Catalyst for allyl acetate production and method for producing catalyst for allyl acetate production

Abstract

The present invention provides a catalyst for allyl acetate production which brings about an improved space time yield when used for producing allyl acetate from propylene, oxygen, and acetic acid. The catalyst for allyl acetate production comprises (a) palladium, (b) iridium, (c) one or more elements selected from among copper, nickel, zinc, and cobalt, and (d) an alkali metal salt which are supported on (e) a support. Particularly, the mass ratio of (a) palladium, (b) iridium, the sum of (c) one or more elements selected from among copper, nickel, zinc, and cobalt, and (d) the alkali metal salt is preferably (a):(b):(c):(d)=100:(5.0-17.0):(5.0-150.0):(150-4,000).

Description

Catalyst for producing allyl acetate and method for producing catalyst for producing allyl acetate

[0001] The present disclosure relates to a catalyst for producing allyl acetate, a method for producing the same, and a method for producing allyl acetate using the catalyst.

[0002] Allyl acetate is an important industrial raw material used as a solvent or a raw material for producing allyl alcohol. One method for producing allyl acetate involves using propylene, acetic acid, and oxygen as raw materials and subjecting them to a gas-phase or liquid-phase reaction to obtain allyl acetate. A catalyst used in this reaction is known and widely used, containing palladium as the main catalyst component and an alkali metal compound and / or alkaline earth metal compound as a promoter component supported on a carrier. For example, Japanese Patent Laid-Open Publication No. 2-91045 (Patent Document 1) discloses a method for producing allyl acetate using a catalyst containing palladium, potassium acetate, and copper supported on a carrier.

[0003] Furthermore, other catalyst components have also been investigated. For example, Japanese Patent Laid-Open Publication No. 52-153908 (Patent Document 2) discloses a method for producing allyl acetate using a catalyst in which activity reduction is suppressed, in which palladium (II) acetylacetonate, molybdenum (VI) dioxyacetylacetonate, and potassium acetate are supported on a carrier.

[0004] Japanese Patent Laid-Open Publication No. 2008-279437 (Patent Document 3) discloses a method for producing allyl acetate using a catalyst in which activity reduction is suppressed, the catalyst comprising a compound containing palladium, gold, and at least one element selected from copper, nickel, zinc, and cobalt, and potassium acetate supported on a carrier.

[0005] Furthermore, although the reaction is different from that in the case of allyl acetate, for example, JP-A No. 2003-525723 (Patent Document 4) discloses a method for producing a catalyst for vinyl acetate production using ethylene as a starting raw material, in which palladium is loaded onto a carrier in the first step, gold is loaded onto a carrier in the second step, and after reduction treatment, copper(II) acetate and potassium acetate are loaded onto a carrier in the third step, thereby suppressing the generation of carbon dioxide.

[0006] Incidentally, catalyst technology for the production of vinyl acetate has been established for a long time, and attempts have been made to apply and develop catalyst technology for the production of vinyl acetate to catalyst technology for the production of allyl acetate. However, when the reaction raw material was changed from ethylene to propylene, the basic performance of the catalyst was significantly inferior, as described in "Catalysts," Vol. 33, No. 1 (1991), pp. 28-32 (Non-Patent Document 1).

[0007] Japanese Patent Laid-Open No. 2-91045 Japanese Patent Laid-Open No. 52-153908 Japanese Patent Laid-Open No. 2008-279437 Special Publication No. 2003-525723

[0008] "Catalyst", Vol. 33, No. 1 (1991), pp. 28-32

[0009] The present disclosure provides a catalyst for the production of allyl acetate that provides improved space-time yields.

[0010] The present inventors have found that a catalyst for producing allyl acetate that provides an improved space-time yield, in which at least palladium, iridium, at least one element selected from copper, nickel, zinc, and cobalt, and an alkali metal salt are supported on a carrier, and the amount of iridium is 5.0 to 17.0 parts by mass per 100 parts by mass of palladium.

[0011] The present disclosure includes the following aspects [1] to [8]. [1] A catalyst for use in producing allyl acetate using propylene, acetic acid, and oxygen as raw materials, the catalyst comprising (a) palladium, (b) iridium, (c) at least one element selected from copper, nickel, zinc, and cobalt, and (d) an alkali metal salt supported on an (e) carrier, wherein the amount of (b) iridium is 5.0 to 17.0 parts by mass per 100 parts by mass of (a) palladium. [2] The catalyst for producing allyl acetate according to [1] above, wherein the total amount of (c) at least one element selected from copper, nickel, zinc, and cobalt is 5.0 to 150.0 parts by mass per 100 parts by mass of (a) palladium. [3] The catalyst for producing allyl acetate according to [1] or [2] above, wherein the (c) at least one element selected from copper, nickel, zinc, and cobalt is at least one selected from copper and zinc. [4] The catalyst for producing allyl acetate according to any one of [1] to [3] above, wherein the (d) alkali metal salt is at least one selected from potassium acetate, sodium acetate, and cesium acetate. [5] The catalyst for producing allyl acetate according to any one of [1] to [4] above, wherein the total amount of (a) palladium, (b) iridium, and (c) at least one element selected from copper, nickel, zinc, and cobalt, and the (d) alkali metal salt are in a mass ratio of (a):(b):(c):(d)=100:5.0-17.0:5.0-150.0:150-4000. [6] A method for producing allyl acetate using propylene, acetic acid, and oxygen as raw materials, using the catalyst according to any one of [1] to [5] above. [7] A method for producing a catalyst for producing allyl acetate, comprising the following steps 1 to 4: (a) palladium, (b) iridium, (c) at least one element selected from copper, nickel, zinc, and cobalt, and (d) an alkali metal salt are supported on an (e) support, and the amount of (b) iridium is 5.0 to 17.0 parts by mass per 100 parts by mass of (a) palladium.Step 1: preparing a solution of a palladium-containing compound, an iridium-containing compound, and a compound having at least one element selected from copper, nickel, zinc, and cobalt, and (e) contacting the solution with a carrier to support the palladium-containing compound, the iridium-containing compound, and the compound having at least one element selected from copper, nickel, zinc, and cobalt on the carrier to obtain a supported carrier (A); Step 2: (f) contacting and impregnating the supported carrier (A) obtained in step 1 with an alkaline solution to obtain an impregnated carrier (B); Step 3: reducing the impregnated carrier (B) obtained in step 2 to obtain a metal-supported carrier (C); Step 4: (d) supporting an alkali metal salt on the metal-supported carrier (C) obtained in step 3; [8] A method for producing a catalyst for use in producing allyl acetate according to the above item [7], wherein the compound having at least one element selected from copper, nickel, zinc, and cobalt is copper chloride.

[0012] According to the present disclosure, it is possible to provide a catalyst for producing allyl acetate that provides an improved space-time yield. By using this catalyst, it is possible to reduce the production cost of allyl acetate and to efficiently produce allyl acetate.

[0013] Preferred embodiments of the present invention will be described below, but it should be understood that the present invention is not limited to these embodiments and that various applications are possible within the spirit and scope of the present invention. In this disclosure, when "to" is used to describe a numerical range, the numerical values ​​at both ends are the upper and lower limits, respectively, and are included in the numerical range. When multiple upper or lower limits are listed, numerical ranges can be created from all combinations of the upper and lower limits. Similarly, when multiple numerical ranges are listed, separate numerical ranges can be created by individually selecting and combining upper and lower limits from those numerical ranges.

[0014] <Catalyst and Catalyst Production Method> In one embodiment, the catalyst for producing allyl acetate comprises (a) palladium, (b) iridium, (c) at least one element selected from copper, nickel, zinc, and cobalt, and (d) an alkali metal salt, all of which are supported on an (e) carrier, with the amount of (b) iridium being 5.0 to 17.0 parts by mass per 100 parts by mass of (a) palladium. The catalyst for producing allyl acetate may optionally contain other components. However, preferably, gold is not supported on the catalyst for producing allyl acetate. By using the catalyst for producing allyl acetate, allyl acetate can be obtained with a high space-time yield and high selectivity. As a result, the production cost of allyl acetate can be reduced, and allyl acetate can be produced efficiently.

[0015] The catalyst for producing allyl acetate is preferably produced by a method comprising the following steps in this order: Step 1: preparing a solution of a palladium-containing compound, an iridium-containing compound, and a compound having at least one element selected from copper, nickel, zinc, and cobalt, and (e) contacting the solution with a carrier to support the palladium-containing compound, the iridium-containing compound, and the compound having at least one element selected from copper, nickel, zinc, and cobalt on the carrier to obtain a supported carrier (A); Step 2: (f) contacting and impregnating the supported carrier (A) obtained in Step 1 with an alkaline solution to obtain an impregnated carrier (B); Step 3: reducing the impregnated carrier (B) obtained in Step 2 to obtain a metal-supported carrier (C); and Step 4: (d) supporting an alkali metal salt on the metal-supported carrier (C) obtained in Step 3. The method for producing a catalyst for producing allyl acetate is not limited to this method, and the order of Step 1 and Step 2 may be reversed. However, step 3 must be performed after steps 1 and 2. Other steps may be performed before or after each step. These components and steps will be described below.

[0016] (a) Palladium In the present disclosure, (a) palladium may have any valence, but is preferably metallic palladium. Here, "metallic palladium" refers to palladium with a valence of zero. Metallic palladium can usually be obtained by reducing divalent and / or tetravalent palladium ions using a reducing agent such as hydrazine or hydrogen gas. It is preferable that substantially all of (a) palladium is metallic palladium. In the catalyst for producing allyl acetate, not all of the palladium needs to be in a metallic state.

[0017] (a) There are no particular limitations on the raw material for palladium, i.e., the compound containing palladium. Metallic palladium can be used, and a palladium precursor that can be converted into metallic palladium can also be used. In the present disclosure, "a compound containing palladium" also encompasses metallic palladium. Examples of palladium precursors include, but are not limited to, palladium chloride, palladium nitrate, palladium sulfate, sodium chloropalladate, potassium chloropalladate, barium chloropalladate, and palladium acetate. Preferably, sodium chloropalladate is used. Palladium-containing compounds may be used alone or in combination of two or more.

[0018] The mass ratio of (a) palladium to (e) support in the catalyst for producing allyl acetate is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and even more preferably 1.0 to 3 parts by mass of (a) palladium per 100 parts by mass of the (e) support. This ratio is a calculated value calculated from the amounts of raw materials charged. For example, when a palladium precursor is used as the palladium raw material, the ratio is calculated as the ratio of the mass of palladium element in the palladium precursor used to the mass of the support.

[0019] (b) Iridium In the present disclosure, (b) iridium may have any valence, but is preferably metallic iridium. Here, "metallic iridium" refers to iridium with a valence of zero. Metallic iridium can usually be obtained by reducing trivalent and / or tetravalent iridium ions using a reducing agent such as hydrazine or hydrogen gas. It is preferable that substantially all of (b) iridium is metallic iridium. In the catalyst for producing allyl acetate, it is not necessary for all iridium to be in a metallic state.

[0020] There are no particular limitations on the iridium raw material, i.e., the iridium-containing compound. Metallic iridium can be used, and an iridium precursor that can be converted into metallic iridium can also be used. In the present disclosure, "a compound containing iridium" also includes metallic iridium. Examples of iridium precursors include, but are not limited to, iridium chloride, chloroiridic acid, sodium chloroiridate, and potassium chloroiridate. Preferably, at least one selected from iridium chloride and sodium chloroiridate is used. The iridium-containing compound may be used alone or in combination of two or more.

[0021] The mass ratio of (b) iridium to (e) support in the catalyst for producing allyl acetate is preferably 0.05 to 0.22 parts by mass, more preferably 0.08 to 0.19 parts by mass, and even more preferably 0.10 to 0.17 parts by mass of (b) iridium per 100 parts by mass of the (e) support. This ratio is a calculated value calculated from the charged amounts of raw materials. For example, when an iridium precursor is used as the iridium raw material, the ratio is calculated as the ratio of the mass of iridium element in the iridium precursor used to the mass of the support.

[0022] The amount of (b) iridium in the catalyst for producing allyl acetate is 5.0 parts by mass or more, preferably 7.0 parts by mass or more, and more preferably 9.0 parts by mass or more, per 100 parts by mass of (a) palladium. The amount of (b) iridium in the catalyst for producing allyl acetate is 17.0 parts by mass or less, preferably 15.0 parts by mass or less, and more preferably 13.0 parts by mass or less, per 100 parts by mass of (a) palladium. The amount of (b) iridium in the catalyst for producing allyl acetate is 5.0 to 17.0 parts by mass, preferably 7.0 to 15.0 parts by mass, and more preferably 9.0 to 13.0 parts by mass, per 100 parts by mass of (a) palladium. This ratio is a calculated value calculated from the amounts of raw materials charged. Note that the mass ratio here is the mass ratio of elemental palladium to elemental iridium. By setting the amount of iridium within the above range, a good balance between catalytic activity and allyl acetate selectivity in the allyl acetate production reaction can be obtained.

[0023] (c) At least one element selected from copper, nickel, zinc, and cobalt. In the present disclosure, each element in (c) at least one element selected from copper, nickel, zinc, and cobalt may have any valence, but is preferably an element in a metallic state such as metallic copper, metallic nickel, metallic zinc, or metallic cobalt. Here, "metallic element" refers to an element with a valence of zero. Elements in a metallic state can be obtained by reducing a precursor convertible to each metal using a reducing agent such as hydrazine or hydrogen gas. It is preferable that substantially all of (c) at least one element selected from copper, nickel, zinc, and cobalt is an element in a metallic state. In a catalyst for producing allyl acetate, not all of the copper, nickel, zinc, and cobalt need to be in a metallic state.

[0024] (c) The raw material of at least one element selected from copper, nickel, zinc, and cobalt, i.e., the compound containing at least one element selected from copper, nickel, zinc, and cobalt, is not particularly limited. It is possible to use at least one element selected from metallic copper, metallic nickel, metallic zinc, and metallic cobalt, as well as precursors convertible to the metal of each of the elements. In the present disclosure, "a compound containing at least one element selected from copper, nickel, zinc, and cobalt" also encompasses metallic copper, metallic nickel, metallic zinc, and metallic cobalt. Soluble salts of these elements, such as nitrates, carbonates, sulfates, organic acid salts, and halides, can be used as precursors convertible to the metal of each element. Examples of organic acid salts include acetates. Examples of halides include chlorides. Generally, compounds that are readily available and water-soluble are preferred. Preferred precursors include, for example, copper nitrate, copper acetate, nickel nitrate, nickel acetate, zinc nitrate, zinc acetate, cobalt nitrate, cobalt acetate, and copper chloride. Among these, from the viewpoints of raw material stability and availability, at least one selected from copper acetate and copper chloride is preferred, and copper chloride is most preferred. The compound containing at least one element selected from copper, nickel, zinc, and cobalt may be used alone or in combination of two or more.

[0025] (c) The at least one element selected from copper, nickel, zinc, and cobalt is preferably at least one element selected from copper and zinc, and more preferably copper.

[0026] The mass ratio of (c) at least one element selected from copper, nickel, zinc, and cobalt to (e) the support in the catalyst for producing allyl acetate is preferably such that the total amount of (c) at least one element selected from copper, nickel, zinc, and cobalt is 0.05 to 2.0 parts by mass, more preferably 0.1 to 1.0 parts by mass, and even more preferably 0.2 to 0.8 parts by mass, per 100 parts by mass of the (e) support. This ratio is a calculated value calculated from the amounts of raw materials charged. For example, when a chloride is used as a raw material for at least one element selected from copper, nickel, zinc, and cobalt, the ratio is calculated as the ratio of the total mass of copper, nickel, zinc, and cobalt elements in the chloride used to the mass of the support.

[0027] The total amount of (c) at least one element selected from copper, nickel, zinc, and cobalt in the catalyst for producing allyl acetate is preferably 5.0 parts by mass or more, more preferably 10.0 parts by mass or more, and even more preferably 30.0 parts by mass or more, per 100 parts by mass of (a) palladium. The total amount of (c) at least one element selected from copper, nickel, zinc, and cobalt in the catalyst for producing allyl acetate is preferably 150.0 parts by mass or less, more preferably 75.0 parts by mass or less, and even more preferably 50.0 parts by mass or less, per 100 parts by mass of (a) palladium. The total amount of (c) at least one element selected from copper, nickel, zinc, and cobalt in the catalyst for producing allyl acetate is preferably 5.0 to 150.0 parts by mass, more preferably 10.0 to 75.0 parts by mass, and even more preferably 30.0 to 50.0 parts by mass, per 100 parts by mass of (a) palladium. This ratio is a calculated value calculated from the amounts of raw materials charged. The mass ratio here is the mass ratio of elemental palladium to the total amount of at least one element selected from copper, nickel, zinc, and cobalt. By setting the mass ratio within the above range, a good balance between catalytic activity and allyl acetate selectivity in the allyl acetate production reaction can be obtained.

[0028] (d) Alkali Metal Salt In the present disclosure, (d) alkali metal salt is at least one compound selected from alkali metal salts. Examples of alkali metals include lithium, sodium, potassium, rubidium, and cesium, with at least one selected from sodium and potassium being preferred, and potassium being more preferred. Examples of alkali metal salts include hydroxides, acetates, nitrates, and bicarbonates of alkali metals. Specific examples include sodium hydroxide, potassium hydroxide, lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, sodium bicarbonate, and potassium bicarbonate. Among these, at least one selected from potassium acetate, sodium acetate, and cesium acetate is preferred, with at least one selected from potassium acetate and cesium acetate being more preferred.

[0029] The mass ratio of the (d) alkali metal salt to the (e) carrier in the catalyst for producing allyl acetate is preferably 2.0 to 50 parts by mass, more preferably 3.0 to 30 parts by mass, and even more preferably 6.0 to 20 parts by mass of the (d) alkali metal salt per 100 parts by mass of the (e) carrier. This ratio is calculated as the ratio of the mass of the alkali metal salt used to the mass of the carrier.

[0030] The amount of (d) alkali metal salt in the catalyst for producing allyl acetate is preferably 150 parts by mass or more, more preferably 200 parts by mass or more, and even more preferably 500 parts by mass or more, per 100 parts by mass of (a) palladium. The amount of (d) alkali metal salt in the catalyst for producing allyl acetate is preferably 4,000 parts by mass or less, more preferably 2,000 parts by mass or less, and even more preferably 1,000 parts by mass or less, per 100 parts by mass of (a) palladium. The amount of (d) alkali metal salt in the catalyst for producing allyl acetate is preferably 150 to 4,000 parts by mass, more preferably 200 to 2,000 parts by mass, and even more preferably 500 to 1,000 parts by mass, per 100 parts by mass of (a) palladium. This ratio is a calculated value calculated from the amounts of raw materials charged. Note that the mass ratio here is the mass ratio between palladium element and alkali metal salt. By setting the amount of alkali metal salt within the above range, a good balance between catalytic activity and allyl acetate selectivity in the allyl acetate production reaction can be obtained.

[0031] (e) Support There are no particular restrictions on the (e) support. As the (e) support, a porous substance generally used as a catalyst support can be used. Preferred specific examples include silica, alumina, silica-alumina, diatomaceous earth, montmorillonite, titania, and zirconia, and silica is more preferred. When using an (e) support containing silica as the main component, the silica content of the (e) support is preferably at least 50 mass%, more preferably at least 90 mass%, based on the mass of the (e) support.

[0032] (e) The carrier has a specific surface area of ​​10 to 1000 m as measured by the BET method. ２ / g, and particularly preferably 100 to 500m ２ / g range. (e) The bulk density of the support is preferably in the range of 50 to 1000 g / L, particularly preferably in the range of 300 to 500 g / L. (e) The water absorption rate of the support is preferably in the range of 0.05 to 3 g / g-support, particularly preferably in the range of 0.1 to 2 g / g-support. (e) The pore structure of the support preferably has an average pore diameter in the range of 1 to 1000 nm, particularly preferably in the range of 2 to 800 nm. If the average pore diameter is 1 nm or more, gas diffusion can be facilitated. On the other hand, if the average pore diameter is 1000 nm or less, the specific surface area of ​​the support required to obtain catalytic activity can be ensured.

[0033] Mercury porosimetry and gas adsorption (BJH) method are widely used to measure the pore size distribution of supports. According to the pore classification of IUPAC (International Union of Pure and Applied Chemistry), mercury porosimetry can measure macropores of 50 nm or more and some mesopores of 2 nm to less than 50 nm, while gas adsorption can measure mesopores and micropores of 2 nm or less. An appropriate measurement method can be selected depending on the pore diameter.

[0034] In this disclosure, the water absorption rate of a carrier refers to a value measured by the following measurement method. 1. Accurately weigh out approximately 5 g of carrier on a balance and place in a 100 mL beaker. The mass at this time is designated w1. 2. Approximately 15 mL of ion-exchanged water is added to the beaker so that the carrier is completely covered. 3. Leave to stand for 30 minutes. 4. Remove the supernatant ion-exchanged water from the carrier. 5. Remove the water adhering to the surface of the carrier by gently pressing with a paper towel until the surface is no longer glossy. 6. Accurately weigh the total mass of the carrier and ion-exchanged water. The mass at this time is designated w2. 7. Calculate the water absorption rate of the carrier using the following formula: Water absorption rate (g / g-carrier) = (w2-w1) / w1

[0035] Therefore, the amount of water absorption (g) of the carrier is calculated by multiplying the water absorption rate of the carrier (g / g-carrier) by the mass (g) of the carrier used.

[0036] (e) There are no particular limitations on the shape of the carrier. Specific examples include, but are not limited to, powder, spheres, pellets, etc. The optimal shape may be selected depending on the reaction type, reactor, etc. to be used.

[0037] There are no particular restrictions on the particle size of the (e) support. When used in a fixed-bed tubular reactor for gas-phase reactions, if the (e) support is spherical, its particle diameter is preferably in the range of 1 to 10 mm, more preferably in the range of 2 to 8 mm. When a tubular reactor is filled with a catalyst to carry out a gas-phase reaction, a particle diameter of 1 mm or more can prevent an excessive increase in pressure loss during gas flow and enable effective gas circulation. On the other hand, a particle diameter of 10 mm or less can facilitate diffusion of the raw material gas into the catalyst, allowing the catalytic reaction to proceed effectively.

[0038] (f) Alkaline Solution The alkaline solution (f) used in step 2 is not particularly limited, and any alkaline solution can be used. The alkaline solution (f) may be a solution of any alkaline compound. Examples of alkaline compounds include hydroxides of alkali metals or alkaline earth metals, bicarbonates of alkali metals or alkaline earth metals, carbonates of alkali metals or alkaline earth metals, and silicates of alkali metals or alkaline earth metals. Preferred alkaline metals are lithium, sodium, and potassium, and preferred alkaline earth metals are barium and strontium. Particularly preferred alkaline compounds include sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, and barium hydroxide. Contact with the alkaline solution (f) can convert some or all of the palladium-containing compound, the iridium-containing compound, and the compound containing at least one element selected from copper, nickel, zinc, and cobalt into oxides or hydroxides.

[0039] The alkaline compound is suitably used in excess relative to the total of (a) palladium, (b) iridium, and (c) at least one element selected from copper, nickel, zinc, and cobalt. For example, the product of the molar amount of the alkaline compound and the valence of the alkaline compound is preferably more than 1.1 times and not more than 3.0 times, more preferably more than 1.5 times and not more than 2.0 times, the sum of the product of the molar amount of the palladium-containing compound and the valence of palladium, the product of the molar amount of the iridium-containing compound and the valence of iridium, and the product of the molar amount of the compound containing at least one element selected from (c) copper, nickel, zinc, and cobalt and the valence of each of the metals.

[0040] The solvent used to form the alkaline compound solution is not particularly limited, and examples thereof include at least one selected from water and alcohol, preferably at least one selected from water, methanol, and ethanol, with water being particularly preferred.

[0041] <Method for Producing a Catalyst for Producing Allyl Acetate> Next, each step of the method for producing a catalyst for producing allyl acetate will be described. Step 1 In this step, a solution of a palladium-containing compound, an iridium-containing compound, and a compound having at least one element selected from copper, nickel, zinc, and cobalt is prepared, and the solution is brought into contact with a (e) carrier to carry out supporting. The compound carried in this step is called a supported carrier (A). The state of support of these compounds on the (e) carrier is preferably a so-called "eggshell type." When obtaining an eggshell-type supported catalyst, there are no particular limitations on the method for supporting the solution of a palladium-containing compound, an iridium-containing compound, and a compound having at least one element selected from copper, nickel, zinc, and cobalt on the (e) carrier, as long as it ultimately results in an eggshell-type supported catalyst. The eggshell type refers to one of the distribution states of active components such as metallic palladium within a carrier particle or molded body, in which most of the active component is present near the outer surface of the carrier particle or molded body. Specific examples of the method include a method in which a raw material compound is dissolved in a suitable solvent such as water or acetone, or in an inorganic or organic acid such as hydrochloric acid, nitric acid, or acetic acid, or a solution thereof, and directly supported on the surface of the support, and an indirect method. Examples of direct support methods include impregnation and spraying. Examples of indirect support methods include, as described below, a method in which a solution of a palladium-containing compound, an iridium-containing compound, and a compound having at least one element selected from copper, nickel, zinc, and cobalt is first supported on a support (step 1), and then (f) the internal palladium-containing compound, the iridium-containing compound, and the compound having at least one element selected from copper, nickel, zinc, and cobalt are transferred to the surface by contact impregnation with an alkaline solution (step 2), followed by reduction (step 3).

[0042] The (e) support of a compound containing palladium, a compound containing iridium, and a compound having at least one element selected from copper, nickel, zinc, and cobalt can be carried out by preparing a solution of a compound containing palladium, a compound containing iridium, and a compound having at least one element selected from copper, nickel, zinc, and cobalt, and impregnating an appropriate amount of the (e) support with the solution. More specifically, a solution is prepared by dissolving a compound containing palladium, a compound containing iridium, and a compound having at least one element selected from copper, nickel, zinc, and cobalt in a suitable solvent such as water or acetone, or a solution containing an inorganic or organic acid such as hydrochloric acid, nitric acid, or acetic acid, and then impregnating the support with the solution to obtain the supported support (A). Drying may be performed following impregnation, but it is preferable to proceed to step 2 without the drying step, as this eliminates the need for a step.

[0043] Step 2: This step involves contacting and impregnating the supported carrier (A) obtained in Step 1 with an alkaline solution (f) to obtain an impregnated carrier (B). There are no particular limitations on the contact conditions between the supported carrier (A) and the alkaline solution (f), but the contact time is preferably in the range of 0.5 to 100 hours, more preferably 3 to 50 hours. By setting the contact time to 0.5 hours or more, the desired amount of catalyst component can be supported, resulting in sufficient catalytic performance. By setting the contact time to 100 hours or less, deterioration of the carrier can be suppressed.

[0044] The contact temperature is not particularly limited, but is preferably in the range of 10 to 80°C, more preferably in the range of 20 to 60°C. By setting the contact temperature to 10°C or higher, the conversion reaction can be allowed to proceed sufficiently. By setting the contact temperature to 80°C or lower, aggregation of palladium, iridium, copper, nickel, zinc, and cobalt can be suppressed. The product obtained by contact impregnation with the alkaline solution obtained in this step is called the impregnated carrier (B).

[0045] Step 3: This step is a step of subjecting the impregnated carrier (B) obtained in Step 2 to a reduction treatment. The reduction reaction is carried out by contacting the impregnated carrier (B) with a reducing agent or a solution thereof. Either liquid phase reduction or gas phase reduction can be used as the reduction method. The metal-supported carrier obtained in this step is referred to as metal-supported carrier (C).

[0046] Liquid-phase reduction may be carried out in either a non-aqueous system using an alcohol or a hydrocarbon, or an aqueous system. Examples of reducing agents that can be used include carboxylic acids and their salts, aldehydes, hydrogen peroxide, sugars, polyhydric phenols, boron compounds, amines, and hydrazine. Examples of carboxylic acids and their salts include oxalic acid, potassium oxalate, formic acid, potassium formate, potassium citrate, and ammonium citrate. Examples of aldehydes include formaldehyde and acetaldehyde. Examples of sugars include glucose. Examples of polyhydric phenols include hydroquinone. Examples of boron compounds include diborane and sodium borohydride. Among these, hydrazine, formaldehyde, acetaldehyde, hydroquinone, sodium borohydride, and potassium citrate are preferred, and hydrazine is more preferred.

[0047] When reduction is carried out by the liquid phase method, the temperature is not particularly limited, but the liquid phase temperature is preferably in the range of 0 to 100°C, and more preferably in the range of 10 to 95°C. When the liquid phase temperature is 0°C or higher, a sufficient reduction rate can be obtained. On the other hand, when the liquid phase temperature is 100°C or lower, aggregation of palladium and iridium can be suppressed.

[0048] The gas phase reduction is carried out by contacting the impregnated carrier (B) with a reducing gas. The reducing agent used in the gas phase reduction may be, for example, at least one selected from the group consisting of hydrogen gas, carbon monoxide, alcohols, aldehydes, and olefins such as ethylene, propylene, and isobutene. The reducing agent is preferably at least one selected from hydrogen gas and propylene.

[0049] When gas phase reduction is performed, the temperature is not particularly limited, but the impregnated carrier (B) is preferably heated to a range of 30 to 350°C, more preferably to a range of 100 to 300°C. When the heating temperature is 30°C or higher, a sufficient reduction rate can be obtained. On the other hand, when the heating temperature is 350°C or lower, aggregation of palladium and iridium can be suppressed.

[0050] The treatment pressure for the gas phase reduction treatment is not particularly limited, but from the viewpoint of equipment, it is preferably in the range of 0.0 to 3.0 MPaG (gauge pressure), and more preferably in the range of 0.1 to 1.0 MPaG (gauge pressure).

[0051] When performing gas phase reduction, the supply rate of the reducing agent is, under standard conditions, a space velocity (hereinafter referred to as SV) of 10 to 15,000 hr. －１ The range is preferably 100 to 8000 hours. －１ It is particularly preferable that the range is:

[0052] Gas-phase reduction may be carried out at any reducing substance concentration, and an inert gas may be added as a diluent, if necessary. Examples of inert gases include helium, argon, and nitrogen gas. Reduction may also be carried out using a reducing agent such as hydrogen gas or propylene in the presence of vaporized water.

[0053] The catalyst before reduction treatment may be packed into a reactor, reduced with propylene gas, and then oxygen and acetic acid may be introduced to produce allyl acetate. In this case, (d) loading of an alkali metal salt in step 4 is carried out between steps 2 and 3.

[0054] The metal-supported carrier (C) may be washed with water as needed. Washing may be carried out continuously or batchwise. The washing temperature is preferably in the range of 5 to 200°C, more preferably in the range of 15 to 80°C. There is no particular limitation on the washing time. It is preferable to select conditions sufficient to remove remaining undesirable impurities. Examples of undesirable impurities include sodium-containing compounds and chlorine-containing compounds. After washing, the metal-supported carrier (C) may be dried by heating as needed.

[0055] Step 4 This step is a step of loading (d) an alkali metal salt onto the metal-loaded carrier (C) obtained in Step 3.

[0056] The (d) alkali metal salt can be supported, for example, by impregnating the metal-supported carrier (C) with a solution containing the required amount of (d) alkali metal salt, followed by drying. The amount of the solution containing the (d) alkali metal salt used is preferably 0.9 to 1.0 times the mass of the carrier's water absorption. There are no particular restrictions on the solvent used. Any solvent can be used as long as it has a solubility that allows the (d) alkali metal salt to be dissolved in a solution that is 0.9 to 1.0 times the mass of the carrier's water absorption. The solvent is preferably water.

[0057] There are no particular limitations on the drying temperature and drying time, and for example, drying may be carried out in an air stream at 90 to 110°C for 2 to 6 hours.

[0058] <Catalyst Component Composition> The mass ratio of (a), (b), (c), and (d) in the catalyst for producing allyl acetate is preferably (a):(b):(c):(d)=100:5.0-17.0:5.0-150.0:150-4000, more preferably (a):(b):(c):(d)=100:7.0-15.0:10.0-75.0:200-2000, and more preferably (a):(b):(c):(d)=100:9.0-13.0:30.0-50.0:500-1000. Note that (a), (b), and (c) refer to the mass ratio of the component elements, and (d) refers to the mass ratio of the alkali metal salt.

[0059] The amounts and composition ratios of the metal elements contained in the catalyst for producing allyl acetate in the present disclosure can also be measured by chemical analysis such as inductively coupled plasma emission spectrometry (hereinafter abbreviated as "ICP"), X-ray fluorescence analysis, or atomic absorption spectrometry.

[0060] As an example of a measurement method, a certain amount of catalyst is crushed in a mortar or the like to obtain a uniform powder, and then the catalyst is added to an acid such as hydrofluoric acid or aqua regia, heated and stirred to dissolve the catalyst into a uniform solution, which is then diluted with pure water to an appropriate concentration and quantitatively analyzed by ICP.

[0061] <Method for producing allyl acetate> Hereinafter, a method for producing allyl acetate using a catalyst for producing allyl acetate will be described. The reaction for producing allyl acetate is preferably carried out in a gas phase using propylene, oxygen, and acetic acid as raw materials. The type of gas phase reaction is not particularly limited and may be a known type. Examples of the type of gas phase reaction include a fixed bed and a fluidized bed. Preferably, it is practically advantageous to employ a fixed bed flow reaction in which a reaction tube is filled with a catalyst for producing allyl acetate.

[0062] The reaction formula is as follows: CH ２ =CHCH ３ +CH ３ COOH + 1 / 2O ２ → CH ２ =CHCH ２ OCOCH ３ +H ２ O

[0063] The feed gas supplied to the reactor contains propylene, oxygen gas, and gaseous acetic acid, and may further contain nitrogen gas, carbon dioxide, a rare gas, or the like as a diluent, as necessary. When propylene, acetic acid, and oxygen are defined as the reaction raw materials, the ratio of the reaction raw materials to the diluent, in terms of molar ratio, is preferably reaction raw materials:diluent=1:0.05-9, and more preferably reaction raw materials:diluent=1:0.1-3. The ratio of acetic acid, propylene, and oxygen in the feed gas, in terms of molar ratio, is preferably acetic acid:propylene:oxygen=1:1-12:0.5-2.

[0064] In the reaction for producing allyl acetate, the presence of water in the reaction system is significantly effective in maintaining the activity of the catalyst and in the production of allyl acetate. The raw material gas preferably contains 0.5 to 25 mol % of water vapor.

[0065] It is preferable to use high-purity propylene as the reaction raw material, but it may be contaminated with lower saturated hydrocarbons such as methane, ethane, and propane.

[0066] Oxygen can be supplied in the form of air diluted with an inert gas such as nitrogen gas or carbon dioxide gas. However, when the reaction gas is circulated, it is generally advantageous to use a high-concentration oxygen gas, preferably an oxygen gas with a purity of 99 mol % or more.

[0067] The reaction raw materials, propylene and acetic acid, may be produced from fossil fuels, biomass, or a mixture thereof. The concentration of C carbon atoms in propylene, acetic acid, and allyl acetate is 1×10 relative to the total number of carbon atoms. －１４ ~2 x 10 －１２ may be.

[0068] There are no particular restrictions on the material of the reactor, but it is preferable that the material be corrosion-resistant.

[0069] There is no particular limitation on the reaction temperature. The reaction temperature is preferably in the range of 100 to 300°C, more preferably in the range of 120 to 250°C. The reaction pressure is not particularly limited, although it is practically advantageous from the viewpoint of equipment to be in the range of 0.0 to 3.0 MPaG (gauge pressure). The reaction pressure is more preferably in the range of 0.1 to 1.5 MPaG (gauge pressure).

[0070] When the reaction is carried out in a fixed bed flow reactor, the raw material gas is reacted at a rate of SV = 10 to 15,000 hr under standard conditions. －１ It is preferable that the catalyst is supplied in the range of 300 to 8000 hr. －１ It is more preferable that the amount of the catalyst be in the range of 1000 to 15000 kJ / kg.

[0071] The present invention will be further explained below with reference to examples and comparative examples, but the present invention is not limited to these descriptions in any way.

[0072] (Example 1) Production of Catalyst A A commercially available silica spherical carrier (sphere diameter 5 mm, specific surface area 155 m) was used as the carrier. ２ / g, water absorption rate 0.85 g / g-carrier, bulk density 473 g / L, water absorption amount 402 g / L, hereinafter simply referred to as "silica carrier"), a catalyst was produced by the following procedure.

[0073] Step 1: 30.3 g of a sodium chloropalladate aqueous solution (Pd: 6.0 g) adjusted to 19.79% by mass of palladium, 12.0 g of a sodium chloroiridate aqueous solution (Ir: 0.6 g) adjusted to 5.0% by mass of iridium, and 6.4 g of copper chloride dihydrate (Cu: 2.4 g) were mixed and made up to 382 mL with pure water. 1 L of the silica carrier was added to this, and the entire amount was absorbed to obtain a supported carrier (A-1). Step 2: 56.2 g of sodium metasilicate nonahydrate was added and dissolved in pure water, and the total volume was made up to 803 mL. The supported carrier (A-1) obtained in step 1 was immersed in this and left to stand at room temperature for 20 hours to obtain an impregnated carrier (B-1) impregnated with the sodium metasilicate solution. Step 3: The slurry of the impregnated carrier (B-1) obtained in Step 2 was heated to 90°C, and then 42.6 g of hydrazine monohydrate was added. After gentle stirring, the mixture was allowed to stand at 90°C for 4 hours. The reduced impregnated carrier (B-1) was filtered and transferred to a glass column equipped with a stopcock, and purified water was passed through it for 40 hours to wash it. Next, it was dried at 110°C for 4 hours under an air stream to obtain a metal-supported carrier (C-1). Step 4: Purified water was added to 52 g of potassium acetate to dissolve it, and the volume was adjusted to 361 mL. The metal-supported carrier (C-1) obtained in Step 3 was added to this, and the entire amount was absorbed. Next, it was dried at 110°C for 4 hours under an air stream to obtain a catalyst A for producing allyl acetate.

[0074] Comparative Example 1 Preparation of Comparative Catalyst B Comparative catalyst B was prepared by repeating the procedure of Example 1, except that the amount of the aqueous sodium chloroiridate solution was changed from 12.0 g to 22.0 g, the amount of sodium metasilicate nonahydrate was changed from 56.2 g to 58.4 g, and the amount of hydrazine monohydrate was changed from 42.6 g to 44.2 g.

[0075] Comparative Example 2: Preparation of Comparative Catalyst C Comparative catalyst C was prepared by repeating the procedure of Example 1, except that the aqueous sodium chloroiridate solution was not added, the amount of sodium metasilicate nonahydrate was changed from 56.2 g to 53.5 g, and the amount of hydrazine monohydrate was changed from 42.6 g to 40.5 g.

[0076] (Comparative Example 3) Preparation of Comparative Catalyst D Step 1: 30.3 g of a sodium chloropalladate aqueous solution adjusted to 19.79 mass% palladium and 6.13 g of a chloroauric acid aqueous solution adjusted to 10 mass% gold were mixed and diluted to 382 mL with pure water. 1 L of silica carrier (bulk specific gravity 473 g / L, water absorption 402 g / L) was added to this and the entire amount was absorbed to obtain a supported carrier (A-4). Step 2: 35.6 g of sodium metasilicate nonahydrate was dissolved in pure water and diluted to 803 mL. The supported carrier (A-4) obtained in Step 1 was immersed in this and allowed to stand at room temperature for 20 hours to obtain an impregnated carrier (B-4) impregnated with the sodium metasilicate solution. Step 3: 26.6 g of hydrazine monohydrate was added to the slurry of the impregnated carrier (B-4) obtained in Step 2, and the mixture was gently stirred and then allowed to stand at 25°C for 4 hours. The reduced impregnated carrier (B-4) was filtered and transferred to a glass column equipped with a stopcock, and washed by passing pure water through it for 40 hours. Next, it was dried at 110°C for 4 hours under an air stream to obtain a metal-supported carrier (C-4). Step 4: Pure water was added to 52 g of potassium acetate and 7.5 g of copper acetate monohydrate to dissolve them, and the volume was adjusted to 361 mL. The metal-supported carrier (C-4) obtained in Step 3 was added to this and the entire amount was absorbed. Next, it was dried at 110°C for 4 hours under an air stream to obtain a comparative catalyst D for the production of allyl acetate.

[0077] (Comparative Example 4) Preparation of Comparative Catalyst E Step 1: 30.3 g of a sodium chloropalladate aqueous solution adjusted to 19.79 mass% palladium and 1.51 g of a chloroauric acid aqueous solution adjusted to 10 mass% gold were mixed and diluted to 382 mL with pure water. 1 L of silica carrier (bulk specific gravity 473 g / L, water absorption 402 g / L) was added to this, and the entire amount was absorbed to obtain a supported carrier (A-5). Step 2: 32.9 g of sodium metasilicate nonahydrate was dissolved in pure water and diluted to 803 mL. The supported carrier (A-5) obtained in Step 1 was immersed in this and allowed to stand at room temperature for 20 hours to obtain an impregnated carrier (B-5) impregnated with the sodium metasilicate solution. Step 3: 24.9 g of hydrazine monohydrate was added to the slurry of the impregnated carrier (B-5) obtained in Step 2, and the mixture was gently stirred and then allowed to stand at 25°C for 4 hours. The reduced impregnated carrier (B-5) was filtered and transferred to a glass column equipped with a stopcock, and washed by passing pure water through it for 40 hours. Next, it was dried at 110°C for 4 hours under an air stream to obtain a metal-supported carrier (C-5). Step 4: Pure water was added to 52 g of potassium acetate and 7.5 g of copper acetate monohydrate to dissolve them, and the volume was adjusted to 361 mL. The metal-supported carrier (C-5) obtained in Step 3 was added to this and the entire amount was absorbed. Next, it was dried at 110°C for 4 hours under an air stream to obtain a comparative catalyst E for the production of allyl acetate.

[0078] Comparative Example 5: Preparation of Comparative Catalyst F Step 1: 30.3 g of an aqueous solution of sodium chloropalladate adjusted to 19.79% by mass of palladium was diluted with pure water to a total volume of 382 mL. 1 L of the silica carrier was added to this, and the entire amount was absorbed to obtain a supported carrier (A-6). Step 2: 32.1 g of sodium metasilicate nonahydrate was dissolved in pure water and diluted to a total volume of 803 mL. The supported carrier (A-6) obtained in Step 1 was immersed in this and allowed to stand at room temperature for 20 hours to obtain an impregnated carrier (B-6) impregnated with the sodium metasilicate solution. Step 3: 24.4 g of hydrazine monohydrate was added to the slurry of the impregnated carrier (B-6) obtained in Step 2, and the mixture was gently stirred and then allowed to stand at 25°C for 4 hours. The reduced impregnated carrier (B-5) was filtered, transferred to a glass column equipped with a stopcock, and washed by passing pure water through it for 40 hours. Next, drying was carried out under an air stream at 110°C for 4 hours to obtain a metal-supported carrier (C-6). Step 4: Pure water was added to 52 g of potassium acetate and 7.5 g of copper acetate monohydrate to dissolve them, and the volume was adjusted to 361 mL. The metal-supported carrier (C-6) obtained in step 3 was added to this and the entire amount was absorbed. Next, drying was carried out under an air stream at 110°C for 4 hours to obtain a comparative catalyst F for producing allyl acetate.

[0079] (Example 2, Comparative Examples 6 to 10) 10.5 mL of each of Catalyst A and Comparative Catalysts B to F obtained in Example 1 and Comparative Examples 1 to 5 was uniformly diluted with 31.5 mL of silica carrier (bulk specific gravity 473 g / L, water absorption 402 g / L), and then packed into a reaction tube (made of SUS316L, inner diameter 25 mm). A gas mixture with a gas composition of propylene:oxygen:acetic acid:water:nitrogen = 35:6:8.0:23:28.0 (molar ratio) was added at a space velocity of 2070 h under conditions of a reaction temperature of 150°C and a reaction pressure of 0.75 MPaG (gauge pressure). －１ The reaction mixture was introduced at a rate of 1 / 400 psi to react with propylene, oxygen, and acetic acid to obtain allyl acetate. After 150 hours had elapsed since the start of the reaction, the reaction product was analyzed.

[0080] The reaction was analyzed by cooling the entire outlet gas that had passed through the catalyst packed bed, recovering the entire condensed reaction liquid, and analyzing it by gas chromatography. The total amount of uncondensed gas that flowed out during the sampling period was measured, and a portion of it was taken and analyzed by gas chromatography.

[0081] The condensed reaction solution was analyzed as follows. Using the internal standard method, 1 g of 1,4-dioxane was added to 6 g of the reaction solution as an internal standard to prepare an analytical solution, and 0.3 μL of this solution was injected and analyzed under the following conditions: Gas chromatography: GC-14B (Shimadzu Corporation) Detector: FID (H ２ Pressure 60 kPaG, air pressure 60 kPaG) Column: Capillary column TC-WAX (length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm) Carrier gas: Nitrogen gas (flow rate 30 mL / min) Temperature conditions: Detector temperature and vaporization chamber temperature 200°C, column temperature held at 40°C for 10 minutes from the start of analysis, then heated to 130°C at a heating rate of 7°C / min and held at 130°C for 20 minutes, then heated to 200°C at a heating rate of 20°C / min and held at 200°C for 5 minutes

[0082] Analysis of uncondensed gas was performed using the absolute calibration curve method, collecting 100 mL of effluent gas and passing the entire amount through a 2 mL gas sampler attached to the gas chromatograph under the following conditions: Gas chromatograph: GC-14B (Shimadzu Corporation) Column: Unibeads IS 60 / 80 mesh (3 mm diameter x 3 m) Carrier gas: Helium (flow rate 20 mL / min) Temperature conditions: Detector temperature 160°C, vaporizer temperature 150°C, column temperature constant at 145°C Detector: TCD (He pressure 600 kPaG, Current 100 mA)

[0083] The activity of the catalyst was evaluated by the space-time yield (STY), which was calculated as the mass of allyl acetate produced per hour per liter of catalyst volume (unit: g / L-cat hr).

[0084] The selectivity to allyl acetate was calculated using the following formula: Allyl acetate selectivity (based on propylene) (%) = [amount of allyl acetate produced (mol) / amount of propylene consumed (mol)] × 100 The selectivity to carbon dioxide was calculated using the following formula: Carbon dioxide selectivity (based on propylene) (%) = [(amount of carbon dioxide produced (mol) / 3) / amount of propylene consumed (mol)] × 100 The selectivity to other by-products was calculated using the following formula: Other by-product selectivity (based on propylene) (%) = 100 - (allyl acetate selectivity (%) + carbon dioxide selectivity (%))

[0085] The results of Example 2 and Comparative Examples 6 to 10 are shown in Table 1. From Table 1, it can be said that Catalyst A of the Example has higher activity than the catalysts of the Comparative Examples and is a superior catalyst.

[0086]

Claims

1. A catalyst for use in producing allyl acetate using propylene, acetic acid, and oxygen as raw materials, comprising (a) palladium, (b) iridium, (c) at least one element selected from copper, nickel, zinc, and cobalt, and (d) an alkali metal salt, supported on (e) a carrier, in which the amount of (b) iridium is 5.0 to 17.0 parts by mass per 100 parts by mass of (a) palladium.

2. The catalyst for producing allyl acetate according to claim 1, wherein the total amount of (c) at least one element selected from copper, nickel, zinc, and cobalt is 5.0 to 150.0 parts by mass per 100 parts by mass of (a) palladium.

3. The catalyst for producing allyl acetate according to claim 1 or 2, wherein (c) at least one element selected from copper, nickel, zinc and cobalt is at least one element selected from copper and zinc.

4. The catalyst for producing allyl acetate according to claim 1 or 2, wherein the alkali metal salt (d) is at least one selected from potassium acetate, sodium acetate and cesium acetate.

5. The catalyst for producing allyl acetate according to claim 1 or 2, wherein the mass ratio of the total amount of (a) palladium, (b) iridium, (c) at least one element selected from copper, nickel, zinc, and cobalt, and (d) the alkali metal salt is (a):(b):(c):(d)=100:5.0-17.0:5.0-150.0:150-4000.

6. A method for producing allyl acetate using propylene, acetic acid and oxygen as raw materials, which uses the catalyst according to claim 1 or 2.

7. A method for producing a catalyst for producing allyl acetate, comprising the following steps 1 to 4: (a) palladium, (b) iridium, (c) at least one element selected from copper, nickel, zinc, and cobalt, and (d) an alkali metal salt are supported on an (e) support, and the amount of (b) iridium is 5.0 to 17.0 parts by mass per 100 parts by mass of (a) palladium. Step 1: A step of preparing a solution of a palladium-containing compound, an iridium-containing compound, and a compound having at least one element selected from copper, nickel, zinc, and cobalt, and (e) bringing the solution into contact with a carrier to support the palladium-containing compound, the iridium-containing compound, and the compound having at least one element selected from copper, nickel, zinc, and cobalt on the carrier to obtain a supported carrier (A); Step 2: A step of (f) contacting and impregnating the supported carrier (A) obtained in Step 1 with an alkaline solution to obtain an impregnated carrier (B); Step 3: A step of reducing the impregnated carrier (B) obtained in Step 2 to obtain a metal-supported carrier (C); Step 4: A step of (d) supporting an alkali metal salt on the metal-supported carrier (C) obtained in Step 3 8. The method for producing a catalyst for producing allyl acetate according to claim 7, wherein the compound containing at least one element selected from copper, nickel, zinc and cobalt is copper chloride.

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