KR20050044916A - Process for production of 4-alkylphenols - Google Patents

Abstract

A process for the production of 4-alkylphenols, characterized by comprising the first step of reacting a 4-unsubstituted phenol with an alkyl alcohol or an alkyl ether in the presence of a synthetic zeolite at a temperature of 50 to 110°C, the second step of removing water contained in the liquid phase of the reaction mixture when an alkyl alcohol is used in the first step or an alcohol contained therein when an alkyl ether is used in the first step, and the third step of subjecting the resulting water- or alcohol-free reaction mixture to rearrangement at a temperature of 90 to 150°C in the presence of an acid catalyst. According to the process, 4-alkylphenols can be industrially advantageously produced with high selectivity and in high yield.

Description

Production method of 4-alkylphenols {PROCESS FOR PRODUCTION OF 4-ALKYLPHENOLS}

The present invention relates to a method for producing 4-alkylphenols.

The 4-alkyl phenols produced by the present invention are used as various synthetic raw materials, and in particular, 4-tert-butylphenol (hereinafter referred to as 4-TBP) is used as a molecular weight regulator of a polycarbonate resin, a phenol resin, a surfactant, or the like. It is useful as a raw material.

Conventionally, as a method of producing 4-alkylphenols, a method of alkylating phenols by reacting phenols with olefins, alcohols or ethers in the presence of a catalyst is known. As a method for producing 4-alkylphenols from phenols and olefins, there is known a method of addition reaction of olefins to phenols in the presence of an acid catalyst, followed by disproportionation reaction (Japanese Patent Laid-Open No. 8-12610). Reference). In the case of this method, in order to suppress the formation of by-products derived from olefin of a raw material, it is necessary to use olefin of high purity. In particular, when using low-boiling olefins, it is difficult to obtain high-purity olefins by distillation or the like. Therefore, alcohols or ethers as raw materials are purified and their dehydration reactions or dealcoholization reactions are selected at high selectivity. In addition, it is necessary to raise the obtained olefin to a desired purity by using purification means such as distillation, and the cost is high and it is not economical. On the other hand, in the case of using alcohol or ether as a raw material, there is an advantage that the preparation cost is low and the handling is easy, as compared with the case of using high purity olefin. On the other hand, when the water produced when using alcohol as a raw material or the ether produced when using ether as a raw material decreases catalytic activity, it is necessary to remove the generated water or alcohol out of the system, respectively.

As a method for producing 4-alkylphenols by reacting phenols with alcohol in the presence of a catalyst, for example, (1) phenol is reacted with secondary or tertiary alcohols at a pressure of 4 atm or less (actually near atmospheric pressure, About 135 to 180 ° C.), a method of reacting water with evaporation in the presence of a dehydration condensation catalyst such as activated clay, sulfuric acid (see US Pat. No. 2,140,782), (2) tert-butanol having a water content of about 12 to 30 wt% (Hereinafter abbreviated as TBA) and a method of reacting phenol at a temperature of 220 to 300 ° C in the presence of a synthetic silica-alumina catalyst (see JP-A-56-57727), (3) Cation exchange resin Methods of alkylating phenols with TBA in the presence [see Catalysis Letters, Vol. 19, pp. 309-317 (1993)] are known.

Said method (1)-(3) is a method of manufacturing 4-alkyl phenols in one stage. The active clay used in the above method (1) has a different property depending on its origin, mining location, etc., and thus lacks reproducibility of catalytic activity, and also the product is adsorbed between layers and the acidity tends to be lowered, resulting in lower catalytic activity. In the case of using sulfuric acid, the protonic acidity of sulfuric acid is remarkably changed depending on the amount of generated water, and the catalytic activity greatly depends. Therefore, in the method (1), it is necessary to evaporate and remove water from a reaction system. Especially, when TBA is used as alcohol, since TBA is azeotropic with water, the amount of TBA is inevitably increased and it is economically disadvantageous. In the above method (2), since the ratio of the ortho-isomer is rapidly increased at a temperature below 220 ° C, it is necessary to perform the reaction under high temperature, and because it is under pressure to maintain the liquid state, a special pressure device is required. do. In the above method (3), in order to continuously carry out the reaction for a long time at a temperature that promotes the dehydration reaction of the TBA, the cation exchange resin has low durability, and the cation exchange resin is gradually decomposed, and acidic components such as sulfonic acid are gradually reacted. Since it is mixed in, there is a problem that operation is complicated, such as necessity of neutralization before the distillation step for obtaining the product.

A method for preparing 4-alkylphenols by reacting phenols and ethers in the presence of a catalyst, for example, (4) alkylating phenol with methyl tert-butylether (hereinafter abbreviated as MTBE) in the presence of a cation exchange resin. [Catalysis Letters, 1993, Vol. 19, pp. 309 to 317], (5) Aromatic compounds such as phenol and pyrocatechol, and alkyl tertiary butyl ether, in the presence of sulfuric acid or ion exchange resin A method of tertiary butylation of the aromatic aromatic compound by removing the alcohol produced by the reaction at a temperature of from 60 to 130 ° C. and completing the reaction in the absence of this alcohol (see JP-A-57-67529). Etc. are known.

In the above methods (4) and (5), since the cation exchange resin has low durability in the presence of the produced alcohol at the temperature at which the cation exchange resin decomposes the ether to generate olefins, the cation exchange resin is gradually decomposed. Since acidic components such as sulfonic acid are gradually mixed into the reaction solution, there is a problem that operation is complicated, such as necessity of neutralization before the distillation step for obtaining the product. In addition, when sulfuric acid is used, since the produced olefin is isomerized by sulfuric acid, there is a problem that the reaction product is complicated.

In recent years, synthetic zeolites have attracted attention as catalysts not only excellent in alkylation activity and selectivity of aromatic compounds, but also non-corrosive, less pollution to the environment, and excellent in durability. When alkylating phenol with TBA, a method using synthetic zeolite, for example, (6) a method of gas phase alkylation using a zeolite catalyst (US Pat. No. 4,391,998, US Pat. No. 4,532,368, Japanese Patent Publication) 52-12181), (7) a method of alkylating phenols with alcohols and / or ethers in a liquid phase, preferably at a temperature of 200 to 320 ° C. in the presence of a metal-containing Y zeolite (JP-A-62) -240637, JP 62-246532), (8) A method of alkylating phenol with TBA using synthetic zeolite, which is reacted in carbon tetrachloride in the presence of HY zeolite [Journal of J. Chem. Research (S), pages 40-41 (1988)], Methods of using large-diameter zeolites such as HY and Hβ [Applied Catalysis A: General, 166 Vol. 89 Page 95 (1998) and the 207, the reference page 183-190 (2001)] and the like are reported.

In the above method (6), since the reaction is performed in the gas phase, not only a large amount of heat is required, but also the selectivity is inevitably lowered because the reaction temperature is close to the decomposition point of 4-TBP, and carbon deposits by phenol Due to this, the deterioration of the catalytic activity is large. In said method (7), there exists a problem that the selectivity of 4-alkyl phenols produced | generated is low, and the 2-alkyl phenols which are difficult to isolate | segment are by-produced. The contents of the literature describing the above method (8) are all the effects of reaction conditions such as the pore structure of the synthetic zeolite, properties such as acidity, temperature, feed rate of raw materials, raw material ratio, etc., on catalyst activity and reaction selectivity. In the reaction example, since the oligomer of C4 hydrocarbon is produced, the selectivity of 4-TBP is low, and the industrially advantageous method for producing 4-TBP in high yield has not been examined.

An object of the present invention is to provide an industrially advantageous method capable of producing 4-alkylphenols at high selectivity and high yield.

Disclosure of the Invention

The present invention is a reaction mixture obtained when the fourth unsubstituted phenols and an alkyl alcohol or alkyl ether are reacted at a temperature of 50 to 110 ° C. in the presence of a synthetic zeolite (first step), and an alkyl alcohol is used in the first step. To remove the produced water contained in the liquid phase, and in the case of using the alkyl ether in the first step, in the obtained reaction mixture, the produced alcohol contained in the liquid phase is removed (second step), and then the produced water or It is a manufacturing method of 4-alkyl phenols characterized by carrying out a potential reaction (3rd process) in the reaction mixture after alcohol removal in the presence of an acidic catalyst at the temperature of 90-150 degreeC.

In a preferred embodiment of the present invention, in the third step, when the alkyl alcohol is used in the first step, the water concentration in the liquid phase of the reaction mixture is adjusted to 0.5% by weight or less, and the alkyl ether is used in the first step. In this case, the alcohol concentration in the liquid phase of the reaction mixture is adjusted to 0.5% by weight or less, and the amount of fourth-position unsubstituted phenols is in the range of 10 to 10 moles relative to the alkyl alcohol or alkyl ether consumed in the alkylation reaction in the first step. It is adjusted to make the potential reaction. In addition, 4-TBP is prepared by using phenol as the 4-position unsubstituted phenols and TBA as alkyl alcohol or MTBE as alkyl ether.

A feature of the present invention is to produce an alkylation reaction of a 4-position unsubstituted phenol at a temperature in the range of 50 to 110 ° C in the presence of a synthetic zeolite (first step), and to produce it in the alkylation reaction contained in the liquid phase in the obtained reaction mixture. 2-alkylated phenols, 3-alkylated phenols, 2,4-dialkylated phenols, 2,6-dialkylated phenols contained in the reaction mixture after the removal of water or alcohol (second step), followed by removal of water or alcohol And by-products such as 2,4,6-trialkylated phenols can be efficiently converted (third step) to 4-alkylphenols in the presence of an acid catalyst at a temperature in the range of 90 to 150 ° C.

According to the above characteristics, there is no significant decrease in the catalytic activity by the water produced in the above method (1), and TBA having a water content of about 12 to 30% by weight may be used as a raw material. The deterioration of the catalyst as seen in the above methods (3) to (5) can be suppressed, and since acidic components are not contained in the reaction solution, complicated operations such as neutralization can be avoided. . In addition, the above-described characteristics can suppress by-products of 2-alkylphenols having high selectivity of 4-alkylphenols and difficult separation in the above-described method (7). Formation of oligomers of C4 hydrocarbons as seen in the above method (8) can be suppressed. In addition, in the above temperature range, the reaction mode is a liquid phase, and deterioration of the catalyst due to carbon deposit seen in the above method (6) can be suppressed. In addition, by removing the water or the alcohol produced in the second step, the lowering of the activity of the acid catalyst in the third step is suppressed and 2,4-dialkylated phenols, 2,6-dialkylated phenols, 2,4,6- The potential reaction of the alkyl group from trialkylated phenols to 4-alkylphenols proceeds in a short time with good selectivity. Further, even when an acidic cation exchange resin is used as the acid catalyst, 4-alkylphenols can be produced with good selectivity, and furthermore, in this case, the temperature of the potential reaction can be lowered to 90 ° C., resulting in the presence of water and alcohol. Since it does not, the outflow of an acidic component and deterioration of an ion exchange resin can be suppressed.

Mode for carrying out the invention

First, the first step will be described.

In the first step, alkylation of the fourth unsubstituted phenol is carried out by reacting the fourth-position unsubstituted phenols with an alkyl alcohol or an alkyl ether at a temperature of 50 to 110 ° C in the presence of the synthetic zeolite.

As the fourth unsubstituted phenols, for example, phenol, 2-cresol, 3-cresol, 2-ethylphenol, 3-ethylphenol, 2-propylphenol, 3-propylphenol, 2-isopropylphenol, 3-iso Propylphenol, 2-tert-butylphenol, 3-tert-butylphenol, and the like.

As alkyl alcohol, the alkyl alcohol matched with the alkyl group to introduce | transduce is used, For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, TBA, pentanol, hexanol, cyclohexanol And benzyl alcohol and the like. It is preferable that it is the range of 0.1-2 mol with respect to 1 mol of 4 position unsubstituted phenols, and, as for the usage-amount of alkyl alcohol, it is more preferable that it is 0.2-1 mol.

As an alkyl ether, the alkyl ether matched with the alkyl group to introduce | transduce is used, For example, dimethyl ether, diethyl ether, din-propyl ether, diisopropyl ether, din-butyl ether, diisobutyl ether, MTBE, Ethyl tert-butyl ether, n-propyl tert-butyl ether, isopropyl tert-butyl ether, n-butyl tert-butyl ether, isobutyl tert-butyl ether and the like. It is preferable that it is the range of 0.1-2 mol with respect to 1 mol of 4 position unsubstituted phenols, and, as for the usage-amount of an alkyl ether, it is more preferable that it is 0.2-1 mol.

As a synthetic zeolite, mesoporous silicates represented by medium diameter zeolites represented by large diameter zeolites, such as X-type, Y-type, β-type, L-type, mordenite, ZSM, SAPO, etc., MCM, etc. are mentioned, for example. have. Among these, Y type, β type, L type and mordenite are preferable. Generally, synthetic zeolites have alkali metals, alkaline earth metals, and the like as ions in the zeolite, and in the present invention, at least one of them is selected from the group consisting of transition metal ions, aluminum ions, and protons. Used in exchange for

As the synthetic zeolite, in order to increase the reaction efficiency, it is preferable that the acidity of the zeolite, that is, the silica / alumina ratio is small, and the alkali metal, the alkaline earth metal, etc. possessed by the zeolite are substituted with hydrogen atoms. Moreover, in order to improve the selectivity of 4-alkylphenols, it is preferable to use the zeolite which has the pore which was in the molecular size of this 4-alkylphenols. For example, when manufacturing 4-TBP, it is preferable to use mordenite and a β-type zeolite as a zeolite species, it is preferable that a silica / alumina ratio is the range of 1-200, and is the range of 5-150. It is more preferable that it is and it is especially preferable that it is the range of 5-50.

The shape of the synthetic zeolite is not particularly limited, and powdered, granular, lumped or the like can be used. Moreover, you may shape | mold and use a powdery and granular thing, and a spherical shape, a cylindrical shape, ring shape, a star shape etc. are mentioned as a shape of a molded article, for example. The size of the particles of the synthetic zeolite is not particularly limited, and the smaller the particles, the larger the surface area and the higher the reaction activity. However, particles of 1 to 800 microns are used in a range that does not affect the normal operation. .

The amount of the synthetic zeolite used varies depending on the reaction method. For example, in the case of batch type, it is preferably in the range of 1 to 100% by weight based on the fourth unsubstituted phenol, and in the range of 5 to 25% by weight in consideration of the reaction efficiency. It is more preferable that is. When the amount of synthetic zeolite is small, the reaction rate tends to be slow, and in many cases, economically disadvantageous, which is not preferable in any case.

The alkylation reaction is carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as it is inert to the reaction, and examples thereof include aliphatic hydrocarbons such as hexane, heptane, octane, nonane, decane and cyclohexane; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and the like. Among these, toluene is preferable. When using a solvent, the usage-amount is not specifically limited, From a viewpoint of reaction efficiency, operability, economical efficiency, etc., it is preferable that it is the range of 1 to 20 times the weight with respect to a 4th unsubstituted phenol.

The alkylation reaction is carried out at a relatively low temperature in the range of 50 to 110 ° C. If the reaction temperature is less than 50 ° C., the progress of the reaction becomes very slow and the reaction efficiency is poor. In addition, when the reaction temperature exceeds 110 ° C, not only the selectivity of the desired 4-alkylphenols is lowered, but also the alkyl alcohol or alkyl ether of the raw material or the 4-position unsubstituted phenols are high molecular weight and have high boiling point. By-products of the compound are increased.

The alkylation reaction can be carried out under any pressure of normal pressure, reduced pressure and pressure. The reaction mode may be batch or continuous. The layer filled with the synthetic zeolite can be carried out in a stationary phase system through which the 4-position unsubstituted phenols and alkyl alcohol or alkyl ether are passed, or also in a fluidized bed system or a mobile bed system.

The alkylation reaction time is preferably in the range of 1 to 30 hours, more preferably in the range of 5 to 10 hours. When the reaction time is less than 1 hour, the reaction does not proceed sufficiently and the reaction efficiency tends to be low, and when it exceeds 30 hours, by-products of the compound having a high boiling point tend to be increased. Not desirable

The reaction mixture obtained by the alkylation reaction is provided to a 2nd process after synthetic zeolite is removed from the reaction mixture as needed.

Next, the second step will be described.

In the second step, water produced in the liquid phase of the reaction mixture obtained when the alkyl alcohol is used in the first step is removed, and alcohol produced in the liquid phase of the reaction mixture obtained when the alkyl ether is used in the first step is removed. do.

As a method of removing water, a method of dehydration by distillation, a method of blowing an inert gas such as nitrogen or argon into the reaction mixture, a dehydration by a moisture adsorbent such as molecular, zeolite, alumina, activated carbon or the like The method etc. are mentioned. As a method of removing alcohol, the method of removing by distillation, the method of blowing inert gas, such as nitrogen and argon into a reaction mixture, and adsorption removal by alcohol adsorbents, for example, molecular, zeolite, alumina, activated carbon, etc. And the like can be mentioned. In order to significantly maintain the activity of the acid catalyst used in the third step described later, it is preferable to adjust the concentration of water or alcohol remaining in the liquid phase of the reaction mixture provided for the potential reaction to 0.5% by weight or less. When it exceeds 0.5 weight%, the activity of an acid catalyst is not fully exhibited and the potential reaction rate in a 3rd process falls remarkably.

Next, a third step will be described.

In the third step, the alkyl group is selected from the 2-alkylated phenols, 3-alkylated phenols, 2,4-dialkylated phenols, 2,6-dialkylated phenols, 2,4,6-trialkylated phenols and the like produced in the first step. It detach | desorbs and the "potential reaction of an alkyl group" added to the 4th position of 4-position unsubstituted phenols produces the 4-alkylphenols.

As an acid catalyst, synthetic zeolite, an acidic cation exchange resin, etc. are mentioned, for example.

As a synthetic zeolite, in order to introduce an alkyl group into the 4th position of the 4th unsubstituted phenols, it is preferable to use the zeolite which has the pore which was in the molecular size of the 4-alkylphenols made into the objective. Moreover, it is preferable that the acidity (silica / alumina ratio) which a zeolite has is small, and the alkali metal, alkaline-earth metal, etc. which a zeolite has are substituted by the hydrogen atom. If the acidity of the synthetic zeolite is too high, it is not preferable because the decomposition reaction of the target 4-alkylphenols is promoted and the selectivity of 4-alkylphenols tends to be lowered. For example, when producing 4-TBP, it is preferable to use a β-type or Y-type zeolite as the zeolite species, the silica / alumina ratio is preferably in the range of 1 to 200, and the range of 5 to 150. It is more preferable, and it is especially preferable that it is the range of 5-50.

Since synthetic zeolite adsorbs water, it is preferable to use it after dehydrating in advance. Dehydration is performed by heating for several hours at the temperature of 100-300 degreeC, for example. You may perform dehydration process under airflow, such as nitrogen and air. In addition, synthetic zeolite may be the same as or different from what was used for alkylation reaction. When performing an electric potential reaction, you may remove the synthetic zeolite used by the alkylation reaction, and you may perform an electric potential reaction without removing.

The amount of synthetic zeolite used depends on the reaction method. For example, in the case of batch type, it is preferably in the range of 1 to 100% by weight based on the total weight of the fourth-position unsubstituted phenols as raw materials and 4-alkylphenols as products. In consideration of the reaction efficiency, the amount is more preferably in the range of 5 to 25% by weight. When the amount of the synthetic zeolite is small, the reaction rate is slow, and in many cases, economically disadvantageous, and neither case is preferable.

As acidic cation exchange resin, what is necessary is just a cation exchange resin which shows acidity, For example, styrene type sulfonic-acid resin etc. are mentioned.

The shape of the acidic cation exchange resin is not particularly limited as long as it is a shape capable of exhibiting a function as a catalyst. Usually, particles having an average particle diameter of 0.01 to 10 mm or particles such as spherical and cylindrical can be used.

The amount of acidic cation exchange resin used varies depending on the reaction method. For example, in the case of batch type, the amount is preferably in the range of 1 to 100% by weight based on the total weight of the fourth-position unsubstituted phenols as raw materials and 4-alkylphenols as products. In consideration of the reaction efficiency, the amount is more preferably in the range of 5 to 25% by weight. When the amount of acidic cation exchange resin is small, the reaction rate is slow, and in many cases, economically disadvantageous, which is not preferable either.

The dislocation reaction is carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as it is inert to the reaction. Examples of the solvent include aliphatic hydrocarbons such as heptane, octane, nonane, decane and methylcyclohexane; Aromatic hydrocarbons such as toluene, xylene and mesitylene; Halogenated hydrocarbons such as chlorobenzene and the like. Among these, it is preferable to use toluene. In the case where the solvent is present, the amount of the solvent is not particularly limited, but considering the reaction efficiency, operability, economical efficiency, etc., it is 1 to 20 times the weight of the total weight of the fourth-position unsubstituted phenols as raw materials and 4-alkylphenols as products. It is preferable that it is a range.

The potential reaction is carried out at a temperature in the range of 90 to 150 ° C. When the reaction temperature is too high, the introduced alkyl group decomposes and returns to the raw material, whereby the conversion rate of the alkylated phenols decreases and the selectivity of 4-alkylphenols decreases. In addition, when the reaction temperature is too low, the rate of dislocation reaction is remarkable and slow, which is economically disadvantageous.

The potential reaction can be carried out under any pressure of normal pressure, reduced pressure, and pressurization. The reaction mode may be batch or continuous. The reaction can be carried out either in a fixed bed system or in a fluidized bed system or a mobile bed system in which the reaction mixture is allowed to pass through the acid catalyst.

The potential reaction time is preferably in the range of 1 to 20 hours from the viewpoint of suppressing the formation of by-products in the reaction and increasing the selectivity of the desired 4-alkylphenols.

When carrying out the potential reaction, by adjusting the fourth unsubstituted phenols to the reaction solution by adjusting the ratio of the fourth unsubstituted phenols in the reaction mixture to a specific range, the selectivity of the 4-alkylphenols is improved to increase the reaction rate. It can increase. The amount of the fourth-position unsubstituted phenols in the reaction mixture is preferably in the range of 1 to 10 times the molar amount of the alkyl group introduced in the first step, that is, the alkyl alcohol or alkyl ether consumed in the alkylation reaction in the first step. When the amount is less than 1 mole, it becomes difficult to cause dislocation reactions of alkyl groups from 2,4-dialkylated phenols, 2,6-dialkylated phenols, 2,4,6-trialkylated phenols, and the like, and exceed 10 moles. In this case, the conversion rate of the fourth-position unsubstituted phenols tends to be low.

The reaction and operation of the first to third steps may be performed in the same reactor, or may be performed in a continuous reactor.

The 4-alkyl phenols produced by the present invention can be isolated and purified by a method used for isolation and purification of ordinary organic compounds. For example, the acid catalyst is separated from the reaction mixture, if necessary, and the filtrate is used for distillation, recrystallization, chromatography, and the like to isolate and purify 4-alkylphenols.

Hereinafter, although an Example demonstrates this invention concretely, this invention is not restrict | limited at all by these Examples. In the table, 2-TBP represents 2-tert-butylphenol and 2,4-DTBP represents 2,4-di-tert-butylphenol. The composition (%) after the reaction was analyzed by gas chromatography [column: G-100 (Chemical Evaluation Research Organization), detector: FID (hydrogen ionization detector), detector / vaporization chamber temperature: 270 ° C, temperature rising pattern: 80 The area | region of each component obtained by hold | maintenance for 3 minutes at <0> C → temperature rise to 250 degreeC by 10 degree-C / min and hold at 250 degreeC for 15 minutes] is shown by the percentage. The percent selectivity of 4-TBP is expressed on the basis of phenol, and the percent yield of 4-TBP is expressed on the basis of TBA or MTBE.

Reference Example 1

(First process)

Into a 100 mL four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, 12.5 g of β-type zeolite (N.E. Campcat, H-β) substituted with phenol and 50.0 g (531 mmol) were added and stirred. The temperature was raised to 100 ° C and 22.6 g (266 mmol) of TBA having a water content of 13% by weight than the syringe was added dropwise over 3 hours. It stirred at the same temperature for 3 hours and made the alkylation reaction. The reaction solution was analyzed by gas chromatography. The composition of the reaction solution was phenol (42.0%), 4-TBP (50.1%), 2-TBP (4.7%), 2,4-DTBP (3.1%), and phenol. The conversion rate of was 46.2%, the selectivity of 4-TBP was 81.9%, the yield of 4-TBP was 75.9%.

Example 1

(First process)

Into a 100 mL four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, 12.5 g of β-type zeolite (Heda Chemical Co., Ltd., H-BEA-25) substituted with phenol and 50.0 g (531 mmol) was added and stirred. . The temperature was raised to 90 ° C, and 22.6 g (266 mmol) of TBA having a water content of 13% by weight was dropped from the syringe over 3 hours. It stirred at the same temperature for 5 hours and made the alkylation reaction. The reaction solution was analyzed by gas chromatography to determine the production ratio of each compound, the conversion rate of phenol, the selectivity and yield of 4-TBP. The results are shown in Table 1.

(Second process)

Β-type zeolite was removed by filtration from the reaction mixture obtained in the first step. The obtained filtrate was removed by distillation under reduced pressure [26.7-4.7 kPa (200-35 mmHg), internal temperature 90-120 degreeC]. It was 0.1 weight% as a result of measuring the water concentration of the mixture after water removal. In addition, the amount of phenol was 1.1 in molar ratio with respect to TBA consumed for the alkylation reaction in the 1st process.

(Third process)

Into a 100 mL four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, 12.5 g of Y-type zeolite (HSZ-360HUA, manufactured by Tosoh Corporation) substituted with a mixture and a proton obtained in the second step was heated to 120 ° C. The mixture was stirred for 1 hour to carry out a potential reaction. The reaction solution was analyzed by gas chromatography to determine the production ratio of each compound and the selectivity and yield of 4-TBP. The results are shown in Table 1.

Item Example 1 1st process 3rd process Composition of reaction solution (%) Phenol4-TBP2-TBP2,4-DTBP 39.454.23.82.6 39.458.01.51.2 Phenolic conversion rate (%) 42.5 Selectivity of 4-TBP (%) 61.2 95.6 Yield of 4-TBP (%) 52.1 81.3

Example 2

(Second process)

Β-type zeolite was removed from the reaction mixture obtained in the first step of Example 1 by filtration. The obtained filtrate was distilled under reduced pressure [26.7-4.7 kPa (200-35 mmHg), internal temperature 90-120 degreeC], and water was removed. The moisture concentration of the mixture after water removal was measured to be 0.1% by weight. In addition, the amount of phenol was 1.1 in molar ratio with respect to TBA consumed for the alkylation reaction in the 1st process.

(Third process)

To the internal volume 200 mL four-necked flask equipped with a stirrer, a cooling tube and a thermometer, 100 g of phenol and a mixture after dehydration obtained in the second step were added. This adjusted the amount of phenol to molar ratio 6 with respect to TBA consumed for the alkylation reaction in a 1st process. There, 12.5 g of Y-type zeolite (as described above) substituted with proton was added thereto, and the temperature was raised to 120 ° C., followed by stirring for 1 hour to conduct a potential reaction. The reaction solution was analyzed by gas chromatography to determine the production ratio of each compound and the selectivity and yield of 4-TBP. The results are shown in Table 2.

Item Example 2 1st process 3rd process Composition of reaction solution (%) Phenol4-TBP2-TBP2,4-DTBP 39.454.23.82.6 80.918.50.460.005 Phenolic conversion rate (%) 42.5 Selectivity of 4-TBP (%) 61.2 97.3 Yield of 4-TBP (%) 52.1 82.7

Example 3

(Second process)

Β-type zeolite was removed from the reaction mixture obtained in the first step of Example 1 by filtration. The obtained filtrate was removed by distillation under reduced pressure [26.7-4.7 kPa (200-35 mmHg), internal temperature 90-120 degreeC]. It was 0.1 weight% as a result of measuring the water concentration of the mixture after water removal. In addition, the amount of phenol was 1.1 in molar ratio with respect to TBA consumed for the alkylation reaction in the 1st process.

(Third process)

Into a 100 mL four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, 12.5 g of a mixture after dehydration obtained in the second step and an acidic cation exchange resin (AMBERLYST 15E, manufactured by Organo Co., Ltd.) were heated to 90 ° C., and heated to 1 hour. The reaction was carried out by stirring. The reaction solution was analyzed by gas chromatography to determine the production ratio of each compound and the selectivity and yield of 4-TBP. The results are shown in Table 3.

Item Example 3 1st process 3rd process Composition of reaction solution (%) Phenol4-TBP2-TBP2,4-DTBP 39.454.23.82.6 38.260.01.00.8 Phenolic conversion rate (%) 42.5 Selectivity of 4-TBP (%) 61.2 97.4 Yield of 4-TBP (%) 52.1 87.7

Example 4

(First process)

Into a 200 mL four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, 122.5 g (1.33 mol) of phenol and 12.5 g of β-type zeolite (H-BEA-25, manufactured by Zud-Khemisa) substituted with protons were added and stirred. It was. The temperature was raised to 100 ° C, and 22.6 g (266 mmol) of TBA having a water content of 13% by weight was dropped from the syringe over 3 hours. It stirred at the same temperature for 3 hours, and made the alkylation reaction. The reaction solution was analyzed by gas chromatography to determine the production ratio of each compound, the conversion rate of phenol, the selectivity and yield of 4-TBP. The results are shown in Table 4.

(Second process)

Β-type zeolite was removed by filtration from the reaction mixture obtained in the first step. The obtained filtrate was distilled under reduced pressure [26.7-4.7 kPa (200-35 mmHg), internal temperature 90-120 degreeC], and water was removed. The moisture concentration of the mixture after water removal was measured and found to be 0.15% by weight.

(Third process)

In a 100 mL four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, 12.5 g of a Y-type zeolite (as described above) substituted with a mixture and a proton obtained after the dehydration obtained in the second step was heated up to 120 ° C. for 1 hour. The reaction was carried out by stirring. The reaction solution was analyzed by gas chromatography to determine the production ratio of each compound and the selectivity and yield of 4-TBP. The results are shown in Table 4.

Item Example 4 1st process 3rd process Composition of reaction solution (%) Phenol4-TBP2-TBP2,4-DTBP 73.623.41.81.2 69.529.60.80.2 Phenolic conversion rate (%) 18.4 Selectivity of 4-TBP (%) 90.9 96.7 Yield of 4-TBP (%) 83.9 89.0

Comparative Example 1

Into a 100 mL four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, 12.5 g of β-type zeolite (manufactured by Zude Chemie, H-BEA-25) substituted with phenol and 50.0 g (531 mmol) was added and stirred. The temperature was raised to 100 ° C, and 22.6 g (266 mmol) of TBA having a water content of 13% by weight was dropped from the syringe over 3 hours. It stirred at the same temperature for 2 hours and made the alkylation reaction. The reaction solution was analyzed by gas chromatography. The composition of the reaction solution was phenol (39.0%), 4-TBP (54.0%), 2-TBP (4.0%), 2,4-DTBP (3.0%), and phenol. The conversion rate was 44.5%, the selectivity of 4-TBP was 88.8%, and the yield of 4-TBP was 79.0%. It was 5.0 weight% when the water concentration of the reaction liquid was measured. Thereafter, the β-type zeolite was removed by filtration.

Into a 100 mL four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, 12.5 g of the above-obtained filtrate and proton-substituted Y zeolite (as described above) was heated to 120 ° C. and stirred for 5 hours. The reaction did not proceed.

Comparative Example 2

Into a 100 mL four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, 12.5 g of β-type zeolite (manufactured by Zude Chemie, H-BEA-25) substituted with phenol 50.0 g (531 mmol) and protons were added thereto and stirred. The temperature was raised to 90 ° C. and 19.7 g (266 mmol) of TBA was added dropwise over 3 hours from the syringe. It stirred at the same temperature for 5 hours and made the alkylation reaction. The reaction solution was analyzed by gas chromatography to determine the production ratio of each compound, the conversion rate of phenol, the selectivity and yield of 4-TBP. The results are shown in Table 5. It was 1.0 weight% when the water concentration of the reaction liquid was measured. Thereafter, the β-type zeolite was removed by filtration.

Into a 100 mL four-necked flask equipped with a stirrer, a cooling tube and a thermometer, 12.5 g of the above-obtained filtrate and proton-substituted Y zeolite (as described above) was heated to 120 ° C., and the potential reaction was carried out under stirring. It was. The reaction solution obtained after 1 hour and 5 hours after the start of the reaction was analyzed by gas chromatography to determine the production ratio of each compound, the conversion rate of phenol, the selectivity and yield of 4-TBP. The results are shown in Table 5.

Item Comparative Example 2 Alkylation reaction Potential reaction 1 hour later 5 hours later Composition of reaction solution (%) Phenol4-TBP2-TBP2,4-DTBP 39.054.63.92.5 40.754.43.01.9 40.456.51.81.3 Phenolic conversion rate (%) 40.2 42.3 43.4 Selectivity of 4-TBP (%) 89.5 91.7 94.8 Yield of 4-TBP (%) 71.9 77.6 82.3

Example 5

(First process)

Into a 100 mL four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, 12.5 g of β-type zeolite (manufactured by Zude Chemie, H-BEA-25) substituted with phenol 50.0 g (531 mmol) and protons were added thereto and stirred. The temperature was raised to 100 ° C and MTBE 24.2 g (266 mmol) was added dropwise over 3 hours from the syringe. It stirred at the same temperature for 5 hours and made the alkylation reaction. The reaction solution was analyzed by gas chromatography to determine the production ratio of each compound, the conversion rate of phenol, the selectivity and yield of 4-TBP. The results are shown in Table 6.

(Second process)

Β-type zeolite was removed by filtration from the reaction mixture obtained in the first step. The obtained filtrate was distilled under reduced pressure [26.7 kPa (200 mmHg), internal temperature 30-40 ° C] to remove methanol. It was 0.1 weight% as a result of measuring the methanol concentration of the mixture after methanol removal. In addition, the amount of phenol was 1.1 in molar ratio with respect to MTBE consumed for the alkylation reaction in the 1st process.

(Third process)

Into a 100 mL four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, 12.5 g of Y-type zeolite (as described above) substituted with a mixture and protons obtained after methanol removal in the second step was heated up to 120 ° C. It stirred for time and made electric potential reaction. The reaction solution was analyzed by gas chromatography to determine the production ratio of each compound and the selectivity and yield of 4-TBP. The results are shown in Table 6.

Item Example 5 1st process 3rd process Composition of reaction solution (%) Phenol4-TBP2-TBP2,4-DTBP 49.245.92.52.4 39.458.01.51.2 Phenolic conversion rate (%) 46.0 Selectivity of 4-TBP (%) 73.0 95.6 Yield of 4-TBP (%) 67.3 81.3

Example 6

(Second process)

Β-type zeolite was removed from the reaction mixture obtained in the first step of Example 5 by filtration. The obtained filtrate was distilled under reduced pressure [26.7 kPa (200 mmHg), internal temperature 30-40 ° C] to remove methanol. It was 0.1 weight% as a result of measuring the methanol concentration of the mixture after methanol removal. In addition, the amount of phenol was 1.1 in molar ratio with respect to MTBE consumed for the alkylation reaction in the 1st process.

(Third process)

To a 200 mL internal volume flask equipped with a stirrer, a cooling tube and a thermometer, 100 g of phenol and a mixture after removal of methanol obtained in the second step were added. Thereby, the amount of phenol was adjusted to the molar ratio 6 with respect to MTBE consumed for the alkylation reaction in the 1st process. 12.5 g of Y-type zeolite (as described above) substituted with proton was added thereto, and the temperature was raised to 120 ° C., followed by stirring for 1 hour to conduct a potential reaction. The reaction solution was analyzed by gas chromatography to determine the production ratio of each compound and the selectivity and yield of 4-TBP. The results are shown in Table 7.

Item Example 6 1st process 3rd process Composition of reaction solution (%) Phenol4-TBP2-TBP2,4-DTBP 49.245.92.52.4 80.918.50.460.005 Phenolic conversion rate (%) 46.0 Selectivity of 4-TBP (%) 73.0 97.3 Yield of 4-TBP (%) 67.3 82.7

Example 7

(Second process)

Β-type zeolite was removed from the reaction mixture obtained in the first step of Example 5 by filtration. The obtained filtrate was distilled under reduced pressure [26.7 kPa (200 mmHg), internal temperature 30-40 ° C] to remove methanol. It was 0.1 weight% as a result of measuring the methanol concentration of the mixture after methanol removal. In addition, the amount of phenol was 1.1 in molar ratio with respect to MTBE consumed for the alkylation reaction in the 1st process.

(Third process)

Into an internal volume 100 mL four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, 12.5 g of the mixture after removal of methanol obtained in the second step and β-type zeolite (manufactured by Zude Chemie, H-BEA-25) were added, and the temperature was increased to 120 ° C. The mixture was stirred for 1 hour to undergo a potential reaction. The reaction solution was analyzed by gas chromatography to determine the production ratio of each compound and the selectivity and yield of 4-TBP. The results are shown in Table 8.

Item Example 7 1st process 3rd process Composition of reaction solution (%) Phenol4-TBP2-TBP2,4-DTBP 49.245.92.52.4 39.558.61.10.81 Phenolic conversion rate (%) 46.0 Selectivity of 4-TBP (%) 73.0 96.8 Yield of 4-TBP (%) 67.3 89.1

Example 8

(Second process)

Β-type zeolite was removed from the reaction mixture obtained in the first step of Example 5 by filtration. The obtained filtrate was distilled under reduced pressure [26.7 kPa (200 mmHg), internal temperature 30-40 ° C] to remove methanol. It was 0.1 weight% as a result of measuring the methanol concentration of the mixture after methanol removal. In addition, the amount of phenol was 1.1 in molar ratio with respect to MTBE consumed for the alkylation reaction in the 1st process.

(Third process)

Into a 100 mL four-necked flask equipped with a stirrer, a cooling tube and a thermometer, 12.5 g of the mixture obtained after the removal of methanol obtained in the second step and an acidic cation exchange resin (AMBERLYST 15E) was heated up to 90 ° C. It stirred for time and made electric potential reaction. The reaction solution was analyzed by gas chromatography to determine the production ratio of each compound and the selectivity and yield of 4-TBP. The results are shown in Table 9.

Item Example 8 1st process 3rd process Composition of reaction solution (%) Phenol4-TBP2-TBP2,4-DTBP 49.245.92.52.4 38.260.01.00.8 Phenolic conversion rate (%) 46.0 Selectivity of 4-TBP (%) 73.0 97.4 Yield of 4-TBP (%) 67.3 87.7

Example 9

(First process)

Into a 200 mL four-necked flask equipped with a stirrer, a cooling tube, and a thermometer was added 12.5 g of β-type zeolite (manufactured by Zude Chemis, H-BEA-25) substituted with phenol 125.0 g (1.33 mol) and stirred. . The temperature was raised to 100 ° C and MTBE 24.2 g (266 mmol) was added dropwise over 3 hours from the syringe. It stirred at the same temperature for 5 hours and made the alkylation reaction. The reaction solution was analyzed by gas chromatography to determine the production ratio of each compound, the conversion rate of phenol, the selectivity and yield of 4-TBP. The results are shown in Table 10.

(Second process)

Β-type zeolite was removed by filtration from the reaction mixture obtained in the first step. The obtained filtrate was distilled under reduced pressure [26.7 kPa (200 mmHg), internal temperature 30-40 ° C] to remove methanol. Methanol concentration of the mixture after methanol removal was measured and found to be 0.15% by weight.

(Third process)

Into a 100 mL four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, 12.5 g of Y-type zeolite (as described above) substituted with a mixture and protons obtained after methanol removal in the second step was heated up to 120 ° C. It stirred for time and made electric potential reaction. The reaction solution was analyzed by gas chromatography to determine the production ratio of each compound and the selectivity and yield of 4-TBP. The results are shown in Table 10.

Item Example 9 1st process 3rd process Composition of reaction solution (%) Phenol4-TBP2-TBP2,4-DTBP 73.623.41.81.2 69.529.60.80.2 Phenolic conversion rate (%) 18.4 Selectivity of 4-TBP (%) 90.9 96.7 Yield of 4-TBP (%) 83.9 89.0

Comparative Example 3

(Second process)

Β-type zeolite was removed from the reaction mixture obtained in the first step of Example 5 by filtration. It was 5.0 weight% when the methanol concentration of the reaction liquid was measured.

Into a 100 mL four-necked flask equipped with a stirrer, a cooling tube, and a thermometer, 12.5 g of the above-obtained filtrate and proton-substituted Y zeolite (as described above) was heated to 120 ° C., and stirred for 5 hours. The reaction did not proceed.

According to the present invention, 4-alkyl phenols can be industrially advantageously produced at high selectivity and high yield. As a result, 4-alkyl phenols of high purity can be produced.

Claims (9)

In the presence of a synthetic zeolite, the fourth unsubstituted phenols and alkyl alcohol or alkyl ether are reacted at a temperature of 50 to 110 ° C. (first step), and in the case of using alkyl alcohol in the first step, When the produced water contained is removed, and when alkyl ether is used in the first step, the produced alcohol contained in the liquid phase is removed in the obtained reaction mixture (second step), and then after removal of the generated water or alcohol A method for producing 4-alkylphenols, characterized in that the reaction reaction is carried out in the reaction mixture at a temperature of 90 to 150 ° C in the presence of an acid catalyst (third step). The reaction mixture according to claim 1, wherein the fourth unsubstituted phenols and the alkyl alcohol are reacted at a temperature of 50 to 110 ° C in the presence of a synthetic zeolite (first step), and the resulting water contained in the liquid phase in the reaction mixture is removed. And (second step), followed by a potential reaction in the presence of an acid catalyst at a temperature of 90 to 150 ° C. (third step) in the reaction mixture after removal of the produced water. The method for producing 4-alkylphenols according to claim 2, wherein the reaction is conducted by adjusting the water concentration in the liquid phase of the reaction mixture to 0.5% by weight or less in the third step. 4. The potential reaction according to claim 2 or 3, wherein the amount of fourth-position unsubstituted phenols in the reaction mixture in the third step is adjusted in a range of 1 to 10 times the molar amount of the alkyl alcohol consumed in the alkylation reaction in the first step. Method for producing 4-alkylphenols. The method for producing 4-alkylphenols according to any one of claims 2 to 4, wherein the fourth-position unsubstituted phenols are phenols and the alkyl alcohol is tert-butanol. The reaction mixture according to claim 1, wherein the fourth unsubstituted phenols and the alkyl ether are reacted at a temperature of 50 to 110 ° C in the presence of a synthetic zeolite (first step), and the produced alcohol contained in the liquid phase is removed in the reaction mixture obtained. And (second step), followed by a potential reaction (third step) in the presence of an acid catalyst at a temperature of 90 to 150 ° C. in the reaction mixture after removal of the produced alcohol. The method for producing 4-alkylphenols according to claim 6, wherein the reaction is carried out by adjusting the alcohol concentration in the liquid phase of the reaction mixture to 0.5% by weight or less in the third step. 8. The potential reaction according to claim 6 or 7, wherein the amount of the fourth-position unsubstituted phenols in the reaction mixture in the third step is adjusted in the range of 1 to 10 times the molar amount of the alkyl ether consumed in the alkylation reaction in the first step. Method for producing 4-alkylphenols. The process for producing 4-alkylphenols according to claim 6, wherein the fourth unsubstituted phenol is phenol and the alkyl ether is methyl tert-butyl ether.