Titanium-containing silicon oxide catalyst

Details Titanium-containing silicon oxide catalyst Titanium-containing silicon oxide catalyst

1999-07-30

2001-11-27

Wood, Elizabeth D. (Department: 1755)

Catalyst, solid sorbent, or support therefor: product or process

Zeolite or clay, including gallium analogs

And additional al or si containing component

C502S234000, C502S236000, C502S237000, C502S239000, C502S240000, C502S242000

Reexamination Certificate

active

06323147

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a titanium-containing silicon oxide catalyst, a method for producing the same, and a method for producing propylene oxide. More particularly, the present invention relates to a titanium-containing silicon oxide catalyst which can produce propylene oxide by reacting propylene with a hydroperoxide, except for ethylbenzene hydroperoxide, in high yield and high selectivity, a method for producing said catalyst, and a method for producing propylene oxide.
2. Description of the Related Art
It is known that a titanium-containing silicon oxide can be produced by using a quarternary ammonium ion as a template. As a titanium-containing silicon oxide having an average pore size of 10 Å or more, Ti-MCM41 disclosed in U.S. Pat. No. 5,783,167, Ti-MCM48 disclosed in JP 07300312 A and the like are known. These known titanium-containing silicon oxides having large pores of 10 Å or more are obtained by removing the template by calcining. When these titanium-containing silicon oxides are used as a catalyst in an epoxidation reaction, catalytic activity is not in the satisfactory level. A catalyst having higher activity has been desired.
SUMMARY OF THE INVENTION
Under these circumstances, the present inventors have intensively studied for a catalyst having a high catalytic activity in an epoxidation reaction, and have found that a catalyst obtained by removing a template via extracting in a solvent has a high catalytic activity in an epoxidation reaction. The present inventors thus completed the present invention.
An object of the present invention is to provide a titanium-containing silicon oxide catalyst which can produce propylene oxide by reacting propylene with a hydroperoxide, except for ethylbenzene hydroperoxide, a method for producing said catalyst, and a method for producing propylene oxide in high yield and high selectivity.
Namely, the present invention relates to a titanium-containing silicon oxide catalyst satisfying all of the following conditions (1) to (4):
(1): An average pore size of 10 Å or more.
(2): A pore size of 90% or more of the total pore volume of 5 to 200 Å.
(3): A specific pore volume of 0.2 cm
3
/g or more.
(4): A quarternary ammonium ion represented by the following general formula (I) is used as a template and then said template is removed by solvent extraction operation;
[NR
1
R
2
R
3
R
4
]
+
  (I)
(wherein, R
1
represents a linear or branched hydrocarbon chain having 2 to 36 carbon atoms, and R
2
to R
4
represent an alkyl group having 1 to 6 carbon atoms).
The present invention also relates to a method for producing said catalyst, wherein said method comprises the following steps of;
mixing and stirring a silica source, titanium source and a quarternary ammonium ion as a template in a solvent to obtain a solid containing a catalyst component and the template, and
extracting the obtained solid in a solvent to obtain a catalyst by removing the template.
The present invention further relates to a method for producing propylene oxide by reacting propylene with a hydroperoxide, except for ethylbenzene hydroperoxide.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The catalyst used in the present invention is a catalyst comprising a titanium-containing silicon oxide satisfying all of the following conditions (1) to (4). The object of the present invention can be fully accomplished by using said catalyst. The main object of the present invention is to produce propylene oxide by reacting propylene with a hydroperoxide, except for ethylbenzene hydroperoxide, in high yield and high selectivity.
The condition (1) is that an average pore size of the catalyst is 10 Å or more.
The condition (2) is that a pore size of 90% or more of the total pore volume of the catalyst is 5 to 200 Å.
The condition (3) is that a specific pore volume of the catalyst is 0.2 cm
3
/g or more. The specific pore volume means pore volume per 1 g of the catalyst.
Measurements of these conditions (1) to (3) can be conducted by known methods such as a physical absorption method using gases such as nitrogen, argon and the like.
The condition (4) is that the catalyst is obtained by using a quarternary ammonium ion represented by the following general formula (I) as a template and then removing said template by a solvent extraction operation;
 [NR
1
R
2
R
3
R
4
]
+
  (I)
(wherein, R
1
represents a linear or branched hydrocarbon chain having 2 to 36 carbon atoms, and R
2
to R
4
represent an alkyl group having 1 to 6 carbon atoms). The condition (4) will be illustrated in detail herein with regard to a method for producing said catalyst.
A catalyst of the present invention preferably has at least one peak showing an interplanar spacing (d) of larger than 18 Å, or no peak showing an interplanar spacing (d) in a X-ray diffraction (XRD) The peak showing an interplanar spacing (d) as herein referred to means a peak derived from the crystallinity and regularity of a solid, and a broad peak derived from an amorphous part may exist. When, a peak showing an interplanar spacing (d) of larger than 18 Å exists in a X-ray diffraction, it is preferable that this peak is a part of a peak group showing the structure of a hexagonal system.
The catalyst of the present invention preferably has an absorption peak in the range of 960±5 cm
−1
in the infrared absorption spectrum. This peak is considered to correspond to titanium introduced into a silica skeleton.
The catalyst of the present invention can be produced by the following method comprising the following steps.
The first step: A step in which a silica source, titanium source and a quarternary ammonium ion as a template are mixing and stirring in a solvent to obtain a solid containing a catalyst component and the template.
The second step: A step in which a catalyst is obtained by extracting the obtained solid in a solvent to remove the template.
The first step is a step which a silica source, a titanium source and a quarternary ammonium ion as a template are mixing and stirring in a solvent to obtain a solid containing a catalyst component and the template. When a reagent to be used is solid, it may be used by dissolving in a solvent, or dispersing in a solvent.
Examples of the silica source include amorphous silica and alkoxysilane such as tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate and the like.
Examples of the titanium source include titanium alkoxides such as tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, tetra-2-ethylhexyl titanate, tetraoctadecyl titanate, and titanium (IV) oxyacetylacetonate, titanium (IV) diisopropoxybisacetyl acetonate and the like, and titanium halides such as titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and the like.
As a template, a quarternary ammonium ion represented by the following general formula (I) is used.
[NR
1
R’R
3
R
4
]
+
  (I)
(wherein, R
1
represents a linear or branched hydrocarbon chain having 2 to 36 carbon atoms, and R
2
to R
4
represent an alkyl group having 1 to 6 carbon atoms).
R
1
represents a linear or branched hydrocarbon chain having 2 to 36 carbon atoms, preferably 10 to 18 carbon atoms.
R
2
to R
4
represent an alkyl group having 1 to 6 carbon atoms, and preferably each of R
2
to R
4
is a methyl group.
Specific examples of the quarternary ammonium ion represented by the general formula (I) include cations such as hexadecyltrimethylammonium, dodecyltrimethylammonium, benzyltrimethylammonium, dimethyldidodecylammonium, hexadecylpyridinium, and the like.
Examples of the solvent include water and alcohol such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, sec-butanol, t-butanol, vinyl alcohol, allyl alcohol, cyclohexanol, benzyl alcohol and the like, and diols, or a mixture thereof, and the like.
A suitable mixing ratio of a

Affiliated with

Also associated with

Rating

Titanium-containing silicon oxide catalyst does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Titanium-containing silicon oxide catalyst, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Titanium-containing silicon oxide catalyst will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2593584