ALDEHYDE HYDROGENATION CATALYST AND PRODUCTION PROCESS THEREFOR

Abstract

A nickel-diatomaceous earth catalyst is provided, which is a catalyst for hydrogenating an aldehyde, the catalyst including Ni, Zr, and diatomaceous earth, wherein Ni is contained in a range of 40 to 90 mass% based on NiO, Zr is contained in a range of 0.5 to 10 mass% based on ZrO2, silicon dioxide is contained in a range of 10 to 40 mass% based on SiO2, and a desorption amount of NH3 in a temperature range of 250°C to 600°C is 1.00 mmol / g or more in the temperature-programmed desorption measurement of NH3, and a method for producing the same.

Description

TECHNICAL FIELD

[0001] The embodiment of the invention relates to a catalyst for hydrogenating an aldehyde. TECHNICAL BACKGROUND

[0002] Catalysts for hydrogenating aldehydes to produce alcohols have long been known. For example, Patent Literature 1 discloses a reduced nickel catalyst containing 3% to 15% nickel in a nickel-diatomaceous earth catalyst as a metallic component of one or more several selected from magnesium, calcium, barium, strontium, and zirconium. Patent Literature 1 discloses a method for hydrogenating saturated or unsaturated aldehydes using this reduced nickel catalyst to produce a corresponding alcohol. Furthermore, Patent Literature 1 discloses side reactions for producing ether and acetal in a hydrogenation reaction of aldehydes using a nickel catalyst as a major problem. Furthermore, focusing on the fact that these side reactions are caused by a nickel catalyst present in the catalyst, Acid, it is disclosed that side reactions are significantly suppressed when the catalyst contains a basic metal salt. Additionally, Patent Literature 2 discloses that side reactions are suppressed by using highly dispersed silica containing an alkali metal component fixed on the surface in a catalyst, and the selectivity of alcohol is increased.

[0003] A method without using a metallic component is also known, and for example, Patent Literature 3 discloses that the selectivity of alcohols is improved by means of a catalyst in which a catalytically active component is supported with a gentle concentration gradient from the surface toward the central part.

[0004] As described above, in the process for producing an alcohol by hydrogenating an aldehyde, it is known that the selectivity of the alcohol is increased by changing the acidity of the catalyst to be used and the loading state of the active metal. CITATION LISTPATENT LITERATURE Patent Literature 1: JP-B-44-17127 Patent Literature 2: JP-A-2020-163334 Patent Literature 3: JP-A-2005-279587 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0005] The embodiment of the invention solves the problem that in a hydrogenation catalyst that produces an alcohol by hydrogenating an aldehyde, a side reaction in which ether, acetal or the like is produced is remarkable in a catalyst in the prior art and therefore the yield of the alcohol is low. SOLVING THE PROBLEMS

[0006] The present inventors investigated a hydrogenation catalyst for producing an alcohol by hydrogenating an aldehyde and found that by using a nickel-diatomaceous earth catalyst containing a large amount of a solid acid having high acid strength in a nickel-diatomaceous earth catalyst containing Ni, Zr, and diatomaceous earth, the generation of ether and the like can be suppressed and the yield of alcohol can be increased. The embodiment of the invention has solved the problems in the prior art by using a catalyst based on this result as a solution.

[0007] An embodiment of the invention relates to a nickel-diatomaceous earth catalyst (hereinafter also referred to as "catalyst of the embodiment of the invention") which is a catalyst for hydrogenating an aldehyde, the catalyst including Ni, Zr and diatomaceous earth, wherein Ni is contained in a range of 40 to 90 mass% based on NiO, Zr is contained in a range of 0.5 to 10 mass% based on ZrO2, silicon dioxide is contained in a range of 10 to 40 mass% based on SiO2, and a desorption amount of NH3 in a temperature range of 250 °C to 600 °C is 1.00 mmol / g or more in the temperature-programmed desorption measurement of NH3, and a method for producing the same. EFFECTS OF THE INVENTION

[0008] When the catalyst of one embodiment of the invention is used in a process for producing an alcohol by hydrogenating an aldehyde, the production of an ether or the like caused by a side reaction can be suppressed to increase the yield of the alcohol. BRIEF DESCRIPTION OF THE DRAWINGS Fig. Figure 1 illustrates NH3-TPD measurement profiles of Example 1, Comparative Example 1, and Comparative Example 2. Fig. Figure 2 illustrates an XPS profile of Example 1. DESCRIPTION OF EMBODIMENTS

[0009] The catalyst of one embodiment of the invention and a method for producing the same will be described in detail below. When a numerical range is indicated by "up to" in the embodiment of the invention, the numerical range includes upper and lower limits. [Catalyst of the embodiment of the invention]

[0010] According to one embodiment of this invention, a nickel-diatomaceous earth catalyst is a catalyst for hydrogenating an aldehyde, the catalyst including Ni, Zr, and diatomaceous earth, wherein Ni is contained in a range of 40 to 90 mass% based on NiO, Zr is contained in a range of 0.5 to 10 mass% based on ZrO2, silicon dioxide is contained in a range of 10 to 40 mass% based on SiO2, and a desorption amount of NH3 in a temperature range of 250°C to 600°C in the temperature-programmed desorption measurement of NH3 is 1.00 mmol / g or more.

[0011] As disclosed in Patent Literature 1, in a catalyst for producing an alcohol by hydrogenating an aldehyde, since a side reaction (reaction for producing a compound other than an alcohol) is promoted by an acid contained in the catalyst, it is known to reduce the acid by adding a basic metal or the like. On the other hand, the embodiment of the invention provides a nickel-diatomaceous earth catalyst containing Ni, Zr, and diatomaceous earth, wherein the nickel-diatomaceous earth catalyst contains a large amount of a solid acid with high acid strength.

[0012] The strength and amount of the solid acid can be determined by temperature-programmed NH3 desorption measurement. This measurement utilizes a phenomenon in which NH3 is adsorbed onto a solid acid, and adsorbed NH3 or the like is desorbed by heating. NH3 adsorbed onto the solid acid with high acid strength is strongly adsorbed onto the solid acid and thus cannot be desorbed unless the temperature is high. Therefore, by measuring the amount of NH3 desorption according to the heating temperature, the amount of the solid acid can be detected according to the acid strength.

[0013] In the catalyst of the embodiment of the invention, the amount of NH3 desorbed in a temperature range of 250°C to 600°C (referring to a high temperature range) in the temperature-programmed NH3 desorption measurement is 1.00 mmol / g or more in the entire high temperature range. As shown in Table 2 described later, in the catalyst of Example 1 of the embodiment of the invention, the NH3 desorption amount in a temperature range of 100°C or higher and lower than 250°C (referring to a low temperature range) is 0.39 mmol / g in the entire low temperature range, but the NH3 desorption amount in the high temperature range of 250°C to 600°C increases sharply and is 1.84 mmol / g in the entire high temperature range.As described above, it is noted that the catalyst of the embodiment of the invention contains a large NH3 desorption amount in a high temperature region and a large solid acid (hereinafter also referred to as “strong solid acid”) having a high solid acid strength.

[0014] The temperature change of the NH3 desorption amount is shown in the NH3-TPD measurement profile in Fig. 1. In the catalyst of Example 1 of the embodiment of the invention, the NH3 desorption amount at each temperature in the low-temperature range of 100 °C or higher and lower than 250 °C is about 0.3 × 10 -3 mmol / g or less, but the NH3 desorption amount in the high temperature range of 250 °C to 600 °C increases rapidly, and the NH3 desorption amount in the high temperature range is about 0.3 x 10 -3 mmol / g to about 0.7 x 10 -3mmol / g and is remarkably large. The NH3 desorption amount in the entire temperature ranges of the low-temperature region and the high-temperature region is a value obtained by integrating the NH3 desorption amount at the measurement temperature in each temperature region.

[0015] In the catalyst of the embodiment of the invention, the NH3 desorption amount in the entire high-temperature region is preferably 1.10 mmol / g or more, more preferably in the range of 1.10 mmol / g or more to 3.00 mmol / g or less, and particularly preferably in the range of 1.10 mmol / g or more to 2.00 mmol / g or less. The NH3 desorption amount of the catalyst of the embodiment of the invention in a low-temperature region may be 0.20 mmol / g or more, may be in the range of 0.20 mmol / g or more and 1.00 mmol / g or less, or may be in the range of 0.20 mmol / g to 0.40 mmol / g. The catalyst of the embodiment of the invention has a high alcohol yield even when the NH3 desorption amount is large in a low-temperature region.

[0016] The catalyst of the embodiment of the invention contains Ni. Ni is present in a state where metallic Ni, Ni oxide, or a part thereof is incorporated into diatomaceous earth in the catalyst. In the reaction for hydrogenating an aldehyde, metallic Ni is an active metal. However, metallic Ni is easily oxidized in the air. Therefore, an oxide catalyst contained in a catalyst in a state of Ni oxide and subjected to pretreatment to be reduced to metallic Ni immediately before the reaction, and a reducing and stabilizing catalyst that forms an oxide film on the surface of metallic Ni and is subjected to pretreatment to remove the oxide film immediately before the reaction are known. The catalyst of the embodiment of the invention may be either of them. From the viewpoint of simplicity of the pretreatment, the catalyst is preferably a reducing and stabilizing catalyst.Furthermore, when Ni is combined with silicon dioxide (SiO2) contained in the diatomaceous earth and integrated into the diatomaceous earth, a strong solid acid is generated, and thus it is preferable that at least a part of the Ni is combined with silicon dioxide of the diatomaceous earth.

[0017] In the catalyst of the embodiment of the invention, the Ni content is in the range of 40 to 90 mass% based on NiO with respect to the total amount of the catalyst. As this content increases, the activity in the hydrogenation reaction of aldehyde also increases, but the price of the catalyst also increases. Therefore, from an economic perspective, the Ni content in the catalyst is preferably in the range of 50 to 85 mass%, and more preferably in the range of 60 to 80 mass%.

[0018] The catalyst of the embodiment of the invention contains Zr. It is assumed that Zr exists in an oxide state, in an integrated state in diatomaceous earth, or in both states in the catalyst. When Zr is integrated into diatomaceous earth, it forms a bond with the silica contained in the diatomaceous earth, and an electronic state of Zr changes. This change in the electronic state can be confirmed by XPS measurement, and the energy level is shifted to a position different from that of Zr in the oxide state. It is assumed that the bond between silica and Zr generates a strong solid acid to affect the above-described NH3 desorption amount. Therefore, it is preferable that part or all of the Zr contained in the catalyst of the embodiment of the invention is integrated into diatomaceous earth.

[0019] As shown in the XPS profile of Fig.As shown in Figure 2, in the catalyst of Example 1 of the embodiment of the invention, the binding energy (peak position originates from the 3d orbital) of Zr contained in the catalyst is 1 eV higher than the binding energy of ZrO2, indicating that at least a part of the Zr contained in the catalyst of Example 1 is bonded to diatomaceous earth silica. In the catalyst of the embodiment of the invention, the binding energy of Zr is preferably 0.4 eV or more higher than the binding energy of ZrO2, and more preferably 0.5 eV or more higher.

[0020] In the catalyst of the embodiment of the invention, the Zr content is in the range of 0.5 to 10 mass% based on ZrO2 with respect to the total amount of the catalyst. When the Zr content is in this range, a strong solid acid is likely to be generated. The Zr content is preferably in the range of 1 to 8 mass%, and more preferably in the range of 1 to 6 mass%.

[0021] The catalyst of the embodiment of the invention includes diatomaceous earth. The diatomaceous earth serves as a carrier for Ni or Zr. The diatomaceous earth contains silica as a main component, and in the catalyst of the embodiment of the invention, it is preferable that a part of Ni and Zr is bonded to silica of the diatomaceous earth, as described above. The diatomaceous earth is preferably contained in the catalyst of the embodiment of the invention in the range of 10 to 40 mass%, more preferably in the range of 10 to 30 mass%, and particularly preferably in the range of 15 to 25 mass%.

[0022] Since the main component of diatomaceous earth is silica, the content of diatomaceous earth contained in the catalyst of the embodiment of the invention can be regarded as the silica content. The silica is preferably contained in the catalyst of the embodiment of the invention in the range of 10 to 40 mass%, more preferably in the range of 10 to 30 mass%, and particularly preferably in the range of 15 to 25 mass%. The catalyst of the embodiment of the invention may contain silica particles as a shaping agent or pore-forming agent separate from the diatomaceous earth.

[0023] The silica content of the catalyst of the embodiment of the invention is the total amount including silica of the forming agent or the pore-forming agent. However, since the silica content is mainly silica from diatomaceous earth, the amount of silica other than diatomaceous earth is limited according to the general mixing amount of the forming agent, the pore-forming agent, and the like in the case where the forming agent, the pore-forming agent, and the like are included. The amount of silica derived from the forming agent, the pore-forming agent, or the like can be considered, for example, 5 mass% or less according to the mixing amount of these raw materials. In this case, the amount of silica derived from diatomaceous earth is 5 to 35 mass% of 10 to 40 mass% of the amount of silica contained in the catalyst of the embodiment of the invention.

[0024] In the catalyst of the embodiment of the invention, a Ni crystallite size is preferably in the range of 2 to 8 nm, more preferably in the range of 3 to 7 nm, and particularly preferably in the range of 4 to 6 nm. The Ni contained in the catalyst of the embodiment of the invention can be determined from a diffraction peak obtained by an X-ray diffraction measurement. In the embodiment of the invention, the Ni crystallite size represents a crystallite size of metallic Ni when the catalyst of the embodiment of the invention is a reducing and stabilizing catalyst, and represents the crystallite size of NiO when the catalyst of the embodiment of the invention is an oxide catalyst. As the Ni crystallite size decreases, the hydrogenation activity of the catalyst of the embodiment of the invention tends to increase.

[0025] The catalyst of the embodiment of the invention preferably has a specific surface area of ​​80 m 2 / g or more, more preferably 90 m 2 / g or more and particularly preferably 100 m 2 / g or more. When the specific surface area of ​​the catalyst of the embodiment of the invention is within the above-mentioned range, the hydrogenation activity tends to be high. The catalyst of the embodiment of the invention may have a specific surface area of ​​300 m 2 / g or less, 250 m 2 / g or less or 200 m 2 / g or less.

[0026] The catalyst of the embodiment of the invention is preferably a shaped body. In the method for producing an alcohol by hydrogenating an aldehyde, the catalyst of the embodiment of the invention can also be used as a powder, but a shaped body is preferred because it is easier to separate and recover after the reaction. The shape of the shaped body can be any shape known in the art. For example, a spherical shape, a columnar shape, or a similar shape is preferred, and a columnar shape or a similar shape is preferred. The columnar shape includes a cylindrical shape, a trilobal shape, a quadruple shape, and the like. Specifically, the catalyst of the embodiment of the invention preferably has a columnar shape, a diameter of 0.5 mm or more and 5 mm or less, and a length of 1 mm or more and 10 mm or less.

[0027] The catalyst of the embodiment of the invention can be used in particular in a process for producing an alcohol by hydrogenating an aldehyde. However, the catalyst of the embodiment of the invention can also be used in a reaction in which Ni serves as the active species. For example, it can also be used for the hydrogenation of unsaturated compounds such as ethylene, propylene, benzene, and toluene.

[0028] The embodiment of the invention relates to the catalyst of the embodiment of the invention and includes a method for producing the catalyst (hereinafter also referred to as "production method of the embodiment of the invention"). The production method of the present invention will be described in detail below. [Production method of the embodiment of the invention]

[0029] A process for producing a catalyst embodying the invention includes the following steps (i) to (vii): (i) an acidic aqueous solution preparation step for obtaining an acidic aqueous solution in which Ni and Zr are dissolved; (ii) a basic suspension preparation step for obtaining a basic suspension in which at least one of NaOH and Na2CO3 is dissolved and diatomaceous earth is dispersed; (iii) a neutralization step of adding the acidic aqueous solution to the basic suspension to obtain a mixed solution; (iv) an aging step of adjusting a pH of the mixed solution to 6.5 or less and storing the mixed solution for 30 minutes or more; (v) a re-aging step of adjusting the pH of the mixed solution obtained in the aging step to a range of 8.5 to 9.5 and holding the mixed solution for 60 minutes or more to obtain a precursor slurry; (vi) a separation step for separating a precursor from the precursor slurry; and (vii) a calcination step for calcining the precursor. Each step is described in detail. [Preparation step for an acidic aqueous solution]

[0030] The production method of the embodiment of the invention includes an acidic aqueous solution preparation step for obtaining an acidic aqueous solution in which Ni and Zr are dissolved. In this step, it is important that Ni and Zr are dissolved and ionized. The ionized Ni and Zr bond with the diatomaceous earth in the neutralization step, the aging step, and the re-aging step described later to form a strong solid acid.

[0031] In this step, the acidic aqueous solution is prepared by dissolving a Ni raw material and a Zr raw material in water. The Ni raw material is not limited as long as it dissolves in the acidic aqueous solution. For example, Ni sulfate, Ni nitrate, Ni acetate, and metallic Ni can be used. In addition, the Zr raw material is not limited as long as it is dissolved in the acidic aqueous solution. For example, Zr sulfate, Zr nitrate, or the like can be used. If these raw materials are not dissolved in water, they can be dissolved using an acid. The type of acid is not limited, but general inorganic acids such as sulfuric acid, nitric acid, and hydrochloric acid can be used.

[0032] The content of Ni and Zr contained in the acidic aqueous solution obtained in this step can be adjusted according to the composition of the catalyst to be ultimately produced. For example, the Ni content can be adjusted within a range of 1 to 12 mass%, 3 to 10 mass%, or 5 to 7 mass%. In addition, the Zr content can be adjusted within a range of 0.01 to 2 mass%, 0.05 to 1 mass%, or 0.1 to 0.5 mass%.

[0033] A pH value of a container containing acidic water obtained in this step is preferably 4 or less, more preferably 3 or less, and particularly preferably 2.5 or less. The lower limit of the pH value is not limited and may be 1 or more. When the pH value is within the above range, Ni and Zr are stably present in the acidic aqueous solution. [Preparation step for a basic aqueous solution]

[0034] The production method of the embodiment of the invention includes a basic suspension preparation step for obtaining a basic suspension in which at least one of NaOH and Na2CO3 is dissolved and diatomaceous earth is dispersed. In this step, it is important that the diatomaceous earth is dispersed in a liquid as a solid, and a part (mainly the surface) thereof is dissolved. The main component of the diatomaceous earth is silicon dioxide and is dissolved in the basic aqueous solution. However, when all the diatomaceous earth is dissolved, the pores of the diatomaceous earth also disappear, and thus, in this step, a suspension in a state where the diatomaceous earth exists as a solid is prepared.Since part of the diatomaceous earth gradually dissolves in the suspension, a bond can easily be formed between Ni and Zr in the acidic aqueous solution mixed in the next neutralization step and the diatomaceous earth.

[0035] The basic suspension can be prepared by a method of dissolving at least one of NaOH and Na2CO3 in water and then adding the diatomaceous earth, or by a method of dispersing the diatomaceous earth in water and then adding at least one of NaOH and Na2CO3. The additional amount of at least one of NaOH and Na2CO3 is not limited, and it is sufficient to add an amount required to adjust the pH to 6.5 or less in the next neutralization step.

[0036] The diatomaceous earth content contained in the basic suspension obtained in this step can be adjusted according to the composition of the catalyst to be ultimately produced. For example, the diatomaceous earth content can be adjusted within a range of 1 to 20 mass%, 2 to 10 mass%, or 3 to 6 mass%. However, if the diatomaceous earth content is too low, all of the diatomaceous earth will be dissolved, and the diatomaceous earth will not be a suspension. Therefore, the diatomaceous earth content can be adjusted to such an extent that the diatomaceous earth can exist in a solid state.

[0037] The pH of the basic suspension obtained in this step is preferably in the range of 9 to 12.5, and more preferably in the range of 10 to 12. If the diatomaceous earth is left at a high pH for a long period of time, the dissolution of the diatomaceous earth continues, and thus it is preferable to proceed to the next step before the diatomaceous earth is completely dissolved. [Neutralization step]

[0038] The production method of the embodiment of the invention includes a neutralization step of adding the acidic aqueous solution to the basic suspension to obtain a mixed solution with a pH of 6.5 or less. This step is a step for precipitating Ni or Zr dissolved in the acidic solution as a precipitate through a neutralization reaction and forming a bond with Zr on the surface of the diatomaceous earth. Therefore, it is preferable to add an acidic aqueous solution to the basic suspension while maintaining a state in which a part of the diatomaceous earth is dissolved.

[0039] The liquid temperatures of the acidic aqueous solution and the basic suspension to be mixed are preferably in the range of 65°C to 95°C, and more preferably in the range of 75°C to 85°C. When the liquid temperature of the acidic aqueous solution and the basic suspension is in this range, a bonding reaction between Zr and diatomaceous earth is promoted.

[0040] The entire amount of the acidic aqueous solution to be mixed is preferably added within a period of 15 minutes to 120 minutes, and more preferably 30 minutes to 90 minutes. When the entire amount of the acidic aqueous solution is added within such a period, a bond is likely to be formed between Zr and diatomaceous earth.

[0041] If the pH of the mixed solution does not reach 6.5 or less even when the entire amount of the acidic aqueous solution is added, the pH can be adjusted to the above-described range by adding the acidic aqueous solution as needed. As the acidic aqueous solution used here, an aqueous solution containing sulfuric acid, nitric acid, hydrochloric acid, acetic acid, or a mixture thereof can be used. [Aging step]

[0042] The production method of the embodiment of the invention includes a step of holding the mixed solution obtained in the neutralization step for 30 minutes or more. In this step, it is important to promote a reaction that forms a bond with Zr on the surface of the diatomaceous earth. The holding time is preferably 45 minutes or more, and more preferably 60 minutes or more. The upper limit of the holding time is not limited, but may be 600 minutes or less, 300 minutes or less, or 150 minutes or less from the viewpoint of productivity. At this time, it is preferable to keep the mixture in a stirred state.

[0043] The temperature of the mixed solution in the aging step is preferably in the range of 65°C to 95°C, and more preferably in the range of 75°C to 85°C. When the temperature of the mixed solution is in the above-mentioned range, the reaction for forming a bond between Zr and diatomaceous earth is promoted. [Re-aging step]

[0044] The production method of the embodiment of the invention includes a step of adjusting the pH of the mixed solution obtained in the aging step to a range of 8.5 to 9.5 and holding the mixed solution for 60 minutes or more to obtain a precursor slurry. In this step, it is important to form a bond between Ni and diatomaceous earth by aging the mixed solution at a pH different from that in the aging step.

[0045] In this step, a basic compound is added to the mixed solution obtained in the aging step to adjust the pH to a range of 8.5 to 9.5. As the basic compound to be added, any basic compound known in the art can be used. For example, NaOH, Na2CO3, ammonia, or the like, or an aqueous solution in which they are dissolved can be used. By adjusting the pH to this range and aging for one hour or more, a bond is further formed between Ni and diatomaceous earth.

[0046] The temperature of the mixed solution at the time of re-aging is preferably in the range of 65°C to 95°C, and more preferably in the range of 75°C to 85°C. When the temperature of the mixed solution is in the above range, the reaction for forming a bond between Ni and diatomaceous earth is promoted. [Separation step]

[0047] The production method of the embodiment of the invention includes a step of separating a precursor from the precursor slurry obtained in the step. In this step, the precursor can be separated from the precursor slurry using a known method in the art. For example, a method of removing water using a dryer, a method of separating water by filtration, a method of separating water by centrifugation, and the like can be used.

[0048] If the precursor slurry contains impurities generated by a neutralization reaction or the like, the impurities can be removed by suspension washing, in which the separated precursor is suspended in water and stirred, and then the precursor is separated again by flow washing, in which a washing liquid such as water flows through the catalyst precursor and washes it, or the like. Particularly, when a large amount of sulfur is contained in the precursor, there is a concern that the catalytic activity will be reduced, and thus, it is preferable to remove sulfur by washing. In addition, when nitrate ions are contained, NO xin a calcination step described later, and thus, it is also preferable to remove the nitrate ions by washing. For example, washing is preferably carried out so that the conductivity of the filtrate after washing is 5 mS / cm or less.

[0049] The separated precursor can be formed into various shapes as needed. For example, it can be formed into a spherical shape, a columnar shape, or a shape similar thereto, and it is preferable to form a columnar shape or a shape similar thereto. The columnar shape includes a cylindrical shape, a trilobal shape, a quadruple shape, and the like. Specifically, it is preferable that the molding be performed so as to have a columnar shape, a diameter thereof being in a range of 0.5 mm or more to 5 mm or less, and a length thereof being in a range of 1 mm or more to 10 mm or less. As a method for molding into such a shape, a method known in the art, such as tabletting or extrusion molding, can be used. [Calcination step]

[0050] The production method of the embodiment of the invention includes a step of calcining the precursor separated in the above-described step. In this step, it is important to decompose the precipitate contained in the precursor to produce nickel oxide. The calcined precursor can be used in a process for hydrogenating an aldehyde to produce an alcohol as an oxide catalyst. When an oxide catalyst is used, it is necessary to perform a pretreatment for reducing nickel oxide with a reducing substance such as hydrogen to form a metallic state.

[0051] In this step, the precursor can be calcined using any device known in the art. For example, the catalyst precursor can be calcined using a muffle furnace, a rotary kiln, a gas furnace, or the like. The calcination temperature depends on the decomposition degree of the precursor, but is preferably in the temperature range of 300°C to 500°C. Furthermore, the calcination time can be in the range of one hour to 24 hours, although it depends on the amount of the precursor. The atmosphere for calcination is preferably an air atmosphere, and the calcination can be carried out in a state where the air is circulated.

[0052] In this step, the oxide catalyst obtained after calcining the precursor can be reduced with hydrogen or the like if necessary. For example, nickel oxide can be reduced to metallic nickel by filling an oxide catalyst into a reactor and maintaining the reaction vessel at a reaction temperature of 380°C to 450°C for 1 to 48 hours with circulating hydrogen. In addition, if the metallic nickel produced by reducing nickel oxide is directly exposed to air, it may generate heat due to an oxidation reaction, causing the catalyst to burn. Therefore, after reducing the nickel oxide, oxygen can be gradually added to form a film of the nickel oxide on the surface of the metallic nickel. It is also possible to adsorb carbon dioxide and the like on the surface of the metallic nickel.The catalyst obtained by such a reduction and stabilization step can be used as a reduction and stabilization catalyst in a process for producing an alcohol by hydrogenating an aldehyde. The reduction and stabilization catalyst is preferred because the time required for pretreatment is significantly shorter than that required for the oxide catalyst described above.

[0053] Below, examples of the embodiment of the invention will be described along with comparative examples. Note that the embodiment of the invention is not limited to these examples. Various measurements and evaluations were performed in examples and comparative examples as follows. [pH measurement]

[0054] A pH value was measured at a liquid temperature of 40 °C using a pH meter (“MM43-X”, manufactured by DKK-TOA YAMAGATA CORPORATION) and a pH electrode (“GST-5841C”, manufactured by DKK-TOA YAMAGATA CORPORATION). [Composition analysis] (Ni, Zr, and Si)

[0055] A sample was dissolved in an acid and a filtrate was diluted with water to an appropriate concentration. Then, the Ni, Zr, and Si contents were measured using an ICP emission spectrometer (730ICP-OES, manufactured by Agilent Technologies International Japan, Ltd., inductively coupled plasma atomic emission spectrometry). Each content was calculated based on the total amount of catalyst, Ni relative to NiO, Zr relative to ZrO2, and Si relative to SiO2. [NH3-TPD measurement]

[0056] The ammonia desorption amount was measured using a temperature-programmed ammonia desorption method (NH3-TPD method). Using BELCAT-II (registered trademark) manufactured by MicrotracBEL Corp., 0.05 g of a sample was placed in a measuring cell and pretreated at 250 °C for one hour in a hydrogen atmosphere. Afterward, the temperature was adjusted to 100 °C, and ammonia gas was introduced and adsorbed for one hour.

[0057] Next, exhaust gas treatment was conducted at 100 °C for one hour in a helium atmosphere. The amount of ammonia desorbed with the temperature increase was detected every second by a TCD detector, increasing the temperature from 100 °C to 600 °C at a rate of 10 °C per minute with a helium gas flow of 30 ml per minute. Finally, a calibration factor was calculated from the TCD signal intensity when circulating 100% helium gas and the TCD signal intensity of 5.14 vol% NH3 / He mixed gas. Using this calibration factor, the TCD signal at 100 °C to 600 °C was converted into the amount of NH3 (mmol), which was divided by a sample weight to determine the amount of ammonia desorbed per 1 g of sample at each time point.A graph was constructed with a vertical axis representing the ammonia desorption amount per 1 g of sample and a horizontal axis representing time. The time from the temperature reaching 250°C to the temperature reaching 600°C was integrated to determine the ammonia desorption amount at 250°C to 600°C. The ammonia desorption amount at 100°C or higher to lower than 250°C was also determined by the same method. These calculations were performed using analysis software provided with the device. [Measurement of crystallite size]

[0058] A sample was subjected to X-ray diffraction measurement using an X-ray diffractometer (Rigaku MultiFlex) manufactured by Rigaku Corporation. First, the sample to be measured was pulverized, packed into a sample plate, and subjected to X-ray diffraction measurement (Cu-Kα ray source) under the conditions of a tube voltage of 40 kV, a tube current of 20 mA, a scanning range of 10° to 70°, a divergence slit of 1.0 mm, a scattering slit of 1.0 mm, a light receiving slit of 0.3 mm, and a scanning speed of 4° / min. In the X-ray diffraction measurement, a diffraction peak with a peak apex near 20 = 44° was detected, and the crystallite size of Ni was calculated by the Scherrer equation using analysis software (JADE version 5.0). The NiO crystallite size of the oxide catalyst was calculated from a diffraction peak having a peak apex near 2θ = 62°. [Measurement of specific surface area]

[0059] The specific surface area was calculated using a nitrogen adsorption method (BET method). Specifically, a sample was placed in a measuring cell of approximately 0.1 g using a specific surface area measuring device (Macsorb1220 from MOUNTECH Co., Ltd.), degassing was performed at 250 °C for 40 minutes in a nitrogen gas stream, and then the sample was kept at liquid nitrogen temperature in a mixed gas stream of 30 vol% nitrogen and 70 vol% helium, and nitrogen was adsorbed until the sample reached equilibrium. Then, the temperature of the sample was gradually raised to room temperature with the above mixed gas flowing, and the amount of nitrogen desorbed during this time was measured and divided by the sample weight after measurement to calculate the specific surface area of ​​the sample. [XPS measurement]

[0060] XPS measurements were performed under the following conditions using a measurement device (ESCALAB 220I-X, manufactured by Thermo Fisher Scientific). Additionally, a commercially available reagent (3N zirconium oxide, manufactured by Kanto Chemical Co., Inc.) was used as a standard sample. Radiation source: Monochromatic Al-Kα radiation Acceleration voltage, current: 10 KV, 19.0 mA Pass energy: 20 eV Dwell time: 50 ms Energy step size: 0.1 eV [Activity assessment: hydrogenation reaction of aldehyde] <vorbehandlung>

[0061] After 4.0 g of a sample was placed into a glass tube, the glass tube was heated to 150 °C for 60 minutes under hydrogen circulation. The interior of the glass tube was then replaced with nitrogen, and the glass tube was cooled to room temperature. The sample was then placed in an autoclave in a nitrogen atmosphere. <hydrierungstest>

[0062] 100.3 g of n-butyraldehyde was charged into the autoclave described above. After charging, the temperature was raised to 100 °C while stirring at 400 rpm. After the temperature was raised, hydrogen was introduced until the pressure in the autoclave reached 5 MPa, and the autoclave was held for 2 hours while maintaining the pressure at 5 MPa. After holding, it was cooled to room temperature to obtain a reaction solution. <analyse>

[0063] The resulting reaction solution was analyzed by gas chromatography (GC-14B, manufactured by Shimadzu Corporation) to measure the mass contents of n-butyraldehyde (NBD), n-butanol (NBA), dibutyl ether (Et), 2-ethyl-1,3-hexanediol (Diol), and butylaldehyde dibutyl acetal (Ac). This was then converted into the molar content of each component, and the conversion and selectivity were calculated using the following formula. [Implementation] Conversion (%) = molar NBD content after reaction − molar NBD content before reaction) / molar NBD content before reaction × 100 [NBA selectivity] NBA selectivity (%) = molar NBD content after reaction / (molar NBD content after reaction − molar NBD content before reaction) × 100 [Et-selectivity] Et selectivity (%) = molar Et content after reaction × 2 / (molar NBD content after reaction − molar NBD content before reaction) × 100 [Diol selectivity] Diol selectivity (%) = molar diol content after reaction × 2 / (molar NBD content after reaction − molar NBD content before reaction) × 100 [Ac selectivity] Ac selectivity (%) = molar Ac content after reaction × 3 / (molar NBD content after reaction − molar NBD content before reaction) × 100 [Example 1] Preparation step for an acidic aqueous solution

[0064] 1418.0 g of nickel sulfate hydrate [Ni(SO4)2 6H2O] (manufactured by FUJIFILM Wako Pure Chemical Corporation) was dissolved in 5.4 L of tap water, and then 94.0 g of a zirconium sulfate solution (manufactured by DAIICHI KIGENSO KAGAKU KOGYO CO., LTD.) was added and adjusted to 80 °C to prepare an acidic aqueous solution. The pH of the acidic aqueous solution was 2.1. Preparation step for a basic suspension

[0065] 3.1 L of tap water was added to a 15 L stirred tank, and 333.0 g of sodium carbonate (Na2CO3, manufactured by KANTO CHEMICAL CO., INC.) was dissolved therein to adjust the temperature to 80 °C. Then, 76.3 g of diatomaceous earth [Celite505] (manufactured by Imerys High Resistance Minerals, Japan) and 53.5 g of diatomaceous earth [FilterCel] (manufactured by Imerys High Resistance Minerals, Japan) were added. The mixture was stirred for 60 minutes to disperse the diatomaceous earth, thereby preparing a basic suspension. The pH of the basic suspension was 11.3. By using two types of diatomaceous earth, good formability and good bondability with Ni and Zr could be obtained. Neutralization step

[0066] The acidic aqueous solution was poured into the basic suspension over 80 minutes using a peristaltic pump to obtain a mixed solution. The pH of the mixed solution was 6.3. Aging step

[0067] Stirring was continued for one hour while keeping the mixed solution at 80 °C. Re-aging step

[0068] 645.0 g of sodium carbonate (manufactured by KANTO CHEMICAL CO., INC.) was dissolved in 3.0 L of tap water and adjusted to 80 °C to prepare a basic aqueous solution for pH adjustment. This was added to the mixed solution after the aging step over 10 minutes using a peristaltic pump to adjust the pH to 9.5. Stirring was continued for 120 minutes, maintaining the temperature at 80 °C even after the completion of casting, thereby obtaining a precursor slurry. Precursor separation step

[0069] The precursor slurry was filtered under reduced pressure using a Nutsche filter to obtain a cake-like precursor. The entire amount of the precursor was poured into 6 L of warm water adjusted to 40 °C and filtered to perform suspension washing. This step was repeated, and once the electrical conductivity of the filtrate reached 1.5 mS / cm, the washing was stopped. The cake-like precursor was dried in a box dryer at 120 °C for 12 hours. After drying, the cake was pulverized using a hammer mill to obtain a powdered precursor. Calcination step of the catalyst precursor

[0070] The precursor was formed into a cylindrical shape having a diameter of 3.2 mm and a height of 3.2 mm using a tablet forming machine. This precursor was calcined at 370°C for 6 hours using a muffle furnace to obtain an oxide catalyst. Further, this oxide catalyst was reduced at 430°C for 10 hours in a hydrogen atmosphere and subjected to a stabilization treatment at 80°C to obtain a catalyst. The production conditions and the like are shown in Table 1. In addition, the above-described measurement or evaluation was performed using this sample. The results are illustrated in Table 2.

[0071] The NH3-TPD measurement profile of this catalyst is shown in Fig. 1 together with the catalysts of Comparative Examples 1 and 2. Fig. Figure 1 illustrates the amount of NH3 desorption according to the heating temperature. The XPS profile of Zr of this catalyst is shown in Fig. 2 compared to ZrO2. [Example 2]

[0072] A catalyst was obtained in the same manner as in Example 1, except that 500.0 g of sodium carbonate (manufactured by KANTO CHEMICAL CO., INC.) was used in the re-aging step and the pH of the mixed solution was adjusted to 8.8. The obtained catalyst was subjected to the above-mentioned measurement or evaluation. [Example 3]

[0073] A catalyst was obtained in the same manner as in Example 1, except that 64.1 g of diatomaceous earth [Celite505] (manufactured by Imerys High Resistance Minerals, Japan) and 45.0 g of diatomaceous earth [FilterCel] (manufactured by Imerys High Resistance Minerals, Japan) were added in the basic suspension preparation step. The obtained catalyst was subjected to the above-mentioned measurement or evaluation. [Example 4]

[0074] A catalyst was obtained in the same manner as in Example 1, except that 43.1 g of a zirconium sulfate solution (manufactured by DAIICHI KIGENSO KAGAKU KOGYO CO., LTD.) was added in the acidic aqueous solution preparation step, and 64.1 g of diatomaceous earth [Celite505] (manufactured by Imerys High Resistance Minerals, Japan) and 45.0 g of diatomaceous earth [FilterCel] (manufactured by Imerys High Resistance Minerals, Japan) were added in the basic suspension preparation step. The obtained catalyst was subjected to the above-mentioned measurement or evaluation. [Comparison example 1]

[0075] A catalyst was obtained in the same manner as in Example 1, except that 379.5 g of sodium carbonate (manufactured by KANTO CHEMICAL CO., INC.) was used in the re-aging step and the pH of the mixed solution was adjusted to 7.5. The obtained catalyst was subjected to the above-mentioned measurement or evaluation. [Comparison example 2]

[0076] A catalyst was obtained in the same manner as in Example 1 except that the holding time in the re-aging step was set to 0. The obtained catalyst was subjected to the above-mentioned measurement or evaluation. [Table 1] Elements Unit Example 1 Example 2 Example 3 Example 4 Comparison example 1 Comparison example 2 Preparation step for an acidic aqueous solution Raw material No - Ni sulfate Ni sulfate Ni sulfate Ni sulfate Ni sulfate Ni sulfate Zi - Zi sulfate Zi-Sulfate Zi sulfate Zi sulfate Zi sulfate Water - tap water tap water tap water tap water tap water tap water Acidic aqueous solution Temperature °C 80 80 80 80 80 80 2,1 2,1 2,5 1,6 2,1 2,1 Preparation step for a basic suspension Raw material Diatomaceous earth - Celite505 FiterCel Celite505 FiterCel Celite505 FilterCel Celite505 FiterCel Celite505 FiterCel Celite505 FiterCel Basic raw material - Na2CO2 Na2CO3 Na2Co3 Na2Co3 Na2CO3 Na2CO3 Water tap water tap water tap water tap water tap water Leakage water Basic suspension temperature °C 80 80 80 80 80 80 pH 11,3 11,3 11,3 11,4 * 10,9 11,1 Neutralization step Neutration conditions Addition process Acidic aqueous solution - basic suspension Acidic aqueous solutionbasic suspension Acidic aqueous solution - basic suspension Acidic aqueous solution - basic suspension Acidic aqueous solution - basic suspension Acidic aqueous solution - basic suspension Encore time minute 80 80 80 80 80 80 Mixed solution temperature °C 80 80 80 80 80 80 pH - 6,3 6,4 6,4 6,4 6,3 6,3 raking step Crop conditions temperature °C 80 80 80 80 80 80 pH (start - end) 6.3 - 6.3 6.4 - 6.4 6.4-6.4 6.4 - 6.4 6.3 - 6.3 6.3 - 6.4 Aging time minute 60 60 60 80 60 60 Reforestation step Re-aging conditions temperature °C 80 80 80 80 80 80 (Start - End) °C 9.5 - 9.4 6.8 - 8.6 9.3 - 9.2 9.0 - 9.0 7.6 - 7.6 9.0 Regeneration time minute 120 120 120 120 120 0 Separation step Separation conditions method - Filtered under reduced pressure Filtered under reduced pressure Filtered under reduced pressure Filtered under reduced pressure Filtered under reduced pressure Filtered under reduced pressure Washing conditions method - Suspension washing Suspension washing Suspension washing Suspension washing Suspension washing Suspension washing solvent - ion-exchanged water Ion-exchanged water Ion-exchanged water Ion-exchanged water Ion-exchanged water Ion-exchanged water temperature °C 40 40 40 40 40 40 Filtrate conductivity mS / cm 1.5 1,7 1,2 1,5 1,5 1,5 Dry method - Heat drying Heat drying Heat drying Heat drying Heat drying Heat drying temperature °C 120 120 120 120 120 120 Time hour 12 12 12 12 12 12 Calcination step Form conditions method - Tablet presses Tablet presses Tablet presses Tablet presses Tablet presses Tablet presses form - 32 mmϕ 3.2 mmϕ 3.2 mmϕ 3.2 mmϕ 32 mmϕ 3.2 mmϕ 3.2 mmH 3.2 mmH 3.2 mmH 3.2 mmH 3.2 mmH 3.2 mmH cylinder cylinder cylinder cylinder cylinder cylinder Calcination conditions Calcination temperature °C 370 370 370 370 370 370 Cat vaccination time hour 6 6 6 6 6 6 atmosphere - Air Air Air Air Air Air Reduction and stabilization step Reduction and stabilization condition Reduction temperature °C 420 420 420 420 420 420 hour 10 10 Reduction time 10 10 10 10 atmosphere - hydrogen hydrogen hydrogen hydrogen hydrogen hydrogen Stabilization temperature °C 80 80 80 60 80 80 Heat limit hour 120 120 120 120 120 120 atmosphere - Air Air Air Air Air Air [Table 2] Elements Unit Example 1 Example 2 Example 3 Example 4 Comparison example 1 Comparison example 2 catalyst Components - - Ni, Zr, diatomaceous earth Ni, Zr, diatomaceous earth Ni, Zr, diatomaceous earth Ni, Zr, diatomaceous earth Ni, Zr, diatomaceous earth Ni, Zr, diatomaceous earth Basic composition Ni (relative to NiO) Mass% 65,9 67,1 71,9 71,6 69,5 67,5 Zr (relative to ZrO2) Mass% 4,4 3,3 4,4 1,7 4,3 4,3 Silicon dioxide (based on SiO2) Mass % 19,5 18,7 16,9 17,8 15,8 18,8 Properties of solid acid NH1 desorption rate in a range of 250 °C to 600 °C mmol / g 1,84 1,37 1,12 1,51 0,77 0,75 NH1 desorption amount in a range of 100 °C or more to less than 250 °C mmol / g 0,39 0,25 0,25 0,28 0,18 0,16 Characteristics Ni crystallite size nm 4,2 4,9 4,7 5,5 9,5 8,4 Specific surface m 2 / g 127 180 112 123 74 76 form 3 mmφ 3 mmφ 3 mmφ 3 mmφ 3 mmφ 3 mmφ 3 mmH 3 mmH 3 mmH cylinder 3 mmH 3 mmH 3 mmH cylinder cylinder cylinder cylinder cylinder Aldehyde hydrogenation test Implementation % 99.97 99.99 99,98 99,98 97,32 99,95 NBA selectivity 91,2 87,9 82,3 86,5 56,7 Et selectivity % 0,1 0,3 1,4 0,3 1,6 0,2 Diol selectivity % 3,0 2,5 2,7 3,8 0,1 3,0 Ac selectivity % 4,5 4,9 13,5 9,3 32,5 13,3 QUOTES CONTAINED IN THE DESCRIPTION

[0000] This list of documents submitted by the applicant was generated automatically and is included solely for the convenience of the reader. This list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions. Cited patent literature

[0000] JP-B-44-17127

[0004] JP-A-2020-163334

[0004] JP-A-2005-279587

[0004] < / analyse> < / hydrierungstest> < / vorbehandlung>

Claims

[1] A nickel-diatomaceous earth catalyst which is a catalyst for hydrogenating an aldehyde, the catalyst comprising: Ni, Zr and diatomaceous earth, wherein Ni is contained in a range of 40 to 90 mass%, based on NiO, Zr is contained in a range of 0.5 to 10 mass%, based on ZrO2, Silicon dioxide is contained in a range of 10 to 40 mass%, based on SiO2, and a desorption amount of NH3 in a temperature range of 250 °C to 600 °C in the temperature-programmed desorption measurement of NH3 is 1.00 mmol / g or more. [2] The nickel-diatomaceous earth catalyst according to claim 1, wherein the Ni crystallite size is in the range of 2 nm to 8 nm. [3] Nickel-diatomaceous earth catalyst according to claim 2, wherein the specific surface area is 80 m 2 / g or more. [4] The nickel-diatomaceous earth catalyst according to any one of claims 1 to 3, wherein a binding energy of Zr is 0.4 eV or more higher than a binding energy of ZrO2. [5] A process for producing a nickel-diatomaceous earth catalyst which is a catalyst for hydrogenating an aldehyde, the process comprising: an acidic aqueous solution preparation step for obtaining an acidic aqueous solution in which Ni and Zr are dissolved; a basic suspension preparation step for obtaining a basic suspension in which at least one of NaOH and Na2CO3 is dissolved and diatomaceous earth is dispersed; a neutralization step of adding the acidic aqueous solution to the basic suspension to obtain a mixed solution; an aging step of adjusting a pH of the mixed solution to 6.5 or less and storing the mixed solution for 30 minutes or more; a re-aging step of adjusting the pH of the mixed solution obtained in the aging step to a range of 8.5 to 9.5 and holding the mixed solution for 60 minutes or more to obtain a precursor slurry; a separation step for separating a precursor from the precursor slurry; and a calcination step to calcine the precursor.

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