JPWO2018225759A1 - Method for producing aliphatic hydrocarbon and carbon monoxide - Google Patents

Abstract

An object of the present invention is to provide a novel method for producing an aliphatic hydrocarbon. Provided is a method for producing an aliphatic hydrocarbon, which comprises a step of causing a catalyst composed of metal fine particles containing a noble metal such as rhodium supported on a silicon wire to act on an aliphatic carboxylic acid or the like and performing a decarboxylation reaction or the like. .

Description

  The present invention relates to a method for producing an aliphatic hydrocarbon and carbon monoxide that can be used for biodiesel fuel and the like, and a catalyst used in the method.

  Alkanes are useful as biodiesel fuels, and carbon monoxide can be used in petroleum synthesis feedstocks. Alkanes can be produced, for example, from aliphatic carboxylic acids, which are fats and oils of biological materials. As a technique for synthesizing an alkane having n-1 carbon atoms from an aliphatic carboxylic acid having n carbon atoms, Non-Patent Documents 1-4 are exemplified.

  In Non-Patent Document 1, a reaction is carried out using as much as 5 mol% of platinum with palmitic acid as a substrate and platinum / carbon as a catalyst. The reaction temperature at this time is as high as 330 ° C. Although the catalyst is reused twice, the corresponding alkane yield is less than 80% (76%), and the yield is not high.

  The reaction of Non-Patent Document 2 is a reaction using a palladium catalyst supported on silica (silicon oxide). However, at very high hydrogen pressures of 270 ° C. under extremely high hydrogen pressures of 60 atm, only 80% of alkanes can be obtained.

  The reaction of Non-Patent Document 3 is a reaction using a nickel catalyst supporting zirconia (zirconium oxide). Using a large amount of catalyst with a catalyst amount of 10 mol Ni, the reaction is carried out at a reaction temperature of 260 ° C under a hydrogen atmosphere of 12 atm according to the High Pressure Gas Safety Law.

  In Non-Patent Document 4, the reaction is performed at a high temperature of 250 ° C. using a large amount (l mol% Pt) of a platinum catalyst supporting niobium oxide.

  In other words, in Non-Patent Documents 1-4, it is necessary to use a large amount of catalyst having a catalyst amount of about 1 to 10 mol%. In addition, the reaction temperature is high, and the reaction is performed in a hydrogen atmosphere exceeding 10 atm, which is referred to as the high pressure gas safety law. In addition, there is no practically effective report on the reuse of the catalyst.Non-Patent Document 1 discusses the reuse, but using a large amount of catalyst of 5 mol% catalyst amount, only two reuses are studied. Only the corresponding alkane was synthesized in a 70% yield.

  Non-Patent Documents 5 to 8 disclose techniques for synthesizing alkanes having n carbon atoms from aliphatic carboxylic acids having n carbon atoms. However, this reaction does not produce carbon monoxide, which is a petroleum synthesis raw material.

  In Non-Patent Document 5, the reaction is carried out under a high temperature of 350 ° C. and a high pressure of hydrogen of 50 atm using a large amount of a tungsten catalyst, and there is also a problem in the selectivity of a product.

  In Non-Patent Document 6, a large amount of a nickel catalyst supported on zirconia (zirconium oxide) is used to carry out a reaction at a high temperature of 260 ° C. and a high pressure of hydrogen of 40 atm.

  In Non-Patent Document 7, a large amount of a nickel catalyst supported on silica alumina is used to carry out a reaction at a high temperature of 260 ° C. and a high pressure of hydrogen of 40 atm.

  In Non-Patent Document 8, a reaction is carried out at a high temperature of 280 ° C. using a large amount of a molybdenum catalyst supported on coal.

  Therefore, there has been a demand for a catalyst for producing an aliphatic hydrocarbon that can be used more efficiently and selectively for biodiesel fuel and the like, and a method for producing an aliphatic hydrocarbon using the catalyst. Further, there has been a demand for a catalyst having high recycling efficiency. Further, there has been a demand for a catalyst capable of producing an aliphatic hydrocarbon under milder conditions.

Energy Environ.Sci., 2010, 3, 311-317 Chemistry Central Journa1 2013, 7, 149 Chem. Eur. J. 2013, 19, 4732-4741 Catal. Sci. Technol. 2014, 4, 3705-3712 Angew. Chem. Int. Ed. 2013, 52, 5089-5092 J. Am. Chem. Soc, 2012, 134, 9400-9405 Angew. Chem. Lnt. Ed. 2012, 51, 2072-2075 Adv. Synth. Catal. 2011, 353, 2577-2583

  The present invention has been made under such circumstances, a novel catalyst that can be used for the production of an aliphatic hydrocarbon, and a method for producing a compound including a catalytic reaction step using the same catalyst, particularly an aliphatic hydrocarbon It is an object of the present invention to provide a method for manufacturing the same.

  The present inventors have conducted intensive studies in order to solve the above problems. As a result, a catalyst in which metal particles containing at least a predetermined noble metal such as rhodium or the like are supported on a silicon wire has a smaller amount of catalyst and a milder condition, and has a carbon number of n-1 from an aliphatic carboxylic acid having carbon number n. It was found that alkanes and carbon monoxide can be selectively synthesized. In particular, it was found that the catalyst using the metal fine particles containing at least rhodium has high recycling efficiency. The present invention has been completed based on such findings.

That is, the gist of the present invention is as follows.
[1] A catalyst comprising a silicon wire and metal fine particles containing at least one noble metal selected from the group consisting of platinum, palladium, and rhodium supported on the silicon wire, is formed from an aliphatic carboxylic acid or an aliphatic carboxylic acid ester. And a catalytic reaction step of acting on at least one substrate selected from the group consisting of aliphatic aldehydes and promoting at least one reaction of decarboxylation, dealkoxycarbonylation and decarbonylation of the at least one substrate,
A method for producing an aliphatic hydrocarbon, comprising:
[2] The method according to [1], wherein the silicon wires are formed as a silicon wire array including a plurality of silicon wires formed on a silicon substrate.
[3] The at least one substrate is an aliphatic carboxylic acid, an aliphatic carboxylic acid ester or an aliphatic aldehyde having an aliphatic hydrocarbon chain having 6 to 25 carbon atoms which may have a substituent. ] Or the method according to [2].
[4] The method according to any one of [1] to [3], wherein part or all of the at least one reaction proceeds under irradiation of microwaves.
[5] The method according to any one of [1] to [4], wherein, in the catalytic reaction step, the catalyst is allowed to act on the at least one type of substrate at a metal amount of 0.001 mol% or more. Method.
[6] The method according to any one of [1] to [5], wherein the at least one noble metal is rhodium.
[7] The method according to any one of [1] to [6], wherein the at least one reaction proceeds in the presence of at least one acid anhydride.
[8] The catalyst reaction step according to [1],
Collecting carbon monoxide produced by at least one of decarboxylation, dealkoxycarbonylation and decarbonylation during and / or after the catalytic reaction step;
A method for producing carbon monoxide, comprising:
[9] A catalyst comprising a silicon wire and metal fine particles containing rhodium supported on the silicon wire.
[10] The catalyst according to [9], wherein the silicon wire is formed as a silicon wire array including a plurality of silicon wires formed on a silicon substrate.
[11] a step of causing the catalyst according to [9] or [10] to act on an unsaturated aliphatic aryl to cause a hydrogenation reaction;
A method for producing a saturated aliphatic aryl, comprising:
[12] The method according to [11], wherein the unsaturated aliphatic aryl is an unsaturated aliphatic aryl having an unsaturated aliphatic hydrocarbon chain having 2 to 25 carbon atoms which may have a substituent.

  According to the present invention, a novel catalyst that can be used for the production of an aliphatic hydrocarbon, and a novel method for producing a compound including a catalytic reaction step using the same catalyst, particularly a novel method for producing an aliphatic hydrocarbon and carbon monoxide A manufacturing method can be provided.

  The catalyst used in the present invention can synthesize an aliphatic hydrocarbon from an aliphatic carboxylic acid or the like (for example, an aliphatic carboxylic acid, an aliphatic carboxylic acid ester and an aliphatic aldehyde) with a smaller catalytic amount. In addition, the reaction using the catalyst has high selectivity, and an aliphatic hydrocarbon such as an alkane having n-1 carbon atoms and carbon monoxide can be selectively synthesized from an aliphatic carboxylic acid having n carbon atoms. In particular, the catalyst using the metal fine particles containing at least rhodium has high recycling efficiency. According to the present invention, since a predetermined catalyst is used, synthesis can be performed under milder conditions. Further, the catalyst of the present invention can synthesize a saturated aliphatic aryl from an unsaturated aliphatic aryl.

FIG. 1 is a view (photograph) showing the result of SEM observation of a cross section of SiNA-Rh. FIG. 2 is a diagram (photograph) showing the results of TEM observation and EDX analysis of SiNA-Rh. 2A and 2B are TEM photographs. FIG. 2A shows that the scale bar is 20 nm and the rhodium nanoparticles are uniformly dispersed, and FIG. 2B shows that the scale bar is 5 nm and the rhodium nanoparticles are homogeneous. It is shown that. FIG. 2C shows the presence of rhodium in the EDX chart. 2D to 2F are EDX images. FIG. 2D shows the entire image, FIG. 2E shows rhodium mapping, and FIG. 2F shows rhodium and silicon combined mapping. FIG. 3 is a diagram showing the results of measuring the particle size distribution of rhodium nanoparticles of SiNA-Rh. FIG. 4 is a view showing the results of XPS analysis of rhodium nanoparticles of SiNA-Rh. FIG. 5 is a diagram showing the results of XPS analysis of rhodium nanoparticles supported on carbon. FIG. 6 (photograph) shows the results of ICP-MS analysis of SiNA-Rh. FIG. 6A is a photograph of SiNA before supporting rhodium, and FIG. 6B is a photograph of SiNA-Rh after supporting rhodium.

  Hereinafter, embodiments of the present invention will be described in detail.

<Catalyst production method>
The catalyst usable in the present invention (hereinafter sometimes referred to as “catalyst used in the present invention”) is a silicon wire and at least one noble metal selected from the group consisting of rhodium, palladium and platinum supported on the silicon wire. A catalyst comprising metal fine particles containing Here, one or more silicon wires may be provided. One form of the catalyst is a catalyst composed of the metal fine particles supported on a silicon substrate and a silicon wire array composed of a plurality of silicon wires formed on the silicon substrate. In a mode in which a silicon wire array formed on the surface of a silicon substrate is used, a nano-order space between silicon wires can be efficiently used for a catalytic reaction, and therefore, the reaction efficiency is excellent. The catalyst of the same form is suitable for a catalyst for a flow reactor.

  The catalyst in the above form can be produced based on the description in the present specification and further by referring to the method described in, for example, the document Angew. Chem. Int. Ed. 2014, 53, 127-131.

Hereinafter, an example of a method for producing a catalyst used in the present invention will be described.
As the silicon substrate, a p-type or n-type silicon substrate can be used. The resistivity is not particularly limited, and may be, for example, a resistivity of 0.01 to 10,000 Ω, or 0.1 to 100 Ω. The silicon substrate may be of any thickness, for example 100 to 1,000 μm. The silicon substrate may have any suitable planar dimensions, such as a 2 inch wafer.

Clean the silicon substrate. The washing solution is not particularly limited, and for example, H ₂ SO ₄ / H ₂ O ₂ (mixing volume ratio 1: 1 to 4: 1) or the like can be used. Next, in order to introduce Si—H surface groups (hydrogen termination) into the silicon substrate, the silicon substrate is treated with HF / H ₂ O (mixing volume ratio 1:10 to 1:50) or the like. Then, a concentrated HF / H ₂ O solution containing an aqueous silver solution such as AgNO ₃ (40 to 48%, particularly 46%) (for example, a silver ion concentration of 0.5 to 5 mg / mL, particularly 1.12 mg / mL), etc. (mixing volume ratio (1: 1 to 5: 1, especially 3: 1) is reacted with a hydrogen-terminated substrate to produce a substrate coated with Ag fine particles.

Next, the Ag-particle-coated substrate is etched in a suitable etching solution. That is, since the etching proceeds with the silver particles as a catalyst, silicon pores are formed in a portion where silver is present, and a portion where the etching does not progress forms a silicon wire. A suitable etching solution is not particularly limited, and for example, HF / H ₂ O ₂ (mixing volume ratio of 3: 1 to 6: 1) or the like can be used. The etching can be performed, for example, for 1 to 10 minutes. For example, if a solution containing about 46% HF is used, the etching can be performed at 60 ° C. for 2-5 minutes.

Next, treatment with HNO ₃ or the like is performed to remove Ag fine particles. Then, HF / H ₂ O (mixing volume ratio 1:10 to 1:50) was treated with or the like, and reconstruction of the Si-H surface.

  As described above, a silicon wire array composed of a plurality of silicon wires generally vertically formed on a silicon substrate and usable in the present invention can be manufactured.

  The space between silicon wires in the silicon wire array of the above-mentioned form usable in the present invention has an average diameter (hereinafter, sometimes referred to as diameter or width), for example, about 1 to 5,000 nm, about 10 to 1,000 nm, or 50 The length (depth) of the space is, for example, about 0.1 to 100 μm, about 0.5 to 50 μm, or about 1 to 10 μm. The aspect ratio (length / diameter) of the space may have from 1 to 500, 10 to 100 or 40 to 80. The above-described nanostructure of the silicon wire array can be confirmed by, for example, a structural analysis of a cross section of the silicon wire array by a scanning electron microscope (Scanning Electron Microscope: SEM) or the like. By the way, what is described as the density of the silicon wire means an average value obtained by observing with a scanning electron microscope and measuring a range of a cross section of the silicon wire array of 38 μm.

  A silicon wire array that can be used in the present invention provides the above nanostructure. The catalyst used in the present invention, which is composed of fine metal particles containing rhodium and the like, carried on the silicon wire array, improves the accessibility of a larger amount of substrate and the catalyst due to the catalytic reaction in the nanospace formed by the silicon wire array. However, it is believed that under milder conditions, higher catalyst activity, catalyst reusability, safety and selectivity can be provided.

  The physical properties of the silicon wire that can be used in the present invention, referring to the description and the known method in the present specification, etching conditions according to the target silicon wire, for example, the size of Ag fine particles, the concentration of the Ag fine particle solution, etching. It can be adjusted by changing the composition of the solution, the etching time, and the like. One form of the silicon wire that can be used in the present invention is a silicon nanowire having a silicon wire made of silicon and having a nano-order diameter (specifically, 1 to 10,000 nm). The average diameter of the silicon nanowire usable in the present invention is, for example, about 1 to 5,000 nm, about 10 to 1,000 nm, or about 50 to 400 nm, and the length is, for example, about 0.1 to 100 μm, 0.5 to 50 μm. Or about 1 to 10 μm. The aspect ratio (length / diameter) of the silicon nanowires can have 1-500, 10-100 or 40-80.

  The catalyst that can be used in the present invention is characterized in that metal fine particles containing rhodium or the like are supported on a silicon wire (in the case of the above-described catalyst, a silicon wire array formed on a silicon substrate). An example of a suitable size of the metal fine particles used in the present invention is nano-order fine particles. Therefore, in this specification, the fine particles may be described as nanoparticles.

  As the nanoparticles used in the present invention, at least one noble metal selected from a noble metal group consisting of platinum, palladium, and rhodium (hereinafter, the “noble metal” refers to these three noble metals) ) Is used. Such a nanoparticle may be a nanoparticle composed of only one kind of the noble metal (for example, rhodium). In addition to the noble metal (for example, rhodium), for example, one or two selected from transition metals and greedy metals Nanoparticles made of an alloy containing at least one kind of metal may be used. Further, two or more kinds of the noble metals may be contained. More specifically, the nanoparticles are nanoparticles composed of only one kind of the noble metal, nanoparticles composed of an alloy containing two or more kinds of the noble metals, or one or more kinds of the noble metals, Or a transition metal group of the sixth to sixth periods and preferably an alloy containing one or more members selected from the group of the transition metal groups (preferably the fourth to sixth period). Examples of metals belonging to the transition metal group and the greedy metal group of the fourth to sixth periods include scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, yttrium, zirconium, Includes niobium, molybdenum, ruthenium, silver, cadmium, indium, tin, antimony, hafnium, tantalum, tungsten, rhenium, osmium, iridium, gold, mercury, thallium, lead and bismuth. Examples of preferred metal groups of the fourth to sixth period transition metal groups include scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, and ruthenium. , Silver, cadmium, tungsten, rhenium, osmium, iridium and gold; and transition metal group 2 composed of nickel, copper, zinc, ruthenium, silver, rhenium, osmium, iridium and gold. An example of a catalyst having a high recycling rate is a catalyst using nanoparticles containing at least rhodium (hereinafter, may be referred to as “catalyst of the present invention”). More specifically, nanoparticles composed only of rhodium; nanoparticles composed of an alloy containing rhodium and one or more of the noble metals (other than rhodium); rhodium and a group of transition metals in the fourth to sixth periods And nanoparticles composed of an alloy containing one or more members selected from the group consisting of rhodium, the noble metal (but not rhodium), the transition metal group of the fourth to sixth periods, and the group of the metal group. Nanoparticles consisting of an alloy containing at least one selected from the group consisting of rhodium, one or more selected from the noble metals (other than rhodium), and a transition metal group of the fourth to sixth periods. Nanoparticles consisting of an alloy containing rhodium, the noble metal (other than rhodium), and one or more selected from transition metal group 1 of the fourth to sixth periods; or rhodium When, A catalyst using a; serial noble metal (but other than rhodium), and fourth to nanoparticles made of an alloy containing one or more and selected from transition metal group 2 of the sixth cycle. More specifically, only rhodium, together with rhodium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, yttrium, zirconium, niobium, molybdenum, ruthenium, palladium, silver , Cadmium, indium, tin, antimony, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead and bismuth (or platinum, copper, nickel, ruthenium, palladium, and iridium) Nanoparticles composed of an alloy containing one or more of the above. The valence of a metal atom such as a noble metal contained in the nanoparticles is not particularly limited as long as it exhibits a catalytic action. In terms of catalytic activity, it is usually preferable that the catalyst has zero valence. However, as long as they exhibit catalytic activity, some of them may be present in the form of metal salts, metal oxides, metal hydroxides and the like. The content ratio of the metal (for example, the content ratio of rhodium to a metal other than rhodium) in the embodiment of the nanoparticles containing two or more metals can be arbitrarily set. When the nanoparticles used in the present invention contain rhodium, particularly high catalytic activity and reusability can be exhibited.

  The average particle size of the nanoparticles supported on the catalyst used in the present invention is (for example, in a mode in which the nanoparticles are supported on a silicon wire array formed on a silicon substrate, the space between the silicon wires of the silicon wire array is impregnated). There is no particular limitation as long as it is supported on the silicon wire and functions as a catalyst, but it is usually about 0.01 to 500 nm, 0.1 to 100 nm, or about 1 to 10 nm. Here, what is described as the average particle size means the average value of the size of 200 particles individually measured by observation with a transmission electron microscope (TEM).

  One example of a method for producing a catalyst used in the present invention is a method including a step of supporting nanoparticles on a silicon wire array formed on a silicon substrate. The method of supporting metal nanoparticles containing at least one of the noble metals such as rhodium on the silicon wire array can be performed by bringing the silicon wire array into contact with an aqueous solution of a metal salt of the noble metal such as rhodium. Examples of the method of contacting the aqueous metal salt solution include a method of dipping the silicon wire array in the aqueous metal salt solution and a method of spraying the silicon wire array onto the silicon wire array.

  The aqueous solution of a metal salt may be any aqueous solution containing a metal salt. For example, in the case of rhodium, an aqueous solution of a rhodium salt such as rhodium chloride or rhodium acetate may be used. Further, not only an aqueous solution but also an organic solvent (for example, a water-miscible organic solvent such as acetone) or a metal salt dissolved in an organic solvent can be used. When a water-miscible organic solvent is added to the aqueous solution, the support on the silicon wire can be promoted. In the present invention, the aqueous metal salt solution can be used alone or in combination. For example, in the case of manufacturing an embodiment including two or more kinds of the noble metals or one or more kinds of the noble metals as the nanoparticles, an aqueous solution containing a metal salt of each metal is used. An aqueous solution of the metal salt of each metal may be prepared and mixed, or may be prepared by simultaneously or sequentially adding the metal salt of each metal to water.

  When the metal nanoparticles are supported on the silicon wire array, the aqueous metal salt solution generally has a metal concentration of 1 to 1,000 mmol / L, or 10 to 100 mmol / L. Those having a metal concentration in the above range can be used. For example, a metal salt aqueous solution can be used for a silicon wire array so as to have a metal amount of, for example, 1 to 1,000 μmol / g or 10 to 100 μmol / g.

  By the above treatment, after contacting the metal salt with the surface of the silicon wire array, water, washed with an organic solvent or the like, and supported on the silicon wire array by drying, from the metal nanoparticles containing the noble metal such as rhodium and the like. Can be produced.

  In the silicon wire array supporting the manufactured metal nanoparticles, the amount of the nanoparticles supported on the silicon wire array is usually 0.1 to 10 μmol / g or 1.0 to 5.0 μmol / g as the amount of metal. In addition, when expressed as mol%, the amount of nanoparticles supported on the silicon wire array is usually 0.001 to 1.0 mol% or 0.01 to 0.1 mol /% as the amount of metal.

  Further, a reduction step may be performed to insolubilize the metal nanoparticles. This reduction step is performed by insolubilizing the water-soluble metal nanoparticles into a pure metal, an oxide or a hydroxide complex or compound, and dissolving the metal nanoparticles in an aqueous metal salt solution or a liquid inside the array. This is to prevent the metal nanoparticles from flowing out of the surface, whereby the metal nanoparticles can be fixed to the array surface. The reduction method may be a liquid phase reduction or a gas phase reduction as long as the metal nanoparticles can be fixed. For example, there is a method in which the array is immersed in an aqueous ammonia solution as the reduction in the liquid phase, and a method in which hydrogen heat treatment is performed by heating as the reduction in the gas phase.

  As the reducing agent used for the insolubilization treatment of the catalyst metal, a compound having a reducing action such as ammonia, hydrazine, sodium borohydride, a reducing gas such as hydrogen, or a basic compound such as sodium hydroxide is used. As a specific method of the reduction step, there is a precipitation precipitation method by adding an alkali to an acid-based catalyst metal salt, and the like.

  After the step of reducing the metal on the surface of the silicon wire array, heat treatment may be performed. The heat treatment is a step of reducing the catalyst metal, which has become a complex or compound of an oxide or a hydroxide in the above reduction step, to a pure metal or removing impurities. When a plurality of catalyst metals having different metal species are used, the process is also a step for alloying them. Note that the reduction by the gas phase may also serve as a heat treatment step.

  The heat treatment may be performed under generally known conditions, such as heating at 200 ° C. for 2 hours. By such a heat treatment, the hydrophobic organic compound impregnated inside the array can be volatilized.

  The average particle size of the nanoparticles supported by the catalyst used in the present invention, the particle size distribution, the composition of the alloy, the supported amount of the nanoparticles, etc., refer to the description in this specification and a known method, depending on the target catalyst It can be adjusted by changing the conditions for bringing the silicon wire array into contact with the aqueous metal salt solution, for example, changing the concentration of the aqueous metal salt solution, reaction temperature, time, etc., and the mixing ratio of the aqueous metal salt solution.

  After the reaction, the catalyst used in the present invention can be reused by washing with water, an organic solvent or the like and drying. In particular, the catalyst of the present invention is excellent in reusability, and is reused, for example, two or more times, five or more times, or ten or more times in a state where the reactivity is maintained (depending on the reaction conditions, for example, the yield is 80% or more). be able to.

<Catalytic reaction>
The catalyst used in the present invention can be used for Mizoroki-Heck reaction, nitro group reduction reaction, hydrosilylation reaction, CH arylation reaction, decarboxylation reaction, decarbonylation reaction, hydrogenation reaction and the like. Specifically, for example, a decarboxylation reaction of an aliphatic carboxylic acid, a dealkoxycarbonylation reaction of an aliphatic carboxylic acid ester, a decarbonylation reaction of an aliphatic aldehyde, a hydrogenation reaction of an unsaturated aliphatic hydrocarbon, It can be suitably used for a partial hydrogenation reaction of a saturated aliphatic aryl. Further, the present invention provides a catalyst for use in the present invention which acts on at least one substrate selected from the group consisting of an aliphatic carboxylic acid, an aliphatic carboxylic acid ester and an aliphatic aldehyde, to remove the at least one substrate. The present invention relates to a method for producing an aliphatic hydrocarbon, which comprises a step of promoting at least one reaction of carboxylation, dealkoxycarbonylation, and decarbonylation (catalytic reaction step). Also, the present invention provides a method for producing carbon monoxide produced by at least one reaction of decarboxylation, dealkoxycarbonylation and decarbonylation during and / or after the catalytic reaction step. Collecting carbon monoxide.

  Hereinafter, examples of the catalytic reaction of the present invention will be described. In the method for producing an aliphatic hydrocarbon and the method for producing carbon monoxide, examples of an aliphatic carboxylic acid, an aliphatic carboxylic acid ester, and an aliphatic aldehyde used as a substrate include a substrate in the following catalytic reaction. The same applies to the examples of the aliphatic carboxylic acid, aliphatic carboxylic acid ester, and aliphatic aldehyde used as the above, and also the conditions of the catalytic reaction step and the like.

(Decarboxylation reaction of aliphatic carboxylic acid and dealkoxycarbonylation reaction of aliphatic carboxylic acid ester)
The decarboxylation reaction of the aliphatic carboxylic acid and the dealkoxycarbonylation reaction of the aliphatic carboxylic acid ester with the catalyst used in the present invention can be performed in either a gas phase or a liquid phase. In a gas phase reaction, a reaction substrate is usually brought into contact with a catalyst in a gas phase with 0.1 to 10 atm hydrogen gas, and in a liquid phase reaction, the reaction substrate is usually mixed with a catalyst in the presence of 0.1 to 10 atm hydrogen gas. The reaction is carried out by contacting with. In the liquid phase reaction, it is not necessary to use a solvent, but a solvent can be used if necessary. Suitable solvents are those that form a homogeneous phase with the reaction substrate, and examples thereof include hydrocarbons, ethers, esters, and alcohols.

  The reaction temperature is usually 50 ° C. or higher, 50 to 500 ° C., 50 to 400 ° C., 50 to 300 ° C., 50 to 250 ° C., or 150 to 200 ° C. The reaction time may be appropriately selected depending on the yield of the target substance and the like, and is not particularly limited, but is usually about several seconds to several tens of hours, about 1 to 48 hours, or about 6 to 24 hours. In order to keep the reaction temperature within the above range, the reaction system (at least the predetermined catalyst and the predetermined reaction substrate may be used before and / or at least partly during the decarboxylation or dealkoxycarbonylation reaction). It is preferable to perform microwave irradiation on the reaction system (including the reaction system). By heating to the above temperature range by microwave irradiation, the progress of the reaction can be remarkably promoted. In addition, you may use together with another heating means. There is no particular limitation on the method of microwave irradiation. For example, a commercially available microwave synthesizer (manufactured by CEM) or the like can be used.

  The amount of the catalyst used in the present invention is generally 0.0001 mol% or more and more than 0.0006 mol% as a metal amount based on the reaction substrate. The upper limit is 1 mol% or less, or less than 1 mol%. Preferably, it is 0.001-1 mol%, 0.01-0.1 mol%, or 0.02-0.07 mol%.

  The method for producing an aliphatic hydrocarbon from an aliphatic carboxylic acid or an aliphatic carboxylic acid ester using a catalyst used in the present invention is characterized by reacting a reaction substrate in the presence of a catalyst. May be carried out in the presence of an additive. By adding the additive, the yield of the target product can be further improved. Such additives include acid anhydrides, such as, for example, pivalic anhydride or 2,4,6-trimethylbenzoic anhydride. The amount of the additive to be added can be appropriately selected from the range of usually 0.1 to 200 mol%, 1 to 100 mol%, or 1.5 to 10 mol% based on the reaction substrate. Further, in an embodiment in which at least one aliphatic carboxylic acid ester is used as a substrate, the progress of the reaction can be promoted by adding water to the reaction system.

  The aliphatic carboxylic acid serving as a reaction substrate in the production method of the present invention is preferably an aliphatic compound which is a compound obtained by substituting a hydrogen of an aliphatic hydrocarbon chain having 6 to 25 carbon atoms which may have a substituent with a carboxyl group. It is a carboxylic acid. The aliphatic hydrocarbon chain which may have a substituent has more preferably 13 to 19 carbon atoms. Here, the aliphatic hydrocarbon chain may be a saturated or unsaturated, linear or branched aliphatic hydrocarbon chain. These aliphatic hydrocarbon chains include linear or branched alkyl (hexyl, heptyl, octyl, nonyl, undecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, nonadecyl, etc.) and one or more at any position. Examples thereof include linear or branched alkenyl having a double bond (hexenyl, heptenyl, octenyl, nonenyl, undecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, nonadecenyl, octadecatrienyl, and the like). Note that the number of carboxyl groups on the aliphatic hydrocarbon chain may be one or more, and preferably one. The substitution position of the carboxyl group is not particularly limited, but is, for example, the terminal of an aliphatic hydrocarbon chain. The substituent is not particularly limited as long as it is a substituent inert to the reaction.Examples include a hydroxy group, an aryl group, an aryloxy group, an alkoxy group, an alkylamino group, an acyl group, an ester group, a cyano group, an amino group, Amide groups and the like. The number of substituents on the aliphatic hydrocarbon chain may be one or more, and is preferably one. The substitution position of the substituent on the aliphatic hydrocarbon chain is not particularly limited, but is, for example, the terminal of the aliphatic hydrocarbon chain. Examples of the aliphatic carboxylic acid ester that can be used as a reaction substrate include the aliphatic carboxylic acid ester that can be used as the above-mentioned reaction substrate (the carbon number of the R portion of -C (= O) OR is C1 to C1). C10, C1-C6 or C1-C4). The aliphatic carboxylic acid ester may be substituted, and examples of the substituent are the same as the examples of the substituent that the aliphatic carboxylic acid may have. When a decarboxylation reaction of an aliphatic carboxylic acid having an unsaturated aliphatic hydrocarbon chain or a dealkoxycarbonylation reaction of an aliphatic carboxylic acid ester is carried out, the same reaction is carried out on the unsaturated aliphatic hydrocarbon chain. It is also possible to carry out a hydrogenation reaction of unsaturated bonds.

  Examples of the aliphatic carboxylic acid serving as a reaction substrate in the production method of the present invention include, but are not limited to, for example, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, arachidic acid, oleic acid, 2-hexyldecane Acid, octadecandioic acid, retinoic acid and the like. Examples of the aliphatic carboxylic acid ester serving as a reaction substrate of the production method of the present invention include, but are not limited to, for example, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, arachidic acid, oleic acid, 2-to- Esters such as xyldecanoic acid, octadecandioic acid, and retinoic acid (the carbon number of the R portion of —C (= O) OR is C1 to C10, C1 to C6, or C1 to C4).

  In the method for producing an aliphatic hydrocarbon from an aliphatic carboxylic acid or an aliphatic carboxylic acid ester using the catalyst used in the present invention, it is possible to efficiently and selectively produce an aliphatic hydrocarbon. According to the production method of the present invention, the yield of the aliphatic hydrocarbon relative to the reaction substrate depends on the reaction conditions and the like, for example, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, It can be 90% or more, 95% or more, or 99% or more. In the method of the present invention, the number of carbon atoms is n (n is an integer of 2 or more; preferably an integer of 6 to 25. However, the number of carbon atoms refers to the carboxylic acid (—COOH) in the aliphatic carboxylic acid. From the number of carbon atoms of the aliphatic carboxylic acid or aliphatic carboxylic acid ester of the aliphatic carboxylic acid ester, or the number of carbon atoms of the ester (—COOR: R is a hydrocarbon group) in the aliphatic carboxylic acid ester. Alternatively, n aliphatic hydrocarbons (eg, saturated aliphatic hydrocarbons) can be produced. In particular, the selectivity of an aliphatic hydrocarbon having n-1 carbon atoms (for example, a saturated aliphatic hydrocarbon) is high.

In the production method of aliphatic hydrocarbons from aliphatic carboxylic acids or aliphatic carboxylic acid ester by catalyst used in the present invention, CO is selectively generated, the generation of CO ₂ is small. The content of CO _{2 in} the gas components generated in the production method of the present invention depends on the reaction conditions and the like, but may be, for example, 10% or less, 5% or less, 1% or less, or 0%.

(Decarbonylation reaction of aliphatic aldehyde)
The decarbonylation reaction of the aliphatic aldehyde with the catalyst used in the present invention can be performed in either a gas phase or a liquid phase. In a gas phase reaction, a reaction substrate is usually brought into contact with a catalyst in the gas phase with an inert gas of 0.1 to 10 atm, and in a liquid phase reaction, the reaction substrate is usually catalyzed in the presence of an inert gas of 0.1 to 10 atm. The reaction is carried out by contacting with a liquid. In the liquid phase reaction, it is not necessary to use a solvent, but a solvent can be used if necessary. Suitable solvents are those that form a homogeneous phase with the reaction substrate, and examples thereof include hydrocarbons, ethers, esters, and alcohols.

  The reaction temperature is usually in the range of 50 to 250 ° C, or 100 to 180 ° C. The reaction time may be appropriately selected depending on the yield of the target substance and the like, and is not particularly limited, but is usually about several seconds to several tens of hours, or about 6 to 18 hours. For specific examples of the heating method, the description in the above decarboxylation reaction of aliphatic carboxylic acid and the like can be referred to.

  With respect to the amount of the catalyst used and the use of the additives, the description in the decarboxylation reaction of the aliphatic carboxylic acid and the like can be referred to.

  Aliphatic aldehyde to be a reaction substrate in the method for producing an aliphatic hydrocarbon from an aliphatic aldehyde by the catalyst used in the present invention is preferably an aliphatic hydrocarbon chain having 6 to 25 carbon atoms which may have a substituent. It is an aliphatic aldehyde that is a compound in which hydrogen has been substituted with an aldehyde group. As examples of the aliphatic hydrocarbon chain, the description in the above-mentioned decarboxylation reaction of the aliphatic carboxylic acid can be referred to. The number of aldehyde groups on the aliphatic hydrocarbon chain may be one or more, preferably one. The substitution position of the aldehyde group on the aliphatic hydrocarbon chain is not particularly limited, but is, for example, the terminal of the aliphatic hydrocarbon chain. As examples of the substituent, the description in the above-mentioned decarboxylation reaction of the aliphatic carboxylic acid can be referred to. The number of substituents may be one or more, and preferably one. The substitution position of the substituent is not particularly limited, but is, for example, an aliphatic hydrocarbon chain terminal. When performing a decarbonylation reaction of an aliphatic aldehyde having an unsaturated aliphatic hydrocarbon chain, it is also possible to perform a hydrogenation reaction of an unsaturated bond on the unsaturated aliphatic hydrocarbon chain at the same time as the reaction. is there.

  Examples of the aliphatic aldehyde serving as a reaction substrate in the production method of the present invention include, but are not limited to, for example, octadecanal.

  In the method for producing an aliphatic hydrocarbon from an aliphatic aldehyde using the catalyst used in the present invention, it is possible to efficiently and selectively produce an aliphatic hydrocarbon. According to the production method of the present invention, the yield of the aliphatic hydrocarbon relative to the reaction substrate depends on the reaction conditions and the like, for example, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, It can be 90% or more, 95% or more, or 99% or more. In the method of the present invention, the number of carbon atoms is n (n is an integer of 2 or more, preferably an integer of 6 to 25, provided that the number of carbon atoms refers to an aldehyde (C (= O) H) in an aliphatic aldehyde. Can be produced from an aliphatic aldehyde having a carbon number of n-1 or n (for example, a saturated aliphatic hydrocarbon). In particular, the selectivity of an aliphatic hydrocarbon having n-1 carbon atoms (for example, a saturated aliphatic hydrocarbon) is high.

In the production method of aliphatic hydrocarbons from aliphatic aldehydes by catalyst used in the present invention, CO is selectively generated, the generation of CO ₂ is small. The content of CO _{2 in} the gas components generated in the production method of the present invention depends on the reaction conditions and the like, but may be, for example, 10% or less, 5% or less, 1% or less, or 0%.

(Partial hydrogenation of unsaturated aliphatic aryl)
The partial hydrogenation of unsaturated aliphatic aryl by the catalyst of the present invention can be performed in either a gas phase or a liquid phase. In a gas phase reaction, a reaction substrate is usually brought into contact with a catalyst in a gas phase with 0.1 to 10 atm hydrogen gas, and in a liquid phase reaction, the reaction substrate is usually mixed with a catalyst in the presence of 0.1 to 10 atm hydrogen gas. The reaction is carried out by contacting with. In the liquid phase reaction, it is not necessary to use a solvent, but a solvent can be used if necessary. Suitable solvents are those that form a homogeneous phase with the reaction substrate, and examples thereof include hydrocarbons, ethers, esters, and alcohols.

  The reaction temperature is usually in the range of 50 to 250 ° C, or 50 to 100 ° C. The reaction time may be appropriately selected depending on the yield of the target substance and the like, and is not particularly limited, but is usually about several seconds to several tens of hours, or about 6 to 24 hours.

  Regarding the amount of the catalyst and the use of the additive, the description in the above-mentioned decarboxylation reaction of the aliphatic carboxylic acid can be referred to.

  The unsaturated aliphatic hydrocarbon chain of the unsaturated aliphatic aryl can be partially hydrogenated by the catalyst of the present invention. The unsaturated aliphatic aryl serving as a reaction substrate in the method for producing a saturated aliphatic aryl from an unsaturated aliphatic aryl using the catalyst of the present invention is preferably an unsaturated aliphatic having 2 to 25 carbon atoms which may have a substituent. Aryl having an aromatic hydrocarbon chain. The unsaturated aliphatic hydrocarbon chain which may have a substituent more preferably has 2 to 20 carbon atoms. Here, the unsaturated aliphatic hydrocarbon chain may be a linear or branched unsaturated aliphatic hydrocarbon chain. These unsaturated aliphatic hydrocarbon chains include linear or branched alkenyl having one or more double bonds at any position (ethenyl, propenyl, butenyl, pentenyl, etc.) and one or more alkenyl at any position. Linear or branched alkynyl having a triple bond (ethynyl, propynyl, butynyl, pentynyl, etc.) and the like can be mentioned. As examples of the substituent, the description in the above-mentioned decarboxylation reaction of the aliphatic carboxylic acid can be referred to. The number of substituents may be one or more, and preferably one. The substitution position of the substituent is not particularly limited, but is, for example, an aliphatic hydrocarbon chain terminal.

  Examples of the unsaturated aliphatic aryl serving as a reaction substrate in the production method of the present invention include, but are not limited to, stilbene and the like.

  The method for producing a saturated aliphatic aryl from an unsaturated aliphatic aryl using the catalyst of the present invention enables efficient and selective production of a saturated aliphatic aryl. According to the production method of the present invention, the yield of the saturated aliphatic aryl relative to the reaction substrate depends on the reaction conditions and the like, for example, the yield is 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% Or more, 95% or more or 99% or more.

  A step of preparing a predetermined catalyst may be added before each catalytic reaction step (including the catalytic reaction step of the method for producing an aliphatic hydrocarbon and carbon monoxide), and / or after each catalytic step. And a step of performing at least one treatment of separating, purifying, collecting, and modifying the product.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but these will not limit the scope of the present invention.

<Example 1>
Preparation of Metal Nanoparticle Catalyst Supported on Silicon Nanowire Array A silicon nanowire array (hereinafter, also referred to as `` SiNA ''), which is a silicon substrate having a nanostructure, was prepared by using a commercially available silicon substrate in the literature Angew. Chem. Int. Ed. 2014, 53, 127-131. The document reports a catalyst in which palladium nanoparticles are supported on a silicon substrate having a nanostructure (hereinafter, also referred to as “SiNA-Pd”). This palladium catalyst has been applied to the Mizorogi-Heck reaction, hydrogenation of alkenes, reduction of nitro groups, hydrosilylation of α, β-unsaturated ketones, CH arylation of aromatic halides with thiophene indole. .

  In the present invention, on a silicon substrate having the above nanostructure, various metal nanoparticles, particularly those supporting rhodium nanoparticles (hereinafter, also referred to as `` SiNA-Rh '') and supporting metal composite nanoparticles containing rhodium One was prepared. Also prepared are those that carry palladium nanoparticles (SiNA-Pd), those that carry platinum nanoparticles (SiNA-Pt), and those that carry nanoparticles of various metal composites on a silicon substrate with a nanostructure. did.

Specifically, it was manufactured by the following method. p-type silicon substrate (2 inches; thickness (325 ± 25) μm; 0.1-100 Ω; 1.45 g) (E & M) treated with H ₂ SO ₄ / H ₂ O ₂ , washed and Si-H surface substrate Treatment with an aqueous solution of hydrofluoric acid (HF) for the introduction of hydrogen (hydrogen termination). AgNO ₃ was reacted with the hydrogen-terminated substrate to obtain a substrate coated with Ag fine particles, and treated with an aqueous HF / H ₂ O ₂ solution to obtain a silicon nanowire array. Removal of Ag fine particles and reconstruction of the Si-H surface of the silicon nanowire array were performed by immersing each in HNO ₃ and 5% HF aqueous solution (10 mL) for 1 minute, followed by washing with pure water and blowing water with nitrogen. Removed.

  Rhodium chloride trihydrate (59.2 mg) was dissolved in pure water (4.5 mL) to prepare a 50 mM aqueous solution. After 1.5 mL of acetone was added thereto, the above-prepared SiNA was immersed in this solution at room temperature for 5 minutes. Thereafter, the substrate was washed with pure water and acetone (20 mL each), and dried by blowing nitrogen thereto, whereby SiNA-Rh was prepared (1.45 g).

  For palladium nanoparticles, platinum nanoparticles, and nanoparticles of metal composites (alloys), silicon nanowire arrays supporting the nanoparticles were produced in the same manner as described above, using the respective aqueous metal salt solutions.

  The structure of the silicon nanowire array on which the rhodium nanoparticle catalyst of the example was immobilized was analyzed.

  FIG. 1 shows an SEM (Scanning Electron Microscope) (JEOL JSM6330F) photograph of a cross section of SiNA-Rh (sample BHY-12-171B). The SEM photograph of the cross section of SiNA-Pd shows that the nanospace length is 5 μm, the nanospace width is less than 800 nm, the average nanospace width is about 80 nm, and the aspect ratio is about 60.

  When the size of 200 particles was measured individually from the TEM (JEOL JEM-2100F) image of SiNA-Rh (sample BHY-12-171B), the diameter of about 1-10 nm (φ = about 4 nm) The dispersion of rhodium nanoparticles was shown (A, B in FIG. 2 and FIG. 3). The energy dispersive X-ray spectroscopy (EDX, JED-2300T) image of the cross section of SiNA-Rh showed that rhodium nanoparticles were supported on the silicon nanowire array (C in FIG. 2). ~ F).

  SiNA-Rh (sample BHY-8-37-Rh) and Rh3d X-ray Photoelectron Spectroscopy (XPS) of rhodium nanoparticles supported on carbon (X-ray Photoelectron Spectroscopy: XPS) (VG ESCALAB 250 spectrometer, Thermo Fisher Scientific KK) The formation of zero-valent rhodium species was shown (FIGS. 4 and 5).

The siNA-Rh (six samples, ² x 2 cm 2) inductively coupled plasma mass spectrometry for (Inductively coupled plasma mass spectrometry: ICP -MS) (Perkin Elmer Nexion TM 300D) are supported amount of rhodium nanoparticles on The siNA Was about 2-5 μmol / g (FIG. 6). The photographs are photographs of SiNA before supporting rhodium (left) (sample BHY-8-37) and SiNA-Rh after supporting rhodium (right) (sample BHY-8-37-Rh).

  Note that a silicon nanowire array carrying other nanoparticles was analyzed in the same manner, and it was confirmed that the silicon nanowire array had the same structure and the same carrying form.

<Example 2>
Synthesis of heptadecane from stearic acid using SiNA-Rh
To a 10 mL pressure-resistant glass container, add SiNA-Rh (67 mg, 270 nmol Rh, 0.054 mol% Rh) and stearic acid (142.3 mg, 0.5 mmol), set to a hydrogen pressure of 9.9 bar, and use a CEM micro The reaction was performed for 6 hours with a wave synthesizer (CEM Discover-SP or CEM Discover System) at 200 ° C and a maximum output of 200 W (30-50 W at stable temperature). After tracking the reaction at normal temperature and normal pressure and sampling a small amount, the reaction was continued at 200 ° C. and a maximum output of 200 W (30-50 W at stable temperature). Micro sampling was performed every 6 hours, and the reaction was completed in 24 hours. To 1 mg of the reaction mixture, 0.1 mL of N, N-dimethylformamide dimethyl acetal was added, and 0.1 mL of methanol was further added.The resultant was dried with a dryer for 30 seconds, and the yield was determined by gas chromatography (DB-WAX, manufactured by Agilent Technologies). It was confirmed. The recovered SiNA-Rh was washed with tetrahydrofuran, ethyl acetate, and acetone, dried by blowing nitrogen, and reused. Table 1 shows the results.

The catalyst supporting rhodium nanoparticles uses stearic acid (0.5 mmol) as a substrate, and uses about 0.05 mol% of SiNA-Rh (for example, a catalyst amount of 1/20 or less of the catalyst of the prior art document), 9, The reaction temperature was set to 200 ° C by microwave irradiation under a hydrogen atmosphere of 9 bar, and the reaction was performed for 24 hours.As a result, heptadecane, a compound having n-1 carbon atoms corresponding to stearic acid having n carbon atoms, was obtained. 94%. Further, octadecane, a compound having n carbon atoms, which is a by-product, which is a problem in the prior art, was not produced. In addition, it was confirmed by gas chromatography that carbon monoxide was obtained as a gas component and no carbon dioxide, which could be a by-product, was generated at all. In Table 1 above, the value of H ₂ : CO: CO ₂ for each entry was obtained by opening the reaction system every 6 hours (6 hours, 12 hours, 18 hours, and 24 hours, respectively). The gas in the system was collected and calculated based on the value obtained by GC analysis (after each opening for 6, 12, and 18 hours, the reaction system was recharged with hydrogen again, and the reaction was continued for another 6 hours. And measured and calculated in the same manner).

When this catalyst was recovered and reused in the same reaction, heptadecane was obtained in 89% in the second reaction, 85% in the third reaction, and 87% in the fourth reaction. At this time, only carbon monoxide was obtained as a gas component, and no carbon dioxide was generated. Furthermore, the catalyst recovery and catalytic reaction (24 hours) were repeated up to 20 times, but the heptadecane yield (P1) was 80% or more. Only carbon was obtained.
The progress of the reaction was attempted in the same manner as for entry 1 in the above table, except that the reaction system was heated to 200 ° C. without performing microirradiation. However, after 6 hours of the reaction time, heptadecane was not detected yet. Was.

<Example 3>
Synthesis of heptadecane from stearic acid using catalysts supporting various metal nanoparticles
To a 10 mL pressure-resistant glass container, add SiNA-Rh (67 mg, 270 nmol Rh, 0.054 mol% Rh) and stearic acid (284 mg, 1 mmol), set to a hydrogen pressure of 9.9 bar, and use a CEM micro The reaction was performed for 6 hours with a wave synthesizer (CEM Discover-SP or CEM Discover System) at 200 ° C and a maximum output of 200 W (30-50 W at stable temperature). To 1 mg of the reaction mixture, 0.1 mL of N, N-dimethylformamide dimethyl acetal was added, and 0.1 mL of methanol was further added.The resultant was dried with a dryer for 30 seconds, and the yield was determined by gas chromatography (DB-WAX, manufactured by Agilent Technologies). It was confirmed. The same reaction was carried out for the catalyst supporting the alloy nanoparticles and the catalyst supporting the metal nanoparticles of noble metals other than rhodium, and the yield was confirmed. Table 2 shows the results.

Heptadecane, a compound having n-1 carbon atoms corresponding to stearic acid having n carbon atoms, was obtained with a catalyst supporting metal nanoparticles. Octadecane, a compound having n carbon atoms, as a by-product was not produced. Carbon monoxide was obtained as a gas component, and no carbon dioxide was produced. The reaction did not proceed for those that did not support the metal nanoparticles (entry 1). In addition, except that the reaction system was heated to 200 ° C. without performing microirradiation, the progress of the reaction was attempted in the same manner as in each entry in the above table. Was not detected.
Further, except that RhCl ₃ .3H ₂ O (0.056 mol% of MNPs) was used as the catalyst, the progress of the catalytic reaction was attempted in the same manner as above, but the reaction did not progress.

  The reusability of the catalyst supporting the alloy nanoparticles and the catalyst supporting the palladium nanoparticles was examined. The recovered catalyst was washed with tetrahydrofuran, ethyl acetate, and acetone, dried by blowing nitrogen, and reused. Table 3 shows the results of the reaction at the time of reuse.

  When the reaction was carried out using SiNA-Pd, heptadecane was produced at a yield of 32% in 6 hours and at a recycling rate of 12% (entry 2). When the reaction was carried out using SiNA-Pt, heptadecane was produced at a yield of 38% in 6 hours and at a reuse rate of 22% (entry 3). When the reaction was carried out using SiNA-PdPt (alloy nanoparticles of palladium and platinum), heptadecane was produced in a yield of 49% in 6 hours and in 15% in reuse (entry 1). When the reaction was performed using SiNA-PdRh (alloy nanoparticles of palladium and rhodium), the yield was 37% in 6 hours, 33% in the second use, 33% in the third use, and 8% in the fourth use. Heptadecane was produced (entry 4). When the reaction was carried out using SiNA-PdPtRh (alloy nanoparticles of palladium, platinum and rhodium), heptadecane was produced in a yield of 39% in 6 hours and in a reuse of 4% (entry 5). When the reaction was carried out using SiNA-PdPtRhNi (alloy nanoparticles of palladium, platinum, rhodium and nickel), heptadecane was produced in 41% in 6 hours and in 26% in reuse (entry 6). When the reaction was carried out using SiNA-PdRu (alloy nanoparticles of palladium and ruthenium), heptadecane was produced in 36% yield in 6 hours and 25% in reuse (entry 7). Comparing with the results in Table 1, when the reaction was observed in 6 hours using SiNA-Rh, heptadecane was produced in a yield of 47%, 41% in the second use, and 57% in the third use, under these conditions. In the reaction system at, the results were better than those described above.

<Example 4>
Synthesis of alkene from carboxylic acid using SiNA-Rh
In a 10 mL pressure-resistant glass container, add SiNA-Rh (70 mg, 265 nmol Rh, 0.053 mol% Rh; or 71.0 mg, 270 nmol Rh, 0.054 mol%) and carboxylic acid (0.5 mmol), and add a hydrogen pressure of 9.9 bar. And the reaction was carried out for 24 hours at a setting of 200 ° C and a maximum output of 200 W (30-50 W at stable temperature) using a microwave synthesizer (CEM Discover-SP or CEM Discover System) manufactured by CEM. . To 1 mg of the reaction mixture, 0.1 mL of N, N-dimethylformamide dimethyl acetal was added, and 0.1 mL of methanol was further added.The resultant was dried with a dryer for 30 seconds, and the yield was determined by gas chromatography (DB-WAX, manufactured by Agilent Technologies). It was confirmed. Table 4 shows the results.

  SiNA-Rh acted on saturated aliphatic carboxylic acids, unsaturated aliphatic carboxylic acids, and branched aliphatic carboxylic acids to produce alkenes. In addition, heptadecane was produced as a main product from oleic acid, and pentadecane was produced as a main product from 2-hexyldecanoic acid.

<Example 5>
Synthesis of heptadecane from stearic acid using SiNA-Rh in pivalic acid added system
In a 10 mL pressure-resistant glass container, add SiNA-Rh (67 mg, 270 nmol Rh, 0.054 mol% Rh), stearic acid (142.3 mg, 0.5 mmol), and pivalic anhydride (0.75 mmol), and add a hydrogen pressure of 9.9 bar. The reaction was carried out for 6 hours at 200 ° C. at a maximum output of 200 W (30-50 W at stable temperature) using a microwave synthesizer (CEM Discover-SP or Discover System) manufactured by CEM. To 1 mg of the reaction mixture, 0.1 mL of N, N-dimethylformamide dimethyl acetal was added, and 0.1 mL of methanol was further added.The resultant was dried with a dryer for 30 seconds, and the yield was determined by gas chromatography (DB-WAX, manufactured by Agilent Technologies). It was confirmed. As a result, heptadecane was obtained at a yield of 89%. Also, carbon monoxide was obtained as a gas component, and no carbon dioxide was generated.

  The recovered SiNA-Rh was washed with tetrahydrofuran, ethyl acetate, and acetone, dried by blowing nitrogen, and reused. 93% for the second reuse, 88% for the third time, 87% for the fourth time, 87% for the fifth time, 89% for the sixth time, 87% for the seventh time, 86% for the eighth time, 86% for the ninth time Heptadecane was obtained in 84%, 89% in the 10th test, and 86% in the 11th test. Carbon monoxide was obtained as a gas component. The efficiency was improved by using pivalic acid. It could be reused more than 10 times.

<Example 6>
Synthesis of heptadecane from octadecanal using SiNA-Rh
A 20 mL test tube was charged with SiNA-Rh (69.941 mg, 270 nmol Rh, 0.054 mol% Rh), octadecanal (134.3 mg, 0.5 mmol) was added, and the mixture was purged with argon for 30 seconds. The reaction was performed at 150 ° C. for 18 hours using a DFC mixer (700 rpm) (Device for Flow Chemistry) under an argon atmosphere (1 atm). After 18 hours, it was cooled to room temperature. Dodecane was added as an internal standard substance, and the yield was confirmed by gas chromatography (DB-WAX, manufactured by Agilent Technologies).

The reaction mixture was dissolved in CH ₂ Cl _2, and evaporated. The reaction mixture was purified by a silica gel column using hexane. The purified solution was evaporated to dryness under vacuum. Analysis was performed by ¹ H NMR (JEOL JNM AL400 spectrometer).

  The catalyst supporting rhodium nanoparticles was prepared by using octadecanal (0.5 mmol) as a substrate, using about 0.05 mol% of SiNA-Rh, and setting the reaction temperature to 150 ° C under an argon atmosphere (1 atm). When subjected to the time reaction, heptadecane, a compound having n-1 carbon atoms corresponding to octadecanal having n carbon atoms, was obtained in a yield of 86% (104 mg) after isolation. Octadecane, a compound having n carbon atoms, as a by-product was not produced.

<Example 7>
Synthesis of bibenzyl from trans-stilbene using SiNA-Rh
A 10 mL test tube was charged with SiNA-Rh (108.16 mg, 465 nmol Rh, 0.093 mol% Rh), stilbene (90.0 mg, 0.5 mmol) was added, and 2 mL EtOH was added. Dodecane was added as an internal standard. Hydrogen bubbling was performed for 1 minute. The reaction was carried out at 70 ° C. for 24 hours under a hydrogen atmosphere (1 atm) using a DFC mixer (700 rpm) (Device for Flow Chemistry). After 24 hours, the mixture was cooled to room temperature, and the yield was confirmed by gas chromatography (HP-1, manufactured by Agilent Technologies).

  Using a catalyst carrying rhodium nanoparticles, trans-stilbene (0.5 mmol) as a substrate, SiNA-Rh in about 0.09 mol%, and a reaction temperature of 70 ° C under a hydrogen atmosphere (1 atm). After 24 hours of reaction, bibenzyl in which trans-stilbene was hydrogenated was obtained in a yield of 99% (90.7 mg).

<Example 8>
Synthesis of aliphatic hydrocarbon from aliphatic carboxylic acid ester SiNA-Rh was produced in the same manner as in Example 1. To a 10 mL pressure-resistant glass container, add SiNA-Rh (67 mg, 270 nmol Rh, 0.054 mol% Rh), methyl stearate (149.3 mg, 0.5 mmol) and H ₂ O (6.5 mol), and add a hydrogen pressure of 9.9 bar. The reaction was carried out for 48 hours at 200 ° C with a maximum output of 200 W (30-50 W at stable temperature) using a CEM microwave synthesizer (CEM Discover-SP or CEM Discover System). . To 1 mg of the reaction mixture, 0.1 mL of N, N-dimethylformamide dimethyl acetal was added, and 0.1 mL of methanol was further added.The resultant was dried with a dryer for 30 seconds, and the yield was determined by gas chromatography (DB-WAX, manufactured by Agilent Technologies). It was confirmed. The results are shown below.

In the same manner as in Example 1, SiNA-Pd ₁ Pt _0.54 was produced. To a 10 mL pressure-resistant glass container, add SiNA-Pd ₁ Pt _0.54 (0.071 mol% Pd ₁ Pt _0.54 ) and ethyl stearate (1 mmol), set to a hydrogen pressure of 9.9 bar, and use a CEM microwave synthesizer ( The reaction was performed for 6 hours at 200 ° C with a maximum output of 200 W (30-50 W at stable temperature) using CEM Discover-SP or CEM Discover System). Thereafter, in the same manner as above, the yield was confirmed by gas chromatography (DB-WAX, manufactured by Agilent Technologies). The results are shown below.

  According to the catalyst of the present invention, aliphatic hydrocarbons and carbon monoxide can be efficiently and selectively produced with a smaller amount of catalyst. Further, according to the catalyst of the present invention, the reaction can be carried out under milder conditions, and the efficiency of reusing the catalyst is high, which is advantageous in terms of cost. The aliphatic hydrocarbon obtained by the production method using the catalyst of the present invention is useful as a biodiesel fuel, and carbon monoxide can be used as a petroleum synthesis raw material.

Claims (12)

A catalyst comprising a silicon wire and metal fine particles containing at least one noble metal selected from the group consisting of platinum, palladium, and rhodium supported on the silicon wire is treated with an aliphatic carboxylic acid, an aliphatic carboxylic acid ester and an aliphatic carboxylic acid ester. A catalytic reaction step of acting on at least one substrate selected from the group consisting of aldehydes and promoting at least one reaction of decarboxylation, dealkoxycarbonylation and decarbonylation of the at least one substrate;
A method for producing an aliphatic hydrocarbon, comprising:   The method of claim 1, wherein the silicon wires are formed as a silicon wire array of a plurality of silicon wires formed on a silicon substrate.   The said at least one kind of substrate is an aliphatic carboxylic acid, an aliphatic carboxylic acid ester or an aliphatic aldehyde having an aliphatic hydrocarbon chain having 6 to 25 carbon atoms which may have a substituent. The method described in.   The method according to any one of claims 1 to 3, wherein a part or all of the at least one reaction proceeds under irradiation with microwaves.   The method according to any one of claims 1 to 4, wherein in the catalyst reaction step, the catalyst is allowed to act on the at least one substrate at a metal amount of 0.001 mol% or more.   The method according to claim 1, wherein the at least one noble metal is rhodium.   The method according to any one of claims 1 to 6, wherein the at least one reaction proceeds in the presence of at least one acid anhydride. A catalytic reaction step according to claim 1,
Collecting carbon monoxide produced by at least one of decarboxylation, dealkoxycarbonylation and decarbonylation during and / or after the catalytic reaction step;
A method for producing carbon monoxide, comprising:   A catalyst comprising a silicon wire and metal particles containing rhodium supported on the silicon wire.   The catalyst according to claim 9, wherein the silicon wires are formed as a silicon wire array including a plurality of silicon wires formed on a silicon substrate. A step of causing the catalyst according to claim 9 or 10 to act on an unsaturated aliphatic aryl to cause a hydrogenation reaction,
A method for producing a saturated aliphatic aryl, comprising:   The method according to claim 11, wherein the unsaturated aliphatic aryl is an unsaturated aliphatic aryl having an unsaturated aliphatic hydrocarbon chain having 2 to 25 carbon atoms which may have a substituent.

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