, it was washed with water and filtered, and dried at 110 ° C. for 24 hours. Furthermore, after crushing, baking is performed at 700 ° C. for 10 hours.
A complex oxide of l ₂ O ₃ —ZrO ₂ was obtained. Al ₂ O ₃ in the composite oxide is 48% by weight, the average pore diameter is 105Å,
The specific surface area was 30 m ² / g. After immersing the composite oxide in a mixed aqueous solution of copper chloride and potassium chloride, 200
It was dried at 15 ° C. for 15 hours to carry 12% by weight of copper chloride and 6% by weight of potassium chloride. This is a gauge pressure 180k
Press-molded at g / cm ² and then crushed and classified with a sieve 1
A catalyst having a particle size of 0 to 15 mesh was used. Catalyst 20
Milliliter was filled in an Inconel reactor having an inner diameter of 14 mm and heated to a required temperature. Hydrogen chloride (HF = 300 ppm) containing methyl chloride and hydrogen fluoride and air were added to this, CH ₃ Cl / HCl / O ₂ = 1.0 / 1.6 / 1.
Table 6 shows the results of reaction by flowing at 0 (molar ratio) and space velocity SV = 1500 h ⁻¹ .

Example 13 A mixed aqueous solution of zirconium oxynitrate and aluminum nitrate 10% ammonia water was gradually added dropwise to stirred water so as to maintain pH = 8 to form a coprecipitated gel. After leaving it to stand for one day, it was washed with water, filtered, and dried at 120 ° C. for 24 hours. Furthermore, after crushing, baking at 900 ° C. for 12 hours
A composite oxide of ₂ O ₃ —ZrO ₂ was obtained. Al ₂ O ₃ in the composite oxide was 21% by weight, the average pore diameter was 150 Å, and the specific surface area was 9 m ² / g. The composite oxide was dipped in a mixed aqueous solution of copper chloride and lanthanum chloride and then dried at 250 ° C. for 12 hours to support copper chloride of 11% by weight and lanthanum chloride of 5% by weight. Gauge pressure 150kg /
After press molding with cm ² , crush and classify with a sieve to 10
A catalyst having a particle size of -15 mesh was used. 20 ml of the catalyst was charged into an Inconel reactor having an inner diameter of 14 mm and heated to a required temperature. Methyl chloride, hydrogen chloride and air were added to this, CH ₃ Cl / HCl / O ₂ = 1.0 / 1.4
/1.0 (molar ratio) and the space velocity SV = 1000 h ^-1 and the results of reaction were shown in Table 7.

Example 14 A mixed aqueous solution of zirconium oxynitrate and aluminum nitrate and a 10% aqueous sodium carbonate solution were gradually added dropwise to stirred water so as to maintain pH = 8 to form a coprecipitated gel. It was After leaving it to stand for one day, it was washed with water and filtered, and dried at 150 ° C. for 18 hours. Further, after pulverizing, it is performed for 10 hours firing at 700 ° C., to obtain a composite oxide of Al ₂ O ₃ -ZrO _2. Al ₂ O ₃ in the composite oxide is 28% by weight, and the average pore diameter is 1
The surface area was 20Å and the specific surface area was 25 m ² / g. The composite oxide is immersed in a mixed aqueous solution of copper chloride, potassium chloride and lanthanum chloride, and then dried at 250 ° C. for 10 hours,
10% by weight of copper chloride, 6% by weight of potassium chloride and 5% by weight of lanthanum chloride were carried. This is 160 gauge pressure
After press-molding at kg / cm ^2, it was crushed and classified with a sieve to obtain a catalyst having a particle size of 7 to 15 mesh. Catalyst 20
Milliliter was filled in an Inconel reactor having an inner diameter of 14 mm and heated to a required temperature. Methane, hydrogen chloride and air were added to this with CH ₄ / HCl / O ₂ = 1.0 / 1.8 / 1.
Table 7 shows the results obtained by causing the reaction to flow at 2 (molar ratio) and space velocity SV = 1300 h ⁻¹ .

Comparative Example 1 Commercially available γ-alumina powder (average pore diameter 15Å, specific surface area 140 m ² / g) was dipped in an aqueous copper chloride solution and then dried at 250 ° C. for 12 hours to obtain 10 parts by weight of copper chloride. % Supported. Next, gauge pressure 150
After press-molding at kg / cm ^2, it was crushed and classified with a sieve to obtain a catalyst having a particle size of 7 to 15 mesh. Catalyst 2
0 cc was filled in an Inconel reactor having an inner diameter of 14 mm and heated to a required temperature. Methyl chloride, hydrogen chloride and air were added to this, CH ₃ Cl / HCl / O ₂ = 1.0 / 1.5 /
Table 8 shows the results of reaction by flowing at a space ratio of 0.7 (molar ratio) and SV = 1000 h ⁻¹ .

[Comparative Example 2] Commercially available γ-alumina powder (average pore diameter 15Å, 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 obtain 10 parts by weight of copper chloride. % Supported. Next, gauge pressure 150
After press-molding at kg / cm ^2, it was crushed and classified with a sieve to obtain a catalyst having a particle size of 7 to 15 mesh. Catalyst 2
0 cc was filled in an Inconel reactor having an inner diameter of 14 mm and heated to a required temperature. Hydrogen chloride (HF = 300 ppm) containing methyl chloride and hydrogen fluoride and air were added to this, CH ₃ Cl / HCl / O ₂ = 1.0 / 1.5 / 0.7
(Mole ratio) and space velocity SV = 1000 h ⁻¹ .

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

[Table 4]

[0066]

[Table 5]

[0067]

[Table 6]

[0068]

[Table 7]

[0069]

[Table 8]

[0070]

(1) According to the method of the present invention, it is possible to suppress the loss of the raw material hydrocarbons and / or partially chlorinated hydrocarbons due to polymerization or oxidation. As a result, the yield of chlorinated hydrocarbon can be increased.

(2) In particular, when an inorganic porous carrier containing zirconium oxide is adopted, even if hydrogen chloride containing hydrogen fluoride is used as hydrogen chloride, a long catalyst life and a long chlorinated hydrocarbon are obtained. A yield can be achieved.

(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.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C07C 19/03 // C07B 61/00 300

Claims (7)

[Claims] 1. When oxychlorinating a hydrocarbon and / or a partially chlorinated hydrocarbon to produce a chlorinated hydrocarbon,
A process for producing a chlorinated hydrocarbon, characterized in that a catalyst comprising (A) copper chloride supported on an inorganic porous carrier having an average pore size of 100Å or more is present. 2. A catalyst in which (A) copper chloride and (B) an alkali metal chloride and / or an alkaline earth metal chloride are supported on an inorganic porous carrier having an average pore size of 100 Å or more. A certain method according to claim 1. 3. The process according to claim 1, wherein the catalyst is a catalyst in which (A) copper chloride and (C) rare earth metal chloride are supported on an inorganic porous carrier having an average pore size of 100 Å or more. 4. A catalyst comprising an inorganic porous carrier having an average pore size of 100Å or more, (A) copper chloride, (B) alkali metal chloride and / or alkaline earth metal chloride, and (C) rare earth metal. 2. The method according to claim 1, which is a catalyst supporting chloride. 5. The method according to claim 1, which is carried on an inorganic porous carrier having an average pore diameter of 100 to 8000 liters. 6. The method according to claim 1, wherein the inorganic porous carrier is an inorganic porous carrier containing zirconium oxide. 7. The method according to any one of claims 1 to 6, wherein oxychlorination is carried out using hydrogen chloride containing hydrogen fluoride.