Nickel phosphide catalyst and method for producing hydrogenated organic compounds using the same

Abstract

To provide a new catalyst that solves problems with a sponge catalyst, conventionally used in hydrogenation of organic compounds.SOLUTION: A catalyst contains nanoparticles of nickel phosphide as an active ingredient.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a catalyst containing nickel phosphide nanoparticles as an active ingredient, and a method for producing a hydrogenated compound and a method for producing a ring-opened compound using the catalyst. [Background technology]

[0002] When nickel or cobalt is used as a catalyst, it is known to use a sponge-like catalyst made of nickel or cobalt. Such a sponge-like catalyst is also known as a Raney catalyst (trademark registration number 3214822) (Patent Document 1, Non-Patent Document 1).

[0003] This sponge-like catalyst (hereinafter referred to as "sponge catalyst") is made by dissolving and removing only the aluminum from an alloy consisting of nickel or cobalt and aluminum (also called Raney alloy) using an aqueous sodium hydroxide solution.

[0004] Such sponge catalysts can use the sponge metal itself as the catalyst, but it is also known to further contain other elements such as manganese, copper, iron, chromium and molybdenum in order to improve the performance of the catalyst (Patent Document 2).

[0005] Specifically, reactions using sponge catalysts include the hydrogenation of various organic compounds, such as the hydrogenation of unsaturated compounds having double or triple bonds, aldehyde compounds, carbonyl compounds, nitrile compounds, and nitro compounds, the hydrogenation of aromatic compounds and heterocycles, dehalogenation, lactam purification, hydrogenolysis, and reductive amination.

[0006] In addition, sponge catalysts using such elements are known to be very unstable in the atmosphere and to pose a risk of ignition (Patent Document 3). Therefore, the preparation of the catalyst, the replacement of the solvent, and all of the reaction processes must be carried out in an anaerobic atmosphere, and exposure to the atmosphere must be strictly avoided during storage, and the catalyst must be stored in water or alcohol. In industry, the catalyst is stored in the form of an alloy of a metal with catalytic activity, such as cobalt, and a metal that can be dissolved and removed with acids or alkalis in which the metal does not dissolve. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 6-121929 [Patent Document 2] JP 2015-143194 A [Non-patent literature]

[0008] [Non-Patent Document 1] Shigeo Nishimura, "Handbook of Heterogeneous Catalytic Hydrogenation for Organic Synthesis", pp. 261 - 263, John Wiley and Sons, New York, 2001 Summary of the Invention [Problem to be solved by the invention]

[0009] An object of the present invention is to provide a new catalyst which solves the problems associated with sponge catalysts which have been conventionally used for the hydrogenation of organic compounds. [Means for solving the problem]

[0010] As a result of intensive research into solving the above problems, the inventors have discovered that the above problems can be solved by using a catalyst containing nickel phosphide nanoparticles as an active ingredient, and have thus completed the present invention.

[0011] That is, the present invention is a catalyst characterized by having nickel phosphide nanoparticles as an active ingredient.

[0012] The present invention also provides a method for producing a hydrogenated organic compound, which comprises hydrogenating an organic compound using the above catalyst.

[0013] Furthermore, the present invention relates to a method for producing a ring-opened compound, which comprises ring-opening a cyclic hetero compound using the above catalyst.

[0014] Furthermore, the present invention relates to a method for producing a hydrogenated ring-opened compound, which comprises carrying out hydrogenation and ring-opening of a cyclic hetero compound having an unsaturated bond in one step using the above catalyst. Effect of the Invention

[0015] The hydrogenation catalyst of the present invention is extremely stable even in the atmosphere and does not pose a risk of ignition.

[0016] Moreover, the method for producing a hydrogenated organic compound of the present invention can produce a hydrogenated organic compound with a high conversion rate and yield.

[0017] Furthermore, the method for producing a ring-opened compound of the present invention can produce the ring-opened compound with a high conversion rate and yield.

[0018] Furthermore, the method for producing a hydrogenated ring-opened compound of the present invention allows hydrogenation and ring-opening to be carried out in one step, and further allows production with good conversion and yield. [Brief description of the drawings]

[0019] [Figure 1] 1 is a HAADF-STEM (High-Angle Annular Dark Field Scanning Transmission Electron Microscope) image of Example Catalyst 1. [Diagram 2]FIG. 1 is a diagram showing the results of X-ray diffraction (XRD: X-Ray diffraction) of Example Catalyst 1 together with a JCPDS (Joint Committee of Powder Diffraction Standards) card [Ni2P (03-953)]. [Diagram 3] A part of Figure 1 is overlaid with an image showing the locations of nickel and phosphorus by EDX (Energy dispersive X-ray spectrometry) line analysis. [Figure 4] 1 is an image of nickel element mapping of Example Catalyst 1 by HAADF-STEM. [Diagram 5] 1 is an image of Example Catalyst 1, in which phosphorus element mapping was performed by HAADF-STEM. [Figure 6] This is an image obtained by superimposing the images in Figures 4 and 5. [Figure 7] 1 is a HAADF-STEM image of Example Catalyst 1'. [Figure 8] FIG. 1 shows the X-ray diffraction results and the JCPDS card [Ni2P (03-953)] for Example Catalyst 1'. [Figure 9] 1 is an image of nickel element mapping of Example Catalyst 1' by HAADF-STEM. [Figure 10] 1 is an image of Example Catalyst 1', where phosphorus element mapping was performed by HAADF-STEM. [Figure 11] 1 is an image of Example Catalyst 1', in which nickel element and phosphorus element were mapped by HAADF-STEM. [Figure 12] FIG. 1 is an Arrhenius plot of HMF hydrogenation using Example Catalyst 1′ and Raney Nickel. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] The catalyst of the present invention (hereinafter referred to as "the catalyst of the present invention") is nickel phosphide (Ni x P y) as an active ingredient. In the present invention, the term "nanoparticles" refers to those having an average particle size of the nano-order, preferably 1 to 500 nm, and more preferably 10 to 300 nm. In the present invention, the average particle size refers to the average value of the observation results obtained by observing an arbitrary number of particles with an electron microscope such as a transmission electron microscope.

[0021] The shape of the nanoparticles is not particularly limited, but examples include spherical, elongated oval, and worm-like nanoparticles (NW).

[0022] Nickel phosphide (Ni x P y The ratio of nickel to phosphorus in the nanoparticles of nickel phosphide (Ni) is preferably 1:0.3 to 1, that is, the molar ratio of phosphorus to nickel is preferably 1 or less, and more preferably 0.8 or less. x P y ) are Ni3P, Ni5P2, Ni 12 P5, Ni2P, Ni5P4, etc. are included, and Ni2P and Ni5P4 are particularly preferred.

[0023] The nickel phosphide as described above can be obtained by a known method, for example, as a precipitate from a mixed solution of a nickel compound solution and a phosphorus compound solution.

[0024] A method for obtaining such a precipitate is also described in detail in the literature (Junfeng Liu and Andreu Cabot et al, J. Mater. Chem. A, 2018, 6, 11453-11462). This method involves heating and holding a nickel salt, a component that suppresses the growth of particle size during reduction of the nickel salt, a solvent, and a phosphorus compound that is easily soluble in the solvent in an inert gas atmosphere.

[0025] The nickel salt used in the above method is not particularly limited, but is preferably one that is easy to handle. Examples of such nickel salts include NiCl2, Ni(acac)2, and Ni(NO3)2.

[0026] Examples of the component that suppresses the growth of particle diameter when reducing the nickel salt used in the above method include one or more capping components selected from the group consisting of compounds having an amine group, such as propylamine, butylamine, octylamine, decylamine, dodecylamine, hexadecylamine, and oleylamine, which are known to suppress the growth of metallic nickel (JP Patent Publication No. 2014-514451). At first glance, it seems that the action of such a capping component that suppresses the growth of metallic nickel is different from that of nickel phosphide, since the capping component can also suppress the particle growth of nickel phosphide, as described below. However, according to the verification by the present inventors, it has been confirmed that the electronic state of nickel in nickel phosphide is the same as that of metallic nickel with a valence of 0, and it is believed that the particle growth during generation is suppressed by the same action as the above-mentioned suppression of the growth of metallic nickel.

[0027] The solvent used in the above method is not particularly limited, but is preferably a polar solvent having a high boiling point, such as 1-octadecene.

[0028] The phosphorus compound used in the above method that is easily soluble in the above solvent is not particularly limited, but is preferably one that is easy to handle. Examples of such phosphorus compounds include tertiary phosphites such as triphenyl phosphite, and tertiary phosphines such as trioctyl phosphine and triphenyl phosphine. The term "easily soluble" refers to the combination of the raw material phosphorus compound and the solvent, and is preferably Ni x P y The solubility of the raw material phosphorus compound is preferably such that the raw material phosphorus compound can be completely dissolved at a heating temperature not higher than the temperature at which the precipitate is formed. For example, a combination that allows the raw material phosphorus compound to dissolve at 14 g / L or more at 100° C. is preferred.

[0029] In the above method, a nickel salt, a component that inhibits the growth of particle diameter when the nickel salt is reduced, and a phosphorus compound that is easily soluble in the solvent are used in a molar amount of 1 to 100, preferably 10 to 50, and a phosphorus compound is used in a molar amount of 1 to 100, preferably 10 to 50, when the nickel salt is 0.1 to 10 or preferably 1 to 5, in a solvent, and the mixture is heated to 250 to 350°C, preferably 280 to 320°C, in an inert gas atmosphere such as argon or nitrogen, and is maintained for about 2 to 6 hours to obtain a precipitate. This precipitate may be washed and filtered. After this washing and filtration, it may be further dried, etc.

[0030] In the above method, in order to promote the action of the catalyst of the present invention, a salt of a metal component such as cobalt, manganese, copper, iron, chromium or molybdenum may be added in place of a part of the nickel salt.

[0031] The catalyst of the present invention thus obtained can be used for hydrogenation and the like in place of conventional sponge catalysts. The reason is unclear, but it is thought that nickel in nickel phosphide is in the same state as metal (0 valence) and is nano-sized. The method for obtaining nickel phosphide of the present invention is not particularly limited, but it can also be obtained by adjusting the amount of phosphorus compound charged as a raw material. When adjusting the amount of phosphorus compound charged in this way, [moles of phosphorus in phosphorus compound / moles of nickel in nickel salt] is preferably 2 to 50, more preferably 2.5 to 30, and further preferably 5 to 25.

[0032] The catalyst of the present invention can be used not only for hydrogenation, but also for ring-opening of cyclic heterocyclic compounds. Although the reason for this is unclear, it is believed that the phosphate sites on the surface of nickel phosphide promote the hydration reaction.

[0033] Furthermore, the catalyst of the present invention can simultaneously hydrogenate and open the ring of a cyclic heterocyclic compound having an unsaturated bond (this is sometimes called a "one-step reaction of hydrogenation and ring-opening"), although the reason for this is not clear.

[0034] The valence of nickel in the catalyst of the present invention can be analyzed, for example, by X-ray absorption fine structure (XAFS). Specifically, by irradiating a metal atom with high-intensity X-rays, preferably high-intensity X-rays with continuously changing energy, the inner shell electrons of the metal atom are excited to an energy level equal to or higher than the unoccupied orbital, and the excited metal atom emits a photoelectron having a kinetic energy equivalent to the difference between the excitation energy of the incident X-rays and the binding energy of the inner shell electrons, and a fine structure appears near the absorption edge in the X-ray absorption spectrum of the metal atom, and the electronic state of the metal atom can be identified by analyzing this fine structure.

[0035] Within this XAFS energy range, the fine structure that appears around 10 eV near the absorption edge is called X-ray absorption near edge structure (XANES). XANES is caused by excitation to unoccupied orbitals, and is a spectral structure that depends on the oxidation number and coordination structure of the metal atom. The energy of the absorption edge in the XANES spectrum varies depending on the electronic state (valence) of the metal atom.

[0036] When the catalyst of the present invention was analyzed by XANES, Ni x P y The energy of the absorption edge of the nanoparticles (Ni2P, Ni5P4, NiP2, and NiP nanoparticles) is located between that of the zero-valent Ni metal and NiO, and Ni x P y This indicates that the average oxidation state of the Ni species in the nanoparticles is in the range of 0 to 2.18. In particular, the absorption edge energies of the Ni2P and Ni5P4 nanoparticles are close to that of metallic Ni, suggesting that they exhibit a metallic-like state in air.

[0037] On the other hand, within the XAFS energy range, the modulation structure that continues from the absorption edge to the high-energy side of about 1000 eV is called the extended X-ray absorption fine structure (EXAFS). EXAFS is a vibration structure obtained due to the interaction between excited electrons and scattered electrons from nearby atoms, and the radial distribution function obtained by Fourier transform contains information about the local structure of the metal atom (surrounding atomic species, number of coordinated atoms, and interatomic distance).

[0038] When the catalyst of the present invention was analyzed by EXAFS, Ni2P nanoparticles and Ni5P4 nanoparticles showed two peaks at distances of 1.7 Å and 2.3 Å, which corresponded to Ni-P bonds and Ni-Ni bonds, respectively.

[0039] When the electronic states of surface Ni and P of the catalyst of the present invention were analyzed by X-ray photoelectron spectroscopy (XPS), the Ni 2p spectrum of the Ni2P nanoparticles mainly showed binding energy peaks of Ni 2p3 / 2 and Ni 2p1 / 2 located at 853.1 eV and 870.1 eV, which are close to the Ni 2p3 / 2 (852.8 eV) and Ni 2p1 / 2 (870.0 eV) of metallic Ni, and were consistent with the above-mentioned XANES results. In addition, the P 2p spectrum showed two peaks at 129.5 eV and 134.4 eV, indicating that P of different electronic states coexist on the surface of the Ni2P nanoparticles. 129.5 eV is P 0 The peak at 134.4 eV is thought to be near the zero to one charge of P, and the ... non-reduced phosphate species PO 3- It is thought that.

[0040] The catalyst of the present invention can be used as a hydrogenation catalyst as it is, but it is preferable to support the catalyst on a carrier, since this facilitates separation of the catalyst from the reaction system and may improve the durability of the catalyst, which is industrially advantageous.

[0041] The carrier capable of supporting the catalyst of the present invention is not particularly limited, and various carriers having a large specific surface area and widely used for catalytic applications can be used. Examples of such carriers include inorganic oxide fine particles and activated carbon. Among these carriers, inorganic oxide fine particles are preferable. The inorganic oxide fine particles may be fine particles of metal oxides such as alumina, silica, titania, zirconia, magnesia, yttrium oxide, niobium pentoxide, and mordenite, as well as combinations of these oxides and fine particles of composite oxides such as hydroxyapatite (HAP), zeolite, and hydrotalcite (HT). The fine particles are not particularly limited as long as they have a particle diameter larger than that of nano-sized nickel phosphide, and examples thereof include powders having a particle diameter of about 10 to 100 μm on a volume basis and spherical particles having a particle diameter of about 0.5 to 5 mm.

[0042] The specific surface area of ​​the carrier is not particularly limited, but may be, for example, 10 to 1000 m 2 / g, and 100 to 500m 2 / g is more preferred.

[0043] Among the above-mentioned carriers capable of supporting the catalyst of the present invention, some have a carrier effect depending on the reaction. For example, when used in a ring-opening reaction, a basic carrier such as hydrotalcite is preferred, and when used in the hydrogenation of carbonyl groups, hydrotalcite is preferred.

[0044] Furthermore, the method for supporting the catalyst of the present invention on a carrier is not particularly limited, and examples thereof include a method in which the carrier is charged into a solution containing a nickel salt or a phosphorus compound used in preparing nickel phosphide, the carrier is impregnated with the nickel salt or the phosphorus compound, and then reduction, drying, or calcination is performed to support nickel phosphide on the carrier; a method in which the carrier is impregnated with a solution in which nickel phosphide nanoparticles are dispersed; and a method in which the carrier is mixed with a solution in which nickel phosphide nanoparticles are dispersed.

[0045] By using the catalyst of the present invention, organic compounds can be hydrogenated to produce hydrogenated organic compounds. The hydrogenation conditions are not particularly limited, and it is sufficient to use the catalyst of the present invention in hydrogenation using a conventional sponge catalyst. There is no need to make large-scale modifications to conventional equipment, and general-purpose synthesis equipment such as an autoclave can be used. In addition, since the catalyst of the present invention has a small particle size of nanoparticles, the yield of hydrogenated organic compounds by hydrogenation is rapidly improved.

[0046] The catalyst of the present invention is a safe alternative to conventional sponge catalysts, and is expected to be effective in all catalytic reactions that can be promoted by conventional sponge catalysts. Examples of catalytic reactions include hydrogenation of unsaturated compounds having double or triple bonds, carbonyl compounds including aldehydes and ketones, nitrile compounds, nitro compounds, etc., hydrogenation of aromatic compounds and heterocycles, dehalogenation, lactam purification, hydrogenolysis, hydrogenation of reductive amination, and other hydrogenation reactions of various organic compounds.

[0047] Examples of organic compounds preferred for the above hydrogenation reaction and hydrogenated organic compounds produced by hydrogenation include the following. <Organic compounds> <Hydrogenated organic compounds> Nitrile compounds Primary amine compounds Nitro compounds Primary amine compounds Carbonyl compounds Alcohol compounds Unsaturated compounds Saturated compounds

[0048] Specifically, when an alcohol compound is produced by hydrogenating an aldehyde compound using the catalyst of the present invention, the aldehyde compound may be hydrogenated in a wet process using the catalyst of the present invention in a heated and pressurized hydrogen-containing atmosphere.

[0049] In this reaction, the catalyst of the present invention is present in the system in an amount sufficient for hydrogenating an organic compound, and the heating conditions are 20 to 200°C, preferably 60 to 180°C, and more preferably 100 to 150°C. The pressure conditions are 0.1 to 10 MPa, and preferably 0.3 to 5 MPa. The hydrogen-containing atmosphere may be hydrogen gas or a mixture of hydrogen gas and an inert gas such as argon, and hydrogen gas or a mixture of hydrogen gas and an inert gas is preferred. The solvent for the wet condition is not particularly limited, and aprotic polar solvents such as tetrahydrofuran (THF), nonpolar solvents such as toluene, various alcohols such as 2-propanol, and protic polar solvents such as water can be used. Among these solvents, protic polar solvents are particularly preferred.

[0050] The carbonyl compound is not particularly limited, and various compounds having a carbonyl group including an aldehyde group or a ketone group can be used.

[0051] In addition, by using the catalyst of the present invention, a ring-opened compound can be produced by hydrolyzing a cyclic hetero compound. The ring-opening conditions are not particularly limited, and it is sufficient to use the catalyst of the present invention. There is no need to make large-scale modifications to conventional equipment, and general-purpose synthesis equipment such as an autoclave can be used. In addition, the catalyst of the present invention has a small particle size of nanoparticles, so the yield is rapidly improved.

[0052] Organic compounds preferred for the ring-opening reaction may have a structure that allows hydration of the α-carbon of the heterocycle, and examples of such compounds include hexoses such as 5-hydroxymethylfurfural (HMF), 5-methylfurfuryl alcohol, glucose, sucrose, lactose, trehalose, maltose, mannose, galactose, fructose, sorbose, and tagatose, pentoses such as arabinose, xylose, ribose, xylulose, and ribulose, and monosaccharides and polysaccharides such as pentosan, xylan, saccharose, starch, and cellulose. Of these, HMF, methylfurfuryl alcohol, glucose, sucrose, lactose, trehalose, and maltose are preferred.

[0053] In this reaction, the catalyst of the present invention is present in the system in an amount sufficient for ring-opening of the organic compound, and the heating conditions are 20 to 200°C, preferably 60 to 180°C, and more preferably 100 to 150°C. The pressure conditions are 0.1 to 10 MPa, and preferably 0.3 to 5 MPa. The atmosphere may be an inert gas such as nitrogen or argon, a mixed gas thereof, or air. The solvent for the wet condition is not particularly limited, and may be an aprotic polar solvent such as tetrahydrofuran (THF), a nonpolar solvent such as toluene, various alcohols such as 2-propanol, or a protic polar solvent represented by water. Among these solvents, a protic polar solvent is particularly preferred.

[0054] Furthermore, by using the catalyst of the present invention, for example, if the cyclic hetero compound has an unsaturated bond, the above-mentioned hydrogenation reaction and ring-opening reaction can be carried out in one step. In that case, it is sufficient that hydrogen necessary for the hydrogenation reaction is present in the system.

[0055] In addition, when it is assumed that the catalyst of the present invention is used for industrial purposes, the reaction apparatus used is not particularly limited, and can be used in various apparatuses used for industrial purposes. Such industrial reaction apparatuses can be broadly classified into batch type (also called batch type) and continuous type. In the batch type, the steps of introducing the substrate and catalyst, reaction, and separation and recovery of the product are carried out one by one in order, and are often used in laboratory facilities. In contrast, a reactor called a continuous type is a device that is often adopted as industrial equipment, and it is possible to carry out each reaction step continuously and simultaneously, and it can be said to be an industrially advantageous reaction apparatus suitable for mass production.

[0056] Continuous reactors can be broadly divided into two types: fluidized bed reactors and fixed bed reactors. In a fluidized bed reactor, the catalyst is mixed in a suspended state with the reactants including the substrate, which is advantageous in terms of ease of contact between the reactant molecules and the catalytic active sites, but after the reaction, the catalyst and the product must be separated. In addition, since the catalyst must be suspended as particles, the catalyst particles used have a small particle size.

[0057] On the other hand, in a fixed bed reactor, only the reactants move as a fluid through the reactor, and the catalyst is fixed in the reactor, and the reactants react as they pass through the fixed catalyst bed to obtain a product. The resulting product is discharged from the reactor separated from the catalyst. For this reason, it is not necessary to remove the catalyst from the reaction system after the reaction, making it suitable for continuous operation and suitable for industrial use. In a fixed bed reactor, the reactants need spaces to pass through the catalyst bed at an appropriate flow rate, and the catalyst used in the fixed bed reactor is often molded into a granular or honeycomb shape, or a granular or honeycomb-shaped carrier on which the catalyst of the present invention is supported or impregnated.

[0058] In addition, reactions using such equipment can be divided into liquid-phase and gas-phase reactions. Liquid-phase reactions are carried out by contacting the reactants or the mixed reaction solution of the substrate and solvent with a catalyst while still in liquid form. Liquid-phase reactions do not require the reactants or reaction solution to be vaporized, so the energy required for the reaction can be reduced. On the other hand, in gas-phase reactions, the reactants are gaseous, so the molecules necessary for the reaction can easily collide with each other, resulting in superior reaction speeds.

[0059] In consideration of such a reaction apparatus and reaction mechanism, the catalyst of the present invention is preferably used in a gas phase reaction using a fixed bed reaction apparatus. EXAMPLES

[0060] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, the yields in the following examples were determined by internal standard gas chromatography (GC) quantitative analysis.

[0061] Example Catalyst 1 Preparation of Ni2P nanoparticles: Nickel chloride (NiCl2) (1 mmol), hexadecylamine (10 mmol), 1-octadecene (10 mL), and triphenyl phosphite (10 mmol) were added to a Schlenk flask and stirred at 120°C in vacuum for 1 hour. After removing impurities, moisture, and oxygen, the mixture was stirred at 300°C for 2 hours under an argon atmosphere to obtain a black colloidal solution. The mixture was then precipitated with acetone, filtered, washed several times with a mixed solvent of chloroform and acetone, and the resulting powder was dried overnight under vacuum to obtain Ni2P nanoparticles. The Ni2P nanoparticle catalyst prepared in this embodiment was a regular particle with an average diameter of 5.4 nm and a narrow size distribution (±1.4 nm). The HAADF-STEM image of Example Catalyst 1 is shown in Figure 1. The obtained Example Catalyst 1 was left to dry in the air for a day, but no ignition occurred, as is a concern with sponge catalysts.

[0062] Example Catalyst 2 Preparation of Ni5P4 nanoparticles: Ni(acac)2 (0.33mmol) and oleylamine (0.5mmol) were dissolved in n-octyl ether (4.7mL), trioctylphosphine (11mmol) was added, and the mixture was stirred at 120℃ for 1 hour in vacuum to remove impurities, moisture, and oxygen, and then stirred at 400℃ for 20 hours in an argon atmosphere to obtain a black colloidal solution. The mixture was then precipitated with acetone, filtered, washed several times with a mixed solvent of chloroform and acetone, and the obtained powder was dried overnight under vacuum to obtain Ni5P4 nanoparticles.

[0063] Example Catalyst 3 Preparation of Ni2P / mordenite: 22 mg of Example Catalyst 1 obtained by the above procedure was added to hexane (50 mL) and subjected to ultrasonic treatment for 1 hour, mordenite (1 g) was added as a carrier, and the mixture was stirred at room temperature for 6 hours. After filtration and washing, the mixture was dried in vacuum to obtain Example Catalyst 3 of the present invention.

[0064] Example Catalyst 4 Preparation of Ni2P / SiO2: Example catalyst 4 of the present invention was obtained in the same manner as Example catalyst 3, except that SiO2 was used as the carrier instead of mordenite.

[0065] Example Catalyst 5 Preparation of Ni2P / ZSM-5: Example catalyst 5 of the present invention was obtained in the same manner as Example catalyst 3, except that ZSM-5 was used as the carrier instead of mordenite.

[0066] Example Catalyst 6 Preparation of NiP2 nanoparticles: Ni(acac)2 (0.33mmol) and oleylamine (0.5mmol) were dissolved in n-octyl ether (2.0mL), trioctylphosphine (16mmol) was added, and the mixture was stirred at 120℃ for 1 hour in vacuum to remove impurities, moisture, and oxygen, and then stirred at 400℃ for 20 hours in an argon atmosphere to obtain a black colloidal solution. The mixture was then precipitated with acetone, filtered, washed several times with a mixed solvent of chloroform and acetone, and the obtained powder was dried overnight under vacuum to obtain NiP2 nanoparticles.

[0067] Comparative Example Catalyst 1 Ni2P: A reagent Ni2P was obtained from the market and used as Comparative Example Catalyst 1.

[0068] Comparative Example Catalyst 2 Co2P nanoparticles: Cobalt chloride (CoCl2) (1.0 mmol), hexadecylamine (10 mmol), triphenyl phosphite (10 mmol), and 1-octadecene (10.0 mL) were added to a Schlenk flask and stirred. The mixture was heated to 150°C for 1 hour under argon flow. The temperature was then raised to the solvent boiling point (approximately 290°C) over 20 minutes, maintained for 2 hours, cooled to 200°C, and then rapidly cooled to room temperature in a water bath to obtain a black product. The black product obtained was washed with acetone, precipitated, collected, and further washed with chloroform and acetone to obtain comparative catalyst 2.

[0069] Test Example 1 Hydrogenation reaction: The hydrogenation reaction was carried out in an autoclave. 6 mol% Ni2P / mordenite catalyst, 10 ml of water, and 0.1 mmol of the substrate 3-hexene-2,5-dione were added to the autoclave, and the following reaction was carried out under a hydrogen pressure atmosphere of 2 MPa and 100°C for 1 hour, resulting in a 96% yield.

[0070] [ka]

[0071] From the above results, it was confirmed that the catalyst of the present invention can give hydrogenated compounds in high yields even under conditions of low hydrogen pressure.

[0072] Test Example 2 Ring-opening reaction: The following reaction was carried out in the same manner as in Test Example 1, except that the substrate was 0.25 mmol of 5-methylfurfuryl alcohol and hydrogen was replaced by a 1 MPa nitrogen atmosphere, and the yield was 41%.

[0073] [ka]

[0074] From the results of Test Example 2, it was confirmed that the catalyst of the present invention can be useful in the ring-opening reaction of cyclic hetero compounds.

[0075] Test Example 3 One-step hydrogenation and ring-opening reaction: The following reaction was carried out in the same manner as in Test Example 2, except that the nitrogen was replaced with a 2 MPa hydrogen atmosphere, and the yield was 79%.

[0076] [ka]

[0077] The results of Test Example 3 demonstrate that the catalyst of the present invention can efficiently carry out hydrogenation and ring-opening reaction of a cyclic hetero compound having an unsaturated bond in one step.

[0078] Test Example 4 Substrate diversity: The following reaction was carried out in the same manner as in Test Example 3 except that the substrate was changed to HMF (5-hydroxymethylfurfural), and the yield was 84%.

[0079] [ka]

[0080] Test Example 5 Catalysts and versatile supports: The following reaction was carried out in the same manner as in Test Example 3, except that the substrate was 5-methylfurfural, the reaction temperature was 130° C., and the reaction time and catalyst were changed as shown in Table 1. The results are shown in Table 1.

[0081] [ka]

[0082] [Table 1]

[0083] As shown in Table 1, the reaction hardly proceeded with powdered Ni2P or Co2P nanoparticles, whereas the reaction with Ni x P y Nanoparticle catalyst and Ni x P y It was found that the catalyst with nanoparticles supported on the carrier promoted the reaction and showed high conversion and yield. x P y It has been found that when the molar ratio of phosphorus to nickel in the nanoparticles is 1 or less, preferably 0.8 or less, the performance as a catalyst is high.

[0084] Test Example 6 Catalyst durability: In order to evaluate the durability of the catalyst of the present invention, the catalyst used in the reaction of Example 4 in Table 1 was filtered, and then the same reaction as that in the comparison of the catalyst was repeated to verify the durability of the catalyst of the present invention. The results are shown in Table 2.

[0085] [Table 2]

[0086] The results in Table 2 show that the catalyst of the present invention has excellent durability.

[0087] In addition, the structure of the catalyst of the present invention was analyzed. The results are shown in Figure 2. Figure 2 shows the results of X-ray diffraction and the JCPDS card [Ni2P (03-953)] for Example Catalyst 1. The vertical bar graph in Figure 2 shows the Ni2P peaks listed on the JCPDS card. A peak characteristic of Ni2P powder was confirmed in Example Catalyst 1 of the present invention. This shows that Example Catalyst 1 contains Ni2P. Similarly, the structures of Example Catalysts 2 and 6 were identified from the results of X-ray diffraction and the JCPDS card, and it was confirmed that they contain Ni5P4 and NiP2, respectively.

[0088] Figure 3 is an image in which the locations of Ni and P were observed by EDX (Energy dispersive X-ray spectrometry) line analysis overlaid on a portion of Figure 1. From this result, it was found that Ni and P elements are uniformly distributed within one nanoparticle in Example Catalyst 1.

[0089] Figures 4 and 5 are images of element mapping performed by HAADF-STEM. Figure 4 is an image showing the distribution of Ni elements, Figure 5 is an image showing the distribution of P elements, and the right side of Figure 6 is an image combining the Ni element distribution and the P element distribution. From these results, it was found that Ni elements and P elements are distributed roughly uniformly without bias in Example Catalyst 1.

[0090] From the results of analysis by XRD and HAADF-STEM, it was found that the example catalyst 1 had a nano-sized crystal structure with a regular shape, the constituent element of which was Ni2P.

[0091] Example Catalyst 1' Preparation of Ni2P NWs (worm-like nanoparticles): Nickel acetylacetonate (Ni(acac)2) (1 mmol), hexadecylamine (10 mmol), and triphenylphosphite (10 mmol) were added to a Schlenk flask and stirred at 120 °C for 1 hour in vacuum. After removing impurities, moisture, and oxygen, the mixture was stirred at 315 °C for 2 hours under an argon atmosphere to obtain a black colloidal solution. The mixture was then cooled to room temperature, acetone was added, and the resulting precipitate was filtered. The powder was washed several times with a mixed solvent of chloroform and acetone (1:1), and dried overnight under vacuum to obtain Ni2P NW. The Ni2P NW catalyst prepared in this experiment had a unique worm-like nanostructure with a length of 25 nm and a width of 3 nm that was regularly formed. The HAADF-STEM image of Example Catalyst 1' is shown in Figure 7. The obtained Example Catalyst 1 was left to dry in the air for a day, but no ignition occurred, as is a concern with sponge catalysts.

[0092] In addition, structural analysis was performed on Example Catalyst 1'. The results are shown in Figure 8. Figure 8 shows the results of X-ray diffraction for Example Catalyst 1' together with the JCPDS card [Ni2P (03-953)]. The vertical bar graph in Figure 8 shows the Ni2P peaks listed on the JCPDS card. A peak characteristic of Ni2P powder was confirmed in Example Catalyst 1' of the present invention. This shows that Example Catalyst 1' contains Ni2P.

[0093] Figures 9, 10, and 11 are images of element mapping performed by HAADF-STEM. Figure 9 is an image showing the distribution of Ni elements, Figure 10 is an image showing the distribution of P elements, and Figure 11 is an image combining the Ni element distribution and the P element distribution. From these results, it was found that in Example Catalyst 1, Ni elements and P elements are distributed roughly uniformly without bias.

[0094] The results of the HAADF-STEM analysis showed that the example catalyst 1 had a nano-sized crystal structure with a regular shape, the crystal structure containing Ni2P as a constituent element.

[0095] Example Catalyst 7 Preparation of Ni2P / HT: 30 mg of Example Catalyst 1' obtained by the above procedure was added to hexane (50 mL) and ultrasonically treated for 1 hour, hydrotalcite (AD-500NS: 1 g, manufactured by Tomita Pharmaceutical Co., Ltd.) was added as a carrier, and the mixture was stirred at room temperature for 6 hours. After filtration and washing, the mixture was dried in vacuum to obtain Example Catalyst 7 of the present invention.

[0096] Example Catalyst 8 Preparation of Ni2P / TiO2: 30 mg of Example Catalyst 1' obtained by the above procedure was added to hexane (50 mL) and subjected to ultrasonic treatment for 1 hour. TiO2 (JRC TIO-4 manufactured by Fuji Silysia Chemical Industries, Ltd.: 1 g) was added as a support, and the mixture was stirred at room temperature for 6 hours. After filtration and washing, the mixture was dried in vacuum to obtain Example Catalyst 8 of the present invention.

[0097] Example Catalyst 9 Preparation of Ni2P / Y2O3: 30 mg of Example Catalyst 1' obtained by the above procedure was added to hexane (50 mL) and ultrasonically treated for 1 hour, and then YO (manufactured by Wako Pure Chemical Industries, Ltd.: 1 g) was added as a carrier, and the mixture was stirred at room temperature for 6 hours. After filtration and washing, the mixture was vacuum dried to obtain Example Catalyst X of the present invention.

[0098] Example Catalyst 10 Preparation of Ni2P / ZrO2: 30 mg of Example Catalyst 1' obtained by the above procedure was added to hexane (50 mL) and subjected to ultrasonic treatment for 1 hour. ZrO2 (JRC ZRO-6: 1 g, manufactured by Fuji Silysia Chemical Ltd.) was added as a carrier, and the mixture was stirred at room temperature for 6 hours. After filtration and washing, the mixture was dried in vacuum to obtain Example Catalyst 10 of the present invention.

[0099] Example Catalyst 11 Preparation of Ni2P / Al2O3: 30 mg of Example Catalyst 1' obtained by the above procedure was added to hexane (50 mL) and subjected to ultrasonic treatment for 1 hour. Al2O3 (AKP-G015: 1 g, manufactured by Sumitomo Chemical Co., Ltd.) was added as a carrier, and the mixture was stirred at room temperature for 6 hours. After filtration and washing, the mixture was dried in vacuum to obtain Example Catalyst 11 of the present invention.

[0100] Example Catalyst 12 Preparation of Ni2P / Nb2O5: 30 mg of Example Catalyst 1' obtained by the above procedure was added to hexane (50 mL) and ultrasonically treated for 1 hour, and then Nb2O5 (manufactured by Wako Pure Chemical Industries, Ltd.: 1 g) was added as a carrier, and the mixture was stirred at room temperature for 6 hours. After filtration and washing, the mixture was vacuum dried to obtain Example Catalyst 12 of the present invention.

[0101] Example Catalyst 13 Preparation of Ni2P / SiO2: 30 mg of Example Catalyst 1' obtained by the above procedure was added to hexane (50 mL) and ultrasonically treated for 1 hour, SiO2 (1 g) was added as a carrier, and the mixture was stirred at room temperature for 6 hours. After filtration and washing, the mixture was dried in vacuum to obtain Example Catalyst 13 of the present invention.

[0102] Test Example 7 Hydrogenation of carbonyl groups (support effect): The hydrogenation reaction of the carbonyl group was carried out in an autoclave. 10 mol% of each catalyst, 3 mL of water, and 0.5 mmol of the substrate were added to a 50 mL stainless steel autoclave, and the reaction was carried out at 100°C for 1 hour under a hydrogen pressure of 2 MPa. The results are shown in Table 3.

[0103] [ka]

[0104] [Table 3]

[0105] Test Example 8 Catalyst durability: After the Ni2P / HT reaction in Table 3 (yield 93%), the catalyst was separated by centrifugation, washed with deionized water, and the reaction was repeated. The yields were 93% in the first run, 94% in the second run, 92% in the third run, 93% in the fourth run, and 90% in the fifth run.

[0106] Test Example 9 Hydrogenation of carbonyl groups: The hydrogenation reaction of the carbonyl group was carried out in an autoclave using Example Catalyst 7 (Ni2P / HT catalyst). 1.5 mol% (41.8 mg), 6 mol% (167 mg), or 12 mol% (333 mg) of Ni2P / HT catalyst, 3 mL of water, and 0.1 mmol of the substrate were added to a 50 mL stainless steel autoclave, and the reaction was then carried out under each of the conditions in the table below in a pressurized hydrogen atmosphere. The results are shown in Table 4.

[0107] [ka]

[0108] [Table 4]

[0109] In addition, the catalyst turnover frequency in the hydrogenation of HMF in Example 30 (60°C, H25 MPa, water 1 mL) was 14.4 for Ni2P / HT of Example Catalyst 7, while it was 0.64 for the Raney nickel catalyst, which was 22 times higher.

[0110] The Arrhenius plots for the hydrogenation of HMF are shown in Figure 12. From the slope of the Arrhenius plot, the activation energies were calculated to be 37.9 kJ / mol for Ni2P / HT and 53.7 kJ / mol for Raney nickel.

[0111] Test Example 10 Hydrogenation of nitrile groups: The hydrogenation reaction of the nitrile group was carried out in an autoclave. 5 mol% (7.4 mg) of Ni2P NW catalyst, 3 mL of ammonia water (NH3aq.), and 0.5 mmol of the substrate were added to a 50 mL stainless steel autoclave, and the reaction was carried out under the conditions shown in the table below in a pressurized hydrogen atmosphere. The results are shown in Table 5.

[0112] [ka]

[0113] [Table 5]

[0114] Test Example 11 Hydrogenation of nitrile groups: The hydrogenation reaction of the nitrile group was carried out in an autoclave. 5 mol% Ni catalyst, 3 mL of 12.5% ​​aqueous ammonia (NH3aq.), and 0.5 mmol of the substrate were added to a 50 mL stainless steel autoclave, and the reaction was carried out under conditions of 4 MPa hydrogen pressure, 130°C, and 6 hours. The results are shown in Table 6.

[0115] [ka]

[0116] [Table 6]

[0117] Test Example 12 Hydrogenation of the nitro group: The hydrogenation reaction of the nitro group was carried out in an autoclave. 5 mol% Ni (7.4 mg) of Example Catalyst 1' (Ni2P NW catalyst), 3 mL of water, and 0.5 mmol of the substrate were added to a 50 mL stainless steel autoclave, and the reaction was carried out under the conditions in the table below in a pressurized hydrogen atmosphere. The results are shown in Table 7.

[0118] [ka]

[0119] [Table 7]

[0120] From the results in Table 7, it can be seen that the catalyst of the present invention was able to selectively hydrogenate only the nitro group, while functional groups including halogen, methoxy, amino, ester, amide, and hydroxyl groups were not hydrogenated.

[0121] Test Example 13 Ring-opening and hydrogenation of monosaccharides (glucose): The hydrogenation reaction of monosaccharides was carried out in an autoclave. A 50 mL stainless steel autoclave was charged with 0.5 mmol of D-glucose as a substrate, 6.6 mol% (200 mg) of the catalyst (as Ni equivalent) shown in Table 8, and 3 mL of water. The reaction was then carried out under the conditions shown in the table below in a pressurized hydrogen atmosphere. The results are shown in Table 8.

[0122] [ka]

[0123] [Table 8]

[0124] The results in Table 8 show that the catalyst of the present invention brings about the ring-opening reaction (hydrolysis) and hydrogenation reaction of monosaccharides such as glucose in excellent yields, and the amount of by-products produced is extremely small.

[0125] Test Example 14 Catalyst durability: After the reaction (99% yield) under the conditions of Example 84 in Table 8 was carried out, the catalyst was centrifuged, and the substrate and solvent were added to the resulting catalyst and the reaction was repeated. The yields were 99% the first time, 99% the second time, 98% the third time, 98% the fourth time, and 97% the fifth time.

[0126] From the above results, it was found that the catalyst of the present invention has excellent durability.

[0127] Test Example 15 Ring-opening and hydrogenation of polysaccharide (maltose): Hydrogenation of polysaccharides was carried out in an autoclave. 0.25 mmol of maltose as a substrate, 6.6 mol% of the active ingredient (as Ni) of the catalyst shown in Table 9, and 3 mL of water were added to a 50 mL stainless steel autoclave, and the reaction was carried out under the conditions shown in the table below in a pressurized hydrogen atmosphere. The results are shown in Table 9.

[0128] [ka]

[0129] [Table 9]

[0130] The results in Table 9 show that the catalyst of the present invention is capable of carrying out the ring-opening reaction (hydrolysis) and hydrogenation reaction of monosaccharides such as glucose in excellent yields.

[0131] Test Example 16 Catalyst durability: After the reaction under the conditions of Example 94 in Table 9, the catalyst was centrifuged, and the substrate and solvent were added to the obtained catalyst and the reaction was repeated. The yield was 94% in the first run, 94% in the second run, 93% in the third run, 93% in the fourth run, and 94% in the fifth run.

[0132] From the above results, it was found that the catalyst of the present invention has excellent durability. [Industrial Applicability]

[0133] The catalyst of the present invention can be used in the hydrogenation and ring-opening reactions of organic compounds simply by replacing the conventional, dangerous sponge catalysts, without requiring large-scale modifications to conventional equipment. This makes it a valuable technology that can be easily applied industrially.

Claims

1. A catalyst containing nickel phosphide nanoparticles as an active ingredient, Nickel phosphide nanoparticles are supported on inorganic oxide fine particles, the inorganic oxide fine particles are one selected from yttrium oxide, mordenite and hydrotalcite; The molar ratio of phosphorus to nickel in the nickel phosphide nanoparticles is 1 or less; A catalyst for hydrogenating an organic compound, comprising:

2. A catalyst containing nickel phosphide nanoparticles as an active ingredient, Nickel phosphide nanoparticles are supported on inorganic oxide fine particles, the inorganic oxide fine particles are one selected from yttrium oxide, mordenite and hydrotalcite; The molar ratio of phosphorus to nickel in the nickel phosphide nanoparticles is 1 or less; A catalyst for ring-opening of a cyclic hetero compound, comprising:

3. A catalyst containing nickel phosphide nanoparticles as an active ingredient, Nickel phosphide nanoparticles are supported on inorganic oxide fine particles, the inorganic oxide fine particles are one selected from yttrium oxide, mordenite and hydrotalcite; The molar ratio of phosphorus to nickel in the nickel phosphide nanoparticles is 1 or less; A catalyst for one-step reaction of hydrogenating and ring-opening a cyclic hetero compound having an unsaturated bond, characterized in that

4. 2. A method for producing a hydrogenated organic compound, comprising hydrogenating an organic compound using the catalyst for hydrogenating an organic compound according to claim 1.

5. 2. A method for producing a hydrogenated organic compound, which comprises hydrogenating an organic compound using the catalyst for hydrogenating an organic compound according to claim 1 in a heated and pressurized hydrogen-containing atmosphere.

6. A method for producing a ring-opened compound, comprising: opening the ring of a heterocyclic compound using the ring-opening catalyst for a heterocyclic compound according to claim 2.

7. A method for producing a hydrogenated ring-opened compound, comprising the steps of hydrogenating and ring-opening a cyclic hetero compound having an unsaturated bond in one step using the catalyst for one-step hydrogenation and ring-opening of a cyclic hetero compound having an unsaturated bond according to claim 3.

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