JP4041575B2 - Titanium-containing solid catalyst and method for producing oxirane compound - Google Patents

Description

【００５２】
【表２】

【００５３】
・ＥＢＨＰ転化率＝消費ＥＢＨＰ（ｍｏｌ）／仕込みＥＢＨＰ（ｍｏｌ）×１００
・ｋ＝ｌｎ（(仕込みＥＢＨＰ（ｍｏｌ）／残存ＥＢＨＰ（ｍｏｌ）)／触媒重量（ｇ）／反応時間（ｈ）
・ＰＯ選択率= 生成ＰＯ（ｍｏｌ）／消費ＥＢＨＰ（ｍｏｌ）×１００
【００５４】
【発明の効果】
以上説明したとおり、本発明により、オレフィン型化合物と有機ハイドロパーオキサイドとを反応させてオキシラン化合物を製造するチタン含有固体触媒であって、活性が高く、公知法より小さな反応器で目的の変換を行うことを可能とする触媒、及び該触媒を用いるオキシラン化合物の製造方法を提供することができた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a titanium-containing solid catalyst and a method for producing an oxirane compound. More specifically, the present invention is a titanium-containing solid catalyst for producing an oxirane compound by reacting an olefin type compound and an organic hydroperoxide, which has a high activity and performs a desired conversion in a reactor smaller than a known method. The present invention relates to a catalyst that makes it possible, and a method for producing an oxirane compound using the catalyst.
[0002]
[Prior art]
A method for converting an olefin type compound into an oxirane compound by reacting an olefin type compound with an organic hydroperoxide using a titanium-containing solid catalyst catalyst is known (Japanese Patent Publication No. 56-35941, Japanese Patent Publication No. 54-40525). Gazette, Japanese Examined Patent Publication No. 54-40526, Japanese Examined Patent Publication No. 50-30049, Japanese Unexamined Patent Publication No. Hei 8-269031).
[0003]
The titanium-containing solid catalyst catalyst can be prepared by various methods. A preparation method in which a carrier silica is impregnated with a titanium compound in a solvent and calcined is one of useful methods. Catalysts made by this method are not sufficiently active and require an excessive reactor in industrial scale production, resulting in increased manufacturing costs.
[0004]
[Problems to be solved by the invention]
In view of the current situation, the problem to be solved by the present invention is a titanium-containing solid catalyst for producing an oxirane compound by reacting an olefin type compound which is propylene with an organic hydroperoxide, which has a high activity and is a known method. The object of the present invention is to provide a catalyst capable of performing the desired conversion in a smaller reactor, and a method for producing an oxirane compound using the catalyst.
[0005]
[Means for Solving the Problems]
That is, one invention of the present invention is a titanium-containing solid catalyst for producing an oxirane compound by reacting an olefin type compound and an organic hydroperoxide,
(1) impregnating carrier silica with water and drying;
(2) A titanium compound is supported on the carrier silica treated in the above (1),
(3) Firing at a temperature exceeding 500 ° C.
Further, it is obtained by silylation (however, the step of calcining between the above (1) and (2) is not used) , and the above olefin type compound relates to a catalyst which is propylene .
[0006]
Another invention of the present invention relates to a method for producing an oxirane compound in which an olefin type compound that is propylene and an organic hydroperoxide are reacted in the presence of the above catalyst.
[0007]
When the method of the present invention was used, the activity was remarkably improved as compared with the case where the carrier silica was not impregnated with water.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Suitable solid silicas are those containing 50% or more, preferably 75% or more, most preferably 90% or more of silicon in the form of dioxide. Solid silica may preferably have a relatively large specific surface area, specific surface area is preferably 1 m ² / g or more, more preferably 25~800m ² / g.
[0009]
The silica is preferably relatively dense and close-packed porous synthetic silica composed of coagulated or mutually bonded amorphous silica particles, examples of which include silica gel and precipitated silica. These processes and properties are described in R.A. G. As described in Chapter VI of "The, Colloid, Chemistry, Ob, Silica, and Silicate" by Eyler (published in Cornell University Press, 1955, New York, USA) and US Pat. No. 2,657,149. Yes. Of the silica gels available on the market, silica gel having a specific surface area of 25 to 700 m ² / g, a pore volume of 0.3 to 2.0 ml / g, and a silica content of 99% by weight or more is preferably used.
[0010]
Also suitable is a synthetic silica powder made of amorphous silica particles produced by a solidification operation, having an open pack structure, easy to disintegrate and loosely bound, examples of which include hydrogen and oxygen. Examples thereof include calcined silica (fumed pyrogenic silica) obtained by performing a combustion operation with silicon tetrachloride or silicon tetrafluoride. This type of silica is manufactured and sold by various vendors, such as those sold by Cabot Corporation (Cab-O-Zill) and Degussa Corporation (Aerosil) (the above-mentioned “Cab-O-Zil” and “Aerosil”). "Is a registered trademark). Among these silica products, a product having a specific surface area of 50 to 500 m ² / g and a silica content of 99% or more is most preferable.
[0011]
Furthermore, crystalline porous silica is also suitable as the solid silica. Examples of the crystalline porous silica include high silica zeolite (containing only a small amount of other metals such as aluminum). As an example of high silica zeolite, silicalite, which is a pentasil type zeolite, is known (RW Grose and EM Flanigen, US4061724 (1977) (to UCC)). Further, although not crystalline, MCM41 (JSBeck, et al., J. Am. Chem. Soc., 114, 10834 (199)) having a regular pore structure can also be used as a carrier.
[0012]
Before supporting the titanium compound, the support silica is impregnated with water. The water may be neutral, acidic or alkaline. To make the water acidic, the acid can be dissolved, and to make the water alkaline, the base can be dissolved in water. Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid, propionic acid and benzoic acid. Examples of the base include inorganic bases such as ammonia, sodium hydroxide, and potassium hydroxide, and organic bases such as triethylamine. The impregnation treatment is performed by immersing the carrier silica in water and leaving it at 10 to 100 ° C. for 1 to 50 hours. Stirring may or may not be performed. After the impregnation treatment, water is removed by a method such as filtration, and the solid is washed with water until the filtrate becomes neutral. The silica is then dried at 100-200 ° C. under vacuum or air or nitrogen stream.
[0013]
Both the vapor phase loading method and the liquid phase loading method can be applied to titanium loading. In vapor phase loading, titanium salts and titanic acid esters of inorganic and organic acids that can become vapor at the loading temperature are applied. In the liquid phase support, titanium salts and titanates of inorganic acids and organic acids that are soluble in a solvent can be used.
[0014]
Examples of titanium compounds include tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, tetra-2-ethylhexyl titanate, tetraoctadecyl titanate, tetrachloride Examples include titanium, titanium tetrabromide, titanium tetraiodide, titanium (IV) oxyacetylacetonate, and titanium (IV) diisopropoxide bisacetylacetonate. It is also possible to use a multi-stage impregnation method with or without a drying and / or firing step.
[0015]
As a suitable solvent for loading and washing in the liquid phase loading, oxa and / or oxo substituted hydrocarbons which are generally liquid at normal temperature having 1 to about 12 carbon atoms can be used. Suitable solvents of this type can be alcohols, ketones, ethers (acyclic and cyclic) and esters. For example, hydroxy substituted hydrocarbons such as methanol, ethanol, ethylene glycol, propylene glycol, isopropanol, n-butanol and octanol; oxo substituted hydrocarbons such as acetone, diethyl ketone, methyl ethyl ketone and methyl isobutyl ketone; diisobutyl ether and tetrahydrofuran And hydrocarbon esters such as methyl acetate, ethyl acetate, butyl acetate and butyl propionate.
[0016]
Subsequent to liquid phase loading, the absorbed solvent is removed. This solvent removal operation may include decantation, filtration, centrifugation, evacuation, drying and other operations. It is important to select the conditions so that at this stage the solvent removal stage removes at least 80%, preferably at least 95% of the excess loading solvent from the silica.
[0017]
As described in JP-A-8-269031, washing is preferably performed after the liquid phase carrying treatment. After thoroughly mixing the cleaning solvent and the titanium-supported catalyst, the liquid phase part is separated by a method such as filtration or decantation. This operation is repeated as many times as necessary. The end of the cleaning can be known, for example, by analyzing the liquid phase part. The washing temperature is preferably 0 to 100 ° C, more preferably 10 to 60 ° C. After the washing is completed, the remaining washing solvent is removed by the same method as in the supported solvent removing step. This removal of the solvent not only recovers a large amount of solvent, but also reduces the risk of ignition during the calcination period, and also causes rapid evaporation of a large amount of volatile solvent in the catalyst structure during subsequent calcination at higher temperatures. This helps to prevent a decrease in the physical strength of the resulting catalyst. Drying at 25 ° C. to 200 ° C. is effective as a solvent removal method.
[0018]
After supporting titanium, the catalyst composition is calcined. That is, heating is performed in an atmosphere of a non-reducing gas such as nitrogen, argon or carbon dioxide or an oxygen-containing gas such as air. One role of calcination is to convert titanium from its supported form, such as halides or alkanolates, to insoluble chemically bonded oxides. Similarly converted to an insoluble chemically bonded oxide. Another role of calcination is to activate the catalyst. A baking temperature of 400 to 900 ° C is sufficient, and a temperature of 400 to 800 ° C is recommended. The normal firing time is 1 to 18 hours.
[0019]
The obtained catalyst is preferably reacted with a silylating agent before use. Examples of silylating agents include organic silanes, organic silylamines, organic silylamides and derivatives thereof, and organic silazanes and other silylating agents.
[0020]
Examples of organic silanes include chlorotrimethylsilane, dichlorodimethylsilane, chlorobromodimethylsilane, nitrotrimethylsilane, chlorotriethylsilane, iododimethylbutylsilane, chlorodimethylphenylsilane, chlorodimethylsilane, dimethyl n-propylchlorosilane, dimethylisopropyl Chlorosilane, t-butyldimethylchlorosilane, tripropylchlorosilane, dimethyloctylchlorosilane, tributylchlorosilane, trihexylchlorosilane, dimethylethylchlorosilane, dimethyloctadecylchlorosilane, n-butyldimethylchlorosilane, bromomethyldimethylchlorosilane, chloromethyldimethylchlorosilane, 3-chloro Propyldimethylchlorosilane, dimethoxymethylchlorosilane, methyl Phenyl chlorosilane, triethoxy chlorosilane, dimethyl phenyl chlorosilane, methyl phenyl vinyl chlorosilane, benzyl dimethyl chlorosilane, diphenyl chlorosilane, diphenylmethylchlorosilane, diphenyl vinyl chlorosilane, tribenzyl chlorosilane, 3-cyanopropyl dimethylchlorosilane and the like.
[0021]
Examples of organic silylamines include N-trimethylsilylimidazole, Nt-butyldimethylsilylimidazole, N-dimethylethylsilylimidazole, N-dimethyln-propylsilylimidazole, N-dimethylisopropylsilylimidazole, N-trimethylsilyldimethylamine, Examples thereof include N-trimethylsilyldiethylamine, N-trimethylsilylpyrrole, N-trimethylsilylpyrrolidine, N-trimethylsilylpiperidine, pentafluorophenyldimethylsilylamine, and 1-cyanoethyl (diethylamino) dimethylsilane.
[0022]
Examples of organic silylamides and derivatives include N, O-bistrimethylsilylacetamide, N, O-bistrimethylsilyltrifluoroacetamide, N-trimethylsilylacetamide, N-methyl-N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltrifluoro Acetamide, N-methyl-N-trime
Examples include silylsilylheptafluorobutyramide, N- (t-butyldimethylsilyl) -N-trifluoroacetamide, and N, O-bis (diethylhydrosilyl) trifluoroacetamide.
[0024]
Examples of organic silazanes include hexamethyldisilazane, heptamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,3-bis (chloromethyl) tetramethyldisilazane, 1,3-divinyl-1 1,3,3-tetramethyldisilazane and 1,3-diphenyltetramethyldisilazane.
[0025]
Other silylating agents include N-methoxy-N, O-bistrimethylsilyl trifluoroacetamide, N-methoxy-N, O-bistrimethylsilyl carbamate, N, O-bistrimethylsilyl sulfamate, trimethylsilyl trifluoromethanesulfonate. N, N-bistrimethylsilylurea.
[0026]
A preferred silylating agent is hexamethyldisilazane.
[0027]
Hydration can also be applied to the calcined catalyst before silylation. This hydration treatment involves contacting the catalyst with water (before silylation) and then heating it, or heating the catalyst at an elevated temperature, generally above 100 ° C, preferably within the range of 150-450 ° C. Meaning contact with water vapor for 5-6 hours. Best results are obtained when the hydration treatment is carried out by exposure to water vapor at a temperature of 300-450 ° C. for 1-6 hours.
[0028]
The catalyst can be used in any physical form such as powders, flakes, spherical particles, pellets.
[0029]
The epoxidation reaction is carried out by a reaction between an organic hydroperoxide and an olefin in the presence of the catalyst prepared by the above method.
[0030]
Organic hydroperoxide is a compound having the general formula R—O—O—H (where R is a monovalent hydrocarbyl group), which reacts with olefinic compounds to produce oxirane compounds and compounds. R-OH is produced. Preferably, the group R is a group having 3 to 20 carbon atoms. Most preferably this is a hydrocarbyl group of 3 to 10 carbon atoms, in particular a secondary or tertiary alkyl group or an aralkyl group. Among these groups, particularly preferred groups are a tertiary alkyl group and a second or third aralkyl group, and specific examples thereof include a tertiary butyl group, a tertiary pentyl group, a cyclopentyl group, 1-phenylethyl- 1 group, 2-phenylpropyl-2 group, and various tetranylyl groups generated by removing hydrogen atoms from the aliphatic side chain of the tetralin molecule.
[0031]
When ethylbenzene hydroperoxide is used, the resulting hydroxyl compound is 1-phenylethanol, which can be converted to styrene by a dehydration reaction. When cumene hydroperoxide is used, the resulting hydroxyl compound is 2-phenyl-2-propanol. This can be converted to α-methylstyrene by a dehydration reaction. Both styrene and α-methylstyrene are industrially useful materials.
[0032]
The third amylene produced by the dehydration reaction of the third pentyl alcohol obtained when the third pentyl hydroperoxide is used is a substance useful as a precursor of isoprene. Tertiary pentyl alcohol is also useful as a precursor of methyl tertiary pentyl ether which is an octane improver. t-Butyl alcohol obtained when t-butyl hydroperoxide is used is a substance useful as a precursor of methyl t-butyl ether which is an octane number improver.
[0033]
The organic hydroperoxide used as the raw material may be a diluted or concentrated purified product or non-purified product.
[0034]
The olefin type compound in the present invention is propylene.
[0035]
Propylene oxide can be converted to useful polymer products by polymerization or copolymerization reactions.
[0036]
The epoxidation reaction can be carried out in the liquid phase using a solvent and / or diluent. The solvent and diluent must be liquid under the temperature and pressure during the reaction and be substantially inert to the reactants and products. The solvent may consist of substances present in the hydroperoxide solution used. For example, when ethylbenzene hydroperoxide (EBHP) is a mixture of EBHP and its starting material ethylbenzene, it can be used as a substitute for the solvent without adding a solvent.
[0037]
A second solvent can also be used as a diluent, and useful solvents as diluents include aromatic monocyclic compounds (eg, benzene, toluene, chlorobenzene, bromobenzene, orthodichlorobenzene), and alkanes (eg, Octane, decane, dodecane). It is also possible to use an excess amount of olefinic reactant as solvent. That is, organic hydroperoxide and
With the solvent supplied together, an excess amount of olefinic reactant can be used as the solvent. The total amount of solvent used is preferably 20 mol or less (per mol of hydroperoxide).
[0039]
The epoxidation reaction temperature is generally 0 to 200 ° C, but a temperature of 25 to 200 ° C is preferable. The pressure may be sufficient to keep the reaction mixture in a liquid state. In general, the pressure is advantageously from 100 to 10,000 KPa.
[0040]
After completion of the epoxidation reaction, the liquid mixture containing the desired product can be easily separated from the catalyst composition. The liquid mixture can then be purified by a suitable method. Purification includes fractional distillation, selective extraction, filtration, washing and the like. The solvent, catalyst, unreacted olefin and unreacted hydroperoxide can be recycled and reused. The process according to the invention can be advantageously carried out using a catalyst in the form of a slurry, fixed bed. For large scale industrial operations, it is preferred to use a fixed bed. The process of the present invention can be carried out by a batch process, a semi-continuous process or a continuous process. When the liquid containing the reactants is passed through a fixed bed, the liquid mixture exiting the reaction zone contains no or substantially no catalyst.
[0041]
【Example】
EXAMPLES The present invention will be described below with reference to examples, but it goes without saying that the present invention is not limited to the examples.
[0042]
Example 1
Catalyst preparation :
Commercially available silica gel (10 to 20 mesh, surface area 326 m ² / g, average pore diameter 10 nm, 55 g) was impregnated in 2N HCl (200 g) and allowed to stand for 14 hours. Filter and wash with deionized water until the furnace fluid is neutral. The solid was vacuum dried (200 ° C., 2 mmHg, 2 h) to obtain pretreated silica. Under a nitrogen stream, acetylacetone (1.6 g) was slowly added dropwise to a solution of tetraisopropyl titanate (2.2 g) in isopropanol (20 ml) with stirring, followed by stirring for 30 minutes at room temperature.
The above solution was added dropwise to a mixture of silica gel (50 g) and isopropanol (230 ml) impregnated with water as described above, and the mixture was filtered after stirring for 1 hour at room temperature. The solid part was washed with isopropanol (60 ° C., 20 h). The solid part was dried at 150 ° C. for 2 hours in an air atmosphere. Further, it was calcined at 600 ° C. for 4 hours in an air atmosphere. This material (10 g), hexamethyldisilazane (4 g), and toluene (50 g) were mixed and heated to reflux for 1 hour with stirring. The liquid was distilled off from the mixture by filtration. The catalyst was obtained by washing with toluene (100 g) and vacuum drying (120 ° C., 10 mmHg, 3 hours).
[0043]
Synthesis of propylene oxide by epoxidation reaction using propylene ethylbenzene hydroperoxide oxa Lee de (EBHP) (PO):
The catalyst synthesized as described above (Ti content of charged base: 0.75 wt%, 3 g), 35% ethylbenzene hydroperoxide (24 g) and propylene (17 g) were charged into an autoclave equipped with a magnetic stirrer at 90 ° C. for 1 hour. Reacted. The reaction results are shown in Table 1.
[0044]
Example 2
A catalyst was obtained by the same method as in Example 1 except that the solid part was washed with isopropanol three times at room temperature instead of 60 ° C. The epoxidation reaction results are shown in Table 1.
[0045]
Example 3
A catalyst was obtained by the same method as in Example 2 except that the water impregnated with the carrier water was HCl water with pH = 3. The epoxidation reaction results are shown in Table 1.
[0046]
Example 4
A catalyst was obtained by the same method as in Example 3 except that the water impregnated with the carrier water was water having a pH of 5.5. The epoxidation reaction results are shown in Table 1.
[0047]
Example 5
A catalyst was obtained by the same method as in Example 4 except that the water impregnated with the carrier water was ammonia water having pH = 11. The epoxidation reaction results are shown in Table 1.
[0048]
Comparative Example 1
A catalyst was obtained by the same method as in Example 1 except that a carrier not subjected to water impregnation treatment was used. The epoxidation reaction results are shown in Table 2.
[0049]
Comparative Example 2
A catalyst was obtained by the same method as in Example 2 except that a carrier not subjected to water impregnation was used. The epoxidation reaction results are shown in Table 2.
[0050]
Tables 1 and 2 show that propylene oxide selectivity does not change by impregnation with carrier water, and the activity increases approximately twice (comparing reaction rate constants). From this result, the effect of carrier water impregnation is clear.
[0051]
[Table 1]

[0052]
[Table 2]

[0053]
EBHP conversion = consumed EBHP (mol) / prepared EBHP (mol) × 100
K = ln ((prepared EBHP (mol) / remaining EBHP (mol)) / catalyst weight (g) / reaction time (h)
PO selectivity = produced PO (mol) / consumed EBHP (mol) x 100
[0054]
【The invention's effect】
As described above, according to the present invention, a titanium-containing solid catalyst for producing an oxirane compound by reacting an olefin type compound and an organic hydroperoxide, which has a high activity and performs a desired conversion in a reactor smaller than a known method. The catalyst which can be performed, and the manufacturing method of the oxirane compound using this catalyst were able to be provided.

Claims (4)

A titanium-containing solid catalyst for producing an oxirane compound by reacting an olefin type compound with an organic hydroperoxide,
(1) impregnating carrier silica with water and drying;
(2) A titanium compound is supported on the carrier silica treated in the above (1),
(3) Firing at a temperature exceeding 500 ° C.
A catalyst obtained by further silylation (however, the step of firing between the above (1) and (2) is not used) , and the olefin type compound is propylene . The manufacturing method of the oxirane compound which makes the olefin type compound which is propylene and organic hydroperoxide react in presence of the catalyst of Claim 1 . The method according to claim 2 , wherein the organic hydroperoxide is ethylbenzene hydroperoxide. The method according to claim 2 , wherein the organic hydroperoxide is t-butyl hydroperoxide.