JPH05163175A - Production of hydrogen-containing chlorocarbon compound - Google Patents

Abstract

PURPOSE:To obtain in high efficiency and selectivity a hydrogen-contg. chloromethane compound like chloroform usable as an important raw material for various kinds of chlorofluorocarbons by reducing with hydrogen a polychloromethane compound (esp. carbon tetrachloride being subject to environmental regulation). CONSTITUTION:The objective compound can be obtained by reaction (esp. pref. liquid phase reaction) using a reducing catalyst consisting mainly of group 8, 9 or 10 element such as palladium, platinum or ruthenium and incorporated with group 11 element like copper, silver or gold.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses polychlorocarbons, particularly carbon tetrachloride, which is regulated from the standpoint of global environment protection, as a raw material, and chloroform which is useful as a raw material for various fluorine compounds. The present invention relates to a method for converting hydrogen-containing chlorocarbons such as

[0002]

2. Description of the Related Art Conventionally, carbon tetrachloride has been mainly used as a raw material for various fluorocarbons. However, not only these fluorocarbons but also carbon tetrachloride as a raw material have been regulated in their production. There is a worldwide demand for a technology for decomposing and removing or converting it to a useful one.

On the other hand, hydrogen-containing chlorocarbons such as chloroform obtained by replacing chlorine atoms in carbon tetrachloride with hydrogen atoms are useful as raw materials for various chemical products. Therefore, there is an urgent need for technological development for efficiently introducing hydrogen into polychlorocarbons such as carbon tetrachloride and converting them into hydrogen-containing chlorocarbons.

[0004]

As a method of introducing hydrogen into carbon tetrachloride, there is a method of electrolytic reduction in the presence of a protic solvent, but it has drawbacks such as a slow reaction rate and is industrially used. Is hard to adopt. On the other hand, the method of reducing hydrogen with a reducing catalyst has a high reaction rate and is considered to be advantageous for industrial development. However, in a hydrogen reduction method using a general-purpose reduction catalyst such as iron or platinum, the catalyst is deactivated extremely rapidly, and a dimer such as hexachloroethane, or a compound having 5 to 7 carbon atoms at a high temperature is used. There is a problem that the yield of the target product is not always high, such as a by-product of the polymer. For example, Japanese Patent Laid-Open No. 3-1339
See the publication No. 39, etc.

[0005]

Means for Solving the Problems As a result of intensive studies on a reaction method capable of suppressing by-products of the polymer, the present inventors have found that at least one element selected from Group 8, Group 9 and Group 10 elements. Hydrogen-containing chlorocarbons can be obtained in high yield by reducing polychlorocarbons with hydrogen in the presence of a reducing catalyst obtained by adding at least one element selected from Group 11 elements to the elements. The present invention has been completed and the present invention has been completed.

The present invention is a reduction catalyst containing as a main component at least one element selected from elements of groups 8, 9 and 10 and to which at least one element selected from elements of group 11 is added. The present invention provides a novel method for producing hydrogen-containing chlorocarbons, which is characterized by reducing polychlorocarbons with hydrogen in the presence of.

Hereinafter, the details of the present invention will be described together with examples.

In the present invention, examples of the polychlorocarbons include carbon tetrachloride, chloroform, methylene chloride, and the like. Specifically, chloroform, methylene chloride, methyl chloride by reduction of carbon tetrachloride,
Reduction of chloroform gives methylene chloride and methyl chloride, and reduction of methylene chloride gives methyl chloride. Also, polychlorocarbons having 2 or more carbon atoms may be used.

In the present invention, a reduction containing at least one element selected from Group 8, 9 and 10 elements as a main component, to which at least one element selected from Group 11 elements is added It is important to use a catalyst. By reducing polychlorocarbons with hydrogen in the presence of the catalyst, hydrogen-containing chlorocarbons can be produced in high yield without rapidly deactivating the catalyst.

The main component element in the reduction catalyst is at least selected from Group 8 elements such as iron, ruthenium and osmium, Group 9 elements such as cobalt, rhodium and iridium, and Group 10 elements such as nickel, palladium and platinum. One element is preferred. Among these main component elements, at least one platinum group element selected from ruthenium, rhodium, platinum, and palladium is particularly preferable because high activity and high durability can be easily obtained. These main component elements may be used alone or in combination of two or more.

The Group 11 element of the additive component may be copper, silver, gold, or a combination thereof. From the viewpoint of ensuring the reaction activity and improving the selectivity, the addition amount of the Group 11 element is 0.01 to 50% by weight, preferably 0.1 to 50% by weight, and particularly preferably 1 to 50% by weight.

The reduction catalyst of the present invention comprises the above main component element (8
.About.10 group element) and an additional component element (11 group element) are contained as essential components, but other elements other than these essential components may be further contained as long as the catalytic performance is not impaired.

These catalytic metals can be used as they are or on a carrier. As the carrier, those commonly used such as activated carbon, alumina, zirconia and silica can be used. Further, the supported amount is preferably about 0.01 to 20% by weight, preferably about 0.5 to 5% by weight, from the viewpoint of catalyst supporting efficiency, reaction activity, dispersion of catalyst components and the like.

The method of loading the catalyst component can be appropriately selected from the range usually adopted. For example, a method of supporting a simple salt or complex salt of the above element by an impregnation method, an ion exchange method or the like can be applied. Further, in using the catalyst, it is not always necessary to carry out the reduction treatment of the catalyst, but it is desirable to carry out hydrogen reduction in advance in order to obtain stable characteristics. As a method of reducing the supported catalyst component, a method of reducing with hydrogen, hydrazine, formaldehyde, sodium borohydride or the like in a liquid phase, a method of reducing with hydrogen in a gas phase, and the like can be applied.

As the reduction reaction process, either a gas phase reaction or a liquid phase reaction in a fixed bed, a suspension bed or the like can be adopted. However, it is more preferable to carry out the reaction in the liquid phase from the viewpoint of catalyst life and reaction selectivity. In the liquid phase reaction,
The use of a reaction solvent is effective for controlling the ratio of products and stabilizing the reaction activity, and can be appropriately performed. For example, alcohols such as methanol and ethanol, amines such as triethylamine, carboxylic acids such as acetic acid, and ketones such as acetone can be used as reaction solvents.

The reduction reaction temperature can be appropriately selected from a wide range of about 0 ° C. to 300 ° C., but is preferably 50 ° C. in a suitable liquid phase reaction.
It is desirable to select a temperature between ℃ and 250 ℃. The supply molar ratio of hydrogen and polychloromethanes is not particularly limited. When the amount of hydrogen is increased, the reaction rate is increased, which is advantageous in terms of the life of the catalyst and the like, but the production ratio of the products that are more dechlorinated and hydrogenated is increased. Hydrogen for 1 mol of polychloromethanes
Although it can be used in an amount of 50 mol or more, it is usually preferable to use hydrogen in an amount of about 0.1 to 20 mol per mol of polychloromethanes. Excess hydrogen can be recycled to increase the utilization rate of hydrogen.

In the gas phase reaction, the reaction pressure is not particularly limited as long as the polychloromethanes involved in the reaction are not liquefied. On the other hand, in the liquid phase reaction, an atmospheric pressure or higher is suitable, and the reaction rate increases as the pressure increases. Pressure of up to several ^{kg / cm 2 · G~10kg / cm} 2 · about G can be employed. If the pressure is too high, there are problems such as an increase in the cost of the apparatus even if the reaction rate increases.

[0018]

The action mechanism of the combination catalyst of specific elements of the present invention is not clear, but the following may be considered. That is, by adding the additional component element of the 11th group to the main component element of the 8th group, 9th group and 10th group, the hydrogenation catalytic ability of the main component element is not hindered and It is considered that the interaction can be effectively suppressed.

A typical example is the reaction of carbon tetrachloride with hydrogen.
This will be described in more detail. As seen in the conventional example, in the reduction reaction of carbon tetrachloride using an ordinary hydrogenation catalyst such as platinum or palladium, many chlorides and polymers are deposited on the catalyst and the catalyst is rapidly deactivated. Phenomena such as a large amount of by-products such as olefins and chloroethanes are observed. This phenomenon indicates that the interaction between the catalyst metal and the chlorine atom in carbon tetrachloride affects the hydrogenation action of the catalyst.

Carbon tetrachloride has a central carbon atom shielded by a large negatively charged chlorine atom, and d orbitals and other orbitals that form an intermediate necessary for the reaction to proceed outside the molecule. Since it does not exist, it is inert to water, strong acid and strong alkali. However, carbon tetrachloride having four chlorine atoms with large polarity has a very large adsorption energy for a metal, and therefore has a long residence time on the metal, and therefore has a property of being easily subjected to a catalytic action. It is possible to have it. In particular, when contacting with a catalyst having a very large surface area, carbon tetrachloride and the catalyst metal are included even in the group of elements such as groups 8, 9 and 10 which are relatively filled with d orbitals among transition metals. It is possible that the reaction with For example, a recent study on the interaction between carbon tetrachloride and iron suggests that when carbon tetrachloride is adsorbed on iron, it is considered to be CCl ₂ or CCl ₃ or their polymerization products even at low temperatures. CCl ₂ = CCl ₂ or CCl ₃ CCl ₃
In addition, it has been confirmed that iron chloride is generated.

On the other hand, when performing hydrogen reduction, it is necessary to consider the interaction with the adsorbed hydrogen atom generated by the adsorption and dissociation of hydrogen molecules on the catalyst. That is, under a hydrogen atmosphere, hydrogen is adsorbed and dissociated on the surface of the catalytic metal to become hydrogen atoms, which are partially diffused and occluded in the metal bulk. Although it is difficult to accurately discuss the interaction between the catalyst metal and the chlorine atom in the carbon tetrachloride molecule when carbon tetrachloride is adsorbed on the catalyst metal in such a state,
Roughly, it is presumed that it becomes a competitive reaction of dehydrochlorination or polymerization reaction and hydrogenation reaction of adsorbed dissociation product of carbon tetrachloride.

Generally, elements of groups 8, 9 and 10, especially
Nickel, cobalt, ruthenium, palladium, rhodium, platinum, etc. easily generate adsorbed hydrogen atoms on the surface when brought into contact with hydrogen gas, and exhibit good hydrogenation catalytic ability.
However, in the case of hydrogen reduction of carbon tetrachloride, the effect of the interaction between the catalyst metal and the chlorine atom as described above is recognized. Therefore, in order to suppress rapid deactivation of the catalyst and by-products, it is considered effective to suppress the interaction with chlorine without hindering the hydrogenation ability of the catalyst.

Among the typical elements, the 11th group element itself has no ability to adsorb and dissociate hydrogen molecules, but the surface diffusion of the hydrogen element is possible, and when added to the 8th group, 9th group and 10th group elements,
It is expected that the hydrogenation ability of the catalyst will not be significantly reduced. On the contrary, it is considered that the hydrogenation activity is improved by the addition. The reason for this may be that addition of catalyst particles facilitates dispersion of the catalyst fine particles, or action due to electron seepage from the 11th group element to the main element such as 8th group, 89th group, or 10th group element. However, it is not always clear.

Furthermore, when considering the chlorination enthalpy of metal as one scale, the enthalpy of chloride formation of the 11th group element has a smaller value than that of the other elements. It is expected to reduce the interaction with carbon tetrachloride by adding it to Group 10 elements. For example, the standard enthalpy of formation of AuCl is −8.3 kcal / mol, while looking at palladium, which is the most typical reduction catalyst, the standard enthalpy of formation of PdCl ₂ is −33.2 kc / mol.
It is al / mol, and the effect of adding the Group 11 element can be expected.

The above inference of the action mechanism is applicable not only to carbon tetrachloride but also to hydrogen reduction of not only chloromethanes such as chloroform and methylene chloride but also polychlorocarbons having 2 or more carbon atoms. .. Further, the above description is for helping understanding of the present invention and does not limit the present invention in any way.

[0026]

EXAMPLES Examples of the present invention will be shown below.

Preparation Example 1 Coconut husk activated carbon powder as a carrier (average particle size 10 to 20 μm)
100 g of m) was added to 1 liter of ion-exchanged water. Ruthenium chloride and chloroauric acid were dissolved in ion-exchanged water at a weight ratio of metal components of 9: 1 and an amount corresponding to 5% of the weight of the carrier. After reducing with an aqueous solution of hydrazine, it was washed with ion-exchanged water and dried at 110 ° C.

Preparation Example 2 Acetylene black powder as a carrier (average particle size 1 μm
100 g of m) was added to 1 liter of ion-exchanged water. Rhodium chloride and chloroauric acid, the weight ratio of each metal component is 9
It was dissolved in ion-exchanged water in a ratio of 5: 5 in an amount corresponding to 2% of the weight of the carrier. After reducing with an aqueous solution of sodium borohydride, it was washed with ion-exchanged water and dried at 110 ° C.

Preparation Example 3 Pitch-based activated carbon powder as a carrier (average particle size 10 to 20 μm)
100 g of m) was added to 1 liter of ion-exchanged water. Palladium chloride and chloroauric acid were dissolved in ion-exchanged water at a weight ratio of metal components of 8: 2 and an amount corresponding to 2% of the weight of the carrier. After reducing with an aqueous solution of hydrazine, it was washed with ion-exchanged water and dried at 110 ° C.

Preparation Example 4 Pitch-based activated carbon powder as a carrier (average particle size: 10 to 20 μm)
100 g of m) was added to 1 liter of ion-exchanged water. Nickel chloride, chloroplatinic acid, and chloroauric acid were dissolved in ion-exchanged water at a weight ratio of metal components of 5: 4: 1 in an amount corresponding to 2% of the weight of the carrier. After reducing with an aqueous solution of sodium borohydride, it was washed with ion-exchanged water and dried at 110 ° C.

Preparation Example 5 Woody activated carbon powder as carrier (average particle size 10 to 20 μm)
Was added to 1 liter of ion-exchanged water. Chloroplatinic acid and chloroauric acid were dissolved in ion-exchanged water in an amount corresponding to 2% of the carrier weight, with the weight ratio of the metal components being 9: 1. After reducing with an aqueous solution of sodium borohydride, it was washed with ion-exchanged water and dried at 110 ° C.

Preparation Example 6 10 of coconut husk activated carbon powder (average particle size 10 to 20 μm) as a carrier
0 g was added to 1 liter of ion-exchanged water. Ruthenium chloride and silver diammine nitrate were dissolved in ion-exchanged water in a weight ratio of metal components of 85:15, respectively, in an amount corresponding to 5% of the carrier weight. Aqueous ammonia was added to make the solution alkaline, and the solution was reduced with an aqueous solution of sodium borohydride. It was washed with ion-exchanged water and dried at 110 ° C.

Preparation Example 7 Coconut husk activated carbon powder as a carrier (average particle size 10 to 20 μm)
100 g of m) was added to 1 liter of ion-exchanged water. Rhodium chloride and silver diammine nitrate were dissolved in ion-exchanged water in a weight ratio of metal components of 9: 1 and in an amount corresponding to 2% of the weight of the carrier. After reducing with an aqueous solution of hydrazine, it was washed with ion-exchanged water and dried at 110 ° C.

Preparation Example 8 Pitch-based activated carbon powder as a carrier (average particle size: 10 to 20 μm)
100 g of m) was added to 1 liter of ion-exchanged water. Palladium chloride and silver diammine were dissolved in ion-exchanged water in a weight ratio of metal components of 95: 5, respectively, in an amount corresponding to 2% of the weight of the carrier. Aqueous ammonia was added to make the solution alkaline, and the solution was reduced with an aqueous solution of hydrazine. It was washed with ion-exchanged water and dried at 110 ° C.

Preparation Example 9 Coconut husk activated carbon powder (average particle size 10 to 20 μm) as a carrier
100 g of m) was added to 1 liter of ion-exchanged water. Chloroplatinic acid and silver diammine were dissolved in ion-exchanged water in a weight ratio of metal components of 9: 1 in an amount corresponding to 2% of the carrier weight. Aqueous ammonia was added to make the solution alkaline, and the solution was reduced with an aqueous solution of hydrazine. It was washed with ion-exchanged water and dried at 110 ° C.

Preparation Example 10 Coconut husk activated carbon powder (average particle size 10 to 20 μm) as a carrier
100 g of m) was added to 1 liter of ion-exchanged water. Ruthenium chloride and copper chloride, the weight ratio of each metal component is 9
It was dissolved in ion-exchanged water at a ratio of 5: 5 in an amount corresponding to 5% of the weight of the carrier. Aqueous ammonia was added to make the solution alkaline, and the solution was reduced with an aqueous solution of sodium borohydride. It was washed with ion-exchanged water and dried at 110 ° C.

Preparation Example 11 Wood-based activated carbon powder as a carrier (average particle size 10 to 20 μm)
Was added to 1 liter of ion-exchanged water. Rhodium chloride and copper chloride were dissolved in ion-exchanged water at a weight ratio of the metal components of 9: 1 and in an amount corresponding to 2% of the weight of the carrier. Aqueous ammonia was added to make the solution alkaline, and the solution was reduced with an aqueous solution of hydrazine. It was washed with ion-exchanged water and dried at 110 ° C.

Preparation Example 12 Pitch-based activated carbon powder as a carrier (average particle size: 10 to 20 μm)
100 g of m) was added to 1 liter of ion-exchanged water. Palladium chloride and copper chloride, the weight ratio of each metal component is 9
It was dissolved in ion-exchanged water in a ratio of 5: 5 in an amount corresponding to 2% of the weight of the carrier. Aqueous ammonia was added to make the solution alkaline, and the solution was reduced with an aqueous solution of hydrazine. It was washed with ion-exchanged water and dried at 110 ° C.

Preparation Example 13 Coconut husk activated carbon powder as a carrier (average particle size: 10 to 20 μm)
100 g of m) was added to 1 liter of ion-exchanged water. The weight ratio of chloroplatinic acid and copper chloride is 9: 1.
Was dissolved in ion-exchanged water in an amount corresponding to 2% of the carrier weight. Aqueous ammonia was added to make the solution alkaline, and the solution was reduced with an aqueous solution of hydrazine. It was washed with ion-exchanged water and dried at 110 ° C.

Example 1 1 liter of carbon tetrachloride was placed in a 2 liter autoclave, and 50 g of the reduction catalyst prepared in Preparation Example 1 was added. After enclosing nitrogen and raising the temperature to 80 ° C., the supply of hydrogen was started. The pressure was kept at 5 kg / cm ² · G. The product was analyzed using gas chromatography for both the gas phase component and the liquid phase component. Hydrogen was continuously supplied at a rate of 3 mol / h to 1 mol / h of carbon tetrachloride to continue the reaction. The reaction rate of carbon tetrachloride 100 hours after the start of the reaction was 86%, and the formation of chloroform (selectivity: 95%), hexachloroethane (selectivity: 5%), etc. was confirmed.

Example 2 The reaction was carried out in the same manner as in Example 1 except that the reduction catalyst of Preparation Example 2 was used and the reaction temperature was 110 ° C. The reaction rate of carbon tetrachloride in 100 hours after the start of the reaction was 78%, and formation of chloroform (selectivity: 85%), hexachloroethane (selectivity: 5%), methylene chloride (selectivity: 8%), etc. was confirmed. Was done.

Example 3 The reaction was carried out in the same manner as in Example 1 except that the reduction catalyst of Preparation Example 3 was used and the reaction temperature was 100 ° C. The reaction rate of carbon tetrachloride 100 hours after the start of the reaction is 85%, and chloroform (selectivity: 90%), hexachloroethane (selectivity: 5%), pentachloroethane (selectivity: 2%),
It was confirmed that tetrachloroethylene (selectivity: 2%) was produced.

Example 4 The reaction was performed in the same manner as in Example 1 except that the reducing catalyst prepared in Preparation Example 4 was used. The reaction rate of carbon tetrachloride at 100 hours after the start of the reaction was 86%, and the reaction rate with chloroform (selectivity: 92
%), Hexachloroethane (selectivity: 4%), etc. were confirmed to be produced.

Example 5 A reaction was carried out in the same manner as in Example 1 except that the reduction catalyst of Preparation Example 5 was used and the reaction temperature was 100 ° C. The reaction rate of carbon tetrachloride 100 hours after the start of the reaction was 84%, and the formation of chloroform (selectivity: 89%), hexachloroethane (selectivity: 6%), etc. was confirmed.

Example 6 The reaction was carried out in the same manner as in Example 1 except that the reducing catalyst prepared in Preparation Example 6 was used. The reaction rate of carbon tetrachloride at 100 hours after the start of the reaction was 90%, and the reaction rate with chloroform (selectivity: 92
%), Hexachloroethane (selectivity: 3%), etc. were confirmed.

Example 7 The reaction was carried out in the same manner as in Example 1 except that the reduction catalyst of Preparation Example 7 was used and the reaction temperature was 110 ° C. The reaction rate of carbon tetrachloride is 75% 100 hours after the start of the reaction, and it is confirmed that chloroform (selectivity: 85%), hexachloroethane (selectivity: 6%), methylene chloride (selectivity: 7%), etc. are produced. Was done.

Example 8 A reaction was carried out in the same manner as in Example 1 except that the reduction catalyst of Preparation Example 8 was used and the reaction temperature was 100 ° C. The reaction rate of carbon tetrachloride 100 hours after the start of the reaction was 71%, and chloroform (selectivity: 90%), hexachloroethane (selectivity: 4%), pentachloroethane (selectivity: 2%),
It was confirmed that tetrachloroethylene (selectivity: 2%) was produced.

Example 9 The reaction was carried out in the same manner as in Example 1 except that the reducing catalyst prepared in Preparation Example 9 was used. The reaction rate of carbon tetrachloride 100 hours after the start of the reaction was 84%, and the reaction rate with chloroform (selectivity: 97
%), Tetrachloroethane (selectivity: 3%), etc. were confirmed to be produced.

Example 10 The reaction was carried out in the same manner as in Example 1 except that the reducing catalyst prepared in Preparation Example 10 was used. The reaction rate of carbon tetrachloride in 100 hours after the start of the reaction was 83%, and the reaction rate in chloroform (selectivity: 69
%), Hexachloroethane (selectivity: 28%), methylene chloride (selectivity: 1%), tetrachloroethylene (selectivity: 2%), etc. were confirmed.

Example 11 A reaction was carried out in the same manner as in Example 1 except that the reducing catalyst prepared in Preparation Example 11 was used and the reaction temperature was 120 ° C. The reaction rate of carbon tetrachloride 100 hours after the start of the reaction was 84%, and the formation of chloroform (selectivity: 87%), hexachloroethane (selectivity: 6%), methylene chloride (selectivity: 7%), etc. was confirmed. Was done.

Example 12 A reaction was carried out in the same manner as in Example 1 except that the reducing catalyst prepared in Preparation Example 12 was used and the reaction temperature was 90 ° C. After starting the reaction
The reaction rate of carbon tetrachloride in 100 hours is 74%, and chloroform (selectivity: 89%), hexachloroethane (selectivity: 5%), pentachloroethane (selectivity: 2%), tetrachloroethylene (selectivity: 3%) ) Etc. were confirmed to be generated.

Example 13 The reaction was carried out in the same manner as in Example 1 except that the reducing catalyst prepared in Preparation Example 13 was used. The reaction rate of carbon tetrachloride at 100 hours after the start of the reaction was 87%, and chloroform (selectivity: 93
%), Hexachloroethane (selectivity: 5%), etc. were confirmed to be produced.

Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that a ruthenium catalyst supported on a commercially available activated carbon powder (support amount: 5% by weight) was used as a reducing catalyst. The reaction rate of carbon tetrachloride is 75% at 100 hours after the start of the reaction, and the formation of chloroform (selectivity: 78%), hexachloroethane (selectivity: 9%), methylene chloride (selectivity: 9%), etc. was confirmed. Was done.

Comparative Example 2 The reaction was carried out in the same manner as in Example 1 except that a commercially available activated carbon powder-supported rhodium catalyst (support amount: 2% by weight) was used as the reduction catalyst. The reaction rate of carbon tetrachloride 100 hours after the start of the reaction was 14%, and the formation of chloroform (selectivity: 74%), hexachloroethane (selectivity: 11%), methylene chloride (selectivity: 15%), etc. was confirmed. Was done.

Comparative Example 3 The reaction was carried out in the same manner as in Example 1 except that a commercially available activated carbon powder-supported palladium catalyst (supported amount: 2% by weight) was used as the reduction catalyst. The reaction rate of carbon tetrachloride 100 hours after the start of the reaction is 43%, and chloroform (selectivity: 81%), hexachloroethane (selectivity: 10%), pentachloroethane (selectivity: 4%), tetrachloroethylene (selectivity: :
5%) etc. was confirmed.

Comparative Example 4 Platinum catalyst supported on commercially available activated carbon powder as a reduction catalyst (support amount: 2
The reaction was carried out in the same manner as in Example 1 except that (% by weight) was used. The reaction rate of carbon tetrachloride in 100 hours after the start of the reaction was 81.
%, And production of chloroform (selectivity: 86%), hexachloroethane (selectivity: 9%), etc. was confirmed.

Comparative Example 5 The reaction was carried out in the same manner as in Example 1 except that commercially available Raney nickel was used as the reducing catalyst. Deactivated immediately after the start of the reaction,
Generation of hydrochloric acid stopped.

[0058]

INDUSTRIAL APPLICABILITY The reducing catalyst of the present invention has the effect of exhibiting extremely high activity when polychlorocarbons such as carbon tetrachloride are reduced with hydrogen to be converted into hydrogen-containing chlorocarbons such as chloroform. Have. Further, the reducing catalyst in the present invention also has an effect that the target hydrogen-containing chlorocarbons can be obtained with high selectivity even if the reaction rate of the raw materials is increased. That is, the present invention has an excellent effect that hydrogen-containing chlorocarbons such as chloroform can be produced with good efficiency and high yield. Furthermore, the reduction catalyst of the present invention can effectively suppress side reactions that generate impurities that impair the catalytic activity,
It is also extremely advantageous from the viewpoint of catalyst life.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C07C 19/04 9280-4H // C07B 61/00

Claims (5)

[Claims] 1. A reduction catalyst containing at least one element selected from Group 8, 9 and 10 elements as a main component, to which at least one element selected from Group 11 elements is added. A method for producing hydrogen-containing chlorocarbons, which comprises reducing polychlorocarbons with hydrogen below. 2. The main component element in the reduction catalyst is ruthenium,
The method according to claim 1, which is at least one platinum group element selected from rhodium, palladium, and platinum. 3. The method according to claim 1, wherein the additive component element in the reduction catalyst is at least one group 11 element selected from copper, silver and gold. 4. The addition amount of the additive component element in the reduction catalyst is 0.01.
The method according to claim 1, wherein the amount is -50% by weight. 5. The method according to claim 1, wherein the reduction temperature is 0 ° C. to 300 ° C.