JPH11309378A - Catalyst for oxidizing olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve an active catalyst by loading an amide having an alkyl group of at least a specified number of carbon atoms in a specified wt.% range into a catalyst comprising a mesopore titanosilicate molecular sieve. SOLUTION: Into a catalyst comprising a mesopore titanosilicate molecular sieve synthesized by a process in which, in the presence of a template of a long chain quaternary ammonium salt, a long chain alkylamine, a long chain alkylamine-N-oxide, a long chain sulfonic acid ester, or the like, a silica source compound is reacted with a titanium oxide source compound, and the template is removed is loaded 0.1-20 wt.% of an amine having an alkyl group, which is a primary, secondary, tertiary, and quaternary alkylammonium salt having an alkyl group of >=8C. In this way, a catalyst easy of handling and excellent in activity can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a catalyst used for an olefin oxidation reaction using hydrogen peroxide.

[0002]

2. Description of the Related Art Mesopore molecular sieves (molecular sieves) are new materials which are expected to be widely used as catalysts, adsorbents and the like as inorganic porous materials having a uniform pore size in the mesopore region. As a method for synthesizing these mesopore molecular sieves, US Pat.
No. 2643, No. 5108725 and Japanese Patent Publication No. 5-503499 describe a method of synthesizing by hydrothermal synthesis using a quaternary ammonium salt or a phosphonium salt having a long-chain alkyl group as a template. Are known. Japanese Patent Application Laid-Open No. 4-238810 discloses a method of synthesizing a layered silica by ion exchange using an alkylammonium cation having a longer chain. WO 94/29 shows that mesopore titanosilicate molecular sieves synthesized in a similar manner exhibit catalytic activity for hydrogen peroxide oxidation of cycloolefins.
022 and the like.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst having excellent activity as a catalyst used in an oxidation reaction of an olefin with aqueous hydrogen peroxide.

[0004]

SUMMARY OF THE INVENTION The present invention provides a catalyst comprising a mesopore titanosilicate molecular sieve, wherein an amine having an alkyl group having 8 or more carbon atoms is contained in the catalyst.
A catalyst for oxidizing olefins, comprising
It is. Hereinafter, the present invention will be described in detail. The catalyst of the present invention is a porous material having a uniform pore size in the range of 1.5 to 10 nm in the mesopore region, and is composed of a mesopore titanosilicate molecular sieve containing an alkylamine having 8 or more carbon atoms.

[0005] As a method for synthesizing a mesopore titanosilicate molecular sieve, it can be synthesized by a known method, for example, the method described above. Specifically, it is synthesized by reacting a silica source compound described below with a titanium oxide source compound in the presence of a template, and then removing the template. Examples of the template for synthesizing the mesopore body include surfactants used in known mesopore body synthesis, such as long-chain quaternary ammonium salts, long-chain alkylamines, long-chain alkylamine-N-oxides, and long-chain alkylamine-N-oxides. Sulfonates, polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters and the like can be mentioned, and any of them can be used.

The atomic ratio of silicon to titanium (Si / Ti) is in the range of 5 to 200, preferably 10 to 100. As the silica source, tetraalkoxysilanes composed of methoxy, ethoxy, propoxy, etc., silica powder, water glass, colloidal silica and the like are usually used. Examples of the titanium oxide source include titanium oxide, titanium sulfate, and titanium alkoxide (for example, tetraethoxytitanium, tetrapropoxytitanium, and tetranabutoxytitanium). In particular, titanium alkoxide is advantageously used.

As the solvent, one or more of water, alcohol and diol are usually used, but an aqueous solvent containing water is preferred. Further, in order to change the pore diameter in the same manner as in a known method, an aromatic hydrocarbon having 6 to 20 carbon atoms, an alicyclic hydrocarbon having 5 to 20 carbon atoms, and 3 to 16 carbon atoms are used as organic auxiliary agents.
And their amines and halogen-substituted products, such as dodecane, hexadecane, cyclododecane, trimethylbenzene, triethylbenzene and the like.

The composition of a reaction mixture comprising a silica source, a titanium oxide source, a template, and a solvent used in the synthesis has an atomic ratio of silicon / titanium of 5 or more, preferably 10 or more, and a molar ratio of silica / template. 1-3
0, preferably 1-10, and the solvent / template molar ratio is 1-1000, preferably 5-500.
The synthesis conditions are such that the reaction temperature is from room temperature (20 ° C.) to 18 ° C.
0 ° C., preferably from room temperature to 100 ° C., and the reaction time is 0.5 to 100 hours, preferably 1 to 50 hours.

The reaction product is usually separated by filtration, thoroughly washed with water, dried, and then removed by a method such as removing the contained template by oxidization by calcination or extraction and removal with an organic solvent such as alcohol. A mesopore titanosilicate molecular sieve can be obtained. Furthermore, if necessary, a surface treatment agent such as a silane coupling agent such as tetraalkoxysilane, monoalkylalkyltrialkoxysilane, dialkyldialkoxysilane, or trialkylalkoxysilane or an alkoxide such as boron is used. It can be treated to modify the surface or control the pore size.

In the present invention, the alkylamine is a primary, secondary, tertiary amine or quaternary alkylammonium salt having an alkyl group having 8 or more carbon atoms, preferably having 8 to 20 carbon atoms. Primary amines, specifically, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosyl Examples thereof include amines, methylalkylamines, dimethylalkylamines, and trimethylalkylammonium halides, which are substituted with a methyl group. Particularly preferably, it has 1 carbon atom
0-18 linear monoalkylamines.

As a method for adding the alkylamine, most of the alkylamines used as a template during the synthesis of the mesopore titanosilicate molecular sieve are removed by a method such as extraction without baking and removing the alkylamines, and a part is left. Any method may be used, such as a method of containing the compound, a method of impregnating a solution containing an alkylamine and adsorbing the amine to evaporate and remove the solvent, and a method of vapor-phase adsorption in which the compound is placed and adsorbed in an atmosphere containing alkylamine vapor.

The content of the amine having an alkyl group having 8 or more carbon atoms contained in the catalyst of the present invention is 0.1
-20% by weight, preferably 0.5-10% by weight, more preferably 1-5% by weight. The alkylamine-containing mesopore titanosilicate molecular sieve obtained by the present invention has excellent activity as an oxidation catalyst using aqueous hydrogen peroxide as an oxidizing agent.

In the present invention, the olefin is a chain hydrocarbon having an ethylene bond, a cyclic hydrocarbon having an ethylene bond in a ring, and a derivative thereof. Specifically, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, olefins such as heptadecene, octadecene, nonadecene, eicosene, and their side chains Derivatives with hydrocarbon groups, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, cyclotridecene, cyclotetradecene, cyclopentadecene, cyclohexadecene, and side chain hydrocarbons in these cyclo rings Derivatives having a group can be mentioned.

Hydrogen peroxide used as an oxidizing agent is usually 20
Used as a ~ 50% aqueous solution. As the reaction system, a polar solvent such as alcohol, dioxane, or acetonitrile may be added as a solvent to an olefin and aqueous hydrogen peroxide. The catalyst of the present invention effectively functions even when no solvent is used. As the liquid phase oxidation reaction conditions, the temperature is usually from room temperature to 150 ° C., and the molar ratio of hydrogen peroxide is 1 to olefin.
About 0.1 to 10 mol is used per mol.

As a form of use of the catalyst, a method using a solid catalyst, such as a slurry suspension method or a fixed bed flow method as a molded catalyst, can be applied. By using the catalyst of the present invention, in the oxidation reaction of olefins using hydrogen peroxide water as an oxidizing agent which is easy to handle, oxidized products such as epoxide (for example, cyclooctene oxide) and nor (for example, cyclohexenol) , Non (for example, cyclohexenone), aldehyde and the like can be efficiently produced.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited thereto. The X-ray diffraction pattern in the examples is obtained by using RADIII type manufactured by Rigaku Denki Co., and the specific surface area and pore distribution are measured by a BET method using nitrogen and a BJH method using a soapmatic 1800 type apparatus manufactured by Carlo Elba. The peak diameter of the differential distribution was shown as the pore diameter. The analysis of the oxidation reaction was measured using GC9A type gas chromatography manufactured by Shimadzu Corporation, and the yield of the oxidation product was shown on the basis of the olefin as the raw material.

[0017]

[Reference Example 1] Using a 500 ml beaker, distilled water 10
80 g of ethanol and 10 g of dodecylamine are added to 0 g and dissolved. The slurry was allowed to stand and reacted at room temperature for 20 hours. The reaction mixture was filtered, washed with water, and dried at 110 ° C. for 5 hours to obtain a white powdery product (19 g).
I got The template (amine) contained in the dried product was removed, and 5 g of the dried product was dispersed in 750 ml of ethanol, extracted for 1 hour at 60 ° C., and filtered 3 times to obtain a mesoporous body. Then, it is washed with alcohol, dried at 150 ° C. for 3 hours under vacuum, and mesopore titanosilicate molecular sieve having methyl group is 3.4 g.
I got Further, 5 g of the dried sample was fired at 550 ° C. in air which is usually used as a method for removing a template (alkylamine) to prepare a fired sample of 3.3 g.

The powder X-ray diffraction pattern of the extracted sample has a d value of 3.
It showed a strong peak at 9.6 °. As a result of measuring a specific surface area and a pore distribution by a nitrogen adsorption / desorption method, the specific surface area was 940 m.
² / g and the pore size was 3.2 nm. C, H, N composition analysis confirmed that 3% by weight of dodecylamine remained. The powder X-ray diffraction pattern of the fired sample had a d value of 4.
It showed a strong peak at 0.0 °. As a result of measuring the specific surface area and the pore distribution by the nitrogen adsorption / desorption method, the specific surface area was 970 m
² / g and the pore size was 3.2 nm. The silica / titania ratio determined by X-ray fluorescence analysis was 31.

[0019]

Reference Example 2 1 g of mesopore titanosilicate (calcined product) synthesized in Reference Example 1 was impregnated with 5 cc of acetone in which 50 mg of n-dodecylamine was dissolved, and evaporated to dryness at room temperature.
Subsequently, the resultant was dried at 110 ° C. for 30 minutes to prepare a mesopore titanosilicate catalyst containing dodecylamine.

[0020]

Reference Example 3 1 g of mesopore titanosilicate (calcined product) synthesized in Reference Example 1 was added to 50 mg of n-hexadecylamine.
Was dissolved in 5 cc of acetone, evaporated to dryness at room temperature, and then dried at 110 ° C. for 30 minutes to prepare a hexadecylamine-containing mesopore titanosilicate catalyst.

[0021]

EXAMPLE 1 6.8 g of cyclooctene was placed in a 50 ml three-necked flask equipped with a condenser and a stirrer, and Reference Example 2 was used as a catalyst.
0.25 g of mesopore titanosilicate containing dodecylamine synthesized in (1) and aqueous hydrogen peroxide (30%)
3.55 g was added, and the mixture was placed in an oil bath heated to a predetermined temperature of 60 ° C., and an oxidation reaction was performed for 4 hours. As a result, the yield of cyclooctene oxide (based on cyclooctene) was 4.4 mol%. The turnover number of cyclooctene oxide is 21 mol / Tim
ol, and the selectivity was 98% or more.

[0022]

Example 2 Cyclooctene was oxidized in the same manner as in Example 1 except that the mesopore titanosilicate containing hexadecylamine prepared in Reference Example 3 was used as a catalyst. As a result, the turnover number of cyclooctene oxide formation in a reaction time of 4 hours was 18 mol / Timo.
l.

[0023]

Example 3 Cyclooctene oxidation reaction was carried out in the same manner as in Example 1 except that the mesopore titanosilicate containing the extracted dodecylamine remaining in Reference Example 1 was used as a catalyst. As a result, the turnover number of cyclooctene oxide formation in a reaction time of 4 hours was 17 mol /
Timol.

[0024]

Example 4 As in Example 1, except that the catalyst was the same as in Reference Example 2, and that instead of dodecylamine, tridecylamine was used, and that mesopore titanosilicate containing tridecylamine by weight% was used. The oxidation reaction of octene was performed. As a result, the turnover number of cyclooctene oxide formation in a reaction time of 4 hours was 18 mol / T
imol.

[0025]

Example 5 As Example 1, except that the catalyst was the same as in Reference Example 2, except that tetradecylamine was used in place of dodecylamine, and that mesopore titanosilicate containing 5% by weight of tetradecylamine was used. An oxidation reaction was performed. As a result, the yield of cyclooctene oxide at a reaction time of 4 hours was 4 mol%, and the turnover number was 19 mol / Timol.

[0026]

Example 6 As in Example 1, except that the catalyst was the same as in Reference Example 2, except that decylamine was used in place of dodecylamine to prepare a mesopore titanosilicate containing 7% by weight of decylamine, and this was used as a catalyst. The oxidation reaction of cyclooctene was performed in the same manner as in Example 1. As a result, the turnover number of cyclooctene oxide formation at a reaction time of 4 hours was 10 mol / Timol.

[0027]

Example 7 Same as Example 1, except that the catalyst was the same as in Reference Example 3, except that cetyltrimethylammonium chloride was used instead of dodecylamine to prepare a mesopotitanosilicate containing 5% by weight of cetyltrimethylammonium chloride. This was used as a catalyst to carry out an oxidation reaction of cyclooctene. As a result, the turnover number of cyclooctene oxide formation at a reaction time of 4 hours was 8 mol / Timol.

[0028]

COMPARATIVE EXAMPLE 1 Cyclooctene oxidation reaction was carried out in the same manner as in Example 1, except that the calcined mesopore titanosilicate prepared in Reference Example 1 was used as a catalyst. As a result, the yield of cyclooctene oxide after 4 hours of the reaction time was 0.3 mol% for the calcined catalyst, and the turnover number of cyclooctene oxide formation per titanium as an active component in the catalyst was 1.6. Met.

[0029]

Example 8 As in Example 1, except that 0.25 g of the extraction treatment catalyst containing dodecylamine prepared in Reference Example 1 was used as the catalyst, 0.55 g of cyclooctene and hydrogen peroxide (concentration: 30 wt. %) And 10 ml of acetonitrile as a solvent were added, and the oxidation reaction of cyclooctene was performed at 60 ° C. for 6 hours. As a result, the yield of cyclooctene oxide at a reaction time of 6 hours was 14 mol%, and the turnover number of cyclooctene oxide generation per titanium was 6.3 mol / Timol.

[0030]

COMPARATIVE EXAMPLE 2 Cyclooctene oxidation reaction was carried out in the same manner as in Example 8, except that the calcined mesopore titanosilicate prepared in Reference Example 1 was used as a catalyst. as a result,
The yield of cyclooctene oxide at the reaction time of 4 hours was 1.9 mol% for the calcined catalyst, and the turnover number of cyclooctene oxide formation per titanium as an active component in the catalyst was 0.8. .

[0031]

Example 9 As in Example 1, except that cyclooctene was replaced by 2.12 g of cyclohexene and hydrogen peroxide solution (30%).
% Aqueous solution) and 0.05 g of the dodecylamine-containing mesopore titanosilicate molecular sieve catalyst of Reference Example 1 were used to carry out cyclohexene oxidation reaction at 60 ° C. As a result, the oxidation product yield after a reaction time of 4 hours was 15 mol% (selectivity was 2% for cyclohexene oxide, 8% for cyclohexenol, 12% for cyclohexenone, 8% for cyclohexanediol, and 8% for cyclohexene peroxide.
0%)).

[0032]

Example 10 The cyclohexene oxidation reaction was carried out at 60 ° C. in the same manner as in Example 9 except that 0.05 g of the hexadecylamine-containing mesopore titanosilicate molecular sieve catalyst of Reference Example 2 was used. As a result, the yield of the oxidation product in a reaction time of 4 hours was 16 mol% (selectivity was 2% for cyclohexene oxide, 9% for cyclohexenol, 16% for cyclohexenone, 4% for cyclohexanediol, and 69% for cyclohexene peroxide). )Met.

[0033]

Example 11 The oxidation reaction of cyclohexene was carried out at 60 ° C. in the same manner as in Example 8, except that 0.41 g of cyclohexene was used instead of cyclooctene. As a result, the yield of the oxidation product after a reaction time of 6 hours was 16 mol% (selectivity was 20% for cyclohexene oxide, 9% for cyclohexenol 9).
%, Cyclohexenone 19% and cyclohexanediol 52%).

[0034]

Example 12 Hexene oxidation reaction was carried out at 60 ° C. in the same manner as in Example 8, except that 0.42 g of 1-hexene was used instead of cyclooctene. As a result, the yield of hexene oxide at a reaction time of 4 hours was 12 mol%.

[0035]

Comparative Example 3 Cyclohexene oxidation reaction was carried out in the same manner as in Example 9 except that the calcined catalyst prepared in Reference Example 1 was used as the catalyst. As a result, the yield of the oxidation product after a reaction time of 4 hours was 1.2 mol%.

[0036]

The catalyst of the present invention has very excellent catalytic activity in the oxidation reaction of olefins using hydrogen peroxide as an oxidizing agent, so that the oxidation product of epoxide (for example, cyclooctene oxide) is obtained. , Nol (eg, cyclohexenol), nonone (eg, cyclohexenone), aldehyde, and the like can be efficiently and easily produced.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07C 49/603 C07C 49/603 C07D 301/12 C07D 301/12 303/04 303/04 // C07B 61/00 300 C07B 61 / 00 300

Claims (2)

[Claims] 1. A catalyst comprising a mesopore titanosilicate molecular sieve, which comprises 0.1 to 20% by weight of an amine having an alkyl group having 8 or more carbon atoms in the catalyst. 2. The catalyst according to claim 1, wherein the alkylamine is a primary amine.