JPH0470943B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a catalyst for liquid phase dehydration reactions made of fluorine-based synthetic mica. Traditionally, it was necessary to synthesize mica containing water of crystallization under high pressure and temperature, but this method replaces the water of crystallization (OH) in natural mica crystals with fluorine (F). Under normal pressure, fluorine-based mica consisting of
It can be synthesized by melting specified blended raw materials such as silica, magnesia, and fluoride, and the fluorine-based synthetic mica synthesized in this way has superior compositional uniformity compared to naturally produced mica. Therefore, various uses are expected. On the other hand, the present inventors have already studied the use of such synthetic mica, and found that in the presence of a synthetic mica catalyst in which at least 10 mol% of the ion exchange capacity consists of metal ions other than alkali metal ions or protons. have discovered that hydroxydiphenylene ethers can be produced in good yield by reacting hydroquinones or reacting hydroquinones with monovalent phenols (Japanese Patent Application Laid-open No. 206326/1983). . As a result of further studies, the present inventors found that fluorine-based synthetic mica is an excellent catalyst not only for the above-mentioned reactions of hydroquinones or reactions of hydroquinones and monovalent phenols, but also for liquid phase dehydration reactions of organic compounds and others. We have discovered that the reaction proceeds with good selectivity at a high raw material conversion rate, and have arrived at the present invention. Mineral acids such as sulfuric acid and organic acids such as p-toluenesulfonic acid have been conventionally known as catalysts for dehydration reactions, but these have the problem of corrosion to equipment and lack of excellent selectivity. The reaction is difficult to perform. Furthermore, when conventional solid acids such as silica and alumina are used, water produced in the reaction is adsorbed at the reaction site, resulting in a significant decrease in activity. In order to prevent this, a high temperature of about 350°C or higher is usually required, and it is virtually impossible to react in a liquid phase. However, the production method using a gas phase flow system has the disadvantage that large amounts of by-products are likely to be produced due to thermal decomposition, side reactions, etc.
Furthermore, when conventional cation exchange resins are used, they have poor reaction selectivity and cannot be used at high temperatures. Further, JP-A No. 56-501515 proposes the use of a layered clay having cation exchange properties as a proton catalyst in a dehydration reaction. The publication describes montmorillonite, which has an idealized stoichiometric composition corresponding to Na _0.67 [Al _3.33 Mg _0.67 ] Si ₈ O ₂₀ (OH) ₄ , as a typical example of layered clay. , bentonite, etc. are also exemplified, and ion-exchanged products of these with metal cations such as chromium and aluminum are also exemplified. However, there is no description regarding the fluorine-based synthetic mica used in the present invention. The publication indicates that the layered clay is used as a catalyst for various reactions, but for the dehydration reaction, one or more types of primary or secondary aliphatic alcohols or polyols are reacted. Therefore, it only describes the production of ether, and in the examples, a primary or secondary aliphatic alcohol having 4 to 8 carbon atoms such as 1-butanol in the presence of Al ³⁺ exchanged bentonite is described. It simply shows that ethers can be obtained from The present inventors have discovered that by using fluorine-based synthetic mica as a catalyst, which is different from conventionally known catalysts,
The present inventors have discovered that not only the production of hydroxydiphenyl ethers as already proposed, but also various dehydration reactions in the liquid phase can be effectively carried out, leading to the present invention. That is, the present invention relates to a catalyst for liquid phase dehydration reactions characterized by being made of fluorine-based synthetic mica. The fluorine-based synthetic mica used in the present invention has the general formula X _1/3-1 Y _2-3 Z ₄ O ₁₀ F ₂ (wherein, Yes, Y is Mg,
A cation selected from Li, Fe, Ni, Mn, Cr and Al, Z is a cation selected from Si or Al, X is a coordination number of 12, Y is a coordination number of 6, and Z is a coordination number It is 4. ) is a fluorine-based synthetic mica obtained by ion-exchanging the synthetic inorganic layered body shown in the following with protons, aluminum and/or transition metals. Such fluorine-based synthetic mica is usually a layered compound whose main component is silicon dioxide, and the silicon is connected in a hexagonal network plate shape based on SiO ₄ tetrahedrons. are stacked in multiple layers, and between the layers are metal layer ions selected from alkali metals and alkaline earth metals, or interlayer ions in which some or all of these are ion-exchanged with protons, aluminum and/or cations selected from transition metals. exists. Specifically, such fluorine-based synthetic micas include: fluorine phlogopite [XMg _2.5 (AlSi ₃ O ₁₀ )] F ₂ (where X is K) tetrasilicon mica XMg _2.5 (Si ₄ O ₁₀ ) F ₂ ( (X is K, Na or Li) Taeniolite XMg _{2 Li} (Si ₄ O ₁₀ ) F ₂ (X _is K _{, Na or} Li) Hectorite )F ₂ (where X is Na or Li) Fluorine-based synthesis obtained by exchanging part or all of an alkali metal ion or alkaline earth metal ion with a cation selected from protons, aluminum, and/or transition metals. An example is mica. Transition metals that may be used for ion exchange include titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium,
Examples include iron, ruthenium, cobalt, rhodium, nickel, palladium, copper, gold, zinc, cadmium, gallium, and indium. In particular, in the present invention, in the fluorine-based synthetic mica described above, 10 mol% or more, particularly 30 to 100 mol%, of the ion-exchangeable interlayer ions are protons, aluminum and/or transition Fluorine-based synthetic mica obtained by ion exchange with cations selected from metals has high catalytic activity and is preferred. As the ion exchange method, a conventionally known ion exchange method can be employed. For example, ion exchange of metal ions such as aluminum and transition metals is carried out by adding an aqueous solution of salts of these metals, such as aluminum sulfate, aluminum nitrate, and aluminum chloride, to a suspension of fluorine-based synthetic mica. There is. For example, to exchange Na-type fluorotetrasilicon mica or Na-type taeniolite with aluminum ions, an aqueous solution of aluminum sulfate, aluminum nitrate, or aluminum chloride is preferably added to a suspension of Na-type fluorotetrasilicon mica or Na-type taeniolite. , the amount of aluminum ions added is about 0.5 to 5 times the gram ion equivalent, preferably about 0.8 to 2 times the gram ion equivalent, relative to the amount of Na ions to be ion-exchanged, and the aluminum ions are added at about room temperature. Stir for 2 to 60 minutes or leave to perform ion exchange treatment, separate the solid phase using a filter or centrifuge, then wash with water and/or ethanol, then under reduced pressure or normal pressure at room temperature or at room temperature. An example is a method of drying at a temperature of about 100°C. This ion exchange treatment may be repeated multiple times as necessary. The ion-exchanged fluorine-based synthetic mica obtained in this way is usually in powder form, and may be used as it is as a catalyst, or if necessary,
It can also be molded into tablets, spheres, cylinders, etc., rings, and honeycombs. The catalyst of the present invention is applicable to various liquid phase dehydration reactions. For example, it is applied to esterification, amidation, etherification, olefination by dehydration of alcohols, aldol condensation, alkylation of aromatic compounds with alcohol, etc. Hydroxy compounds used when applying fluorine-based synthetic mica to the esterification reaction of hydroxy compounds and carboxylic acids include alcohols and phenols, and alcohols are not particularly limited; Among them, the following general formula (In the formula, R ¹ and R ² are hydrogen or an organic group) A primary alcohol or a secondary alcohol is preferable, and the organic group is, for example, a linear or branched alkyl group having about 1 to 20 carbon atoms, such as methyl. ,
Monocyclic and bicyclic alkyl groups such as ethyl, n-propyl, isopropyl, n-butyl, n-octyl, 2-ethylhexyl, dodecyl, etc., aryl groups such as cyclopentyl, cyclohexyl, dicyclo[2.2.1]heptyl, etc. , such as phenyl, naphthyl, xylyl, tolyl, t-butylphenyl, aralkyl groups, such as benzyl, beta-phenylethyl, 3-phenylpropyl, etc., other functionally substituted alkyl groups, such as beta-hydroxyethyl, ethoxymethyl,
Examples include ethoxyethyl, phenoxyethyl, alkoxy groups such as methoxy, ethoxy, n-propoxy, methoxyethoxy, and aryloxy groups such as phenoxy, naphthoxy. More specifically, these compounds include methanol, ethanol, n-propyl alcohol,
n-butyl alcohol, iso-butyl alcohol,
primary alcohols such as n-hexyl alcohol, n-octyl alcohol, benzyl alcohol;
Examples include secondary alcohols such as iso-propyl alcohol, 1-methyl-n-propyl alcohol, α-phenylethyl alcohol, α-methylbenzyl alcohol, and diphenylmethanol.
Phenols include monohydric phenols such as phenol and cresol, hydroquinones such as hydroquinone and methylhydroquinone, and other polyhydric phenols. Among these, monohydric phenols are preferably represented by the following formula [B]. It is what is shown. (In the formula,
indicates an integer. ) Specifically, phenol, o-
Cresol, m-cresol, p-cresol,
3,4-xylenol, 3,5-xylenol,
2,4-xylenol, 3,4,5-trimethylphenol, 2,3,4-trimethylphenol, p-ethylphenol, p-n-propylphenol, p-n-hexylphenol, p-benzylphenol, m- benzylphenol, p
-Phenylphenol, m-phenylphenol, p-(p'-tolyl)phenol, p-chlorophenol, m-chlorophenol, p-bromophenol, m-bromophenol, 2,4-dichlorophenol, p- Methoxyphenol, m
-methoxyphenol, m-nitrophenol,
Examples include p-nitrophenol, m-methoxyphenol, p-methoxyphenol, p-acetylphenol, m-acetylphenol, and p-benzoylphenol. The hydroquinones are preferably those represented by the following formula [C]. (In the formula, Y represents an alkyl group or a halogen, and n represents an integer of 0 to 4.) Specifically, hydroquinone, methylhydroquinone, 2,5-dimethylhydroquinone, 2,6-dimethylhydroquinone,
trimethylhydroquinone, ethylhydroquinone,
Examples include isopropylhydroquinone, n-hexylhydroquinone, chlorohydroquinone, 2,6-dichlorohydroquinone, and bromohydroquinone. In addition, carboxylic acids include aliphatic carboxylic acids such as acetic acid and propionic acid, as well as the following general formula [D]
There are aromatic carboxylic acids represented by (In the formula, Z represents an alkyl group, an aralyl group, an aryl group, a lower alkoxy group, a halogen, a nitro group, an acyl group, an aroyl group, etc., and p is 0 to 5.
indicates an integer. ) Specific examples include benzoic acid, toluic acid, and p-phenylbenzoic acid. Other aromatic carboxylic acids include α- or β-naphthoic acid, terephthalic acid, and trimellitic acid. These esterification reactions may not require a reaction medium such as a solvent, but a reaction medium can also be used. Such reaction media are not particularly limited as long as they are inert to the reaction, and include, for example, benzene, toluene, xylene, ethylbenzene, mesitylene, chlorobenzene, dichlorobenzene, bromobenzene, alkylbenzenes such as biphenyl and terphenyl, and diphenyl. Aromatic ethers such as enyl ether and aromatic ketones can be used, but among these,
Particularly preferred are alkylbenzenes such as toluene, xylene and mesitylene. The amount of reaction medium used is usually such that the concentration of the starting compound is from 2 to 80%, preferably from 5 to 20%. The reaction temperature is usually in the range of about 80 to about 25°C, particularly preferably in the range of about 110 to about 200°C. The reaction may be carried out by heating a mixture of a synthetic mica catalyst, an optional solvent, and reaction raw materials at a predetermined temperature. The heating time is usually about 10 minutes to about 6 hours, preferably about 30 minutes to about 2 hours. As the reaction method, various methods can be adopted, such as a conventional batch method, a continuous method using a tube type reaction method, and the like. Furthermore, the reaction can be carried out under reduced pressure, atmospheric pressure, or increased pressure. Furthermore, since the reaction of the present invention is a dehydration reaction, water is produced as the reaction progresses, so if the reaction is carried out while removing water in the system by a conventional method, the reaction will proceed more easily. After the reaction is completed, the catalyst is separated from the reaction mixture, or without being separated, a general separation means such as distillation is applied to separate and recover the product. Another example of liquid phase dehydration reaction is a method of producing alkoxyphenols from phenols and alcohols by etherification reaction, and the phenols and alcohols used include those mentioned above. The conditions for this etherification reaction are not significantly different from those for the esterification reaction described above, and can be carried out under substantially the same conditions. Furthermore, when synthesizing amide compounds from amino compounds and carboxylic acids, fluorine-based synthetic mica catalysts are suitably used.Amino compounds used include aliphatic amines such as alkyl amines and dialkyl amines, as well as aromatic amines. , aniline, toluidine, xylidine, diphenylamine, phenylenediamine, etc., and the carboxylic acids include those mentioned above. The conditions for the amidation reaction are the same as those for the esterification reaction, and can be carried out under substantially the same conditions. As another example of a dehydration reaction, a fluorine-based synthetic mica catalyst is preferably used to produce an aromatic ether compound through a liquid phase dehydration reaction of a vic-dihydroxy compound and an unsaturated aliphatic alcohol or an aliphatic aldehyde compound. The vic-dihydroxy compounds used include ethylene glycol, 1,2
-dihydroxyalkanes, catechols, alkyl-substituted catechols, etc., and unsaturated aliphatic alcohols include methallyl alcohol,
- Aliphatic aldehydes such as propenol and 2-ethyl-2-butenol include isobutyraldehyde,
Examples include butanal. The conditions for the liquid phase dehydration reaction of the vic-dihydroxy compound and the unsaturated aliphatic alcohol or aliphatic aldehyde compound are not significantly different from those for the esterification reaction, and can be carried out under substantially the same conditions. In addition, fluorine-based synthetic mica is suitably used in the production of olefins by the dehydration reaction of alcohols, for example, in the production of cyclic olefins such as cyclohexene by the liquid phase dehydration reaction of alicyclic alcohols such as cyclohexanol. Further, a fluorine-based synthetic mica catalyst is preferably used in the aldol condensation reaction of carbonyl compounds such as aldehydes and ketones. The conditions for producing these olefins or the aldol condensation reaction are not significantly different from those for the esterification reaction, and can be carried out under substantially the same conditions. Another example of liquid phase dehydration reaction is the alkylation reaction of aromatic compounds using alcohols as the alkylating agent, and the aliphatic compounds used include:
Examples include benzene, toluene, xylene, ethylbenzene, naphthalene and the like, and examples of alcohols include those mentioned above. The conditions for these alkylation reactions are not significantly different from those of the esterification reactions described above and can be carried out under substantially the same conditions. The present invention will be explained below with reference to Examples. Example 1 Sodium tetrasilismic mica (NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ ), a synthetic mica manufactured by Topy Industries, Ltd.
Suspend 100g of 10wt% aqueous solution in 1 water, add 185ml of 5%-Ti( _SO4 ) ₂ aqueous solution while stirring well,
Stirring was continued for an additional 25 minutes to perform ion exchange into the titanium type. The synthetic mica ion-exchanged into titanium type was recovered by centrifugation, thoroughly washed with water, and dried (40°C, 50mmHg, 10 hours) before being used in the reaction. The ion exchange rate of this titanium ion exchange synthetic mica was 68 mol%. This titanium-exchanged synthetic mica 1.0g, phenol 2.6g, benzoic acid 2.3
g. A mixture of 15 ml of mesitylene was placed in a reaction vessel equipped with a Dean Stark water trap, and while the generated water was removed from the system by azeotropy with mesitylene, the mixture was heated and stirred for 2.5 hours under mesitylene reflux to perform an ester synthesis reaction. Ivy. The reaction results were as follows. Benzoic acid conversion rate 100% Phenyl benzoate selectivity 98% (benzoic acid standard) Example 2 Titanium-exchanged synthetic mica 1.0g, aniline 2.8g,
1.6 g of benzoic acid was reacted under the same conditions as in Example 1,
Performed amide synthesis. The reaction results were as follows. Benzoic acid conversion rate 46% Benzanilide selectivity 97% (benzoic acid standard) Example 3 100g of a 10wt% aqueous solution of sodium tetrasilisicumica, a synthetic mica manufactured by Topy Industries, Ltd.
of 5%-Al while stirring well.
200 ml of (NO ₃ ) ₃ aqueous solution was added, and stirring was continued for an additional 25 minutes to perform ion exchange into the aluminum mold. Synthetic mica ion-exchanged with aluminum is recovered by centrifugation, thoroughly washed with water, and dried (40℃,
50 mmHg for 10 hours) and then used for the reaction. The ion exchange rate of this aluminum ion-exchanged synthetic mica was 72 mol%. A mixture of 0.7 g of this aluminum-exchanged synthetic mica and 2.2 g of n-octanol was placed in a reaction vessel equipped with a Dean-Stark water trap and heated and stirred at 150°C for 1 hour while removing the generated water from the system. I did dehydration.
The reaction results were as shown in Mitsuru. n-octanol conversion rate 45% Dioctyl ether selectivity 60% Octene selectivity 31% Example 4 Titanium-exchanged synthetic mica 1.0g, catechol 1.7
g, xylene (10 ml) was placed in a reaction vessel equipped with a Dean Stark water trap, and the xylene was refluxed beforehand. A mixture of 1.2 g of methallyl alcohol and 5 ml of xylene was added dropwise to the mixture using a dropping funnel over 1 hour and 15 minutes. After the dropwise addition was completed, the mixture was further heated and stirred for 10 minutes under reflux of xylene for dehydration. The reaction results were as follows. Catechol conversion rate 51% 2,2-dimethyl-1,4-benzodioxane

[Formula] Selectivity 91% (catechol standard) Example 5 A mixture of 0.7 g of aluminum-exchanged synthetic mica, 2.3 g of cyclohexanol, and 15 ml of toluene was placed in a reaction vessel equipped with a Dean Stark water trap and refluxed with toluene for 1 hour. Continue heating and stirring,
I did dehydration. The reaction results were as follows. Cyclohexanol conversion rate 42% Cyclohexene selectivity 91% Example 6 Titanium-exchanged synthetic mica 0.6g, catechol 1.1
g, xylene (10 ml) was placed in a reaction vessel equipped with a Dean Stark water trap, and the xylene was refluxed beforehand. A mixture of 0.7 g of isobutyraldehyde and 5 ml of xylene was added dropwise thereto over 30 minutes using a dropping funnel. After completion of the dropwise addition, continue heating and stirring under xylene reflux for another 20 minutes.
A dehydration reaction was performed. The reaction results were as follows. Catechol conversion rate 69% 2-isopropyl-1,33-benzodioxole

[Formula] Selectivity 100% (based on catechol) 2-isopropyl-1,3-bezodioxole is a compound that can be used as a raw material for agricultural chemical carbofuran. Example 7 Aluminum-exchanged synthetic mica 1.0g, benzene
10 g of the mixture was placed in a reaction vessel fitted with a Dean Stark water trap and the benzene was pre-refluxed. In this, benzyl alcohol 5.5
g was added dropwise over 10 minutes. 10 more after completion of dripping
The dehydration reaction was continued under heating and stirring under benzene reflux for several minutes. The reaction results were as follows. Benzyl alcohol conversion rate 100% Diphenylmethane selectivity
71% (based on benzyl alcohol) Example 8 1.6 g of aluminum-exchanged synthetic mica, toluene
20 g of the mixture was placed in a reaction vessel fitted with a Dean Stark water trap and the toluene was pre-refluxed. 6.9g of isopropanol in this
was added dropwise over 2 hours. 30 more after completion of dripping
The mixture was heated and stirred under reflux of toluene for several minutes to perform dehydration. The reaction results were as follows. Isopropanol conversion rate: 22% Cymene selectivity: 88% (based on isopropanol) Diisopropyl ether selectivity: 10% Example 9 A mixture of 1.4 g of aluminum-exchanged synthetic mica, 2.2 g of phenol, and 10 ml of chlorobenzene was attached to a Dean Stark water trap. The mixture was placed in a reaction vessel, and chlorobenzene was refluxed in advance.
A mixture of 2.0 g of isopropanol and 5 ml of chlorobenzene was added dropwise to this over 1 hour. After completion of the dropwise addition, heating and stirring were continued for another 30 minutes under refluxing of chlorobenzene to carry out a dehydration reaction. The reaction results were as follows. Phenol conversion rate 82% Isopropylphenol selectivity
80% (phenol conversion rate) Example 10 100 g of a 10 wt% aqueous solution of sodium tetrasilisic mica, a synthetic mica manufactured by Topy Industries, Ltd.
of water, 56 ml of a 5% CuCl ₂ aqueous solution was added with thorough stirring, and stirring was continued for an additional 25 minutes to perform ion exchange into a copper mold. The synthetic mica ion-exchanged into copper type was recovered by centrifugation, thoroughly washed with water, and dried (40° C., 50 mmHg, 10 hours) before being used in the reaction. The ion exchange rate of this copper ion exchange synthetic mica was 63 mol%. A mixture of 0.4 g of this copper-exchanged synthetic mica, 1.7 g of hydroquinone, 0.7 g of benzyl alcohol, and 15 ml of xylene was placed in a reaction vessel equipped with a Dean-Stark water trap, and the mixture was heated and stirred for 3 minutes under reflux of mesitylene to perform dehydration. . The reaction results were as follows. Benzyl alcohol conversion rate 100% 2-benzylhydroquinone selectivity
93% (HQ standard) Example 11 100 g of a 10 wt% aqueous solution of sodium tetrasilismic mica, a synthetic mica manufactured by Topy Industries, Ltd.
While suspending in water, 200 ml of 5% NiCl ₂ aqueous solution was added, and stirring was continued for an additional 25 minutes to perform ion exchange to nickel type. Synthetic mica ion-exchanged into nickel type is recovered by centrifugation, washed thoroughly with water,
After further drying (40°C, 50mmHg, 10 hours), it was used in the reaction. The ion exchange rate of this nickel ion exchange synthetic mica was 74%. 1.0g of this nickel-exchanged synthetic mica, 2.2g of hydroquinone
g, xylene (15 ml) was placed in a reaction vessel equipped with a Dean Stark water trap, and the xylene was previously refluxed. A mixture of 1.7 g of isopropanol and 5 ml of xylene was added dropwise into the mixture using a dropping funnel over a period of 1 hour and 20 minutes. After completion of the dropwise addition, heating and stirring were continued for another 20 minutes under reflux of xylene to effect dehydration. The reaction results were as follows. Hydroquinone conversion rate 46% Hydroquinone monoisopropyl ether selectivity
76% (HQ standard) 2-isopropylhydroquinone selectivity
18% (HQ standard) Example 12 A mixture of 0.5 g of titanium-exchanged synthetic mica, 1.0 g of cyclohexanone, and 15 ml of mesitylene was
The mixture was placed in a reaction vessel equipped with a Stark water collection trap, and heated under reflux for 7 hours while the produced water was removed from the system by azeotropy with mesitylene. The reaction results were as follows. Cyclohexanone conversion rate 80% 2-cyclohexyl-2-cyclohexenone (dehydrated dimer) selectivity 77% cyclohexanone dehydrated trimer 8.3% Comparative example 1 In Example 12, the titanium-exchanged synthetic mica was replaced with 190 mg of para-toluenesulfonic acid. , reaction time 3/4
The reaction was carried out in the same manner as in Example 12, except that the time was changed. The reaction results are as follows. Cyclohexanone conversion rate 70% 2-cyclohexyl 2-cyclohexenone selectivity
52.4% Cyclohexanone dehydrated trimer 47.5% Example 13 Aluminum exchanged synthetic mica 0.25g, 1,4-
A mixture of 0.9 g of pentanediol was placed in a reaction vessel and a reaction was carried out at a temperature of 180°C for 10 minutes. The reaction results are as follows. 1,4-pentanediol conversion rate 91.1% 2-methyltetrahydrofuran selectivity 96.4% 1-pentanol-3-ene selectivity 3.0% Example 14 0.3 g of aluminum-exchanged synthetic mica, 0.5 g of phenol, 0.32 g of acetic acid, 10 ml of chlorobenzene was added to the autoclave, and the reaction was carried out at 180°C for 7 hours. The reaction results are as follows. Phenol conversion rate 12% Phenyl acetic acid selectivity 82% (based on phenol) Acetyl phenol selectivity
18% (based on phenol) Example 15 Lithium hectorite manufactured by Topy Industries [Li _1/3
Suspend 5 g of Mg _22/3 Li _1/3 (Si ₄ O ₁₀ ) F ₂ in 1 water and add 5% aluminum nitrate aqueous solution while stirring.
100 ml was added and stirring was continued for an additional 3 hours to perform ion exchange. The ion-exchanged hectorite was collected by centrifugation, thoroughly washed with water, and further dried (40°C, 50mmHg, 10 hours). The ion exchange rate of this aluminum hectorite was 82 mol%. The reaction was carried out in the same manner as in Example 12, except that the titanium-exchanged synthetic mica in Example 12 was changed to aluminum hectorite and the reaction time was changed to 2.5 hours. The reaction results were as follows. Cyclohexanone conversion rate 83% 2-cyclohexyl-2-cyclohexenone selectivity 80% cyclohexanone dehydrated trimer 5.2% Example 16 Lithium taeniolite manufactured by Topy Industries [LiMg ₂ Li (Si ₄ O ₁₀ ) E ₂ ] 5 g was added to 1 of 5% aluminum nitrate aqueous solution while stirring.
200 ml was added and stirring was continued for an additional 3 hours to perform ion exchange. The ion-exchanged taeniolite was collected by centrifugation, thoroughly washed with water, and further dried (40°C, 50mmHg, 10 hours). The ion exchange rate of this aluminum taeniolite was 75 mol%. The reaction was carried out in the same manner as in Example 12, except that the titanium-exchanged synthetic mica in Example 12 was changed to aluminum teniolite and the reaction time was changed to 4 hours.
The reaction results are as follows. Cyclohexanone conversion rate 70% 2-cyclohexyl-2-cyclohexenone (dehydrated dimer) selectivity 85% Cyclohexanone dehydrated trimer selectivity 4.8% Comparative example 2 In Example 1, titanium ion exchange synthetic mica was used as the catalyst. The reaction was carried out in the same manner as in Example 1, except that 1.0 g of sodium tetrasilicium squid was used. The reaction results were as follows. Benzoic acid conversion rate 0.2% Phenyl benzoate selectivity 95% (benzoic acid standard) Comparative example 3 In Example 15, lithium hectorite was used as a catalyst instead of aluminum hectorite.
The reaction was carried out in the same manner as in Example 15, except that 0.5 g was used. The reaction results were as follows. Cyclohexanone conversion rate 0.5% 2-cyclohexyl-2-cyclohexenone selectivity 70% Comparative example 4 In Example 16, lithium taeniolite was used as a catalyst instead of aluminum taeniolite.
The reaction was carried out in the same manner as in Example 16, except that 0.5 g was used. The reaction results were as follows. Cyclohexanone conversion rate 2.2% 2-cyclohexyl-2-cyclohexenone selectivity 72% Example 17 100g of a 10wt% aqueous solution of sodium tetrasilismicica, a synthetic mica manufactured by Topy Industries, Ltd.
200 ml of a 5% iron nitrate aqueous solution was added while stirring well, and stirring was continued for an additional 25 minutes to perform ion exchange into an iron mold. The synthetic mica ion-exchanged with iron was recovered by centrifugation, thoroughly washed with water, and dried (40° C., 50 mmHg, 10 hours) before being used in the reaction. The ion exchange rate of this iron ion exchange synthetic mica was 82 mol%. In Example 2, the reaction was carried out in the same manner as in Example 2, except that 1.0 g of the above iron ion-exchanged synthetic mica was used in place of the titanium-exchanged synthetic mica. The reaction results were as follows. Benzoic acid conversion rate 41% Benzanilide selectivity 96% (benzoic acid standard) Example 18 100g of a 10wt% aqueous solution of sodium tetrasilisichmica, a synthetic mica manufactured by Topy Industries, Ltd.
200 ml of a 5% zirconium nitrate aqueous solution was added while stirring well, and stirring was continued for an additional 25 minutes to perform ion exchange into a zirconium form. Synthetic mica ion-exchanged with zirconium is recovered by centrifugation, thoroughly washed with water, and dried (40℃,
50 mmHg for 10 hours) and then used for the reaction. The ion exchange rate of this zirconium ion exchange synthetic mica was 61 mol%. In Example 4, 1.0 g of the above zirconium ion-exchanged synthetic mica was used instead of the titanium-exchanged synthetic mica.
The reaction was carried out in the same manner as in Example 4 except that . The reaction results were as follows. Catechol conversion rate 45% 2,2-dimethyl-1,4-benzodioxane selectivity 88% (catechol standard) Example 19 100 g of a 10 wt% aqueous solution of sodium tetrasilismic mica, a synthetic mica manufactured by Topy Industries, Ltd.
of water, add 200 ml of 5% chromium nitrate aqueous solution while stirring well, and continue stirring for an additional 25 minutes.
Ion exchanged to chromium type. Synthetic mica ion-exchanged with chromium is recovered by centrifugation, thoroughly washed with water, and further dried (40℃, 50mmHg, 10 hours).
After that, it was used for the reaction. The ion exchange rate of this chromium ion-exchanged synthetic mica was 72 mol%. In Example 4, the reaction was carried out in the same manner as in Example 4, except that 1.0 g of the above chromium ion exchanged synthetic mica was used in place of the titanium exchanged synthetic mica. The reaction results were as follows. Catechol conversion rate 41% 2,2-dimethyl-1,4-benzodioxane selectivity 89% (catechol standard) Example 20 5 g of lithium teniolite manufactured by Topy Industries, Ltd.
200 ml of 5% hydrochloric acid aqueous solution was added to the suspension while stirring well, and stirring was continued for an additional 3 hours to exchange lithium ions with protons. The ion-exchanged taeniolite was collected by centrifugation, thoroughly washed with water, and dried (40℃, 50mmHg,
After 10 hours), it was used for the reaction. The ion exchange rate of this proton teniolite was 61 mol%. In Example 16, the reaction was carried out in the same manner as in Example 16, except that 0.5 g of the above proton teniolite was used in place of aluminum teniolite.
The reaction results were as follows. Cyclohexanone conversion rate 51% 2-cyclohexyl-2-cyclohexenone selectivity 81% cyclohexanone dehydration trimer selectivity 4.8% Example 21 100 g of a 10 wt% aqueous solution of sodium tetrasilismic mica, a synthetic mica manufactured by Topy Industries, Ltd.
of water, add 200 ml of 5% gallium nitrate aqueous solution while stirring well, and continue stirring for an additional 25 minutes.
Ion exchanged to gallium type. The synthetic mica ion-exchanged with gallium was recovered by centrifugation, thoroughly washed with water, and dried (40° C., 50 mmHg, 10 hours) before being used in the reaction. The ion exchange rate of this gallium ion exchange synthetic mica is 65 mol%.
It was hot. In Example 1, the reaction was carried out in the same manner as in Example 1, except that 1.0 g of the above gallium ion exchanged synthetic mica was used in place of the titanium exchanged synthetic mica.
The reaction results were as follows. Benzoic acid conversion rate 98% Phenyl benzoate selectivity 97% (benzoic acid standard) Example 22 5 g of lithium hectorite manufactured by Topy Industries, Ltd.
While stirring, add 100 ml of 5% indium nitrate aqueous solution and continue stirring for another 3 hours.
Ion exchanged. The ion-exchanged hectorite was collected by centrifugation, thoroughly washed with water, and further dried (40°C, 50mmHg, 10 hours). The ion exchange rate of this indium hectorite was 81 mol%. In Example 15, the reaction was carried out in the same manner as in Example 15, except that 0.5 g of the above indium hectorite was used in place of aluminum hectorite. The reaction results were as follows. Cyclohexanone conversion rate 80% 2-cyclohexyl-2-cyclohexenone selectivity 78% Cyclohexanone dehydration trimer selectivity 6.2%

Claims (1)

[Claims] 1 Fluorine-based synthetic mica has the general formula X _1/3~1 Y _2~3 Z ₄ O ₁₀ F ₂ (wherein, ion, Y is Mg,
A cation selected from Li, Fe, Ni, Mn, Cr and Al, Z is a cation selected from Si or Al, X is a coordination number of 12, Y is a coordination number of 6, and Z is a coordination number It is 4. A catalyst for a liquid phase dehydration reaction, characterized in that it is a fluorine-based synthetic mica obtained by ion-exchanging the synthetic inorganic layered body shown in ) with protons, aluminum and/or transition metals.