WO2008123530A1 - Method for production of solid acid catalyst comprising carbonaceous material having sulfonate group, and use of the solid acid catalyst - Google Patents

Abstract

Disclosed is a solid acid catalyst comprising a carbonaceous material having a sulfonate group, which is useful for various acid catalyst reactions including the hydration of an olefin and has a high reaction activity. A solid acid catalyst comprising a carbonaceous material having a sulfonate group can be produced by employing a two-step process comprising heating an organic material such as a cellulose, a phenol resin, a wood plant and a grass plant to carbonize the organic material and then sulfonating the carbonized product, wherein the conditions for the carbonization and the time required for the sulfonation in the sulfonation step are controlled. The solid acid catalyst has a high reaction activity in various acid catalyst reactions including the hydration of an olefin.

Description

 --

A method for producing a solid acid catalyst comprising a sulfonic acid group-containing carbonaceous material and its use

Technical field

 The present invention relates to a method for producing a solid acid catalyst comprising a sulfonic acid group-containing carbonaceous material obtained by subjecting an organic substance to carbonization treatment by heating and then sulfonation treatment, and use thereof. Background art

Sulfuric acid is an important catalyst widely used in various chemical reactions. However, in general, a large amount of sulfuric acid is required, there is a problem of corrosion of the equipment, separation of sulfuric acid from the product after the reaction, recovery, purification, reuse process, in the product There are many problems such as neutralization of residual sulfuric acid, removal and disposal of the salt produced thereby, and wastewater treatment, and the fact that these processes require a lot of energy. is there. By using a solid acid catalyst as a substitute for a mineral acid catalyst such as sulfuric acid, the apparatus does not corrode, and the various steps after the above reaction can be omitted or greatly simplified. Therefore, it is useful as a catalyst for various chemical reactions, and various solid acids have been developed. Typical solid acids include inorganic compounds such as silica alumina, crystalline aluminosilicate (zeolite), and heteropoly acid. On the other hand, olefin hydration is an industrially important reaction for the production of alcohols and ketones, and an acid catalyst is used for this reaction. Iso Pro Pill Alcohol or 2 — Buyu Knoll is produced by various methods using hydration of propylene or n-butene (Non-patent Document 1, Non-patent Document 2). In many processes of the hydration reaction process, sulfuric acid is used as a catalyst. In addition to the above-mentioned problems, there are problems with many by-products, and in order to solve these problems, solid acid is used. Some catalysts are also used. In this case, the inorganic solid acid catalyst described above is generally not used because its activity decreases in the presence of water, and a catalyst having phosphoric acid supported on an inorganic carrier is used. There is a problem that phosphoric acid is detached from the carrier. In addition, strong acid ion exchange resins that are polymers having sulfonic acid groups on the crosslinked polystyrene skeleton are also used, but the range of use is limited due to problems such as low heat resistance and high cost. Has been. Super strong solid acid “Nafion” based on fluorine-substituted polyolefin with heat resistance

^ Dunn registered trademark) has also been developed, but it is too expensive for industrial use. Under such circumstances, a sulfonated carbonaceous material obtained by carbonizing and sulfonating aromatic compounds, heavy petroleum oils, sugars, and other organic substances with potassium hydroxide has been developed (Patent Document 1). As a solid acid catalyst, it has attracted attention recently due to its high activity in various chemical reactions, excellent heat resistance, and low sulfur content. Attempts have been made to evaluate the catalyst as a hydrolysis reaction, alkylation reaction, hydration reaction of a refin (non-patent document 3, non-patent document 4, non-patent document 5, patent Reference 2). However, for example, the hydration reaction of olefins has been reported to hydrate 2,3-dimethyl-2-butene to obtain 2,3-dimethyl-2-butanol in low yield. However, from the viewpoint of practicality, development of a solid acid having higher catalytic activity is desired. However, it is well known that hydration of normal benzene yields 2-butanol and dehydrogenation of 2-bubutane yields methyl X tilketone. . Methyl ethyl ketone is an industrial chemical that is extremely important as a solvent for paints, adhesives, etc., and as a cleaning agent for various applications. Currently, 2 butyl alcohol uses sulfuric acid as a catalyst. It is produced by a method that uses a slightly heavy P-po acid catalyst. However, the sulfuric acid method has the problem of waste sulfuric acid and the corrosion of the equipment, while the te polyacid method is technically difficult, such as using a supercritical state, and is inexpensive. Efficient 2 — manufacturing technology of buenoluol is desired.

In addition, a method for producing acetone and phenol by decomposing cumene hydroperoxide is an extremely important chemical process industrially. This reaction proceeds in the presence of an acid catalyst, and dilute sulfuric acid is currently used (Non-patent Document 6). The sulfuric acid aqueous solution is highly corrosive and has a problem of waste sulfuric acid. In addition, there is a problem that a large amount of energy is required to separate the product from the reaction solution, and an alternative solid acid catalyst is also desired. The sulfonation method for producing the sulfonated carbonaceous material is based on the conventional method of sulfonated organic carbonized product, if <is directly organic material is concentrated sulfuric acid, <is sulfonated in fuming sulfuric acid. It is clear that it can be obtained. However, the optimum sulfonation conditions for the production of solid acid catalysts are not clarified. Furthermore, it is not completely clarified whether the one-step method for directly sulfonating organic substances is good or the two-step method for sulfonating organic substances after carbonization. There is known a method for obtaining a solid acid catalyst by heat-treating polycyclic aromatic hydrocarbons in concentrated sulfuric acid or fuming sulfuric acid, but what about the two-stage method? No mention. --As described above, the optimization of the sulfonation process for the production of solid acid catalyst in the production of the sulfonated carbonaceous material has not yet been made.

 Non-Patent Document 1: Catalyst, 18 (6), 180 (1976)

 Non-Patent Document 2: Journal of Petroleum Society, 34 (3), 201 (1991)

 Non-Patent Document 3: Domen et al., “Synthesis Conditions and Catalysis of Carbon-Based Solid Strong Acids”, The 85th Annual Meeting of the Chemical Society of Japan (2005) .2B5-43 Non-Patent Document 4: Hara, M. et al. Nature, 438 (10),

178, November (2005)

 Non-patent document 5: Hara et al., PETROTECH 29 (6), 411 (2006) Non-patent document 6: New petrochemical process, P 239 (1986)

 Patent Document 1: Japanese Patent Application Laid-Open No. 2004-238311

 Patent Document 2: International Publication WO 2005/029508 A1 Disclosure of Invention

An object of the present invention is to provide a method for producing a solid acid catalyst comprising a sulfonic acid group-containing carbonaceous material having high reaction activity, which is useful for each acid catalyzed reaction such as olefin hydration. Installing by it was or in, in the this to provide an efficient manufacturing method of O Lev fin hydration reaction or by that the esterification reaction compound obtained in fatty acids using a solid acid catalyst ₀ It also provides an inexpensive and efficient method for producing ketons, and also provides an inexpensive and efficient method for producing phenols. In view of the above-mentioned problems of the prior art, the present inventors conducted extensive research and as a result, in the production process of the solid acid catalyst comprising the sulfonic acid group-containing carbonaceous material, the organic matter was heat treated and carbonized. The use of a two-stage process for sulfonation later and the control of carbonization conditions further As a result, the inventors have found that the reaction activity as a solid acid catalyst can be dramatically improved by controlling the conversion time, and the present invention has been completed. That is, the first aspect of the present invention is the production of a solid acid catalyst comprising a carbonic material containing a threphonic acid group obtained by carbonizing and sulfonating an organic substance by heating in an inert gas atmosphere.

The Jo method is characterized in that after carbonization treatment, sulfonation treatment is performed, the temperature of the carbonization treatment is 300,600 t: and the sulfonation time force is 5 minutes to 1 o 0 minutes. The present invention relates to a method for producing a solid acid catalyst comprising a sulfonic acid group-containing ash-containing material.

 The first aspect of the present invention relates to a method for producing a solid acid catalyst comprising a sulfonic acid group-containing carbonaceous material characterized in that, in the first aspect of the present invention, the sulfonation temperature force is 2025.

Further, a third aspect of the present invention comprises a sulfonic acid group-containing carbonaceous material characterized in that, in the first to second aspects of the present invention, concentrated sulfuric acid is used as a sulfonating agent. The present invention relates to a method for producing a solid acid catalyst.

 Furthermore, a fourth aspect of the present invention relates to a method for producing a sulfonic acid group-containing carbonaceous material characterized in that cellulose is used as an organic substance in the second aspect of the present invention.

 Furthermore, a fifth aspect of the present invention is a solid acid comprising a sulfonic acid group-containing carbonaceous material characterized in that a phenol resin is used as the organic substance in the first to third aspects of the present invention. Regarding catalyst production methods

 Further, a sixth aspect of the present invention is a sulfonic acid group-containing carbonaceous material characterized in that woods and z or herbs are used as organic substances in the first to third aspects of the present invention. Is a method for producing a solid acid catalyst

Further, the seventh aspect of the present invention is the product of the D peak of the Raman analysis value of the sulfonic acid group-containing carbonaceous material according to the first to sixth aspects of the present invention. The integral intensity of the partial intensity / G peak is 0 to 0.7 or the peak of the Raman spectrum is not observed.

The present invention relates to a method for producing a solid acid catalyst comprising a sulfonic acid group-containing ashy material.

 Furthermore, according to the eighth aspect of the present invention, the olefin hydration reaction is carried out using the solid acid catalyst obtained by the method described in the first to seventh aspects of the present invention. The present invention relates to a method for producing an olefin hydrate product characterized by this.

 Further, according to a ninth aspect of the present invention, an epoxy etherification reaction is carried out using the solid acid catalyst obtained by the methods described in the first to seventh aspects of the present invention. A method for producing ethers characterized by

 Furthermore, a tenth aspect of the present invention is characterized in that an acid decomposition reaction of an aralkylhydroxide is performed using the solid acid catalyst produced by the method according to any one of the first to seventh aspects of the present invention. It relates to the method of making phenols from aralkyl hydride P-peroxide.

 Further, the eleventh aspect of the present invention is that the aralkylhydride peroxide is cumenehydride peroxide and the phenols are phenol. Relates to a method for producing the phenols according to 10.

 Furthermore, in the twelfth aspect of the present invention, an esterification reaction of alcohol and strong rubonic acid is carried out using the solid acid catalyst obtained by the method described in the first to seventh aspects of the present invention. The present invention relates to a characteristic ester production method.

 Furthermore, the thirteenth aspect of the present invention relates to a method for producing a kenne characterized by carrying out a dehydrogenation reaction of the olefin hydrate product obtained according to the eighth aspect of the present invention.

Further, according to the fourteenth aspect of the present invention, the olefin hydration product is 2-butanol, and the keton obtained by the dehydrogenation reaction is methyl X The present invention relates to a method for producing ketones according to the twelfth aspect of the present invention, which is tilketone. The invention's effect

 The solid acid catalyst comprising the sulfonic acid group-containing ash material of the present invention can be used in various chemical reactions, including hydration reaction of olefins, etherification reaction, or aralkyl hydride peroxide. It has high activity as a solid acid catalyst for acid decomposition reactions, etc., and can be produced easily and inexpensively; therefore, it can be supplied in large quantities for industrial use, and also contains the sulfonic acid group of the present invention. Manufacture of olefin hydrates, ethers, etc. using solid acid catalysts made of carbonaceous materials, or phenols by the acid decomposition reaction of aralkylhydride or Πperoxy. In this case, the activity of the catalyst is high <, the steps of neutralizing and purifying the catalyst after the reaction are unnecessary, the catalyst can be easily separated and reused, and there is no problem of corrosion of the apparatus. Can produce huge products efficiently with low costIn addition, the solid acid catalyst comprising the sulfonic acid group-containing ash-like material of the present invention is also used for esterification reaction, hydrolysis reaction of esters and ethers, and the like.

 In addition, when the solid acid catalyst of the present invention is used, the olefin hydrate can be produced at low cost and efficiently as described above. By dehydrogenating fin hydrate, canes can be produced efficiently at low cost. BEST MODE FOR CARRYING OUT THE INVENTION

 The present invention will be described in more detail below.

The solid acid catalyst comprising the sulfonic acid group-containing argylic material of the present invention is obtained by carbonizing the organic synthetic compound or organic natural compound as a starting material, or a composition thereof, and then sulfonating the composition. . --

(About raw materials)

 Any raw material for producing a solid acid catalyst comprising a sulfonic acid group-containing carbonaceous material can be used as long as it can be carbonized. For example, organic low molecular weight compounds such as aromatic hydrocarbons, heavy oil, petroleum heavy hydrocarbon mixtures such as petroleum pitch and tar, saccharides and starches, natural organic materials such as cellulose and amylose, and phenols Organic polymer compounds such as thermosetting resins such as vinyl resins, furan resins, urea resins, melamine resins, unsaturated polyester resins, and epoxy resins. Among these organic materials, when cellulose or an organic material containing cellulose is used as a raw material, the resulting solid acid made of a sulfonic acid group-containing carbonaceous material has excellent heat resistance, and is particularly preferable. . In particular, when woods and / or herbs are used as organic substances containing cellulose, they are extremely inexpensive, unlike refined cellulose, and are therefore less expensive than sulfonic acid group-containing carbonaceous materials. This solid acid catalyst can also be produced at a very low cost. Further, when a phenol resin is used as a raw material, the activity of the resulting solid acid catalyst comprising a sulfonic acid group-containing carbonaceous material is excellent, which is particularly preferable.

(Conditions for production of solid acid catalyst consisting of sulphonic acid-containing ashy material)

 In the production of the solid acid catalyst comprising the sulfonic acid group-containing carbonaceous material of the present invention, the sulfonation treatment is performed after the carbonization treatment. In a method in which carbonization treatment and sulfonation are simultaneously performed, a highly active solid acid catalyst cannot be obtained. The following describes the preferred mode when sulfonated after carbonization.

(Carbonization)

Carbonization is heated in an inert gas atmosphere such as nitrogen or argon. --It is done by doing. The conditions for the carbonization treatment are selected weekly depending on the type of raw material used and the properties of the solid acid catalyst comprising the desired sulfonic acid group-containing cherryous material, and thereby an amorphous black solid. (Carbide) is obtained. The temperature is 3 0 0 6 0 0, good

5 or 3 o 0 ~; When the temperature of the carbonization treatment is less than the lower limit of this range, the activity of the solid acid catalyst made of a sulfonic acid group-containing ashy material obtained by sulfonating this is inferior, or It tends to cause problems such as high solubility in water or organic matter. On the other hand, the temperature exceeds the upper limit of this range.

In the case of 10 degrees, a sufficient amount of soap is required for sulfonation.

J-Leonic acid group cannot be imparted, and the catalytic activity for various chemical reactions of t * l acid catalyst from the resulting sulfonic acid group-containing carbonaceous material tends to be insufficient. It is in.

 The heating time for carbonization is:! ~ 100 hours, preferably

15 is 2 to 1 δ hours. When the carbonization treatment time is less than the lower limit of <„, the activity of the solid acid catalyst comprising the sulfonic acid group-containing carbonaceous material obtained by sulfonation treatment is inferior or water While there is a tendency to cause problems such as a large amount dissolved in organic matter, etc., carbonization required in the upper limit of this range is required.

20 is progressing well and it is not necessary to spend more than that.

 If wood or herb is used as a raw material, it is desirable to make the particle size uniform by pre-grinding in order to promote uniform carbonization.

 Δ 5

 (Sulfonation)

 The conditions for the sulfonation treatment are appropriately selected depending on the properties of the solid acid catalyst made of the desired sulfonic acid group-containing ash-based material of the raw material used, but the carbide obtained by the carbonization treatment is used. ,nitrogen,

30 In concentrated sulfuric acid or fuming sulfuric acid in an inert gas atmosphere such as argon The sulfonic acid group is added to the carbide skeleton. When fuming sulfuric acid is used, the content of sulfonic acid groups to be introduced increases, but the activity of the resulting solid acid catalyst comprising the sulfonic acid group-containing carbonaceous material tends to decrease. It is preferable to use concentrated sulfuric acid. The amount of concentrated sulfuric acid or fuming sulfuric acid to be used is not particularly limited, but it is 5 100 times (mass ratio), preferably 10 80 times the amount of carbide to be sulfonated. If the lower limit of this range is not reached, a sufficient amount of sulfonic acid groups cannot be imparted to the carbide, and the resulting solid acid catalyst comprising a sulfonic acid group-containing carbonaceous material can be used for various chemical reactions. If the catalyst activity tends to be insufficient, if the upper limit of this range is exceeded, more concentrated sulfuric acid or fuming sulfuric acid will be used, and the spent sulfuric acid will be treated. Including cost increase

 The temperature of the sulfonation treatment is 2 0 2 o 0 t :, preferably 5

0 2 0 0. If the degree of sulfonation treatment is less than the lower limit of this range, sufficient sulfonic acid groups cannot be imparted to the carbide, resulting in a solid acid catalyst comprising a sulfonic acid group-containing carbonaceous material. When the temperature exceeds the upper limit of one range, the catalytic activity for various chemical reactions tends to be insufficient, and the added sulfonic acid group is decomposed. The sulfonation time should be between o minutes and 1550 minutes, more preferably between 15 minutes and 90 minutes. The sulfonation time is below the lower limit of this range. If it is not possible to impart sufficient sulfonic acid groups to the carbide, the control becomes extremely difficult. However, since the catalytic activity per unit sulfonic acid group tends to be higher as the time is shorter, sulfonation over 1550 minutes is not preferable because the reaction activity is not sufficient. In addition, since the amount of sulfonic acid is almost saturated by 1550 minutes, it is possible to increase the sulfonic acid group for more than 1550 minutes. --There is no need for time. It has been known so far that a solid acid catalyst comprising a sulfonic acid group-containing carbonaceous material can be obtained with high activity by a sulfonation treatment in a short time of 5 minutes to 1500 minutes or less. In the past, it has been considered that a sulfonation treatment for a long time of 5 hours or longer is desired (Patent Document 2). After the carbonization and sulfonation treatment steps, excess sulfuric acid is removed by washing the sulfonated product, preferably with hot water, and further dried to obtain a black powder. A solid acid catalyst comprising the sulfonic acid group-containing carbonaceous material of the present invention can be obtained. Washing with hot water is about

It is convenient to carry out under reflux at 100. It is also possible to shorten the cleaning time by washing at a high temperature under pressure.

(About acid group content)

 The acid group content of the sulfonic acid group-containing carbonaceous material of the present invention is not less than 1 mmol / g, preferably not less than 1.5 mmol / g. When the acid group content is less than 1 mmol / g, the resulting solid acid catalyst comprising a sulfonic acid group-containing carbonaceous material is not active as a solid acid catalyst for various chemical reactions. It tends to be sufficient. Here, the acid group content is a value obtained by measuring a solid acid made of a sulfonic acid group-containing carbonaceous material by a back titration method, and the sulfonic acid produced by the sulfonation treatment. This refers to the content of a combination of a group and the force generated during carbonization.

(Degree of graphitization = Raman spectroscopy)

In general, the degree of carbonization when carbonizing organic substances by heating is often expressed by the degree of graphitization. As an indicator of the degree of graphitization, the D peak in Raman spectroscopy is used. And G --The strength ratio of the coffee is used. In other words, D peak integrated intensity Z

It is shown that the graphitization degree progresses as the value of the integrated intensity ratio of the G peak increases. For example, in a conventional sulfonated carbonaceous material disclosed in Non-Patent Document 5 using aromatic hydrocarbon, heavy oil, glucose or the like as a starting material, the graphitization degree by this lan spectroscopic analysis is used. An estimate of the magnitude of the measurement, or the force of one pound 卜 has been made. Even in the solid acid catalyst comprising the sulfonic acid group-containing carbonaceous material of the present invention, as the sulfonation time increases, the integrated intensity ratio of the D peak integrated intensity ZG peak increases. It is recognized that the catalyst activity decreases <_ if it becomes too large. Preferred integral intensity of D peak G integral ratio of G peak is 0.0 to 07. Also, for producing a solid acid catalyst comprising a sulfonic acid group-containing ashy material of the present invention Depending on the raw material, there are those that do not give the peak of the Raman spectrum, but these are also preferably used.

(About X-ray diffraction analysis)

The solid acid catalyst comprising the sulfonic acid group-containing carbonaceous material of the present invention cannot have any structure from the X-ray diffraction pattern, and is substantially amorphous. In Patent Document 1, it is described that when carbonizing raw material pitch or the like, a carbonaceous mesomorph X is formed. This is because the obtained sulfonated ash material is crystalline. According to Patent Document 3, it is preferable that the peak of the [0 0 2] plane be detected in the obtained carbonaceous material into which the sulfonic acid group is introduced. However, “amorphous carbon” is suggested, suggesting that it has a partially crystalline structure. However, the sulfonic acid group-containing carbonaceous material of the present invention is different from the sulfonated carbonaceous materials disclosed in these prior arts. --

The solid acid catalyst of the present invention may be in the form of a powder or may be formed into a granular shape, a spherical shape, a plate shape, a pellet shape, or the like. When molding into these shapes, the binder

Molding may be performed by blending an inorganic substance called “-”. This binder is intended to improve the moldability, the strength of the molded catalyst, and improve mechanical properties such as frictional properties. Silica and aluminum are preferred.

<Used. The solid acid catalyst comprising the sulfonic acid group-containing carbonaceous material of the present invention obtained as described above has sufficient acid strength and acid for various chemical reactions as a solid acid catalyst. Yes. The solid acid catalyst comprising the sulfonic acid group-containing ash-based material of the present invention is a hydration reaction or etherification reaction of phenol, esterification reaction of alcohol and acid, It is particularly useful as a catalyst for reactions under various polar conditions such as hydrolysis. In other words, it exhibits excellent activity and tolerance in reactions using polar substances such as alcohol and water as the reaction substrate, and therefore ⁽ —shows excellent properties as a solid acid catalyst for these polar reactions. Oxygen decomposition reaction of peroxidic oxide, which exhibits excellent properties as a catalyst ο Below, olefin hydration reaction using a solid acid catalyst comprising a sulfonic acid group-containing carbonaceous material of the present invention ( We will explain the reaction between olefin and water, etherification reaction (reaction between olefin and alcohol), and esterification reaction (reaction between carboxylic acid and alcohol).

(Reaction raw materials)

The polyolefin used in the present invention is not particularly limited and is linear. --It may be in the shape of a ring, a branch, or a ring, but it has 2 carbon atoms

 Olefins of ~, specifically butenes such as propylene, 1-butene, 2 butene and isobutene are preferred. The water used for the hydration reaction is not particularly limited, but it is preferable to use ion exchange water or distilled water (including steam condensed water).

 There are no particular restrictions on the alcohols used in the etherification reaction, but alcohols having 1 to 4 carbon atoms, specifically methanol, ether, and organic pills. One is preferred.

 The molar ratio of water or alcohols to olefins is not particularly limited, but if the amount of water or alcohols is too small, side reactions such as dimerization of olefins will occur, and too much will occur. This is not preferable as productivity will deteriorate.

 Alcohols used in the esterification reaction according to the present invention can be the same as the above alcohols. Examples of the carponic acid include saturated or unsaturated carboxylic acids having 1 to 4 carbon atoms, such as acetic acid, acrylic acid, and maleic acid. The molar ratio of the alcohol to the acid is not particularly limited, but is usually from 0.! To 100. Ί: i, anhydride may be used for carboxylic acid. (About reaction conditions)

The reaction conditions of the olefin hydration reaction and etherification reaction using the solid acid catalyst comprising the sulfonic acid group-containing carbonaceous material of the present invention can be selected. However, if the reaction temperature exceeds 2550 V, the sulfonic acid group-containing carbonaceous material may be decomposed during the reaction. In addition, the reaction conditions can be selected weekly in the case of esterification of strong uronic acid with alcohols. Further, in each of the above reactions using the solid acid catalyst containing sul 71 of the present invention and an acid group-containing chlorophyll material, it is possible to use means for reactive distillation. --The reaction pressure is not particularly limited and can be selected as appropriate.

If it exceeds 20 M Pa, problems such as an increase in equipment cost 生 ず る arise.

 As the reaction phase, any of a gas phase, a liquid phase, and a gas-liquid mixed phase can be adopted. In the case of an esterification reaction, the reaction is likely to proceed if water generated as the reaction proceeds is appropriately removed from the reaction system. A solvent can be used for the hydration reaction. O The solvent is preferably amphiphilic to prevent the reaction solution from separating into an aqueous phase and an oil phase. For example, ethers, glycol ethers, alcohols, canes and the like can be used. In the case of the etherification reaction, a solvent can be used in the same manner.

(Reaction process using the solid acid catalyst of the present invention)

 Since the hydration reaction of the polyolefin using the solid acid catalyst comprising the sulfonic acid group-containing carbonaceous material of the present invention is a direct hydration method (one-stage reaction), indirect hydration using a sulfuric acid catalyst. Compared with the method (two-stage reaction of sulfate esterification and hydrolysis), the process is simple. In addition, the indirect hydration method requires a neutralization purification step for sulfuric acid removal and a concentration step for sulfuric acid reuse, and the process is complicated. In the method of the present invention, the catalyst is solid. The catalyst can be easily separated and reused by filtration, centrifugation, etc., and the reaction solution after removing the catalyst contains no acid catalyst component. Such a neutralization purification step is unnecessary. After removing the catalyst, it can be appropriately purified by distillation or the like. Reactive distillation is also possible. The ether etherification reaction of the present invention is generally performed by reaction distillation or fixed bed.

There are no particular restrictions on the form of the reactor in the hydration reaction, etherification reaction, or esterification reaction of the present invention. --However, it can be batch, continuous, or semi-continuous. Further, it may have any shape such as a tank reactor, a tower reactor, or a loop reactor. The type of contact between the catalyst and the reactant may be any of suspended phase, fixed bed, etc. In particular, a method in which the catalyst is suspended in a tank reactor equipped with a stirring device or a method in which the catalyst is used as a solid bed and the reactants are continuously circulated is preferably used.

 In both the hydration reaction and the etherification reaction or the esterification reaction, the use of the solid acid catalyst comprising the sulfonic acid group-containing carbonaceous material of the present invention makes it possible to achieve high heat resistance. It is possible to operate at high temperatures, and as a result, the reaction rate is improved, and the reactor can be downsized. In addition, the catalyst replacement frequency is reduced due to the heat resistance of the catalyst. Next, the acid decomposition reaction of aralkylhydroxide using a solid acid catalyst comprising a sulfonic acid group-containing carbonaceous material according to the present invention will be described. A secondary or secondary ash atom in the side chain of an aromatic hydrocarbon compound is substituted with a hydroxy group, and has the structure represented by Formula D 1 below. In the presence of an acid catalyst, the corresponding phenols and canes or aldehydes are produced. And passwords are generated.

Ar- C- OOH

 [Formula 1]

In Formula 1, R i and R ₂ are alkyl groups — — Or represents a hydrogen atom, and the total number of carbon atoms in R ₂ is 1 or more.

[Equation 2] Regarding the method of acid decomposition of aralkyl hydroperoxide, we will use cumene hydroperoxide as an example. The reaction is carried out in the liquid phase. As the form of the reactor, either a solid phase flow type filled with a solid acid catalyst or a batch type stirred layer type reactor in which the catalyst is suspended in the reaction solution can be used. The reaction temperature is 50 to 90, preferably 60 to 80. Since the acid decomposition reaction of cumene-and-peroxide is an exothermic reaction, it is desirable to dilute the reaction solution with an inert diluent if necessary to mitigate the temperature rise due to heat of reaction. . When using a batch reactor, it is possible to maintain the reaction temperature and remove the heat of reaction by using a diluent with an appropriate boiling point and boiling and refluxing the diluent. It is. In the case of batch reaction, the proportion of the sulfonic acid group-containing carbonaceous material of the present invention used as a solid acid catalyst is 1/100 to 1 of the charged hydroperoxide (weight ratio). ) The reaction time is preferably 15 minutes to 8 hours. In the case of the stationary phase flow type, the LHSV of the reaction raw material mixture is preferably from 0.1 to 1.0 (L-feed / L-catalyst / Hr). Here we touch on the production of ketons. The sulfonic acid of the present invention Using a solid acid catalyst made of a group-containing carbonaceous material, the second alcohol can be produced by the above-mentioned olefin hydration reaction (reaction between olefin and water). I can do it. By dehydrogenating the secondary alcohol, the corresponding keton can be produced. For example, 2-hydrogen obtained from hydration of propylene can be obtained by dehydrogenating 2-propanol, and 2-butanol obtained from hydration of normal butene. Methylethylketone can be produced by dehydrating the alcohol. The dehydrogenation reaction can be performed by a generally known method. For example, using copper-zinc catalyst, reaction temperature 3 0 0-5 0

0, pressure 0 — Can be done with I M Pa. This dehydrogenation reaction is an endothermic reaction, so it is advantageous from the viewpoint of chemical equilibrium at a high temperature.However, an excessively high temperature is preferable because it causes a decomposition reaction or causes sintering of the catalyst. The above-mentioned temperature range is preferable. In addition, since it is a dehydrogenation reaction, the reaction proceeds more advantageously at a lower pressure. The alcohol produced using the solid acid catalyst comprising the sulfonic acid group-containing carbonaceous material of the present invention is produced by a conventional method using sulfuric acid or a method using super-polyacid using supercritical conditions. Compared to alcohol. The manufacturing method is simple and the equipment is less corroded and less wasteful, so it is inexpensive and can be manufactured by dehydrating it. I can do it. In other words, the present invention provides a method for producing methyl ethyl ketone from normal butene which is economical and economically less burdensome on the environment. The present invention will be specifically described below by way of examples. It is not limited to this

[Example 1]

(Preparation of solid acid catalyst consisting of sulfonic acid group-containing carbonaceous material) --40.0g of cellulose was heated at 400T for 4 hours under nitrogen atmosphere to obtain 11.2g of carbide. Concentrated sulfuric acid (150 g) was added to the carbide (3.0 g), and the mixture was heat-treated in a nitrogen atmosphere for 150 minutes for 15 minutes for sulfonation. After sulfonation, the black solid is filtered using a glass filter, washed repeatedly with hot water under reflux (at about 100), and continued until no sulfuric acid is detected in the washing solution. It was. Next, drying was performed to obtain 3.1 g of a solid acid catalyst A made of an amorphous black powder containing a sulfonic acid group-containing carbonaceous material. The acid amount of the obtained solid acid catalyst comprising the sulfonic acid group-containing carbonaceous material was examined by back titration. As a result, it was 2.3 mmol / g.

(Analysis of solid acid catalyst)

 X-ray analysis of solid acid catalyst A made of sulfonic acid group-containing carbonaceous material was performed. For X-ray analysis, measurement was performed using an X-ray diffractometer (MXP18VAHF) manufactured by MacScience. As a result, no peak that could identify the structure was detected from the analysis pattern of the solid acid catalyst made of the resulting sulfonic acid group-containing carbonaceous material, indicating that it was an amorphous substance. Elemental analysis of solid acid catalyst A made of sulfonic acid group-containing carbonaceous material was performed. Elemental analysis was performed using Elementar Vario EL. As a result, in the solid acid catalyst composed of the sulfonic acid group-containing carbonaceous material, 7.0 × 10-3 sulfur was detected in the S / C ratio, and it was found that the sulfonic acid group was introduced. . A 13C-DDMAS nuclear magnetic resonance spectrum analysis of the solid acid catalyst A made of a sulfonic acid group-containing carbonaceous material was performed. In this analysis, measurement was performed using NMR System 400WB manufactured by Varian. As a result, it was confirmed that most of the carbon was derived from aromatics.

Solid acid catalyst made of carbonaceous material containing sulfonic acid group A graphite --The degree of conversion was measured. For the measurement, a Raman spectroscopic analyzer was used. For this analysis, a laser Raman spectrometer HOLOLAB 5000R was used. At that time, calculates the integrated intensity ratio of D peak observed around G peak and 1400 cm ¹ observed around 1580 cm ^1, was the peak intensity ratio D / G and degree of graphitization. As a result, the graphitization degree was confirmed to be 0.597.

(Hydration reaction)

 A 200 cc autoclave with a stirrer is charged with 9.0 g (0.5 mol) of distilled water and 15.0 g of dioxane (solvent), and 0.20 g of solid acid catalyst A composed of a sulfonic acid group-containing carbonaceous material is added and sealed. 10.5 g (0.25 mol) of propylene was enclosed. Next, the temperature was raised to 120 with stirring at 700 rpm, the pressure was adjusted to 5 MPa with nitrogen, and the hydration reaction was carried out for 2 hours while maintaining 120. After completion of the reaction, the reaction solution was cooled and quantitative analysis was performed by TCD-GC. As a result, the amount of isopropyl alcohol converted per unit catalyst amount per unit time was 0.57 mmol / g-cat. / Hr. The results are shown in Table 1. (Etherification reaction)

Into a 200 cc autoclave with a stirrer is charged 15 g (0.25 mol) of isopropyl alcohol, 0.20 g of a solid acid catalyst A made of a sulfonic acid group-containing carbonaceous material is added and sealed, and propylene is added. 21.0 g (0.5 mol) was sealed. Next, the temperature was raised to 110 while stirring at 700 rpm, the pressure was adjusted to 5 MPa with nitrogen, and then the etherification reaction was carried out for 2 hours while maintaining at 110. After completion of the reaction, the reaction solution was cooled and the product was quantitatively analyzed by TCD-GC. As a result, the amount of di-propyl ether converted per unit catalyst amount per unit time was 1.26 mmol / g-cat. / Hr. The results are shown in Table 1. --

[Example 2] and [Comparative Examples 1 and 2]

 (Preparation of solid acid catalyst comprising sulfonic acid group-containing carbonaceous material) The raw materials, carbonization treatment and sulfonation treatment conditions described in Table 1 were used, and the other operations were performed in the same manner as in Example 1 above. Solid acid catalysts B, D,

E was manufactured. The cellulose used as the raw material was the same as that used in Example 1. Table 1 shows the results of a back titration study of the amount of acid in the solid acid catalyst made of the sozorephonic acid group-containing carbonaceous material.

(Analysis of solid acid catalyst made of sulfonic acid group-containing carbonaceous material) Solid acid catalyst B, D, made of sulfonic acid group-containing carbonaceous material

For E, the X-ray analysis, 13 C-DD MAS nuclear magnetic resonance spectrum analysis, and measurement of graphitization degree were performed. The same results as in Example 1 were obtained for the X-ray analysis and 13 D DMAS nuclear magnetic resonance spectrum analysis.

 In the same manner as in Example 1, the elemental analysis and carbonization measurement (Raman spectroscopic analysis) of solid acid catalysts B, D, and E made of sulfonic acid group-containing carbonaceous materials were performed. The results are shown in Table 1. It was.

(Hydration reaction)

Instead of the solid acid catalyst A made of a sulfonic acid group-containing carbonaceous material as a catalyst, the solid acid made of the sulfonic acid group-containing carbonaceous material obtained in Example 2 and Comparative Examples 1 and 2 was used. The hydration reaction of propylene was carried out under the same conditions and operating methods as in Example 1 except that the catalyst was used. Table 1 shows the amount of isopropyl alcohol generated per unit catalyst amount per unit time. (Etherification reaction) --In the etherification reaction of Comparative Example 2, instead of the solid acid catalyst A made of a sulfonic acid group-containing ash-like material as the catalyst, a solid acid catalyst made of a sulfonic acid group-containing carbonaceous material Except for using E

,

 Note: The synthesis reaction of diisopropylene was carried out under the same conditions and operating methods as in Example 1. As a result, the amount of disulfur pill ether produced per unit time and unit catalyst amount is shown in Table 1.

[Example 3] and [Comparative Example 3]

 (Preparation of solid acid catalyst comprising sulfonic acid group-containing carbonaceous material) The raw materials, carbonization treatment and sulfonation treatment conditions described in Table 2 were used, and the other procedures were the same as in Example 1 above. Solid acid catalysts C and F made of carbonaceous materials containing sulfonic acid groups were produced. The novolak type phenolic resin used as a raw material is a composition containing 8% by mass of hexane methyl tereamine as a curing agent (a phenolic manufactured by Dainippon Ink & Chemicals, Inc.). It (registered trademark) TD-739A) was used. The acid amount of the obtained solid acid catalyst comprising the sulfonic acid group-containing carbonaceous material was examined by back titration. The results are shown in Table 2.

(Analysis of solid acid catalyst made of sulfonic acid group-containing carbonaceous material) For solid acid catalysts C and F made of sulfonic acid group-containing carbonaceous material, the above X-ray analysis, 13 C-D DMAS nuclear magnetism Resonance spectrum analysis and graphitization degree measurement were performed. The same results as in Example 1 were obtained for the X-ray analysis and 13 C-DD MAS nuclear magnetic resonance spectrum analysis. Table 2 shows the results of elemental analysis of the solid acid catalysts C and F made of a sulfonic acid group-containing carbonaceous material in the same manner as in Example 1. On the other hand, in the carbonization measurement (Raman spectroscopic analysis), solid acid catalysts C and F made of sulfonic acid group-containing carbonaceous materials, that is, a novolak phenol resin as a raw material, are used. --As shown in Table 2, the solid acid catalyst composed of the sulfonic acid group-containing carbonaceous material used did not have a clear spectrum, and the degree of carbonization could not be determined.

(Hydration reaction)

 Instead of the solid acid catalyst A made of a sulfonic acid group-containing carbonaceous material as a catalyst, the solid acid catalyst made of the sulfonic acid group-containing carbonaceous material obtained in Example 3 and Comparative Example 3 was used. The hydration reaction of propylene was carried out under the same conditions and operation methods as in Example 1 except that they were used. The amount of unit catalyst and the amount of isopropylene converted per unit time m. Is set to 2.

[Comparative Example 4]

 (Solid acid catalyst made of sulfonic acid group-containing ashy material made by a / I) The same raw materials as in Example 3 were used except that the carbonization treatment conditions and sulphonation treatment conditions were changed to the conditions shown in Table 2. Use with sulfonic acid group

¾ The acid of the solid acid catalyst G made of the sulfonic acid group-containing ash-containing material that produced the solid acid catalyst G made of the ash * material was prepared by back titration. As shown in 2, there was very little.

(Analysis of solid acid catalyst made of sulfonic acid group-containing carbonaceous material) X-ray analysis of solid acid catalyst G made of sulfonic acid group-containing carbonaceous material using the same method as in Example 3, 13 C-DD MAS nuclear magnetic resonance spectrum analysis and degree of graphitization were performed. The same results as in Example 3 were obtained for X-ray analysis and 1 3 C-DD MAS nuclear magnetic resonance spectrum analysis. In addition, the results of elemental analysis of the solid acid catalyst G made of a sulfonic acid group-containing carbonaceous material by the same method as in Example 3 showed that the sulfur content was not detected, as shown in Table 2. The introduction of groups was not permitted. On the other hand, carbonization measurement (La --In the Mann spectroscopy, the solid acid catalyst G made of sulfonic acid group-containing carbonaceous material showed a high carbonization degree as shown in Table 2.

(Hydration reaction)

 As shown in Table 2, the solid acid catalyst G made of a sulfonic acid group-containing carbonaceous material of Comparative Example 4 produced by carbonizing at an extremely high carbonization temperature and then sulfonating was used as an olefin. Did not show any hydration activity. The results are shown in Table 2.

(Acum decomposition reaction of cumene hydroperoxide)

 [Example 4 and Comparative Example 5]

 Using the raw materials, carbonization treatment conditions, and sulfonation treatment conditions described in Table 3, the solid acid catalyst HI made of a sulfonic acid group-containing carbonaceous material was used in the same manner as in Example 1 above. OH is the solid acid catalyst of the present invention, and I is the solid acid catalyst for comparison.

 13.8 g ethanol and 13.8 g ethanol were added to a 100 cc three-necked flask that had been subjected to an acid-decomposition reaction that decomposed cumene hydroloxide using solid acid catalysts H and I to produce phenol. Each 0.2 g of a solid acid catalyst comprising an acid group-containing ash material was charged and heated and stirred at a flow temperature (at 80) in a nitrogen atmosphere. Peroxide (percentage 88%) 15.2 g was added dropwise. After 2 hours from completion, the reaction solution was cooled and quantitative analysis was performed using a sieve. It was. The results are shown in Table 3. As is clear from Table 3, the solid acid catalyst of the present invention has a higher reflex than the solid acid catalyst of the comparative example.

X yield is shown.

(Synthesis of ethyl acetate)

 [Example 5 and Comparative Example 6]

Raw materials, carbonization and sulfonation conditions listed in Table 3 The solid acid catalysts J and K made of a sulfonic acid group-containing carbonaceous material were produced in the same manner as in Example 1 except for the above. J is the solid acid catalyst of the present invention, and K is a solid acid catalyst for comparison.

 Into an eggplant-shaped flask with an internal volume of lOO ml, 30 ml of ethanol was added, and acetic acid was added at a molar ratio of 1/50 with respect to the alcohol to obtain a sulfonic acid group-containing carbonaceous material. 0.20 g was added and heated. The mixture was reacted at reflux temperature (80) for 2 hours with stirring, and then quenched in a water bath to stop the reaction. After the reaction was completed, the product was quantitatively analyzed by gas chromatograph with FID detector. The results are also shown in Table 3. As is apparent from Table 3, the solid acid catalyst of the present invention shows a higher ethyl acetate yield than the solid acid catalyst of the comparative example. [Example 6] and [Comparative Example 7]

 (Manufacture of sulfonic acid group-containing carbonaceous materials from wood)

Using the raw materials, carbonization treatment and sulfonation treatment conditions described in Table 3, except that the solid acid catalyst L and the sulfonic acid group-containing carbonaceous material were used in the same manner as in Example 1, respectively. M was manufactured. The number average particle diameter of the eucalyptus powder used as a raw material is 0.250 mm. Table 3 shows the results of a titration of the sulfonic acid group-containing carbonaceous material.

(Butene 1 hydration reaction)

Charge 45.0 g (2.5 mol) of distilled water into a 500 cc autoclave reactor, add 4. O g of solid acid catalyst L made of carbonaceous material containing sulfonic acid groups, seal it, and then add butene-1 to 92.5 g (1.25 mol) was enclosed. Next, the temperature was raised to 145 while stirring at 200 rpm, the pressure was adjusted to 5 MPa with nitrogen, and the hydration reaction was carried out for 7.5 hours while maintaining 150. After the reaction is complete, cool the reaction solution. --Quantitative analysis was performed by TCD-GC. As a result, the unit catalyst amount of 2-butanol and the amount of product converted per unit time were obtained using the sulfonic acid group-containing carbonaceous material L and the sulfonic acid group-containing carbonaceous material M. In this case, they were 0.78 mmol / g-cat. / Hr and 0.42 mmol / g-cat. / Hr, respectively. The amounts produced were 1.7 g and 0.9 g, respectively.

[Example 7]

 (2 — Dehydrogenation of butanol)

 The 2-butanol obtained in Example 6 was dehydrogenated. Add lOOcc of autoclave with stirrer, part 2—1.7 g of methanol and copper zinc catalyst (Aldrich) O.lg, seal, and then stir at 700 rpm. However, the temperature was raised to 500 and a dehydrogenation reaction was carried out for 1 hour. After completion of the reaction, the reaction solution was cooled and quantitative analysis was performed by TCD-GC. It was confirmed that 0.8 g of methyl ethyl ketone was obtained. As described above, the solid acid catalyst comprising the sulphonic acid group-containing carbonaceous material produced by the production method of the present invention is more solid than the ash material containing the sulfonic acid group produced by the conventional production technology. As a result, it is clear that it has high activity for acid-catalyzed reactions such as olefin hydration and etherification. Sex

As described above, according to the present invention, the present invention has a high activity for acid catalyzed reactions such as olefin hydration reaction, etherification reaction or esterification reaction. It is possible to provide a method for producing a solid acid catalyst comprising a sulfonic acid group-containing carbonaceous material. In addition, according to the present invention, cheaply known as cocoons or herbs. --It is possible to provide a method for producing a solid acid catalyst comprising a sulfonic acid group-containing carbonaceous material from raw materials. As a result, the solid acid catalyst obtained by the production method can be used. Thus, it is possible to provide an efficient production process for products using an olefin hydration reaction product or an acid-catalyzed reaction process such as ethers or esters. In addition, the second butyl alcohol can be produced efficiently by the hydration reaction of norlemalbutene using the solid acid catalyst of the present invention, and the efficiency can be improved by dehydrogenating it. In addition, methyl ethyl ketone can be produced at low cost. The solid acid catalyst of the present invention is also effective for the production of phenol by acid decomposition reaction of cumene hydroloxide.

table 1

Table 2

Table 3

Note: CHP Xumen Hydropa Type 1 side

Claims

The scope of the claims 1. In the method for producing a solid acid catalyst comprising a carbonaceous material containing a sulfonic acid group obtained by carbonizing and sulfonating an organic substance by heating in an inert gas atmosphere, sulfonation is performed after carbonization. A solid acid comprising a sulfonic acid group-containing carbonaceous material, wherein the carbonization temperature is 300 to 600, and the sulfonation time is 5 to 150 minutes A method for producing a catalyst. 2. The method for producing a solid acid catalyst comprising the sulfonic acid group-containing carbonaceous material according to claim 1, wherein the sulfonation temperature is 20 to 2500. A process for producing a solid acid catalyst comprising: 3. The method for producing a solid acid catalyst comprising a sulfonic acid group-containing carbonaceous material according to claim 1 or 2, wherein concentrated sulfuric acid is used as a sulfonating agent, and the solid comprising a sulfonic acid group-containing carbonaceous material A method for producing an acid catalyst. 4. The method for producing a solid acid catalyst comprising a sulfonic acid group-containing carbonaceous material according to any one of claims 1 to 3, wherein cellulose is used as the organic substance, and the solid acid catalyst comprising the sulfonic acid group-containing carbonaceous material. Manufacturing method. In the method for producing a solid acid catalyst comprising a sulfonic acid group-containing carbonaceous material according to any one of claims 1 to 3, a solid acid comprising a sulfonic acid group-containing carbonaceous material, wherein a phenol resin is used as the organic substance. A method for producing a catalyst. 6. A method for producing a solid acid catalyst comprising the sulfonic acid group-containing carbonaceous material according to any one of claims 1 to 3, wherein woods and Z or herbs are used as organic substances. A method for producing a solid acid catalyst comprising a porous material. 7. In the method for producing a solid acid catalyst comprising the sulfonic acid group-containing carbonaceous material according to any one of claims 1 to 6, the integrated intensity of the D peak of the Raman analysis value of the solid acid catalyst has an integrated intensity of the ZG peak of 0.0. A method for producing a solid acid catalyst comprising a sulfonic acid group-containing carbonaceous material, wherein the peak of ˜0.7 or the Raman spectrum is not observed. 8. A method for producing an olefin hydrate product, wherein the olefin hydration reaction is carried out using the solid acid catalyst obtained by the method according to claims 1 to 7. 9. A method for producing ethers, wherein an etherification reaction of olefin is performed using the solid acid catalyst obtained by the method according to any one of claims 1 to 7. 10. A method for producing phenols from aralkyl hydroperoxide, characterized by carrying out an acid decomposition reaction of aralkyl hydroperoxide using the solid acid catalyst obtained by the method according to claim 1. 11. The method for producing phenols according to claim 10, wherein the aralkylki droperoxide is cumene dropperoxide and the phenols are phenols. 1 2. The esterification reaction of alcohol and carboxylic acid using the solid acid catalyst obtained by the method according to claims 1 to 7 A method for producing esters. 1 3. A process for producing a ketone, which comprises dehydrogenating the olefin hydrate product obtained according to claim 8 14. The method for producing a ketone according to claim 13, wherein the olefin hydration product is 2-butanol and the ketone is methyl ethyl ketone.