WO2008123530A1 - Procédé de fabrication d'un catalyseur acide solide comprenant un matériau carboné qui comporte un groupement sulfonate et utilisation du catalyseur acide solide - Google Patents

Procédé de fabrication d'un catalyseur acide solide comprenant un matériau carboné qui comporte un groupement sulfonate et utilisation du catalyseur acide solide Download PDF

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WO2008123530A1
WO2008123530A1 PCT/JP2008/056513 JP2008056513W WO2008123530A1 WO 2008123530 A1 WO2008123530 A1 WO 2008123530A1 JP 2008056513 W JP2008056513 W JP 2008056513W WO 2008123530 A1 WO2008123530 A1 WO 2008123530A1
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solid acid
acid catalyst
carbonaceous material
producing
sulfonic acid
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PCT/JP2008/056513
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English (en)
Japanese (ja)
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Shinichirou Yanagawa
Hidesato Kondo
Michikazu Hara
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Nippon Oil Corporation
Tokyo Institute Of Technology
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Priority to JP2009509268A priority Critical patent/JP5360719B2/ja
Publication of WO2008123530A1 publication Critical patent/WO2008123530A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/08—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by decomposition of hydroperoxides, e.g. cumene hydroperoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
    • C07C39/04—Phenol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • B01J31/10—Ion-exchange resins sulfonated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • 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.
  • Sulfuric acid is an important catalyst widely used in various chemical reactions.
  • 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
  • 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.
  • 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.
  • 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).
  • sulfuric acid is used as a catalyst.
  • solid acid is used.
  • 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.
  • 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.
  • Patent Document 1 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).
  • Patent Document 1 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).
  • Patent Document 2 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).
  • Non-patent Document 6 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.
  • 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.
  • 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),
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • the olefin hydration product is 2-butanol
  • 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 ⁇ peroxy.
  • 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 cost
  • 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.
  • the olefin hydrate can be produced at low cost and efficiently as described above.
  • canes can be produced efficiently at low cost.
  • 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. . --
  • 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.
  • 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.
  • the resulting solid acid made of a sulfonic acid group-containing carbonaceous material has excellent heat resistance, and is particularly preferable.
  • 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.
  • 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.
  • the sulfonation treatment is performed after the carbonization treatment.
  • a highly active solid acid catalyst cannot be obtained. The following describes the preferred mode when sulfonated after 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
  • 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
  • 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.
  • 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,
  • the temperature of the sulfonation treatment is 2 0 2 o 0 t :, preferably 5
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • the degree of carbonization when carbonizing organic substances by heating is often expressed by the degree of graphitization.
  • the D peak in Raman spectroscopy is used.
  • G --The strength ratio of the coffee is used.
  • the graphitization degree progresses as the value of the integrated intensity ratio of the G peak increases.
  • 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 ⁇ has been made.
  • 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.
  • 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.
  • 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.
  • 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.
  • “amorphous carbon” is suggested, suggesting that it has a partially crystalline structure.
  • 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.
  • 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.
  • 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 ⁇
  • 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).
  • 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).
  • alcohols used in the etherification reaction 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.
  • ⁇ : i, anhydride may be used for carboxylic acid.
  • 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.
  • reaction phase any of a gas phase, a liquid phase, and a gas-liquid mixed phase can be adopted.
  • 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.
  • the solvent is preferably amphiphilic to prevent the reaction solution from separating into an aqueous phase and an oil phase.
  • ethers, glycol ethers, alcohols, canes and the like can be used.
  • a solvent can be used in the same manner.
  • 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.
  • the process is simple.
  • 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.
  • 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.
  • the reactor in the hydration reaction, etherification reaction, or esterification reaction of the present invention 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.
  • 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.
  • 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.
  • 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.
  • Formula D 1 the structure represented by Formula D 1 below.
  • 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. .
  • 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.
  • 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 second alcohol can be produced by the above-mentioned olefin hydration reaction (reaction between olefin and water). I can do it.
  • the secondary alcohol By dehydrogenating the secondary alcohol, the corresponding keton can be produced.
  • 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
  • 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.
  • 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
  • a Raman spectroscopic analyzer was used.
  • 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.
  • Example 1 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.
  • Solid acid catalyst B, D made of sulfonic acid group-containing carbonaceous material
  • Example 2 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.
  • Example 2 the solid acid made of a 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
  • 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.
  • 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.
  • 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.
  • Table 2 The results are shown in Table 2.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.

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Abstract

L'invention concerne un catalyseur acide solide qui comprend un matériau carboné qui comporte un groupement sulfonate. Ce catalyseur est utile pour diverses réactions catalysées par des acides, notamment l'hydratation d'une oléfine, et présente une activité réactionnelle élevée. Un catalyseur acide solide qui comprend un matériau carboné qui comporte un groupement sulfonate peut être produit par un procédé à deux étapes qui comprend : le chauffage d'un matériau organique tel que la cellulose, une résine de phénol, du bois et du gazon pour carboniser le matériau organique, puis la sulfonation du produit carbonisé. Selon l'invention, les conditions de carbonisation et la durée requise pour la sulfonation à l'étape de sulfonation sont contrôlées. Le catalyseur acide solide présente une activité réactionnelle élevée dans diverses réactions catalysées par des acides, notamment l'hydratation d'une oléfine.
PCT/JP2008/056513 2007-03-27 2008-03-26 Procédé de fabrication d'un catalyseur acide solide comprenant un matériau carboné qui comporte un groupement sulfonate et utilisation du catalyseur acide solide WO2008123530A1 (fr)

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JP2014004561A (ja) * 2012-06-26 2014-01-16 Futamura Chemical Co Ltd セルロース系バインダー成形固体酸及びその製造方法
JP2014004560A (ja) * 2012-06-26 2014-01-16 Futamura Chemical Co Ltd 粒状固体酸及びその製造方法
CN105013533A (zh) * 2015-07-13 2015-11-04 天津师范大学 交联的磺化聚芳香（硫）醚固体酸催化剂及其制备方法与应用
KR20160058818A (ko) * 2013-09-18 2016-05-25 후타무라 가가쿠 가부시키가이샤 합성 수지 바인더 성형 고체산 및 그 제조 방법
CN106362804A (zh) * 2016-09-21 2017-02-01 华南理工大学 一种磁性炭基固体酸催化剂及其制备方法与应用
WO2020218345A1 (fr) * 2019-04-22 2020-10-29 パナソニックＩｐマネジメント株式会社 Appareil de détermination d'état de fluide fonctionnel et système de détermination d'état de fluide fonctionnel
CN113289659A (zh) * 2021-05-25 2021-08-24 西安工程大学 磺酸基官能团改性氮化碳光催化材料的制备方法及应用
CN113385191A (zh) * 2020-03-13 2021-09-14 湘潭大学 无机固体硅基磺酸和/或磷酸催化剂及其制备方法和应用
CN114669326A (zh) * 2022-04-13 2022-06-28 武汉工程大学 新型磁性固体酸催化剂及在黄姜总皂苷中提取皂素的应用
CN115770623A (zh) * 2022-12-09 2023-03-10 梧州黄埔化工药业有限公司 一种樟脑酯化反应用离子交换膜的制备方法

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JP2014004560A (ja) * 2012-06-26 2014-01-16 Futamura Chemical Co Ltd 粒状固体酸及びその製造方法
JP2014004561A (ja) * 2012-06-26 2014-01-16 Futamura Chemical Co Ltd セルロース系バインダー成形固体酸及びその製造方法
KR102201533B1 (ko) * 2013-09-18 2021-01-12 후타무라 가가쿠 가부시키가이샤 합성 수지 바인더 성형 고체산 및 그 제조 방법
KR20160058818A (ko) * 2013-09-18 2016-05-25 후타무라 가가쿠 가부시키가이샤 합성 수지 바인더 성형 고체산 및 그 제조 방법
CN105792933A (zh) * 2013-09-18 2016-07-20 二村化学株式会社 合成树脂粘结剂成型固体酸及其制备方法
EP3047906A1 (fr) * 2013-09-18 2016-07-27 Futamura Kagaku Kabushiki Kaisha Lieur de résine synthétique-acide solide moulé, et son procédé de production
EP3047906A4 (fr) * 2013-09-18 2017-05-03 Futamura Kagaku Kabushiki Kaisha Lieur de résine synthétique-acide solide moulé, et son procédé de production
CN105013533A (zh) * 2015-07-13 2015-11-04 天津师范大学 交联的磺化聚芳香（硫）醚固体酸催化剂及其制备方法与应用
CN106362804A (zh) * 2016-09-21 2017-02-01 华南理工大学 一种磁性炭基固体酸催化剂及其制备方法与应用
WO2020218345A1 (fr) * 2019-04-22 2020-10-29 パナソニックＩｐマネジメント株式会社 Appareil de détermination d'état de fluide fonctionnel et système de détermination d'état de fluide fonctionnel
CN113385191A (zh) * 2020-03-13 2021-09-14 湘潭大学 无机固体硅基磺酸和/或磷酸催化剂及其制备方法和应用
CN113385191B (zh) * 2020-03-13 2022-11-18 湘潭大学 无机固体硅基磺酸和/或磷酸催化剂及其制备方法和应用
CN113289659A (zh) * 2021-05-25 2021-08-24 西安工程大学 磺酸基官能团改性氮化碳光催化材料的制备方法及应用
CN113289659B (zh) * 2021-05-25 2023-09-01 西安工程大学 磺酸基官能团改性氮化碳光催化材料的制备方法及应用
CN114669326A (zh) * 2022-04-13 2022-06-28 武汉工程大学 新型磁性固体酸催化剂及在黄姜总皂苷中提取皂素的应用
CN114669326B (zh) * 2022-04-13 2024-05-14 武汉工程大学 新型磁性固体酸催化剂及在黄姜总皂苷中提取皂素的应用
CN115770623A (zh) * 2022-12-09 2023-03-10 梧州黄埔化工药业有限公司 一种樟脑酯化反应用离子交换膜的制备方法
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