JP5403530B2 - Mesoporous aluminosilicate and synthesis method thereof - Google Patents

Description

  The present invention relates to a method for synthesizing a novel mesoporous aluminosilicate. The present invention also relates to a mesoporous aluminosilicate having many strong solid acid sites and excellent crushing strength.

Mesoporous materials have regular pores with a pore diameter of 2 to 10 nm, and several materials with different structures have been reported. For example, MCM-41 using trimethylcetylammonium bromide (hereinafter abbreviated as CTMABr) as a structure-regulating agent (SDA), Brij30 (block copolymer EO of ethylene oxide and propylene oxide) which is a nonionic surfactant. Typical examples thereof include MCM-48 using _m PO _n EO _m (m = 33 to 70, n = 5 to 26), SB-15 using dicetyldimethylammonium bromide, and the like.

  These mesoporous materials have mesopores (pore diameter 2 to 10 nm) larger than micropores (pore diameter of about 3 to 8 mm) of zeolite, high specific surface area, and high heat resistance. Therefore, as materials utilizing these characteristics, development of new uses such as a catalyst support capable of synthesizing bulky materials that cannot be handled by zeolite, various organic inorganic hosts, adsorbents, and the like has been expected.

  However, since the basic structure of the mesoporous material is an amorphous glass structure and has no crystallinity, problems such as low mechanical strength and hydrothermal stability have been revealed. In addition, solid acidity introduced at the time of synthesizing a mesoporous material with an acid-expressing substance such as aluminum or by a method of modification after synthesis is too low for various reactions to proceed smoothly as a solid acid catalyst. (Non-patent document 1: CT Kresge, ME Leonowicz, WJ Roth, JC Vartuli, JS Beck, Nature 1992, 359, 22, 710).

  The inventors of the present invention have solved these problems, and, as a result of conducting research aimed at creating a mesoporous material having excellent hydrothermal stability and mechanical strength and high solid acidity, When mixed with a nonionic surfactant, the mechanical strength (crushing strength) is higher than that of the conventional MCM-48, the solid acidity is higher, and the conventional zeolite is substantially inactive. The present invention was completed by finding that it exhibits extremely high activity in the condensation cyclization reaction between isophytol, which is a large molecular weight reactant, and 2,3,4-trimethylhydroquinone.

C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli, J. S. Beck, Nature 1992, 359, 22, 710

  An object of the present invention is to provide a novel mesoporous aluminosilicate production method and a novel mesoporous aluminosilicate which can be suitably used for a catalytic reaction involving a reactant having a large molecular weight and a product.

The method for synthesizing mesoporous aluminosilicate of the present invention is characterized by including the following steps (a) to (d).
A mesoporous aluminosilicate synthesis precursor comprising (a) (I) a first organic structure regulator, (II) a silica source, (III) an alumina source, (IV) a second organic structure regulator, and (V) water. Step of preparing (b) Step of hydrothermal treatment at 80 to 150 ° C (c) Step of cooling to 20 to 50 ° C and adjusting pH to 9 to 12 (d) Step of hydrothermal treatment at 80 to 150 ° C

It is preferable that the first organic structure regulating agent is a surfactant and the second organic structure regulating agent is a quaternary ammonium salt or a hydroxide.
The first organic structure regulating agent is preferably composed of a nonionic surfactant and a cationic surfactant.
The molar ratio of the nonionic surfactant to the cationic surfactant (nonionic surfactant / cationic surfactant) is preferably in the range of 0.1 to 1.0.

The composition of the mesoporous aluminosilicate synthesis precursor is such that (I) the first organic structure regulator is 0.1 to 0.4 mol, and (III) the alumina source with respect to 1 mol of SiO ₂ of the (II) silica source. There 0.001 mol as Al ₂ O _3, (IV) a second organic structure directing agent is 0.1 to 1.0 mole, in the range of 50 to 200 mol of the H ₂ O (V) water Preferably there is.

The mesoporous aluminosilicate of the present invention has a structure similar to that of MCM-48, the peak temperature of the desorption spectrum of chemisorbed NH ₃ by the temperature programmed desorption method is in the range of 260 to 300 ° C., and the final desorption temperature is It is 400 degreeC or more.
The mesoporous aluminosilicate preferably has a chemisorbed NH ₃ amount in the range of 0.005 to 0.3 meq / g by a temperature programmed desorption method. The crushing strength is preferably 3 MPa or more.

According to the mesoporous aluminosilicate of the present invention, it is suitable for a catalytic reaction involving a product having a large molecular weight and molecular size, which is difficult with a conventional zeolite having only a micropore (crystalline aluminosilicate) and a product having a large molecular size. Can do. In addition, the novel mesoporous aluminosilicate can be easily produced.

[Method of synthesizing mesoporous aluminosilicate]
The method for synthesizing mesoporous aluminosilicate according to the present invention includes the following steps (a) to (d).
A mesoporous aluminosilicate synthesis precursor comprising (a) (I) a first organic structure regulator, (II) a silica source, (III) an alumina source, (IV) a second organic structure regulator, and (V) water. Step of preparing (b) Step of hydrothermal treatment at 80 to 150 ° C (c) Step of cooling to 20 to 50 ° C and adjusting pH to 9 to 12 (d) Step of hydrothermal treatment at 80 to 150 ° C

Step (a)
As the (I) first organic structure regulating agent used in the present invention, a surfactant is preferably used, and as the surfactant, a cationic surfactant and a nonionic surfactant are used.
Specifically, trimethyl cetyl ammonium, trimethyl stearyl ammonium, trimethyl myristyl ammonium, triethyl cetyl ammonium, triethyl stearyl ammonium, triethyl myristyl ammonium, dimethyl dicetyl ammonium, dimethyl distearyl ammonium, dimethyl dimyristyl ammonium, etc. as cationic surfactants One or two or more selected from hydrohalides, sulfates, carboxylates, hydroxides, and the like can be used.

Nonionic surfactants include polyethylene oxide long chains such as block copolymers EO _m PO _n EO _m (m = 33 to 70, n = 5 to 26) of ethylene oxide and propylene oxide, Tween 20, Tween 40, and Tween 60. Examples include fatty acid esters, polyethylene oxide long chain fatty ethers such as Brij30, Brij35, and Brij48, long sugar chain alkyl ethers such as Dodecyl-BD-maltopyranoside, and polyethylene oxide octylphenyl ethers such as Triton x-100. .

  At this time, if a cationic surfactant and a nonionic surfactant such as Brij30 are present, a mesoporous aluminosilicate having the same structure as MCM-48 having a three-dimensional structure can be obtained. On the other hand, when there is one long chain group such as CTMABr, a mesoporous aluminosilicate having the same one-dimensional structure as MCM-41 is obtained.

The molar ratio of nonionic surfactant to cationic surfactant (nonionic surfactant / cationic surfactant) is in the range of 0.1 to 1.0, more preferably 0.2 to 0.8. It is preferable that it exists in.
When the nonionic surfactant / cationic surfactant molar ratio is less than 0.1, a mesoporous material having a one-dimensional structure such as MCM-41 may be formed. On the other hand, if this molar ratio exceeds 1.0, the formation of zeolite subunits (ZSU) may be incomplete, or characteristics determined from the desorption spectrum of chemisorbed NH ₃ by the temperature programmed desorption method described later. That is, there is a case where a large amount of chemically adsorbed NH ₃ and a strong adsorbing characteristic may not be obtained, and a sufficient activity may not be obtained even when used as a catalyst.

(II) As the silica source, a conventionally known silica source used for the synthesis of zeolite, mesoporous silicate, etc. can be used. For example, silica fine powder such as silica sol, alkoxide or aerosil can be used.
(III) As the alumina source, a conventionally known alumina source used for the synthesis of zeolite can be used. For example, aluminum salts such as aluminum chloride, aluminum sulfate, aluminum acetate, aluminum nitrate, aluminum isopoloxide, etc. And complex compounds such as aluminum acetylacetonate.
(IV) As the second organic structure regulating agent, quaternary ammonium salts or hydroxides are used. Specifically, various salts such as tetramethylammonium, tetraethylammonium, tetrapropylammonium, dibenzyldimethylammonium ( However, chlorides and the like, and bromides are excluded), hydroxides, and mixtures thereof.

The composition of the mesoporous aluminosilicate synthetic precursors, the (II) with respect to SiO ₂ 1 mole of the silica source, (I) a first organic structure directing agent is 0.1 to 0.4 mol, further 0. It is preferably in the range of 15 to 0.3 mol. (I) When the first organic structure-regulating agent is less than 0.1 mol, regular pores (mesopores) having a pore diameter of 2 to 10 nm may not be sufficiently formed, while (I) the first organic Even if the structure-regulating agent exceeds 0.4 mol, the properties of mesoporous aluminosilicate obtained are not further improved, and the economic efficiency is lowered.

Further, (III) alumina source is in the range of 0.001 to 0.05 mol, further 0.005 to 0.03 as Al ₂ O _{3 with} respect to 1 mol of SiO _{2 of the} silica source (II). It is preferable. (III) When the alumina source is less than 0.001 mol as Al ₂ O ₃ , the resulting mesoporous aluminosilicate has few solid acid sites, and the catalytic reaction activity in which these solid acid sites act as active sites cannot be obtained sufficiently. There is a case. On the other hand, when (III) the alumina source exceeds 0.05 mol as Al ₂ O _3, it is considered that the alumina is too much and crystalline aluminosilicate is formed on the mesoporous surface of the mesoporous aluminosilicate (in the present invention, β-zeolite (BEA)). In some cases, the activity of the catalytic reaction in which the solid acid sites act as active sites becomes insufficient.

Next, (IV) the second organic structure-regulating agent is in the range of 0.1 to 1.0 mol, more preferably 0.2 to 0.9 mol with respect to 1 mol of SiO _{2 of the} silica source (II). Preferably there is. (IV) When the second organic structure-regulating agent is less than 0.1 mol, the amount of the second organic structure-regulating agent is small, so that crystalline aluminosilicate (β-zeolite (BEA in the present invention) is formed on the mesoporous surface of the mesoporous aluminosilicate. ) Which is considered as a structural unit) is not formed, and the catalytic reaction may be insufficient. On the other hand, (IV) when the amount of the second organic structure-regulating agent exceeds 1.0 mol, crystalline aluminosilicate (β-zeolite (in the present invention) is formed on the mesoporous surface of the mesoporous aluminosilicate even if there is too much second organic structure-limiting agent. In some cases, the activity of the catalytic reaction is insufficient due to the formation of (BEA) structural units).

It is preferable that (V) water is in the range of 50 to 200 mol, more preferably 60 to 150 mol as H ₂ O, with respect to 1 mol of SiO _{2 of the} silica source (II). When (V) water is less than 50 mol as H ₂ O, the obtained mesoporous aluminosilicate may be obtained as an aggregate, while (V) when water exceeds 200 mol as H ₂ O, crystallization occurs. Even if it takes a long time or is obtained, the crystallinity may be insufficient. For this reason, the activity may be insufficient when used as a catalyst.

Step (b)
The mesoporous aluminosilicate synthesis precursor is hydrothermally treated at 80 to 150 ° C., preferably 90 to 120 ° C.
When the hydrothermal treatment temperature is less than 80 ° C., it may take a long time for crystallization, or even if obtained, a highly ordered mesoporous structure may not be generated. When the hydrothermal treatment temperature exceeds 150 ° C., quartz or the like is produced, and mesoporous aluminosilicate having a mesoporous structure and a β-zeolite (BEA) structural unit may not be obtained.
The hydrothermal treatment time is usually 5 to 200 hours, more preferably 10 to 100 hours.

Step (c)
Next, the pH of the mesoporous aluminosilicate synthesis precursor that has been cooled to 20 to 50 ° C. and hydrothermally treated is adjusted to 9 to 12, preferably 10 to 11.
An acid is usually used for pH adjustment. As the acid, hydrochloric acid, nitric acid, sulfuric acid and other organic acids such as acetic acid can be used.
If the pH of the hydrothermally treated mesoporous aluminosilicate synthesis precursor is adjusted outside the above range, mesoporous aluminosilicate may not be obtained, and even if obtained, the formation of mesopores with a pore diameter of 2 to 10 nm is insufficient. May be.

Step (d)
Next, the mesoporous aluminosilicate synthesis precursor whose pH has been adjusted is hydrothermally treated again at 80 to 150 ° C., preferably 90 to 120 ° C.
When the hydrothermal treatment temperature is less than 80 ° C., it may take a long time to produce mesoporous aluminosilicate, or even if obtained, a highly ordered mesoporous structure may not be produced. When the hydrothermal treatment temperature exceeds 150 ° C., quartz or the like is produced, and mesoporous aluminosilicate having a mesoporous structure and a β-zeolite (BEA) structural unit may not be obtained.
The hydrothermal treatment time is usually 5 to 200 hours, more preferably 10 to 100 hours also at this time.

The obtained mesoporous aluminosilicate can be separated, washed, dried if necessary and then calcined.
There is no particular limitation on the washing method, and a conventionally known method can be adopted, but it is preferable to use alcohol such as water, methanol, ethanol or the like for washing the mesoporous aluminosilicate of the present invention.
The drying method is not particularly limited as long as the cleaning liquid mixture can be removed, and a conventionally known method can be employed. The drying temperature is usually 80 to 150 ° C.

The firing method is not particularly limited as long as the first organic structure restricting agent and the second organic structure restricting agent remaining in the mesoporous aluminosilicate can be removed, but usually 300 to 700 ° C., preferably 450, in an air or oxygen atmosphere. Bake at ~ 600 ° C.
When the calcination temperature is less than 300 ° C., the removal of the first organic structure restricting agent and the second organic structure restricting agent is insufficient, and the activity may be insufficient when used as a catalyst. Since the first organic structure-regulating agent and the second organic structure-regulating agent can be substantially removed, it is not necessary to perform baking at a higher temperature.

[Mesoporous aluminosilicate]
The mesoporous aluminosilicate according to the present invention has a structure similar to that of MCM-48, the peak temperature of the desorption spectrum of chemisorbed NH ₃ by the temperature programmed desorption method is in the range of 260 to 300 ° C., and the final desorption temperature. Is 400 ° C. or higher.
Having an analogous structure to MCM-48 has a main peak in the vicinity of 2θ = 2.5 ° in the X-ray diffraction spectrum, and the nitrogen relative pressure (P / P ₀ ) is 0 in nitrogen isothermal adsorption / desorption. .1 to 0.4 means exhibiting significant adsorption and desorption characteristics of nitrogen.

Further, the mesoporous aluminosilicate according to the present invention has a peak temperature in the desorption spectrum of chemisorbed NH ₃ by the temperature programmed desorption method in the range of 260 to 300 ° C., preferably 270 to 290 ° C.
When the peak temperature of the desorption spectrum of chemisorbed NH ₃ is less than 260 ° C., there is no difference from mesoporous aluminosilicate having MFI-zeolite structural unit obtained using tetrapropylammonium bromide as the second organic structure regulator. Even when used as a catalyst, sufficient activity and selectivity may not be obtained. It is difficult to obtain a chemisorbed NH ₃ desorption spectrum having a peak temperature exceeding 300 ° C.

  The final desorption temperature is preferably 400 ° C. or higher. When the final desorption temperature is less than 400 ° C., there is no difference from mesoporous aluminosilicate having MFI-zeolite structural unit obtained by using tetrapropylammonium bromide as the second organic structure regulator, and it can be used as a catalyst. Activity and selectivity may not be obtained.

Such a desorption spectrum of chemisorbed NH ₃ can be obtained as follows. That is, BELL TPD-66 made by Nippon Bell Co., Ltd. was used, about 0.1 gram of sample was exhausted at 500 ° C for 1 hour, the temperature was lowered to 100 ° C, and ammonia gas was introduced at 100 ° C for 1 hour. Adsorb. Next, after exhausting again at 100 ° C. for 1 hour, the amount of desorbed NH ₃ was measured while raising the temperature from 100 ° C. to 700 ° C. at 10 ° C./min under a flow of He gas of 50 ml / min. After obtaining the spectrum, the spectrum is separated, and the spectrum on the high temperature side is obtained as the desorption spectrum of chemisorbed NH ₃ .

The amount of chemisorbed NH ₃ by the temperature programmed desorption method of the mesoporous aluminosilicate according to the present invention is preferably in the range of 0.005 to 0.3 meq / g, more preferably 0.02 to 0.3 meq / g.
The chemically adsorbed NH ₃ amount is considered the amount of solid acid that can be active sites of the catalyst, if chemically adsorbed NH ₃ amount is less than 0.001meq / g, there is the activity may be insufficient, chemical It is difficult to obtain an adsorbed NH ₃ amount exceeding 0.3 meq / g.
The amount of chemisorbed NH ₃ can be determined by dividing the amount of NH ₃ desorbed at 100 ° C. or higher in the spectrum measured above by the weight (g) of mesoporous aluminosilicate.

The crushing strength of the mesoporous aluminosilicate according to the present invention is preferably 3 MPa or more.
When the crushing strength is less than 3 MPa, the crystallinity is easily lowered without changing from the conventional MCM-48, so that there is a limitation in the use and usage, and it is not suitable for practical use.
The crushing strength was measured by placing the sample in a tablet forming machine (manufactured by JASCO Corporation), compressing the pressure for 30 minutes with a hydraulic press manufactured by Iuchi Co., Ltd., measuring the X-ray diffraction spectrum, and 2θ = 2.5. The maximum pressure at which the spectrum was substantially maintained was taken as the crushing strength by looking at the remaining proportion of the main spectrum near 0 °.

  EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[Example 1]
Synthesis of mesoporous aluminosilicate (MPAS-1) An aqueous solution of Brij30 and CTMABr, which are first organic structure-regulating agents, silica sol (manufactured by Nissan Chemical Co., Ltd .: Ludox HS-400), TEAOH which is the second organic structure-regulating agent An aqueous solution and aluminum nitrate were mixed with an oxide molar ratio of mesoporous aluminosilicate synthesis precursor of 1 SiO ₂ : 0.168 CTMBr: 0.032 Brij 30: 0.01 Al ₂ O ₃ : 0.7 TEAOH: 80.0 H ₂ O (SiO ₂ / Al ₂ O ₃ = 100) and mixed for 1 hour.

A mesoporous aluminosilicate synthesis precursor was placed in a propylene container and hydrothermally treated at 100 ° C. for 2 days. Thereafter, the container was rapidly cooled to room temperature (20 ° C.). At this time, the pH was 11.5. Next, an aqueous acetic acid solution was added with stirring to adjust the pH to 10.5, and then hydrothermally treated at 100 ° C. for 2 days.
The resulting mesoporous aluminosilicate is then filtered, separated, thoroughly washed with water and ethanol, dried at 100 ° C. for 2 hours, and then calcined at 550 ° C. for 2 hours to obtain mesoporous aluminosilicate (MPAS-1). It was.

X-ray diffraction spectrum was measured for mesoporous aluminosilicate (MPAS-1), and the result is shown in FIG. 1a. Also, the adsorption / desorption isotherm is shown in FIG. 1b. Further, an infrared absorption spectrum was measured, and the result is shown in FIG. 1c (lower solid line). Further, MAS-Al-NMR was measured and shown in FIG.
Judging from the XRD of FIG. 1a and the nitrogen adsorption of FIG. 1b, mesoporous aluminosilicate (MPAS-1) is found to have a mesoporous structure. Moreover, IR of FIG. 1c has absorption in 550-600 / cm vicinity, and it turns out that it has a zeolite frame | skeleton (reference literature Sakthivel, A .; Huang, SJ; Chen, WH; Lan, ZH; Chen, KH; Lin, HP; Mou, CY; Liu, SB Adv. Funct. Mater. 2005, 15, 253). Since the SDA used is TEAOH, it is considered to have Beta zeolite structural units. Further, from MAS-Al-NMR, it is judged that aluminum is tetracoordinated and incorporated in the zeolite skeleton.

FIG. 2 shows changes in physical properties when treated under various conditions. (a) is a sample heated at 550 ° C. for 12 hours, (b) is a sample heated at 900 ° C. for 6 hours, (c) is a sample heated at 700 ° C. for 4 hours while passing water vapor saturated at 25 ° C., d) shows the XRD of the sample boiled at 100 ° C. for 48 hours in water, (e) the sample boiled at 100 ° C. for 120 hours in water, and (f) the sample compressed for 30 minutes at 50 MPa.
These results indicate that the mesoporous structure is not destroyed when heated at 900 ° C., steamed at 700 ° C., boiled at 100 ° C., and compressed at 50 MPa.

In addition, an ammonia desorption spectrum, which is a measure of solid acidity, is shown in FIG. 3 (bottom row). The peak temperature was 280 ° C. The final desorption temperature was 400 ° C. or higher. Was also 0.055meq / g was calculated chemisorption NH ₃ amount.
Table 1 shows the crushing strength and ammonia adsorption / desorption characteristics of mesoporous aluminosilicate (MPAS-1) together with the composition at the time of synthesis described above together with examples and comparative examples described later.

Catalytic reaction characteristics evaluation Mesoporous aluminosilicate (MPAS-1) 0.074g, isophytol 0.74g, 2,3,4-trimethylhydroquinone 0.38g, and dry ice 33g were charged in a high pressure reaction vessel The reaction was performed at a temperature of 120 ° C. and a reaction pressure of 12 MPa for 2 hours. This reaction formula is shown in [Chemical Formula 1].
Next, the high-pressure reaction vessel was cooled to room temperature, carbon dioxide was released, the contents were washed out with acetone, and the remaining raw materials and products (vitamin E: γ-tocopherol) were analyzed with a gas chromatograph. The yield of γ-tocopherol was 96 mol%.

[Examples 2 to 4]
Synthesis Example 1 of Mesoporous Aluminosilicate (MPAS-2 to 4) In Example 1, the molar ratio of Al ₂ O ₃ is 0.02, 0.0067, 0.005 (the SiO ₂ / Al ₂ O ₃ ratio is 50 in order) , 150, and 200), except that the composition is the same as in Example 1 except that the composition is constant, and the mesoporous aluminosilicate (MPAS-2) and mesoporous with different SiO ₂ / Al ₂ O ₃ ratios are used. Aluminosilicate (MPAS-3) and mesoporous aluminosilicate (MPAS-4) were obtained.

An X-ray diffraction spectrum was measured for each mesoporous aluminosilicate. FIG. 4 shows the measurement results, which are (MPAS-2), (MPAS-3), and (MPAS-4) in order from the bottom.
The spectrum is similar to that of mesoporous aluminosilicate (MPAS-1) and has a mesoporous structure. In addition, the infrared absorption spectrum was similar to that of mesoporous aluminosilicate (MPAS-1), so it is considered to have a zeolite skeleton.

[Comparative Example 1]
Synthesis of Mesoporous Aluminosilicate (MPAS-R1) Mole oxide molar ratio of the mesoporous aluminosilicate synthesis precursor of Example 1, 1SiO ₂ : 0.168 CTMBr: 0.032 Brij30: 0.01Al ₂ O ₃ : 0.7TEAOH: 80. In 0H ₂ O (SiO ₂ / Al ₂ O ₃ = 100), without using Brij30 and TEAOH, 1SiO ₂ : 0.168 CTMBr: 0.01Al ₂ O ₃ : 80.0H ₂ O (SiO ₂ / Al ₂ A mesoporous aluminosilicate (MPAS-R1) was obtained in the same manner except that O ₃ was adjusted to 100).
An X-ray diffraction spectrum was measured for mesoporous aluminosilicate (MPAS-R1), and the result is shown in FIG.

Further, the processing of (a) to (f) was performed under the same conditions as in Example 1, and the XRD after the processing is shown in FIG.
(a) is a sample after firing, (b) is a sample heat treated at 900 ° C., (c) is a sample treated at 700 ° C., (d) and (e) are samples boiled at 100 ° C. and (f) Indicates the XRD of the sample pressurized at 50 MPa.
Further, an infrared absorption spectrum was measured, and the result is shown in FIG. 1c (dotted line). In this mesoporous aluminosilicate (MPAS-R1), almost no absorption was observed in the vicinity of 550-600 / cm.

In addition, an ammonia desorption spectrum, which is a measure of solid acidity, was measured and shown in FIG. The peak temperature was 260 ° C. The final desorption temperature was less than 400 ° C. Was also 0.045meq / g was calculated chemisorption NH ₃ amount.

Evaluation of catalytic reaction characteristics In Example 1, the reaction was carried out in the same manner except that mesoporous aluminosilicate (MPAS-R1) was used. The yield of the product (γ-tocopherol) was 10 mol%.

[Comparative Example 2]
Synthesis of Mesoporous Aluminosilicate (MPAS-R2) Oxide molar ratio of mesoporous aluminosilicate synthesis precursor of Example 1 1SiO ₂ : 0.168 CTMBr: 0.032 Brij30: 0.01Al ₂ O ₃ : 0.7TEAOH: 80. In 0H ₂ O (SiO ₂ / Al ₂ O ₃ = 100), instead of TEAOH, tetrapropylammonium bromide (TPABr), which is an SDA of MFI synthesis, was used, and 1SiO ₂ : 0.168 CTMBr: 0.032 Brij 30: 0 .01Al ₂ O ₃ : 0.7TPABr: 80.0H ₂ O (SiO ₂ / Al ₂ O ₃ = 100) In the same manner as described above, mesoporous aluminosilicate (MPAS-R2) was obtained.

  When mesoporous aluminosilicate (MPAS-R2) was measured for the X-ray diffraction spectrum and nitrogen adsorption / desorption isotherm in the same manner as in Example 1, it was found to have a mesoporous structure. Moreover, when the infrared absorption spectrum was measured, it showed that it had a zeolite unit from showing absorption in the vicinity of 550-600 / cm. (Neither shown)

Further, an ammonia desorption spectrum serving as a measure of the solid acidity was measured and shown in FIG. 3 (middle). The peak temperature was 250 ° C. The final desorption temperature was less than 400 ° C. Was also 0.045meq / g was calculated chemisorption NH ₃ amount.

[Comparative Example 3]
Catalytic reaction characteristic evaluation In Example 1, faujasite type zeolite (manufactured by Catalytic Chemical Industry Co., Ltd .: HY ₅ , SiO ₂ / Al ₂ O ₃ = 5.0, Na ₂ O = 0.5 wt%, specific surface area = 650 m ² / g, product fired at 550 ° C. for 2 hours), the reaction was carried out in the same manner. The yield of the product (γ-tocopherol) was 5 mol%.

FIG. 1a shows the X-ray diffraction spectrum of mesoporous aluminosilicate (MPAS-1), FIG. 1b shows the nitrogen adsorption / desorption isotherm, FIG. 1c shows the infrared absorption spectrum, and FIG. 1d shows the MAS-Al-NMR. The X-ray diffraction spectrum after processing mesoporous aluminosilicate (MPAS-1) on various conditions is shown. 2 shows ammonia desorption spectra of mesoporous aluminosilicates (MPAS-1), (MPAS-R1) and (MPAS-R2). The X-ray diffraction spectrum of mesoporous aluminosilicate (MPAS-2), (MPAS-3), (MPAS-4) and (MPAS-R1) is shown. The X-ray diffraction spectrum after processing mesoporous aluminosilicate (MPAS-R1) under various conditions is shown.

Claims (6)

A method for synthesizing mesoporous aluminosilicate comprising the following steps (a) to (d).
(A) (I) Nonionic surfactant and cationic surfactant as the first organic structure regulator, (II) Silica source, (III) Alumina source, (IV) As the second organic structure regulator A step of preparing a mesoporous aluminosilicate synthesis precursor comprising a quaternary ammonium salt or hydroxide excluding chloride and bromide, and (V) water (b) a hydrothermal treatment at 80 to 150 ° C. (c) Step of cooling to 20-50 ° C. and adjusting pH to 9-12 (d) Step of hydrothermal treatment at 80-150 ° C. Claim 1, wherein the molar ratio of nonionic surfactant and a cationic surfactant (nonionic surfactant / cationic surfactant) is characterized in that in the range of 0.1 to 1.0 A method for synthesizing mesoporous aluminosilicate as described in 1. The composition of the mesoporous aluminosilicate synthesis precursor is such that (I) the first organic structure-regulating agent is 0.1 to 0.4 mol, and (III) the alumina source with respect to 1 mol of SiO _{2 of the} silica source (II). There 0.001 mol as _Al 2 _{O 3,} (IV) a second organic structure directing agent is 0.1 to 1.0 mole, in the range of 50 to 200 mol of the _{H 2} O (V) water synthesis of mesoporous aluminosilicate according to any one of claims 1-2, characterized in that. In the X-ray diffraction spectrum, it has a main peak in the vicinity of 2θ = 2.5 °, and in nitrogen isothermal adsorption / desorption, nitrogen is adsorbed significantly when the relative pressure of nitrogen (P / P ₀ ) is 0.1 to 0.4. And a mesoporous aluminosilicate exhibiting desorption characteristics, the peak temperature of the chemisorption NH ₃ desorption spectrum by the temperature programmed desorption method is in the range of 260 to 300 ° C., and the final desorption temperature is 400 ° C. or more. Mesoporous aluminosilicate. The mesoporous aluminosilicate according to claim 4 , wherein the amount of chemisorbed NH ₃ by a temperature programmed desorption method is in the range of 0.005 to 0.3 meq / g. Mesoporous aluminosilicate of claim 4 or 5 crushing strength is equal to or not less than 3 MPa.

Images