JP2020189765A - Titanosilicate and production method thereof - Google Patents

Abstract

To provide a method for producing titanosilicate by which the titanosilicate can be produced more efficiently than when aluminosilicate MCM-68 is used as a basic skeleton.SOLUTION: A method for producing titanosilicate by replacing a portion of aluminum in a skeleton of aluminosilicate with titanium comprises, in order, the steps of: preparing a mixture of a first silica source, an alkali source, water and a structure-defining agent while stirring; heating the mixture while stirring; cooling the mixture; adding a second silica source and an alumina source to the mixture and re-preparing the mixture while stirring; heating the mixture; washing and filtering the mixture followed by drying; heating an obtained organic composite to remove an enclosed organic substance to obtain aluminosilicate YNU-5; baking the YNU-5; treating the YNU-5 with an acid; and heating the YNU-5 together with titanium chloride or titanium alkoxide in a gas phase.SELECTED DRAWING: Figure 2

Description

The present invention relates to titanosilicate obtained by replacing a part of aluminum in the skeleton of aluminosilicate YNU-5 with titanium, and a method for producing the same.

Aluminosilicate MCM-68 is a relatively new zeolite first synthesized by Mobil (Patent Document 1). This zeolite has a structure in which large pores (12-membered ring pores) and medium pores (10-membered ring pores) are three-dimensionally intersected. Since this type of zeolite generally has a large surface area and a large internal space, it is considered to be useful as a catalyst in petroleum refining and petroleum chemical processes, and as a catalyst using a relatively bulky organic molecule as a substrate.

Since MCM-68 has a Si / Al ratio of 9 to 12, it has a relatively large Al content, that is, an active site, and is more stable, so that it is being studied as an acid catalyst. In addition, MCM-68 has a high ability to adsorb hydrocarbons, and reactions involving it, such as alkylation of aromatic hydrocarbons and transalkylation of alkyl aromatic hydrocarbons, isomerization, disproportionation, and dealkylation. It shows high activity in such cases. Therefore, MCM-68 is expected as a base material for a catalyst for a hydrocarbon conversion reaction.

On the other hand, titanium silicalite-1 (TS-1) is a representative of titanium silicate-based zeolite, and is known to exhibit high activity and selectivity as a catalyst for oxidation reaction of organic compounds (Patent Documents). 2). As a method for synthesizing a zeolite having a high catalytic activity such as TS-1, for example, a technique for introducing titanium into a zeolite by treating dealuminum mordenite with a steam of high temperature TiCl ₄ is known. (Non-Patent Document 1). Further, a method for producing titanosilicate having a catalytic performance equal to or higher than that of TS-1 by replacing the aluminum constituting MCM-68 with titanium is also known (Patent Document 3).

Special Table 2002-535227 Japanese Unexamined Patent Publication No. 2004-175801 Japanese Patent No. 4923248

J. Phys. Chem. 1996, 100, 10316-10322

However, in the production method of Patent Document 3, MCM-68, which is a raw material of titanosilicate, is used for the synthesis of N, N, N', N'-tetraethylbicyclo [2.2.2] oct-7-ene-2,3. : 5,6-dipyrrolidinium [or contains N, N, N', N'-tetraethylbicyclo [2.2.2] octo-7-en-2, 3: 5,6-dipyrrolidinium] (TEBOP ²⁺ ) ions It is necessary to use an organic compound as a structure defining agent. Since TEBOP ²⁺ has a complicated structure and is a material with a high manufacturing cost, it is necessary to improve the manufacturing efficiency of MCM-68 using this material, and by extension, the manufacturing efficiency of titanosilicate using MCM-68 as a raw material. Is difficult.

The present invention has been made in view of such circumstances, and provides a method for producing titanosilicate, which enables more efficient production of titanosilicate than when aluminosilicate MCM-68 is used as a basic skeleton. The purpose is to provide.

Another object of the present invention is to provide a titanosilicate obtained by using the production method, which has the same catalytic performance as that when MCM-68 is used as a basic skeleton.

The aluminosilicate having YNU-5 as a basic skeleton has a particle size about 10 times larger than that having MCM-68 as a basic skeleton. Generally, it is considered that the larger the particle size, the lower the activity rate as a catalyst, and there is an inhibitory factor in producing titanosilicate using YNU-5 as a basic skeleton.

As a result of diligent studies by the present inventor under such circumstances, it was found that the use of YNU-5 provides phenolic oxidation activity and paraselectivity comparable to those of the use of MCM-68.

The present invention provides the following means.
[1] A method for producing titanosilicate in which a part of aluminum in the aluminosilicate skeleton is replaced with titanium, in which a mixture of a primary silica source, an alkali source, water, and a structure defining agent is stirred. A second step of preparing the mixture while stirring, a second step of heating the prepared mixture with stirring, a third step of cooling the heated mixture, and adding a second silica source and an alumina source to the cooled mixture. In addition, the fourth step of re-preparing with stirring, the fifth step of heating the re-prepared mixture, the sixth step of washing, filtering and drying the heated mixture, and the sixth step are performed. The seventh step of heating the organic composite obtained through the process to remove the encapsulated organic matter to obtain the aluminosilicate YNU-5, the eighth step of firing the aluminosilicate YNU-5, and the fired aluminosilicate. A titanosilicate having, in order, a ninth step of acid-treating YNU-5 and a tenth step of heating the acid-treated aluminosilicate YNU-5 together with a gas phase titanium chloride or titanium alkoxide. Manufacturing method.
[2] Colloidal silica is used as the first silica source, Y-type zeolite is used as the second silica source and the alumina source, and dimethyldipropylammonium is used as the structure-determining agent [1]. The method for producing titanosilicate according to.
[3] The acid treatment of [1] or [2] is characterized in that the molar ratio (Si / Al) of silicon and aluminum contained in the aluminosilicate YNU-5 is 300 or more. The method for producing titanosilicate according to any one.
[4] In the ninth step, any one of [1] to [3], wherein the aluminosilicate YNU-5 is immersed in an aqueous solution containing 60% by weight or more of nitric acid (HNO ₃ ). The method for producing titanosilicate according to.
[5] A method for producing titanosilicate according to any one of [1] to [4], wherein in the ninth step, the aluminosilicate YNU-5 is heated at a temperature of 100 ° C. or higher.
[6] The method for producing titanosilicate according to any one of [1] to [5], which comprises adding alcohol to the mixture in the first step.
[7] The method for producing titanosilicate according to any one of claims [1] to [6], wherein the molar ratio of the water to the first silica source is 6 or more and 8 or less. ..
[8] The method for producing titanosilicate according to any one of [1] to [7], which comprises further firing after the tenth step.
[9] Aluminosilicate A titanosilicate characterized in that a part of aluminum in the skeleton of YNU-5 is replaced with titanium and the particle size is 1000 nm or more and 2000 nm or less.
[10] The titanosilicate according to [9], wherein the molar ratio (Si / Ti) of silicon and titanium contained in the skeleton of the aluminosilicate YNU-5 is 60 or more.

In the method for producing titanosilicate of the present invention, aluminosilicate YNU-5 is used as a basic skeleton. As the structure-determining agent in the synthesis of YNU-5, one having a simpler structure than TEBOP used when MCM-68 is used as a basic skeleton can be used. Therefore, in the present invention, the aluminosilicate of the basic skeleton can be easily synthesized, and the cost and energy saving in producing the titanosilicate by that amount can be reduced.

As described above, according to the method for producing titanosilicate of the present invention, it is possible to efficiently produce titanosilicate as compared with the case where MCM-68 is used as the basic skeleton. The titanosilicate synthesized by the method for producing titanosilicate of the present invention has a particle size of 1000 nm or more and 2000 nm or less, and is larger than or equivalent to the titanosilicate obtained by using MCM-68 as a basic skeleton. Can demonstrate the catalytic performance of.

It is a figure which shows the configuration example of the apparatus which performs titanium treatment with respect to aluminosilicate YNU-5. It is a graph which shows the result of having performed the analysis by X-ray diffraction about the manufactured titanosilicate. It is a graph which shows the DR / UV-vis measurement result with respect to the manufactured titanosilicate. (A) to (d) SEM images in the manufacturing process of titanosilicate.

Hereinafter, titanosilicate, which is an embodiment to which the present invention is applied, and a method for producing the same will be described in detail with reference to the drawings. In addition, in the drawings used in the following description, in order to make the features easy to understand, the featured parts may be enlarged for convenience, and the dimensional ratio of each component may not be the same as the actual one. Absent. Further, the materials, dimensions, etc. exemplified in the following description are examples, and the present invention is not limited thereto, and the present invention can be appropriately modified without changing the gist thereof.

[First Embodiment]
The method for producing titanosilicate according to the first embodiment is to prepare titanosilicate [Ti] -YNU-5 by substituting a part of Al constituting the aluminosilicate YNU-5 with Ti in the same type. .. The processing of each manufacturing process will be described below.

<First step (first preparation step)>
First, as a raw material for aluminosilicate YNU-5, a first silica source, an alkali source, water, and a structure-defining agent are placed in a container and stirred to prepare a mixture (gel) thereof. Alcohols such as ethanol, methanol and isopropyl alcohol may be further added as a raw material for the aluminosilicate YNU-5. In this case, an effect such as being able to control the particle size can be obtained.

Examples of the first silica source include one or more of colloidal silica, amorphous silica, sodium silicate, tetraethyl orthosilicate, and aluminosilicate gel. In this embodiment, it is preferable to use colloidal silica ((SiO ₂ ) _Ludox , LUDOX (registered trademark)).

The alkali source is not particularly limited, but for example, one or two of sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH), cesium hydroxide (CsOH), and the like. It is preferable to use the above, and among them, sodium hydroxide (NaOH) and potassium hydroxide (KOH) are more preferable.

As the structure defining agent, for example, a dimethyldipropylammonium salt (compound) is preferable, and dimethyldipropylammonium hydroxide (Me ₂ Pr ₂ NOW) is more preferable. Me and Pr represent a methyl group (CH ₃ ) and a propyl group (CH ₃ CH ₂ CH ₂ ), respectively. The method for producing Me ₂ Pr ₂ NOH will be described later as a production example.

The water content ratio (molar ratio) to all the primary silica sources in the mixture is preferably 6 or more and 8 or less. By lowering the water content ratio in this way, a zeolite having a high organic matter concentration and a large pore volume can be obtained.

<Second step (first heating step)>
Next, the mixture prepared in the first step is heated with stirring. Specifically, while stirring the mixture on a hot plate heated to 60 ° C. or higher, a part of water is evaporated in order to concentrate the mixture to a predetermined amount.

<Third process (cooling process)>
Next, the mixture heated in the first heating step is cooled to about room temperature. The second step and the third step can be omitted as a set.

<Fourth step (second preparation step)>
The mixture cooled in the third step is then reprepared by adding a second silica source and an alumina source, if necessary. As the second silica source and the alumina source, Y-type zeolite (SiO ₂ ) _FAU , (AlO ₃ ) _FAU ) is used. The molar ratio (Si / Al) of silicon to aluminum in the Y-type zeolite is usually 2.5 or more and 50 or less, preferably 3 or more and 20 or less, more preferably 3.5 or more and 10 or less, and 4 or more and 6 or less. The following is more preferable, and about 5.3 is the most preferable. As the alumina source, for example, one or more of aluminum sulfate, sodium aluminate, aluminum hydroxide, aluminum chloride, aluminosilicate gel, metallic aluminum and the like can be used.

In the _reprepared mixture, the content ratio (mol%) of (SiO ₂ ) _{Ludox to} the total silica source ((SiO ₂ ) _Ludox , (SiO ₂ ) FAU) is usually 30 to 90%, which is 50. From 80% is preferable, more preferably 60 to 75% is more preferable, and about 74% is most preferable. The content ratio (mol%) of the alkali source (NaOH or the like) to the total silica source in the same mixture is usually 0.05 to 0.6%, preferably 0.1 to 0.5%, and more. It is preferably 0.2 to 0.4%. When both NaOH and KOH are used, the content ratio of NaOH and KOH is preferably about 0.15%. The content ratio of the structure defining agent to the total silica source in the same mixture is usually 0.05 to 0.5%, preferably 0.1 to 0.4%, more preferably 0.15 to 0. It is 3%, most preferably about 0.17%. The content ratio (molar ratio) of (SiO ₂ ) _FAU to the total silica source in the same mixture is usually 10 to 70%, preferably 15 to 50%, more preferably 20 to 35%. It is preferable, and most preferably about 25%.

So that the above-mentioned _{composition, (SiO 2) Ludox, NaOH} , KOH, for _{H 2} O is such that the content ratios mentioned above, to adjust the amount of mixing in the first step. Further, for (SiO ₂ ) _FAU and (AlO ₃ ) _FAU, it is preferable to adjust the amount of mixing in the fourth step so as to have the above-mentioned content ratio.

Furthermore, in the mixture which was again prepared, the content ratio of water _(H 2 O) to the total silica source (molar ratio) is usually 4-50, preferably if 5 to 30, with 5.5 to 12 Is more preferable, 6 to 8 is more preferable, and about 7 is most preferable. By of H _{2 O} content ratio in the mixture is such low, high concentration of organic substances, so that the zeolite pore volume is large is obtained.

<Fifth process (second heating process)>
The mixture (raw material) reprepared in the fourth step is usually stirred at room temperature and then heated. The heating here is usually 100 to 200 ° C., preferably 120 to 190 ° C., more preferably 140 to 180 ° C., still more preferably 150 to 170 ° C., with the mixture at room temperature housed in an autoclave. The temperature is most preferably about 160 ° C. It is usually carried out in an oven for about 12 hours to 10 days, preferably about 1 to 7 days, in a standing or stirring state.

<Sixth process (drying process)>
The mixture heated in the second heating step is then washed, filtered and further dried. Examples of the drying method here include a method in which the washed and filtered mixture is allowed to stand overnight in an oven at about 80 ° C., a method in which the mixture is dried in the sun, and the like.

Through the above steps, an organic composite (powder) containing a crystalline solid of zeolite is obtained.

(7th step (3rd heating step))
By further heating (calcining) the organic composite obtained through the drying step, the included organic matter (Me ₂ Pr ₂ NOH used as a structure defining agent) can be removed. For heating here, the obtained crystalline solid is heated at about 550 ° C. in a state of being housed in a muffle furnace. Specifically, the temperature is raised from room temperature to about 550 ° C. at about 1.5 ° C./min, this temperature is maintained for about 6 hours, and finally allowed to cool.

By going through the first step to the seventh step, a crystallized zeolite (aluminosilicate YNU-5) containing a large amount of aluminum can be obtained.

The structure of the aluminosilicate YNU-5 can be uniquely identified from the analysis results by X-ray diffraction (XRD). In the examples described later, the analysis result of X-ray diffraction with respect to the aluminosilicate YNU-5 has been obtained, and a person skilled in the art will estimate the actual structure of the aluminosilicate YNU-5 based on this analysis result. be able to.

That is, the aluminosilicate YNU-5 according to the present embodiment is a zeolite in which at least the lattice plane spacing d (d-spacing) (Å) shown in Table 1 is detected by the measurement by the powder X-ray diffraction method. More specifically, aluminosilicate YNU-5 is a zeolite having an X-ray diffraction pattern including at least the lattice spacing d (Å) and relative intensity shown in Table 1 as measured by powder X-ray diffraction. As for the relative intensity, the intensity of the maximum peak among the peaks included in the X-ray diffraction pattern is set to 100, and the ratio of the intensities of other peaks to this is shown. Here, the intensity of the peak corresponding to the lattice plane spacing d (Å) of 3.43 ± 0.10. Is the maximum.

Aluminosilicate YNU-5 uses a dimethyldipropylammonium compound as a structure-determining agent having a simple structure, and further, the ratio of water used as a raw material is about 6 to 8 times that of a silica source also used as a raw material. Obtained by. As a result, the aluminosilicate YNU-5 can be easily and surely produced with high purity as compared with the conventional zeolite produced by increasing the ratio of water, and it becomes easy to realize mass production. In addition, since the synthesis of the structure-defining agent is simplified, the energy required for the synthesis process can be reduced, and the manufacturing cost can be significantly reduced.

(8th process)
Next, the crystallized YNU-5 powder is calcined. The firing temperature is preferably in the range of 400 ° C. or higher and 900 ° C. or lower, and more preferably about 500 ° C. The firing time is preferably in the range of 3 hours or more and 24 hours or less, and more preferably 10 hours.

(Ninth step)
The calcined YNU-5 powder (crystal) is subjected to acid treatment (dealumination treatment) using an acidic solution such as nitric acid, hydrochloric acid, or sulfuric acid. Specifically, the YNU-5 powder is mixed with an acidic solution, stirred for a certain period of time, and then heated to dry. As a result, a part of aluminum can be removed (dealuminum) from the skeleton of YNU-5. Regarding the acidic solution used for this acid treatment, its concentration, drying temperature, and drying time, the molar ratio of silicon to aluminum (Si / Al) contained in YNU-5 after dealumination takes into consideration the stability of the crystal structure. , 300 or more is adjusted and determined. Actually, as the acidic solution, a solution containing an acid treatment agent such as nitric acid or sulfuric acid at a concentration of about 55% by weight or more and 65% by weight or less, preferably about 60% by weight is used. The acid treatment is carried out at a temperature of about 100 ° C. or higher and 150 ° C. or lower for about 1 to 24 hours. If the acid treatment is performed under conditions weaker than this, aluminum cannot be sufficiently removed and titanium cannot be taken in, so that the efficiency of replacing aluminum with titanium becomes low. Further, if the acid treatment is performed under conditions stronger than this, aluminum is excessively removed, so that the balance between the remaining crystal particles is lost and the crystal structure of YNU-5 is broken.

(10th process)
The acid-treated YNU-5 powder is treated with titanium, that is, a treatment for introducing titanium into the site from which aluminum has been removed from the skeleton of YNU-5 is performed. Specifically, the acid-treated YNU-5 is heated together with the vapor phase titanium chloride or titanium alkoxide. FIG. 1 is a diagram showing a configuration example of the titanium processing apparatus 10.

The titanium processing apparatus 10 mainly contains a glass tube 11, a heater (heater) 12 arranged around the glass tube 11, a temperature controller 13 connected to the heater 12, and a container 14 containing a titanium source. And a supply source 15 for an inert gas. The glass tube 11, the titanium source container 14, and the inert gas supply source 15 are connected to each other by a tube via a four-way valve 16, and the flow path directly directed to the glass tube 11 and titanium for the inert gas. The flow path to the glass tube 11 via the source container 14 is configured to be switched at any time.

The procedure for titanium treatment will be described with reference to FIG. First, the acid-treated YNU-5 crystal S is surrounded by a fiber material (not shown) such as quartz wool, and fixed inside the glass tube 11 via the fiber material.

Subsequently, the flow path is switched so that the inert gas goes directly to the glass tube 11, and the YNU-5 crystal S is heated with the inert gas such as argon, nitrogen, and helium flowing through the glass tube 11. Do. The heating temperature is preferably 300 ° C. or higher and 800 ° C. or lower, and more preferably about 500 ° C. or lower. The heating time is preferably 1 hour or more and 12 hours or less, and more preferably about 4 hours.

Subsequently, the inert gas is switched to a flow path toward the glass tube 11 via the titanium source container 14, and the inert gas and the vapor phase titanium chloride or titanium alkoxide serving as the titanium source are circulated in the glass tube 11. In this state, the YNU-5 crystal S is heated. The heating temperature is preferably 300 ° C. or higher and 800 ° C. or lower, and more preferably about 600 ° C. or lower. The heating time is preferably 0.5 hours or more and 6 hours or less, and more preferably about 1 hour.

Examples of titanium chloride used here include TiCl ₄ , TiCl _{3, and the} like. Further, examples of the titanium alkoxide used here include Ti (OMe) ₄ , Ti (OEt) ₄ , Ti (OPr) ₄ , Ti (OPr-i) ₄ , Ti (OBu) _{4, and the} like.

Subsequently, the flow path is switched so that the inert gas goes directly to the glass tube 11, and the inert gas is circulated again in the glass tube 11 without changing the heating temperature and heating time, whereby the crystals of YNU-5 are crystallized. The unreacted titanium source remaining in S is removed.

Finally, the titanium-treated YNU-5 crystals S are allowed to cool to room temperature, washed with distilled water and dried in an oven at about 80 ° C.

By the above-mentioned process treatment, titanosilicate [Ti] -YNU-5 having a basic skeleton of aluminosilicate YNU-5 and having a part of Al replaced with Ti can be synthesized. In the skeleton of the synthesized titanosilicate, the molar ratio (Si / Ti) of silicon to titanium is 60 or more.

From the viewpoint of improving the catalytic function, it is preferable to further calcin the synthesized [Ti] -YNU-5 (step 11). The firing temperature is preferably in the range of 300 ° C. or higher and 800 ° C. or lower, and more preferably about 650 ° C. The firing time is preferably in the range of 1 hour or more and 12 hours or less, and more preferably about 4 hours.

The titanosilicate after the tenth step or the eleventh step has a particle size of 1000 nm or more and 2000 nm or less, which is larger than the titanosilicate obtained by using MCM-68 as a basic skeleton, but will be described later as an example. As described above, the catalytic performance equivalent to this can be exhibited. The particle size of the obtained titanosilicate can be measured by using, for example, an image analysis method defined by Japanese Industrial Standards JIS Z8827-1.

As described above, in the method for producing titanosilicate according to the present embodiment, aluminosilicate YNU-5 is used as a basic skeleton. As the structure-determining agent in the synthesis of YNU-5, one having a simpler structure than TEBOP used when MCM-68 is used as a basic skeleton can be used. Therefore, in the present embodiment, the aluminosilicate of the basic skeleton can be easily synthesized, and the cost and energy saving in producing the titanosilicate by that amount can be reduced.

As described above, according to the method for producing titanosilicate according to the present embodiment, it is possible to efficiently produce titanosilicate as compared with the case where MCM-68 is used as the basic skeleton.

Hereinafter, the effects of the present invention will be clarified by Examples. The present invention is not limited to the following examples, and can be appropriately modified and implemented without changing the gist thereof.

(Manufacturing example of structural regulator)
An example of production of dimethyldipropylammonium hydroxide used as a structure-determining agent for the zeolite of the present invention ([Ti] -YNU-5cal) is shown.

[Step 1]
First, dipropyldimethylammonium was synthesized as shown by the following formula.

This synthesis was carried out in the following procedure. First, 60 mL of dipropylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 350 mL of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) are mixed in a 1 L eggplant flask, and potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) is mixed. ) 90 g was added, and the mixture was stirred at room temperature for 10 minutes. To this, 68 mL of iodomethane (manufactured by Wako Pure Chemical Industries, Ltd.) was slowly added over 30 minutes, and finally 50 mL of methanol was added.

Next, the mixture was stirred at room temperature for 72 hours, 200 mL of chloroform (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was further stirred at room temperature for 20 minutes.

Next, suction filtration was performed using a glass filter (G4), and the obtained solid was washed with 150 mL of chloroform. The filtrate and the washing solution were combined and placed in a 1 L eggplant flask, which was depressurized at 40 ° C. using an evaporator and dried.

Next, 200 mL of chloroform (manufactured by Wako Pure Chemical Industries, Ltd.) was added to extract the product, and the insoluble inorganic salt was removed by suction filtration. The filtrate was placed in a 1 L eggplant flask, and the pressure was reduced again to dry it. The product was extracted with 200 mL of chloroform, inorganic salts were removed by suction filtration, and a clear filtrate was received in a 1 L eggplant flask. The filtrate was dried under reduced pressure, and then 100 mL of benzene (manufactured by Wako Pure Chemical Industries, Ltd.) was added and dried again.

Next, 150 mL of 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated on an oil bath at 100 ° C. to dissolve the crude crystals. After allowing to cool, 150 mL of diethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) was slowly added to reprecipitate the crystals. This was suction filtered using a glass filter (G3), and the solid was washed with 150 mL of a mixed solution of diethyl ether: 2-propanol = 3: 2 (volume ratio). The obtained crystals were vacuum dried. The yield of the product Me ₂ Pr ₂ NI (dimethyldipropylammonium iodide) was 105.5 g (yield 90%).

The chemical shifts δ obtained when measured by ¹ H NMR (500 MHz, CDCl ₃ ) and when measured by ¹³ C NMR (126 MHz, CDCl ₃ ) are shown below as NMR analysis values of the product.

(I) δ when measured by ¹ H NMR (500 MHz, CDCl ₃ ):
1.07 (6H, t, J = 7.4Hz, CH _2- CH _2- CH ₃ )
1.82 (4H, m, CH _2- CH _2- CDCl ₃ )
3.38 (6H, s, N ⁺ -CH ₃ )
3.54 (4H, m, N ⁺ -CH _2- CH ₂ )
(Ii) δ when measured by ¹³ C NMR (126 MHz, CDCl ₃ ):
10.58, 16.40, 51.52, 65.80

[Step 2]
Next, as shown in the following formula, the Me ₂ Pr ₂ NI obtained in step 1 was converted to Me ₂ Pr ₂ NOH (dimethyldipropylammonium hydroxide).

This conversion was performed in the following procedure. First, 75.22 g of dimethyldipropylammonium iodide synthesized in step 1 is placed in a 1 L PP bottle, followed by 325.73 g of a strongly basic anion exchange resin (SA10A (OH) manufactured by Mitsubishi Chemical Corporation). added. _Then, added H 2 O (Milli-Q) 500mL, After shaking lightly vessel was allowed to stand in a cool, dark place for 120 hours.

Then suction filtered through a glass filter (G4), the resin on the filter is washed well with _{H 2 O (Milli-Q)} 300mL, and concentrated under reduced pressure the combined filtrates and washings. The weight of the obtained solution was 133.37 g, and the concentration of Me ₂ Pr ₂ NOH determined by 0.05 M hydrochloric acid titration was 2.097 mmol / g (ion exchange rate 96%). The conversion of Me ₂ Pr ₂ NI to Me ₂ Pr ₂ NOH is merely ion exchange, and the NMR spectrum of Me ₂ Pr ₂ NOH is similar to that for Me ₂ Pr ₂ NI.

(Example 1)
Zeolite (aluminosilicate YNU-5) was synthesized using Me ₂ Pr ₂ NOH obtained in Production Example 1 as a structure-determining agent. This synthesis was carried out in the following procedure. First, 16.21 g of the Me ₂ Pr ₂ NOW aqueous solution (2.097 mmol / g) obtained in Production Example 1 was placed in a fluororesin (PFA) container having an internal volume of 150 mL, and 9.37 g of the NaOH aqueous solution (3.20 mmol) was taken. / G), 9.53 g of an aqueous KOH solution (3.153 mmol / g), and 21.39 g of Fluorox AS-40 (manufactured by Aldrich) were sequentially added (first step).

Next, 20.26 g of water was evaporated by stirring on a hot plate at 80 ° C. or higher for 3 hours (second step). After cooling the obtained mixture to room temperature (third step), 4.99 g of Y-zeolite (H _30.5 Al _30.5 Si _161.5 O ₃₈₄ , manufactured by Tosoh Corporation, HSZ-350HUA) was added. In addition (fourth step), the mixture was stirred at room temperature for 10 minutes. The composition of the resulting mixture _became a _{1.0SiO 2 -0.025Al 2 O 3 -0.17Me 2} Pr 2 NOH-0.15NaOH-0.15KOH-7H 2 O.

The mixture was transferred to an autoclave with an inner cylinder made of fluororesin (PTFE) having an internal volume of 125 mL, and this was allowed to stand in an oven at 160 ° C. for 165 hours (fifth step). The obtained solid product was collected by filtration and dried overnight in an oven at 80 ° C. (sixth step). The weight of the obtained white powder was 6.84 g.

Of this, 5.02 g was taken in an alumina petri dish, heated from room temperature at a rate of 1.5 ° C. per minute under the air atmosphere in the muffle furnace, held at 550 ° C. for 6 hours, and then allowed to cool (7th). Process (firing process)). In this way, 4.90 g of white powder (after firing) was obtained.

2.023 g of a sample of [Ti] -YNU-5 crystals obtained by firing was placed in a glass eggplant-shaped flask, and 83.33 g of a concentrated nitric acid aqueous solution (commercially available product, concentration 13.4 M) was added thereto. The mixture was refluxed and stirred for 24 hours while heating in an oil bath at 148 ° C. (8th step). Then, the sample is filtered, washed with distilled water until the filtered filtrate becomes neutral, dried at room temperature, and dealuminated [Al] -YNU-5 crystals (1.551 g of white powder) are obtained. Obtained. At this point, some aluminum in the crystals was removed, and the content ratio of aluminum in the sample was 0.012 mmol / g.

Using the titanium processing apparatus 10 of FIG. 1, titanium was introduced into the site from which aluminum was removed from the skeleton of YNU-5 (9th step).

First, the acid-treated YNU-5 crystal S was surrounded by quartz wool and fixed inside the glass tube 11 via the quartz wool.

Subsequently, the flow path was switched so that the argon gas directly directed to the glass tube 11, and the YNU-5 crystal S was heated with the argon gas flowing through the glass tube 11. The heating temperature was 500 ° C. and the heating time was 4 hours. The flow rate of the argon gas to be circulated was 30 mL / min.

Subsequently, the argon gas is switched to the flow path toward the glass tube 11 via the titanium source container 14, and the argon gas and the vapor phase titanium tetrachloride serving as the titanium source are circulated in the glass tube 11. , YNU-5 crystal S was heated. The heating temperature was 600 ° C. and the heating time was 1 hour. The flow rate of the argon gas to be circulated was 30 mL / min. The flow rate of titanium tetrachloride was set to 2.2 mL / min.

Subsequently, the flow path is switched so that the inert gas goes directly to the glass tube 11, and the inert gas is circulated again in the glass tube 11 without changing the heating temperature and heating time, whereby the YNU-5 crystal S The unreacted titanium source remaining therein was removed.

Finally, the crystals S were allowed to cool to room temperature, washed with distilled water and dried in an oven at about 80 ° C.

By the above-mentioned process treatment, it was possible to synthesize titanosilicate [Ti] -YNU-5 having the basic skeleton of aluminosilicate YNU-5 in which a part of Al was replaced with Ti.

The synthesized [Ti] -YNU-5 was further calcined (10th step). Specifically, in an air atmosphere, the temperature was raised from room temperature to 650 ° C. at about 1 ° C./min, held at 650 ° C. for 4 hours, and finally allowed to cool. In the skeleton of the calcined titanosilicate, the molar ratio of silicon to aluminum (Si / Al) was 375, and the molar ratio of silicon to titanium (Si / Ti) was 64.9.

(Example 2)
In the method for producing titanosilicate of the present invention, [Ti] -YNU-5 particle samples that had undergone the first to ninth steps were prepared. The specific manufacturing procedure was the same as in the first to ninth steps of Example 1. Within the skeleton of the synthesized titanosilicate, the molar ratio of silicon to aluminum (Si / Al) was 370, and the molar ratio of silicon to titanium (Si / Ti) was 63.1.

(Comparative Example 1)
In the method for producing titanosilicate of the first embodiment, a YNU-5 particle sample (deAl-YNU-5) that had undergone the first to eighth steps was prepared. The specific manufacturing procedure was the same as in the first to eighth steps of Example 1. In the skeleton of the aluminosilicate after the dealumination treatment, the molar ratio (Si / Al) of silicon to aluminum was 300.

(Comparative Example 2)
In the method for producing titanosilicate of the first embodiment, YNU-5 particle samples ([Al] -YNU-5cal) that had undergone the first to seventh steps were prepared. The specific manufacturing procedure was the same as in the first step and the seventh step of Example 1. In the skeleton of the calcined aluminosilicate, the molar ratio of silicon to aluminum (Si / Al) was 8.7.

(Comparative Example 3)
In the method for producing titanosilicate of the first embodiment, YNU-5 particle samples ([Al] -YNU-5as) that had undergone the first to sixth steps were prepared. The specific production procedure was the same as in the first step of Example 1.

(Comparative Example 4)
Titanium silicalite-1 (TS-1), which has been designated and distributed by the Catalysis Society as an Asian Reference Catalyst (ARC), was prepared.

[Evaluation of X-ray diffraction pattern]
X-ray diffraction (XRD) analysis was performed on the samples of Examples 1 and 2 and Comparative Examples 1 to 3. The diffraction pattern showing the analysis result is shown in the graph of FIG. The horizontal axis of the graph shows the diffraction angle, and the vertical axis shows the diffraction intensity. The diffraction patterns of the samples of Examples 1 and 2 and Comparative Examples 1 to 3 are arranged in order from the upper side to the lower side. Similar XRD patterns were obtained in all the samples, and it can be seen that high crystallinity was maintained before and after each step.

[Evaluation of Ti coordination status]
The Ti contents in the samples of Example 1 and Comparative Example 4 were 0.262 mmol / g and 0.367 mmol / g, respectively. DR / UV-vis measurements were performed on these samples to evaluate the Ti coordination state. The measured DR / UV-Vis spectrum is shown in the graph of FIG. The horizontal axis of the graph shows the wavelength (nm), and the vertical axis shows the Kubelka-Munk function. The DR / UV-Vis spectra of (a) and (b) in the graph correspond to the samples of Example 1 and Comparative Example 4, respectively.

The region having a wavelength of 200 to 230 nm is a region showing absorption corresponding to 4-coordinated Ti in the skeleton. The region having a wavelength of 250 to 290 nm is a region showing absorption corresponding to 5-coordinated to 6-coordinated Ti outside the skeleton.

The DR / UV-Vis spectra corresponding to the sample of Example 1 all have a peak in the wavelength region of 200 to 230 nm, similarly to the sample of Comparative Example 4. From this result, it can be seen that titanium is correctly introduced into the skeleton even when titanosilicate is synthesized using YNU-5 as the basic skeleton.

(SEM image evaluation)
4 (a) to 4 (d) are SEM images of samples obtained as Comparative Example 2, Comparative Example 1, Example 2, and Example 1, respectively. From the comparison of the four SEM images, it can be seen that the shape and size of the particles contained in the sample are almost the same. That is, it can be seen that the replacement of Al constituting YNU-5 with Ti is stably performed without destroying the crystal structure of YNU-5.

[Evaluation of catalytic performance for phenol oxidation reaction]
An experiment of the phenol oxidation reaction shown in the following chemical reaction formula was carried out using the samples of Example 1 and Comparative Example 4 as catalysts.

The specific procedure of the experiment will be described. First, 20 mg of catalyst, 2.00 g (21.3 mmol) of phenol, and 0.48 g (4.25 mmol) of hydrogen peroxide solution (30 wt%) were mixed in a glass pressure-resistant container, and the mixture was stirred at 70 ° C. for 60 minutes. .. After completion of the reaction, the container was diluted with 2.0 g (16.64 mmol) of sulfolane while cooling with ice. 0.225 g (2.080 mmol) of anisole was added as an internal standard substance and mixed well, and then the reaction solution and the catalyst were separated by centrifugation (1000 rpm, 10 minutes).

Next, an excess amount of acetic anhydride (about 0.4 g) and potassium carbonate (about 0.6 g) are added to about 100 mg of the supernatant, and the whole reaction solution is left at about 20 to 30 ° C. for 20 minutes with occasional vibration. Thoroughly acetylated the existing phenolic compounds. Then, it was diluted with chloroform and analyzed using a gas chromatograph device (GC-2014 manufactured by Shimadzu Corporation, detector: FID, column: DB-1 0.25 mm × 30 m × 1.00 μm). Further, in order to quantify unreacted hydrogen peroxide, 0.5 g of the supernatant solution for centrifugation and 0.8 g of potassium iodide were added to 50 mL of a 2.0 mol / L hydrochloric acid aqueous solution, and an accurate value of about 0.1 mol / L was added. It was titrated with a concentrated aqueous solution of sodium thiosulfate.

As a result of the above analysis, hydroquinone (para-isomer of dihydric phenol) HQ, catechol (ortho-isomer of dihydric phenol) CL, and parabenzoquinone p-BQ in which HQ was further oxidized were detected.

The content of Ti of each sample in this experiment (Ti content), catalyst turnover number (TON), yield (yield), the selectivity of paralogs (p-sel. (%) ), The conversion of H 2 _{O 2 (H 2 O 2 (%)} conv.), the effective utilization rate of the H 2 _{O 2} for _{(H 2 O 2 (%)} eff.), shown in Table 1. (Eff. Is an abbreviation for Efficiency.)

In Table 1, the upper row shows the results of the sample of Example 1, and the lower row shows the results of the sample of Comparative Example 4. It can be seen that in the sample of Example 1, HQ and CL are produced at the same ratio, and about half of HQ reacts to become p-BQ. Further, in the sample of Comparative Example 4, it can be seen that HQ is the main product, a small amount is p-BQ due to overreaction, and a small amount of CL is also produced.

The sum of the yields of HQ, p-BQ, and CL is shown as total (total yield). Further, the para-form selectivity (p-sel.) Is shown as the sum of HQ and p-BQ divided by total. TON (catalyst rotation speed) is the total amount of substance (number of moles) of the product divided by the number of moles of the Ti active site. That is, TON is an index of how many times the catalytic cycle has rotated from the start of the reaction to the end of the reaction (here, 10 minutes).

H ₂ O ₂ (%) eff. (H ₂ O ₂ effective utilization rate) is an effective utilization rate of hydrogen peroxide, and is an index showing how efficiently oxygen in hydrogen peroxide was involved in phenol oxidation.

From the results in Table 1, the sample of titanium silicate [Ti] -YNU-5 showed sufficient phenol oxidation activity and paraselectivity, and from the comparison of TON, a comparative example using titanium silicalite TS-1. It can be seen that it has the same performance as the sample of 4.

As a catalyst for phenol oxidation, ethanol (EtOH), n-propyl alcohol (1-propanol; n-PrOH), isopyrropyl alcohol (2-propanol; i-PrOH), n-butyl alcohol, along with the sample of Example 1. Analysis was performed when a co-solvent such as (1-butanol; n-BuOH) was added. Ti content, catalyst speed, yield, para-form selectivity, H ₂ O ₂ conversion rate, H ₂ O _{2 in} each case with the addition of co-solvent and without the addition of co-solvent. The effective utilization rate of (H ₂ O ₂ (%) eff.) Is shown in Table 2.

From the results in Table 2, a large amount of CL was produced when no co-solvent was added to the catalyst [Ti] -YNU-5, or when ethanol was added as a co-solvent, and when n-PrOH was added. , HQ and CL are produced to the same extent, and it can be seen that when i-PrOH and n-BuOH are added, a large amount of HQ is produced. Therefore, the isomer to be produced can be selected by changing the type of co-solvent to be added.

[Evaluation of catalytic performance for cyclohexene oxidation reaction]
An experiment of the cyclohexene oxidation reaction shown in the following chemical reaction formula was carried out using the samples of Example 1 and Comparative Example 4 as catalysts.

The specific procedure of the experiment will be described. First, 25 mg of catalyst, 0.4108 g (5.0 mmol) of cyclohexene, 0.5486 g (5.0 mmol) of hydrogen peroxide solution (30 wt%), and 5 ml of acetonitrile are mixed in a glass pressure-resistant container, and 120 at 60 ° C. Stirred for minutes. The liquid after stirring was analyzed. As a result of the analysis, an epoxide body (Epoxide), a diol body (Diol), a hydroperoxide body (OOH), an alcohol body (1-Ol), and a ketone body (1-One) were detected.

Table 3 shows the Ti content (Ti content), catalyst rotation speed (TON), yield (yield), and selectivity (selectivity (%)) of each sample in this experiment.

In Table 3, the upper and middle rows show the results of the two samples prepared under the conditions of Example 1, and the lower rows show the results of the samples prepared under the conditions of Comparative Example 4. In the two samples of Example 1, it can be seen that Epoxide is the main product and Diol, OOH, 1-Ol are small amounts of by-products. Further, in the sample of Comparative Example 4, it can be seen that OOH is the main product and Epoxide, Diol, and 1-Ol are small amounts of by-products.

From the results in Table 3, the titanium silicate [Ti] -YNU-5 sample showed sufficient cyclohexene oxidation activity and product selectivity, and from the comparison of TON, the comparison using titanium silicalite TS-1. It can be seen that the performance far exceeds that of the sample of Example 4.

[Evaluation of catalytic performance for 1-hexene oxidation reaction]
An experiment of the cyclohexene oxidation reaction shown in the following chemical reaction formula was carried out using the samples of Example 1 and Comparative Example 4 as catalysts.

The specific procedure of the experiment will be described. First, 25 mg of catalyst, 0.4208 g (5.0 mmol) of 1-hexene, 0.5486 g (5.0 mmol) of hydrogen peroxide solution (30 wt%), and 5 ml of acetonitrile are mixed in a glass pressure-resistant container at 60 ° C. Was stirred for 120 minutes. The liquid after stirring was analyzed. As a result of the analysis, epoxide and diol were detected.

Table 4 shows the Ti content (Ti content), catalyst rotation speed (TON), yield (yield), and selectivity (%) of each sample in this experiment.

In Table 4, the upper row shows the results of the sample prepared under the conditions of Example 1, and the lower row shows the results of the sample prepared under the conditions of Comparative Example 4. It can be seen that in the sample of Example 1, Epoxide is the main product and Diol is a small amount of by-product. It can also be seen that in the sample of Comparative Example 4, Epoxide is the main product and Diol is a small amount of by-product.

From the results in Table 4, the titanium silicate [Ti] -YNU-5 sample showed sufficient 1-hexene oxidation activity and product selectivity, and from the comparison of TON, titanium silicalite TS-1 was used. It can be seen that the performance is higher than that of the sample of Comparative Example 4.

The method for producing titanosilicate of the present invention can be used as a method for obtaining a catalyst in a production process for ethylene oxide, propylene oxide, divalent phenols and the like, which are major basic chemicals.

10 Titanium processing device 11 Glass tube 12 Heater 13 Temperature controller 14 Titanium source container 15 Inert gas supply source 16 Four-way valve

Claims (10)

A method for producing titanosilicate, in which a part of aluminum in the skeleton of aluminosilicate is replaced with titanium.
In the first step of preparing a mixture of a first silica source, an alkali source, water, and a structure defining agent with stirring,
In the second step of heating the prepared mixture with stirring,
The third step of cooling the heated mixture and
A fourth step of adding a second silica source and an alumina source to the cooled mixture and re-preparing with stirring, and
The fifth step of heating the reprepared mixture and
The sixth step of washing, filtering and drying the heated mixture,
The seventh step of heating the organic composite obtained through the sixth step to remove the included organic matter to obtain aluminosilicate YNU-5, and the seventh step.
The eighth step of firing the aluminosilicate YNU-5 and
The ninth step of acid-treating the calcined aluminosilicate YNU-5, and
A method for producing titanosilicate, which comprises, in order, a tenth step of heating the acid-treated aluminosilicate YNU-5 together with titanium chloride or titanium alkoxide in the gas phase. The first aspect of the present invention, wherein colloidal silica is used as the first silica source, Y-type zeolite is used as the second silica source and the alumina source, and dimethyldipropylammonium is used as the structure-determining agent. Manufacturing method of titanosilicate. The invention according to claim 1 or 2, wherein the acid treatment is performed so that the molar ratio (Si / Al) of silicon and aluminum contained in the aluminosilicate YNU-5 is 300 or more. Manufacturing method of titanosilicate. The method for producing titanosilicate according to any one of claims 1 to 3, wherein in the ninth step, the aluminosilicate YNU-5 is immersed in an aqueous solution containing 60% by weight or more of nitric acid. .. The method for producing a titanosilicate according to any one of claims 1 to 4, wherein in the ninth step, the aluminosilicate YNU-5 is heated at a temperature of 100 ° C. or higher. The method for producing titanosilicate according to any one of claims 1 to 5, wherein in the first step, alcohol is added to the mixture. The method for producing titanosilicate according to any one of claims 1 to 6, wherein the molar ratio of the water to the first silica source is 6 or more and 8 or less. The method for producing titanosilicate according to any one of claims 1 to 7, wherein further firing is performed after the tenth step. Aluminosilicate is a titanosilicate in which a part of aluminum in the skeleton of YNU-5 is replaced with titanium and the particle size is 1000 nm or more and 2000 nm or less. The titanosilicate according to claim 9, wherein the molar ratio (Si / Ti) of silicon and titanium contained in the skeleton of the aluminosilicate YNU-5 is 60 or more.