JP2018130674A - Catalyst for oxidation reaction - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst for oxidation reaction which has high catalytic activity even at low temperature, low pressure, and in the absence of a solvent, and which retains the catalytic activity.SOLUTION: A catalyst for oxidation reaction of the invention is made of a combination of a main catalyst carrying on a carrier at least one metal compound selected from the group consisting of metal salts and metal complexes, and not carrying a compound containing N-hydroxyimide, and an imide compound having a cyclic imide skeleton as a cocatalyst which is blended into a reaction substrate containing hydrocarbon.SELECTED DRAWING: None

Description

  The present invention relates to an oxidation reaction catalyst. Further, the present invention relates to an oxide production method using the oxidation reaction catalyst, a flow reactor using the oxidation reaction catalyst, and an oxidation reaction apparatus having the flow reactor.

  The oxidation reaction is one of the most basic reactions in the chemical industry, and various oxidation reaction catalysts have been developed. The oxidation reaction using these oxidation reaction catalysts is performed in the presence or absence of a solvent, and a polar solvent is generally used when the oxidation reaction is performed in the presence of a solvent. However, some reaction substrates are decomposed by a polar solvent, which causes a problem that the yield of the reaction product decreases. In the first place, when a solvent is used in the oxidation reaction, a process for separating the solvent and the product is required, which is not effective from the viewpoint of production efficiency.

  Examples of the method for oxidizing the reaction substrate in the absence of a solvent include a method in which only the reaction substrate is subjected to an oxidation reaction in the liquid phase, and a method in which the reaction substrate is oxidized in the gas phase. Examples of the method for subjecting only the reaction substrate to the oxidation reaction in the liquid phase include a method for oxidizing alkanes and the like disclosed in Non-Patent Document 1.

  Patent Document 1 discloses a reduction of a main catalyst (specifically, an N-hydroxyimide group-containing compound) that generates an alkyl radical by extracting a hydrogen atom from a hydrocarbon, and an alkyl hydroperoxide generated from the alkyl radical. Thus, a catalyst is disclosed in which a co-catalyst (specifically, a transition metal compound or the like) that generates alcohol is supported on a carrier.

International Publication Number 2015/076305

Polyhedron, 69,119-126 (2014)

  However, since the method for oxidizing alkanes described in Non-Patent Document 1 is performed under high temperature and high pressure, equipment capable of withstanding this is required.

  In addition, the catalyst described in Patent Document 1 has a N-hydroxyimide group-containing compound as a main catalyst and a transition metal compound as a cocatalyst supported on a carrier at the same time, thereby allowing each catalyst and a reaction substrate to react with each other. There is a problem that the contact area is reduced and the contact frequency between the N-hydroxyimide group-containing compound directly involved in the oxidation reaction and the reaction substrate is lowered, resulting in low catalytic activity. Further, when the oxidation reaction is carried out, it is considered that the N-hydroxyimide group-containing compound on the support gradually changes in quality and its catalytic activity is reduced or deactivated, making it difficult to reuse.

  Thus, an oxidation reaction catalyst that exhibits high catalytic activity even under conditions such as low temperature and in the absence of a solvent and that maintains the catalytic activity has not been developed so far.

  Accordingly, an object of the present invention is to provide an oxidation reaction catalyst having good catalytic activity for a reaction substrate having a low polarity such as alkanes even at a low temperature, a low pressure and in the absence of a solvent. Another object of the present invention is to provide a method for producing an oxide that oxidizes the reaction substrate. Another object of the present invention is to provide an oxide (for example, high octane gasoline) obtained by the above production method. Another object of the present invention is to provide a flow reactor using a catalyst having a specific structure. Another object of the present invention is to provide an oxidation reaction apparatus including the flow reactor.

  As a result of intensive investigations to solve the above problems, the present inventors have shown that an oxidation reaction catalyst having a specific configuration exhibits good catalytic activity even for a reaction substrate having a low polarity such as alkanes, and has a low temperature and low pressure. The present invention was completed by finding that the oxidation reaction can be carried out efficiently even under the absence of a solvent and that the catalytic activity is sustained.

  That is, the present invention comprises a main catalyst in which at least one metal compound selected from the group consisting of a metal salt and a metal complex is supported on a carrier and an N-hydroxyimide group-containing compound is not supported; There is provided an oxidation reaction catalyst comprising a combination with an imide compound having a cyclic imide skeleton as a co-catalyst blended in a reaction substrate.

  The metal is preferably cobalt or manganese.

  The metal salt is preferably a carboxylic acid metal salt, and the metal complex is preferably a β-diketone metal complex.

  In the present invention, at least one metal compound selected from the group consisting of a metal salt and a metal complex is supported on the support, and the cyclic imide is present in the presence of a catalyst not supporting the N-hydroxyimide group-containing compound. The present invention also provides a method for producing an oxide characterized by oxidizing a reaction substrate containing a hydrocarbon mixed with an imide compound having a skeleton.

  Moreover, it is preferable that the reaction temperature in the manufacturing method of the said oxide is 120 degrees C or less.

  In the oxide production method, the oxidation reaction is preferably performed under a pressure condition of 10 MPa or less.

  In the oxide production method, the oxidation reaction is preferably performed in a liquid phase.

  In addition, the oxide production method uses a catalyst in which at least one metal compound selected from the group consisting of a metal salt and a metal complex is supported on a support and an N-hydroxyimide group-containing compound is not supported. It is preferable to carry out the oxidation reaction by circulating a reaction substrate containing a hydrocarbon in which an imide compound having a cyclic imide skeleton is dissolved in a flow reactor.

  Moreover, it is preferable that the usage-amount of the imide compound which has cyclic imide frame | skeleton is 0.001-5.0 weight part with respect to 100 weight part of reaction substrates.

  Moreover, in the said oxide manufacturing method, it is preferable to manufacture the gasoline which oxidized the gasoline base material as said reaction substrate, and raised the octane number.

  Moreover, in the said oxide manufacturing method, it is preferable that the ratio of the reaction substrate in preparation amount is 99 weight% or more.

  Further, in the present invention, a flow reactor using a catalyst in which at least one metal compound selected from the group consisting of a metal salt and a metal complex is supported on a support and an N-hydroxyimide group-containing compound is not supported. Also provide.

  The present invention also provides an oxidation reaction apparatus including a flow path through which the flow reactor and a reaction substrate containing a hydrocarbon in which an imide compound having a cyclic imide skeleton is dissolved flow.

  The catalyst for oxidation reaction of the present invention has high catalytic activity even at low temperature, low pressure, and in the absence of a solvent, and further maintains the catalytic activity. Therefore, the reaction substrate containing hydrocarbons has a high conversion rate. It is possible to obtain the corresponding oxide with high yield. In addition, since the method for producing an oxide of the present invention uses the oxidation reaction catalyst, the oxide can be obtained at a high conversion rate and a high yield even at low temperature and low pressure even in the absence of a solvent. it can. Further, in the method for producing an oxide of the present invention, when a gasoline base material is used as a reaction substrate, it is possible to obtain high octane gasoline (a gasoline composition exhibiting a high octane number). Further, by using the flow reactor of the present invention, an oxide can be obtained at a high conversion rate and a high yield even at low temperature and low pressure even in the absence of a solvent. Further, by using the oxidation reaction apparatus of the present invention, an oxide can be obtained more efficiently with a high conversion rate and a high yield.

It is the schematic which shows an example of the apparatus for oxidation reaction of this invention.

  In the present invention, a main catalyst on which at least one metal compound selected from the group consisting of metal salts and metal complexes is supported on a carrier and an N-hydroxyimide group-containing compound is not supported, and a reaction containing hydrocarbons Provided is an oxidation reaction catalyst comprising a combination with an imide compound having a cyclic imide skeleton as a co-catalyst blended in a substrate. The oxidation reaction catalyst may be referred to as “the oxidation reaction catalyst of the present invention”. In addition, the main catalyst in the oxidation reaction catalyst may be simply referred to as “main catalyst”. Further, the promoter in the oxidation reaction catalyst may be simply referred to as “promoter”.

  In the present invention, at least one metal compound selected from the group consisting of a metal salt and a metal complex is supported on the support, and the cyclic imide is present in the presence of a catalyst not supporting the N-hydroxyimide group-containing compound. Provided is a method for producing an oxide characterized by oxidizing a reaction substrate containing a hydrocarbon mixed with an imide compound having a skeleton (sometimes referred to as “the method for producing an oxide of the present invention”). In addition, a flow reactor using a catalyst on which at least one metal compound selected from the group consisting of a metal salt and a metal complex is supported on a support and an N-hydroxyimide group-containing compound is not supported (“invention of the present invention”). Sometimes referred to as a "flow reactor"). In addition, an oxidation reaction apparatus (sometimes referred to as an “oxidation reaction apparatus of the present invention”) including a flow path and a flow path through which a reaction substrate containing a hydrocarbon in which an imide compound having a cyclic imide skeleton is dissolved flows. )I will provide a.

<Catalyst for oxidation reaction>
The catalyst for oxidation reaction (main catalyst) of the present invention has at least one metal compound selected from the group consisting of a metal salt and a metal complex supported on a carrier, so that the contact efficiency between the metal compound and the reaction substrate is improved. improves. As a result, the oxidation reaction catalyst of the present invention exhibits excellent catalytic activity. In addition, a part of the metal compound (a part of the metal or a part of the compound) may be supported on the support through a chemical bond, but it must be supported on the support without a chemical bond. Is preferable from the viewpoint of catalytic activity. Further, since the N-hydroxyimide group-containing compound is not supported on the carrier, the catalyst activity is not lowered and the catalyst is hardly deteriorated. Furthermore, catalytic activity is sustained by using an imide compound having a cyclic imide skeleton blended in a reaction substrate containing hydrocarbon as a co-catalyst.

  Further, after the oxidation reaction is completed, the main catalyst and the reaction product can be easily separated by physical separation means such as filtration and centrifugation. Furthermore, the separated main catalyst can be reused in the state contained in the solvent used for the oxidation reaction, or can be reused after operations such as washing and drying. .

  The metal (metal atom) in the metal compound (metal salt and metal complex) is not particularly limited as long as it exhibits a catalytic action in the oxidation reaction. For example, a transition metal (transition metal atom) is preferable. Examples of the transition metal include group 3 elements (scandium, lanthanoid elements, actinoid elements, etc.), group 4 elements (titanium, zirconium, hafnium, etc.), group 5 elements (vanadium, etc.), group 6 elements (chromium), etc. , Molybdenum, tungsten, etc.), Group 7 elements (manganese, etc.), Group 8 elements (iron, ruthenium, etc.), Group 9 elements (cobalt, rhodium, etc.), Group 10 elements (nickel, palladium, platinum, etc.), Group 11 elements (Such as copper). Among these, cobalt and manganese are preferable from the viewpoint of catalytic activity. In addition, although the valence of the metal is not particularly limited, for example, 0 to 6 valence is preferable, and 2 or 3 valence is more preferable. In addition, a metal compound can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  The metal is supported on a carrier in the form of a metal compound, and examples of the metal compound include metal salts and metal complexes. Examples of the metal salt include organic acid metal salts and inorganic acid metal salts, and organic acid metal salts are preferable. Examples of the metal complex include organometallic complexes and inorganic metal complexes, and organometallic complexes are preferred. As in the present invention, an oxidation reaction catalyst comprising a carrier on which an organic metal compound such as an organic acid metal salt or an organic metal complex is supported as a metal compound is supported in a state where the metal is an inorganic metal (for example, a metal oxide). Compared with the case where a catalyst comprising a supported carrier or an organic metal salt itself is used as a catalyst, the catalytic activity is good. The reason for this is not clear, but by supporting the organometallic compound on the support while maintaining the structure of the organometallic compound, contact between the organometallic compound and the non-polar compound such as hydrocarbon contained in the reaction substrate is improved. It is considered that the efficiency is improved, and as a result, the catalytic activity is improved.

  The organic acid metal salt is preferably a metal salt having a carboxylate (carboxylate metal salt), for example, cobalt acetate, cobalt octylate, cobalt naphthenate, cobalt malonate, cobalt neodecanoate, cobalt stearate, propion. Carboxylic acid cobalt salts such as cobalt acid, cobalt benzoate, cobalt p-hydroxybenzoate, cobalt rosinate, cobalt versatate, and cobalt tall oil; manganese acetate, manganese octoate, manganese dimethyldithiocarbamate, manganese diethyldithiocarbamate And manganese carboxylates such as manganese dipropyldithiocarbamate, manganese dibutyldithiocarbamate, manganese diphenyldithiocarbamate, and ethylenediaminetetraacetate manganese. Examples of the organometallic complex include ammine metal complexes, carbonyl metal complexes, β-diketone metal complexes (for example, acetylacetonate metal complexes), and nitroso metal complexes. For example, acetyl such as cobalt (acetylacetonate). Examples include acetonate metal complexes.

  Among these, as a metal compound in the oxidation reaction catalyst (main catalyst) of the present invention, cobalt acetate, cobalt naphthenate, cobalt stearate, cobalt benzoate, and cobalt (acetylacetonate) are preferable from the viewpoint of catalytic activity.

  The carrier may be a known or conventional carrier used as a catalyst carrier, and is not particularly limited. Examples of the inorganic carrier include silica, alumina, silica alumina (aluminosilicate), ceria, magnesia. , Oxide-based inorganic carriers such as calcia, titania, silica titania (titanosilicate), zirconia, and zeolite; carbon-based inorganic carriers such as activated carbon, graphene, and carbon nanotubes, and organic polymer carriers Styrene polymer, polyolefin, (meth) acrylic acid polymer, and epoxy resin. Among the carriers, inorganic carriers (oxide-based or carbon-based inorganic carriers) are preferable, and silica, alumina, and zeolite are particularly preferable. In addition, a support | carrier can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  The average particle diameter of the carrier is not particularly limited, but is preferably 50 to 20000 μm, more preferably 100 to 500 μm from the viewpoint of catalytic activity. Moreover, the shape of the said support | carrier is not specifically limited, You may shape | mold in the powder form, the granular form, the pellet form, the tablet form, etc.

  The content of the metal supported on the carrier (in terms of metal atoms) is not particularly limited, but is preferably about 0.01 to 10% by weight, more preferably 0.1% with respect to the total amount (100% by weight) of the main catalyst. It is about -8.0 weight%, More preferably, it is about 0.5-5.0 weight%, Most preferably, it is about 1.0-3.0 weight%. When the metal content is within the above range, the conversion rate of the reaction substrate is improved. The total amount of the main catalyst refers to the total weight of the support and a catalyst such as a metal compound supported on the support.

  The method for supporting the metal compound on the carrier is not particularly limited, but the following methods (1) to (3) are more preferable from the viewpoint of catalytic activity.

  Generally, as a method of supporting a metal or a metal compound on a carrier, (1) a method of impregnating the carrier with a solution containing the metal compound and then drying, (2) kneading the metal compound and the carrier in the solution (3) A method in which a solution containing a metal compound is applied to the surface of the carrier and drying, (4) a method in which the carrier is impregnated with a solution containing the metal compound, followed by drying and further firing. 5) After impregnating the support with a solution containing a metal compound, the pH of the solution is adjusted, and a metal is deposited on the support surface. The supporting methods (1) to (3) are characterized in that the metal compound itself is supported on a carrier. On the other hand, the supporting methods (4) and (5) are characterized in that the metal (metal element) itself is supported on the carrier because it undergoes a firing step and a pH adjustment step. For example, in the supporting method (4), when metal nitrate is used as the metal compound, nitrate ions are volatilized as nitric acid gas by thermal decomposition, and only the metal is supported on the carrier.

  A catalyst comprising a carrier carrying a metal compound (for example, a catalyst obtained by the carrying method of (1) to (3) above) is a catalyst comprising a carrier carrying a metal itself (eg, the above ( Compared with the catalyst obtained by the loading method of 4) and (5)), the catalyst activity tends to be high. Although the reason for this is not clear, in the supporting methods (1) to (3), the metal compound is supported on the carrier while maintaining its properties, whereas in the supporting methods (4) and (5), the firing is performed. It is considered that the cause is that the metal compound is altered through the process and the pH adjustment process. That is, in the loading methods of (4) and (5), the catalytic activity inherently possessed by the metal compound is reduced, or the affinity between the metal compound and the nonpolar compound is reduced, thereby reducing the contact efficiency. As a result, it is considered that the catalytic activity is lowered. Further, in the loading methods (1) to (3), since the metal compound is dispersed and supported on the support, the contact efficiency with the reaction substrate is improved, and as a result, it is assumed that high catalytic activity is exhibited.

  The oxidation reaction catalyst (main catalyst) of the present invention is characterized in that an N-hydroxyimide group-containing compound is not supported on a carrier. “Not supported on a carrier” means “not substantially supported on a carrier”. For example, the content of an N-hydroxyimide group-containing compound supported on a carrier (in terms of metal atoms) ) Is 0.001% by weight or less, preferably 0.0001% by weight or less, more preferably 0.00001% by weight or less, based on the total amount (100% by weight) of the main catalyst. More preferably, it is 0% by weight.

  In addition, the N-hydroxyimide group containing compound in this invention is used as a catalyst which draws out a hydrogen atom from a hydrocarbon, and produces | generates an alkyl radical, Comprising: The compound which has an N-hydroxyimide group is pointed out. Examples of the N-hydroxyimide group-containing compound include N-hydroxyphthalimide and derivatives thereof, and “imide compound having a cyclic imide skeleton” described later is also included as one type thereof.

  The cocatalyst in the oxidation reaction catalyst of the present invention is an imide compound having a cyclic imide skeleton mixed with a reaction substrate containing hydrocarbon. In addition, the reaction substrate and the imide compound having a cyclic imide skeleton will be described in the section of the oxide production method described later.

<Oxide production method>
In the method for producing an oxide of the present invention, at least one metal compound selected from the group consisting of a metal salt and a metal complex is supported on a support, and the presence of a catalyst on which an N-hydroxyimide group-containing compound is not supported The reaction substrate is characterized in that a reaction substrate containing a hydrocarbon mixed with an imide compound having a cyclic imide skeleton (hereinafter sometimes simply referred to as “imide compound”) is oxidized. The catalyst used in the oxide production method of the present invention may be the same as that used for the main catalyst in the oxidation reaction catalyst of the present invention. Further, the imide compound in the oxide production method of the present invention may be the same as that used for the promoter in the oxidation reaction catalyst of the present invention.

  The reaction substrate mixed with the imide compound may be in a slurry state, or the imide compound may be dissolved in the reaction substrate. From the viewpoint of catalytic activity and handling, the imide compound Is preferably dissolved in the reaction substrate.

[Reaction substrate]
The reaction substrate is not particularly limited as long as it is a reaction substrate containing a hydrocarbon. Examples of such a reaction substrate include a gasoline base material. In the method for producing an oxide of the present invention, when a gasoline base is used as a reaction substrate, a high octane gasoline (hereinafter sometimes referred to as “the high octane gasoline of the present invention”) can be obtained. That is, the oxidation reaction catalyst of the present invention is used as a gasoline reforming catalyst.

  Although it does not specifically limit as hydrocarbon contained in a reaction substrate, For example, C3-C10 linear or branched aliphatic hydrocarbon, C3-C10 alicyclic hydrocarbon, and C6-C6 It is preferable to contain at least one hydrocarbon selected from the group consisting of 10 to 10 aromatic hydrocarbons.

  Examples of the linear or branched aliphatic hydrocarbon having 3 to 10 carbon atoms include n-propane, n-butane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, C3-C10 linear alkane such as n-decane; 2-methylpropane, 2-methylbutane, 2,2-dimethylpropane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2 -C3-C10 branched alkane such as methylhexane, 3-methylhexane, 3,4-dimethylhexane, 3-methyloctane, 2,2,4-trimethylpentane; propylene, isobutylene, 1-pentene, 3 to 10 carbon atoms such as 1-hexene, 2-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1,4-hexadiene Such as linear or branched alkenes or alkadienes and the like.

  Examples of the alicyclic hydrocarbon having 3 to 10 carbon atoms include cycloalkanes having 3 to 10 carbon atoms such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, and cyclodecane; cyclopropene, cyclobutene , Cycloalkene having 3 to 10 carbon atoms such as cyclopentene, cyclooctene, cyclohexene, cycloheptene and cyclododecaene; cyclohexane having 3 to 10 carbon atoms such as cyclopentadiene, 1,3-cyclohexadiene and 1,5-cyclooctadiene Examples include alkadienes.

  Examples of the aromatic hydrocarbon having 6 to 10 carbon atoms include benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, naphthalene and the like.

  The hydrocarbon content in the reaction substrate is not particularly limited. For example, the hydrocarbon content is preferably 20% by weight or more, more preferably 40% by weight or more, still more preferably 60% by weight or more, and particularly preferably 80% by weight. % By weight or more.

  When the reaction substrate contains a hydrocarbon other than a linear or branched aliphatic hydrocarbon having 3 to 10 carbon atoms, it contains a linear or branched aliphatic hydrocarbon having 3 to 10 carbon atoms Although the amount is not particularly limited, for example, it is preferably 10 to 99% by weight of the total amount of hydrocarbons, more preferably 30 to 95% by weight, and still more preferably 50 to 90% by weight.

  When the reaction substrate contains a hydrocarbon other than the aromatic hydrocarbon having 6 to 10 carbon atoms, the content of the aromatic hydrocarbon having 6 to 10 carbon atoms is not particularly limited. It is preferably 1 to 90% by weight, more preferably 5 to 70% by weight, and still more preferably 10 to 50% by weight.

  The gasoline base is usually a petroleum fraction obtained by subjecting crude oil to various refining processes. For example, light naphtha or heavy naphtha obtained by atmospheric distillation of crude oil, the light naphtha or heavy naphtha. Desulfurized light naphtha and desulfurized heavy naphtha obtained by desulfurization treatment, cracked gasoline obtained by catalytic cracking and hydrocracking, light cracked gasoline and heavy cracked gasoline obtained by distillation separation of the cracked gasoline, contact Alkylates obtained by adding lower olefins to hydrocarbons such as fractions from which benzene has been removed from reformed gasoline obtained by the reforming method (debenzene reformed gasoline), polymerized gasoline obtained by olefin polymerization, and isobutane Isomerates obtained by isomerization of linear lower paraffinic hydrocarbons (isomerized gasoline), de-N-paraffin oils, and specific categories thereof. Such as fractions and aromatic hydrocarbons.

[High octane gasoline]
In the method for producing an oxide of the present invention, for example, high octane gasoline can be produced by oxidizing a gasoline base material. That is, the high octane gasoline of the present invention includes a gasoline base material and a gasoline base material oxidized by an oxidation reaction.

  The components contained in the high octane gasoline of the present invention include gasoline base materials (for example, the above-mentioned linear or branched aliphatic hydrocarbons having 3 to 10 carbon atoms, alicyclic hydrocarbons having 3 to 10 carbon atoms, Aromatic hydrocarbons having 6 to 10 carbon atoms) and oxides thereof. Examples of the oxide include ketones having 3 to 10 carbon atoms, aldehydes having 3 to 10 carbon atoms, alcohols having 3 to 10 carbon atoms, carboxylic acids having 3 to 10 carbon atoms, and other oxygen-containing hydrocarbons. It is done. The high octane gasoline of the present invention may contain one of these components alone, or may contain two or more.

  Examples of the ketone having 3 to 10 carbon atoms include a linear ketone having 3 to 10 carbon atoms, a branched ketone having 3 to 10 carbon atoms, an alicyclic ketone having 3 to 10 carbon atoms, and 7 to 10 carbon atoms. Of the aromatic ketone. Moreover, although the number of carbonyl groups in a C3-C10 ketone molecule is not specifically limited, For example, it is preferable that it is 1-6, and it is more preferable that it is 1-3. The high octane gasoline of the present invention may contain one of these ketones alone or two or more.

  The linear ketone having 3 to 10 carbon atoms is not particularly limited as long as at least one carbon atom of the linear hydrocarbon is substituted with a carbonyl group. For example, acetone, methyl ethyl ketone, 2-pentanone, C3-C10 linear having one carbonyl group such as 2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, nonan-2-one and positional isomers of the carbonyl group Ketone; C3-C10 linear ketones having two carbonyl groups such as 2,3-heptanedione and acetylacetone. The branched chain ketone having 3 to 10 carbon atoms is not particularly limited as long as it is a ketone in which at least one carbon atom of the branched chain hydrocarbon is substituted with a carbonyl group, but 2,2-dimethyl-1-propanone, Examples include 2,2,4-trimethyl-3-pentanone, 2,5-hexanedione, 2,3-heptanedione, and positional isomers of the carbonyl group (for example, 3-heptanone). The alicyclic ketone having 3 to 10 carbon atoms is not particularly limited as long as it is a ketone in which at least one carbon atom of the alicyclic hydrocarbon is substituted with a carbonyl group. For example, cyclobutanone, cyclopentanone, cyclohexanone, Examples include cycloheptanone, cyclooctanone, and positional isomers of the carbonyl group.

  In addition, as a C3-C10 ketone, acetone, 2-heptanone, 3-heptanone, and 2,2,4-trimethyl-3-pentanone are preferable from a viewpoint of an octane improvement. That is, as a C3-C10 ketone, a C3-C10 linear ketone and a C3-C10 branched ketone are preferable from a viewpoint of an octane improvement.

  Examples of the aldehyde having 3 to 10 carbon atoms include a linear aldehyde having 3 to 10 carbon atoms, a branched aldehyde having 3 to 10 carbon atoms, and an aromatic aldehyde having 7 to 10 carbon atoms. In addition, the high octane gasoline of the present invention may contain one of these aldehydes alone or two or more.

  The straight-chain aldehyde having 3 to 10 carbon atoms is not particularly limited as long as the carbon atom at the terminal of the straight-chain hydrocarbon is substituted with a carbonyl group. For example, butanal, pentanal, hexanal, heptanal, octanal And nonanal. The branched aldehyde having 3 to 10 carbon atoms is not particularly limited as long as the terminal carbon atom of the branched hydrocarbon is substituted with a carbonyl group. For example, 2,2-dimethyl-1-propanal (Pivalaldehyde), 2,4,4-trimethyl-2-pentanal and the like. The aromatic aldehyde is not particularly limited as long as it is an aldehyde in which the carbon atom at the terminal of the hydrocarbon having an aromatic hydrocarbon group is substituted with a carbonyl group, and examples thereof include benzaldehyde.

  In addition, as a C3-C10 aldehyde, a heptanal, a 2, 2- dimethyl- 1-propanal, and a benzaldehyde are preferable from a viewpoint of an octane improvement, and a benzaldehyde is more preferable. That is, as the aldehyde having 3 to 10 carbon atoms, from the viewpoint of improving the octane number, a linear aldehyde having 3 to 10 carbon atoms, a branched aldehyde having 3 to 10 carbon atoms, and an aromatic aldehyde having 7 to 10 carbon atoms. Are preferred, and aromatic aldehydes having 7 to 10 carbon atoms are more preferred.

  Examples of the alcohol having 3 to 10 carbon atoms include linear or branched alcohol having 3 to 10 carbon atoms, alicyclic alcohol having 3 to 10 carbon atoms, and aromatic alcohol having 6 to 10 carbon atoms. . In addition, although the number of the hydroxyl groups in a C3-C10 alcohol molecule is not specifically limited, For example, it is preferable that it is 1-6, and it is more preferable that it is 1-3. In addition, the high octane gasoline of the present invention may contain one of these alcohols alone or two or more.

  The linear alcohol having 3 to 10 carbon atoms is not particularly limited as long as it is an alcohol in which at least one hydrogen atom of the linear hydrocarbon is substituted with a hydroxyl group. For example, 1-propanol, 1-butanol, 1 -Pentanol, 1-hexanol, 1-heptanol, 1-octanol and positional isomers of hydroxyl groups thereof (for example, 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol) , 2-heptanol, 3-heptanol, 4-heptanol, 2-octanol, 3-octanol), etc., a straight-chain alcohol having 3 to 10 carbon atoms; 1,2-propanediol, 1,3- Propanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1 5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol and its hydroxyl group C3-C10 linear alcohol etc. which have two hydroxyl groups, such as a positional isomer, are mentioned. The branched chain alcohol having 3 to 10 carbon atoms is not particularly limited as long as it is an alcohol in which at least one hydrogen atom of the branched chain hydrocarbon is substituted with a hydroxyl group. For example, isobutyl alcohol, 2,2-dimethyl-1 -Propanol, 2,2,4-trimethyl-1-pentanol, 2,2,4-trimethyl-2-pentanol, 2,2,4-trimethyl-3-pentanol and positional isomers of hydroxyl groups thereof (for example, Tertiary butyl alcohol, 2-ethylhexanol) and the like. The alicyclic alcohol having 3 to 10 carbon atoms is not particularly limited as long as it is an alcohol in which at least one hydrogen atom of the alicyclic hydrocarbon is substituted with a hydroxyl group. For example, cyclopropanol, cyclobutanol, cyclopentanol , Cyclohexanol, cycloheptanol, cyclooctanol and the positional isomers of the hydroxyl group thereof. The aromatic alcohol having 6 to 10 carbon atoms is not particularly limited as long as it is an alcohol in which at least one hydrogen atom of an aromatic hydrocarbon is substituted with a hydroxyl group. For example, it relates to phenol, benzyl alcohol, salicyl alcohol and the hydroxyl group thereof. And positional isomers.

  In addition, as alcohols having 3 to 10 carbon atoms, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1,2-heptanediol, 1,7-heptanediol, , 2-dimethyl-1-propanol, 2,2,4-trimethyl-1-pentanol, 2,2,4-trimethyl-2-pentanol, 2,2,4-trimethyl-3-pentanol, benzyl alcohol 1-heptanol, 2-heptanol, 2,2-dimethyl-1-propanol, 2,4,4-trimethyl-2-pentanol, or benzyl alcohol is more preferable, and 2,2-dimethyl-1-propanol 2,4,4-trimethyl-2-pentanol and benzyl alcohol are more preferable. That is, as alcohol having 3 to 10 carbon atoms, from the viewpoint of improving octane number, linear alcohol having 3 to 10 carbon atoms, branched alcohol having 3 to 10 carbon atoms, and aromatic alcohol having 6 to 10 carbon atoms. Are preferred, and branched alcohols having 3 to 10 carbon atoms and aromatic alcohols having 6 to 10 carbon atoms are more preferred.

  Examples of the carboxylic acid having 3 to 10 carbon atoms include a linear carboxylic acid having 3 to 10 carbon atoms, a branched carboxylic acid having 3 to 10 carbon atoms, and an aromatic carboxylic acid having 7 to 10 carbon atoms. It is done. Moreover, although the number of carboxyl groups in a C3-C10 carboxylic acid molecule is not specifically limited, For example, it is preferable that it is 1-4, and it is more preferable that it is 1-2. In addition, the high octane gasoline of the present invention may contain one of these carboxylic acids alone or two or more.

  The linear carboxylic acid having 3 to 10 carbon atoms is not particularly limited as long as it is a carboxylic acid in which the terminal carbon atom of the linear hydrocarbon is substituted with a carboxyl group. For example, butanoic acid, pentanoic acid, hexane Examples thereof include linear monocarboxylic acids having 3 to 10 carbon atoms such as acid, heptanoic acid and octanoic acid, and linear dicarboxylic acids having 3 to 10 carbon atoms such as heptanedioic acid. The branched chain carboxylic acid having 3 to 10 carbon atoms is not particularly limited as long as the terminal carbon atom of the branched hydrocarbon is substituted with a carboxyl group. For example, 2,2-dimethyl-1- Examples include propanoic acid (pivalic acid) and isooctanoic acid. The aromatic carboxylic acid is not particularly limited as long as it is a carboxylic acid in which the carbon atom at the terminal of the hydrocarbon having an aromatic hydrocarbon group is substituted with a carboxyl group, and examples thereof include benzoic acid and phthalic acid.

  The carboxylic acid having 3 to 10 carbon atoms is preferably 2,2-dimethyl-1-propanoic acid, heptanoic acid, heptanedioic acid, or benzoic acid, and more preferably benzoic acid, from the viewpoint of improving the octane number. That is, the carboxylic acid having 3 to 10 carbon atoms is preferably a branched carboxylic acid having 3 to 10 carbon atoms or an aromatic carboxylic acid having 7 to 10 carbon atoms, from the viewpoint of improving the octane number, Aromatic carboxylic acids are more preferred.

  As described above, the high-octane gasoline of the present invention is a straight-chain ketone having 3 to 10 carbon atoms, a branched chain ketone having 3 to 10 carbon atoms, or 7 to 10 carbon atoms as an oxide from the viewpoint of improving the octane number. Containing at least one compound selected from the group consisting of aromatic aldehydes, branched chain alcohols having 3 to 10 carbon atoms, aromatic alcohols having 6 to 10 carbon atoms, and aromatic carboxylic acids having 7 to 10 carbon atoms. Is preferred. In addition, it is preferable that content (total amount) of the said compound in the high octane gasoline of this invention will be 0.1 weight% or more (for example, 0.1 to 50 weight%).

  The high octane gasoline of the present invention is an oxygen-containing hydrocarbon other than an alcohol having 3 to 10 carbon atoms, a ketone having 3 to 10 carbon atoms, an aldehyde having 3 to 10 carbon atoms, and a carboxylic acid having 3 to 10 carbon atoms (other Oxygen-containing hydrocarbon). In the present invention, “oxygen-containing hydrocarbon” refers to a compound obtained by oxidizing a hydrocarbon (for example, alcohol, ketone, aldehyde, carboxylic acid, etc.). Examples of other oxygen-containing hydrocarbons include alcohols having 11 or more carbon atoms, aldehydes having 11 or more carbon atoms, carboxylic acids having 11 or more carbon atoms, and ethers.

  The research octane number in the high octane gasoline of the present invention is preferably 93 or more, more preferably 95 or more, and still more preferably 98 or more.

  The high octane gasoline of the present invention is a constituent component of an alcohol having 3 to 10 carbon atoms, a ketone having 3 to 10 carbon atoms, an aldehyde having 3 to 10 carbon atoms, a carboxylic acid having 3 to 10 carbon atoms, and other oxygen-containing compounds. Since hydrocarbons (hereinafter sometimes referred to as “alcohols having 3 to 10 carbon atoms”) are obtained by oxidizing a gasoline base material, they do not emit SOx or NOx when used as fuel. In addition, since the CO content in the exhaust gas is small, the environment is not adversely affected, and the fuel consumption characteristics are further improved.

[Imide compound having a cyclic imide skeleton]
Examples of the imide compound having a cyclic imide skeleton include compounds having a structure represented by the following formula (I).

  In the formula (I), n represents 0 or 1. X represents an oxygen atom or an —OR group (R represents a hydrogen atom or a hydroxyl-protecting group). The bond between the nitrogen atom and X is a single bond or a double bond. The imide compound may have a plurality of cyclic imide skeletons represented by the formula (I) in the molecule. In the imide compound, when X is an —OR group and R is a protecting group for a hydroxyl group, a portion of the cyclic imide skeleton excluding R (N-oxy cyclic imide skeleton) It may be bonded via.

In the formula (I), examples of the protecting group for the hydroxyl group represented by R include an alkyl group (for example, a C _1-4 alkyl group such as methyl and t-butyl group), an alkenyl group (for example, an allyl group, etc.). ), Cycloalkyl group (for example, cyclohexyl group, etc.), aryl group (for example, 2,4-dinitrophenyl group, etc.), aralkyl group (for example, benzyl, 2,6-dichlorobenzyl, 3-bromobenzyl, 2-nitro) Substituted methyl group (for example, methoxymethyl, methylthiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl, 2,2,2-trichloroethoxymethyl, bis (2- Chloroethoxy) methyl, 2- (trimethylsilyl) ethoxymethyl group, etc.), substituted ethyl groups (for example, 1-ethoxy Ethyl, 1-methyl-1-methoxyethyl, 1-isopropoxyethyl, 2,2,2-trichloroethyl, 2-methoxyethyl group, etc.), tetrahydropyranyl group, tetrahydrofuranyl group, 1-hydroxyalkyl group (for example, 1-hydroxyethyl, 1-hydroxyhexyl, 1-hydroxydecyl, 1-hydroxyhexadecyl, 1-hydroxy-1-phenylmethyl group, etc.), a group capable of forming an acetal or hemiacetal group, etc .; acyl A group (for example, a C _1-20 aliphatic acyl group such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, lauroyl, myristoyl, palmitoyl, stearoyl group, etc. Saturated or Saturated acyl group; acetoacetyl group; alicyclic acyl group such as cycloalkanecarbonyl group such as cyclopentanecarbonyl and cyclohexanecarbonyl group; aromatic acyl group such as benzoyl and naphthoyl group; sulfonyl group (methanesulfonyl, ethanesulfonyl) , Trifluoromethanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, naphthalenesulfonyl group, etc.), alkoxycarbonyl groups (for example, C _1-4 alkoxy-carbonyl groups such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl groups, etc.), aralkyl Oxycarbonyl groups (for example, benzyloxycarbonyl group, p-methoxybenzyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl groups (for example, carbamoyl, methylcarbamoyl, phenylcarba Yl group), inorganic acid (sulfuric acid, nitric acid, phosphoric acid, boric acid, etc.), OH group removed, dialkylphosphinothioyl group (for example, dimethylphosphinothioyl group, etc.), diarylphosphinothioyl Groups (for example, diphenylphosphinothioyl group) and substituted silyl groups (for example, trimethylsilyl, t-butyldimethylsilyl, tribenzylsilyl, triphenylsilyl groups, etc.).

  In the case where X is an —OR group, R in the case where a plurality of portions (N-oxycyclic imide skeleton) excluding R are bonded via R in the cyclic imide skeleton includes, for example, oxalyl, malonyl Polycarboxylic acid acyl groups such as succinyl, glutaryl, adipoyl, phthaloyl, isophthaloyl, terephthaloyl groups; carbonyl groups; polyvalent hydrocarbon groups such as methylene, ethylidene, isopropylidene, cyclopentylidene, cyclohexylidene, benzylidene groups ( In particular, a group that forms an acetal bond with two hydroxyl groups).

  Preferable R includes, for example, a hydrogen atom; a group capable of forming an acetal or hemiacetal group with a hydroxyl group; an OH group is removed from an acid such as carboxylic acid, sulfonic acid, carbonic acid, carbamic acid, sulfuric acid, phosphoric acid or boric acid. And hydrolyzable protecting groups that can be removed by hydrolysis of the above groups (acyl group, sulfonyl group, alkoxycarbonyl group, carbamoyl group, etc.).

  In the formula (I), n represents 0 or 1. That is, Formula (I) represents a 5-membered cyclic imide skeleton when n is 0, and represents a 6-membered cyclic imide skeleton when n is 1.

  A typical example of the imide compound is an imide compound represented by the following formula (1).

In the formula (1), n represents 0 or 1. X represents an oxygen atom or an —OR group (R represents a hydrogen atom or a hydroxyl-protecting group). R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, A substituted oxycarbonyl group, an acyl group or an acyloxy group is shown. At least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be bonded to each other to form a double bond, and form a ring with the carbon atoms constituting the cyclic imide skeleton. May be. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , or R ⁶ , or at least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are bonded together. In the ring formed together with the carbon atom constituting the double bond or the cyclic imide skeleton, one or more cyclic imide groups represented by the above formula (1) may be further formed.

The halogen atoms in the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ of the imide compound represented by the formula (1) include iodine, bromine, chlorine, and fluorine atoms. Examples of the alkyl group include about 1 to 30 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, decyl, dodecyl, tetradecyl, and hexadecyl groups (particularly, carbon number). About 1 to 20) linear or branched alkyl group.

  Examples of the aryl group include phenyl and naphthyl groups, and examples of the cycloalkyl group include cyclopentyl and cyclohexyl groups. The alkoxy group includes, for example, about 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, butoxy, t-butoxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, tetradecyloxy, octadecyloxy groups (particularly carbon An alkoxy group of about 1 to 20).

Examples of the substituted oxycarbonyl group include C _1-30 alkoxy-carbonyl groups such as methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, t-butoxycarbonyl, hexyloxycarbonyl, decyloxycarbonyl, hexadecyloxycarbonyl group and the like. (Especially C _1-20 alkoxy-carbonyl group); cycloalkyloxycarbonyl group such as cyclopentyloxycarbonyl, cyclohexyloxycarbonyl group (especially 3-20 membered cycloalkyloxycarbonyl group); phenyloxycarbonyl, naphthyloxycarbonyl group aryloxycarbonyl group such as (in particular, C _6-20 aryloxy - carbonyl group); aralkyloxycarbonyl group such as benzyloxycarbonyl group (particularly, C _7-21 Ararukiruo Sheet - carbonyl group).

Acyl groups include, for example, C _1-30 aliphatic acyl groups such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl, hexanoyl, octanoyl, decanoyl, lauroyl, myristoyl, palmitoyl, stearoyl groups (especially C ₁ Aliphatic saturated or unsaturated acyl groups such as _-20 aliphatic acyl groups; acetoacetyl groups; alicyclic acyl groups such as cycloalkanecarbonyl groups such as cyclopentanecarbonyl and cyclohexanecarbonyl groups; aromatics such as benzoyl and naphthoyl groups Group acyl group and the like.

Acyloxy groups include, for example, formyloxy, acetyloxy, propionyloxy, butyryloxy, isobutyryloxy, valeryloxy, pivaloyloxy, hexanoyloxy, octanoyloxy, decanoyloxy, lauroyloxy, myristoyloxy, palmitoyloxy, stearoyloxy An aliphatic saturated or unsaturated acyloxy group such as a C _1-30 aliphatic acyloxy group (particularly a C _1-20 aliphatic acyloxy group); an acetoacetyloxy group; a cyclopentanecarbonyloxy group, a cyclohexanecarbonyloxy group, etc. Examples include alicyclic acyloxy groups such as cycloalkanecarbonyloxy group; aromatic acyloxy groups such as benzoyloxy and naphthoyloxy groups.

Examples of the ring that may be formed together with the carbon atoms constituting the cyclic imide skeleton by bonding at least two of the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ to each other, for example, A 5- to 12-membered ring (particularly preferably a 6- to 10-membered ring). The ring includes a hydrocarbon ring, a heterocyclic ring, and a condensed heterocyclic ring. Specific examples of such a ring include a non-aromatic alicyclic ring (a cycloalkane ring which may have a substituent such as a cyclohexane ring, a cyclohexane which may have a substituent such as a cyclohexene ring). Alkene ring, etc.), non-aromatic bridged ring (bridged hydrocarbon ring optionally having substituent such as 5-norbornene ring), aromatic ring optionally having substituent ( (Including a condensed ring) (benzene ring, naphthalene ring, etc.). Examples of the substituent that the ring may have include, for example, an alkyl group, a haloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, a substituted oxycarbonyl group, an acyl group, an acyloxy group, a nitro group, a cyano group, and an amino group. And halogen atoms.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , or R ⁶ , or at least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are bonded together. In the ring formed together with the carbon atoms constituting the double bond or the cyclic imide skeleton, one or more cyclic imide groups represented by the above formula (1) may be further formed, for example, R ^{When 1} , R ² , R ³ , R ⁴ , R ⁵ , or R ⁶ is an alkyl group having 2 or more carbon atoms, the cyclic imide group is formed including two adjacent carbon atoms constituting the alkyl group. May be. Further, when at least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are bonded to each other to form a double bond, the cyclic imide group is formed including the double bond. May be. Further, when at least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are bonded to each other to form a ring with the carbon atoms constituting the cyclic imide skeleton, the ring is formed. The cyclic imide group may be formed including two adjacent carbon atoms.

Preferred imide compounds include compounds represented by the following formulas (1a) to (1i). In the formula, R ^{11 to} R ¹⁶ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, a substituted oxycarbonyl group, an acyl group, or an acyloxy group. Indicates a group. R ^{17 to} R ²⁶ are the same or different and each represents a hydrogen atom, an alkyl group, a haloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, a substituted oxycarbonyl group, an acyl group, an acyloxy group, a nitro group, a cyano group, an amino group, Or a halogen atom is shown. R ^{17 to} R ²⁶ are groups in which adjacent groups are bonded to each other to form a 5-membered or 6-membered member represented by the formula (1c), (1d), (1e), (1f), (1h), or (1i) The cyclic imide skeleton may be formed. A represents a methylene group or an oxygen atom. X is the same as above.

Halogen atom in the substituents R ¹¹ to R ^16, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, substituted oxycarbonyl group, an acyl group, the acyloxy group, in the R ¹ to R ⁶ Examples corresponding to the corresponding groups are exemplified.

In the substituents R ^{17 to} R ²⁶ , the alkyl group includes an alkyl group similar to the above exemplified alkyl group (preferably an alkyl group having about 1 to 20 carbon atoms, more preferably an alkyl group having about 1 to 6 carbon atoms, Particularly preferably, a lower alkyl group having 1 to 4 carbon atoms is exemplified, and examples of the haloalkyl group include a haloalkyl group having about 1 to 20 carbon atoms (preferably about 1 to 4 carbon atoms) such as a trifluoromethyl group, and an alkoxy group. Are the same alkoxy groups as above (particularly lower alkoxy groups having about 1 to 4 carbon atoms), and the substituted oxycarbonyl group is the same as the above substituted oxycarbonyl group (alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryl). An oxycarbonyl group, an aralkyloxycarbonyl group, etc.). Examples of the acyl group include the same acyl groups as described above (aliphatic saturated or unsaturated acyl group, acetoacetyl group, alicyclic acyl group, aromatic acyl group, etc.), and the acyloxy group is the same as described above. Examples include acyloxy groups (aliphatic saturated or unsaturated acyloxy groups, acetoacetyloxy groups, alicyclic acyloxy groups, aromatic acyloxy groups, etc.). Examples of the halogen atom include fluorine, chlorine and bromine atoms. As the substituents R ^{17 to} R ²⁶ , in particular, a hydrogen atom, a lower alkyl group having about 1 to 20 carbon atoms (preferably about 1 to 4 carbon atoms), a carboxyl group, a substituted oxycarbonyl group, a nitro group, and a halogen atom are included. preferable.

  Typical examples of compounds having a 5-membered cyclic imide skeleton among preferred imide compounds include N-hydroxysuccinimide, N-hydroxy-α-methylsuccinimide, N-hydroxy-α, α-dimethylsuccinimide. N-hydroxy-α, β-dimethylsuccinimide, N-hydroxy-α, α, β, β-tetramethylsuccinimide, N-hydroxymaleimide, N-hydroxyhexahydrophthalimide, N, N ′ -Dihydroxycyclohexanetetracarboxylic acid diimide, N-hydroxyphthalimide, N-hydroxytetrabromophthalimide, N-hydroxytetrachlorophthalimide, N-hydroxyhetic acid imide, N-hydroxyheimic acid imide, N-hydroxytrimellitic acid imide, N, N'-dihydroxy Romellitic acid diimide, N, N′-dihydroxynaphthalenetetracarboxylic acid diimide, α, β-diacetoxy-N-hydroxysuccinimide, N-hydroxy-α, β-bis (propionyloxy) succinimide, N-hydroxy- α, β-bis (valeryloxy) succinimide, N-hydroxy-α, β-bis (lauroyloxy) succinimide, α, β-bis (benzoyloxy) -N-hydroxysuccinimide, N-hydroxy- 4-methoxycarbonylphthalimide, 4-ethoxycarbonyl-N-hydroxyphthalimide, N-hydroxy-4-pentyloxycarbonylphthalimide, 4-dodecyloxy-N-hydroxycarbonylphthalimide, N-hydroxy-4-phenoxycarbonylphthalimide, N- Hydro Xy-4,5-bis (methoxycarbonyl) phthalimide, 4,5-bis (ethoxycarbonyl) -N-hydroxyphthalimide, N-hydroxy-4,5-bis (pentyloxycarbonyl) phthalimide, 4,5-bis ( Dodecyloxycarbonyl) -N-hydroxyphthalimide, N-hydroxy-4,5-bis (phenoxycarbonyl) phthalimide and the like, wherein X is an —OR group and R is a hydrogen atom; Corresponding compounds wherein R is an acyl group such as an acetyl group, propionyl group, benzoyl group; formulas such as N-methoxymethyloxyphthalimide, N- (2-methoxyethoxymethyloxy) phthalimide, N-tetrahydropyranyloxyphthalimide X in (1) is an —OR group and R is a hydroxy group. A compound capable of forming an acetal or hemiacetal bond with an alkyl group; X in formula (1) such as N-methanesulfonyloxyphthalimide, N- (p-toluenesulfonyloxy) phthalimide and the like is an -OR group and R is A compound which is a sulfonyl group; in formula (1) such as N-hydroxyphthalimide sulfate, nitrate, phosphate or borate, X is an —OR group and R is a group obtained by removing an OH group from an inorganic acid. A certain compound etc. are mentioned.

  Typical examples of compounds having a 6-membered cyclic imide skeleton among preferred imide compounds include N-hydroxyglutarimide, N-hydroxy-α, α-dimethylglutarimide, N-hydroxy-β, β-dimethylglutarimide. N-hydroxy-1,8-decalin dicarboxylic acid imide, N, N′-dihydroxy-1,8; 4,5-decalin tetracarboxylic acid diimide, N-hydroxy-1,8-naphthalenedicarboxylic acid imide (N— Hydroxy naphthalimide), N, N′-dihydroxy-1,8; compounds such as 4,5-naphthalenetetracarboxylic acid diimide wherein X is an —OR group and R is a hydrogen atom; Wherein R is an acyl group such as an acetyl group, a propionyl group, or a benzoyl group; N-methoxymethyl X in the formula (1) such as oxy-1,8-naphthalenedicarboxylic acid imide, N, N′-bis (methoxymethyloxy) -1,8; 4,5-naphthalenetetracarboxylic acid diimide is an —OR group; A compound in which R is a group capable of forming an acetal or hemiacetal bond with a hydroxyl group; N-methanesulfonyloxy-1,8-naphthalenedicarboxylic imide, N, N′-bis (methanesulfonyloxy) -1,8; A compound in which X in formula (1) such as 4,5-naphthalenetetracarboxylic acid diimide is —OR group and R is sulfonyl group; N-hydroxy-1,8-naphthalenedicarboxylic acid imide or N, N′-dihydroxy -1,8; 4,5-naphthalene tetracarboxylic acid diimide sulfate ester, nitrate ester, phosphate ester or boric acid ester Examples include compounds in which X in Formula (1) such as stealth is an —OR group and R is a group obtained by removing an OH group from an inorganic acid.

  Among the imide compounds, a compound in which X is an —OR group and R is a hydrogen atom (N-hydroxyimide compound) is a conventional imidization reaction, for example, reacting a corresponding acid anhydride with hydroxylamine, It can be produced by a method of imidizing via ring opening and ring closing of an acid anhydride group. Of the imide compounds, a compound in which X is an —OR group and R is a hydroxyl protecting group is introduced into a compound (N-hydroxyimide compound) in which the corresponding R is a hydrogen atom (N-hydroxyimide compound). It can manufacture by introduce | transducing a desired protecting group using reaction. For example, N-acetoxyphthalimide can be produced by reacting N-hydroxyphthalimide with acetic anhydride or reacting acetyl halide in the presence of a base.

A particularly preferred imide compound is an N-hydroxyimide compound derived from an aliphatic polyvalent carboxylic anhydride or an aromatic polycarboxylic anhydride (for example, N-hydroxysuccinimide (SP value: 33.5 [( MPa) ^1/2 ]), N-hydroxyphthalimide (SP value: 33.4 [(MPa) ^1/2 ]), N, N′-dihydroxypyromellitic diimide, N-hydroxyglutarimide, N-hydroxy- 1,8-naphthalenedicarboxylic acid imide, N, N′-dihydroxy-1,8; 4,5-naphthalenetetracarboxylic acid diimide, etc.), and by introducing a protecting group into the hydroxyl group of the N-hydroxyimide compound The resulting compound is included.

  An imide compound can be used individually by 1 type or in combination of 2 or more types, The method of mix | blending with a reaction substrate is not specifically limited. Examples of the imide compound include commercially available products such as trade name “N-hydroxyphthalimide” (manufactured by Wako Pure Chemical Industries, Ltd.) and trade name “N-hydroxysuccinimide” (manufactured by Wako Pure Chemical Industries, Ltd.). Can be preferably used.

  The amount of the imide compound used (concentration with respect to the reaction substrate) is, for example, 0.001 to 5.0 parts by weight, preferably 0.001 to 2.5 parts by weight with respect to 100 parts by weight of the reaction substrate. By using the imide compound within the above range, the oxidation reaction can proceed at an excellent reaction rate.

[Other oxidation reaction conditions]
In the oxide production method of the present invention, the oxidation reaction may be carried out in the liquid phase or in the gas phase, but it is preferably carried out in the liquid phase from the viewpoint of reaction efficiency. That is, in the oxide production method of the present invention, the reaction substrate is preferably oxidized in the liquid phase.

  Oxygen as the oxidant used in the method for producing an oxide of the present invention may be pure oxygen, oxygen diluted with an inert gas such as nitrogen, helium, argon, carbon dioxide, or normal pressure or pressurization. (1 to 100 atmospheres) of air may be used. Although the usage-amount of oxygen is not specifically limited, For example, it is 1 mol or more with respect to 1 mol of reaction substrates.

  In the method for producing an oxide of the present invention, a solvent may be used, but it is preferable not to use a solvent. When the solvent is not used (substantially), it is not necessary to separate the reaction substrate and oxide from the solvent, so that the complexity of the manufacturing process can be eliminated.

  In the method for producing an oxide of the present invention, the ratio of the reaction substrate in the charged amount is not particularly limited, but is preferably about 70% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight. Above, particularly preferably 99% by weight or more. Further, the proportion of the hydrocarbon in the charged amount is not particularly limited, but is preferably about 70% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, and particularly preferably 99% by weight. That's it. The charged amount means the total amount of reaction substrate and the like (for example, reaction substrate, imide compound, solvent, etc.) used for the oxidation reaction. Specifically, for example, in the case of a batch reactor, it means the total amount of reaction substrates and the like charged into the reactor before the oxidation reaction, and in the case of a continuous reactor, the reaction substrates and the like are supplied to the oxidation reactor. This means the total amount of reaction substrate.

  As the solvent, known or conventional solvents used in oxidation reactions can be used, for example, nitriles such as acetonitrile, propionitrile, and benzonitrile; amides such as formamide, acetamide, dimethylformamide, and dimethylacetamide. Halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, trifluoromethylbenzene; nitro compounds such as nitrobenzene, nitromethane, nitroethane; esters such as ethyl acetate and butyl acetate; and mixed solvents thereof Etc. In addition, it is preferable that the solvent applicable to the said reaction substrate and its oxide is not contained. Moreover, it is desirable that the solvent is less oxidizable than the reaction substrate.

  The amount of catalyst used in the method for producing an oxide of the present invention (total amount when two or more are used; metal atom conversion) is not particularly limited, but is, for example, 0.001 to 1% by weight with respect to the total amount of the reaction substrate. Is preferable, and 0.01 to 0.5 weight% is more preferable.

  The reaction time in the oxidation reaction can be appropriately adjusted according to the reaction temperature and pressure, and is, for example, about 0.05 to 20 hours.

  In the method for producing an oxide of the present invention, the reaction temperature in the oxidation reaction can be appropriately selected according to the type of reaction substrate, the type of target product, and the like, for example, 120 ° C. or less (for example, 20 to 120 ° C.). ), Preferably 30 to 110 ° C, more preferably 40 to 100 ° C, still more preferably 50 to 90 ° C. Moreover, an oxidation reaction can be performed under a normal pressure or pressurization, for example, 10 MPa or less (for example, about 0.1-10 MPa), Preferably it is 0.1-5 MPa, Most preferably, it is 0.1-1 MPa.

  In addition, the temperature control of the flow reactor described later is, for example, a method in which the flow reactor has a multi-tube structure, a heat medium or a refrigerant is passed through the inner tube or the outer tube, and a method in which the flow reactor is immersed in a heat medium bath or a refrigerant bath. Or the like.

  The oxidation reaction can be performed by a conventional method such as a batch method or a continuous method. In this case, the reaction can be performed using a batch reactor, a continuous reactor, or the like. In addition, when using a flow reactor as a continuous reactor, it is preferable to perform an oxidation reaction by distribute | circulating the reaction substrate containing the hydrocarbon which dissolved the imide compound in the flow reactor. That is, it is preferable to oxidize a solution prepared by dissolving a specific amount of an imide compound with respect to a reaction substrate containing hydrocarbon by using a flow reactor.

  After completion of the oxidation reaction, unreacted reaction substrates and oxides can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination of these. .

<Flow reactor>
The flow reactor of the present invention is a flow reactor using a catalyst on which at least one metal compound selected from the group consisting of a metal salt and a metal complex is supported, and an N-hydroxyimide group-containing compound is not supported. For example, a flow reactor in which the catalyst is fixed on the inner wall thereof, or a flow reactor in which the catalyst is filled in the inside thereof may be mentioned. In addition, the said reactor may be fixed to the inner wall, and the flow reactor by which the said catalyst was further filled into the inside may be sufficient. The shape of the flow reactor is not particularly limited, and examples thereof include a column shape, a capillary shape, a tube shape, and a microreactor type flow reactor. The catalyst in the flow reactor of the present invention may be the same as that used for the main catalyst in the oxidation reaction catalyst of the present invention.

  Examples of the flow reactor in which the catalyst is fixed to the inner wall include a flow reactor in which part or all of the inner wall is made of a catalyst, and a flow reactor in which the inner wall is made of a resin containing the catalyst. In this case, at least a part of the catalyst needs to come into contact with the gas-liquid mixture (a gas mixture containing a reaction gas-containing liquid and oxygen). That is, a part of the inner wall of the flow reactor may be subjected to resin coating, glass lining, etc., but it is preferably not applied from the viewpoint of reaction efficiency. The catalyst can be fixed to the inner wall of the flow reactor by a known or well-known method in this field.

  Examples of the flow reactor in which the inside is filled with a catalyst include those in which a particulate catalyst is filled in the inside of the flow reactor. Although the particle diameter of a particulate catalyst is not specifically limited, 10-10000 micrometers is preferable, More preferably, it is about 20-10000 micrometers. The catalyst can be filled into the flow reactor by a known or well-known method in this field.

  The material of the flow reactor is not particularly limited as long as it is inert and does not dissolve in the gas or liquid used in the reaction. For example, resin [fluorine resin such as Teflon (registered trademark), Daiflon, polyester, etc. Resins, polyolefin resins, polycarbonate resins, polystyrene resins, polyamide resins, polyimide resins, etc.], inorganic oxides (silica, etc.), glass, metals (titanium, alloys such as stainless steel, etc.) can be used. When the flow reactor is made of metal or the like, a resin coating or glass lining may be applied to a portion that comes into contact with the gas-liquid mixture.

  The inner diameter of the flow reactor is preferably 100 mm or less (for example, 0.3 to 20 mm), for example. Although the length of a flow reactor can be suitably selected according to reaction rate etc., 100 mm-20 m are preferable, for example. By setting the inner diameter of the flow reactor in the above range, the reaction substrate can be oxidized efficiently.

<Oxidation reaction equipment>
The apparatus for oxidation reaction of the present invention is not particularly limited as long as it includes the flow reactor of the present invention and a reaction substrate-imide compound mixed liquid channel, and a liquid introduction channel into which a liquid containing a reaction substrate is introduced, A gas introduction channel into which a gas containing oxygen is introduced, a gas-liquid mixing unit that mixes the liquid introduced from the liquid introduction channel and the gas introduced from the gas introduction channel, and the flow reactor; May be provided. In addition, the reaction substrate-imide compound mixed solution channel means a channel through which a reaction substrate containing a hydrocarbon in which an imide compound having a cyclic imide skeleton is dissolved flows. In addition, the imide compound having a cyclic imide skeleton may be supplied to the reaction substrate through an imide compound introduction channel described later, or may be dissolved in the reaction substrate in advance.

  FIG. 1 is a schematic flow diagram showing an example of the oxidation reaction apparatus of the present invention. The present invention is not limited to the oxidation reaction flow reactor shown in FIG. 1 will be described below.

  In FIG. 1, hydrocarbon as a reaction substrate is supplied to a gas-liquid mixing unit (gas-liquid mixer) 3 through a supply channel 1 for a reaction substrate. If necessary, the hydrocarbon may be supplied in the form of a solution dissolved in a solvent. On the other hand, oxygen or an oxygen-containing gas (for example, air) is supplied to the gas-liquid mixing unit 3 through the gas introduction channel 2. After mixing an inert gas such as nitrogen into a gas containing oxygen, the gas may be supplied to the gas-liquid mixing unit 3.

  The gas-liquid mixing unit (gas-liquid mixer) 3 is not particularly limited as long as it has a structure capable of generating the gas-liquid mixed liquid by mixing the gas and the liquid. For example, the mixing efficiency of the gas and the liquid From the viewpoint of dispersibility of bubbles in the liquid, a microbubble generator can be used. A microbubble refers to a bubble having a bubble diameter of 50 μm or less (generally 10 to 40 μm). Microbubble generators can be broadly divided into two types, a pressure dissolution method and a two-phase flow swirl method, but any type of microbubble generator can be used in the present invention. Moreover, a commercially available microbubble generator (microbubble generator) can be used.

  The material of the gas-liquid mixer (gas-liquid mixing unit 3) is not particularly limited as long as it is inert and does not dissolve in the gas or liquid used in the reaction. For example, resin [Teflon (registered trademark), Daiflon , Fluorine resins such as polyvinylidene fluoride, polyester resins, polyolefin resins, polycarbonate resins, polystyrene resins, polyamide resins, polyimide resins, etc.], glass, metals (titanium; alloys such as stainless steel), etc. Can be used. When the gas-liquid mixer is made of metal or the like, a resin coating or a glass lining may be applied to a portion that comes into contact with the gas-liquid mixture.

  The gas containing oxygen and the liquid containing hydrocarbon as a reaction substrate supplied to the gas-liquid mixing unit 3 are discharged as a gas-liquid mixed solution in the gas-liquid mixer, and flow through the gas-liquid mixture channel 4. It circulates in the reactor 5. In the flow reactor 5, the reaction substrate is oxidized to produce a corresponding oxide.

  The reaction mixture discharged from the flow reactor 5 is introduced into the gas-liquid separator 7 through the reaction mixture channel 6 and separated into gas and liquid. The flow reactor 5 may be directly connected to the gas-liquid separator 7. The separated gas is discharged from the exhaust gas line 10 into the engine room. Note that at least a part of the separated gas is recycled to the reaction system by returning to the gas introduction channel 2 through the gas circulation channel 9 as necessary. On the other hand, at least a part of the liquid separated by the gas-liquid separator 7 can be recycled to the reaction system from the liquid introduction flow path 12 through the liquid circulation flow path 8 using, for example, a pump. Further, the liquid separated by the gas-liquid separator 7 can be recovered from the liquid recovery flow path 13. The imide compound introduction channel 11 may be provided on the upstream side of the flow reactor 5, preferably on the gas-liquid mixing unit 3 or on the upstream side thereof. In this case, the liquid introduction flow path 12 or the gas-liquid mixture flow path 4 and the liquid introduction flow path 12 become a reaction substrate-imide compound mixed liquid flow path. When an imide compound having a cyclic imide skeleton is previously dissolved in the reaction substrate, the reaction substrate supply channel 1 is also a reaction substrate-imide compound mixed solution channel.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.

[Example 1 (Preparation of cobalt (II) acetate supported silica catalyst)]
0.6 g of cobalt (II) acetate was dissolved in 17.3 g of water to obtain an aqueous solution. This aqueous solution was added to 10.1 g of silica, mixed well, and allowed to stand at room temperature for 12 hours. This mixture was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain 12.0 g of the target product, cobalt (II) acetate-supported silica catalyst. The resulting catalyst had a cobalt content of 1.7%.

[Example 2 (Preparation of cobalt (II) stearate supported silica catalyst)]
2.1 g of cobalt (II) stearate was added to 100 ml of toluene and heated to 90 ° C. with stirring to completely dissolve. 10.0 g of silica gel was added thereto and stirred for 5 hours while maintaining the temperature at 90 ° C. From this mixture, the solvent was distilled off using a rotary evaporator, and the obtained powder was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain the target cobalt (II) stearate supported catalyst. 0.2 g was obtained. The resulting catalyst had a cobalt content of 1.7%.

[Example 3 (Preparation of cobalt naphthenate (II) -supported silica catalyst)]
2.5 g of cobalt (II) naphthenate was added to 100 ml of toluene and heated to 90 ° C. with stirring to completely dissolve. 10.0 g of silica gel was added thereto and stirred for 5 hours while maintaining the temperature at 90 ° C. From this mixture, the solvent was distilled off using a rotary evaporator, and the obtained powder was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain the target cobalt (II) naphthenate-supported catalyst. 0.7 g was obtained. The resulting catalyst had a cobalt content of 1.9%.

[Example 4 (Preparation of cobalt benzoate (II) -supported silica catalyst)]
1.2 g of cobalt (II) benzoate was added to 100 ml of methanol and completely dissolved at room temperature. 10.0 g of silica gel was added thereto and left at room temperature for 12 hours. From this mixture, the solvent was distilled off using a rotary evaporator, and the obtained powder was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain the target cobalt (II) stearate supported silica catalyst. 11.2 g was obtained. The cobalt content of the obtained catalyst was 2.1%.

Example 5 (Preparation of cobalt (acetylacetonate) supported silica catalyst)
1.1 g cobalt (acetylacetonate) (II) was added to 75 ml acetone and heated to 40 ° C. with stirring to completely dissolve. 10.0 g of silica gel was added thereto and stirred for 5 hours while maintaining the temperature at 40 ° C. From this mixture, the solvent was distilled off using a rotary evaporator, and the obtained powder was dried in a vacuum dryer at 100 ° C. for 12 hours to carry the target product, cobalt (acetylacetonate) (II). 11.3 g of silica catalyst was obtained. The resulting catalyst had a cobalt content of 1.9%.

[Comparative Example 1 (Preparation of cobalt-supported sulfated zirconia catalyst)]
To a 1000 ml beaker, 55.0 g of zirconium oxide and 825 ml of sulfuric acid (0.5 mol / L) were added and stirred at room temperature for 30 minutes. The solid obtained by filtering the slurry was dried at 100 ° C. for 5 hours using a vacuum dryer and then calcined at 500 ° C. for 3 hours in a nitrogen stream to obtain sulfated zirconia. An aqueous solution in which 5.0 g of cobalt nitrate hexahydrate was dissolved in 70 ml of water was added to 50.0 g of the sulfated zirconia obtained and mixed at room temperature for 3 hours. After evaporating to dryness at 100 ° C. using an evaporator, it was dried overnight at 120 ° C. using a vacuum dryer. The obtained solid was calcined at 400 ° C. for 5 hours under a nitrogen stream to obtain 51.0 g of cobalt-supported sulfated zirconia. The obtained catalyst had a cobalt content of 2.0% by weight.

[Example 6]
As a gasoline surrogate fuel equivalent to regular gasoline with a research octane number of 90, in a 100 mL SUS316 pressure-resistant reactor (TVS-1 type, manufactured by Pressure Glass Industrial Co., Ltd.) equipped with a gas feed line, an insertion rod, and a stirring blade, 70 ml of a mixed solution of 20% by weight of toluene, 63% by weight of 2,2,4-trimethylpentane, and 17% by weight of n-heptane (hereinafter referred to as raw material), 0.1 g of N-hydroxyphthalimide, 3.4 g of the cobalt-supported silica catalyst prepared in Example 1 (the cobalt content in the catalyst is 0.058 g) was added. After immersing the reactor in an oil bath and adjusting the liquid temperature to 95 ° C., air was bubbled at a rate of 20 mL / min while stirring at a rotational speed of 550 rpm to oxidize the raw material. After reacting for 60 minutes, the air supply was stopped and the reactor was cooled to room temperature. Components of the reaction solution were analyzed by gas chromatography (column: 007-FFAP). Thereafter, the research octane number was measured by subjecting the obtained reaction liquid (gasoline composition) to a spray ignition test. These results are shown in Table 1. The “conversion rate of the raw material” was calculated by [the disappearance amount of the raw material in the reaction liquid (mole)] / [the raw material before the reaction (mole)]. In addition, the composition and content (% by weight) of the reaction substrate and its oxide obtained by component analysis are described in the column “Composition (% by weight)”.

[Comparative Example 2]
The research octane number was measured by subjecting the raw material to a spray ignition test. Table 1 shows the content ratios of the components contained in the reaction solution together with the results.

[Examples 7 to 10]
The same operation as in Example 6 was performed except that the cobalt-supported silica catalyst prepared in Example 1 was replaced with the cobalt-supported silica catalyst prepared in Examples 2 to 5. The cobalt-supported silica catalyst was added so that the addition amount as cobalt was 0.12% by weight with respect to the raw material (the cobalt content in the catalyst was 0.058 g). The results are shown in Table 1.

[Comparative Example 3]
The same operation as in Example 6 was performed except that the cobalt-supported silica catalyst prepared in Example 1 was replaced with 2.9 g of the cobalt-supported catalyst prepared in Comparative Example 1 (the cobalt content in the catalyst was 0.058 g). It was. The results are shown in Table 1.

[Comparative Example 4]
The same operation as in Example 6 was performed, except that the cobalt-supported silica catalyst prepared in Example 1 was replaced with 0.17 g of cobalt (II) acetate (the cobalt content in the catalyst was 0.058 g). The results are shown in Table 1.

[Example 11]
The cobalt-supported silica catalyst was recovered from the reaction solution obtained in Example 6 by suction filtration, washed with 30 ml of the raw material solution, and then dried. The same procedure as in Example 6 was performed except that this catalyst was used, and the research octane number of the obtained reaction liquid (gasoline composition) was measured. The results are shown in Table 1.

[Comparative Example 5 (Preparation of catalyst supporting cobalt (II) acetate and N-hydroxyphthalimide)]
0.6 g of cobalt acetate (II) and 0.3 g of N-hydroxyphthalimide were dissolved in 17.3 g of methanol to prepare a solution. This solution was added to 10.1 g of silica, mixed well, and allowed to stand at room temperature for 12 hours. This mixture was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain 11.0 g of the target catalyst. The resulting catalyst had a cobalt content of 1.7%.

[Comparative Example 6]
2. A catalyst prepared in Comparative Example 5 with 70 ml of raw material in a 100 mL SUS316 pressure resistant reactor (TVS-1 type, pressure resistant glass industry Co., Ltd.) equipped with a gas feed line, an insertion rod, and a stirring blade 4 g (cobalt content in the catalyst was 0.058 g) was added. After immersing the reactor in an oil bath and adjusting the liquid temperature to 95 ° C., air was bubbled at a rate of 20 mL / min while stirring at a rotational speed of 550 rpm to oxidize the raw material. After reacting for 60 minutes, the air supply was stopped and the reactor was cooled to room temperature. Thereafter, the research octane number, the conversion rate of the raw materials, the composition of the reaction substrate and its oxide and the content (wt%) were measured in the same manner as in Example 6. The results are shown in Table 1.

[Comparative Example 7]
The catalyst was recovered from the reaction solution obtained by the operation of Comparative Example 6 by suction filtration, washed with 30 ml of the raw material solution, and dried to obtain a catalyst. The same operation as in Comparative Example 6 was performed except that this catalyst was used, and the research octane number of the obtained reaction liquid (gasoline composition) was measured. The results are shown in Table 1.

[Example 12]
Cobalt prepared in Example 1 with 93 ml of raw material and 0.1 g of N-hydroxyphthalimide in a 500 mL SUS316 pressure resistant reactor (manufactured by Toyo High Pressure Co., Ltd.) equipped with a gas feed line, an insertion rod, and a stirring blade 5.4 g of supported silica catalyst (cobalt content in the catalyst was 0.092 g) was added. The container was sealed, and a mixed gas of oxygen and nitrogen (oxygen: 5.5% by volume, nitrogen: 94.5% by volume) was applied until the gauge pressure reached 4.0 MPa. Note that the oxygen concentration in the mixed gas may be referred to as a “charged gas oxygen concentration”. The reactor was immersed in an oil bath, and the contents were stirred. After the liquid temperature reached 95 ° C., the reaction was performed for 30 minutes, and then the reactor was cooled to room temperature. The oxygen concentration in the off-gas (sometimes referred to as “off-gas oxygen concentration”) was measured while depressurizing the container, and it was 3.8% by volume. The oxygen consumption rate (%) in the oxidation reaction was determined by the following formula and listed in Table 2 together with the charged gas oxygen concentration and off-gas oxygen concentration.
Oxygen consumption rate (%) = [feed gas oxygen concentration (volume%) − off-gas oxygen concentration (volume%)] / feed gas oxygen concentration (volume%) × 100

[Example 13]
The same operation as in Example 12 was performed except that the raw material was changed to regular gasoline (described in JIS K2202 2), and the charged gas oxygen concentration, off-gas oxygen concentration, and oxygen consumption rate are shown in Table 2. From this result, it became clear that the catalyst for oxidation reaction of the present invention exhibits a good catalytic activity even for gasoline.

1 Reaction substrate supply channel 2 Gas introduction channel 3 Gas-liquid mixing part (gas-liquid mixer)
4 Gas-liquid mixture channel (reaction substrate-imide compound mixture channel)
5 Flow reactor 6 Reaction mixture flow path 7 Gas-liquid separator 8 Liquid circulation flow path 9 Gas circulation flow path 10 Exhaust gas line 11 Imido compound introduction flow path 12 Liquid introduction flow path (reaction substrate-imide compound mixed liquid flow path)
13 Liquid recovery channel

Claims (13)

A main catalyst on which at least one metal compound selected from the group consisting of a metal salt and a metal complex is supported on a support and an N-hydroxyimide group-containing compound is not supported;
An oxidation reaction catalyst comprising a combination with an imide compound having a cyclic imide skeleton as a co-catalyst blended in a reaction substrate containing a hydrocarbon.   The oxidation reaction catalyst according to claim 1, wherein the metal is cobalt or manganese.   The oxidation catalyst according to claim 1 or 2, wherein the metal salt is a carboxylic acid metal salt, and the metal complex is a β-diketone metal complex.   An imide compound having a cyclic imide skeleton in the presence of a catalyst in which at least one metal compound selected from the group consisting of a metal salt and a metal complex is supported on a support and an N-hydroxyimide group-containing compound is not supported. A method for producing an oxide comprising oxidizing a reaction substrate containing a blended hydrocarbon.   The method for producing an oxide according to claim 4, wherein the reaction temperature is 120 ° C or lower.   The method for producing an oxide according to claim 4 or 5, wherein the oxidation reaction is performed under a pressure condition of 10 MPa or less.   The method for producing an oxide according to any one of claims 4 to 6, wherein the oxidation reaction is performed in a liquid phase.   A flow reactor using a catalyst in which at least one metal compound selected from the group consisting of a metal salt and a metal complex is supported on a support and an N-hydroxyimide group-containing compound is not supported has a cyclic imide skeleton. The method for producing an oxide according to any one of claims 4 to 7, wherein an oxidation reaction is performed by circulating a reaction substrate containing a hydrocarbon in which an imide compound is dissolved.   The method for producing an oxide according to any one of claims 4 to 8, wherein an amount of the imide compound having a cyclic imide skeleton is 0.001 to 5.0 parts by weight with respect to 100 parts by weight of the reaction substrate.   The method for producing an oxide according to any one of claims 4 to 9, wherein high octane gasoline is produced by oxidizing a gasoline base material as a reaction substrate.   The method for producing an oxide according to any one of claims 4 to 10, wherein a ratio of the reaction substrate in the charged amount is 99% by weight or more.   A flow reactor using a catalyst in which at least one metal compound selected from the group consisting of a metal salt and a metal complex is supported on a support and an N-hydroxyimide group-containing compound is not supported.   An oxidation reaction apparatus comprising: a flow reactor according to claim 12; and a flow path through which a reaction substrate containing a hydrocarbon in which an imide compound having a cyclic imide skeleton is dissolved flows.

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