JP2001010813A - Binderless zeolite molded product and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently utilize zeolite by preparing a zeolite molded product where zeolite has a ZSM5-type crystal structure and a metal component constituting the crystal skeleton is substantially silicon. SOLUTION: This binderless zeolite molded product where zeolite has a ZSM5-type crystal structure and a metal component constituting the crystal skeleton is substantially silicon alone or a combination of silicon and at least one metal element selected from the group consisting of iron, boron, chromium, cobalt, nickel, zinc and potassium and an atomic ratio of the metal element to silicon is 0.0001 to 0.5 is prepared. The molded product also has a specific surface area of 300-550 m2/g when measured by nitrogen absorption in the BET method, and a pore diameter of >=6 nm when measured by the method of mercury penetration, the pore surface area of 2-150 m2/g and the pore volume of 0.15-1.5 mL/g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a ZSM5 type binderless zeolite molded product and a method for producing a binderless zeolite molded product.

[0002]

2. Description of the Related Art ZSM5 type zeolite is disclosed in U.S. Pat.
It is a crystalline metallosilicate represented by crystalline aluminosilicate having 10-membered oxygen ring pores disclosed for the first time in the specification of US Pat. No. 702,886. The metal component constituting the zeolite crystal skeleton (hereinafter sometimes referred to as T atom)
The crystalline aluminosilicate composed of silicon and aluminum is mainly used for controlling the acidity thereof.
It is widely practiced to replace the l ³⁺ cation with another metal ion. In general, ZSM5 including silicalite without aluminum having the same structure and crystalline metallosilicate in which aluminum is replaced with another metal ion is generally used. It is called type zeolite.

As a method of synthesizing these ZSM5 type zeolites, a so-called hydrothermal synthesis method using an aqueous reaction slurry using tetra-n-propylammonium ion as a template agent as a raw material is conventionally known.

[0004] However, in the conventional hydrothermal reaction method, a part of the raw material components are dissolved in water at the time of heating, so that not only the ratio of the components converted into crystals necessarily decreases, but also the alkali components are diluted. The crystallization time becomes very long. In such a slow crystallization method, large crystals are likely to grow, and foreign metal components (M) other than silicon (Si) are easily removed outside the crystal lattice. M (M represents a T atom other than silicon)
Atomic ratio and Si in the synthesized ZSM5 zeolite
/ M does not always match, industrially, a relatively large volume of a closed vessel is required for heating the aqueous slurry to heat the aqueous slurry, and a large amount of expensive template agent is used. Need to be used for
Further, there are problems such as generation of a large amount of waste liquid, filtration of zeolite powder, and complicated firing process.

[0005] Further, when a conventional zeolite molded body is manufactured, it is necessary to first synthesize a zeolite powder by a hydrothermal synthesis method and then mold it using an inorganic binder, because the moldability of zeolite alone is poor. there were. In this method, it is necessary to select a binder that does not adversely affect the intended use, and not only does the zeolite content in the molded body decrease because a large amount of inorganic binder is required to obtain sufficient strength. There is a problem that zeolite buried in the binder cannot be used effectively.

Therefore, several methods for producing a zeolite molded article substantially containing no binder have been proposed. For example, Japanese Patent Application Laid-Open No. 59-162952 (TSZ-type aluminosilicate) and Japanese Patent Application Laid-Open No. 61-72620 (MOR) Type aluminosilicate) and JP-A-62-138320 (F
Several types of crystal-type binderless aluminosilicate moldings, such as AU-type aluminosilicate, are known.
These methods use a pre-synthesized zeolite powder as a secondary raw material, and convert the binder formed into a zeolite by reacting it with an alkali solution formed of an inorganic binder such as a clay mineral or silica alumina, Requires substantially twice hydrothermal synthesis. For this reason, there is a problem in that the process becomes longer and the amount of waste liquid increases.

Further, a method for synthesizing a binderless silicalite molded article in which the metal component constituting the crystal skeleton is substantially composed of only silicon or a binderless crystalline metallosilicate molded article composed of T atoms other than aluminum. Was not known.

As described above, a ZSM5 type binderless zeolite molded article substantially free of a binder such as silicalite and crystalline metallosilicate having a T atom other than Al useful for controlling acid properties and its simple and efficient properties The typical production method was not known.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention has been made in view of the above problems, and it is an object of the present invention to provide a ZS in which T atoms constituting a crystal skeleton are substantially composed of only silicon.
The M5 type binderless zeolite molded body or the Z atom in which the T atom constituting the crystal skeleton is composed of silicon and at least one metal element selected from the group consisting of iron, boron, chromium, cobalt, nickel, zinc and gallium.
An object of the present invention is to provide an SM5 type binderless zeolite molded body.

Another object of the present invention is to provide a simple and efficient method for producing a molded zeolite without using a binder.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a ZSM5 type binderless zeolite molded product.
After supporting the tetraalkylammonium component and the alkali metal component, the total amount of silica is crystallized while maintaining the shape of the silica molded body by a method of contacting with saturated steam under specific conditions, essentially A binder-free ZSM5 type binderless zeolite molded body can be easily produced with a high yield. Further, after supporting other metal components together, the above-described method essentially incorporates the metal component as a T atom into a binder. The present inventors have found that a ZSM5 type binderless metallosilicate molded article containing no can be easily and efficiently produced, and have completed the present invention.

That is, the present invention relates to a binderless zeolite molded article, wherein the zeolite has a ZSM5 type crystal structure, and the metal component constituting the crystal skeleton is substantially only silicon. (A).

Another aspect of the present invention is a binderless zeolite molded product, wherein the zeolite has a ZSM5 type crystal structure, and the metal components constituting the crystal skeleton are silicon, iron, boron, and chromium. , At least one selected from the group consisting of cobalt, nickel, zinc and gallium
The present invention relates to a binderless zeolite molded article (B) comprising a kind of metal element, wherein a composition ratio (atomic ratio) of the metal element to silicon is in a range of 0.0001 to 0.5.

The binderless zeolite molded body is
For example, the specific surface area determined from nitrogen adsorption measurements by BET method, which is binderless zeolite molded body is 300m ² / g~550m ² / g.

The binderless zeolite molded body is
For example, the pore diameter determined by mercury intrusion porosimetry has pores of more than 6 nm, the surface area of the pores is 2m ² / g~150m ² /
g and the pore volume of the pores is 0.15 ml /
g-1.5 ml / g.

According to another aspect of the present invention, there is provided a compound represented by the following formula (1): Si ₁ (SDA) _x M ¹ _y M ² _z (1) wherein SDA is an alkyl group having 1 to 5 carbon atoms. Tetraalkyl ammonium, M ¹ is an alkali metal, M ² is iron,
Represents at least one element selected from the group consisting of boron, chromium, cobalt, nickel, zinc, and gallium, wherein x is 0.001-1, y is 0.0001-1, and z is 0-0.5. Represents The present invention relates to a method for producing a binderless zeolite molded body, which comprises contacting the zeolite precursor represented by the formula (1) with saturated steam at 120 to 240 ° C.

The zeolite precursor is selected from the group consisting of a tetraalkylammonium component having an alkyl group having 1 to 5 carbon atoms, an alkali metal component and, if desired, iron, boron, chromium, cobalt, nickel, zinc and gallium. It is preferred that the raw material containing at least one selected component is a zeolite precursor supported on a silica molded body.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below.

The zeolite precursor used in the method for producing a binderless zeolite molded article of the present invention is represented by the following formula (1): Si ₁ (SDA) _x M ¹ _y M ² _z (1) Is a tetraalkyl ammonium having 1 to 5 carbon atoms in the alkyl group, M ¹ is an alkali metal, M ² is iron,
Represents one or more elements selected from the group consisting of boron, chromium, cobalt, nickel, zinc, and gallium;
001 to 1, y represents a range of 0.0001 to 1, and z represents a range of 0 to 0.5. ) Is not particularly limited. Further, in the above formula (1), x is 0.002
, Y is preferably 0.0001-1 and z is preferably 0-0.5. In the above formula (1), x is 0.003-0.8, and y is 0. 0002-0.
More preferably, z is a composition in the range of 0 to 0.3.

The method for preparing the zeolite precursor is not particularly limited, but a tetraalkylammonium component having an alkyl group having 1 to 5 carbon atoms, an alkali metal component,
Iron, boron, chromium, cobalt, supported as desired
A method of supporting a raw material containing at least one component selected from the group consisting of nickel, zinc and gallium on a silica molded body is preferred.

When the tetraalkylammonium component and the alkali metal component are supported on the silica molding, a binderless ZSM composed of only T atoms of silicon is used.
A 5-type silicalite molded body can be produced, and when one or more components selected from the group consisting of iron, boron, chromium, cobalt, nickel, zinc, and gallium are supported in addition to the two components, A binderless ZSM5 type crystalline metallosilicate molded body in which this is incorporated as a T atom can be produced.

The silica molded body is not particularly limited, and a commercial product can be used. Silica molded body used suitably is relatively large molded specific surface area, specific surface area determined from nitrogen adsorption measurements by conventional BET method, for example, 5m ² / g~800m ² / g, preferably 20 m ² / g to Those having a range of 600 m ² / g are used.
If the specific surface area is too small, crystallization requires a long time, and the degree of crystallization may be deteriorated.

The silica molded body has pores having a pore diameter of 6 nm or more determined by, for example, a mercury intrusion method, and the surface area and the pore volume of the pores are each 5 m ² / g to 5 m ² / g.
Is a 800m ² /g,0.1ml/g~1.5ml/g, preferably 20m ² / g~600m ² /g,0.2m
It is in the range of 1 / g to 1.3 ml / g.

The tetraalkylammonium component includes tetraethylammonium, tetra-n-propylammonium, tetraisopropylammonium,
Examples of halides and hydroxides of tetra n-butyl ammonium, tetra n-pentyl ammonium, triethyl n-propyl ammonium, tri n-propyl methyl ammonium, tri n-butyl methyl ammonium, etc. It is preferable to use a compound containing -propyl ammonium ion,
Usually, tetra n-propyl ammonium hydroxide is used. By using tetra-n-propylammonium salt, a ZSM5-type aluminosilicate can be efficiently synthesized.

As the alkali metal component, lithium,
Examples thereof include sodium and potassium, and hydroxides, halides or silica carriers thereof and / or
Alternatively, an alkali component in a metal salt compound can be used.

When synthesizing a ZSM5 type binderless crystalline metallosilicate molded body, a salt of a metal to be a T atom is supported on a silica carrier together with a tetraalkylammonium component and an alkali metal component. Examples of these metal salts include iron, boron, chromium, cobalt, nickel, zinc, gallium and other nitrates, sulfates, halides, oxoacid salts, hydroxides, and the like.
It is preferable to use these in the form of an aqueous solution. These metal components are converted into binderless metallosilicate by being incorporated into the zeolite framework during crystallization.

The above-mentioned molded silica is composed of a tetraalkylammonium component having an alkyl group having 1 to 5 carbon atoms and an alkali metal component, and iron, boron, chromium, cobalt, nickel, zinc, and gallium supported as required. The method of supporting the raw material containing one or more components selected from the group is not particularly limited, but it is desirable to uniformly support the raw material in the silica molded body,
Usually, it is carried out by drying after impregnation with an aqueous solution. As an example, a predetermined amount of each component is made into a uniform aqueous solution, which is prepared and impregnated so as to have an aqueous solution amount corresponding to the water absorption amount of the silica molded body. At this time, each component may be supported at the same time, or each component or a uniform mixed solution may be supported by dividing it into several times. Has no effect on

The drying temperature after the impregnation with the aqueous solution is not particularly limited, but is preferably from 20 ° C. to 120 ° C., more preferably from 50 ° C. to 50 ° C. in that the decomposition of the tetraalkylammonium salt is small, and the water content is reduced. ° C to 120 ° C
Will be implemented. The water content of the precursor is preferably 30% or less, more preferably 20% to 0.1%, in that the supported components are not eluted during crystallization and the yield is good.

The method of drying is not particularly limited, and the drying can be carried out under reduced pressure or normal pressure. Drying under an air stream at normal pressure is preferred because it is simple.

[0030] The production method of the present invention is characterized in that the zeolite precursor is brought into contact with saturated steam.

The temperature of the above-mentioned saturated steam is not particularly limited, and the crystallization rate is high, the decomposition of the contained tetraalkylammonium component is small, and a ZSM5 type binderless zeolite molded article having a high crystallinity can be obtained.
The range is preferably from 240 to 240 ° C, more preferably from 130 to 220 ° C.

The contact time with the saturated steam may be short, and is usually in the range of 2 to 50 hours, preferably 3 to 35 hours. If the crystallization time is too short, the crystallinity will decrease,
If it is too long, mixed crystals with other zeolites may be formed.

The method and apparatus for heating the zeolite precursor by bringing it into contact with saturated steam are not particularly limited. For example, it can be carried out by installing a precursor in the hollow of a pressure-resistant container, enclosing water corresponding to a saturated steam amount determined by a reaction temperature and a volume of the container in a lower portion of the container, and then heating in a constant temperature bath. Embodiments are not limited to this. The precursor may be placed in a vessel and a closed vessel containing water outside the vessel may be used, or the precursor may be continuously synthesized by a moving bed reactor.

By using the production method of the present invention, crystallization can be carried out by contacting the zeolite precursor with saturated steam without dispersing the zeolite precursor in water and causing a hydrothermal reaction. If desired, the supported metal component can be converted to a ZSM5 type zeolite having T atoms. As a result, the whole amount of the silica molded body as a raw material is converted into zeolite while maintaining its shape, so that the zeolite to be produced essentially contains no binder, and it is presumed that a ZSM5 type binderless zeolite molded body can be easily produced. Is done.

Since no binder is used in the production method of the present invention, the zeolite molded body synthesized by the production method of the present invention has a zeolite content of almost 100%.
Has a very high crystallinity. By selecting an appropriate precursor composition ratio, crystallization temperature and crystallization time from the above conditions, the crystallinity of the molded article can be controlled, for example, 95% or more, preferably 98% or more. . The crushing strength can be controlled by the crystallinity.

In the production method of the present invention, the silica molded body is molded into an arbitrary shape such as a sphere, a cylinder or a ring by a conventional method, and then converted into a zeolite by the method according to the invention to obtain a sphere or a cylinder. A binderless zeolite molded article having an arbitrary shape such as a mold and a ring mold can be manufactured. Since the silica carrier itself as the raw material is converted into the zeolite as it is, a binderless zeolite molded body which maintains the shape of the silica molded body can be obtained.

In the production method of the present invention, not only the appearance of the raw silica molded body is maintained, but also the crushing strength, macropore distribution, and the like are reflected. For this reason, by controlling the physical properties of the silica molded body used as a raw material in a conventional manner, the physical properties of the binderless zeolite molded body can be easily controlled.

The binderless zeolite molded article (A) of the present invention is characterized in that (1) the zeolite has a ZSM5 type crystal structure, and (2) the metal component constituting the crystal skeleton consists essentially of silicon. Features.

The binderless zeolite molded article (B) of the present invention comprises (1) a zeolite having a ZSM5 type crystal structure, and (2) a metal component constituting a crystal skeleton,
Silicon, iron, boron, chromium, cobalt, nickel,
At least one element selected from the group consisting of zinc and gallium; and (3) the composition ratio (atomic ratio) of silicon and the metal constituting the zeolite crystal structure to silicon 1 is as follows: 0.0001-
0.5.

The zeolite in the molded article of the present invention is ZSM.
It has a type 5 crystal structure. This can be confirmed by powder X-ray diffraction measurement or the like. The structure of the ZSM5-type zeolite forms a zeolite crystal skeleton by three-dimensionally bonding a TO ₄ tetrahedron in which four oxygen atoms are coordinated at the vertices centering on a T atom. For this reason, silicalite in which T atoms consist only of silicon is electrically neutral and does not exhibit solid acidity. Replacing Si ⁴⁺ with another valence metal gives T
It is well known that cations such as protons are present in the crystal to electrically neutralize the O ₄ anion, which causes solid acidity. The amount and the strength of the solid acidic acid to be expressed can be controlled by the amount and type of the element introduced as the T atom. The solid acidity can be evaluated by a thermal desorption (TPD) method of ammonia or the like.

The molded article (A) of the present invention comprises a T
It is a zeolite molded body into which atoms are not introduced, and examples thereof include a ZSM5 type binderless silicalite molded body.

In the molded article (B) of the present invention, the composition ratio (atomic ratio) of the metal component constituting the zeolite crystal structure in the molded article is such that iron, boron, chromium, cobalt, One or more elements selected from the group consisting of nickel, zinc and gallium are in the range of 0.0001 to 0.5, preferably in the range of 0.003 to 0.3.

The molded article of the present invention has a specific surface area of, for example, 300 m ² /
g to 550 m ² / g, preferably 315 m ² / g to
It is in the range of 500 m ² / g.

The molded article of the present invention has, for example, secondary pores having a pore diameter of 6 nm or more determined by a mercury intrusion method,
The surface area and pore volume of the pores are 2 m ² / g, respectively.
１５０150 m ^{2 /} g, 0.15 ml / g to 1.5 ml / g
, And the preferably 4m ² / g~100m ² /g,0.2
The range is from ml / g to 1.3 ml / g.

The molded article of the present invention can be simply and efficiently produced by the above-mentioned method for producing a binderless zeolite molded article.

Examples of the shape of the molded article of the present invention include a sphere, a cylinder and a ring.
There is no particular limitation.

Since the molded article of the present invention can easily control the shape, size, macropore distribution, etc., it can be used as an adsorbent, a catalyst for a chemical reaction, or a catalyst carrier in various chemical processes. , An alkylation reaction catalyst,
Isomerization reaction catalyst, cracking reaction catalyst, Beckmann rearrangement reaction catalyst, hydration reaction catalyst, alcohol addition reaction catalyst,
It is suitably used as a catalyst for synthesizing alkanolamines by the liquid ammonium method.

[0048]

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

Example 1. Hydroxidation at a concentration of 0.2 mol / l
9.84 ml of an aqueous sodium solution was added to a 10% by weight
Tetra-n-propyl chloride (abbreviated as TPA-OH) in water
Dissolved in 26.70 g of liquid and distilled water to make a total volume of 33 ml
And Silica beads dried at 120 ° C for 24 hours
"Carrier Q-50" manufactured by Shirishi Chemical Co., 10-2
0 mesh) to 23.67 g, and 33 ml of the aqueous solution to 1
Sodium hydroxide on silica beads
TPAOH was loaded. The composition ratio is Si₁Na_0.005TP
A _0.03It is.

This was transferred to an evaporating dish, dried in a 100 ° C. water bath, and then dried in an 80 ° C. oven under a nitrogen stream for 5 hours. The obtained precursor was placed in a Teflon cup and placed in a hollow Teflon crucible with a volume of 100 ml with a jacket. Add 1.00 g of distilled water to the bottom of the crucible container,
Heated at 180 ° C. for 8 hours. The product taken out after cooling the crucible to room temperature was packed in a column, washed with 500 ml of distilled water, and dried at 120 ° C. for 5 hours. The obtained white solid was calcined at 540 ° C. for 3.5 hours in an air stream to remove excess organic components, thereby obtaining 23.87 g of a white product. This is designated as product A.

The shape of the product A was 10 to 20 mesh size beads while maintaining the appearance of the silica beads used as the raw material. As a result of powder X-ray diffraction measurement after crushing the product A, it was a ZSM5 type silicalite as shown in FIG.

The BET three-point method for nitrogen at 77K (P /
P0 = 0.01, 0.03, 0.06), the specific surface area was 350 m ² / g, and the pore distribution was measured by the mercury porosimetry. As a result, the pore distribution curve shown in FIG. Give
The total macropore volume of 6 nm or more was 1.10 ml / g, and the surface area of the macropores was 15 m ² / g.

Example 2. Except that 3.28 ml of a 4 mol / l sodium hydroxide aqueous solution was used instead of the 0.2 mol / l sodium hydroxide aqueous solution, and the supporting composition ratio was changed to Si ₁ Na _0.03 TPA _0.03. In the same manner as in Example 1, 23.98 g of a white product was obtained. This is designated as product B.

The product B was 10 to 20 mesh size beads while maintaining the appearance of the silica beads used as the raw material. As a result of powder X-ray diffraction measurement after pulverizing the product B, a diffraction pattern essentially identical to that of FIG. 1 was obtained, and it was a ZSM5 type silicalite.

BET three-point method for nitrogen at 77K (P /
(P0 = 0.01, 0.03, 0.06), the specific surface area was 370 m ² / g, and the pore distribution was measured by a mercury intrusion method. .92 ml / g, and the surface area of the macropores was 5.92 ml / g.
It was 6 m ² / g.

Embodiment 3 FIG. Iron (III) nitrate nonahydrate 4.7
An aqueous solution obtained by dissolving 5 g in distilled water to make 30 ml
21.18 g of silica beads ("Caractact Q-50" manufactured by Fuji Silysia Chemical Ltd., 10 to 20 mesh) dried at 20C for one day was impregnated for one hour. After drying all day and night at 120 ° C., 1 mol / l TPAO
A mixture of 21.75 g of an aqueous H solution and 3.9 ml of a 4 mol / l aqueous sodium hydroxide solution (diluted with distilled water to a total volume of 30 ml) was impregnated for 1 hour, and aluminum hydroxide and TPAOH were added to the silica beads. Iron nitrate was supported. The composition ratio is Si ₁ Na _0.05 TPA _0.07 Fe _0.03 .

This was carried out in the same manner as in Example 1 to obtain 22.98 g of a light brown product. This is designated as product C.

The shape of the product C was 10 to 20 mesh size beads while maintaining the appearance of the silica beads used as the raw material. As a result of powder X-ray diffraction measurement after pulverizing the product C, the result was essentially the same as that in FIG. 1 and was a ZSM5-type ferrisilicate.

The BET three-point method for nitrogen at 77K (P /
P0 = 0.01, 0.03, 0.06), the specific surface area was 465 m ² / g, and the pore distribution was measured by mercury porosimetry. .78 ml / g, and the surface area of the macropores was 18
m ² / g.

Comparative Example The composition ratio after loading without using sodium hydroxide was Si ₁
An experiment was performed in the same manner as in Example 1 except that Na ₀ TPA was set to _0.03 . As a result of powder X-ray diffraction measurement of the product, no zeolite was formed and the product was amorphous.

[0061]

The ZSM5 type binderless zeolite molded article of the present invention essentially contains no binder, so that the zeolite content in the molded article is extremely high, and zeolite is not buried in the inorganic binder. Therefore, zeolite can be used efficiently and there is no adverse effect due to impurities such as an inorganic binder.

According to the method of the present invention, since the precursor to be molded is brought into contact with saturated steam for crystallization,
It is possible to easily produce a binderless ZSM5 type zeolite molded body.

Further, according to the method of the present invention, the time required for crystallization is short, and since the raw material components do not elute into water, the metal components are efficiently incorporated into the crystal lattice. In addition, a ZSM5 type crystalline metallosilicate having a composition almost identical to the raw material charging composition can be produced with high yield.

According to the method of the present invention, the binderless ZSM5 type zeolite molded product produced reflects the properties of the raw material silica molded product as it is, so that the physical properties such as the secondary pore structure can be easily controlled. Further, the amount of expensive tetraalkylammonium used can be reduced, and almost no waste liquid is generated, so that there is no need to collect and treat waste liquid, and it is economical.

[Brief description of the drawings]

FIG. 1 shows a CuKα X-ray diffraction diagram of product A.

FIG. 2 shows a pore distribution curve of a product A by a mercury intrusion method.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G073 BA04 BA28 BA36 BA40 BA44 BA52 BA56 BA58 BA63 BB02 BB48 BD26 CZ13 CZ52 CZ54 CZ63 FB01 FB30 FB36 FB50 FC18 GA12 GA13 GA14 UA01 UA06

Claims (6)

[Claims] 1. A binderless zeolite molded body, wherein the zeolite has a ZSM5 type crystal structure, and a metal component constituting the crystal skeleton is substantially only silicon. 2. A binderless zeolite molded body, wherein the zeolite has a ZSM5 type crystal structure, and the metal components constituting the crystal skeleton are silicon, iron, boron, chromium, cobalt, nickel, zinc, and And at least one metal element selected from the group consisting of gallium, and the composition ratio (atomic ratio) of the metal element to silicon is:
A binderless zeolite molded product having a range of 0.0001 to 0.5. Wherein binderless zeolite molded body according to claim 1 or 2 ratio was determined from the nitrogen adsorption measurement according to the BET method surface area of 300m ² / g~550m ² / g. 4. The pore diameter determined by a mercury intrusion method is 6 nm.
It has the above pores, and the surface area of the pores is 2 m ² / g to 15
0 m ² / g and the pore volume of the pores is 0.1
The binderless zeolite molded product according to any one of claims 1 to 3, wherein the content is 5 ml / g to 1.5 ml / g. 5. The following formula (1): Si ₁ (SDA) _x M ¹ _y M ² _z (1) wherein SDA is a tetraalkylammonium having an alkyl group having 1 to 5 carbon atoms, M ¹ Is an alkali metal, M ² is iron,
Represents at least one element selected from the group consisting of boron, chromium, cobalt, nickel, zinc, and gallium, wherein x is 0.001-1, y is 0.0001-1, and z is 0-0.5. Represents A method for producing a binderless zeolite molded body, comprising contacting the zeolite precursor represented by the formula (1) with saturated steam. 6. The zeolite precursor comprises a tetraalkylammonium component having an alkyl group having 1 to 5 carbon atoms, an alkali metal component, and, if desired, iron, boron, chromium, cobalt, nickel, zinc and gallium. The method according to claim 5, wherein the raw material containing at least one component selected from the group consisting of a zeolite precursor supported on a silica molded body.