JP3125355B2 - Method for producing allyl chloride - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing allyl chloride useful in the organic chemical industry.

[0002]

2. Description of the Related Art Allyl chloride is a very important compound as a raw material of epichlorohydrin or as an intermediate in the production of various organic compounds.
It is produced by a non-catalytic hot chlorination reaction at a high temperature of 500 ° C.

In a non-catalytic thermal chlorination reaction, a large amount of energy is required because the reaction is performed at a high temperature.
There are many points to be improved, such as by-producing hydrogen chloride and the need to periodically regenerate the reactor for carbonaceous deposition. For this reason, studies have been made to produce allyl chloride catalytically at a relatively low temperature of 200 to 300 ° C. using a catalyst.

For example, in Japanese Patent Publication No. 48-34569,
A method is disclosed in which an activated carbon-supported catalyst is prepared using a solution of tellurium oxide and cupric chloride dissolved in hydrochloric acid, and this is used as a catalyst to synthesize allyl chloride by oxychlorination of propylene at 200 ° C. It states that nickel, lead, silver and platinum group elements can be used in addition to copper.

Also, in Dutch Patent No. 7108153, tellurium tetrachloride supported on silica gel,
A method of performing an oxychlorination reaction of propylene at 240 ° C. using a ternary catalyst of copper and potassium chloride is disclosed in German Patent No. 1300930, palladium chloride supported on γ-alumina, copper chloride, potassium chloride The oxychlorination reaction of propylene at 350 ° C. using a ternary catalyst is disclosed in Japanese Patent Application Laid-Open No. 49-1504. Rhodium, palladium, platinum or iridium is used as a catalyst, 20
A method for performing propylene oxychlorination reaction at 0 ° C. is disclosed.

[0006]

As can be seen in the above references, tellurium compounds, copper salts or platinum group metals are activated carbon,
It is well known that allyl chloride can be produced by the oxychlorination reaction of propylene using a catalyst supported on silica or alumina.

[0007]

In view of the above situation,
The present inventors have studied in detail the oxychlorination of propylene, and surprisingly found that when a catalyst made of an alloy of tellurium supported on a carrier or an alloy of tellurium and an alkali metal compound is used, allyl has high activity and selectivity. The present inventors have found a novel fact that chloride can be obtained, and have completed the present invention.

That is, the present invention provides a method for producing allyl chloride by oxychlorination of propylene in which propylene, hydrogen chloride and oxygen are reacted in the presence of an alloy catalyst of tellurium supported on a carrier, and an alloy of tellurium is further added to an alkali. An object of the present invention is to provide a method for producing allyl chloride using a catalyst containing a metal compound.

[0009]

The present invention will be described below in more detail. In the method of the present invention, a catalyst in which an alloy of tellurium or an alloy of tellurium and an alkali metal compound is supported on a carrier is used.

When a tellurium alloy catalyst supported on a carrier is used, the other component that forms an alloy with tellurium (hereinafter, abbreviated as “the other component”) is one that forms an alloy with tellurium. There is no particular limitation as long as it can be done. For example, the group VIII metal of the periodic table, Va
Group metals, group Ib metals, and the like. More specific examples include iron, cobalt, nickel, palladium, ruthenium, group VIII metals such as iridium,
Examples thereof include Group Va metals such as antimony and bismuth, and Group Ib metals such as copper.

The tellurium carrying rate forming this tellurium alloy is not uniquely determined because it depends on the reaction conditions such as the reaction temperature and the flow rate of the raw material gas, but the total weight of the catalyst (including the carrier) is determined. Can be used in the range of 0.1% to 50%. More preferably, it is in the range of 0.1% to 20%. If the loading exceeds 50%, the effect does not increase much, and if the loading is less than 0.1%, sufficient activity may not be obtained.

The loading of the other component alloying with tellurium can be defined as the atomic ratio with tellurium. The atomic ratio of tellurium to the other component is from 40: 1 to 1: 2
Used in the range of 0. More preferably, it is in the range of 20: 1 to 1:15. If the atomic ratio of tellurium to the other component exceeds 40, the alloying effect may not be sufficiently exhibited. If the other component exceeds 20 times the atomic ratio with respect to tellurium, problems may occur in the activity and selectivity.

In the method of the present invention, it is also possible to use a catalyst in which an alkali metal compound is supported on a carrier together with an alloy of tellurium supported on the carrier.

When the alkali metal compound coexists, the alkali metal compound to be used is not particularly limited as long as the alloy of tellurium and the alkali metal compound coexist on the carrier, and various alkali metal compounds can be used.
Examples of the alkali metal compound include chlorides, nitrates, sulfates, acetates, and oxides as inorganic salts of the alkali metal. More specifically, chlorides such as lithium chloride, sodium chloride, potassium chloride and cesium chloride, nitrates such as potassium nitrate and cesium nitrate, sulfates such as potassium sulfate and cesium sulfate, and acetates such as potassium acetate and cesium acetate Can be mentioned.
Various organic salts can also be used. For example, organic salts such as naphthenates and oxalates can be mentioned as typical examples. Among them, some of the compounds used may be changed to other compounds during the reaction, but this does not matter at all.

The amount of the alkali metal compound used depends on the carrier,
It may be 0.01 to 30% based on the total weight of the tellurium alloy and alkali metal compound. Preferably,
0.05-20%. If it is less than 0.01%, a sufficient effect cannot be obtained, and if it exceeds 30%, the activity of the catalyst per unit weight tends to be low.

In the method of the present invention, when a catalyst in which an alloy of tellurium and an alkali metal compound coexist on a carrier is used, there is no particular limitation on the method of loading on the carrier. For example, the alloy of tellurium is first placed on the carrier. After being formed thereon, the alkali metal compound may be supported, or conversely, after the alkali metal compound is supported first, an alloy of tellurium may be formed on the support. Furthermore, the tellurium alloy may be formed after the tellurium, the respective raw materials of the other component, and the alkali metal compound are simultaneously supported.

The raw material of tellurium used in the method of the present invention may be tellurium metal itself, and is not particularly limited as long as it can be converted into metallic tellurium by an alloying operation. Examples of those that become metallic tellurium by an alloying operation include inorganic tellurium compounds such as telluric acid, tellurium chloride, tellurium oxychloride, tellurium dioxide, monoalkyl tellurides, dialkyl tellurides, alkyl telluride chlorides, etc. Organic tellurium compounds can be mentioned. As for the raw material of the other component that forms an alloy with tellurium, the other component may be the metal itself, or may be changed to a metal by an alloying operation. Examples of specific compounds include inorganic compounds such as chlorides, nitrates, sulfates, acetates and oxides of the other component, or organic acid salts such as naphthenic acid, stearic acid and oxalic acid. Organic compounds can be mentioned.

In the method of the present invention, the catalyst component is used by being supported on a carrier. The support is not particularly limited as long as a tellurium alloy or a catalyst comprising a tellurium alloy and an alkali metal salt does not adversely affect its performance.For example, it is generally considered to be neutral in terms of acidity and basicity. Silica carriers, alumina carriers generally called acidic, and magnesia carriers generally called basic can be used as carriers. Besides, zirconia, titania or activated carbon can be mentioned as examples.

In the method of the present invention, a catalyst in which tellurium and the other component form an alloy on a support or a catalyst in which an alkali metal salt is supported on a support together with an alloy of tellurium is used. It suffices to finally obtain an alloy supported on the carrier, and there is no particular limitation on the method of alloying.

As a method of alloying, for example, a method in which metallic tellurium and the other metallic component are physically mixed with a carrier and then an alloy is formed by a method such as heating, a tellurium compound or another compound is used. A method in which one of the compounds of one component is first supported on a carrier, and then the other component is supported and then alloyed, or both the tellurium compound and the compound of the other component are simultaneously supported, Thereafter, a method of alloying and the like can be mentioned. In this case, when the alkali metal compound is allowed to coexist, the alkali metal compound may be supported on the carrier in advance as described above, or after each component of the alloy is supported, the alloy may be further supported. Even if it is carried after being formed, it does not matter at all.

In cases other than using metallic tellurium and the other metallic component as raw materials, the tellurium compound and / or the compound of the other component must be supported on a carrier. There are no particular restrictions.
For example, the tellurium compound and / or the compound of the other component and the carrier may be physically mixed and supported, or the tellurium compound and / or the compound of the other component may be dissolved in an appropriate solvent in advance. Alternatively, the carrier may be supported by a so-called impregnation method in which the carrier is immersed in this solution.

The solvent to be supported by the impregnation method is not particularly limited as long as it can dissolve the tellurium compound and / or the compound of the other component.
For example, acids such as water, hydrochloric acid and nitric acid, and organic solvents such as acetone and ethanol can be used.

In cases other than using metallic tellurium and the other metallic component as raw materials, it is necessary to reduce the supported tellurium compound and / or the compound of the other component to form an alloy. However, the reducing agent is not particularly limited as long as the tellurium compound and / or the compound of the other component can be reduced to zero valence. Representative examples of such reducing agents include inorganic gaseous reducing agents such as hydrogen and carbon monoxide, olefins such as propylene, alcohols such as methanol, and formic acid and formate esters. Formic acid compounds, hydrazine, lithium aluminum hydride, and the like can be given.

When alloying using these reducing agents, it is necessary to alloy at a temperature at which the tellurium compound and / or the compound of the other component can be reduced to zero valence. The alloying temperature varies depending on the ease of reduction of the raw material to be used with tellurium and / or the other component. Therefore, the range cannot be unconditionally determined, but the alloying temperature can be from room temperature to 1000 ° C. Preferably, the temperature is from 20 ° C to 800 ° C. If the temperature is lower than 20 ° C., it is difficult to reduce tellurium and / or the other component to zero valence, and alloying may not be performed. If the temperature exceeds 1000 ° C., the alloyed catalytically active component may grow particles, The activity of the resulting catalyst may be low, which is not preferable.

There is no particular limitation on the alloying method.
It may be performed in a gas phase or in a liquid phase.
When the reaction is performed in a gas phase, a gas consisting of a reducing agent or a gas containing a reducing agent may be passed through a precursor of a catalyst to be alloyed. On the other hand, when the reaction is carried out in a liquid phase, alloying can be carried out by contacting the precursor of the catalyst and the reducing agent or a liquid containing the reducing agent in a liquid flow or in a batch system. Of course, it goes without saying that reduction and alloying can be performed under different conditions. For example, tellurium and the other component may be reduced to zero valence at a relatively low temperature, and then alloyed at a high temperature in an inert gas atmosphere.

In the method of the present invention, a catalyst in which a tellurium alloy is supported on a carrier is used regardless of whether or not an alkali metal salt is present. The formation of the alloy can be confirmed by diffraction measurement or by a scanning and transmission electron microscope (STEM). In X-ray diffraction, it is possible to check whether a diffraction pattern characteristic of an alloy can be obtained. In this case, however, the relative intensity ratio of the peak obtained by the alloying method or the like changes. There is.

In the method of the present invention, the allyl chloride synthesis reaction by oxychlorination of propylene may be carried out in a liquid phase or a gas phase, but the gas phase is preferred.

The reaction temperature in the case of carrying out the reaction in the gas phase cannot be unconditionally determined because the performance varies depending on the catalyst, but it is typically 100 ° C. to 400 ° C., preferably 100 ° C. to 35 ° C.
0 ° C. If the temperature is lower than 100 ° C., sufficient activity cannot be obtained. If the temperature exceeds 400 ° C., by-products tend to increase and the selectivity of the target allyl chloride tends to decrease.

It is difficult to determine the range of the reaction pressure because the required pressure varies depending on the performance of the catalyst, but it is typically in the range of normal pressure to 50 atm, preferably in the range of normal pressure to 30 atm. It is. Even if the reaction pressure exceeds 50 atm, the effect of increasing the pressure further is small and may be uneconomical.

In the method of the present invention, propylene, hydrogen chloride and oxygen are used as reaction raw materials. If necessary,
It is also possible to use a gas for dilution. The gas for dilution only needs to be inert to the reaction,
For example, nitrogen, argon, or the like can be used. Each raw material can be used without any particular limitation as long as it is industrially available. Each raw material can be used typically in the following range, in which the composition is represented by volume%.

Propylene; 4 to 90% hydrogen chloride; 1 to 50% oxygen; 1 to 50% diluent gas; 0 to 90% If each component of propylene, hydrogen chloride and oxygen is less than the lower limit of the above composition, industrially sufficient Reaction rate cannot be obtained, and
When hydrogen chloride exceeds the upper limit, the generation of by-products increases,
Further, if the oxygen exceeds the upper limit, the amount of combustion products may increase.

The feed rate of the raw material gas depends on the performance of the catalyst or the selectivity and generation rate of the product, and it is difficult to determine the range uniformly. Gas space velocity (S
The reaction can be carried out in the range of 100 to 50,000 h ^-1 represented by V). If the SV is less than 100, an industrially satisfactory allyl chloride production rate cannot be obtained. On the other hand, if the SV exceeds 50,000, the conversion rate of the raw material may be reduced, which may be uneconomical.

In the method of the present invention, the reaction is carried out in a fixed bed,
It can be carried out by either a fluidized bed or a moving bed.

[0034]

EXAMPLES The present invention will be described in detail with reference to the following examples, but it goes without saying that the present invention is not limited by these examples.

Example 1 25 g of activated carbon (Granular Shirasagi C, Takeda Pharmaceutical Co., Ltd.) adsorbing 5% water was added to 250 ml of 1N nitric acid.
For 3 hours under reflux. After filtering the aqueous solution, the remaining activated carbon was washed with warm water of 98 ° C. until the pH reached 6. The obtained activated carbon was dried at 80 ° C. all day and night, and was further cooled from room temperature to 30 ° C. under a nitrogen flow of 300 ml / min.
A heat treatment was performed at 10 ° C./min to 0 ° C. and kept at 300 ° C. for 3 hours. 1.23 g of cobalt dichloride hexahydrate and 1.39 g of tellurium tetrachloride were dissolved in 40 ml of a 6N hydrochloric acid aqueous solution, and 10 g of the above-treated activated carbon was added to the aqueous solution. After a lapse of 20 hours, the hydrochloric acid solution was dried on a warm bath at 60 ° C. Further, the temperature was raised from room temperature to 150 ° C. at a rate of 10 ° C./min under a nitrogen stream, and the system was dried in a system kept at 150 ° C. for 1 hour, and then cooled to room temperature in that state.
The nitrogen flow was changed to 10% hydrogen residual nitrogen and the total flow rate was 200
ml / min. 10 ℃ per minute from room temperature to 150 ℃
And kept at the same temperature for 2 hours. In addition, 10 ° C per minute
To 400 ° C. and kept at the same temperature for 1 hour to prepare a tellurium-cobalt alloy catalyst supporting activated carbon. The catalyst thus prepared had a tellurium loading of 6% as a metal and an atomic ratio of tellurium to cobalt of 1. The obtained catalyst was subjected to X-ray diffraction (40K
(V, 24 mA, CuKα ray), it was confirmed that a catalyst having an X-ray diffraction pattern of a Te—Co alloy shown in Table 1 was produced. 2 g of the obtained catalyst
Was charged into a glass fixed-bed flow reactor, and a mixed gas of propylene: hydrogen chloride: oxygen: nitrogen = 2: 2: 1: 2 was supplied at an SV of 670 per hour. Raise the temperature to a predetermined temperature,
After holding at that temperature for 30 minutes, the product was analyzed by gas chromatography. Table 2 shows the obtained results.

[0036]

[Table 1]

Examples 2-6 Nickel nitrate hexahydrate, cupric chloride dihydrate, iridium chloride 1 instead of cobalt dichloride hexahydrate of Example 1
Te-Ni, Te supported on activated carbon exactly in the same manner as in Example 1 except that hydrate, chloroplatinic acid hexahydrate, and rhodium chloride trihydrate were used and the amount of tellurium tetrachloride was adjusted, respectively.
-Cu, Te-Ir, Te-Pt, and Te-Rh alloy catalysts were prepared. The obtained catalyst had a tellurium loading of 6% as a metal, and the atomic ratio of tellurium to each metal was 1.
Using the obtained catalyst, a reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as in Example 1. Table 2 shows the obtained results.

[0038]

[Table 2]

Example 7 0.456 g of palladium chloride, 1.39 g of tellurium tetrachloride
Activated carbon-supported Te-Pd catalyst was prepared in exactly the same manner as in Example 1 except for using. The prepared catalyst has a tellurium loading of 6% as a metal and an atomic ratio of tellurium to palladium of 2%.
Met. As a result of analyzing the obtained catalyst by X-ray diffraction, the X-ray diffraction pattern of PdTe ₂ shown in Table 3 and FIG.
It was confirmed that a catalyst having a catalyst was formed. Using 2 g of the obtained catalyst, a reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as in Example 1. Table 4 shows the obtained results.

[0040]

[Table 3]

Example 8 0.937 g of palladium chloride, 1.42 g of tellurium tetrachloride
A Te—Pd alloy catalyst supported on activated carbon was prepared in exactly the same manner as in Example 1 except for using. The prepared catalyst had a tellurium loading of 6% and an atomic ratio of tellurium to palladium of 1. Using 2 g of this catalyst, a reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as in Example 1. Table 4 shows the obtained results.

Example 9 1.057 g of palladium chloride, 0.65 g of tellurium tetrachloride
A Te—Pd alloy catalyst supported on activated carbon was prepared in exactly the same manner as in Example 1 except for using. The prepared catalyst had a tellurium loading of 2.8% as a metal and an atomic ratio of tellurium to palladium of 0.48. Using 2 g of this catalyst, a reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as in Example 1. Table 4 shows the obtained results.

Example 10 A Te—Pd alloy catalyst supported on activated carbon was prepared in exactly the same manner as in Example 1 except that the atomic ratio of tellurium to palladium was kept at 1 and the loading of tellurium was 1%. A reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as in Example 1 using 2 g of the prepared and obtained catalyst. Table 4 shows the obtained results.

Example 11 Activated carbon which had been heated only from room temperature to 300 ° C. at a rate of 10 ° C. per minute under a nitrogen flow of 300 ml / min and kept at 300 ° C. for 3 hours without performing nitric acid treatment was used as a carrier. Further, an activated carbon-supported Te-Pd alloy catalyst was prepared in exactly the same manner as in Example 1 except that the amount of palladium chloride was changed to 0.937 g and the amount of tellurium tetrachloride was changed to 1.42 g, and 2 g of the obtained catalyst was used. The reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as in Example 1. Table 4 shows the obtained results.

Examples 12 to 16 α-alumina, γ-alumina, titania, magnesia,
Alternatively, various Te-Pd alloy catalysts were prepared in exactly the same manner as in Example 8 except that silica was used as a carrier instead of activated carbon, and propylene and propylene were respectively used in exactly the same manner as in Example 1 using 2 g of the obtained catalyst. The reaction of hydrogen chloride and oxygen was performed. Table 4 shows the obtained results.

Example 17 1.186 g of palladium acetate, 1.42 g of tellurium tetrachloride
Was prepared in exactly the same manner as in Example 1 except that a solution prepared by dissolving in acetone 80 ml was used. The catalyst thus prepared had a tellurium loading of 6% as a metal and an atomic ratio of tellurium to palladium of 1. A reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as in Example 1 except that 2 g of this catalyst was used. Table 4 shows the obtained results.

[0047]

[Table 4]

Example 18 The procedure of Example 1 was repeated, except that 0.671 g of ruthenium chloride trihydrate and 1.38 g of tellurium tetrachloride were used.
An activated carbon supported Te-Ru catalyst was prepared. The catalyst thus prepared had a tellurium loading of 6% as a metal and an atomic ratio of tellurium to ruthenium of 2. As a result of analyzing the obtained catalyst by X-ray diffraction, an X-ray diffraction pattern of RuTe ₂ shown in Table 5 was obtained.
It was confirmed that a catalyst having a catalyst was formed. Using 2 g of the obtained catalyst, a reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as in Example 1. Table 6 shows the obtained results.

[0049]

[Table 5]

[0050]

[Table 6]

Example 19 1.762 g of bismuth trichloride, 1.51 g of tellurium tetrachloride
, And activated carbon-supported Te-
A Bi catalyst was prepared. The catalyst thus prepared had a tellurium loading of 6% as a metal and an atomic ratio of tellurium to bismuth of 1. The obtained catalyst was analyzed by X-ray diffraction. As a result, it was confirmed that a catalyst having the Te-Bi X-ray diffraction pattern shown in Table 7 and FIG. 2 was formed. Using 2 g of the obtained catalyst, the reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as in Example 1. Table 8 shows the obtained results.
Shown in

[0052]

[Table 7]

[0053]

[Table 8]

Example 20 0.793 g of antimony trichloride, 1.41 tellurium tetrachloride
g and the temperature of reduction and alloying with hydrogen at 550 ° C.
Activated carbon-supported Te exactly as in Example 1 except that
A -Sb catalyst was prepared. The prepared catalyst has a tellurium loading of 6% as a metal and an atomic ratio of tellurium to antimony of 1.5.
Met. As a result of analyzing the obtained catalyst by X-ray diffraction, it was confirmed that a catalyst having an X-ray diffraction pattern of Sb ₂ Te ₃ shown in Table 9 and FIG. 3 was formed. Using 2 g of the obtained catalyst, a reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as in Example 1. Table 10 shows the obtained results.

[0055]

[Table 9]

Example 21 2.599 g of antimony trichloride, 1.54 tellurium tetrachloride
g, the temperature of reduction and alloying with hydrogen is 400 ° C
A Te—Sb alloy catalyst supported on activated carbon was prepared in exactly the same manner as in Example 1 except that the above conditions were satisfied. The catalyst thus prepared had a tellurium loading of 6% as a metal and an atomic ratio of tellurium to antimony of 0.5. Using 2 g of this catalyst, the reaction was carried out in exactly the same manner as in Example 1 except that the composition of the mixed gas was changed to propylene: hydrogen chloride: oxygen: nitrogen = 10: 1: 2: 1 without changing the gas supply rate. went. Table 10 shows the obtained results.

[0057]

[Table 10]

Example 22 0.411 g of anhydrous ferric chloride, 1.367 of tellurium tetrachloride
An activated carbon-supported Te-Fe catalyst was prepared in exactly the same manner as in Example 1 except that g was used. The prepared catalyst had a tellurium loading of 6% as a metal and an atomic ratio of tellurium to iron of 2. The obtained catalyst was analyzed by X-ray diffraction. As a result, it was confirmed that a catalyst having an X-ray diffraction pattern of FeTe ₂ shown in Table 11 and FIG. 4 was formed. Using 2 g of the obtained catalyst, a reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as in Example 1. Table 12 shows the obtained results.

[0059]

[Table 11]

Example 23 0.835 g of anhydrous ferric chloride, 1.387 tellurium tetrachloride
A Te—Fe alloy catalyst supported on activated carbon was prepared in exactly the same manner as in Example 1 except that g was used. The catalyst thus prepared had a tellurium loading of 6% as a metal and an atomic ratio of tellurium to iron of 1. Using 2 g of this catalyst, the total gas supply amount was not changed, and the SV was changed by 2 hours per hour by changing the amount of catalyst.
A reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as in Example 1 except that the reaction was changed to 400. Table 12 shows the obtained results.

Example 24 0.204 g of anhydrous ferric chloride, 1.358 of tellurium tetrachloride
A Te—Fe alloy catalyst supported on activated carbon was prepared in exactly the same manner as in Example 1 except that g was used. Of the prepared catalyst
The Te loading was 6% as a metal, and the atomic ratio between tellurium and iron was 4. Using 2 g of this catalyst, a reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as in Example 1. Table 12 shows the obtained results.

Example 25 0.0815 g of anhydrous ferric chloride, 1.32 of tellurium tetrachloride
A Te—Fe alloy catalyst supported on activated carbon was prepared in exactly the same manner as in Example 1 except that 5 g was used. The catalyst thus prepared had a tellurium loading of 6% as a metal and an atomic ratio of tellurium to iron of 10. Example 1 using 2 g of this catalyst
The reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as described above. Table 12 shows the obtained results.

Example 26 Using 2 g of the catalyst prepared in Example 22, without changing the total gas supply amount, the composition of the mixed gas was propylene: hydrogen chloride: oxygen: nitrogen = 4: 2: 1: 0. Except for Example 1
The reaction was carried out in exactly the same manner as described above. Table 12 shows the obtained results.
Shown in

Example 27 Using 2 g of the catalyst prepared in Example 22, without changing the total gas supply amount, the composition of the mixed gas was propylene: hydrogen chloride: oxygen: nitrogen = 10: 2: 1: 1. The reaction was carried out in exactly the same manner as in Example 1 except for the above. Table 1 shows the obtained results.
It is shown in FIG.

[0065]

[Table 12]

Example 28 0.443 g of anhydrous ferric chloride, 1.462 of tellurium tetrachloride
g of Example 1 except that 0.69 g of potassium chloride was used.
Activated carbon-supported Te-Fe-KCl catalyst was prepared in exactly the same manner as described above. The tellurium loading of the prepared catalyst was 6 as metal.
% And the atomic ratio of tellurium to iron was 2. The loading of potassium chloride was 6%. The resulting catalyst is X
As a result of analysis by X-ray diffraction, it was confirmed that a catalyst having an X-ray diffraction pattern of FeTe ₂ and potassium chloride shown in FIG. 5 was formed. Using 2 g of the obtained catalyst, a reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as in Example 1. Table 13 shows the obtained results.

Example 29 1.083 g of palladium chloride, 1.647 of tellurium tetrachloride
g, and 1.56 g of potassium chloride, a Te-Pd-KCl catalyst supported on activated carbon was prepared in exactly the same manner as in Example 1. The tellurium loading of the prepared catalyst was 6% as a metal, and the atomic ratio of tellurium to palladium was 1. The loading of potassium chloride was 12%. A reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as in Example 1 except that 2 g of this catalyst was used. Table 13 shows the obtained results.

Example 30 0.981 g of palladium chloride, 1.491 of tellurium tetrachloride
An activated carbon-supported Te-Pd alloy catalyst was prepared in exactly the same manner as in Example 1 except that g was used. Cesium chloride 0.4
7 g was dissolved in 20 ml of distilled water, and the Te-Pd alloy catalyst prepared above was added thereto.
The aqueous solution was dried on a warm bath. Further, the temperature is raised from room temperature to 150 ° C. at a rate of 10 ° C. per minute under a nitrogen gas flow, and drying is performed in a system maintained at 150 ° C. for 1 hour, to thereby obtain activated carbon-supported Te-Pd.
-A Cs catalyst was obtained. The tellurium loading of the prepared catalyst was 6% as a metal, and the atomic ratio of tellurium to palladium was 1. The loading of cesium chloride was 4%.
A reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as in Example 1 except that 2 g of this catalyst was used. Table 13 shows the obtained results.

Example 31 0.72 g of sodium chloride was dissolved in 20 ml of distilled water, and 10 g of activated carbon was treated in the same manner as in Example 1.
Was added. After a lapse of 20 hours, the aqueous solution was dried on a hot bath at 80 ° C. Further, the temperature was raised from room temperature to 150 ° C. at a rate of 10 ° C. per minute under a nitrogen stream, and drying was performed in a system maintained at 150 ° C. for 1 hour. 1.270 g of palladium acetate and 1.527 g of tellurium tetrachloride were dissolved in 40 ml of acetone. Activated carbon carrying sodium chloride was added to this solution, and
After a lapse of time, the acetone solution was dried on a warm bath at 60 ° C. Further, the temperature is increased from room temperature to 150 ° C. in a nitrogen stream at a rate of
After the temperature was raised at 0 ° C. and drying was performed in a system kept at 150 ° C. for 1 hour, the temperature was lowered to room temperature as it was. The nitrogen flow was changed to 10% hydrogen residual nitrogen, and the total flow rate was 200 ml / m
in. The temperature was raised from room temperature to 150 ° C. at a rate of 10 ° C./min, and kept at the same temperature for 2 hours. In addition, at 10 ° C / min.
The temperature was raised to 0 ° C and maintained at the same temperature for 1 hour,
A -Pd-NaCl catalyst was prepared. The prepared catalyst had a tellurium loading of 6% as a metal and an atomic ratio of tellurium to palladium of 2. The loading of sodium chloride was 6%. Example 1 except that 2 g of this catalyst was used.
The reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as described above. Table 13 shows the obtained results.

[0070]

[Table 13]

[0071]

By using the tellurium alloy of the present invention as a catalyst, an oxychlorination reaction can be performed at a low temperature, and scale such as charcoal does not accumulate in the reaction system. Also, hydrogen chloride can be used for chlorination instead of chlorine.

[Brief description of the drawings]

FIG. 1 is a view showing an X-ray diffraction pattern of a catalyst prepared in Example 7.

FIG. 2 is a view showing an X-ray diffraction pattern of a catalyst prepared in Example 19.

FIG. 3 is a view showing an X-ray diffraction pattern of a catalyst prepared in Example 20.

FIG. 4 is a view showing an X-ray diffraction pattern of a catalyst prepared in Example 22.

FIG. 5 is a view showing an X-ray diffraction pattern of a catalyst prepared in Example 28.

──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 2-290772 (32) Priority date September 11, 1990 (September 11, 1990) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 2-240081 (32) Priority date September 12, 1990 (September 12, 1990) (33) Priority claim country Japan (JP) (31) Priority claim number Patent application 2-240082 (32) Priority date September 12, 1990 (September 12, 1990) (33) Priority claiming country Japan (JP) (31) Priority claim number 32) Priority date July 29, 1991 (July 29, 1991) (33) Priority country Japan (JP) (56) References JP-A-4-257534 (JP, A) 40323 (JP, B1) JP 4834569 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 17/156 B01J 27/057 C07C 21/067 CA (STN)

Claims (4)

(57) [Claims] 1. A process for producing allyl chloride by oxychlorination of propylene, wherein propylene, hydrogen chloride and oxygen are reacted under an alloy catalyst of tellurium supported on a carrier. 2. A method for producing allyl chloride, wherein the alloy of tellurium according to claim 1 is an alloy of tellurium and at least one metal selected from the group VIII, Va and Ib of the periodic table. 3. The group VIII of the periodic table according to claim 2, Va.
At least one metal selected from Group Ib and Group Ib,
A method for producing allyl chloride which is iron, cobalt, nickel, palladium, ruthenium, iridium, antimony, bismuth or copper. 4. A method for producing allyl chloride, wherein the tellurium alloy catalyst according to claim 1 is a catalyst containing an alkali metal compound.