JPH0585969A - Production of allyl chloride - Google Patents

Abstract

PURPOSE:To obtain in high selectivity the title compound useful as a raw material for epichlorohydrin or an intermediate for synthesizing various organic compounds by oxychlorination of propylene in the presence of a tellurium-contg. alloy catalyst. CONSTITUTION:Reaction is made at 100-350 deg.C between propylene, hydrogen chloride and oxygen pref. in a gaseous phase using a catalyst containing an allay made up of tellurium and group VIII (e.g. Fe), group Va (e.g. Sb) and/or group Ib (e.g. Cu) metal(s) carried on a carrier, thus affording the objective allyl chloride. The allay may be incorporated with an alkali metal compound. Use of the above catalyst will enable the oxychlorination at lower temperatures and result in no accumulation of carbon scale in the reaction system. For the oxychlorination, hydrogen chloride can be used rather than chlorine.

Description

Detailed Description of the Invention

[0001]

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 for epichlorohydrin or as an intermediate in the production of various organic compounds.
It is manufactured by a non-catalytic thermal chlorination reaction at a high temperature of 500 ° C.

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

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

Further, in the Dutch Patent No. 7108153, there is disclosed tellurium tetrachloride and second chloride chloride supported on silica gel.
A method of carrying out 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, copper chloride and potassium chloride supported on γ-alumina. In the method of carrying out the oxychlorination reaction of propylene at 350 ° C. using the three-way catalyst of JP-A No. 49-1504, activated carbon carrying rhodium, palladium, platinum or iridium is used as a catalyst. 20
Each method of carrying out an oxychlorination reaction of propylene at 0 ° C is disclosed.

[0006]

As can be seen from the above-mentioned reference, a tellurium compound, a copper salt or a platinum group metal is added to 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]

[Means for Solving the Problems] In view of the current situation,
As a result of detailed investigations on oxychlorination of propylene, the present inventors have surprisingly found that when an alloy of tellurium or a catalyst of tellurium alloy and an alkali metal compound supported on a carrier is used, allyl with high activity and selectivity is obtained. The inventors have found a new fact that chloride can be obtained, and 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 under an alloy catalyst of tellurium supported on a carrier, and an alloy of tellurium is further alkalinized. It is intended to provide a method for producing allyl chloride using a catalyst containing a metal compound.

[0009]

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

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

The supporting rate of tellurium forming the alloy of tellurium is not uniquely determined because it depends on reaction conditions such as reaction temperature and flow rate of raw material gas, but the total weight of the catalyst (including the carrier) is not limited. 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 rate exceeds 50%, the effect does not increase so much, and if the loading rate is less than 0.1%, sufficient activity may not be obtained.

The loading rate 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 40: 1 to 1: 2.
Used in the 0 range. 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 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 used is not particularly limited as long as the tellurium alloy 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 alkali metals. Further, 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 be used, and, for example, organic acid salts such as naphthenate and oxalate can be mentioned as typical examples. Among them, depending on the compound used, there are some that change to another compound during the reaction, but there is no problem.

The amount of the alkali metal compound used depends on the carrier,
It can be 0.01 to 30% with respect to the total weight of the alloy of tellurium and the alkali metal compound. Preferably,
It is 0.05 to 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, the method of loading on the carrier is not particularly limited. There is no problem even if an alkali metal compound is supported on the carrier after forming the above, or conversely, an alloy of tellurium is formed on the carrier after supporting the alkali metal compound first. Furthermore, the tellurium alloy may be formed after simultaneously supporting tellurium and the respective raw materials of the other component and the alkali metal compound.

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 is a metal-like tellurium by the alloying operation. Examples of those which become metallic tellurium by alloying operation include inorganic tellurium compounds such as telluric acid, tellurium chloride, tellurium oxychloride, tellurium dioxide, monoalkyl telluride, dialkyl telluride, alkyl tellurium chlorides, etc. The organic tellurium compound can be mentioned. Regarding the raw material of the other component forming the alloy with tellurium, the other component may be the metal itself, or may be changed to the metal by the 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 supporting it on a carrier. The carrier is not particularly limited as long as the tellurium alloy or the catalyst composed of the tellurium alloy and the alkali metal salt does not adversely affect the performance of the carrier.For example, it is generally said to be neutral in terms of acidity and basicity. The silica carrier, the alumina carrier which is generally said to be acidic, and the magnesia carrier which is generally said to be basic can be used as the carrier. Besides, zirconia, titania, or activated carbon can be cited as an example.

In the method of the present invention, a catalyst in which tellurium and the other component form an alloy on a carrier or a catalyst in which an alkali metal salt is supported on a carrier together with an alloy of tellurium is used. The alloy supported on the carrier is finally obtained, and the alloying method is not particularly limited.

As an alloying method, for example, a metallic tellurium and another 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. Either one of the compounds of one component is first loaded on the carrier, then the remaining components are loaded and then alloyed, or both the tellurium compound and the compound of the other component are loaded simultaneously, A method of alloying after that is mentioned. In this case, when the alkali metal compound is allowed to coexist, it may be preliminarily supported on the carrier as described above, or, after each component of the alloy is supported, it may be further supported. There is no problem even if it is carried after being formed.

When the tellurium compound in the metallic form and the other component in the metallic form are not used as raw materials, the tellurium compound and / or the compound of the other component must be supported on a carrier. There is no particular limitation.
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 advance in an appropriate solvent. Alternatively, the carrier may be supported by a so-called impregnation method in which the carrier is immersed in this solution.

There are no particular restrictions on the solvent used for carrying by the impregnation method, as long as it is capable of dissolving the tellurium compound and / or the compound of the other component,
For example, water, acids such as hydrochloric acid and nitric acid, and organic solvents such as acetone and ethanol can be used.

In cases other than using the metallic tellurium and the metallic other component as the 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. Typical examples of such reducing agents include hydrogen, carbon monoxide and other inorganic gaseous reducing agents, olefins such as propylene, alcohols such as methanol, formic acid, formic acid esters and the like. Examples thereof include formic acid compounds, hydrazine, lithium aluminum hydride and the like.

When alloying with 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 easiness of reduction of the raw material used for tellurium and / or the other component, and therefore the range cannot be determined unconditionally, but it can be performed at room temperature to 1000 ° C. Preferably, it is 20 ° C to 800 ° C. If this temperature is lower than 20 ° C., it may be difficult to reduce the tellurium and / or the other component to zero valence and alloying may not be possible, and if it exceeds 1000 ° C., the alloyed catalytically active component may grow into particles. The activity of the resulting catalyst may decrease, which is not preferable.

The alloying method is not particularly limited,
It does not matter whether it is carried out in the gas phase or in the liquid phase.
When it is carried out in the gas phase, a gas consisting of a reducing agent or containing a reducing agent may be passed to the precursor of the catalyst to be alloyed. On the other hand, when it is carried out in the liquid phase, the precursor of the catalyst and the liquid containing the reducing agent or containing the reducing agent can be alloyed by bringing them into contact with each other 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 an alloy of tellurium is supported on a carrier is used regardless of whether or not an alkali metal salt is allowed to coexist, but whether or not the alloy is formed is determined by, for example, ordinary X-rays. It is also possible to confirm the formation of the alloy by diffraction measurement or by scanning / transmission electron microscope (STEM). In X-ray diffraction, it can be investigated whether or not the diffraction pattern characteristic of the alloy can be obtained. In this case, the relative intensity ratio of the peak obtained by the alloying method etc. changes. There is.

In the method of the present invention, the allyl chloride synthesis reaction by oxychlorination of propylene may be carried out in either the liquid phase or the 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.
It is 0 ° C. If it is less than 100 ° C, sufficient activity cannot be obtained, and if it exceeds 400 ° C, the amount of by-products tends to increase and the selectivity of the desired allyl chloride tends to decrease.

It is difficult to unconditionally determine the reaction pressure because the pressure required depends on the performance of the catalyst, but it is typically in the range of atmospheric pressure to 50 atm, preferably atmospheric pressure to 30 atm. Is. Even if the reaction pressure exceeds 50 atm, the effect of further pressurization may be small and 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 may be any gas inert to this reaction,
For example, nitrogen, argon or the like can be used. Each raw material can be used without particular limitation as long as it is industrially available. The composition of each raw material can be expressed in volume% and typically used in the following ranges.

Propylene: 4-90% hydrogen chloride; 1-50% oxygen; 1-50% diluent gas: 0-90% If each component of propylene, hydrogen chloride and oxygen is less than the lower limit of the above composition, it is industrially sufficient. I can not get a good reaction rate,
If hydrogen chloride exceeds the upper limit, the amount of by-products will increase,
Furthermore, if oxygen exceeds the upper limit, combustion products may increase.

It is difficult to uniformly determine the range of the feed rate of the raw material gas because the feed rate of the raw material gas depends on the performance of the catalyst or the selectivity and production rate of the product. Gas space velocity (S
Expressed as V), the reaction can be carried out in the range of 100 to 50,000 h ^-1 . If the SV is less than 100, an industrially satisfactory rate of production of allyl chloride cannot be obtained. On the other hand, if the SV is more than 50,000, the conversion rate of the raw material may be lowered and it may not be economical.

In the process of the present invention, the reaction is a fixed bed,
It is possible to use either a fluidized bed method or a moving bed method.

[0034]

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

Example 1 To 250 ml of 1N nitric acid, 25 g of activated carbon (Granular Egret C, Takeda Chemical Co., Ltd.) having 5% water adsorbed was added, and the mixture was heated to 80 ° C.
Under reflux for 3 hours. After filtering the aqueous solution, the remaining activated carbon was washed with warm water at 98 ° C. until the pH reached 6. The obtained activated carbon was dried at 80 ° C. for a whole day and night, and further from room temperature to 30 under a nitrogen flow of 300 ml / min.
The temperature was raised to 0 ° C. at 10 ° C./min, and heat treatment was performed 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 6N hydrochloric acid aqueous solution, and 10 g of the above-mentioned treated activated carbon was added to this aqueous solution. After 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 after drying in a system kept at 150 ° C. for 1 hour, the temperature was lowered to room temperature as it was.
Change the nitrogen flow to 10% hydrogen remaining nitrogen and change the total flow to 200
It was set to ml / min. 10 ℃ per minute from room temperature to 150 ℃
The temperature was raised by and kept at the same temperature for 2 hours. In addition, 10 ℃ per minute
The temperature was raised to 400 ° C. and maintained at the same temperature for 1 hour to prepare an activated carbon-supported tellurium-cobalt alloy catalyst. The prepared catalyst had a tellurium loading of 6% as a metal, and the atomic ratio of tellurium to cobalt was 1. The obtained catalyst was subjected to X-ray diffraction (40K
As a result of analysis by V, 24 mA, CuKα ray), it was confirmed that a catalyst having the X-ray diffraction pattern of the Te—Co alloy shown in Table 1 was prepared. 2 g of the obtained catalyst
Was charged in 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. The results obtained are shown in Table 2.

[0036]

[Table 1]

Examples 2 to 6 Nickel nitrate hexahydrate, cupric chloride dihydrate, iridium chloride 1 instead of the cobalt dichloride hexahydrate of Example 1
Te-Ni and Te supported on activated carbon were carried out in exactly 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.
-Cu, Te-Ir, Te-Pt, Te-Rh alloy catalysts were prepared. The resulting 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, propylene, hydrogen chloride and oxygen were reacted in exactly the same manner as in Example 1. The results obtained are shown in Table 2.

[0038]

[Table 2]

Example 7 0.456 g of palladium chloride and 1.39 g of tellurium tetrachloride
An activated carbon-supported Te-Pd catalyst was prepared in exactly the same manner as in Example 1 except that was used. 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, an X-ray diffraction pattern of PdTe ₂ shown in Table 3 and FIG.
It was confirmed that a catalyst having a catalyst was prepared. 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. The results obtained are shown in Table 4.

[0040]

[Table 3]

Example 8 0.937 g of palladium chloride and 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 that was used. The prepared catalyst had a tellurium loading of 6%, and the atomic ratio of tellurium to palladium was 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. The results obtained are shown in Table 4.

Example 9 Palladium chloride 1.057 g, tellurium tetrachloride 0.65 g
A Te-Pd alloy catalyst supported on activated carbon was prepared in exactly the same manner as in Example 1 except that was used. The prepared catalyst had a tellurium loading of 2.8% as a metal, and the atomic ratio of tellurium to palladium was 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. The results obtained are shown in Table 4.

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 supporting rate of tellurium was 1%. Using 2 g of the catalyst thus prepared, propylene, hydrogen chloride and oxygen were reacted in exactly the same manner as in Example 1. The results obtained are shown in Table 4.

Example 11 Activated carbon which was not subjected to nitric acid treatment, was heated from room temperature to 300 ° C. at 10 ° C./min under nitrogen flow of 300 ml / min and kept at 300 ° C. for 3 hours was used as a carrier. 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 0.937 g and the amount of tellurium tetrachloride was 1.42 g, and 2 g of the obtained catalyst was used. Then, the reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as in Example 1. The results obtained are shown in Table 4.

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 2 g of the obtained catalyst was used in exactly the same manner as in Example 1 to obtain propylene, The reaction of hydrogen chloride and oxygen was carried out. The results obtained are shown in Table 4.

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

[0047]

[Table 4]

Example 18 Exactly the same as Example 1 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 prepared catalyst had a tellurium loading of 6% as a metal, and the atomic ratio of tellurium to ruthenium was 2. As a result of analyzing the obtained catalyst by X-ray diffraction, the RuTe ₂ X-ray diffraction pattern shown in Table 5 was obtained.
It was confirmed that a catalyst having a catalyst was prepared. 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. The obtained results are shown in Table 6.

[0049]

[Table 5]

[0050]

[Table 6]

Example 19 1.762 g of bismuth trichloride and 1.51 g of tellurium tetrachloride
Was used in the same manner as in Example 1 except that the temperature of the reduction with hydrogen and the alloying was 250 ° C.
A Bi catalyst was prepared. The prepared catalyst had a tellurium loading of 6% as a metal, and the atomic ratio of tellurium to bismuth was 1. As a result of analyzing the obtained catalyst by X-ray diffraction, it was confirmed that a catalyst having the Te-Bi X-ray diffraction pattern shown in Table 7 and FIG. 2 was prepared. 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 Antimony trichloride 0.793 g, tellurium tetrachloride 1.41
g, and the temperature of reduction and alloying with hydrogen is 550 ° C.
Te in the same manner as in Example 1 except that
-Sb catalyst was prepared. The prepared catalyst has a tellurium loading of 6% as a metal, and the atomic ratio of tellurium to antimony is 1.5.
Met. As a result of analyzing the obtained catalyst by X-ray diffraction, it was confirmed that a catalyst having the X-ray diffraction pattern of Sb ₂ Te ₃ shown in Table 9 and FIG. 3 was prepared. 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. The results obtained are shown in Table 10.

[0055]

[Table 9]

Example 21 2.599 g of antimony trichloride, 1.54 tellurium tetrachloride
g, and 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 prepared catalyst had a tellurium loading of 6% as a metal, and the atomic ratio of tellurium to antimony was 0.5. A reaction was carried out in the same manner as in Example 1 except that 2 g of this catalyst was used and the gas supply rate was not changed, and the composition of the mixed gas was propylene: hydrogen chloride: oxygen: nitrogen = 10: 1: 2: 1. went. The results obtained are shown in Table 10.

[0057]

[Table 10]

Example 22 0.411 g of anhydrous ferric chloride and tellurium tetrachloride 1.367
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 the atomic ratio of tellurium to iron was 2. As a result of analyzing the obtained catalyst by X-ray diffraction, it was confirmed that a catalyst having the X-ray diffraction pattern of FeTe ₂ shown in Table 11 and FIG. 4 was produced. 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. The results obtained are shown in Table 12.

[0059]

[Table 11]

Example 23 0.835 g of anhydrous ferric chloride and tellurium tetrachloride 1.387
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 prepared catalyst had a tellurium loading of 6% as a metal, and the atomic ratio of tellurium to iron was 1. Using 2 g of this catalyst, the total gas supply amount was not changed, but the SV was changed to 2 per hour by changing the catalyst amount.
The reaction of propylene, hydrogen chloride and oxygen was carried out in exactly the same manner as in Example 1 except that the temperature was set to 400. The results obtained are shown in Table 12.

Example 24 0.204 g of anhydrous ferric chloride and tellurium tetrachloride 1.358
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 prepared catalyst
The Te loading was 6% as a metal, and the atomic ratio of tellurium to 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. The results obtained are shown in Table 12.

Example 25 Anhydrous ferric chloride 0.0815 g, tellurium tetrachloride 1.32
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 prepared catalyst had a tellurium loading of 6% as a metal, and the atomic ratio of tellurium to iron was 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 in. The results obtained are shown in Table 12.

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

Example 27 2 g of the catalyst prepared in Example 22 was used, the total gas supply rate was not changed, and the composition of the mixed gas was propylene: hydrogen chloride: oxygen: nitrogen = 10: 2: 1: 1. The reaction was performed in exactly the same manner as in Example 1 except for the above. The results obtained are shown in Table 1.
2 shows.

[0065]

[Table 12]

Example 28 0.443 g of anhydrous ferric chloride and 1.462 tellurium tetrachloride
g, and Example 1 except that 0.69 g of potassium chloride was used.
An Te-Fe-KCl catalyst supporting activated carbon was prepared in exactly the same manner as in. The prepared catalyst has a tellurium loading of 6 as a metal.
%, And the atomic ratio of tellurium to iron was 2. Further, the carrying rate of potassium chloride was 6%. The obtained catalyst is X
As a result of analysis by line diffraction, it was confirmed that the catalyst having the X-ray diffraction pattern of FeTe ₂ and potassium chloride shown in FIG. 5 was prepared. 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. The results obtained are shown in Table 13.

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

Example 30 0.981 g of palladium chloride, tellurium tetrachloride 1.491
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, the Te-Pd alloy catalyst prepared above was added thereto, and after 20 hours, 80 ° C.
The aqueous solution was dried on the warm bath of. Further, the temperature was raised from room temperature to 150 ° C. at 10 ° C./min under a nitrogen stream, and the temperature was maintained at 150 ° C. for 1 hour.
-Cs catalyst was obtained. The prepared catalyst had a tellurium loading of 6% as a metal, and the atomic ratio of tellurium to palladium was 1. The cesium chloride loading was 4%.
Reaction of propylene, hydrogen chloride and oxygen was carried out in the same manner as in Example 1 except that 2 g of this catalyst was used. The results obtained are shown in Table 13.

Example 31 0.72 g of sodium chloride was dissolved in 20 ml of distilled water, and 10 g of activated carbon treated in the same manner as in Example 1 was dissolved therein.
Was added. After 20 hours, the aqueous solution was dried on a warm bath at 80 ° C. Further, under a nitrogen stream, the temperature was raised from room temperature to 150 ° C. at 10 ° C./min, and drying was carried out in the system kept at 150 ° C. for 1 hour. Palladium acetate (1.270 g) and tellurium tetrachloride (1.527 g) were dissolved in 40 ml of acetone, and activated carbon carrying sodium chloride was added to the solution.
After a lapse of time, the acetone solution was dried on a warm bath at 60 ° C. Furthermore, under a nitrogen stream, from room temperature to 150 ° C 1 / min
The temperature was raised at 0 ° C., the temperature was kept at 150 ° C. for 1 hour, drying was performed in the system, and then the temperature was lowered to room temperature. Change the nitrogen flow to 10% hydrogen remaining nitrogen, and change the total flow rate to 200 ml / m.
in. The temperature was raised from room temperature to 150 ° C. at 10 ° C./min and kept at the same temperature for 2 hours. Furthermore, 40 at 10 ° C / min
The temperature was raised to 0 ° C and kept at the same temperature for 1 hour.
-Pd-NaCl catalyst was prepared. The prepared catalyst had a tellurium loading of 6% as a metal, and the atomic ratio of tellurium to palladium was 2. Further, the supporting rate 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 in. The results obtained are shown in Table 13.

[0070]

[Table 13]

[0071]

By using the alloy of tellurium of the method of the present invention as a catalyst, the oxychlorination reaction can be carried out at a low temperature, and the scale of charcoal or the like does not accumulate in the reaction system. It is also possible to use hydrogen chloride instead of chlorine for chlorination.

[Brief description of drawings]

FIG. 1 is a diagram 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 the catalyst prepared in Example 20.

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

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese patent application No. 2-239072 (32) Priority date Hei 2 (1990) September 11 (33) Priority claim country Japan (JP) (31) Priority Claim number Japanese patent application No. 2-240081 (32) Priority date No. 2 (1990) September 12, (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese patent application No. 2-240082 (32) Priority Hihei 2 (1990) September 12 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-210473 (32) Priority Day Hei 3 (1991) July 29 (33) ) Japan claiming priority (JP)

Claims (4)

[Claims] 1. A process for producing allyl chloride by oxychlorination of propylene, which comprises reacting propylene, hydrogen chloride and oxygen under an alloy catalyst of tellurium supported on a carrier. 2. A process 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 Group VIII, Va and Ib of the Periodic Table. 3. A periodic table VIII group, Va according to claim 2.
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.