Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2001-11-13
2004-07-06
Trinh, Ba K. (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C549S531000, C502S107000, C502S242000
Reexamination Certificate
active
06759540
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a crystalline titanosilicate catalyst having a structural (or framework type) code of MWW, which is usable as a catalyst in an oxidation reaction of the carbon-carbon double bond of a compound having a carbon-carbon double bond and at least one other functional group. The present invention also relates to a process for producing such a catalyst and a process for producing an oxidized compound using this catalyst.
More specifically, the present invention relates to a crystalline titanosilicate catalyst having a structural code of MWW, which is usable as a catalyst in an oxidation reaction of the carbon-carbon double bond of a compound having a carbon-carbon double bond and at least one other functional group using a peroxide as an oxidizing agent; a process for producing such a catalyst; and a process for producing an oxidized compound (particularly, an epoxy compound) comprising performing an oxidation reaction of the carbon-carbon double bond of a compound having a carbon-carbon double bond and at least one other functional group in the presence of the catalyst.
BACKGROUND ART
In general, “zeolite” is a generic term for crystalline and porous aluminosilicates for, and the basic unit of the structure of a zeolite is (SiO
4
)
4−
or (AlO
4
)
5−
having a tetrahedral structure. However, it has recently been clarified that a structure peculiar to or analogous to such a zeolite is also present in many other oxides such as aluminophosphate.
In addition, according to the International Zeolite Association (hereinafter, simply referred to as “IZA”) who defines the zeolite in W. Meier, D. H. Meier, D. H. Olxon and Ch. Baerlocher,
Atlas of Zeolite Structure Types
, 4
th
Edition, Elsevier (1996) (hereinafter, simply referred to as “Atlas”), substances having the same structure, other than aluminosilicate, are described as an object substance in prescribing the structure, and these substances are called “zeolite-like materials” in the Atlas.
The history of this definition is described in detail in Yoshio Ono and Takeaki Yajima,
Zeolite no Kagaku to Kogaku
(
Science and Engineering of Zeolites
), pp. 1-2, published by Kodansha (Jul. 10, 2000).
In the present specification, the definition of “zeolite” follows the above definition as described in Yoshio Ono and Takeaki Yajima,
Zeolite no Kagaku to Kogaku
(
Science and Engineering of Zeolite
), published by Kodansha (Jul. 10, 2000), where the term “zeolite” may include not only aluminosilicates but also substances (such as titanosilicate) having a structure analogous to aluminosilicate.
In the present specification, the structures of zeolite and zeolite-like materials are denoted by a structural code, using three alphabetic capital letters, approved by IZA and originated in the standard substance which had first been used for the clarification of the structure thereof. The structural codes includes those contained in Atlas and those approved in the 4
th
edition, et seq.
In the present specification, the terms “aluminosilicate” and “titanosilicate” are not limited at all by the properties and/or states thereof (such as crystalline or amorphous, or porous or not porous). Therefore, in the present specification, these terms denote “aluminosilicates” and “titanosilicates” of all properties, unless specifically indicated otherwise.
In the present specification, the term “molecular sieve” means an activity or operation for classifying molecules by the size thereof, and the term also means a substance having such a function. zeolite is also included in the definition of a molecular sieve. The details thereon are described in the portion relating to “molecular sieve” in
Hyojun Kagaku Yogo Jiten
(
Standard Chemical Glossary
), edited by the Chemical Society of Japan, published by Maruzen (Mar. 30, 1991).
In recent years, various studies have been made on the oxidation reactions of organic compounds by using a titanosilicate which is a zeolite, as a catalyst, and using a peroxide as an oxidizing agent. Among these, a catalyst named “TS-1”, which is a crystalline titanosilicate, has been found to show an activity in an oxidation reaction using various peroxides, after the process for synthesizing the same was disclosed in U.S. Pat. No. 4,410,501, and TS-1 has been applied to various reactions. Specific examples thereof include the method disclosed in JP-B-4-5028 (“JP-B” as used herein means an “examined Japanese Patent publication”), where TS-1 is used as a catalyst in the epoxidation of an olefin compound using hydrogen peroxide or an organic peroxide as an oxidizing agent.
The structural code of the titanosilicate TS-1 is “MFI”, which is the same code as the structural code of a representative synthetic zeolite ZSM-5, and TS-1 contains a ring structure containing ten (10) oxygen atoms (as described in Yoshio Ono and Takeaki Yajima,
Zeolite no Kagaku to Kogaku
, p. 4, published by Kodansha). As TS-1 has a relatively small pore size of 0.51 nm to 0.56 nm in terms of a calculated value therefor, the scope of olefin compounds which can be epoxidized by using TS-1 is limited. Further, both of the rate of the diffusion of an olefin compound as a reaction starting material into the inside of a pore and the rate of the effusion of an epoxy compound as a reaction product from the pore are low, so that a reaction activity which is sufficiently high, in view of the industrial use of TS-1, cannot be achieved in many cases. Furthermore, there is a problem such that a ring-opening reaction of the epoxy group of an epoxy compound as a reaction product is liable to occur, and the resultant selectivity is disadvantageously decreased.
On the other hand, JP-A-7-242649 (“JP-A” as used herein means “unexamined Japanese Patent publication”) discloses a method of performing an epoxidation reaction of an olefin compound by using a crystalline titanium-containing molecular sieve having a structure similar to aluminum-free zeolite Beta (structural code: *BEA) as a catalyst and by using hydrogen peroxide or an organic peroxide as an oxidizing agent.
Since the *BEA has a large pore diameter as compared with that of the structural code of MFI for the titanosilicate TS-1, an effect of enabling a reaction of a sterically bulky compound or an effect of elevating the diffusion rate to thereby improve the resultant reaction rate was expected. In some examples of the above-mentioned Patent publication, a compound which does not react even in the case using the titanosilicate TS-1 can be actually oxidized. However, there are caused problems that the conversion of an oxidizing agent is low when hydrogen peroxide is used as the oxidizing agent for the epoxidation reaction, and that a ring-opening reaction of the epoxide is caused to produce a corresponding glycol, and as a result, the resultant selectivity is decreased. Further, in the case of the molecular sieve as described in this Patent publication, the decreasing rate of activity is rather high. That is, the catalyst life is short, and therefore it is necessary to repeat the regeneration of the catalyst frequently, whereby this point seriously hinders the implementation of such a molecular sieve on an industrial scale.
On the other hand, in recent years, synthetic zeolites having a structural code of MWW, which is different from those of MFI or *BEA, are attracting attention. The process for producing the same is disclosed, for example, in JP-A-63-297210.
Further, according to Peng Wu, Takashi Tatsumi and Takayuki Komatsu,
Chemistry Letters
, 774 (2000), it has been reported that when a crystalline titanosilicate having the structural code of MWW and containing a titanium atom in the crystal structure thereof is produced, and cyclohexene is oxidized by using this crystalline titanosilicate as a catalyst and by using hydrogen peroxide, cyclohexene oxide can be produced.
However, the yield of the intended product is rather low, while both of the resultant epoxide and diol are produced in a considerably large amount, whereby a tendency of selectively providing any
Oguchi Wataru
Tatsumi Takashi
Tsuji Katsuyuki
Wu Peng
Showa Denko K.K.
Sughrue & Mion, PLLC
Trinh Ba K.
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