JPWO2018061827A1 - Zeolite and its production method - Google Patents

Abstract

The zeolite of the present invention has an X-ray diffraction pattern including at least lattice spacing d (Å) shown in Table 1 below, as measured by powder X-ray diffraction.
[Table 1]

Description

The present invention relates to a zeolite having a novel framework and a method for producing the same.
Priority is claimed on Japanese Patent Application No. 2016-191110, filed Sep. 29, 2016, the content of which is incorporated herein by reference.

  Zeolites of various structures have been discovered and noted as materials having a catalytic function. The variation of the zeolitic framework has increased from about 100 to about 230 in the last 20 years. The use of organic template molecules, that is, structure directing agents (SDA), is effective in creating various zeolite structures.

  In particular, in the synthesis of large pore zeolite having a ring structure of oxygen and tetrahedral atoms (= T atom; silicon etc.) and having pores of 12 or more rings counted by oxygen, complex and bulky organic molecules, The way of thinking used as a regulator is the mainstream (Non-Patent Document 1). However, when bulky organic polymers are used, zeolites of high silica composition with a low aluminum content tend to be synthesized, and since they have few ion exchange sites as they are, development of NOx reduction catalysts etc. using ion exchange as a key Not suitable for In addition, in the case of producing zeolite with a large pore size according to the conventional concept, precise design and synthesis are required, and furthermore, the success rate is low.

  In order to synthesize a novel framework zeolite having a high aluminum content, it is considered necessary to use a structure directing agent having a simpler structure. For example, quaternary ammonium compounds, such as tetraalkylammonium, when properly designed, act as templates in the hydrothermal synthesis of zeolites to induce crystallization of various framework structures. In addition, dimethyldipropylammonium compounds have simple structures and are known to be templates for MSE, which is a useful backbone.

"Nano-Spatial Materials Handbook", Chapter 3, Section 2, NTS Co., Ltd., February 8, 2016, p. 226-235

  However, in the conventional method of performing hydrothermal synthesis using silica source, alumina source, alkali source, and the above-mentioned structure defining agent as raw materials, and further using water of about 40 times or more the amount of silica source Inclusion (for example, Si / Al = 7 to 10) can not obtain a zeolite with a novel skeleton.

  The present invention has been made in view of such circumstances, and it is an object of the present invention to provide a zeolite having a novel framework with a high aluminum content. Another object of the present invention is to provide a method for producing zeolite, which enables the zeolite to be produced more reliably using a structure directing agent having a simple structure.

The inventors of the present invention have conducted intensive studies, made the ratio of water used as the raw material lower than in the past, and make the zeolite having a novel skeleton approximately 6 to 8 times the silica source used similarly as the raw material. Found out. The present invention provides the following features or means.
[1] A zeolite according to one aspect of the present invention has an X-ray diffraction pattern including at least lattice spacing d (Å) and relative intensity shown in Table 1 below, as measured by powder X-ray diffraction method, and the relative The intensity indicates the ratio of the intensity of the other peak to the intensity of the largest peak among the peaks included in the X-ray diffraction pattern.
In the zeolite described in [2] [1], the pore volume estimated by nitrogen adsorption measurement is preferably 0.12 ml / g or more and 0.25 ml / g or less.
In the zeolite according to any of [3] [1] or [2], the plurality of oxygen 8-membered rings and the plurality of oxygen 12-membered rings which are independent of each other, and the plurality of oxygen 8-membered rings are divided into a plurality of groups In each group, the oxygen 8-membered rings overlap so as to have a common through hole in one direction, and the plurality of oxygen 12-membered rings are present in a plurality of groups, and each group In the above, the oxygen 12-membered rings overlap so as to have a common through hole in a direction parallel to one plane, and the overlapping direction of the oxygen 8-membered rings and the overlapping direction of the oxygen 12-membered rings intersect each other Is preferred.
In the zeolite described in [4] and [3], the oxygen 8-membered ring is connected so that pairs and an isolated one form a line alternately in one direction intersecting the overlapping direction. Preferably, the rows are connected such that the pair of oxygen 8-membered rings and the isolated pair of oxygen 8-membered rings are adjacent to each other.
In the zeolite according to any of [5] [3] or [4], the oxygen 12-membered ring is connected side by side at equal intervals in two directions in a plane intersecting with the overlapping direction preferable.
In the zeolite according to any one of [6] [3] to [5], in the case where the pore diameter of the oxygen 8-membered ring subtracts the length of two ion radii (0.135 nm) of oxygen, 0 .295 nm or more and 0.454 nm or less, or 0.565 nm or more and 0.724 nm or less when not subtracted, 0.595 nm when the pore diameter of the oxygen 12-membered ring subtracts the length of two ion radius (0.135 nm) of oxygen The thickness is preferably 0.710 nm or less and, if not subtracted, 0.865 nm or more and 0.980 nm or less.
[7] In the zeolite according to any one of [1] to [6], the number density of T atoms contained is preferably 15 atoms / nm ³ or more and 18 atoms / nm ³ or less.
[8] The method for producing a zeolite according to one aspect of the present invention is a method for producing a zeolite according to any one of [1] to [7], which comprises: a first silica source, an alkali source, water, And preparing a mixture of structure-directing agents while stirring, a first heating step of heating the prepared mixture while stirring, a cooling step of cooling the heated mixture, and cooling A second preparation step of adding a second silica source and an alumina source to the mixture and reconstituting while stirring, a second heating step of heating the reconditioned mixture, washing the heated mixture, The method further includes a drying step of filtering and drying, and a third heating step of heating the organic complex obtained through the drying step to remove the clathrated organic substance, the first preparation step Amount of water used in 6-8 times the sum of the substance mass of the first silica source and the substance mass of the second silica source, and using colloidal silica as the first silica source, the second silica source and the alumina A Y-type zeolite is used as a source, and a dimethyldipropyl ammonium compound is used as the structure directing agent.

  The zeolite of the present invention is a crystalline aluminosilicate porous body having a novel framework, has a high aluminum content, and contains many ion exchange sites, so it is suitable for the development of catalysts that use ion exchange as a key (for example, NOx reduction catalyst) ing. Moreover, since the zeolite of the present invention can introduce a hetero element through dealumination, it may be used as a catalyst for producing various basic chemicals.

  Furthermore, the zeolite of the present invention can be applied as a solid catalyst that promotes the catalytic cracking of paraffins. Further, in the zeolite of the present invention, a part of aluminum constituting the zeolite can be isomorphously substituted with a transition metal (titanium, tin or the like). For example, zeolite homomorphically substituted with titanium is an excellent catalyst for selective oxidation of olefins, paraffins and aromatic rings using oxygen, hydrogen peroxide, alkyl hydroperoxides and the like as oxidizing agents.

  According to the method for producing a zeolite of the present invention, a zeolite having a high aluminum content and having a novel skeleton can be obtained. In the method for producing a zeolite according to the present invention, as an example, a dimethyldipropylammonium compound is used as a structure directing agent having a simple structure, and the amount of water used as a raw material is the same as the amount of the silica source used as a raw material About six to eight times As a result, the zeolite can be easily and reliably produced with high purity as compared with the case of using the conventional production method in which the amount of substance of water is about 40 times the amount of substance of silica source. It becomes easy to realize production. Further, since the synthesis of the structure-directing agent is simplified, the energy required for the synthesis process can be reduced, and the production cost can be significantly reduced.

It is the figure which planarly viewed the structure of the zeolite which concerns on one Embodiment of this invention from one direction. It is the figure which planarly viewed the structure of the zeolite which concerns on one Embodiment of this invention from other one direction. It is a graph which shows the result of having performed the analysis by X-ray diffraction about the zeolite which concerns on one Embodiment of this invention. It is a graph which shows the result of having performed nitrogen adsorption measurement about the zeolite which concerns on one Example of this invention. It is a graph which shows the result of having performed ²⁷ Al MAS NMR measurement about the zeolite which concerns on one Example of this invention. It is a graph which shows the result of having performed ²⁹ Si MAS NMR measurement about the zeolite which concerns on one Example of this invention. It is a SEM photograph of the zeolite concerning one example of the present invention. It is a SEM photograph of the zeolite which concerns on the other Example of this invention.

  Hereinafter, a zeolite 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 the drawings used in the following description, in order to make the features easy to understand, the features that are the features may be enlarged for the sake of convenience, and the dimensional ratio of each component may be limited to the same as the actual Absent. In addition, the materials, dimensions, and the like exemplified in the following description are merely examples, and the present invention is not limited to them, and can be appropriately changed and implemented without changing the gist of the invention.

[Composition of zeolite]
The structure of the zeolite 100 which concerns on one Embodiment of this invention is demonstrated using FIG. 1A, 1B. Here, the three-dimensional space is represented by x-axis, y-axis and z-axis orthogonal to one another, and a direction substantially parallel to x-axis, y-axis and z-axis is x-axis direction, y-axis direction and z-axis direction It shall be called. FIG. 1A is a plan view of the structure of the zeolite 100 from one direction (z-axis direction). FIG. 1B is a plan view of the structure of the zeolite 100 from another direction (x-axis direction).

  The zeolite (crystalline aluminosilicate porous body) 100 has a plurality of oxygen 8-membered rings 101 (101a, 101b) and a plurality of oxygen 12-membered rings 102 which are independent of each other. As will be described later, the oxygen 8-membered ring 101a is isolated in the y-axis direction, that is, separated from the other oxygen 8-membered rings 101a in the y-axis direction. The oxygen 8-membered ring 101b is in contact with another oxygen 8-membered ring 101b in the y-axis direction to form a pair.

  The pore diameter of the oxygen eight-membered ring 101 is 0.295 nm or more and 0.454 nm or less in consideration of the ion radius of oxygen (0.135 nm), ie, when the length of two ion radius of oxygen is subtracted. Is preferred. In addition, the pore diameter of the oxygen eight-membered ring 101 is 0.565 nm or more, when the ion radius of oxygen (0.135 nm) is not taken into consideration, that is, when the length of two ion radii of oxygen is not subtracted. It is preferable that it is 724 nm or less.

  The pore diameter of the oxygen 12-membered ring 102 is 0.595 nm or more and 0.710 nm or less when considering the ion radius (0.135 nm) of oxygen, ie, when subtracting the length of two ion radius of oxygen Is preferred. In addition, the pore diameter of the oxygen 12-membered ring 102 is 0.865 nm or more when the ion radius (0.135 nm) of oxygen is not taken into consideration, that is, when the length corresponding to two ion radii of oxygen is not subtracted. It is preferable that it is not more than .980 nm.

  The pore volume of the entire zeolite 100 estimated by nitrogen adsorption measurement is usually 0.12 ml / g or more and 0.25 ml / g or less, and preferably 0.15 ml / g or more and 0.20 ml / g or less. It is more preferable that it is 0.16 ml / g or more and 0.19 ml / g or less.

The framework density of the zeolite 100, that is, the number density of T atoms contained (number of T atoms (such as silicon) per 1 nm ³ ) is usually 15 atoms / nm ³ or more and 18 atoms / nm ³ or less, 16 preferably pieces / nm ³ or more 17 / nm ³ or less, more preferably not more than 16.6 pieces / nm ³ nm.

  The plurality of oxygen 8-membered rings 101a are separately present in the plurality of groups 101A, and in each group 101A, the oxygen 8-membered rings 101a overlap so as to have a common through hole in one direction (z-axis direction). Further, the plurality of oxygen 8-membered rings 101b are separately present in a plurality of groups 101B, and in each group 101B, the oxygen 8-membered rings 101b overlap so as to have a common through hole in one direction (z-axis direction) There is. The plurality of groups 101A and 101B are arranged such that pairs of the group 101A and the group 101B alternate in the y-axis direction.

  Each of the plurality of oxygen 8-membered rings 101a constituting each group 101A is connected to each of the plurality of oxygen 8-membered rings 101b constituting the adjacent group 101B via an oxygen 6-membered ring. In addition, each of the plurality of oxygen 8-membered rings 101b constituting each group 101B is connected to each of the plurality of oxygen 8-membered rings 101a constituting the adjacent one group 101A via the oxygen 6-membered ring There is. Further, each of the plurality of oxygen 8-membered rings 101b constituting each group 101B is directly linked to each of the plurality of oxygen 8-membered rings 101b constituting the other adjacent group 101B.

  The overlapping direction of the oxygen eight-membered rings 101a and 101b is preferably substantially parallel to the z-axis direction. In one direction (y-axis direction) intersecting the overlapping direction (z-axis direction) of the oxygen 8-membered ring, the group 101B of oxygen 8-membered rings forming a pair and the group 101A of isolated oxygen 8-membered rings are alternately arranged. Are connected to form a row 101C. The two pairs of groups 101B are both arranged along the y-axis direction. The separation distance d1 between one of the paired groups 101B and the isolated group 101A is about 0.519 to 0.530 nm.

  Rows 101C are connected via a plurality of oxygen 5-membered rings such that pairs of oxygen 8-membered rings 101a and pairs of oxygen 8-membered rings 101b are adjacent to each other. The separation distance d2 between the columns 101C is about 0.27 nm.

  The plurality of oxygen 12-membered rings 102 are divided into a plurality of groups 102A, and in each group 102A, the oxygen 12-membered rings 102 are preferably in a direction substantially parallel to the xy plane (a direction substantially parallel to one plane), Are overlapped so as to have a common through hole in the direction parallel to the xy plane (the direction parallel to one plane). The plurality of groups 102A are arranged in the y-axis direction. The plurality of oxygen 12-membered rings 102 constituting each group 102A are respectively linked to the plurality of oxygen 12-membered rings 102 constituting the adjacent group 102A via an oxygen 4-membered ring and / or an oxygen 5-membered ring. There is. The overlapping direction of the oxygen 12-membered ring 102 is preferably substantially parallel to the x-axis direction.

  Groups 102A of oxygen 12-membered rings are arranged at equal intervals (d3, d4) in two directions (y-axis direction, z-axis direction) in a plane intersecting with the overlapping direction (x-axis direction) of oxygen 12-membered rings It is connected. Specifically, the groups 102A are arranged at intervals of about 0.810 to 0.830 nm (d3) in the y-axis direction and at intervals of about 0.240 to 0.260 nm (d4) in the z-axis direction.

  The overlapping direction of the oxygen 8-membered ring and the overlapping direction of the oxygen 12-membered ring intersect each other. In practice, they intersect at an angle of about 89 degrees or more and 91 degrees or less, and tend to be substantially orthogonal (almost orthogonal), but are preferably orthogonal.

  In the structure described above, the molar ratio (Si / Al) of silicon and aluminum contained is 8.0 or more and 9.1 or less. This molar ratio can be confirmed by, for example, elemental analysis by inductively coupled plasma atomic emission spectrometry (ICP-AES), atomic absorption analysis, fluorescent X-ray analysis, or the like.

  The structure of the zeolite can be uniquely identified from the analysis result by X-ray diffraction (XRD). In the examples described later, analysis results of X-ray diffraction for the zeolite 100 are obtained, and those skilled in the art can judge that the zeolite 100 actually has the above-described structure based on the analysis results. it can. In addition, about the zeolite 100 having the above-mentioned structure, it is verified also by the analysis of the X-ray diffraction of a specialized agency.

  That is, the zeolite 100 according to the present embodiment is a zeolite in which at least a lattice spacing d (d-spacing) (Å) shown in Table 2 is detected by powder X-ray diffraction. More specifically, the zeolite 100 is a zeolite having an X-ray diffraction pattern including at least interplanar spacing d (Å) and relative intensities shown in Table 2 as measured by powder X-ray diffraction. The relative intensity indicates the ratio of the intensity of the other peak to the intensity of the largest peak among the peaks included in the X-ray diffraction pattern as 100. Here, the peak intensity corresponding to the lattice spacing d (Å) of 3.43 ± 0.10 is maximum.

The zeolite according to the present embodiment preferably has the following chemical composition represented by a molar ratio.
X ₂ O ₃ : (n) YO ₂

  The above X is a trivalent element. The trivalent element is not particularly limited, but in general, boron, aluminum, iron and gallium are preferable, and boron, aluminum and gallium are particularly preferable in terms of the easiness of formation of a zeolite crystal and the like. The trivalent element X may consist of one kind of trivalent element, or may be a combination of two or more kinds of trivalent elements. Among them, the zeolite according to the present embodiment preferably contains aluminum as the trivalent element X. The content of aluminum in this case is preferably 50 mol% or more of the whole X, and more preferably 80 mol% or more.

  The above Y is a tetravalent element. The tetravalent element is not particularly limited, but generally, silicon, germanium, tin, titanium, or zirconium is preferable, and silicon, germanium, tin, or titanium is particularly preferable in terms of the ease of formation of a zeolite crystal, etc. . The tetravalent element Y may consist of one kind of tetravalent element, or may be a combination of two or more kinds of tetravalent elements. Among them, the zeolite according to the present embodiment preferably contains silicon as the tetravalent element Y. The silicon content in this case is preferably 50 mol% or more, and more preferably 80 mol% or more of the whole of Y.

  The value of n represents a molar ratio of the oxide of trivalent element X to the oxide of tetravalent element Y, and the value of n / 2 is usually 5 or more and 1000 or less, preferably 6 or more and 100 or less, More preferably, they are 6.5 or more and 30 or less, more preferably 7 or more and 10 or less.

  The zeolite according to the present embodiment may contain a metal element other than the trivalent element X and the tetravalent element Y. Such "containing a metal element" may be either the case where the metal element is present in the framework of the zeolite or the case where it is present outside the framework, and also includes the case where it is a mixture. When the zeolite according to the present embodiment contains another metal element, the metal element is not particularly limited, but iron, cobalt, magnesium are generally used from the viewpoint of the characteristics of the adsorbent application and the catalyst application. And transition metals of Groups 3 to 12 of the periodic table, such as zinc, copper, palladium, iridium, platinum, silver, gold, cerium, lanthanum, praseodymium, titanium, and zirconium.

  When the zeolite according to the present embodiment contains another metal element, the content of the metal element in the zeolite is preferably 0.1% by weight or more and 20% by weight or less, and 0.3% by weight or more and 10% by weight It is more preferable if it is the following. By including other metal elements such as iron and copper, an effect of generating an active site of the catalyst is obtained. Furthermore, by setting the content to the above lower limit value or more, an excellent catalytic effect is obtained, and by setting the content to the above upper limit value, it becomes easy to uniformly disperse the metal element in the zeolite, It is preferable because excellent catalytic activity can be obtained.

The zeolite according to the present embodiment may contain metal cations such as sodium, potassium and cesium, and nonmetal cations such as ammonium ions (NH ₄ ⁺ ) and hydrogen ions (H ⁺ ). May be In addition, metal cations and nonmetal cations may be simultaneously contained. The cations in the zeolite crystals can be replaced by other ions by ion exchange.

  The zeolite according to the present embodiment is characterized by having an X-ray powder diffraction pattern shown in Table 2 and FIG. 2 regardless of the presence or absence of other metal elements or metal cations and the presence or absence of ion exchange.

  The zeolite according to the present embodiment is a crystalline aluminosilicate porous body having a novel skeleton, which contains a large amount of aluminum (for example, Si / Al = 8.0 to 9.1) and contains many ion exchange sites, so that it is an ion It is suitable for the development of a catalyst (for example, NOx reduction catalyst) whose key is exchange. The zeolite according to the present embodiment is not particularly limited as to its use, but is preferably used as a catalyst, an adsorbent, a separation material, and the like because it has a unique crystal structure. In addition, since the zeolite according to the present embodiment can introduce a hetero element through dealumination, it may be used as a catalyst for producing various basic chemicals.

  Furthermore, the zeolite according to the present embodiment can be applied as a solid catalyst that promotes the catalytic cracking of paraffins. In the zeolite of the present invention, part of the constituent aluminum can be isomorphously substituted with a transition metal (titanium, tin, etc.). For example, zeolite homomorphically substituted with titanium is an excellent catalyst for selective oxidation of olefins, paraffins and aromatic rings using oxygen, hydrogen peroxide, alkyl hydroperoxides and the like as oxidizing agents.

[Method of producing zeolite]
The manufacturing method of the zeolite 100 based on this embodiment is demonstrated. The manufacturing method of the zeolite 100 mainly includes a first preparation step, a first heating step, a cooling step, a second preparation step, a second heating step, a drying step, and a third heating step in this order. ing.

<First preparation step>
First, a mixture (gel) of a first silica source, an aluminum source, an alkali source, water, and a structure directing agent (SDA) is prepared.

As the first silica source, for example, one or more of colloidal silica, amorphous silica, sodium silicate, tetraethylorthosilicate, aluminosilicate gel and the like can be used. Preferably, colloidal silica ((SiO ₂ ) _Ludox , LUDOX (registered trademark)) is used.

  As an aluminum source, 1 type or 2 types or more can be used among aluminum sulfate, sodium aluminate, aluminum hydroxide, aluminum chloride, aluminosilicate gel, metal aluminum etc., for example. Moreover, it is also possible to use zeolites, such as Y-type zeolite, as an aluminum source.

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

As a structure directing agent, for example, dimethyl dipropyl ammonium salt is preferable, and dimethyl dipropyl ammonium hydroxide (Me ₂ Pr ₂ NOH) is more preferable. Me and Pr indicate 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 an example.

<First heating step>
Next, the mixture prepared in the first preparation step is heated with stirring. Specifically, while stirring the mixture on a hot plate heated to 60 ° C. or higher, the water is partially evaporated to concentrate the mixture to a predetermined amount.

<Cooling process>
Next, the mixture heated in the first heating step is cooled to about room temperature using a water bath. Note that the first heating step and the cooling step can be omitted.

<Second preparation step>
Next, the mixture cooled in the cooling step is re-prepared by adding a second silica source and an alumina source, as necessary. Y-type zeolite (SiO ₂ ) _FAU , (Al ₂ O ₃ ) _FAU ) is used as the second silica source and the alumina source. 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 more. The following are more preferred, and about 5.3 is most preferred.

In the reconstituted mixture, the content ratio (mol%) of (SiO ₂ ) _{Ludox to} the total silica sources ((SiO ₂ ) _Ludox , (SiO ₂ ) _FAU ) is usually 30 to 90%, preferably Is 50 to 80%, more preferably 60 to 75%, and more preferably about 74%. Also, the content ratio (mol%) of the alkali source (NaOH etc.) to the total silica source in the same mixture is usually 0.05 to 0.6%, preferably 0.1 to 0.5%, Preferably it is 0.2 to 0.4%. When both NaOH and KOH are used, the content ratio of NaOH and KOH is preferably about 0.15%. Also, the content ratio of the structure directing 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% and most preferably about 0.17%. Also, 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 most preferable to set it as%.

As for the composition described above, with regard to (SiO ₂ ) _Ludox , NaOH, KOH, and H ₂ O, the amount to be mixed in the first preparation step is adjusted so as to achieve the content ratio described above. Further, with regard to (SiO ₂ ) _FAU and (Al ₂ O ₃ ) _FAU, it is preferable to adjust the amount to be mixed in the second preparation step so as to _achieve the above-mentioned content ratio.

Furthermore, in the reconstituted mixture, the content ratio (molar ratio) of water (H ₂ O) to the total silica source is usually 4 to 50, preferably 5 to 30, and more preferably 5.5 to 12, more preferably 6 to 8, and most preferably about 7. By thus reducing the content ratio of H ₂ O in the mixture, a zeolite having a high organic concentration and a large pore volume is obtained.

<Second heating step>
The mixture (raw material) re-prepared in the second preparation step is generally heated with stirring at room temperature.
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. About 160 ° C. is most preferred. In an oven, usually, it is left still or stirred for about 12 hours to about 10 days, preferably about 1 day to about 7 days.

<Drying process>
Next, the mixture heated in the second heating step is washed, filtered and further dried. As a method of drying here, there is, for example, a method of leaving the washed and filtered mixture in an oven at about 80 ° C. overnight, a method of drying it in the sun, and the like.

  Through the above steps, an organic complex (powder) containing a crystalline solid of zeolite 100 is obtained.

<Third heating step>
The organic complex (Me ₂ Pr ₂ NOH used as a structure directing agent) which is clathrated can be removed by further heating (baking) the organic complex obtained through the drying step. The heating here heats about 550 degreeC in the state which accommodated the obtained crystalline solid in the 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, it is allowed to cool.

  According to the manufacturing method of zeolite 100 concerning this embodiment, aluminum content is many (Si / Al = 7-10), and it can obtain the zeolite which has a new frame. In the method for producing the zeolite 100 of the present embodiment, a dimethyldipropylammonium compound is used as a structure directing agent having a simple structure, and the ratio of water used as a raw material is also about 6 to 8 of the silica source used as a raw material. It is about doubled. As a result, the zeolite can be produced easily and reliably with high purity as compared with the conventional production method in which the ratio of water is about 40 times that of the silica source, and mass production is realized. It will be easier. Further, since the synthesis of the structure-directing agent is simplified, the energy required for the synthesis process can be reduced, and the production cost can be significantly reduced.

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

(Production Example 1)
The production example 1 of dimethyl dipropyl ammonium hydroxide used as a structure directing agent of the zeolite of the present invention is shown.

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

This synthesis was performed 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.) 90g was added and 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, and the pressure was reduced at 40 ° C. using an evaporator to dryness.

  Next, 200 mL of chloroform (manufactured by Wako Pure Chemical Industries, Ltd.) was added to extract the product, and insoluble inorganic salts were removed by suction filtration. The filtrate was placed in a 1-L eggplant flask and depressurized again to dryness. The product was extracted with 200 mL of chloroform, the inorganic salts were removed by suction filtration, and the clear filtrate was received in a 1 L eggplant flask. The filtrate was evaporated to dryness under reduced pressure, 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 the mixture was heated on an oil bath at 100 ° C. to dissolve crude crystals. After cooling, 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 crystals obtained were dried under vacuum. The yield of the product Me ₂ Pr ₂ NI (dimethyldipropylammonium iodide) was 105.5 g (90% yield).

As NMR analysis values of the ^{product, 1 H NMR (500MHz, CDCl} 3) and as measured ^{at, 13 C NMR (126MHz, CDCl} 3) when measured in the resulting chemical shift [delta], shown below.

(I) δ as measured by ¹ H NMR (500 MHz, CDCl ₃ ):
1.07 (6 H, t, J = 7.4 Hz, 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 as measured by ¹³ C NMR (126 MHz, CDCl ₃ ):
10.58, 16.40, 51.52, 65.80

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

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. Next, 500 mL of H ₂ O (Milli-Q) was added, the container was shaken lightly, and allowed to stand in a cold dark place for 120 hours.

Next, suction filtration was performed using a glass filter (G4), the resin on the filter was thoroughly washed with 300 mL of H ₂ O (Milli-Q), and the filtrate and the washing solution were combined and concentrated under reduced pressure. The weight of the obtained solution was 133.37 g, and the concentration of Me ₂ Pr ₂ NOH determined by titration with 0.05 M hydrochloric acid was 2.097 mmol / g (ion exchange rate 96%). The conversion of Me ₂ Pr ₂ NI to Me ₂ Pr ₂ NOH is a simple 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 was synthesized using Me ₂ Pr ₂ NOH obtained in Production Example 1 as a structure defining agent. This synthesis was performed in the following procedure. First, 16.21 g of the Me ₂ Pr ₂ NOH aqueous solution (2.097 mmol / g) obtained in Production Example 1 is taken in a 150 mL fluorine resin (PFA) container, and 9.37 g of a NaOH aqueous solution (3.200 mmol) / G), 9.53 g of KOH aqueous solution (3.153 mmol / g), 21.39 g of Ludox AS-40 (manufactured by Aldrich, including 41.3 wt% SiO ₂ ) were sequentially added (first preparation step) ).

Next, 20.26 g of water (4.41 g of water used for washing in the first preparation step) was prepared by stirring for about 3 hours on a hot plate set so that the liquid temperature was about 60 ° C. Water) was evaporated (first heating step). The resulting mixture is cooled to room temperature using a water bath (cooling step), then 4.99 g of Y-type zeolite (composition H _30.5 Al _30.5 Si _161.5 O ₃₈₄ as dry, Tosoh (strain) ) Ltd., HSZ-350HUA, actually in this embodiment, _SiO 2 of 63.9wt%, 10.2wt% of _Al 2 _O 3, which contains 25.9wt% of _{H 2} O) was added ( The second preparation step was stirred at room temperature for 10 minutes. The composition of the resulting _{mixture, 1.0SiO 2 -0.025Al 2 O 3 -0.17Me} 2 Pr 2 NOH-0.15NaOH-0.15KOH-7H 2 O, the total weight of the mixture becomes 45.64g The

  This mixture was transferred to an autoclave having an inner volume of 125 mL of a fluorocarbon resin (PTFE) inner cylinder, and this was allowed to stand in an oven at 160 ° C. for 165 hours (second heating step). The resulting solid product was collected by filtration and dried in an oven at 80 ° C. overnight (drying step). The weight of the obtained white powder was 6.84 g.

  Of this, 5.02 g was put into a petri dish made of alumina, heated at a rate of 1.5 ° C. per minute from room temperature in an air atmosphere in a muffle furnace, held at 550 ° C. for 6 hours, and then allowed to cool (third Heating process (baking process)). Thus, 4.90 g of white powder (after firing) was obtained.

(Example 2)
Zeolite was synthesized using Me ₂ Pr ₂ NOH obtained in Production Example 1 as a structure defining agent. This synthesis was performed in the following procedure. First, 46.77 g (68.0 mmol) of the Me ₂ Pr ₂ NOH aqueous solution (1.454 mmol / g) obtained in Production Example 1 is placed in a 150 mL inner volume container made of fluorocarbon resin (PFA), and 19.81 g of NaOH Aqueous solution (3.029 mmol / g, 60.0 mmol), 20.81 g of aqueous KOH solution (2.883 mmol / g, 60.0 mmol), 42.78 g of Ludox AS-40 (manufactured by Aldrich, 41.3 wt% SiO ₂ The solution was added sequentially to 17.67 g-SiO ₂ , 293.8 mmol-SiO ₂ ) (first preparation step).

Next, 53.40 g of water (4.52 g of water used for washing in the first preparation step) was prepared by stirring for about 6 hours on a hot plate set so that the liquid temperature was about 60 ° C. Water) was evaporated (first heating step). The resulting mixture is cooled to room temperature using a water bath (cooling step), then 9.99 g of Y-type zeolite (composition H _30.5 Al _30.5 Si _161.5 O ₃₈₄ as dried, Tosoh (strain) ) Ltd., HSZ-350HUA, # 35UA3502, Si / Al = 5.3, in fact in this embodiment, _SiO 2 of 63.9wt%, 10.2wt% of _Al 2 _O 3, _25.9wt% of H ₂ ) was added (second preparation step) and stirred at room temperature for 10 minutes. The composition of the obtained _{mixture, 1.0SiO 2 -0.025Al 2 O 3 -0.17Me} 2 Pr 2 N + OH - -0.15NaOH-0.15KOH-7.0H 2 O, the total weight of the mixture It became 91.28 g.

  This mixture was transferred to an autoclave having an inner volume of 125 mL of a fluorocarbon resin (PTFE) inner cylinder, which was allowed to stand in an oven at 160 ° C. for 166 hours (second heating step). The resulting solid product was collected by filtration and dried in an oven at 80 ° C. overnight (drying step). The weight of the obtained white powder was 13.07 g.

  Of this, 2.60 g was put into a petri dish made of alumina, heated at a rate of 1.5 ° C. per minute from room temperature in an air atmosphere in a muffle furnace, held at 550 ° C. for 6 hours, and then allowed to cool (third Heating process (baking process)). Thus, 2.51 g of white powder (after firing) was obtained.

(Example 3)
Zeolite was synthesized using Me ₂ Pr ₂ NOH obtained in Production Example 1 as a structure defining agent. This synthesis was performed in the following procedure. First, 58.97 g (68.0 mmol) of the Me ₂ Pr ₂ NOH aqueous solution obtained in Production Example 1 is taken in a container made of fluorine resin (PFA) having an inner volume of 150 mL, and 19.81 g of NaOH solution (3.029mmol / g, 60.0mmol), KOH aqueous solution of 20.82g (2.883mmol / g, 60.0mmol) , Ludox AS-40 ( Aldrich Co. 42.78g, 41.3wt% SiO ₂ (17. 67 g-SiO ₂ , 293.8 mmol-SiO ₂ ) were sequentially added (first preparation step).

Next, by stirring for about 7 hours on a hot plate set so that the liquid temperature is about 60 ° C., 65.17 g of water (4.10 g of water used for washing in the first preparation step) Water) was evaporated (first heating step). The resulting mixture is cooled to room temperature using a water bath (cooling step), then 9.99 g of Y-type zeolite (composition H _30.5 Al _30.5 Si _161.5 O ₃₈₄ as dried, Tosoh (strain) ) Ltd., HSZ-350HUA, # 35UA3502, Si / Al = 5.3, in fact in this embodiment, _SiO 2 of 63.9wt%, 10.2wt% of _Al 2 _O 3, _25.9wt% of H ₂ ) was added (second preparation step) and stirred at room temperature for 10 minutes. The composition of the obtained _{mixture, 1.0SiO 2 -0.025Al 2 O 3 -0.17Me} 2 Pr 2 N + OH - -0.15NaOH-0.15KOH-7.0H 2 O, the total weight of the mixture It became 91.28 g.

  This mixture was transferred to an autoclave having an inner volume of 125 mL and made of a fluorocarbon resin (PTFE), and it was allowed to stand in an oven at 160 ° C. for 20 hours under rotation conditions of 20 rpm (second heating step). The resulting solid product was collected by filtration and dried in an oven at 80 ° C. overnight (drying step). The weight of the obtained white powder was 14.10 g.

  Of this, 3.02 g was put into a petri dish made of alumina, heated from room temperature to 1.5 ° C. per minute in an air atmosphere in a muffle furnace, held at 550 ° C. for 6 hours, and then allowed to cool (third Heating process (baking process)). In this way, 2.85 g of white powder (after calcination) was obtained.

(Example 4)
The zeolite was synthesized using Me ₂ Pr ₂ NOH from Sachem as a structure directing agent. This synthesis was performed in the following procedure. First, 25.54 g (68.0 mmol) of an aqueous solution of Me ₂ Pr ₂ NOH (2.663 mmol / g) manufactured by Sachem in an amount of 150 mL of a fluorocarbon resin (PFA) container is charged with 21.04 g of an aqueous NaOH solution ( 2.852 mmol / g, 60.0 mmol), 18.80 g of aqueous KOH solution (3.191 mmol / g, 60.0 mmol), 42.78 g of Ludox AS-40 (manufactured by Aldrich, containing 41.3 wt% SiO ₂₎ Therefore, 17.67 g of SiO ₂ and 293.8 mmol of SiO ₂ were sequentially added (first preparation step).

Next, 29.52 g of water (3.01 g of water used for washing in the first preparation step) was prepared by stirring for about 3 hours on a hot plate set so that the liquid temperature would be about 60.degree. Water) was evaporated (first heating step). The obtained mixture is cooled to room temperature using a water bath (cooling step), 9.71 g of Y-type zeolite (composition H _30.5 Al _30.5 Si _161.5 O ₃₈₄ as dry, Tosoh (strain) ), HSZ-350 HUA, # 35 UA 35 Y 2, Si / Al = 5.5, actually 68.1 wt% SiO ₂ , 10.5 wt% Al ₂ O ₃ , 21.4 wt% H in this example. ₂ ) was added (second preparation step) and stirred at room temperature for 10 minutes. The composition of the obtained _{mixture, 1.0SiO 2 -0.025Al 2 O 3 -0.17Me} 2 Pr 2 N + OH - -0.15NaOH-0.15KOH-7.0H 2 O, the total weight of the mixture It became 91.36g.

  This mixture was transferred to an autoclave having an inner volume of 125 mL and made of a fluorocarbon resin (PTFE), and it was allowed to stand in an oven at 160 ° C. for 20 hours under a rotation condition of 20 rpm (second heating step). The resulting solid product was collected by filtration and dried in an oven at 80 ° C. overnight (drying step). The weight of the obtained white powder was 13.73 g.

  Of this, 3.13 g was put in a petri dish made of alumina, heated at a rate of 1.5 ° C. per minute from room temperature in an air atmosphere in a muffle furnace, held at 550 ° C. for 6 hours, and then allowed to cool (third Heating process (baking process)). Thus, 3.09 g of white powder (after firing) was obtained.

  FIG. 2 is a graph showing the analysis results by X-ray diffraction (XRD) of the zeolite of Example 1 obtained by the inventor. The horizontal axis indicates the diffraction angle 2θ [°], and the vertical axis indicates the diffraction intensity [cps]. The diffraction spectrum (XRD pattern) by the sample from which the organic matter was removed by calcination is shown on the upper side, and the diffraction spectrum from the unbaked sample is shown on the lower side. The lattice spacing d (Å) shown in Table 2 was detected from FIG.

The X-ray diffraction was measured under the following conditions.
Device used: Ultima-IV powder X-ray analyzer manufactured by RIGAKU Co., Ltd. X-ray source: CuKα1 = 1.54057 Å, applied voltage: 40 kV, tube current: 20 mA
Measurement range: 2θ = 2.040 to 52.000 degrees Scan speed: 2.000 deg. / Min, sampling interval: 0.040 degree divergence slit: 1.00 deg, scattering slit: 1.00 deg, light receiving slit: 0.30 mm
Measurement method: Continuous method, normal method The lattice spacing d is in angstrom units.

  As shown in FIG. 2, the diffraction spectra obtained for the samples before and after calcination both have characteristic peaks not found in known zeolites. From this result, it is understood that all the samples are zeolites in which a crystalline phase having a novel framework structure is formed.

  The Si / Al ratio after firing was determined by a calibration curve method (aqueous solution mode) using an inductively coupled plasma atomic emission spectrometer (ICP-9000E manufactured by Shimadzu Corporation). As a result, it was Si / Al = 9.5.

The nitrogen adsorption of the zeolite was measured under the following conditions.
Device used: Microtrack Bell Belsorp max fully automatic adsorption measuring device Measuring temperature: -196 ° C
Air bath temperature: 40 ° C
Equilibrium adsorption time: 300 seconds Sample pretreatment condition: 400 ° C, 2 hours

The nitrogen adsorption measurement results are shown in the graph of FIG. The graph in FIG. 3 shows the adsorption isotherm.
The horizontal axis of the graph indicates relative pressure (ratio of adsorption equilibrium pressure to saturated vapor pressure), and the vertical axis indicates nitrogen adsorption amount (cm ³ (S.T.P.) / G). S. T. P. The term “standard temperature and pressure” means that the adsorption amount is a value converted to a volume (cm ³ ) at 0 ° C. and 1 atm. The lower part of the graph shows the adsorption isotherm before H ⁺ ion exchange, and the upper part of the graph shows the adsorption isotherm after H ⁺ ion exchange. The black circle plot is in the adsorption process, and the white circle plot is in the desorption process.

The BET specific surface area calculated from the lower graph is 434 m ² / g, the external surface area is 5.1 m ² / g, and the pore volume is 0.173 ml / g. Incidentally, according to elemental analysis of this sample by ICP-AES, Si / Al was 9.09. Na / Al and K / Al were 0.12 and 0.52, respectively.

The BET specific surface area calculated from the upper graph is 487 m ² / g, the external surface area is 6.7 m ² / g, and the pore volume is 0.194 ml / g. Incidentally, according to elemental analysis of this sample by ICP-AES, Si / Al was 9.33. Na / Al and K / Al were each less than 0.03.

The ²⁷ Al MAS NMR of the zeolite was measured under the following conditions.
Equipment used: Bruker AVANCE III 600
1H resonance frequency: 600 MHz
Rotor rotational speed: 13 kHz
Repetition time: 0.5 sec, integration number: 1024 times

The ²⁹ Si MAS NMR of the zeolite was measured under the following conditions.
Equipment used: Bruker AVANCE III 600
1H resonance frequency: 600 MHz
Rotor rotational speed: 10 kHz
Repetition time: 30.0 sec, integration number: 1024 times

^The spectra obtained by ²⁷ Al MAS NMR and ²⁹ Si MAS NMR are shown in the graphs of FIGS. The horizontal axis of each graph indicates a chemical shift. The spectrum before firing is shown at the bottom, and the spectrum after firing is shown at the top.

In the ²⁷ Al-MAS NMR spectrum after firing of FIG. 4, (1) a major peak with a chemical shift of 56.5 ± 2 ppm and (2) a minor peak present at 0 ± 2 ppm were observed. The peak of (1) is a peak attributed to Al in the skeleton, while the peak of (2) is a peak attributed to Al desorbed out of the skeleton. Before firing, the peak of (2) was not observed, and only the peak of (1) was observed.

Three peaks included in the ²⁹ Si-MAS NMR spectrum of FIG. 5 are signals of Si corresponding to coordination forms of Si (2Al), Si (1 Al), and Si (0 Al) sequentially from the left side. The Si / Al in the skeleton was estimated to be about 10 from the area ratio of these peaks. Here, Si (nAl) means a signal of Si described first from the left among (AlO) _n Si (OSi) _4-n (here, n = 0, 1, 2).

A scanning electron microscope (SEM) photograph of the zeolite of Example 1 was obtained under the following conditions.
Device used: JSM-7001F manufactured by JEOL
Acceleration voltage: 1.00 kV or 3.00 kV

  The obtained SEM photographs are shown in FIGS. 6A and 6B. FIGS. 6A (a) to (i) are SEM photographs of the samples crystallized for 165 hours, respectively, while changing the magnification (displaying the dimensions to be compared) from various directions. This sample corresponds to Example 1. FIG. 6B is a SEM photograph (same magnification as FIG. 6A (a)) of a sample crystallized in 45 hours shorter than Example 1.

  The zeolite of the present invention can be used as an adsorbent for moisture and the like in air conditioners and heat pumps, and can also be used as a catalyst used for synthesis of chemical products and a purification catalyst for exhaust gas of automobiles.

100 Zeolite 101 (101a, 101b) Oxygen 8-Membered Ring 101A, 101B, 102A Group 101C Row 102 Oxygen 12-Membered Ring

Claims (8)

It has an X-ray diffraction pattern including at least interplanar spacing d (Å) and relative intensity shown in Table 1 below, as measured by powder X-ray diffraction method;
The above-mentioned relative intensity shows the ratio of the intensity of the other peak to the intensity of the largest peak among the peaks contained in the above-mentioned X-ray diffraction pattern.
  The zeolite according to claim 1, wherein the pore volume estimated by nitrogen adsorption measurement is 0.12 ml / g or more and 0.25 ml / g or less. It has a plurality of oxygen 8-membered rings and oxygen 12-membered rings which are mutually independent,
The plurality of oxygen 8-membered rings are divided into a plurality of groups, and in each group, the oxygen 8-membered rings overlap so as to have a common through hole in one direction,
The plurality of oxygen 12-membered rings are divided into a plurality of groups, and in each group, the oxygen 12-membered rings overlap so as to have a common through hole in a direction parallel to one plane,
The zeolite according to any one of claims 1 and 2, wherein the overlapping direction of the oxygen 8-membered ring and the overlapping direction of the oxygen 12-membered ring intersect each other.   The oxygen eight-membered ring is connected in a row alternately with pairs forming an isolated one in one direction intersecting the overlapping direction, and the rows form a pair The zeolite according to claim 3, wherein the oxygen 8-membered ring and the isolated oxygen 8-membered ring are connected to be adjacent to each other.   The zeolite according to any of claims 3 or 4, wherein the oxygen 12-membered ring is connected side by side at equal intervals in two directions in a plane intersecting the overlapping direction.   The pore diameter of the oxygen 8-membered ring is 0.295 nm or more and 0.454 nm or less when subtracting the length of two ion radius (0.135 nm) of oxygen, and 0.565 nm or more and 0.724 nm or less without subtraction The pore diameter of the oxygen 12-membered ring is 0.595 nm or more and 0.710 nm or less when subtracting the length of two ion radii (0.135 nm) of oxygen, and 0.865 nm or more and 0.980 nm or less without subtraction The zeolite according to any one of claims 3 to 5, characterized in that The number density of 15 T atoms containing / nm ³ or more 18 / nm ³ zeolite according to any one of claims 1 to 6, characterized in that less. It is a manufacturing method of the zeolite according to any one of claims 1 to 7,
Preparing a mixture of a first silica source, an alkali source, water, and a structure directing agent while stirring;
A first heating step of heating the prepared mixture while stirring;
A cooling step of cooling the heated mixture;
A second preparation step of adding the second silica source and the alumina source to the cooled mixture, and reconstituting it while stirring;
A second heating step of heating the reconstituted mixture;
Drying the heated mixture, washing and filtering and drying;
And heating the organic complex obtained through the drying step, and a third heating step of removing the contained organic substance in order;
A method for producing a zeolite comprising: colloidal silica as the first silica source, Y-type zeolite as the second silica source and alumina source, and a dimethyldipropylammonium compound as the structure directing agent.