JP6975635B2 - MWF type zeolite - Google Patents

Description

The present invention relates to MWF-type zeolite.

Zeolites can be used as adsorbents, desiccants, separators, catalysts, catalyst carriers, detergent aids, ion exchangers, wastewater treatment agents, fertilizers, food additives, cosmetic additives, etc., especially as catalyst applications. It is useful.
Here, the MWF-type zeolite means a zeolite having an MWF structure with a code defining the structure of the zeolite defined by the International Zeolite Association (IZA). Patent Document 1 discloses ZSM-25, which is a kind of MWF-type zeolite, and is shown to have catalytic performance for olefin oligomerization reaction and cracking of n-hexane. Further, as described in Patent Document 2 and Non-Patent Document 1, the structure of ZSM-25, which is a kind of MWF-type zeolite, has been clarified in recent years. It is reported that the structure is a zeolite having a space group of Im3 m of a regular hexahedral crystal system and having pores composed of an oxygen 8-membered ring.

U.S. Patent 4,247,416 Korean patent 10155514

Peng Guo, Jiho Shin, Alex G. Greenaway, Jung Gi Min, Jie Su, Hyun June Choi, Leafeng Liu, Paul A. Cox, Suk Bong Hong, Paul A. Wright, Xiaodong Zou. "A zeolite family with expanding spectral complete completeness and embedded isoreticular nature" Nature. 2015, 524, 74-78.

In recent years, the development of shale gas and the development of natural gas have progressed, and the production of hydrocarbons having 1 or 2 carbon atoms has been increasing. Further, a method of obtaining ethylene by a dehydrogenation reaction using ethanol that can be produced from biomass as a raw material can also be efficiently performed by using a solid catalyst. Hydrocarbons with 4 or more carbon atoms, such as butene and butadiene, are also important raw materials for the production of useful chemicals, and polymerization reactions (especially oligomerization) that produce high carbon number hydrocarbons from low carbon number hydrocarbons. Expectations for reaction) are rising.
However, the oligomerization reaction of hydrocarbons causes caulking in which polymer-like hydrocarbons are generated and closes the active points of the catalyst, so that there is a problem that the life of the catalyst is short. Caulking occurs due to the excessive progress of the oligomerization reaction due to the long-term presence of hydrocarbons in the active site. Since the 8-membered ring pores of the MWF-type zeolite are as small as 3.6 Å, caulking caused by the hydrocarbon molecules penetrating into the pores and staying inside for a long time is relatively small. However, if the 8-membered ring structure is unclear and contains defects or the like, it is considered that hydrocarbons stay in the narrow pores for a long time and caulking occurs. The MWF-type zeolite disclosed in Patent Document 1, Patent Document 2, Non-Patent Document 1, etc. does not have sufficient performance from the viewpoint of catalyst life.

The present invention has been made in view of the above circumstances, and there are few distortions and defects in the crystal lattice, the fine structure of the crystal and the 8-membered ring of the higher-order structure are clearly formed, and caulking occurs in the hydrocarbon polymerization reaction. It is an object of the present invention to provide an MWF-type zeolite that can be used as a polymerization catalyst having a small amount of water and a long life.

As a result of diligent studies to solve the above problems, the present inventors have determined that the intensity ratio of a specific diffraction peak is within a predetermined range in the diffraction pattern obtained by subjecting the MWF type zeolite to the X-ray diffraction measurement. We have found that the problem of the present application can be solved, and have come to the present invention.

That is, the present invention is as follows.
[1]
MWF-type zeolite satisfying 0.30 ≦ B / A <0.61 when the peak heights around 2θ = 11.1 and 13.8 ° are A and B, respectively, in the peak obtained by X-ray diffraction. ..
[2]
The MWF-type zeolite according to [1], wherein the half width of the peak near 2θ = 11.1 ° satisfies 0.31 or less in the peak obtained by X-ray diffraction.

According to the present invention, as a polymerization catalyst having less distortion and defects in the crystal lattice, clearly forming an 8-membered ring having a fine crystal structure and a higher-order structure, and having less caulking in the hydrocarbon polymerization reaction, and having a long life. MWF-type zeolites that can be used can be provided.

FIG. 3 is an X-ray diffraction (XRD) diagram of the MWF-type zeolite obtained in Example 1. It is a schematic diagram which illustrates the reaction apparatus composition at the time of carrying out the oligomerization reaction of a hydrocarbon using the MWF type zeolite which concerns on one Embodiment of this invention.

Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following description, and can be variously modified and carried out within the scope of the gist thereof.

[X-ray diffraction peak]
The MWF-type zeolite of the present embodiment has a peak obtained by X-ray diffraction, where 0.30 ≦ B / A < Satisfy 0.61.
Here, the X-ray diffraction pattern is obtained by irradiating a surface in which zeolite is uniformly fixed on a non-reflective sample plate for powder with X-rays having CuKα as a radiation source and setting the scanning axis to θ / 2θ.
The peak near 2θ = 11.1 ° refers to the largest peak existing in the range of 11.1 ° ± 0.1 °.
The peak near 2θ = 13.8 ° refers to the largest peak existing in the range of 13.8 ° ± 0.2 °.

Of the X-ray diffraction peaks of the MWF-type zeolite of the present embodiment at 25 ° C., the peaks near 2θ = 11.1 and 13.8 ° are the diffraction peaks of (440) and (550), respectively. .. That is, these are diffractions due to parallel crystal lattice planes, and when the heights of the diffraction peaks of (440) and (550) are A and B, respectively, it is finer when the B / A is large. The structure is clear. That is, there are few defects in the Si—O or Al—O bond, the bond length and angle are highly uniform, and the selectivity contributes to defects such as hydrocarbon molecules entering the crystal lattice and other than the desired reaction. Since it is difficult to generate active sites that reduce the catalyst life, it is considered that a high reaction selectivity can be obtained as well as a small decrease in catalyst life. From this viewpoint, the B / A is 0.30 or more, preferably 0.35 or more, and more preferably 0.40 or more.
On the other hand, the large value of the peak height A suggests that the higher-order structure such as the 8-membered ring structure is clear, that is, the fine structures are regularly arranged and the pores are appropriately formed. It is thought that it is. When the pore structure is properly formed without defects, the molecular sieving effect of MWF-type zeolite on gas molecules of different sizes works, and hydrocarbon molecules are difficult to enter into the pores, so that excess oligomers are present in the pores. It is considered that the selectivity of the desired reaction can be improved because the chemical reaction can be reduced, the reduction in catalyst life due to coking can be suppressed, and the catalytic reaction can be performed only on the surface of the catalyst. From this viewpoint, it is also important that the value of A is relatively large, and the B / A is less than 0.61, preferably 0.58 or less, and more preferably 0.56 or less.
That is, the range of B / A is caulking because the fine structure is clear, there are few defects in the Si—O or Al—O bond, and the higher-order structure is clear and the pores are appropriately formed. It is in the range of 0.30 or more and less than 0.61 from the viewpoint of reducing the amount of water to increase the catalyst life and improving the desired reaction selectivity.

The B / A value can be measured by the method described in Examples described later, and in each case, the composition ratio of the mixed gel, the conditions for hydrothermal synthesis (heating temperature and heating time), etc. will be described later. It can be adjusted to the above range by a method of adjusting to a preferable range or the like.

The peak width at half maximum obtained by X-ray diffraction indicates the crystallinity of the crystal lattice plane where the diffraction occurs, and it is preferable that the peak width is narrow. Among them, the peak near 2θ = 11.1 ° shows a higher-order structure such as an 8-membered ring structure, which indicates the appropriate formation of pores, and therefore a large gas in the pores of the MWF-type zeolite. It is especially important that the half width is narrow, as it affects the molecular sieving effect of molecular shielding. The range of the peak half width around 2θ = 11.1 ° is preferably 0.31 deg or less, more preferably 0.28 deg or less, and further preferably 0.25 deg or less. According to the structure of the MWF-type zeolite suggested by having such a peak width at half maximum, the amount of caulking due to the excessive oligomerization reaction is reduced without the hydrocarbon molecules penetrating into the crystal lattice, and the desired reaction is performed. The inventor presumes that the selectivity of a desired reaction can be maximized by eliminating defects that are active points that contribute to reactions other than the above.
The value of the peak half width can be adjusted to the above range by a method of adjusting the composition ratio of the mixed gel, the conditions at the time of hydrothermal synthesis (heating temperature and heating time), etc. to a preferable range described later. ..

[Synthesis method]
The method for producing the MWF type zeolite according to the present embodiment is a silica source containing silicon, an aluminum source containing aluminum, an alkali metal source containing at least one selected from an alkali metal (M1) and an alkaline earth metal (M2). And a step of preparing a mixed gel containing water.
Hereinafter, the mixed gel and each component contained therein will be described.

[Preparation process of mixed gel]
The step of preparing the mixed gel is not particularly limited, and is, for example, a mixing step of mixing a silica source, an aluminum source, an alkali metal source, water, and an organic structure-defining agent as needed, at one time or in multiple steps, and this mixing. It may include the aging step of the mixture obtained in the step.
The mixing step can mix these components, including a silica source, an aluminum source, an alkali metal source, water, and optionally an organic structure defining agent, at one time or in multiple steps.
The order of mixing in multiple stages is not limited, and may be appropriately selected depending on the conditions to be used. When mixing in multiple stages, either stirring or no stirring may be performed, but a precursor that forms a gis structure that is a component of the MWF-type zeolite and is considered to contain no organic structure-defining agent is produced. From the viewpoint, it is preferable to use a mixed solution containing an alkali metal source, an aluminum source, and a silica source, and to have a stirring step and an aging step. When the aluminum source and the silica source are mixed and aged, it is preferable to lower the temperature from the viewpoint of suppressing an excessive condensation reaction of Al and Si and achieving both precursor formation and uniform mixing. Specifically, the temperature in the mixing, stirring, and aging steps is preferably 15 ° C. or lower. The mixing, stirring, and aging steps are preferably 10 minutes or more and 24 hours or less, more preferably 20 minutes or more and 12 hours or less, and more preferably 30 minutes or more, from the viewpoint of preventing an excessive condensation reaction and sufficiently uniformly mixing. Most preferably 8 hours or less.

From the viewpoint of promoting the formation of the skeleton of the MWF-type zeolite by forming a precursor of the gis structure, which is the internal structure of the MWF-type zeolite, and then surrounding them to form a precursor of the lta or pau structure containing an organic structure-determining agent. It is preferable to mix the alkali metal source, the aluminum source, and the silica source first, and then add the organic structure defining agent to the mixed solution containing these. The temperature and time of the mixing, stirring, and aging steps of the mixed gel in which the organic structure defining agent is mixed with the alkali metal source, aluminum source, and silica source can prevent excessive condensation reaction and can be sufficiently uniformly mixed. 10 minutes or more and 24 hours or less are preferable, 12 ° C. or less, 20 minutes or more and 12 hours or less are more preferable, and 10 ° C. or less, 45 minutes or more and 8 hours or less are most preferable. As a result, the fine structure and the long-period structure are appropriately formed, and by high crystallization, the B / A and the half width are optimized, and the catalyst life is extended and the reaction selectivity is high by improving the caulking resistance. It is estimated that.
The stirring method is not particularly limited as long as it is a generally used stirring method, and specific examples thereof include a method using blade stirring, vibration stirring, shaking stirring, centrifugal stirring and the like.
The rotation speed of stirring is not particularly limited as long as it is a generally used stirring speed, and examples thereof include 1 rpm and more and less than 2000 rpm.
The time of the mixing step is not particularly limited and may be appropriately selected depending on the temperature of the mixing step, and examples thereof include more than 0 minutes and 1000 hours or less.
From the viewpoint of excellent economic efficiency, the faster the addition rate of the raw material in the mixing step, the higher the production efficiency and the more preferable. On the other hand, from the viewpoint of suppressing an excessive condensation reaction of Al and Si and achieving both the formation of a precursor and uniform mixing, a slow addition rate is preferable. From these viewpoints, when preparing a mixed gel of about 100 cc, it is preferably 0.1 cc / min or more and 100 cc / min or less, more preferably 0.2 cc / min or more and 50 cc / min or less, and 0. Most preferably, it is 5 cc / min or more and 10 cc / min or less.
The aging step may be carried out by either standing or stirring.
The stirring method in the aging step is not particularly limited as long as it is a generally used stirring method, and specific examples thereof include a method using blade stirring, vibration stirring, shaking stirring, centrifugal stirring and the like. ..
The rotation speed of stirring is not particularly limited as long as it is a generally used stirring speed, and examples thereof include 1 rpm and more and less than 2000 rpm.

[Mixed gel]
The mixed gel in the present embodiment is a mixture containing a silica source, an aluminum source, an alkali metal source, and water as essential components, preferably containing an organic structure defining agent.
The silica source refers to the components in the mixed gel which is the raw material of silicon contained in the zeolite produced from the mixed gel, and the aluminum source refers to the raw material of aluminum contained in the zeolite produced from the mixed gel. The component in the mixed gel, which is a raw material for the alkali metal and / or the alkaline earth metal contained in the zeolite produced from the mixed gel, is referred to as the component in the mixed gel.

[Silica source]
The silica source is not particularly limited as long as it is generally used, but specific examples thereof include amorphous silica, colloidal silica, wet silica, dry silica, silica gel, sodium silicate, and amorphous aluminosilicate. Examples thereof include gel, tetraethoxysilane (TEOS) and trimethylethoxysilane. These compounds may be used alone or in combination of two or more. Here, the amorphous aluminosilicate gel is both a silica source and an aluminum source.
Among these, amorphous silica, colloidal silica, wet silica, dry silica, and silica gel are preferable because zeolite having a high degree of crystallinity tends to be obtained. From the same viewpoint, colloidal silica, wet silica, and dry silica are more preferable.
Examples of colloidal silica include, but are not limited to, Ludox (registered trademark), Syon (registered trademark), Nalco (registered trademark), and Snowtex (registered trademark).
The wet method silica is not limited to the following, and is, for example, Hi-Sil (registered trademark), Ultrasil (registered trademark), Vulcasil (registered trademark), Santocel (registered trademark), Valron-Estersil (registered trademark), Tokusil (registered trademark). Registered Trademarks), Zeosil®, Carplex®, Mizukasil®, Sylsia®, Syloid®, Gasil®, Silklon®, Nipgel® ), Nipsil®.
Examples of the dry method silica include HDK (registered trademark), Aerosil (registered trademark), Reolosil (registered trademark), Cab-O-Sil (registered trademark), Francil (registered trademark), and ArcSilica (registered trademark).

[Aluminum source]
The aluminum source is not particularly limited as long as it is generally used, but specific examples thereof include sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum acetate, aluminum hydroxide, aluminum oxide, aluminum chloride, and aluminum alkoxide. , Metallic aluminum, amorphous aluminum nosilicate gel and the like. These compounds may be used alone or in combination of two or more.
Among these, sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum acetate, aluminum hydroxide, aluminum chloride, and aluminum alkoxide are preferable because zeolite having a high degree of crystallization tends to be obtained. From the same viewpoint, sodium aluminate and aluminum hydroxide are more preferable, and sodium aluminate is further preferable.

[Alkali metal source]
The type of alkali in the alkali metal source is not particularly limited, and any alkali metal and / or any alkaline earth metal compound can be used.
The alkali metal source is not limited to the following, and examples thereof include hydroxides, hydrogen carbonates, carbonates, acetates, sulfates, and nitrates of alkali metals or alkaline earth metals. These compounds may be used alone or in combination of two or more.
As the alkali metal and alkaline earth metal used as the alkali metal source, Li, Na, K, Rb, Cs, Ca, Mg, Sr, Ba and the like can be usually used. From the viewpoint of facilitating crystal formation of the MWF-type skeleton, Na and K are preferable, and Na is more preferable. Further, the alkali metal and the alkaline earth metal used as the alkali metal source may be used alone or in combination of two or more.
Specifically, the alkali metal source is not limited to the following, but for example, sodium hydroxide, sodium acetate, sodium sulfate, sodium nitrate, sodium carbonate, sodium hydrogencarbonate, potassium hydroxide, potassium acetate, potassium sulfate, potassium nitrate. , Potassium carbonate, potassium hydrogen carbonate, lithium hydroxide, lithium acetate, lithium sulfate, lithium nitrate, lithium carbonate, lithium hydrogen carbonate, rubidium hydroxide, rubidium acetate, rubidium sulfate, rubidium nitrate, rubidium carbonate, rubidium hydrogen carbonate, hydroxylated Cesium, cesium acetate, cesium sulfate, cesium nitrate, cesium carbonate, cesium hydrogen carbonate, calcium hydroxide, calcium acetate, calcium sulfate, calcium nitrate, calcium carbonate, calcium hydrogen carbonate, magnesium hydroxide, magnesium acetate, magnesium sulfate, magnesium nitrate , Magnesium carbonate, magnesium hydrogen carbonate, strontium hydroxide, strontium acetate, strontium sulfate, strontium nitrate, strontium carbonate, strontium hydrogen carbonate, barium hydroxide, barium acetate, barium sulfate, barium nitrate, barium carbonate, barium hydrogen carbonate, etc. Be done.
Among these, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, calcium hydroxide, magnesium hydroxide, strontium hydroxide and barium hydroxide are preferable, and sodium hydroxide and potassium hydroxide are used. Lithium hydroxide, rubidium hydroxide and cesium hydroxide are more preferred, and sodium hydroxide is even more preferred.

[Organic structure regulator]
The organic structure-defining agent for producing zeolite by hydrothermal synthesis of a mixed gel is a compound that promotes crystallization into a zeolite structure. In the crystallization of zeolite, an organic structure defining agent can be used if necessary. It is preferable to synthesize using a mixed gel containing an organic structure-defining agent because the crystal formation of the MWF-type skeleton becomes easier and / or the synthesis time is shortened and the synthesis is excellent in economic efficiency when producing zeolite. ..
The organic structure defining agent may be of any kind as long as it can form a desired MWF-type zeolite. Further, the organic structure defining agent may be used alone or in combination of two or more.
The organic structure defining agent includes, but is not limited to, amines, quaternary ammonium salts, alcohols, ethers, amides, alkylureas, alkylthioureas, cyanoalkans, and nitrogen as a heteroatom. Alicyclic heterocyclic compounds can be used, preferably a quaternary ammonium salt, more preferably a tetraalkylammonium salt, and even more preferably a tetraethylammonium salt.
Such salts are accompanied by anions. Representatives of such anions include, but are not limited to, ^{e.g., Cl -, Br -, I} - halogen ions and hydroxide ions, such as, acetate ion, sulfate ion, nitrate ion, carbonate ion and carbonate Contains hydrogen ions. Among these, halogen ions and hydroxide ions are preferable, and halogen ions are more preferable, from the viewpoint of facilitating crystal formation of the MWF type skeleton.
[Composition ratio of mixed gel]
Silica source and OH in the mixed gel ^- ratio of, OH for SiO ₂ ^- molar ratio, i.e., OH ^- / expressed in SiO ₂ (OH ^- hydroxide contained in the alkali metal source, and / or an organic structure directing agent It is a substance ion). In order to synthesize the MWF-type zeolite of the present embodiment, it is desirable to control the conditions for synthesizing the precursor oligomer.
By forming the 8-membered ring structure without defects, it is possible to obtain a long catalyst life and high reaction selectivity by improving caulking resistance. In order to have a high intensity ratio of peak A derived from a higher-order structure such as an 8-membered ring structure, that is, to clearly form an 8-membered ring structure, the gis structure and its precursor are assembled without collapsing. It is desirable to form a higher order structure. From these viewpoints, it is preferable to prevent the redissolution of the grown zeolite, and it is preferable that the amount ^{of OH − is small in order to suppress the dissolution.}
On the other hand, if there is a defect or strain in the fine structure constituting the 8-membered ring or the skeleton, that is, the bond of Si—O or Al—O, the active sites that contribute to the reaction other than the desired reaction increase, and the desired reaction points are increased. The reaction selectivity may be reduced. When such a fine structure is formed without defects or distortion, the peak B derived from the finer structure is relatively high in parallel with the plane belonging to the peak A. In order not to cause deficiency or bond distortion of Si—O or Al—O, it is preferable to dissolve the silica source or aluminum source as raw materials more, and in order to dissolve these more, it is preferable to have a large amount ^{of OH −.} preferable.
Therefore, the MWF-type zeolite that can obtain high reaction selectivity at the same time as extending the catalyst life by improving the caulking resistance is limited to the case where the B / A is in a specific range. Results inventors have studied intensively, OH present in the synthesis solution ^- the amount of, with respect to SiO _2, 0.10 ≦ OH ^- / if SiO ₂ ≦ 0.53, the SiO or Al-O It is possible to synthesize an MWF-type zeolite capable of making a specific ratio of B / A without causing a defect or distortion of the bond.
Within the above range, OH ⁻ / SiO ₂ is more preferably 0.15 or more, and further preferably 0.18 or more.
Within the above range, OH ⁻ / SiO ₂ is more preferably less than 0.50, and even more preferably 0.40 or less.
The ratio of the silica source to the aluminum source in the mixed gel is expressed as _{the molar ratio of the oxides of each element, that is, SiO 2} / Al ₂ O _3.
The SiO ₂ / Al ₂ O ₃ is not particularly limited as long as it can form a zeolite, but 5.0 or more is preferable because it tends to suppress the formation of a zeolite having a skeleton different from that of the MWF type skeleton. , 6.0 or more is more preferable. From the same viewpoint, it is more preferably 6.8 or more.
Since SiO ₂ / Al ₂ O ₃ tends to suppress the formation of zeolite having a skeleton different from that of the MWF type skeleton, it is preferably 12 or less, and more preferably 10 or less. From the same viewpoint, it is more preferably 7.8 or less.
The ratio of the aluminum source to the alkali metal source in the mixed gel is expressed as the added molar ratio of M1 _{2 O and M 2 O to Al 2} O _{3 , that is, (M1 2} O + M 2 O) / Al ₂ O ₃ (where M 1 is an alkali metal). , And M2 indicates an alkaline earth metal). The amount of (M1 ₂ O + M2O) / Al ₂ O ₃ is preferably 1.3 or more, and more preferably 1.5 or more, from the viewpoint of facilitating crystal formation of the MWF type skeleton. From the same viewpoint, it is more preferably 1.7 or more.
(M1 ₂ O + M2O) / Al ₂ O ₃ is preferably less than 3.1, more preferably less than 2.7, from the viewpoint of suppressing the formation of zeolite having a skeleton different from that of the MWF type skeleton. From the same viewpoint, it is more preferably less than 2.6.
If the mixed gel comprising an organic structure directing agent, the ratio of aluminum source and an organic structure directing agent in the mixed gel, the molar ratio of the organic structure-directing agent for Al ₂ O _3, i.e. expressed as R / Al ₂ O ₃ (Here, R indicates an organic structure regulator). From the viewpoint of facilitating crystal formation of the MWF-type skeleton and / or shortening the synthesis time and being excellent in economic efficiency in producing zeolite, 2.0 or more is preferable, and 3.0 or more is more preferable. preferable. It is more preferably 4.0 or more from the viewpoint of suppressing the formation of zeolite having a skeleton different from that of the MWF type skeleton.
R / Al ₂ O ₃ is preferably 50 or less, more preferably 30 or less, from the viewpoint of shortening the synthesis time and being excellent in economic efficiency in producing zeolite. It is more preferably 20 or less from the viewpoint of suppressing the formation of zeolite having a skeleton different from that of the MWF type skeleton.
The ratio of aluminum source to water in the mixed gel is expressed as the molar ratio of water to _{Al 2} O _{3 , that is, H 2} O / Al ₂ O _3. Since the components in the mixed gel tend to be more uniformly dispersed, it is preferably 70 or more, and more preferably 80 or more. From the viewpoint of suppressing the formation of zeolite having a skeleton different from that of the MWF type skeleton, 90 or more is more preferable.
H ₂ O / Al ₂ O ₃ is preferably 3000 or less, and more preferably 1000 or less, from the viewpoint of shortening the synthesis time and being excellent in economic efficiency in producing zeolite. It is more preferably 500 or less from the viewpoint of suppressing the formation of zeolite having a skeleton different from that of the MWF type skeleton.
As described above, the method for producing the MWF type zeolite according to the present embodiment is at least one selected from a silica source containing silicon, an aluminum source containing aluminum, an alkali metal (M1) and an alkaline earth metal (M2). The step of preparing a mixed gel containing an alkali metal source containing water and water is included, and the molar ratio of each component in the mixed gel is set to the silicon, aluminum, alkali metal (M1) and alkaline earth metal (M2). When calculated as an oxide of each element, the molar ratios α, β, γ, and δ represented by the following formulas (1), (2), (3), and (4) are 5.0 ≦ α ≦. It is particularly preferable to satisfy 12, 1.3 ≦ β <3.1, 70 ≦ γ ≦ 3000 and 0.10 ≦ δ ≦ 0.53. It is particularly preferable that the MWF-type zeolite according to the present embodiment is obtained by the above-mentioned method for producing the MWF-type zeolite according to the present embodiment.
α = SiO ₂ / Al ₂ O ₃ (1)
β = (M1 ₂ O + M2O) / Al ₂ O ₃ (2)
γ = H ₂ O / Al ₂ O ₃ (3)
_{^{δ = OH - / SiO 2 (}} 4)
Further, in the method for producing MWF type zeolite according to the present embodiment, the molar ratios α, β, γ, and δ satisfy the above range, the mixed gel further contains the organic structure defining agent R, and the following formula ( It is more preferable that the molar ratio ε represented by 5) satisfies 2.0 ≦ ε ≦ 50.
ε ＝ R / Al ₂ O ₃ (5)
It is not always necessary for the seed crystal to be present in the mixed gel, but the MWF-type zeolite of the present embodiment can also be obtained by adding a pre-produced MWF-type zeolite as a seed crystal to the mixed gel.

[Hydrothermal synthesis process]
In the method for producing MWF-type zeolite according to the present embodiment, it is preferable to further include a hydrothermal synthesis step in which the hydrothermal synthesis temperature is 100 ° C to 170 ° C. That is, preferably, the mixed gel obtained in the preparation step is hydrothermally synthesized by holding the mixed gel at a predetermined temperature for a predetermined time in a stirring or standing state.
The temperature of hydrothermal synthesis is not particularly limited as long as it is a generally used temperature, but it is preferably 100 ° C. or higher from the viewpoint of shortening the synthesis time and excellent economic efficiency in zeolite production. From the viewpoint of suppressing the formation of zeolite having a skeleton different from that of the MWF type skeleton, the temperature is more preferably 110 ° C. or higher, and further preferably 115 ° C. or higher.
The temperature is preferably 170 ° C. or lower because it tends to suppress the decomposition of the organic structure controlling agent. From the viewpoint of suppressing the formation of zeolite having a skeleton different from that of the MWF type skeleton, the temperature is more preferably 155 ° C or lower, further preferably 145 ° C or lower.
The temperature of hydrothermal synthesis may be constant or may be changed stepwise.
The time for hydrothermal synthesis is not particularly limited as long as it is a generally used time, and can be appropriately selected depending on the temperature of hydrothermal synthesis.
The time for hydrothermal synthesis is preferably 3 hours or more, and more preferably 10 hours or more, from the viewpoint of forming the MWF skeleton. From the viewpoint of increasing the yield of the MWF-type zeolite and being excellent in economy, it is more preferably 24 hours or more.
Since the decomposition of the organic structure controlling agent tends to be suppressed, it is preferably 30 days or less, and more preferably 20 days or less. It is more preferably 10 days or less from the viewpoint of suppressing the formation of zeolite having a skeleton different from that of the MWF type skeleton.
In the hydrothermal synthesis step, the container in which the mixed gel is placed is not particularly limited as long as it is a generally used container, but it is used when the pressure inside the container increases at a predetermined temperature or under gas pressure that does not inhibit crystallization. In that case, it is preferable to put it in a pressure-resistant container and hydrothermally synthesize it.
The pressure-resistant container is not particularly limited, and various shapes such as a spherical shape, a vertically long shape, and a horizontally long shape can be used.
When stirring the mixed gel in the pressure-resistant container, the pressure-resistant container is rotated in the vertical direction and / or in the horizontal direction, preferably in the vertical direction.
When the pressure-resistant container is rotated in the vertical direction, the rotation speed is not particularly limited as long as it is generally used, but 1 to 50 rpm is preferable, and 10 to 40 rpm is more preferable.
In the hydrothermal synthesis step, in order to preferably stir the mixed gel, a vertically long container is used as a pressure resistant container, and a method of rotating the mixed gel in the vertical direction can be mentioned.

[Separation / drying process]
After the hydrothermal synthesis step, the product solid and the liquid containing water are separated, but the separation method is not particularly limited as long as it is a general method, and filtration, decantation, spray drying method (rotary spraying, rotary spraying). (Nozzle spraying and ultrasonic spraying, etc.), drying method using a rotary evaporator, vacuum drying method, freeze-drying method, natural drying method, etc. can be used, and usually separation can be performed by filtration or decantation.
The separated material may be used as it is, or may be washed with water or a predetermined solvent. If necessary, the separated material can be dried.
The temperature at which the separated material is dried is not particularly limited as long as it is a general drying temperature, but is usually 150 ° C. or lower from room temperature.
The atmosphere at the time of drying is not particularly limited as long as it is a generally used atmosphere, but usually an air atmosphere, an atmosphere to which an inert gas such as nitrogen or argon is added, or an atmosphere to which oxygen is added is used.

[Baking process]
If necessary, MWF-type zeolite can be calcined and used. The firing temperature is not particularly limited as long as it is a generally used temperature, but when it is desired to remove the organic structure defining agent, the remaining ratio can be reduced, so that it is preferably 300 ° C. or higher, preferably 350 ° C. or higher. Is more preferable. It is more preferably 400 ° C. or higher from the viewpoint that the firing time is shortened and the zeolite is excellent in economic efficiency.
Since the crystallinity of the zeolite tends to be maintained, the temperature is preferably less than 550 ° C, more preferably 530 ° C or lower, and further preferably 500 ° C or lower.
The firing time is not particularly limited as long as the organic structure defining agent is sufficiently removed, and can be appropriately selected depending on the firing temperature, but the proportion of the organic structure defining agent remaining tends to be reduced. Therefore, it is preferably 0.5 hours or more, more preferably 1 hour or more, and further preferably 3 hours or more.
Since the crystallinity of the zeolite tends to be maintained, it is preferably 20 days or less, more preferably 10 days or less, and further preferably 7 days or less.
The atmosphere of firing is not particularly limited as long as it is a generally used atmosphere, but usually an air atmosphere, an atmosphere to which an inert gas such as nitrogen or argon is added, or an atmosphere to which oxygen is added is used.

[Cation exchange]
If necessary, the MWF-type zeolite can be cation-exchanged to the desired cation-type. Cationic exchange is not limited to, but is, for example, NH ₄ NO ₃ , LiNO ₃ , NaNO ₃ , KNO ₃ , RbNO ₃ , CsNO ₃ , Be (NO ₃ ) ₂ , Ca (NO ₃ ) ₂ , Mg (NO _3). ) ₂ , Sr (NO ₃ ) ₂ , Ba (NO ₃ ) _2, etc. Nitrate, or nitrate ion contained in the nitrate is halide ion, sulfate ion, carbonate ion, hydrogen carbonate ion, acetate ion, phosphate ion, phosphorus Salts that are hydrogen acid ions and acids such as nitric acid and hydrochloric acid can be used.
The temperature of the cation exchange is not particularly limited as long as it is a general cation exchange temperature, but is usually 100 ° C. or lower from room temperature.
When separating zeolite after cation exchange, the separation method is not particularly limited as long as it is a general method, and filtration, decantation, spray drying method (rotary spray, nozzle spray, ultrasonic spray, etc.), rotary evaporator, etc. A drying method, a vacuum drying method, a freeze-drying method, a natural drying method, or the like can be used, and usually the particles can be separated by filtration or decantation.
The separated material may be used as it is, or may be washed with water or a predetermined solvent. If necessary, the separated material can be dried.
The temperature at which the separated material is dried is not particularly limited as long as it is a general drying temperature, but is usually 150 ° C. or lower from room temperature.
The atmosphere at the time of drying is not particularly limited as long as it is a generally used atmosphere, but usually an air atmosphere, an atmosphere to which an inert gas such as nitrogen or argon is added, or an atmosphere to which oxygen is added is used.
Further, the ammonium-type zeolite can be converted into a proton-type zeolite by calcining the zeolite.

(Polymerization catalyst)
The MWF-type zeolite of the present embodiment can be suitably used as a polymerization catalyst in the polymerization reaction of hydrocarbons. In particular, it is preferably used as an oligomerization catalyst in a hydrocarbon oligomerization reaction, and more preferably used as an oligomerization catalyst in an ethylene oligomerization reaction.

[Reactor and reaction conditions]
The reactor that can be used for the polymerization reaction of hydrocarbons using MWF-type zeolite as a polymerization catalyst is not particularly limited, but for example, a raw material tank, a pump for transferring raw materials, and a reactor for supplying raw materials to carry out the reaction. Etc. can be provided. The reactor is not particularly limited, but for example, a fixed bed type reactor, a stirring type reactor and the like can be used. FIG. 2 shows a schematic diagram of an example of the reaction apparatus used for the hydrocarbon polymerization reaction in the present embodiment. In the polymerization reaction of hydrocarbons, for example, the raw material contained in the raw material tank 1 is supplied to the fixed-bed reactor 3 by a pump 2, and the raw material and the catalyst are brought into contact with each other in the fixed-bed reactor 3 to carbonize the raw material. This can be done by polymerizing hydrogen. After that, the desired polymerization was performed from the hydrocarbons and high boiling point components polymerized in a facility equipped with a reactor, a device for separating the polymerized hydrocarbons and high boiling point components, and if necessary, other devices and the like. Hydrocarbons can be removed. Other devices and the like are not particularly limited, but are, for example, devices such as compressors and heat exchangers that compress and liquefy a gas containing polymerized hydrocarbons and high boiling point components, a dissipation tower and a high boiling point separation tower. Examples include a device for removing impurities. The size of the reactor may be appropriately selected depending on the amount of the polymerized hydrocarbon to be purified and the high boiling point component.

When a fixed-bed reactor is used, the reaction temperature is preferably 150 ° C. or higher and 450 ° C. or lower, more preferably 200 ° C. or higher and 400 ° C. or lower, and further preferably 250 ° C. or higher and 350 ° C. or lower. When the temperature is within the above range, an appropriate reaction activity is obtained, and a stable hydrocarbon polymerization reaction tends to be carried out.

The reaction pressure is preferably 0.01 to 0.4 MPa / G, more preferably 0.01 to 0.2 MPa / G. When the pressure is within the above range, the yield of the polymerized hydrocarbon tends to be further improved.

The contact time between the raw material gas and the catalyst is preferably ^{0.5 to 20 g · sec / cm 3.} When the contact time is within the above range, the yield of the polymerized hydrocarbon tends to be further improved.

Hereinafter, the present embodiment will be described in more detail with reference to examples and the like, but these are exemplary examples, and the present embodiment is not limited to the following examples. One of ordinary skill in the art can make various modifications to the embodiments shown below to implement the present embodiment, and such modifications are included in the scope of the present invention as long as the predetermined requirements of the present embodiment are satisfied.

[Crystal structure analysis]
The crystal structure analysis was performed by the following procedure.
(1) The dried product (MWF type zeolite) obtained in each Example and Comparative Example was used as a sample and pulverized in an agate mortar.
(2) The sample of (1) above was uniformly fixed on a non-reflective sample plate for powder, crystal structure analysis was performed under the following conditions, and a predetermined peak intensity and half width were measured.
X-ray diffractometer (XRD): Rigaku powder X-ray diffractometer "RINT2500 type" (trade name)
X-ray source: Cu tube (40 kV, 200 mA)
Measurement temperature: 25 ° C
Measurement range: 5 to 60 ° (0.02 ° / step)
Measurement speed: 0.2 ° / min Slit width (scattering, divergence, light reception): 1 °, 1 °, 0.15 mm

[Example 1]
(Manufacturing of MWF type zeolite)
Dissolve by adding 67.85 g of water, 1.46 g of 50 mass% sodium hydroxide aqueous solution (NaOH, manufactured by Wako Pure Chemical Industries, Ltd.) and 1.64 g of _{sodium aluminate (NaAlO 2, manufactured by Wako Pure Chemical Industries, Ltd.).} To obtain an aqueous solution. 4.33 g of Aerosil (Aerosil 300, manufactured by Nippon Aerosil Co., Ltd.) was added at a rate of 1 cc / min while stirring this aqueous solution at 10 ° C. After stirring this solution at 10 ° C. for 1 hour, 11.15 g of tetraethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and mixed as an organic structure regulator, and the mixture was stirred at 10 ° C. for 3 hours to form a mixed gel. Prepared. The composition of the mixed gel is α = SiO ₂ / Al ₂ O ₃ = 7.2, β = Na ₂ O / Al ₂ O ₃ = 1.9, γ = H ₂ O / Al ₂ O ₃ = 381, δ = OH ⁻ / SiO ₂ = 0.25 and ε = R / Al ₂ O ₃ = 5.3. The mixed gel was placed in a 200 mL autoclave containing a fluororesin inner cylinder, hydrothermally synthesized at 125 ° C for 7 days while holding at a vertical stirring speed of 20 rpm, the product was filtered and dried at 120 ° C, and then dried. A powdery zeolite was obtained.
The XRD spectrum of the obtained zeolite is shown in FIG. From the spectrum, it was confirmed that the obtained zeolite was an MWF type zeolite. Furthermore, since no peak derived from other zeolites or amorphous silica alumina was observed, it was evaluated as a high-purity MWF-type zeolite. The peak intensity ratio obtained from the XRD pattern was B / A = 0.55, and the peak half width was 0.14 deg for A and 0.24 deg for B.

(Manufacturing of fixed bed catalyst)
5 g of the obtained MWF-type zeolite was placed in 1000 mL of a 0.1 N ammonium chloride aqueous solution and stirred at 60 ° C. and 100 rpm for 3 hours. The product was filtered and dried at 120 ° C. to give a powdered catalyst precursor.
Part of the obtained catalyst precursor and MWF-type zeolite before treatment with ammonium chloride aqueous solution were thermally dissolved in sodium hydroxide aqueous solution or royal water, respectively, and ICP-luminescence spectroscopic analysis (Seikoin) was performed using an appropriately diluted solution. When the sodium concentration in the zeolite was measured by SPS3520UV-DD manufactured by Suzuru Co., Ltd .: device name), it was 0.2% by mass and 2.1% by mass, respectively.
The powder of the catalyst precursor having a reduced sodium content was compression-molded at 40 MPa to form particles of 1 mm or more and 3 mm or less, which were used as a fixed bed catalyst for an ethylene oligomerization reaction described later.

[Ethylene oligomerization reaction]
As an apparatus for producing an ethylene oligomer, an apparatus having the same configuration as that shown in FIG. 2 was used. That is, a device provided with a fixed-bed reactor 3 connected to the raw material tank 1 via a pump 2 was used. As the fixed-bed reactor 3, a SUS306 tube having a length of 3/8 inch and a length of 10 cm was used. 1 g of the fixed bed catalyst of Example 1 was put into the fixed bed type reactor 3, and glass wool was packed at both ends and fixed. The raw material ethylene was diluted with He so that ethylene: He = 1: 9 and supplied to the raw material tank 1, and then supplied from the upper part of the fixed bed reactor 3 at 15 mL / min by the pump 2. The ethylene oligomerization reaction was carried out by setting the internal pressure of the fixed bed reactor 3 to normal pressure and the reaction temperature to 350 ° C.
[Analysis of products]
The composition of the product was analyzed by introducing a part of the product obtained by the reaction into gas chromatography. "HP6890" (trade name) manufactured by Hewlett-Packard Co., Ltd. was used for the analysis. As the column, "HP-AL / S 19091P-S12" (trade name) [inner diameter 0.32 mm, length 25 m] manufactured by AGIRENT was used. The temperature of the sampling line was maintained at 150 ° C., and the amount of sample gas was 1 mL. The carrier gas was He, and the column flow rate was 30 mL / min. The column heating program was held at 90 ° C. for 4 minutes from the start of analysis, then heated to 200 ° C. at 10 ° C./min, and then held at 200 ° C. for 15 minutes.
One hour after the start of the reaction, the product had a selectivity of butenes (C4 =: isobutene, 1-butene, cis-2-butene, trans-2-butene) of 83.2% and C5 or more. The selectivity was 4.1%, the selectivity of C3 was 2.2%, and the conversion of ethylene was 18.2%. Furthermore, 12 hours after the start of the reaction, the product had a butene selectivity of 82.8%, a selectivity of C5 or higher of 5.2%, a selectivity of C3 of 1.9%, and ethylene conversion. The rate was 17.8%.

[Example 2]
Water 72.05g 50 wt% aqueous solution of sodium hydroxide 4.75g of aluminum isopropoxide _{(C 9 H 21 O 3 Al} , Aldrich) 6.90 g was added and dissolved to obtain an aqueous solution. 48.7 g of colloidal silica (Nalco2326, manufactured by Nalco) was added at a rate of 1 cc / min while stirring this aqueous solution at 10 ° C. After stirring this solution at 10 ° C. for 1 hour, 17.60 g of tetraethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) and a 30 mass% tetrapropylammonium hydroxide aqueous solution (manufactured by Tokyo Chemical Industry Co., Ltd.) are used as organic structure regulators. A mixed gel was prepared by adding 1.35 g, mixing, and stirring at 10 ° C. for 4 hours. The composition of the mixed gel is α = SiO ₂ / Al ₂ O ₃ = 7.2, β = Na ₂ O / Al ₂ O ₃ = 1.75, γ = H ₂ O / Al ₂ O ₃ = 384, δ = OH ⁻ / SiO ₂ = 0.53, ε = R / Al ₂ O ₃ = 5.3. Zeolites were synthesized by hydrothermal synthesis, filtration, and drying in the same manner as in Example 1. From the XRD pattern of the obtained MWF-type zeolite, B / A = 0.35, and the peak half width was 0.16 deg for A and 0.19 deg for B.
The obtained zeolite was treated with an aqueous solution of ammonium nitrate in the same manner as in Example 1 and dried to obtain a powdery catalyst precursor. When the amount of Na of the obtained catalyst precursor was measured in the same manner as in Example 1, it was 0.2% by mass.
This catalyst precursor was compression-molded in the same manner as in Example 1 to prepare a fixed bed catalyst, and an ethylene oligomerization reaction was carried out in the same manner as in Example 1. As a result, a product 1 hour after the start of the reaction. The selectivity of butenes was 82.6%, the selectivity of C5 or higher was 3.9%, the selectivity of C3s was 2.3%, and the conversion rate of ethylene was 15.6%. Furthermore, 12 hours after the start of the reaction, the product had a butene selectivity of 82.6%, a selectivity of C5 or higher of 3.2%, a selectivity of C3 of 1.7%, and ethylene conversion. The rate was 13.9%.

[Comparative Example 1]
Add 69.76 g of water, 0.85 g of sodium hydroxide (NaOH, manufactured by _{Wako Pure Chemical Industries, Ltd.) and 1.64 g of sodium aluminate (NaAlO 2} , manufactured by Wako Pure Chemical Industries, Ltd.) to dissolve and dissolve the aqueous solution. Obtained. 13.53 g of colloidal silica (Ludox AS-40, manufactured by Grace) was added at a rate of 1 cc / min while stirring this aqueous solution at 28 ° C. After stirring this solution at 28 ° C. for 1 hour, 39.36 g of tetraethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and mixed as an organic structure regulator, and the mixture was stirred at 28 ° C. for 3 hours to form a mixed gel. Prepared. The composition of the mixed gel is α = SiO ₂ / Al ₂ O ₃ = 9.0, β = Na ₂ O / Al ₂ O ₃ = 3.1, γ = H ₂ O / Al ₂ O ₃ = 428, δ = OH ⁻ / SiO ₂ = 0.47, ε = R / Al ₂ O ₃ = 18.7. The mixed gel was hydrothermally synthesized at 125 ° C. for 7 days with stirring, and the product was filtered and dried at 120 ° C. to obtain a powdery zeolite.
From the XRD pattern of the obtained MWF-type zeolite, B / A = 0.88, and the peak half width was 0.45 deg for A and 0.36 deg for B.
The obtained zeolite was treated with an aqueous solution of ammonium nitrate in the same manner as in Example 1 and dried to obtain a powdery catalyst precursor. When the amount of Na of the obtained catalyst precursor was measured in the same manner as in Example 1, it was 0.2% by mass.
This catalyst precursor was compression-molded in the same manner as in Example 1 to prepare a fixed bed catalyst, and an ethylene oligomerization reaction was carried out in the same manner as in Example 1. As a result, a product 1 hour after the start of the reaction. The selectivity of butenes was 78.8%, the selectivity of C5 or higher was 4.3%, the selectivity of C3s was 2.1%, and the conversion rate of ethylene was 12.2%. Furthermore, 12 hours after the start of the reaction, the product had a butene selectivity of 72.6%, a selectivity of C5 or higher of 4.2%, a selectivity of C3 of 2.3%, and ethylene conversion. The rate was 2.6%.

[Comparative Example 2]
A mixture of 20.00 g of water, 1.52 g of sodium hydroxide (NaOH, manufactured by Wako Pure Chemical Industries, Ltd.) and 11.15 g of tetraethylammonium bromide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as an organic structure regulator, and water 42. A mixture of .00 g, 1.94 g of aluminum hydroxide (Al (OH) ₃ , manufactured by Aldrich) and 10.67 g of colloidal silica (Ludox AS-40, manufactured by Grasse) was mixed and stirred at 28 ° C. for 24 hours. To prepare a mixed gel. The composition of the mixed gel is α = SiO ₂ / Al ₂ O ₃ = 7.1, β = Na ₂ O / Al ₂ O ₃ = 1.9, γ = H ₂ O / Al ₂ O ₃ = 380, δ = OH ⁻ / SiO ₂ = 0.54, ε = R / Al ₂ O ₃ = 5.3. The mixed gel was hydrothermally synthesized at 125 ° C. for 7 days with stirring, and the product was filtered and dried at 120 ° C. to obtain a powdery zeolite.
From the XRD pattern of the obtained MWF-type zeolite, B / A = 0.62, and the peak half width was 0.21 deg for A and 0.22 deg for B.
The obtained zeolite was treated with an aqueous solution of ammonium nitrate in the same manner as in Example 1 and dried to obtain a powdery catalyst precursor. When the amount of Na of the obtained catalyst precursor was measured in the same manner as in Example 1, it was 0.2% by mass.
This catalyst precursor was compression-molded in the same manner as in Example 1 to prepare a fixed bed catalyst, and an ethylene oligomerization reaction was carried out in the same manner as in Example 1. As a result, a product 1 hour after the start of the reaction. The selectivity of butenes was 79.2%, the selectivity of C5 or higher was 3.3%, the selectivity of C3s was 2.6%, and the conversion of ethylene was 15.3%. Furthermore, 12 hours after the start of the reaction, the product had a butene selectivity of 80.1%, a selectivity of C5 or higher of 3.2%, a selectivity of C3 of 2.1%, and ethylene conversion. The rate was 5.8%.

[Comparative Example 3]
62.02 g of water and 1.64 g of sodium aluminate were added and dissolved to obtain an aqueous solution. 10.67 g of colloidal silica (Ludox AS-40, manufactured by Grace) was added at a rate of 1 cc / min while stirring this aqueous solution at 10 ° C. After stirring this solution at 10 ° C. for 1 hour, 11.15 g of tetraethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and mixed as an organic structure regulator, and the mixture was stirred at 10 ° C. for 3 hours to form a mixed gel. Prepared. The composition of the mixed gel is α = SiO ₂ / Al ₂ O ₃ = 7.1, β = Na ₂ O / Al ₂ O ₃ = 1.1, γ = H ₂ O / Al ₂ O ₃ = 380, δ = OH ⁻ / SiO ₂ = 0.32, ε = R / Al ₂ O ₃ = 5.3. The mixed gel was placed in a 200 mL autoclave containing a fluororesin inner cylinder, hydrothermally synthesized at 130 ° C. for 8 days while holding at a vertical stirring speed of 20 rpm, the product was filtered and dried at 120 ° C., and then dried. A powdery zeolite was obtained.
The XRD spectrum of the obtained zeolite is shown in FIG. From the spectrum, it was confirmed that the obtained zeolite was an MWF type zeolite. Furthermore, since no peak derived from other zeolites or amorphous silica alumina was observed, it was evaluated as a high-purity MWF-type zeolite. The peak intensity ratio obtained from the XRD pattern was B / A = 0.29, and the peak half width was 0.28 deg for A and 0.31 deg for B.
The obtained zeolite was treated with an aqueous solution of ammonium nitrate in the same manner as in Example 1 and dried to obtain a powdery catalyst precursor. When the amount of Na of the obtained catalyst precursor was measured in the same manner as in Example 1, it was 0.1% by mass.
This catalyst precursor was compression-molded in the same manner as in Example 1 to prepare a fixed bed catalyst, and an ethylene oligomerization reaction was carried out in the same manner as in Example 1. As a result, a product 1 hour after the start of the reaction. The selectivity of butenes was 65.8%, the selectivity of C5 or higher was 4.7%, the selectivity of C3s was 8.6%, and the conversion of ethylene was 6.7%. Furthermore, 12 hours after the start of the reaction, the product had a butene selectivity of 63.8%, a selectivity of C5 or higher of 4.2%, a selectivity of C3 of 9.1%, and ethylene conversion. The rate was 2.7%.

Α to ε in Table 1 represent the following molar ratios.
α = SiO ₂ / Al ₂ O ₃ ,
β = (M1 ₂ O + M2O) / Al ₂ O ₃ ,
γ = H ₂ O / Al ₂ O ₃ ,
δ ⁼ OH - / SiO _2,
ε = R / Al ₂ O ₃ (R represents an organic structure regulator)
Further, the B / A in Table 1 is obtained as follows.
B / A = (Peak intensity near 2θ = 13.8 °) / (Peak intensity near 2θ = 11.1 °)

The MWF-type zeolite according to the present invention includes a hydrocarbon oligomerization reaction catalyst, a separating agent for various gases and liquids, an electrolyte membrane such as a fuel cell, a filler for various resin molded bodies, a membrane reactor, hydrocracking, archylation and the like. Potential for industrial use as catalysts, catalyst carriers for supporting metals, metal oxides, adsorbents, desiccants, detergent aids, ion exchangers, wastewater treatment agents, fertilizers, food additives, cosmetic additives, etc. Has.

Claims (2)

MWF type that satisfies 0.30 ≦ B / A <0.61 when the peak heights near 2θ = 11.1 ° and 13.8 ° are A and B, respectively, in the peak obtained by X-ray diffraction. Zeolites. The MWF-type zeolite according to claim 1, wherein in the peak obtained by X-ray diffraction, the half width of the peak near 2θ = 11.1 ° satisfies 0.31 deg or less.

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