Method for producing conjugated dienes

Abstract

To provide a method for producing a conjugated diene that can be compactly produced and has sufficient product selectivity in a liquid phase reaction.SOLUTION: In the method for producing a conjugated diene, a catalyst comprising at least one metal selected from the group consisting of groups 8, 9 and 10 of the periodic table supported on a carrier is used, and a monoolefin having 4 or more carbon atoms such as butene is subjected to an oxidative dehydrogenation reaction with an oxygen-containing gas in a liquid phase to produce the corresponding conjugated diene such as 1,3-butadiene.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing conjugated dienes, in which a monoolefin having 4 or more carbon atoms is subjected to an oxidative dehydrogenation reaction with an oxygen-containing gas in a liquid phase using a catalyst to produce the corresponding conjugated diene. [Background technology]

[0002] Conventionally, there has been known a method for producing conjugated dienes corresponding to monoolefins, such as 1,3-butadiene and isoprene, by catalytic oxidative dehydrogenation of monoolefins having 4 or more carbon atoms, such as butene and isopentene, with an oxygen-containing gas.

[0003] For example, Patent Document 1 describes a method for producing conjugated dienes in which a catalytic oxidative dehydrogenation reaction is carried out in a gas phase using a composite oxide catalyst containing molybdenum, bismuth, cobalt, nickel, iron, silica, etc. and having a specific specific surface area, pore distribution, etc., thereby improving the reaction efficiency. Furthermore, Patent Document 2 describes a reaction in which a dehydrogenation reaction of a hydrocarbon is carried out in a gas phase or a liquid phase using a heterogeneous photocatalyst in the absence of oxygen. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-170336 [Patent Document 2] WO2015 / 082159 Brochure Summary of the Invention [Problem to be solved by the invention]

[0005] The production method described in Patent Document 1 is a gas-phase reaction, which requires large equipment. Patent Document 2 also describes a liquid-phase reaction, but the reaction is carried out using a photocatalyst in the absence of oxygen, and the reaction efficiency is not high. To increase the reaction efficiency, it is necessary to add large equipment and continue the reaction for a long time.

[0006] Therefore, an object of the present invention is to provide a method for producing conjugated dienes which does not require large facilities, can be produced in a compact manner, and has a sufficient product selectivity in a liquid phase reaction. [Means for solving the problem]

[0007] The present inventors have found that by using a liquid phase reaction and a specific catalyst, production can be carried out in a compact manner and product selectivity can be increased, leading to the completion of the present invention. That is, the gist of the present invention lies in the following [1] to [8]. [1] A method for producing a conjugated diene by subjecting a monoolefin having 4 or more carbon atoms to an oxidative dehydrogenation reaction with an oxygen-containing gas using a catalyst, wherein the oxidative dehydrogenation reaction is a liquid-phase reaction, and the catalyst is a catalyst comprising a carrier carrying at least one metal selected from the group consisting of Groups 8, 9, and 10 of the periodic table. [2] The method for producing a conjugated diene according to [1], wherein the monoolefin having 4 or more carbon atoms is butene, and the conjugated diene is 1,3-butadiene. [3] The method for producing a conjugated diene according to [2], wherein the butene is 1-butene. [4] The method for producing a conjugated diene according to any one of [1] to [3], wherein the metal comprises palladium and / or iridium. [5] The method for producing a conjugated diene according to any one of [1] to [4], wherein the carrier is the following (1) or (2): (1) An oxide of at least one metal selected from the group consisting of magnesium, aluminum, silicon, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, strontium, yttrium, zirconium, niobium, molybdenum, technetium, silver, cadmium, indium, tin, antimony, barium, lanthanum, hafnium, thallium, tungsten, and rhenium. (2) Activated carbon or activated carbon fiber. [6] The method for producing a conjugated diene according to any one of [1] to [5], wherein the oxidative dehydrogenation reaction is carried out in the presence of a solvent. [7] The method for producing a conjugated diene according to [6], wherein the solvent contains an aromatic hydrocarbon and / or an aliphatic carboxylic acid. [8] The method for producing a conjugated diene according to any one of [1] to [7], wherein the maximum temperature of the oxidative dehydrogenation reaction is within the range of 80°C or higher and 240°C or lower. [Effects of the Invention]

[0008] In this invention, since a liquid phase reaction is carried out, the equipment can be made compact, and by using a specific catalyst in the liquid phase reaction, a sufficient product selectivity can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, an embodiment of the present invention will be described in detail. The present invention relates to a method for producing conjugated dienes, in which a monoolefin having 4 or more carbon atoms is subjected to an oxidative dehydrogenation reaction with an oxygen-containing gas in a liquid phase using a catalyst to produce the corresponding conjugated diene.

[0010] <Monoolefins and conjugated dienes with 4 or more carbon atoms> Examples of the monoolefins having 4 or more carbon atoms include butenes such as 1-butene and 2-butene (cis isomer, trans isomer), pentenes such as 1-pentene, 2-pentene (cis isomer, trans isomer), and isopentene, and examples of the corresponding conjugated dienes include 1,3-butadiene, 1,3-pentadiene, and isoprene.

[0011] <Catalyst> The catalyst used in the present invention is a carrier carrying at least one specific metal (hereinafter sometimes referred to as "specific metal") or an alloy of multiple metals including this specific metal.

[0012] [Specific metal] Examples of the specific metal include metals in Group 8, Group 9, or Group 10 (hereinafter simply referred to as "Group 8," "Group 9," or "Group 10") of the long-form periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). Specific examples of Group 8 metals include iron (Fe), ruthenium (Ru), and osnium (Os). Examples of Group 9 metals include cobalt (Co), rhodium (Rh), and iridium (Ir). Examples of Group 10 metals include nickel (Ni), palladium (Pd), and platinum (Pt). Among these, it is preferable to use one or both of palladium and iridium as the specific metal from the viewpoint of product selectivity.

[0013] [Carrier] The support may be a metal oxide support (1) or a carbon-based support (2). Specific examples include the following. By using these supports, it is possible to obtain a sufficient product selectivity in the liquid-phase reaction. (1) Magnesium, aluminum, silicon, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, strontium, yttrium an oxide of at least one metal selected from the group consisting of tungsten, zirconium, niobium, molybdenum, technetium, silver, cadmium, indium, tin, antimony, barium, lanthanum, hafnium, thallium, tungsten, and rhenium; (2) Activated carbon or activated carbon fiber.

[0014] <Catalyst Preparation Method> Next, a method for preparing the catalyst according to the present invention will be described. First, a carrier or a carrier raw material compound is added to an aqueous solution of a compound containing the specific metal (hereinafter sometimes referred to as a "specific metal compound"), and the carrier or carrier raw material compound is impregnated with the catalyst component compound to support it. In this case, the type of specific metal in the specific metal compound may be one type or two or more types of the specific metals described above. Furthermore, the type of carrier or carrier raw material compound may be one type or two or more types. Next, after separating the solid content, a calcination step is carried out in the atmosphere, and then a reduction step is carried out under predetermined conditions to obtain a catalyst.

[0015] [Specific metal loading rate] The loading rate of the specific metal in this catalyst is not particularly limited, but is preferably 0.5% or more, and more preferably 0.7% or more, based on the total catalyst content. It is also preferably 5.0% or less, and more preferably 3.0% or less. If it is less than 0.5%, sufficient catalytic activity, i.e., sufficient product selectivity, may not be obtained in the liquid-phase reaction. On the other hand, although it may be more than 3.0%, the improvement in catalytic activity commensurate with the loading rate of the specific metal tends to be insufficient, and 3.0% is sufficient.

[0016] [Specific metal compounds] The specific metal compound is a compound containing the specific metal. When the specific metal is iron, examples of the compound include iron chloride, iron bromide, iron fluoride, iron nitrate, iron sulfate, iron oxalate, iron acetate, iron hydroxide, iron carbonate, and ammonium iron sulfate. When the specific metal is ruthenium, examples of the compound include ruthenium chloride. When the specific metal is osnium, examples of the compound include osnium chloride. When the specific metal is cobalt, examples of the compound include cobalt chloride, cobalt bromide, cobalt fluoride, cobalt nitrate, cobalt sulfate, cobalt oxalate, cobalt acetate, cobalt hydroxide, cobalt carbonate, and ammonium cobalt sulfate. When the specific metal is rhodium, examples of the compound include rhodium chloride and rhodium nitrate. When the specific metal is iridium, examples of the compound include iridium chloride. When the specific metal is nickel, examples of the compound include nickel chloride, nickel bromide, nickel fluoride, nickel iodide, nickel nitrate, nickel sulfate, nickel oxalate, nickel acetate, nickel hydroxide, nickel carbonate, and nickel ammonium sulfate. When the specific metal is palladium, examples of the compound include palladium chloride and palladium nitrate. When the specific metal is platinum, examples of the compound include platinum chloride, hexachloroplatinic acid, dichlorodiamine platinum, and dinitrodiamine platinum.

[0017] [Support raw material compound] The carrier raw material compound refers to a compound that becomes the metal oxide carrier by calcination when a metal oxide is used as the carrier. Examples of such compounds include hydroxides of the respective metals and other compounds. Specific examples include magnesium hydroxide, aluminum hydroxide, titanium hydroxide, vanadium hydroxide, chromium hydroxide, manganese hydroxide, iron hydroxide, cobalt hydroxide, nickel hydroxide, copper hydroxide, zinc hydroxide, gallium hydroxide, germanium hydroxide, strontium hydroxide, yttrium hydroxide, zirconium hydroxide, niobium hydroxide, molybdenum hydroxide, technetium hydroxide, silver hydroxide, cadmium hydroxide, indium hydroxide, tin hydroxide, antimony hydroxide, barium hydroxide, lanthanum hydroxide, hafnium hydroxide, thallium hydroxide, tungsten hydroxide, and rhenium hydroxide. Specific examples of other compounds include titanium isopropoxide, titanium butoxide, zirconium propoxide, alkoxides such as tetraethoxysilane, etc.

[0018] This carrier raw material compound can be converted into a metal oxide carrier by carrying out the calcination step after the specific metal compound is loaded. Alternatively, the carrier raw material compound may be calcined before the specific metal compound is loaded into the carrier to convert into a metal oxide carrier. The calcination conditions can be the same as those for the calcination step described below.

[0019] [Firing process] The calcination step refers to a high-temperature heat treatment in the atmosphere using a furnace such as a muffle furnace. The calcination conditions include, for example, a temperature of 300°C to 600°C and a time of 1 hour to 6 hours. When a carrier raw material compound is used, this can be converted into a metal oxide carrier, and a calcined body can be obtained in which a specific metal compound is supported on the carrier. When a carrier itself is used instead of a carrier raw material compound, a calcined body can be obtained in which a specific metal compound is supported on the carrier.

[0020] [Reduction process] The reduction step involves filling a furnace such as a tubular furnace with the calcined product obtained in the calcination step, and reducing the product at high temperature while passing a mixed gas containing a reducing agent such as hydrogen through it. Reduction conditions include, for example, a temperature of 200°C to 400°C for 30 minutes to 3 hours. This allows the compound containing the specific metal to be converted into the specific metal itself, which can then be used as a catalyst.

[0021] The mixed gas can be a gas obtained by mixing a reducing agent such as hydrogen with a predetermined amount of inert gas. Examples of the inert gas include nitrogen and noble gases such as helium, neon, argon, krypton, and xenon. The content of the reducing agent (hydrogen) in the mixed gas is sufficient if it is 5% by volume or more and 20% by volume or less, based on the total volume of the reducing agent (hydrogen) and the inert gas. The amount of the mixed gas passed through the firing furnace should be 10 ml / min or more and 100 ml / min or less, and preferably 30 ml / min or more and 70 ml / min or less.

[0022] <Oxidative dehydrogenation reaction> In the present invention, the catalyst is used to carry out an oxidative dehydrogenation reaction of a monoolefin having 4 or more carbon atoms with an oxygen-containing gas in a liquid phase, thereby producing the corresponding conjugated diene. Specifically, the catalyst is used to dissolve the monoolefin having 4 or more carbon atoms in a solvent under pressure and heat, and the reaction is carried out in the liquid phase. Because the reaction is carried out in the liquid phase, it is possible to make the equipment more compact.

[0023] [solvent] Examples of the solvent include aromatic hydrocarbons, aliphatic carboxylic acids and their esters, alcohols, ethers, etc. These may be used alone or in combination. The use of these solvents can prevent the deposition of organic matter on the catalyst surface and exhibit the characteristic of maintaining catalytic performance for a long period of time. Specific examples of the aromatic hydrocarbon include benzene, toluene, o-xylene, m-xylene, p-xylene, naphthalene, and biphenyl. Specific examples of the aliphatic carboxylic acid include formic acid, acetic acid, acetic anhydride, propionic acid, butyric acid, valeric acid, lauric acid, tridecylic acid, palmitic acid, stearic acid, acrylic acid, methacrylic acid, oleic acid, linoleic acid, linolenic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid. Specific examples of the esters of the aliphatic carboxylic acids include ethyl formate and ethyl acetate. can be done. Specific examples of the alcohol include methanol, ethanol, propanol, butanol, ethylene glycol, glycerin, and benzyl alcohol. Specific examples of the ether include dimethyl ether, ethyl methyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, furan, benzofuran, and tetrahydropyran.

[0024] [Reaction flow] Specific examples of the oxidative dehydrogenation reaction according to the present invention are described below. First, the solvent and catalyst are placed in a high-temperature, high-pressure reactor and sealed. This high-temperature, high-pressure reactor is equipped with a pressure gauge, gas inlet / outlet pipes, an internal temperature sensor, and a stirring blade, allowing gas inlet / outlet, pressure, temperature measurement, etc. Then, the raw material monoolefin having 4 or more carbon atoms, air, and an inert gas are introduced to adjust the pressure to a predetermined level. Examples of the inert gas include nitrogen, helium, and neon. Next, the temperature of the high-temperature, high-pressure reactor is gradually increased and maintained at a predetermined temperature. This allows the oxidative dehydrogenation reaction to proceed. After a predetermined time has passed, the reactor is cooled, and the gas is recovered from the gas inlet / outlet pipes of the high-temperature, high-pressure reactor, allowing the reaction product to be recovered.

[0025] [Pressure during oxidative dehydrogenation reaction] The pressure in the oxidative dehydrogenation reaction of the present invention is preferably 8 bar or more, and more preferably 10 bar or more, and is preferably 20 bar or less, and more preferably 17 bar or less. By setting the pressure within this range, sufficient product selectivity can be obtained in the liquid phase reaction. This pressure can be set by the amount of the monoolefin having 4 or more carbon atoms as the raw material, the amount of air and the inert gas introduced into the reaction vessel, and the reaction temperature. If a sufficient pressure is not obtained, the pressure can be adjusted by adding the inert gas.

[0026] [Maximum temperature in oxidative dehydrogenation reaction] The maximum temperature in the oxidative dehydrogenation reaction of the present invention is preferably 80°C or higher, and more preferably 130°C or higher. If the temperature is lower than 80°C, the reaction rate may be slow in the liquid phase reaction, and the product selectivity may decrease. The upper limit of the reaction temperature is preferably 240°C or lower, and more preferably 220°C or lower. If the temperature is higher than 240°C, decomposition of the raw materials and side reactions may occur easily in the liquid phase reaction, and the product selectivity may decrease.

[0027] [Oxidative dehydrogenation reaction time] The time for the oxidative dehydrogenation reaction of the present invention is preferably 6 hours or more, and more preferably 7 hours or more, and is preferably 200 hours or less, and more preferably 150 hours or less. By setting the time within this range, sufficient product selectivity can be obtained in the liquid phase reaction. [Example]

[0028] The present invention will be explained in more detail below by way of examples, but the present invention is not limited to the following examples in any way as long as it does not depart from the gist of the invention.

[0029] The butene conversion, 1,3-butadiene selectivity, and 1,3-butadiene yield in the oxidative dehydrogenation reaction are defined as follows, and were determined by gas chromatography analysis of the gas obtained by the oxidative dehydrogenation reaction. Butene conversion rate (%) = {1 - {(amount of butene remaining after reaction) / (amount of butene introduced)}} × 100

[0030] 1,3-Butadiene selectivity (%) when using 1-butene = [(amount of 1,3-butadiene produced) × 4 / {(amount of 1,3-butadiene produced) × 4 + (amount of 2-butene produced) × 4 + (amount of isobutene produced) × 4 + (amount of methane produced) + (amount of ethylene produced) × 2 + (amount of propane produced) × 3 + (amount of CO2 produced)}] × 100 1,3-Butadiene selectivity (%) when using 2-butene = [(amount of 1,3-butadiene produced) × 4 / {(amount of 1,3-butadiene produced) × 4 + (amount of 1-butene produced) × 4 + (amount of isobutene produced) × 4 + (amount of methane produced) + (amount of ethylene produced) × 2 + (amount of propane produced) × 3 + (amount of CO2 produced)}] × 100 1,3-Butadiene yield (%) = {(butene conversion (%)) × (1,3-butadiene selectivity (%))} / 100

[0031] [raw materials] (Specific metal compounds) Palladium chloride...Sigma Aldrich Iridium chloride…Alfa Aesar Hexachloroplatinic acid...Sigma Aldrich

[0032] (Carrier or carrier raw material compound) Zirconium hydroxide...Chemieliva Titanium isopropoxide...Lancaster Titanium oxide…manufactured by Degussa Silica...Evonik Activated carbon...Cabot

[0033] <Preparation of Catalyst A> Palladium chloride was impregnated into zirconium hydroxide so that the palladium loading was 1%, to prepare a catalyst support. The catalyst support was introduced into a muffle furnace and calcined in the atmosphere at 500°C for 4 hours to produce a calcined catalyst. The calcination converted the zirconium hydroxide into zirconium oxide. The calcined catalyst was then loaded into a tubular calcination furnace and subjected to reduction treatment at 300°C for 1 hour while a mixed gas (volume ratio of hydrogen:argon = 1:9) was passed through at a rate of 50 ml / min to obtain catalyst A.

[0034] <Preparation of Catalyst B> Zirconium hydroxide was heated at 500° C. for 4 hours to form zirconium oxide, which was then impregnated with palladium chloride to provide a palladium loading of 1%, to form a catalyst support. The catalyst support was introduced into a muffle furnace and calcined in air at 300°C for 4 hours to obtain a calcined catalyst. The calcined catalyst was then loaded into a tubular calcination furnace and reduced at 300°C for 1 hour while flowing a mixed gas (volume ratio of hydrogen:argon = 1:9) at a rate of 50 ml / min to obtain catalyst B.

[0035] <Preparation of catalyst C> Titanium-containing zirconium oxide was obtained by impregnating zirconium hydroxide with titanium isopropoxide so that the titanium content was 4%, and then heating at 500°C for 4 hours. Palladium chloride was impregnated and supported on the titanium-containing zirconium oxide so that the palladium loading was 1%, to obtain a catalyst support. The catalyst support was introduced into a muffle furnace and calcined in air at 300°C for 4 hours to obtain a calcined catalyst. The calcined catalyst was then loaded into a tubular calcination furnace and reduced at 300°C for 1 hour while a mixed gas (volume ratio of hydrogen:argon = 1:9) was passed through at a rate of 50 ml / min to obtain catalyst C.

[0036] <Preparation of Catalyst D> Titanium oxide was impregnated with palladium chloride so that the palladium loading rate was 1%, to prepare a catalyst support. The catalyst support was introduced into a muffle furnace and calcined in air at 300°C for 4 hours to obtain a calcined catalyst. The calcined catalyst was then loaded into a tubular calcination furnace and reduced at 300°C for 1 hour while a mixed gas (volume ratio of hydrogen:argon = 1:9) was passed through at a rate of 50 ml / min to obtain catalyst D.

[0037] <Preparation of Catalyst E> Silica was impregnated with palladium chloride so that the palladium loading was 1%, to prepare a catalyst support. The catalyst support was introduced into a muffle furnace and calcined in air at 300°C for 4 hours to obtain a calcined catalyst. The calcined catalyst was then loaded into a tubular calcination furnace and reduced at 300°C for 1 hour while a mixed gas (volume ratio of hydrogen:argon = 1:9) was passed through at a rate of 50 ml / min to obtain catalyst E.

[0038] <Preparation of Catalyst F> Activated carbon was impregnated with palladium chloride so that the palladium loading was 3%, to prepare a catalyst support. The catalyst support was introduced into a muffle furnace and calcined in air at 300°C for 4 hours to obtain a calcined catalyst. The calcined catalyst was then loaded into a tubular calcination furnace and reduced at 300°C for 1 hour while a mixed gas (volume ratio of hydrogen:argon = 1:9) was passed through at a rate of 50 ml / min to obtain catalyst F.

[0039] <Preparation of Catalyst G> Silica was impregnated with palladium chloride so that the palladium loading rate was 1% and with iridium chloride so that the iridium loading rate was 1%, to prepare a catalyst support. The catalyst support was introduced into a muffle furnace and calcined in air at 300°C for 4 hours to obtain a calcined catalyst. The calcined catalyst was then loaded into a tubular calcination furnace and reduced at 300°C for 1 hour while a mixed gas (volume ratio of hydrogen:argon = 1:9) was passed through at a rate of 50 ml / min to obtain catalyst G.

[0040] <Preparation of catalyst H> Silica was impregnated with iridium chloride so that the iridium loading was 1%, to prepare a catalyst support. The catalyst support was introduced into a muffle furnace and calcined in air at 300°C for 4 hours to obtain a calcined catalyst. The calcined catalyst was then packed into a tubular calcination furnace and reduced at 300°C for 1 hour while a mixed gas (volume ratio of hydrogen:argon = 1:9) was passed through at a rate of 50 ml / min to obtain catalyst H.

[0041] <Preparation of Catalyst I> Silica was impregnated with palladium chloride so that the palladium loading rate was 1% and with hexachloroplatinic acid so that the platinum loading rate was 0.33% to prepare a catalyst support. The catalyst support was introduced into a muffle furnace and calcined in air at 300°C for 4 hours to obtain a calcined catalyst. The calcined catalyst was then loaded into a tubular calcination furnace and reduced at 300°C for 1 hour while a mixed gas (volume ratio of hydrogen:argon = 1:9) was passed through at a rate of 50 ml / min to obtain Catalyst I.

[0042] <Preparation of Catalyst J> Silica was impregnated with hexachloroplatinic acid so that the platinum loading was 1%, to prepare a catalyst support. The catalyst support was introduced into a muffle furnace and calcined in the atmosphere at 300°C for 4 hours to obtain a calcined catalyst. The calcined catalyst was then filled into a tubular calcination furnace and mixed with a gas mixture (volume ratio: water The catalyst was subjected to reduction treatment at 300° C. for 1 hour while passing nitrogen:argon (1:9) through the catalyst at a rate of 50 ml / min, to obtain catalyst J.

[0043] [Example 1] <Liquid-phase oxidative dehydrogenation of 1-butene> 50 ml of toluene and 500 mg of catalyst A were placed in a high-temperature, high-pressure reaction vessel (internal volume 300 ml) equipped with a pressure gauge, gas inlet / outlet pipes, an internal temperature sensor, and a stirring blade, and the vessel was sealed. While stirring with the stirring blade at 250 rpm, a mixed gas (volume ratio of 1-butene:nitrogen = 1:9) was introduced through the inlet / outlet pipe to adjust the internal pressure to 3.4 bar. Next, air was introduced through the inlet / outlet pipe to adjust the internal pressure to 6.0 bar. Nitrogen was then introduced through the inlet / outlet pipe to adjust the internal pressure to 10.5 bar.

[0044] The internal temperature of the high-temperature, high-pressure reactor was raised at a rate of 10°C / min using a heater and maintained at 150°C, whereupon the liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out for 6.2 hours. The high-temperature, high-pressure reactor was then cooled with ice water prepared in advance. After the internal temperature of the high-temperature, high-pressure reactor reached 25°C, a gas collection bag was connected to the gas inlet / outlet piping, and the gas inside the high-temperature, high-pressure reactor was collected. The results are shown in Table 1.

[0045] [Example 2] The liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 1, except that the liquid-phase oxidative dehydrogenation reaction time of 1-butene was changed to 72.2 hours. The results are shown in Table 1.

[0046] [Example 3] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 1, except that 1000 mg of catalyst A was charged into the high-temperature, high-pressure reactor and the reaction time was 112.2 hours. The results are shown in Table 1.

[0047] [Example 4] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 1, except that 2000 mg of catalyst A was charged into the high-temperature, high-pressure reactor and the reaction time was 72.2 hours. The results are shown in Table 1.

[0048] [Example 5] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 1, except that the catalyst A charged into the high-temperature, high-pressure reactor was changed to catalyst B. The results are shown in Table 1.

[0049] [Example 6] The liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 5, except that the liquid-phase oxidative dehydrogenation reaction time of 1-butene was changed to 72.2 hours. The results are shown in Table 1.

[0050] [Example 7] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 5, except that 4000 mg of catalyst B was charged into the high-temperature, high-pressure reaction vessel and the reaction time was 72.2 hours. The results are shown in Table 1.

[0051] [Example 8] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 1, except that the catalyst A charged into the high-temperature, high-pressure reactor was changed to catalyst C. The results are shown in Table 1.

[0052] [Example 9] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 8, except that the reaction time was changed to 72.2 hours. The results are shown in Table 1.

[0053] [Example 10] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 1, except that the catalyst A charged into the high-temperature, high-pressure reactor was changed to catalyst D. The results are shown in Table 1.

[0054] [Example 11] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 10, except that the reaction time was changed to 72.2 hours. The results are shown in Table 1.

[0055] [Example 12] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 1, except that 25 ml of toluene was charged into the high-temperature, high-pressure reactor and catalyst A was changed to catalyst E. The results are shown in Table 1.

[0056] [Example 13] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 12, except that 150 ml of toluene was charged into the high-temperature, high-pressure reactor and the reaction time was set to 72.2 hours. The results are shown in Table 1.

[0057] [Example 14] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 12, except that 25 ml of toluene and 25 ml of acetic acid were charged into the high-temperature, high-pressure reactor. The results are shown in Table 1.

[0058] [Example 15] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 12, except that 50 ml of toluene and 15.13 g of naphthalene were charged into a high-temperature, high-pressure reactor and the naphthalene was dissolved in toluene to prepare a solution. The results are shown in Table 1.

[0059] [Example 16] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 12, except that 50 ml of toluene and 18.2 g of biphenyl were charged into a high-temperature, high-pressure reactor and the biphenyl was dissolved in toluene to form a solution. The results are shown in Table 1.

[0060] [Example 17] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 12, except that 50 ml of acetic acid and 18.2 g of biphenyl were charged into a high-temperature, high-pressure reactor and the biphenyl was dissolved in acetic acid to prepare a solution. The results are shown in Table 1.

[0061] [Example 18] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 12, except that 25 ml of acetic acid and 25 ml of acetic anhydride were charged into the high-temperature, high-pressure reactor. The results are shown in Table 1.

[0062] [Example 19] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 12, except that 50 ml of ethyl acetate was added to the high-temperature, high-pressure reactor. The results are shown in Table 1.

[0063] [Example 20] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 12, except that 25 ml of acetic acid and 25 ml of cyclohexane were charged into the high-temperature, high-pressure reactor. The results are shown in Table 1.

[0064] [Example 21] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 1, except that Catalyst A was changed to Catalyst F. The results are shown in Table 1.

[0065] [Example 22] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 21, except that the reaction time was changed to 72.2 hours. The results are shown in Table 1.

[0066] [Example 23] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 1, except that Catalyst A was changed to Catalyst G. The results are shown in Table 1.

[0067] [Example 24] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 1, except that Catalyst A was changed to Catalyst H. The results are shown in Table 1.

[0068] [Example 25] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 1, except that Catalyst A was changed to Catalyst I. The results are shown in Table 1.

[0069] [Example 26] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 1, except that Catalyst A was changed to Catalyst J. The results are shown in Table 1.

[0070] [Example 27] <Liquid-phase oxidative dehydrogenation of trans-2-butene> A liquid-phase oxidative dehydrogenation reaction of trans-2-butene was carried out in the same manner as in Example 1, except that 1-butene was changed to trans-2-butene. The results are shown in Table 1.

[0071] [Example 28] The liquid-phase oxidative dehydrogenation reaction of trans-2-butene was carried out in the same manner as in Example 27, except that the liquid-phase oxidative dehydrogenation reaction time of trans-2-butene was changed to 72.2 hours. The results are shown in Table 1.

[0072] [Example 29] A liquid-phase oxidative dehydrogenation reaction of trans-2-butene was carried out in the same manner as in Example 27, except that the catalyst A charged into the high-temperature, high-pressure reactor was changed to catalyst B. The results are shown in Table 1.

[0073] [Example 30] The liquid-phase oxidative dehydrogenation reaction of trans-2-butene was carried out in the same manner as in Example 29, except that the liquid-phase oxidative dehydrogenation reaction time of trans-2-butene was changed to 72.2 hours. The results are shown in Table 1.

[0074] [Example 31] A liquid-phase oxidative dehydrogenation reaction of trans-2-butene was carried out in the same manner as in Example 29, except that 25 ml of toluene and 25 ml of acetic acid were charged into the high-temperature, high-pressure reaction vessel. The results are shown in Table 1.

[0075] [Comparative Example 1] A liquid-phase oxidative dehydrogenation reaction of 1-butene was carried out in the same manner as in Example 14, except that no catalyst was charged into the high-temperature, high-pressure reactor. The results are shown in Table 1.

[0076] Comparative Example 2 A liquid-phase oxidative dehydrogenation reaction of trans-2-butene was carried out in the same manner as in Example 31, except that no catalyst was charged into the high-temperature, high-pressure reactor. The results are shown in Table 1.

[0077] [Table 1]

Claims

1. A method for producing a corresponding conjugated diene by subjecting a monoolefin having 4 or more carbon atoms to an oxidative dehydrogenation reaction with an oxygen-containing gas using a catalyst, comprising: the oxidative dehydrogenation reaction is a liquid phase reaction, The oxidative dehydrogenation reaction is carried out in the presence of a solvent, The solvent contains one or more selected from the group consisting of aromatic hydrocarbons, aliphatic carboxylic acids and esters thereof, and The method for producing conjugated dienes, wherein the catalyst is a catalyst comprising at least one metal selected from the group consisting of Groups 9 and 10 of the periodic table supported on a carrier made of an oxide of at least one metal selected from the group consisting of zirconium, titanium, and silicon, or activated carbon.

2. 2. The method for producing a conjugated diene according to claim 1, wherein the monoolefin having 4 or more carbon atoms is butene, and the conjugated diene is 1,3-butadiene.

3. The method for producing a conjugated diene according to claim 2, wherein the butene is 1-butene.

4. The method for producing a conjugated diene according to any one of claims 1 to 3, wherein the metal comprises palladium and / or iridium.

5. The method for producing a conjugated diene according to any one of claims 1 to 4, wherein the maximum temperature of the oxidative dehydrogenation reaction is in the range of 80°C or higher and 240°C or lower.

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