Catalyst for hydrogenation reaction, dehydrogenation reaction or isomerization reaction, and method for producing same

Abstract

The present invention provides a catalyst which exhibits excellent heat resistance and which exhibits high activity as a catalyst for a hydrogenation reaction, without containing chromium. The present invention is a catalyst which is for a hydrogenation reaction, a dehydrogenation reaction, or an isomerization reaction and which contains copper, zinc and aluminum as constituent metal elements and can be used in any of a hydrogenation reaction, a dehydrogenation reaction or an isomerization reaction, the catalyst being characterized in that in the catalyst, the content ratio of copper element is 35-70 mass% in terms of copper (II) oxide relative to 100 mass% of the catalyst, the content ratio of zinc element is 25-60 mass% in terms of zinc oxide relative to 100 mass% of the catalyst, the content ratio of aluminum element is 1.5-25 mass% in terms of aluminum oxide relative to 100 mass% of the catalyst, the content ratio of zirconium oxide is 3.0 mass% or less relative to 100 mass% of the catalyst, and the content ratio of sulfur element is 0.1-1.0 mass% in terms of sulfur trioxide relative to 100 mass% of the catalyst.

Description

Catalyst for hydrogenation, dehydrogenation or isomerization reaction and method for producing the same

[0001] The present invention relates to a catalyst for hydrogenation, dehydrogenation or isomerization, and a method for producing the same.

[0002] Fatty alcohols are important intermediate raw materials in the chemical industry and are used as raw materials for surfactants and other products. These fatty alcohols are produced by catalytically hydrogenating fatty acid esters obtained from natural fats and oils under high pressure. Copper-based catalysts, particularly copper-chromium catalysts, have traditionally been used for hydrogenation reactions. While copper-chromium catalysts have excellent performance, the harmful effects of chromium have led to the development of chromium-free catalysts. Generally, chromium as a catalytic component is known to impart heat resistance to catalysts and stabilize the catalyst structure. Previously, chromium-free catalysts for hydrogenation reactions have been disclosed, including a catalyst obtained by calcining a copper compound, a zinc compound, and at least one compound selected from the group consisting of aluminum, zirconium, magnesium, rare earth elements, and mixtures thereof at a temperature of 200°C to 400°C (see Patent Document 1), and a catalyst containing copper oxide, zinc oxide, aluminum oxide, and sodium oxide in specified proportions, having a specified surface area, and whose surface is formed by pores of specified sizes (see Patent Document 2).

[0003] Special Publication No. 10-508531 Publication No. 07-116518

[0004] There is a demand for a switch from conventional copper-chromium catalysts to chromium-free copper catalysts for the hydrogenation of aliphatic alkyl esters. However, chromium-free copper catalysts tend to have reduced activity due to a decrease in specific surface area caused by insufficient heat resistance, and therefore there is a demand for the development of catalysts with better catalytic activity and heat resistance.

[0005] In view of the above-mentioned current situation, an object of the present invention is to provide a catalyst which does not contain chromium and which exhibits high activity as a catalyst for hydrogenation reactions and also has excellent heat resistance.

[0006] The present inventors have investigated catalysts that exhibit high catalytic activity in hydrogenation reactions without containing chromium and that also have excellent heat resistance, and have found that a catalyst containing copper, zinc, and aluminum as constituent metal elements in specified proportions, with a zirconium oxide content of not more than a specified proportion, when further containing a sulfur-containing component, results in a catalyst that exhibits high catalytic activity in hydrogenation reactions and has high heat resistance. The present inventors have also found that this catalyst can also be used as a catalyst for dehydrogenation reactions and isomerization reactions, and have completed the present invention.

[0007] That is, the present invention is as follows: [1] A catalyst for use in any one of a hydrogenation reaction, a dehydrogenation reaction, or an isomerization reaction, containing copper, zinc, and aluminum as constituent metal elements, wherein the content of elemental copper in the catalyst is 35 to 70 mass% relative to 100 mass% of the catalyst in terms of copper (II) oxide, the content of elemental zinc in terms of zinc oxide is 25 to 60 mass% relative to 100 mass% of the catalyst in terms of zinc oxide, and the content of elemental aluminum in terms of aluminum oxide is 1.5 to 25 mass% relative to 100 mass% of the catalyst, the content of zirconium oxide is 3.0 mass% or less relative to 100 mass% of the catalyst, and the content of elemental sulfur in terms of sulfur trioxide is 0.1 to 1.0 mass% relative to 100 mass% of the catalyst.

[0008] [2] The catalyst for hydrogenation, dehydrogenation, or isomerization according to [1], characterized in that the catalyst exhibits a maximum thermal weight loss rate per hour of 0.15% / min or more in the temperature range of 135°C to 180°C in differential thermogravimetry.

[0009] [3] The catalyst for hydrogenation, dehydrogenation or isomerization according to [1] or [2], further comprising 0.08 to 5.0 mass% of a Group 2 element of the periodic table, based on 100 mass% of the catalyst.

[0010] [4] The catalyst is L ＊ a ＊ b ＊ L in color system ＊ Value 0≦L ＊ ≦20, and a ＊ The value is 0≦a ＊The catalyst for hydrogenation, dehydrogenation or isomerization according to any one of [1] to [3],

[0011] [5] The catalyst for hydrogenation, dehydrogenation, or isomerization according to any one of [1] to [4], further comprising 0.1 to 3.0 mass% of zirconium element in terms of zirconium oxide relative to 100 mass% of the catalyst.

[0012] [6] The catalyst for hydrogenation, dehydrogenation, or isomerization according to any one of [1] to [5], further comprising sodium element in an amount of 0.03 to 1.0% by mass relative to 100% by mass of the catalyst in terms of sodium.

[0013] [7] The catalyst for hydrogenation, dehydrogenation, or isomerization according to any one of [1] to [6], further comprising 0.5 to 4.5 mass% of magnesium element in terms of magnesium oxide relative to 100 mass% of the catalyst.

[0014] [8] The catalyst for hydrogenation, dehydrogenation, or isomerization reactions according to any one of [1] to [7], further comprising 0.1 to 10 mass% of silicon element in terms of silicon oxide relative to 100 mass% of the catalyst.

[0015] [9] The catalyst for hydrogenation, dehydrogenation, or isomerization according to any one of [1] to [8], characterized in that it is used in a methanol synthesis reaction.

[0016]

[10] A method for producing a catalyst for hydrogenation, dehydrogenation or isomerization containing copper, zinc and aluminum as constituent metal elements, the method comprising: a mixing step of mixing an aqueous solution containing copper sulfate, zinc sulfate and aluminum sulfate with an aqueous solution of carbonate and / or hydrogencarbonate; and a water washing step of washing the precipitate obtained in the mixing step with water until the filtrate has an electrical conductivity of 50 mS / m or less.

[0017]

[11] The method for producing a catalyst for hydrogenation, dehydrogenation or isomerization according to

[10] , wherein the carbonate and / or hydrogencarbonate is a sodium salt.

[0018]

[12] A method for producing a carboxylic acid, an alcohol, a diol, an amine, or carbon monoxide, comprising a step of reacting an unsaturated hydrocarbon compound and / or a heteroatom-containing compound with a hydrogen-containing gas in the presence of the catalyst for hydrogenation, dehydrogenation, or isomerization according to any one of [1] to [9].

[0019] The catalyst for hydrogenation, dehydrogenation or isomerization of the present invention does not contain toxic chromium and exhibits high catalytic activity for hydrogenation, dehydrogenation or isomerization, and also has excellent heat resistance, making it useful as a catalyst for these reactions.

[0020] Preferred embodiments of the present invention will be specifically described below, but the present invention is not limited to the following description and can be appropriately modified and applied within the scope that does not change the gist of the present invention.

[0021] 1. Catalyst for Hydrogenation, Dehydrogenation, or Isomerization Reactions The catalyst for hydrogenation, dehydrogenation, or isomerization reaction of the present invention (hereinafter also referred to as the catalyst of the present invention) contains copper, zinc, and aluminum as constituent metal elements, characterized in that the copper content in the catalyst is 35 to 70 mass% relative to 100 mass% of the catalyst in terms of copper(II) oxide, the zinc content is 25 to 60 mass% relative to 100 mass% of the catalyst in terms of zinc oxide, the aluminum content is 1.5 to 25 mass% relative to 100 mass% of the catalyst in terms of aluminum oxide, the zirconium oxide content is 3.0 mass% or less relative to 100 mass% of the catalyst, and the sulfur content is 0.1 to 1.0 mass% relative to 100 mass% of the catalyst in terms of sulfur trioxide. By containing copper, zinc, aluminum, and sulfur in these proportions, the catalyst of the present invention exhibits high catalytic activity and also has excellent heat resistance. Furthermore, by containing copper and zinc in these proportions, copper oxide and zinc oxide can be in a crystalline state with excellent activity and durability. Furthermore, zirconium oxide is hard and has excellent heat resistance when used in a catalyst, but catalysts containing zirconium oxide may damage the equipment used to manufacture and use the catalyst. However, the catalyst of the present invention has a low zirconium oxide content, so that the production of the catalyst of the present invention and the reaction using the catalyst of the present invention can proceed without damaging the equipment.

[0022] The catalyst of the present invention may have the constituent elements in the above-described proportions. However, the copper content, calculated as copper(II) oxide, is preferably 35 to 70 mass% relative to 100 mass% of the catalyst. More preferably, it is 40 to 67.5 mass%, and even more preferably, it is 45 to 65 mass%. The zinc content, calculated as zinc oxide, is preferably 25 to 60 mass% relative to 100 mass% of the catalyst. More preferably, it is 26.5 to 55 mass%, and even more preferably, it is 28 to 50 mass%. The aluminum content, calculated as aluminum oxide, is preferably 1.5 to 25 mass% relative to 100 mass% of the catalyst. More preferably, it is 1.75 to 20 mass%, and even more preferably, it is 2.0 to 15 mass%. The sulfur content, calculated as sulfur trioxide, is preferably 0.1 to 1.0 mass% relative to 100 mass% of the catalyst. More preferably, it is 0.12 to 0.9 mass%, and even more preferably, it is 0.15 to 0.8 mass%. The content of zirconium oxide is preferably 3.0 mass% or less, more preferably 2.5 mass% or less, and even more preferably 2.0 mass% or less, relative to 100 mass% of the catalyst. The contents of these elements and compounds contained in the catalyst of the present invention can be measured by the method described in the examples below.

[0023] The catalyst of the present invention is preferably one that, in differential thermogravimetry, exhibits a maximum rate of thermal weight loss per hour of 0.15% / min or more in the range of 135°C to 180°C. If such requirements are satisfied, the catalyst will be more excellent in hydrogenation reactions, dehydrogenation reactions, and isomerization reactions. The maximum rate of thermal weight loss per hour in the range of 135°C to 180°C is more preferably 0.16% / min or more, and even more preferably 0.18% / min or more. Differential thermogravimetry of the catalyst of the present invention can be carried out by the method described in the Examples below.

[0024] The catalyst of the present invention preferably further contains a Group 2 element of the periodic table in an amount of 0.08 to 5.0 mass% relative to 100 mass% of the catalyst. The inclusion of a Group 2 element of the periodic table provides the catalyst with superior heat resistance. The content of the Group 2 element of the periodic table is more preferably 0.09 to 3.0 mass%, and even more preferably 0.10 to 1.0 mass%, relative to 100 mass% of the catalyst. As the Group 2 element of the periodic table, one or more of magnesium, calcium, strontium, barium, and the like can be used. As the Group 2 element of the periodic table, magnesium and calcium are preferred. The content of the Group 2 element of the periodic table contained in the catalyst of the present invention can be measured by the method described in the Examples below.

[0025] When the catalyst of the present invention contains magnesium as a Group 2 element of the periodic table, it preferably contains 0.5 to 4.5 mass% of magnesium oxide equivalent relative to 100 mass% of the catalyst. The inclusion of magnesium increases catalytic activity. The magnesium content, relative to 100 mass% of the catalyst, is more preferably 1.0 to 4.0 mass%, even more preferably 1.5 to 3.5 mass%, and particularly preferably 1.5 to 2.5 mass%, relative to 100 mass% of the catalyst, in terms of magnesium oxide.

[0026] The catalyst of the present invention is L ＊ a ＊ b ＊ L in color system ＊ Value 0≦L ＊ ≦20, and a ＊ The value is 0≦a ＊ It is preferable that the catalyst of the present invention is such L ＊ Value, a ＊ If the catalyst satisfies the requirements of the L value, the copper oxide and zinc oxide will be in a crystalline state with excellent activity and durability, and the catalyst will be more excellent in hydrogenation reactions, dehydrogenation reactions, or isomerization reactions. ＊ a ＊ b ＊ L in color system ＊ The value is more preferably 1≦L ＊ ≦19, and more preferably 2≦L ＊ ≦18. ＊ The value is more preferably 0.05≦a＊ and more preferably, 0.1≦a ＊ The L of the catalyst of the present invention ＊ a ＊ b ＊ L in color system ＊ Value, a ＊ The value can be measured by the method described in the Examples below.

[0027] The catalyst of the present invention preferably further contains 0.03 to 1.0 mass% of sodium element, calculated as sodium, relative to 100 mass% of the catalyst. The inclusion of sodium element provides the catalyst with superior heat resistance. The sodium element content is more preferably 0.06 to 0.9 mass%, and even more preferably 0.09 to 0.8 mass%, calculated as sodium, relative to 100 mass% of the catalyst. The sodium element content in the catalyst of the present invention can be measured by the method described in the examples below.

[0028] The catalyst of the present invention preferably further contains 0.1 to 10 mass% of silicon element, calculated as silicon oxide, relative to 100 mass% of the catalyst. The inclusion of silicon element provides the catalyst with superior heat resistance. The silicon element content is more preferably 1.0 to 9.0 mass%, and even more preferably 2.0 to 8.0 mass%, calculated as silicon oxide, relative to 100 mass% of the catalyst. The silicon element content in the catalyst of the present invention can be measured by the method described in the Examples below.

[0029] The catalyst of the present invention preferably further contains zirconium element in an amount of 0.1 to 3.0 mass% relative to 100 mass% of the catalyst, calculated as zirconium oxide. The inclusion of zirconium element increases catalytic activity. The content of zirconium element, calculated as zirconium oxide, is more preferably 0.3 to 2.7 mass% relative to 100 mass% of the catalyst, even more preferably 0.5 to 2.5 mass%, and particularly preferably 0.5 to 1.5 mass%. The content of zirconium element contained in the catalyst of the present invention can be measured by the method described in the Examples below.

[0030] In the catalyst of the present invention, the crystallite diameter of the copper oxide contained in the catalyst is preferably 50 to 350 Å. When the copper oxide has such a crystallite diameter, the catalyst has better heat resistance due to the combined effect of the catalyst containing elemental sulfur and the like. The crystallite diameter of the copper oxide is more preferably 100 to 325 Å, and even more preferably 125 to 300 Å. The crystallite diameter of the copper oxide contained in the catalyst of the present invention can be measured by the method described in the examples below.

[0031] The catalyst of the present invention contains copper, zinc, and aluminum as constituent metal elements, and may further contain sulfur, and may contain components containing other metal elements such as chromium. However, the content of components containing metal elements other than copper, zinc, and aluminum is preferably 3.0% by mass or less, based on 100% by mass of the catalyst. More preferably, it is 1.0% by mass or less, and even more preferably, it is 0.5% by mass or less. In particular, the content of components containing chromium is preferably 1.5% by mass or less, based on 100% by mass of the catalyst. More preferably, it is 1.0% by mass or less, and even more preferably, it is 0.5% by mass or less.

[0032] 2. Method for Producing a Catalyst for Hydrogenation, Dehydrogenation, or Isomerization The present invention also relates to a method for producing a catalyst for hydrogenation, dehydrogenation, or isomerization containing copper, zinc, and aluminum as constituent metal elements, the method comprising: a mixing step of mixing an aqueous solution containing copper sulfate, zinc sulfate, and aluminum sulfate with an aqueous solution of carbonate and / or bicarbonate; and a water washing step of washing the precipitate obtained in the mixing step with water until the filtrate has an electrical conductivity of 50 mS / m or less (hereinafter also referred to as a method for producing the catalyst of the present invention). Such a production method is a suitable method for producing the catalyst of the present invention.

[0033] The carbonates and bicarbonates used in the catalyst production method of the present invention may be carbonates and bicarbonates of any metal element, but are preferably sodium salts. By using sodium carbonate or sodium bicarbonate, the produced catalyst contains sodium element and becomes a catalyst with better heat resistance.

[0034] The mass proportion of the copper compound used in the catalyst production method of the present invention is preferably 35 to 70 mass% in terms of copper(II) oxide relative to 100 mass% of the total mass of the copper sulfate (as converted to copper(II) oxide), zinc sulfate (as converted to zinc oxide), and aluminum sulfate (as converted to aluminum oxide) used in the catalyst production method of the present invention. It is more preferably 40 to 67.5 mass%, and even more preferably 45 to 65 mass%. The mass proportion of zinc sulfate used in the catalyst production method of the present invention is preferably 25 to 60 mass% in terms of zinc oxide relative to 100 mass% of the total mass of the copper sulfate (as converted to copper(II) oxide), zinc sulfate (as converted to zinc oxide), and aluminum sulfate (as converted to aluminum oxide) used in the catalyst production method of the present invention. It is more preferably 26.5 to 55 mass%, and even more preferably 28 to 50 mass%. The mass proportion of aluminum sulfate used in the catalyst production method of the present invention is preferably 1.5 to 25 mass% in terms of aluminum oxide, more preferably 1.75 to 20 mass%, and even more preferably 2.0 to 15 mass%, relative to 100 mass% of the total mass of copper sulfate in terms of copper(II) oxide, zinc sulfate in terms of zinc oxide, and aluminum sulfate in terms of aluminum oxide used in the catalyst production method of the present invention.

[0035] The mass proportion of the zirconium compound contained in the raw materials for the catalyst production method of the present invention is preferably 3.0 mass% or less, calculated as zirconium oxide, relative to 100 mass% of the total mass of the copper sulfate (calculated as copper(II) oxide), zinc sulfate (calculated as zinc oxide), and aluminum sulfate (calculated as aluminum oxide) used in the catalyst production method of the present invention. It is more preferably 2.5 mass% or less, and even more preferably 2.0 mass% or less. When producing a catalyst containing zirconium element as the catalyst of the present invention, the mass proportion of the zirconium compound contained in the raw materials is preferably 0.1 to 3.1 mass% in terms of zirconium oxide, relative to 100 mass% of the total mass of the copper sulfate (calculated as copper(II) oxide), zinc sulfate (calculated as zinc oxide), and aluminum sulfate (calculated as aluminum oxide) used in the catalyst production method of the present invention. It is more preferably 0.3 to 2.8 mass%, even more preferably 0.5 to 2.6 mass%, and particularly preferably 0.5 to 1.6 mass%.

[0036] When producing a catalyst containing zirconium element as the catalyst of the present invention, the aqueous solution containing copper sulfate, zinc sulfate, and aluminum sulfate may be used in the mixing step by further adding a zirconium compound. The zirconium compound may be any of zirconium oxide, chloride, sulfate, nitrate, carbonate, phosphate, acetate, alkali salt, hydroxide, and organic complex, but sulfate is preferred in terms of its low environmental impact and ease of handling during production.

[0037] The concentration of the aqueous solution containing copper sulfate, zinc sulfate, and aluminum sulfate used in the mixing step is preferably 30.0 to 52.0 mass% in total of copper sulfate, zinc sulfate, and aluminum sulfate relative to 100 mass% of the aqueous solution containing copper sulfate, zinc sulfate, and aluminum sulfate. The total mass of copper sulfate, zinc sulfate, and aluminum sulfate is more preferably 31.0 to 51.0 mass%, and even more preferably 32.0 to 50.0 mass%, relative to 100 mass% of the aqueous solution.

[0038] The amount of carbonate and / or hydrogencarbonate used in the catalyst production method of the present invention is preferably 92.0 to 190.0 mass%, more preferably 96.0 to 186.0 mass%, and even more preferably 100.0 to 182.0 mass%, relative to 100 mass% of the total mass of copper sulfate (converted to copper(II) oxide), zinc sulfate (converted to zinc oxide), and aluminum sulfate (converted to aluminum oxide).

[0039] The concentration of the aqueous carbonate solution used in the mixing step is preferably 7.0 to 19.0 mass %, more preferably 8.0 to 18.0 mass %, and even more preferably 9.0 to 17.0 mass %, in terms of the total of the carbonate and hydrogencarbonate contained in 100 mass % of the aqueous carbonate solution.

[0040] In the mixing step, either the aqueous solution containing copper sulfate, zinc sulfate, and aluminum sulfate or the aqueous carbonate solution may be added to the other and mixed, or both of these aqueous solutions may be added to separate reaction vessels and mixed. In either case, the aqueous solutions may be added all at once, in portions, or continuously. Among these mixing methods, in the mixing step, it is preferable to continuously add both the aqueous solution containing copper sulfate, zinc sulfate, and aluminum sulfate and the aqueous carbonate solution to a reaction vessel at the same time and mix them. This makes copper, zinc, and aluminum more reactive, and the catalyst has better hydrogenation reaction, dehydrogenation reaction, isomerization reaction, or heat resistance.

[0041] When a Group 2 element compound of the periodic table is used in the catalyst production method of the present invention, the amount of the Group 2 element compound used is preferably an amount equivalent to 0.5 to 4.6 mass% in terms of the Group 2 element of the periodic table, more preferably 1.0 to 4.1 mass%, even more preferably 1.5 to 3.6 mass%, and particularly preferably 1.5 to 2.6 mass%, relative to 100 mass% of the total mass of copper sulfate (converted to copper(II) oxide), zinc sulfate (converted to zinc oxide), and aluminum sulfate (converted to aluminum oxide) used in the catalyst production method of the present invention.

[0042] When producing a catalyst containing a Group 2 element of the periodic table as the catalyst of the present invention, the aqueous solution containing copper sulfate, zinc sulfate, and aluminum sulfate may be used in the mixing step, to which a Group 2 element compound has been added. The Group 2 element compound may be any of oxides, chlorides, sulfates, nitrates, carbonates, phosphates, acetates, alkali salts, hydroxides, and organic complexes of Group 2 elements of the periodic table such as magnesium, calcium, strontium, and barium, but sulfates are preferred in terms of their environmental friendliness and ease of handling during production.

[0043] When producing a catalyst containing silicon element as the catalyst of the present invention, the aqueous solution containing copper sulfate, zinc sulfate, and aluminum sulfate may be used in the mixing step, to which a silicon compound has been further added. The silicon compound may be any compound containing silicon element, such as oxide, chloride, sulfate, nitrate, carbonate, phosphate, acetate, alkali salt, hydroxide, or organic complex, but oxide is preferred in terms of heat resistance. Diatomaceous earth and activated clay containing silicon oxide as a component may also be used as the silicon compound.

[0044] When a silicon compound is used in the catalyst production method of the present invention, the amount of the silicon compound used is preferably 0.1 to 10 mass% in terms of silicon oxide, more preferably 0.5 to 9 mass%, and even more preferably 1.0 to 8 mass%, relative to 100 mass% of the total mass of copper sulfate in terms of copper(II) oxide, zinc sulfate in terms of zinc oxide, and aluminum sulfate in terms of aluminum oxide used in the catalyst production method of the present invention.

[0045] The temperature at which the mixing step is carried out is preferably 30 to 90°C. By carrying out the mixing step at such a temperature, the reaction between the aqueous solution containing the copper compound, the zinc compound, and the aluminum compound and the aqueous carbonate solution can be more fully promoted. The temperature at which the mixing step is carried out is more preferably 40 to 85°C, and even more preferably 50 to 80°C. When a step of further adding an aqueous solution containing aluminum sulfate and an aqueous carbonate solution is carried out after the mixing step, the temperature at this step is preferably the same as the temperature at which the mixing step is carried out.

[0046] The time for carrying out the mixing step is not particularly limited, but is preferably 0.5 to 10 hours in consideration of the efficiency of catalyst production and the need to sufficiently promote the reaction between the aqueous solution containing copper sulfate, zinc sulfate, and aluminum sulfate and the aqueous carbonate solution. It is more preferably 1 to 8 hours, and even more preferably 2 to 6 hours. When a step of further adding an aqueous solution containing aluminum sulfate and an aqueous carbonate solution is carried out after the mixing step, the time including this step is preferably as described above.

[0047] The method for producing a catalyst for hydrogenation, dehydrogenation, or isomerization of the present invention includes a water-washing step in which the product obtained in the mixing step (including, if further included, a step of adding an aqueous solution containing aluminum sulfate and an aqueous carbonate solution) is washed with water until the filtrate conductivity becomes 50 mS / m or less. The water-washing step may be carried out until the filtrate conductivity becomes 50 mS / m or less, preferably 35 mS / m or less, more preferably 20 mS / m or less. By washing the product with water until the filtrate conductivity becomes 50 mS / m or less, the excess sulfur content, which acts as a catalyst poison, can be reduced to an appropriate level.

[0048] The method for producing a catalyst for hydrogenation, dehydrogenation, or isomerization of the present invention may include a step of drying the water-washed product after the water-washing step. The method for carrying out the step of drying the water-washed product is not particularly limited as long as the product is dried, but it is preferable to dry the product at 60 to 150°C. More preferably, it is dried at 80 to 120°C. The drying time is also not particularly limited as long as the product is dried, but it is preferably 1 to 120 hours in consideration of sufficient drying of the product and production efficiency. More preferably, it is 6 to 72 hours.

[0049] The method for producing a catalyst for hydrogenation, dehydrogenation, or isomerization of the present invention preferably includes a step of calcining the product obtained in the water-washing step (including the drying step if a drying step is also performed). In the calcination step, carbon dioxide is removed from the product obtained in the water-washing step (including the drying step if a drying step is also performed), resulting in the product particles having pores. This results in a more highly active catalyst. The calcination temperature is preferably 150 to 800°C. More preferably, it is 150 to 600°C, and even more preferably, it is 200 to 500°C. Particularly preferably, it is 200 to 400°C, and most preferably, it is 200 to 320°C. The calcination time is preferably 3 to 24 hours. More preferably, it is 6 to 20 hours, and even more preferably, it is 8 to 18 hours.

[0050] The method for producing a catalyst for hydrogenation, dehydrogenation or isomerization of the present invention may include other steps in addition to the above-mentioned mixing step, the step of further adding an aqueous solution containing aluminum sulfate and an aqueous carbonate solution, the water-washing step, the drying step, and the step of calcining the obtained product.

[0051] The catalyst of the present invention can be used in the hydrogenation and isomerization reactions of unsaturated hydrocarbon compounds such as alkenes and alkynes; fatty acid esters such as dimethyl 1,4-cyclohexanedicarboxylate and methyl laurate; and heteroelement-containing compounds containing carbon, hydrogen, and a heteroelement, such as aldehydes, ketones, and nitro compounds. It can also be used in the dehydrogenation reactions of heteroelement-containing compounds such as alcohols, diols, and amines. Furthermore, the catalyst of the present invention can be suitably used in the production of alcohols, diols, amines, carbon monoxide, and the like, such as in the synthesis of carboxylic acids and methanol, using the above reactions. The present invention also encompasses hydrogenation, dehydrogenation, or isomerization reactions using the catalyst of the present invention in processes for producing carboxylic acids, alcohols, diols, amines, or carbon monoxide, which involve reacting an unsaturated hydrocarbon compound and / or a heteroelement-containing compound with a hydrogen-containing gas in the presence of the catalyst.

[0052] Specific examples are given below to explain the present invention in detail, but the present invention is not limited to these examples. Unless otherwise specified, "%" and "wt%" mean "weight % (mass %)." The methods for measuring each physical property are as follows.

[0053] 1. Catalyst Production Example 1 200.0 g of copper(II) sulfate pentahydrate (manufactured by Mitsubishi Materials Corporation), 200.0 g of zinc(II) sulfate heptahydrate (manufactured by Mitsui Mining & Smelting Co., Ltd.), and 80.0 g of 26.8% aqueous aluminum sulfate solution (manufactured by Furukawa Chemicals Co., Ltd.) were dissolved in 600 mL of de-ironized water, and additional de-ironized water was added to make the final volume 850 mL, to prepare a copper-zinc-aluminum aqueous solution. 165.0 g of sodium carbonate (manufactured by Tokuyama Corporation) was dissolved in 500 mL of de-ironized water, and additional de-ironized water was added to make the final volume 1320 mL, to prepare a sodium carbonate aqueous solution. 500 mL of ion-exchanged water was placed in a 5 L stainless steel beaker, heated and maintained at 70°C, and the copper-zinc-aluminum aqueous solution was added dropwise over 3 hours with stirring. Simultaneously, 1320 mL of aqueous sodium carbonate solution was added dropwise. The obtained precipitate was filtered and washed with water until the conductivity of the filtrate reached 20 mS / m or less to remove sodium ions and sulfate ions. The precipitate was then dried at 110°C overnight and calcined at 340°C for 10 hours to obtain the catalyst of Example 1.

[0054] Example 2 A catalyst of Example 2 was obtained by producing a catalyst in the same manner as in Example 1, except that the temperature during heating and stirring was changed to 80°C.

[0055] Example 3: 240.0 g of copper(II) sulfate pentahydrate (manufactured by Mitsubishi Materials Corporation), 155.0 g of zinc(II) sulfate heptahydrate (manufactured by Mitsui Mining & Smelting Co., Ltd.), 39.0 g of 26.8% aqueous aluminum sulfate solution (manufactured by Furukawa Chemicals Co., Ltd.), and 22.3 g of Snowtex ST-O (manufactured by Nissan Chemical Industries, Ltd.) were dissolved in 600 mL of de-ironized water, and additional de-ironized water was added to make the final volume 1000 mL, to prepare a copper-zinc-aluminum-silicon aqueous solution. 165.0 g of sodium carbonate (manufactured by Tokuyama Corporation) was dissolved in 500 mL of de-ironized water, and further de-ironized water was added to make the final volume 1330 mL, to prepare a sodium carbonate aqueous solution. 500 mL of ion-exchanged water was placed in a 5 L stainless steel beaker, heated and maintained at 70°C, and the copper-zinc-aluminum-silicon aqueous solution was added dropwise over 3 hours while stirring. At the same time, 1330 mL of sodium carbonate aqueous solution was added dropwise. The obtained precipitate was filtered and washed with water until the conductivity of the filtrate reached 20 mS / m or less to remove sodium ions and sulfate ions. The precipitate was then dried at 110°C overnight and calcined at 340°C for 10 hours to obtain the catalyst of Example 3.

[0056] Example 4: 240.0 g of copper(II) sulfate pentahydrate (manufactured by Mitsubishi Materials Corporation), 155.0 g of zinc(II) sulfate heptahydrate (manufactured by Mitsui Mining & Smelting Co., Ltd.), and 80.0 g of 26.8% aluminum sulfate aqueous solution (manufactured by Furukawa Chemicals Co., Ltd.) were dissolved in 600 mL of de-ironized water, and additional de-ironized water was added to bring the final volume to 1000 mL, to prepare a copper-zinc-aluminum aqueous solution. 218.8 g of sodium carbonate (manufactured by Tokuyama Corporation) was dissolved in 500 mL of de-ironized water, and additional de-ironized water was added to bring the final volume to 1165 mL, to prepare a sodium carbonate aqueous solution. 500 mL of ion-exchanged water was placed in a 5 L stainless steel beaker, heated and maintained at 70°C, and the copper-zinc-aluminum aqueous solution was added dropwise over 3 hours with stirring. Simultaneously, 1165 mL of sodium carbonate aqueous solution was added dropwise. The obtained precipitate was filtered and washed with water until the conductivity of the filtrate reached 20 mS / m or less to remove sodium ions and sulfate ions. The precipitate was then dried at 110°C overnight and calcined at 340°C for 10 hours to obtain the catalyst of Example 4.

[0057] Example 5: 300.0 g of copper(II) sulfate pentahydrate (manufactured by Mitsubishi Materials Corporation), 160.0 g of zinc(II) sulfate heptahydrate (manufactured by Mitsui Mining & Smelting Co., Ltd.), and 92.0 g of 26.8% aqueous aluminum sulfate solution (manufactured by Furukawa Chemicals Co., Ltd.) were dissolved in 600 mL of de-ironized water, and additional de-ironized water was added to bring the final volume to 850 mL, to prepare a copper-zinc-aluminum aqueous solution. 190.0 g of sodium carbonate (manufactured by Tokuyama Corporation) was dissolved in 500 mL of de-ironized water, and additional de-ironized water was added to bring the final volume to 1320 mL, to prepare a sodium carbonate aqueous solution. 500 mL of ion-exchanged water was placed in a 5 L stainless steel beaker, heated to 70°C, and the copper-zinc-aluminum solution was added dropwise over 3 hours while stirring. Simultaneously, 1320 mL of aqueous sodium carbonate solution was added dropwise. The precipitate obtained by the neutralization reaction was filtered and washed with water until the conductivity of the filtrate reached 20 mS / m or less to remove sodium ions and sulfate ions. The precipitate was then dried at 110°C overnight and calcined at 340°C for 10 hours to obtain the catalyst of Example 5.

[0058] Example 6: 150.0 g of copper(II) sulfate pentahydrate (manufactured by Mitsubishi Materials Corporation), 300.0 g of zinc(II) sulfate heptahydrate (manufactured by Mitsui Mining & Smelting Co., Ltd.), and 92.0 g of 26.8% aqueous aluminum sulfate solution (manufactured by Furukawa Chemicals Co., Ltd.) were dissolved in 600 mL of de-ironized water, and additional de-ironized water was added to bring the final volume to 850 mL, to prepare a copper-zinc-aluminum aqueous solution. 185.0 g of sodium carbonate (manufactured by Tokuyama Corporation) was dissolved in 500 mL of de-ironized water, and additional de-ironized water was added to bring the final volume to 1320 mL, to prepare a sodium carbonate aqueous solution. 500 mL of ion-exchanged water was placed in a 5 L stainless steel beaker, heated to 70°C, and the copper-zinc-aluminum solution was added dropwise over 3 hours while stirring. Simultaneously, 1320 mL of aqueous sodium carbonate solution was added dropwise. The precipitate obtained by the neutralization reaction was filtered and washed with water until the conductivity of the filtrate reached 20 mS / m or less to remove sodium ions and sulfate ions. The precipitate was then dried at 110°C overnight and calcined at 340°C for 10 hours to obtain the catalyst of Example 6.

[0059] Example 7: 200.0 g of copper(II) sulfate pentahydrate (Mitsubishi Materials Corporation), 200.0 g of zinc(II) sulfate heptahydrate (Mitsui Mining & Smelting Co., Ltd.), and 82.5 g of 26.8% aluminum sulfate aqueous solution (Furukawa Chemicals Co., Ltd.) were dissolved in 600 mL of de-ironized water, and additional de-ironized water was added to bring the final volume to 1000 mL, to prepare a copper-zinc-aluminum aqueous solution. 210.0 g of sodium carbonate (Tokuyama Corporation) was dissolved in 500 mL of de-ironized water, and additional de-ironized water was added to bring the final volume to 1400 mL, to prepare a sodium carbonate aqueous solution. 500 mL of ion-exchanged water was placed in a 5 L stainless steel beaker, heated to 70°C, and the copper-zinc-aluminum solution was added dropwise over 3 hours while stirring. Simultaneously, 1400 mL of sodium carbonate aqueous solution was added dropwise. The precipitate obtained by the neutralization reaction was filtered and washed with water until the conductivity of the filtrate reached 20 mS / m or less to remove sodium ions and sulfate ions. The precipitate was then dried at 110°C overnight and calcined at 340°C for 10 hours to obtain the catalyst of Example 7.

[0060] Example 8: 240.0 g of copper(II) sulfate pentahydrate (manufactured by Mitsubishi Materials Corporation), 155.0 g of zinc(II) sulfate heptahydrate (manufactured by Mitsui Mining & Smelting Co., Ltd.), and 80.0 g of 26.8% aluminum sulfate aqueous solution (manufactured by Furukawa Chemicals Co., Ltd.) were dissolved in 600 mL of de-ironized water, and additional de-ironized water was added to bring the final volume to 1000 mL, to prepare a copper-zinc-aluminum aqueous solution. 218.8 g of sodium carbonate (manufactured by Tokuyama Corporation) was dissolved in 500 mL of de-ironized water, and additional de-ironized water was added to bring the final volume to 1165 mL, to prepare a sodium carbonate aqueous solution. 500 mL of ion-exchanged water was placed in a 5 L stainless steel beaker, heated to 70°C, and the copper-zinc-aluminum aqueous solution was added dropwise over 3 hours while stirring. Simultaneously, 1165 mL of sodium carbonate aqueous solution was added dropwise. The obtained precipitate was filtered and washed with water until the conductivity of the filtrate reached 20 mS / m or less to remove sodium ions and sulfate ions, and then the precipitate was dried at 110°C overnight and calcined at 290°C for 10 hours to obtain the catalyst of Example 8.

[0061] Example 9: 250.0 g of copper(II) sulfate pentahydrate (manufactured by Mitsubishi Materials Corporation), 150.0 g of zinc(II) sulfate heptahydrate (manufactured by Mitsui Mining & Smelting Co., Ltd.), 84.0 g of 26.8% aluminum sulfate aqueous solution (manufactured by Furukawa Chemicals Co., Ltd.), and 10 g of zirconium sulfate aqueous solution (manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) were dissolved in 400 mL of deferrous water, and deferrous water was added to make the final volume 1000 mL, to prepare a copper-zinc-aluminum-zirconium aqueous solution. 240.7 g of sodium carbonate (manufactured by Tokuyama Corporation) was dissolved in 500 mL of deferrous water, and further deferrous water was added to make the final volume 1282 mL, to prepare a sodium carbonate aqueous solution. 500 mL of ion-exchanged water was placed in a 5 L stainless steel beaker and heated to 70 °C. The copper-zinc-aluminum-zirconium aqueous solution was added dropwise over 3 hours while stirring. At the same time, 1282 mL of sodium carbonate aqueous solution was added dropwise. The obtained precipitate was filtered and washed with water until the conductivity of the filtrate reached 20 mS / m or less to remove sodium ions and sulfate ions. The precipitate was then dried at 110°C overnight and calcined at 290°C for 10 hours to obtain the catalyst of Example 9.

[0062] Example 10: 240.0 g of copper(II) sulfate pentahydrate (Mitsubishi Materials Corporation), 155.0 g of zinc(II) sulfate heptahydrate (Mitsui Mining & Smelting Co., Ltd.), 80.0 g of 26.8% aluminum sulfate aqueous solution (Furukawa Chemicals Co., Ltd.), and 20 g of magnesium sulfate (Makai Chemical Industry Co., Ltd.) were dissolved in 400 mL of de-ironized water, and additional de-ironized water was added to bring the final volume to 1000 mL, to prepare a copper-zinc-aluminum-magnesium aqueous solution. 240.7 g of sodium carbonate (Tokuyama Corporation) was dissolved in 500 mL of de-ironized water, and additional de-ironized water was added to bring the final volume to 1282 mL, to prepare a sodium carbonate aqueous solution. 500 mL of ion-exchanged water was placed in a 5 L stainless steel beaker, heated to 70°C, and the copper-zinc-aluminum-magnesium aqueous solution was added dropwise over 3 hours while stirring. Simultaneously, 1282 mL of sodium carbonate aqueous solution was added dropwise. The obtained precipitate was filtered and washed with water until the conductivity of the filtrate reached 20 mS / m or less to remove sodium ions and sulfate ions, and then the precipitate was dried at 110°C overnight and calcined at 290°C for 10 hours to obtain the catalyst of Example 10.

[0063] Comparative Example 1: A copper-zinc aqueous solution was prepared by dissolving 96.8 g of copper(II) nitrate trihydrate (manufactured by Matsugaki Pharmaceutical Co., Ltd.), 103.5 g of zinc(II) nitrate heptahydrate (manufactured by Matsugaki Pharmaceutical Co., Ltd.), and 40.0 g of 26.8% aqueous aluminum sulfate solution (manufactured by Furukawa Chemicals Co., Ltd.) in 440 mL of deferrous water. A sodium carbonate aqueous solution was prepared by dissolving 109.0 g of sodium carbonate (manufactured by Tokuyama Corporation) in 545 mL of deferrous water. 250 mL of ion-exchanged water was placed in a 2-L stainless steel beaker and heated to 70°C. The copper-zinc-aluminum aqueous solution was added dropwise over 3 hours while stirring. At the same time, 545 mL of aqueous sodium carbonate solution was added dropwise. The resulting precipitate was filtered and washed with water until the conductivity of the filtrate reached 20 mS / m or less to remove sodium ions and sulfate ions. The precipitate was then dried overnight at 110°C and calcined at 320°C for 10 hours to obtain the catalyst of Comparative Example 1.

[0064] Comparative Example 2 A catalyst of Comparative Example 2 was obtained by producing a catalyst in the same manner as in Comparative Example 1, except that the copper raw material in Comparative Example 1 was changed to 53.8 g of copper(II) chloride dihydrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and the zinc raw material was changed to 47.4 g of zinc(II) chloride (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).

[0065] Comparative Example 3 A catalyst of Comparative Example 3 was obtained by producing a catalyst in the same manner as in Example 1, except that the sodium carbonate in Example 1 was changed to 149.6 g of ammonium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0066] Comparative Example 4 A catalyst of Comparative Example 4 was obtained by producing a catalyst in the same manner as in Example 1, except that the sodium carbonate in Example 1 was changed to 62.3 g of sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0067] Comparative Example 5 304 g of copper(II) nitrate trihydrate (manufactured by Matsugaki Pharmaceutical Co., Ltd.) and 263 g of chromium(III) nitrate nonahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were dissolved in 2,450 mL of deferrous water to prepare a copper-chromium aqueous solution. 500 g of ammonium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in 2,000 mL of deferrous water to prepare an ammonium carbonate aqueous solution. 250 mL of ion-exchanged water was placed in a 5-L stainless steel beaker, and the copper-chromium solution was added dropwise over 3 hours while stirring at room temperature. Simultaneously, 2,000 mL of ammonium carbonate aqueous solution was added dropwise. The precipitate obtained by the neutralization reaction was filtered and washed with water until the conductivity of the filtrate reached 20 mS / m or less. The precipitate was dried at 110°C overnight and calcined at 230°C for 10 hours to obtain the catalyst of Comparative Example 5.

[0068] 2. Confirmation of Catalyst Composition The compositions of the catalysts produced in Examples 1 to 10 and Comparative Examples 1 to 5 were measured by the following method. The results are shown in Table 1. <Measurement of the Contents of Copper Oxide, Zinc Oxide, Aluminum Oxide, Silicon Dioxide, Sulfur Trioxide, Chromium Oxide, Calcium Oxide, Zirconium Oxide, and Magnesium Oxide> The contents of the above components contained in each Example and Comparative Example were measured using a scanning X-ray fluorescence analyzer ZSX Primus II manufactured by Rigaku Corporation. <Measurement of Sodium Content> The content of the sodium component contained in each Example and Comparative Example was measured using an ICP optical emission spectrometer PS3500DDII manufactured by Hitachi High-Tech Science Corporation.

[0069]

[0070] 3. Evaluation of Catalyst Properties The catalysts produced in Examples 1 to 10 and Comparative Examples 1 to 5 were subjected to the following various measurements. The results are shown in Table 2. <Preparation of Acid Solution of Catalyst Powder> The powders of each Example and Comparative Example were dissolved using a Speedwave XPERT microwave sample decomposition system manufactured by Actac Corporation to prepare an acid solution. <Measurement of Specific Surface Area> The specific surface area was measured using a Macsorb HM-1220 manufactured by Mountec Co., Ltd. after heat-treating the sample in a nitrogen atmosphere at 200°C for 60 minutes. <Measurement of Copper Oxide Crystallite Size> The crystal structure of copper oxide was evaluated by powder X-ray diffraction using a Bruker D8 ADVANCE X-ray diffractometer, and the crystallite size of copper oxide was calculated. The half-width β of the peak corresponding to the (111) plane was calculated from the obtained XRD pattern. The crystallite size was calculated using this half-width according to the following formula (1): An X-ray diffractometer was used, and the half-width was determined from the results of peak fitting after background removal from the measurement results. Crystallite diameter (Å) = κλ / (β cos θ) (1) In the above formula (1), κ is the Scherrer constant (κ = 0.890), λ is the λ when CuKα radiation is used as the radiation source, which is 1.54186 Å. θ is the θ value of the calculated XRD peak. <Heat Resistance Test> 15.0 g of each sample obtained in the Examples and Comparative Examples was placed in an alumina crucible. The crucible was placed in an electric furnace, heated to 400°C over 4 hours, and held at 400°C for 6 hours. The specific surface area of ​​the obtained powder was measured.

[0071] <Evaluation of solid basicity by temperature-programmed desorption measurement using carbon dioxide> CO ２ -TPD (carbon dioxide temperature programmed desorption) is a method of desorbing carbon dioxide by continuously raising the temperature at a constant rate after adsorbing carbon dioxide onto a solid catalyst. ２ Amount and CO ２ This method measures the desorption temperature of carbon dioxide. Carbon dioxide adsorbed on weakly basic sites among the basic sites of a solid catalyst desorbs at low temperatures, while carbon dioxide adsorbed on strongly basic sites desorbs at high temperatures. This allows the amount of base and basic strength of the catalyst to be measured. Using a catalyst analyzer (Microtrac BEL Corporation's "BEL-CAT"), the CO2 desorption was measured by the carbon dioxide temperature-programmed desorption method. ２The basicity of the catalyst was evaluated by TPD measurement. Peak detection was performed using a thermal conductivity detector. ２ After the adsorption treatment, TPD measurement was performed. ２ The desorption temperature was measured. ２ The desorption temperature indicates the basicity of the support, and CO ２ A higher desorption temperature indicates a higher basicity. Pretreatment: The temperature is raised to 350°C in He gas over 15 minutes and maintained at that temperature for 30 minutes. The temperature is lowered to 50°C in He gas over a given time period and maintained at that temperature for 5 minutes. CO ２ Adsorption treatment: 50°C, 5% CO ２ / He mixed gas 50 ml / min for 30 minutes ２ TPD measurement: He gas is passed through at 30 mL / min, and the temperature is increased to 550° C. at a rate of 5° C. / min.

[0072] <Evaluation of reducibility by temperature-programmed reaction measurement using hydrogen> TPR (temperature-programmed reaction method) is a measurement technique that determines the oxidation / reduction characteristics and reactivity of adsorbed gases by continuously increasing the temperature of a solid under the flow of reactive gas and measuring the consumption rate of the reactive gas or the production rate of reaction products. ２ -TPR is a method for measuring the reducibility by increasing the temperature under hydrogen flow. ２ The reduction properties of the catalyst were evaluated by TPR measurement. The peaks were detected using a thermal conductivity detector. After pretreatment was carried out in the following order under the following conditions, TPR measurement was carried out. ２ The reduction temperature was measured. ２ The reduction temperature indicates the reducing ability of the catalyst, and H ２ The lower the desorption temperature, the higher the reducing ability. Pretreatment: 5% H ２ The temperature is raised to 100°C in 10 minutes in Ar gas and maintained at that temperature for 60 minutes. ２ / Ar gas, the temperature is lowered to 50 ° C in any time and held for 10 minutes. TPR measurement: 5% H ２Ar gas was passed through at 50 mL / min, and the temperature was raised to 550° C. at a rate of 5° C. / min.

[0073] <Measurement of Maximum Rate of Weight Loss on Heat by Differential Thermogravimetry> 10.0 mg of each sample obtained in the Examples and Comparative Examples was dispensed into an aluminum container, and measurement was carried out using a simultaneous thermogravimetry and differential thermogravimetry analyzer STA7300 manufactured by Hitachi High-Tech Science Corporation at a heating rate of 10°C / min with an air flow of 200 mL / min, using aluminum oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name "Wako Special Grade Aluminum Oxide") as a reference, to calculate the maximum rate of weight loss on heat of the powder sample within a temperature range from room temperature to 500°C.

[0074] <L ＊ a ＊ b ＊ L in color system ＊ Value, a ＊ b ＊ Measurement of L value> A color difference meter (manufactured by Konica Minolta Japan, product name "CR-5") was used. ＊ a ＊ b ＊ Lightness L in the color system ＊ , chromaticity a ＊ b ＊ The values ​​were measured.

[0075]

[0076] 4. Catalytic Activity Evaluation Using the catalysts of Example 1 and Comparative Example 5, the activity of the hydrogenation reaction of methyl laurate was evaluated by the following method. The results are shown in Table 3. <Hydrogenation Activity Test for Methyl Laurate> 0.25 g of each catalyst sample obtained in the Examples and Comparative Examples and 50.0 g of methyl laurate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a fixed-bed reactor. Nitrogen gas was circulated through the fixed-bed reactor at atmospheric pressure to perform nitrogen gas replacement. Next, hydrogen gas was circulated through the fixed-bed reactor at atmospheric pressure to perform hydrogen gas replacement. After hydrogen gas replacement, the hydrogen pressure in the fixed-bed reactor was increased to 17 MPa. The temperature was then raised to 250°C, and the reaction was carried out for 2 hours from the time the temperature reached 250°C. After completion of the reaction, the obtained product was analyzed by gas chromatography, and the conversion and selectivity were calculated using the following equations (2) and (3). Conversion (%) = (amount of methyl laurate before reaction - amount of methyl laurate after reaction) x 100 / (amount of methyl laurate before reaction) (%) (2) Selectivity (%) = (amount of lauryl alcohol after reaction) x 100 / (amount of methyl laurate before reaction - amount of methyl laurate after reaction) (%) (3)

[0077]

[0078] Using the catalyst of Example 1, the activity of the hydrogenation reaction of dimethyl 1,4-cyclohexanedicarboxylate was evaluated by the following method. The results are shown in Table 4. <Hydrogenation Activity Test of Dimethyl 1,4-Cyclohexanedicarboxylate> The catalyst powder obtained in Example 1 was formed into cylindrical objects with a diameter of 3 mm and a thickness of 3 mm using a rotary tableting machine to obtain tablet-molded products. 75.0 g of the obtained tablet-molded product and 200 mL of 1-butanol were loaded into a fixed-bed reactor and subjected to reduction treatment at a hydrogen pressure of 20 MPa and a reaction temperature of 180°C for 3 hours to obtain a hydromolded catalyst. The obtained hydromolded catalyst and 250 mL of dimethyl 1,4-cyclohexanedicarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were loaded into a fixed-bed reactor and subjected to a hydrogenation reaction under conditions of a hydrogen pressure of 20 MPa and a reaction temperature of 220°C. The reaction product obtained was analyzed by gas chromatography, and the amounts of alcohol (trans-1,4-cyclohexanedimethanol, cis-1,4-cyclohexanedimethanol) and ester (dimethyl 1,4-cyclohexanedicarboxylate) in the reaction product were calculated and used as indicators of the conversion rate and selectivity of the catalyst.

[0079]

[0080] The reverse water gas shift reaction activity was evaluated using the catalysts of Example 1, Example 4, and Comparative Example 5 by the following method. The results are shown in Table 5. <Reverse Water Gas Shift Reaction Activity Test> 2.0 g of each catalyst sample obtained in Example 1, Example 4, and Comparative Example 5 was pressure-molded using a press, crushed, and then sized using sieves with 600 μm and 1400 μm openings to prepare granules. 0.5 g of the prepared granules was placed in a fixed-bed reactor, heated to 200°C, and reduced for 60 minutes by flowing hydrogen gas. After the reduction, the reverse water gas shift reaction was carried out under predetermined temperature conditions while flowing a carbon dioxide / hydrogen mixed gas. The resulting reaction gas was analyzed by gas chromatography, and the amount of carbon monoxide in the reaction gas was calculated and used as an index of conversion.

[0081]

[0082] Using the catalysts of Examples 8 to 10, the activity of the methanol synthesis reaction was evaluated by the following method. The results are shown in Table 6. <Methanol synthesis activity test> 5.00 g of each catalyst powder obtained in Examples 8 to 10 was placed in a φ20 mm mold and pressed at a pressure of 30 MPa using a pressure press. The resulting pellets were passed through a sieve with openings of 600 μm to 1.4 mm, and the molded powder on the sieve was collected to obtain a sample for methanol synthesis activity test. 1.98 g of the resulting sample was loaded into a methanol synthesis activity evaluation device. Pretreatment was performed using 100% H ２ The catalyst was heated to a temperature of 150°C under a gas flow rate of 100 ml / min, and when the catalyst temperature stabilized at 150°C, the temperature was gradually increased by 10°C each time. Once the catalyst temperature stabilized at 200°C, the temperature was maintained for 3 hours. The methanol synthesis activity test was performed at catalyst temperatures of 200°C and 250°C under pressures of 7 MPaG and 10 MPaG, respectively. ２ Gas 8.3 ml / min, H ２ The reaction was carried out at a gas flow rate of 25.0 ml / min. The resulting reaction gas was analyzed by gas chromatography, and the amount of methanol in the reaction gas was calculated as an index of conversion. It was confirmed that the conversion and selectivity were equivalent to those at equilibrium at 250°C.

[0083]

[0084] As shown in Table 2, the specific surface area of ​​the catalysts of Examples 1 to 10 after the heat resistance test did not change significantly compared to before the heat resistance test, indicating that they have excellent heat resistance. Regarding catalytic activity, the results of Table 2 show that the catalysts of Examples 1 to 10 have a higher CO ２The high desorption temperature indicates that the catalysts strongly adsorb to substances containing carbon and oxygen, have good reactivity with hydrogen, and can be suitably used as catalysts. The results in Table 5 indicate that the catalysts of Examples 1 and 4 have higher reverse water gas shift reaction activity than the catalyst of Comparative Example 5. Furthermore, the catalysts of Examples 1 to 10 have lower reduction temperatures than the catalysts of Comparative Examples 2 to 4, indicating that they have good reactivity with hydrogen and can be suitably used as catalysts for hydrogenation and dehydrogenation reactions. This was confirmed by the hydrogenation activity test of methyl laurate shown in Table 3 and the hydrogenation activity test of dimethyl 1,4-cyclohexanedicarboxylate shown in Table 4. Furthermore, in the hydrogenation activity test of dimethyl 1,4-cyclohexanedicarboxylate shown in Table 4, the cis and trans isomers were obtained as products of the hydrogenation reaction. The selectivities of the cis and trans isomers were reversed between the 1.0- and 5.5-hour reaction times, confirming that isomerization of the cis to trans isomers was occurring simultaneously with the hydrogenation reaction. Furthermore, the catalysts of Examples 8 to 10 exhibited conversion rates equivalent to the equilibrium conversion rates in the methanol synthesis activity test shown in Table 6, demonstrating high methanol synthesis activity. The results in Tables 2 to 6 demonstrate that the catalysts of the present invention can be used in hydrogenation reactions, including the reverse water-gas shift reaction, and isomerization reactions of compounds containing carbon and hydrogen, such as fatty acid esters, aldehydes, ketones, alkenes, nitro compounds, carbon monoxide, and carbon dioxide. Furthermore, the properties of the catalysts of the present invention shown in Table 2 demonstrate that they can also be used in dehydrogenation reactions of compounds containing carbon and hydrogen, such as alcohols, diols, and amines. The catalysts of the present invention can be suitably used to produce carboxylic acids, alcohols, diols, amines, carbon monoxide, and the like, through these reactions. From the above, it was confirmed that the catalysts of the present invention, without containing elemental chromium, exhibit high activity as catalysts for hydrogenation reactions, isomerization reactions, dehydrogenation reactions, and the reverse water-gas shift reaction, and also have excellent heat resistance.

Claims

1. A catalyst for hydrogenation, dehydrogenation, or isomerization containing copper, zinc, and aluminum as constituent metal elements, for use in any one of hydrogenation, dehydrogenation, or isomerization reactions, characterized in that the copper content in the catalyst, calculated as copper (II) oxide, is 35 to 70% by mass relative to 100% by mass of the catalyst; the zinc content, calculated as zinc oxide, is 25 to 60% by mass relative to 100% by mass of the catalyst; the aluminum content, calculated as aluminum oxide, is 1.5 to 25% by mass relative to 100% by mass of the catalyst; the zirconium oxide content is 3.0% by mass or less relative to 100% by mass of the catalyst; and the sulfur content, calculated as sulfur trioxide, is 0.1 to 1.0% by mass relative to 100% by mass of the catalyst.

2. The catalyst for hydrogenation, dehydrogenation, or isomerization reactions according to claim 1, characterized in that the catalyst exhibits a maximum thermal weight loss rate per hour of 0.15% / min or more in the temperature range of 135°C to 180°C in differential thermogravimetry.

3. The catalyst for hydrogenation, dehydrogenation or isomerization according to claim 1, further comprising 0.08 to 5.0 mass % of a Group 2 element of the periodic table, based on 100 mass % of the catalyst.

4. The catalyst is L ＊ a ＊ b ＊ L in color system ＊ Value 0≦L ＊ ≦20, and a ＊ The value is 0≦a ＊ 2. The catalyst for hydrogenation, dehydrogenation or isomerization according to claim 1, wherein 5. The catalyst for hydrogenation, dehydrogenation or isomerization according to claim 1, further comprising zirconium element in an amount of 0.1 to 3.0 mass % relative to 100 mass % of the catalyst in terms of zirconium oxide.

6. The catalyst for hydrogenation, dehydrogenation or isomerization according to claim 1, further comprising sodium element in an amount of 0.03 to 1.0 mass % relative to 100 mass % of the catalyst in terms of sodium.

7. The catalyst for hydrogenation, dehydrogenation or isomerization according to claim 1, further comprising 0.5 to 4.5 mass % of magnesium element calculated as magnesium oxide relative to 100 mass % of the catalyst.

8. The catalyst for hydrogenation, dehydrogenation or isomerization according to claim 1, further comprising 0.1 to 10 mass % of silicon element calculated as silicon oxide relative to 100 mass % of the catalyst.

9. The catalyst for hydrogenation, dehydrogenation or isomerization according to any one of claims 1 to 8, which is used in a methanol synthesis reaction.

10. A method for producing a catalyst for hydrogenation, dehydrogenation, or isomerization containing copper, zinc, and aluminum as constituent metal elements, the method comprising: a mixing step of mixing an aqueous solution containing copper sulfate, zinc sulfate, and aluminum sulfate with an aqueous solution of carbonate and / or bicarbonate; and a water washing step of washing the precipitate obtained in the mixing step with water until the filtrate has an electrical conductivity of 50 mS / m or less.

11. The method for producing a catalyst for hydrogenation, dehydrogenation or isomerization reactions according to claim 10, wherein the carbonate and / or hydrogencarbonate is a sodium salt.

12. A method for producing a carboxylic acid, an alcohol, a diol, an amine, or carbon monoxide, comprising a step of reacting an unsaturated hydrocarbon compound and / or a heteroatom-containing compound with a hydrogen-containing gas in the presence of the catalyst for hydrogenation, dehydrogenation, or isomerization described in any one of claims 1 to 9.

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