JP4620197B2 - Binderless zeolite molding and method for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a ZSM5 type binderless zeolite molding and a method for producing a binderless zeolite molding.
[0002]
[Prior art]
ZSM5 type zeolite is a crystalline metallosilicate typified by crystalline aluminosilicate having oxygen 10-membered ring pores first disclosed in US Pat. No. 3,702,886. A crystalline aluminosilicate composed of silicon and aluminum, which is a metal component that constitutes the zeolite crystal skeleton (hereinafter sometimes referred to as T atom), mainly contains Al ³⁺ cations in the crystal lattice for the purpose of controlling its acidity. Substitution with other metal ions is widely performed, and it is generally said to be ZSM5 type zeolite including silicalite having the same structure and aluminum-containing crystalline metallosilicate in which aluminum is substituted with other metal ions. ing.
[0003]
As a method for synthesizing these ZSM5 type zeolites, a so-called hydrothermal synthesis method using an aqueous reaction slurry using tetra n-propylammonium ions as a template agent as a raw material has been known.
[0004]
However, in the conventional hydrothermal reaction method, since a part of the raw material components are dissolved in water during heating, not only the ratio of the components converted into crystals is inevitably decreased, but also the alkali components are diluted, so that 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 excluded from the crystal lattice. The atomic ratio of M (M represents a T atom other than silicon) does not necessarily match the atomic ratio of Si / M in the synthesized ZSM5 type zeolite, and industrially, the aqueous slurry is heated. Therefore, it is necessary to use a closed container having a relatively large volume with respect to the weight of the generated crystal, to use a large amount of expensive templating agent, to generate a large amount of waste liquid, to filter the zeolite powder, There are problems such as a complicated firing process.
[0005]
Further, in the case of producing a conventional zeolite molded body, since the moldability of zeolite alone is poor, it has been necessary to first synthesize zeolite powder by a hydrothermal synthesis method and then mold it using an inorganic binder. In this method, it is necessary to select a binder that does not adversely affect the intended use, and in order to obtain sufficient strength, a large amount of an inorganic binder is required. However, there is a problem that the zeolite buried in the binder cannot be effectively used.
[0006]
In view of this, several methods for producing a molded zeolite containing substantially no binder have been proposed. For example, Japanese Patent Application Laid-Open Nos. 59-162952 (TSZ type aluminosilicate) and Japanese Patent Application Laid-Open No. 61-72620 (MOR type aluminosilicate). ) And Japanese Patent Application Laid-Open No. 62-138320 (FAU type aluminosilicate), several types of crystalline binderless aluminosilicate moldings are known. These methods use pre-synthesized zeolite powder as a secondary raw material, and convert the binder into zeolite by reacting it with an alkaline solution, which is molded with an inorganic binder such as clay mineral or silica alumina. Substantially twice hydrothermal synthesis is required. For this reason, there are problems in that the process becomes longer and the amount of waste liquid increases.
[0007]
Furthermore, a method for synthesizing a binderless silicalite molded body in which the metal component constituting the crystal skeleton is substantially composed only of silicon or a binderless crystalline metallosilicate molded body composed of T atoms other than aluminum is known. It wasn't.
[0008]
As described above, ZSM5 type binderless zeolite moldings substantially free of binder, such as silicalite and crystalline metallosilicates having T atoms other than Al useful for acid property control, and a simple and efficient production method thereof Was not known.
[0009]
[Problems to be solved by the invention]
Accordingly, the object of the present invention has been made in view of the above problems, and is a ZSM5 type binderless zeolite molded body in which the T atom constituting the crystal skeleton is substantially composed only of silicon, or the T constituting the crystal skeleton. It is an object to provide a ZSM5 type binderless zeolite molding in which atoms are composed of silicon and at least one metal element selected from the group consisting of iron, boron, chromium, cobalt, nickel, zinc and gallium.
[0010]
Another object of the present invention is to provide a simple and efficient method for producing a zeolite molded body that does not use a binder.
[0011]
[Means for Solving the Problems]
As a result of intensive studies on the ZSM5 type binderless zeolite moldings, the present inventors have identified, for example, after supporting a tetraalkylammonium component having 1 to 5 carbon atoms in the alkyl group and an alkali metal component on the silica molding. The method of contacting with saturated water vapor under the above conditions allows the entire amount of silica to be crystallized while maintaining the shape of the silica molded body, and a ZSM5 type binderless zeolite molded body containing essentially no binder can be easily produced with good yield. In addition, after supporting other metal components together, a ZSM5 type binderless metallosilicate molded body containing essentially no binder and incorporating the metal components as T atoms can be easily and efficiently produced by the above method. The headline and the present invention were completed.
[0012]
That is, the present invention is a binderless zeolite molding, wherein the zeolite has a ZSM5 type crystal structure, and the metal component constituting the crystal skeleton is substantially composed only of silicon (A) About.
[0013]
Further, another invention of the present invention is a binderless zeolite molding, wherein the zeolite has a ZSM5 type crystal structure, and the metal components constituting the crystal skeleton are silicon, iron, boron, chromium, cobalt, It consists of at least one metal element selected from the group consisting of nickel, zinc and gallium, and the composition ratio (atomic ratio) of the metal element to silicon is in the range of 0.0001 to 0.5. The present invention relates to a binderless zeolite molding (B).
[0014]
The binderless zeolite molded body, 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.
[0015]
The binderless zeolite molded body, for example, the pore diameter determined by mercury intrusion porosimetry has pores of more than 6 nm, the surface area of the pores is a 2m ² / g~150m ² / g, and the fine This is a binderless zeolite molded body having a pore volume of 0.15 ml / g to 1.5 ml / g.
[0016]
Another invention of the present invention is represented by the following formula (1):
Si ₁ (SDA) _x M ¹ _y M ² _z (1)
(In the formula, SDA is a tetraalkylammonium whose alkyl group has 1 to 5 carbon atoms, M ¹ is an alkali metal, M ² is at least one selected from the group consisting of iron, boron, chromium, cobalt, nickel, zinc and gallium. And x represents a range of 0.001 to 1, y represents a range of 0.0001 to 1, and z represents a range of 0 to 0.5.)
It is related with the manufacturing method of the binderless zeolite molded object characterized by making the zeolite precursor represented by these contact with saturated steam of 120-240 degreeC.
[0017]
The zeolite precursor is at least selected from the group consisting of a tetraalkylammonium component having an alkyl group having 1 to 5 carbon atoms and an alkali metal component, and optionally iron, boron, chromium, cobalt, nickel, zinc and gallium. It is preferable that it is a zeolite precursor formed by supporting a raw material containing one kind of component on a silica molded body.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Details of the present invention will be described below.
[0019]
The zeolite precursor used in the method for producing a binderless zeolite molding of the present invention is represented by the following formula (1):
Si ₁ (SDA) _x M ¹ _y M ² _z (1)
(Wherein SDA is a tetraalkylammonium having 1 to 5 carbon atoms in the alkyl group, M ¹ is an alkali metal, M ² is one or more selected from the group consisting of iron, boron, chromium, cobalt, nickel, zinc, gallium) X represents 0.001-1, y represents 0.0001-1, and z represents a range of 0-0.5.)
If it is a composition represented by, it will not specifically limit. Further, in the formula (1), x is preferably 0.002 to 1, y is preferably 0.0001 to 1, and z is preferably in the range of 0 to 0.5. In the formula (1), x Is more preferably 0.003 to 0.8, y is 0.0002 to 0.5, and z is 0 to 0.3.
[0020]
The method for preparing the zeolite precursor is not particularly limited, but a tetraalkylammonium component having 1 to 5 carbon atoms in the alkyl group and an alkali metal component, and optionally supported iron, boron, chromium, cobalt, nickel, A method of supporting a raw material material containing one or more components selected from the group consisting of zinc and gallium on a silica molded body is preferable.
[0021]
When the tetraalkylammonium component and the alkali metal component are supported on the silica molded body, a binderless ZSM5 type silicalite molded body consisting of silicon-only T atoms can be produced. In addition to the two components, When one or more components selected from the group consisting of iron, boron, chromium, cobalt, nickel, zinc, and gallium are supported, a binderless ZSM5 type crystalline metallosilicate molded body in which these are incorporated as T atoms is manufactured. can do.
[0022]
The silica molded body is not particularly limited, and a commercially available 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 in the range of 600 m ² / g are used. This is because if the specific surface area is too small, a long time is required for crystallization, and the degree of crystallization may deteriorate.
[0023]
Further the silica molded body, for example, the pore diameter determined by mercury intrusion porosimetry has pores of more than 6 nm, surface area and pore volume due to pores each ^{5m 2 / g~800m 2 / g,} 0 a .1ml / g~1.5ml / g, and preferably from 20m ² / g~600m ² /g,0.2ml/g~1.3ml/g.
[0024]
Examples of the tetraalkylammonium component include tetraethylammonium, tetran-propylammonium, tetraisopropylammonium, tetran-butylammonium, tetran-pentylammonium, triethyln-propylammonium, trin-propylmethylammonium, trin- Examples thereof include halides such as butylmethylammonium and hydroxides, but it is preferable to use a compound containing tetra n-propylammonium ion, and usually tetra n-propylammonium hydroxide is used. By using tetra n-propylammonium salt, ZSM5 type aluminosilicate can be synthesized efficiently.
[0025]
Examples of the alkali metal component include lithium, sodium, potassium, etc., and hydroxides, halides, silica carriers and / or alkali components in metal salt compounds can also be used.
[0026]
When synthesizing a ZSM5 type binderless crystalline metallosilicate molded body, a metal salt that becomes a T atom is supported on a silica support together with a tetraalkylammonium component and an alkali metal component. Examples of these metal salts include nitrates such as iron, boron, chromium, cobalt, nickel, zinc, and gallium, sulfates, halides, oxoacid salts, hydroxides, and the like. It is preferable to use it. These metal components are converted into a binderless metallosilicate by being incorporated into the zeolite framework during crystallization.
[0027]
The silica molding is selected from the group consisting of a tetraalkylammonium component having 1 to 5 carbon atoms in the alkyl group and an alkali metal component, and iron, boron, chromium, cobalt, nickel, zinc, gallium supported as desired. The method of supporting the raw material containing one or more components is not particularly limited, but it is desirable to uniformly support the raw material in the silica molded body. Made by doing. As an example, a predetermined amount of each component is made into a uniform aqueous solution, and is prepared and impregnated so as to have an aqueous solution amount that matches 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 divided and supported in several times. Will not be affected.
[0028]
The drying temperature after impregnation with the aqueous solution is not particularly limited, but is preferably 20 ° C. to 120 ° C., more preferably 50 ° C. to 120 ° C., in that the decomposition of the tetraalkylammonium salt is small and the water content is suppressed efficiently. Performed at ° C. The water content of the precursor is preferably 30% or less, and more preferably in the range of 20% to 0.1% in that the supported component does not elute during crystallization and the yield is good.
[0029]
Further, the drying method is not particularly limited, and the drying can be carried out under any conditions of reduced pressure and normal pressure. Since it is easy to dry under an air stream at normal pressure, it is preferable.
[0030]
The production method of the present invention is characterized in that the zeolite precursor is brought into contact with saturated steam.
[0031]
The temperature of the saturated water vapor is not particularly limited, and is 120 to 240 ° C. in that a ZSM5 type binderless zeolite molded body having a high crystallization rate, less decomposition of the contained tetraalkylammonium component and high crystallinity can be obtained. The range is preferably 130 ° C. to 220 ° C.
[0032]
The contact time with the saturated water vapor may be a short time, usually 2 to 50 hours, preferably 3 to 35 hours. If the crystallization time is too short, the crystallinity is lowered, and if it is too long, a mixed crystal with another zeolite may be formed.
[0033]
The method and apparatus for heating the zeolite precursor in contact with saturated steam is not particularly limited. For example, it can be carried out by placing the precursor in the hollow of the pressure vessel and enclosing water corresponding to the saturated water vapor amount determined by the reaction temperature and the volume of the vessel at the bottom of the vessel, followed by heating in a thermostatic chamber, The embodiment is not limited to this. The precursor may be put in a container and a sealed container with water outside may be used, or the precursor may be continuously synthesized by a moving bed reactor.
[0034]
By using the production method of the present invention, the zeolite precursor can be crystallized by contacting with saturated steam without being dispersed in water and subjected to hydrothermal reaction. The ZSM5 type zeolite having T atoms as the metal component supported in this manner can be converted. As a result, the silica molded body as a raw material is entirely converted into zeolite while maintaining its shape, and it is assumed that the resulting zeolite is essentially free of binder and can easily produce a ZSM5 type binderless zeolite molded body. Is done.
[0035]
Since no binder is used in the production method of the present invention, the ZSM5 type zeolite molded body synthesized by the production method of the present invention has a very high crystallinity with a zeolite content of almost 100%. By selecting an appropriate composition ratio of precursor, crystallization temperature and crystallization time from the above conditions, the crystallinity of the molded product can be controlled, for example, 95% or more, preferably 98% or more. . The crushing strength can be controlled by the degree of crystallinity.
[0036]
Further, in the production method of the present invention, a silica molded body is molded into an arbitrary shape such as a spherical shape, a cylinder shape, or a ring shape by a conventional method, and then converted into a zeolite by the method according to the present invention, whereby a spherical shape, a cylinder shape, a ring shape is obtained. A binderless zeolite molded body having an arbitrary shape such as a mold can be produced. Since the silica support itself as a raw material is converted into zeolite as it is, a binderless zeolite molded body maintaining the shape of the silica molded body can be obtained.
[0037]
Moreover, in the manufacturing method of this invention, not only the external appearance of a raw material silica molded object is hold | maintained but crushing strength, macropore distribution, etc. are reflected. For this reason, the physical property of a binderless zeolite molding can be easily controlled by controlling the physical property of the silica molding used for a raw material by a conventional method.
[0038]
The binderless zeolite molding (A) of the present invention is
(1) the zeolite has a ZSM5 type crystal structure;
(2) The metal component constituting the crystal skeleton is substantially composed only of silicon.
[0039]
The binderless zeolite molding (B) of the present invention is
(1) the zeolite has a ZSM5 type crystal structure;
(2) The metal component constituting the crystal skeleton is composed of silicon and at least one element selected from the group consisting of iron, boron, chromium, cobalt, nickel, zinc and gallium, and (3) zeolite The composition ratio (atomic ratio) of silicon constituting the crystal structure and the metal is in a range of 0.0001 to 0.5 for the metal with respect to silicon 1.
[0040]
The zeolite in the molded body of the present invention has a ZSM5 type 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 TO ₄ tetrahedrons in which four oxygen atoms are coordinated at the apex with T atoms as the center. For this reason, silicalite whose T atom is composed only of silicon is electrically neutral and therefore does not exhibit solid acidity. It is well known that when Si ⁴⁺ is replaced by another valent metal, cations such as protons exist in the crystal to electrically neutralize the TO ₄ anion, and thereby solid acidity is expressed. ing. The amount of solid acidic acid and the acid strength that are expressed can be controlled by the amount and type of elements introduced as T atoms. The solid acidity can be evaluated by a temperature desorption (TPD) method of ammonia.
[0041]
The molded body (A) of the present invention is a zeolite molded body into which T atoms other than silicon are not introduced, and examples thereof include a ZSM5 type binderless silicalite molded body.
[0042]
In the molded body (B) of the present invention, the composition ratio (atomic ratio) of the metal components constituting the zeolite crystal structure in the molded body is iron, boron, chromium, cobalt, nickel, zinc with respect to silicon 1. One or more elements selected from the group consisting of gallium are in the range of 0.0001 to 0.5, preferably in the range of 0.003 to 0.3.
[0043]
The molded body of the present invention are, for example, the specific surface area determined from nitrogen adsorption measurements by the BET method was 300m ² / g~550m ² / g, preferably in the range of 315m ² / g~500m ² / g.
[0044]
The molded body of the present invention has, for example, secondary pores having a pore diameter of 6 nm or more determined by a mercury intrusion method, and the surface area and pore volume of each pore are 2 m ² / g to 150 m ² / g, a 0.15ml / g~1.5ml / g, preferably in the range of 4m ² / g~100m ² /g,0.2ml/g~1.3ml/g.
[0045]
The molded body of the present invention can be easily and efficiently manufactured by, for example, the above-described method for manufacturing a binderless zeolite molded body.
[0046]
Examples of the shape of the molded body of the present invention include a spherical shape, a cylinder shape, and a ring shape, but are not particularly limited.
[0047]
The molded body of the present invention can be used as an adsorbent, a catalyst for a chemical reaction, or a catalyst carrier in various chemical processes because the shape, size, macropore distribution, etc. can be easily controlled. It is suitably used for an alkylation reaction catalyst, an isomerization reaction catalyst, a cracking reaction catalyst, a Beckmann rearrangement reaction catalyst, a hydration reaction catalyst, an alcohol addition reaction catalyst, a liquid ammonium alkanolamine synthesis catalyst, and the like.
[0048]
【Example】
The present invention is specifically described by the following examples, but the present invention is not limited to these examples.
[0049]
Example 1.
Dissolve 9.84 ml of 0.2 mol / l sodium hydroxide aqueous solution in 26.70 g of 10% strength by weight tetra n-propyl hydroxide aqueous solution (abbreviated as TPA-OH) and bring the total volume to 33 ml with distilled water. did. 23.67 g of silica beads (Fuji Silysia Chemical's “Caract Q-50”, 10-20 mesh) dried for 1 day at 120 ° C. were impregnated with 33 ml of the aqueous solution for 1 hour, and sodium hydroxide was placed on the silica beads. And TPAOH were supported. The composition ratio is Si ₁ Na _0.005 TPA _0.03 .
[0050]
This was transferred onto an evaporating dish, dried on a 100 ° C. hot water bath, and then dried in an 80 ° C. oven under a nitrogen stream for 5 hours. The obtained precursor was put into a Teflon cup and placed in a hollow Teflon crucible with a jacket having a volume of 100 ml. 1.00 g of distilled water was placed in the bottom of the crucible container and 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 in an air stream at 540 ° C. for 3.5 hours to remove excess organic components, thereby obtaining 23.87 g of a white product. This is product A.
[0051]
The shape of the product A was 10 to 20 mesh size beads while maintaining the appearance of the silica beads used as a raw material. As a result of powder X-ray diffraction measurement after pulverizing the product A, it was ZSM5 type silicalite as shown in FIG.
[0052]
The specific surface area of nitrogen at 77 K by the BET three-point method (P / P0 = 0.01, 0.03, 0.06) is 350 m ² / g, and as a result of measuring the pore distribution by the mercury intrusion method, The pore distribution curve shown in FIG. 2 was given, 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.
[0053]
Example 2
The same procedure as in Example 1 was carried out except that 3.28 ml of 4 mol / l aqueous sodium hydroxide solution was used instead of 0.2 mol / l aqueous sodium hydroxide solution and the loading composition ratio was changed to Si ₁ Na _0.03 TPA _0.03. As a result, 23.98 g of a white product was obtained. This is product B.
[0054]
The shape of the product B was 10 to 20 mesh size beads while maintaining the appearance of the silica beads used as a raw material. As a result of powder X-ray diffraction measurement after pulverizing the product B, the diffraction pattern was essentially the same as that shown in FIG.
[0055]
The specific surface area of nitrogen at 77 K by the BET three-point method (P / P0 = 0.01, 0.03, 0.06) is 370 m ² / g, and the pore distribution was measured by mercury porosimetry, The total macropore volume of 6 nm or more was 0.92 ml / g, and the surface area of the macropores was 5.6 m ² / g.
[0056]
Example 3
Silica beads obtained by dissolving 4.75 g of iron (III) nitrate nonahydrate in distilled water to make 30 ml were dried at 120 ° C. for one day and night (“CARTIACT Q-50” manufactured by Fuji Silysia Chemical, 10 20 mesh) 21.18 g was impregnated for 1 hour. After drying overnight at 120 ° C., a mixed solution of 21.75 g of a 1 mol / l aqueous TPAOH 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 subsequently obtained. It was impregnated for 1 hour, and aluminum hydroxide, TPAOH and iron nitrate were supported on silica beads. The composition ratio is Si ₁ Na _0.05 TPA _0.07 Fe _0.03 .
[0057]
In the same manner as in Example 1, 22.98 g of a light brown product was obtained. This is product C.
[0058]
The shape of the product C was 10 to 20 mesh size beads while maintaining the appearance of the silica beads used as a raw material. As a result of powder X-ray diffraction measurement after pulverizing the product C, it was essentially the same as FIG. 1 and was a ZSM5 type ferric silicate.
[0059]
The specific surface area of nitrogen at 77 K by the BET three-point method (P / P0 = 0.01, 0.03, 0.06) is 465 m ² / g, and, as a result of measuring the pore distribution by the mercury intrusion method, The total macropore volume of 6 nm or more was 0.78 ml / g, and the surface area of the macropores was 18 m ² / g.
[0060]
Comparative Example An experiment was performed in the same manner as in Example 1 except that sodium hydroxide was not used and the composition ratio after loading was Si ₁ Na ₀ TPA _0.03 . As a result of powder X-ray diffraction measurement of the product, no zeolite was produced and it was amorphous.
[0061]
【The invention's effect】
Since the ZSM5 type binderless zeolite molding of the present invention contains essentially no binder, the zeolite content in the molding is extremely high, and the zeolite is not buried in the inorganic binder. For this reason, there is a feature that zeolite can be efficiently used and there is no adverse effect caused by impurities such as an inorganic binder.
[0062]
According to the method of the present invention, since the molded precursor and saturated water vapor are brought into contact with each other for crystallization, a binderless ZSM5 type zeolite molded body can be easily produced.
[0063]
Further, according to the method of the present invention, the time required for crystallization is short, and since the raw material component does not elute in water, the metal component is efficiently taken into the crystal lattice. A ZSM5 type crystalline metallosilicate having a composition almost identical to the composition can be produced with good yield.
[0064]
Further, according to the method of the present invention, the produced binderless ZSM5 type zeolite molded body reflects the properties of the raw material silica molded body as it is, and therefore it is easy to control physical properties such as secondary pore structure. Further, since the amount of expensive tetraalkylammonium used can be reduced and almost no waste liquid is generated, there is no need for recovery and waste liquid treatment, which is economical.
[Brief description of the drawings]
FIG. 1 shows a CuKα X-ray diffractogram of product A.
FIG. 2 shows a pore distribution curve of product A by mercury porosimetry.

Claims (4)

A raw material comprising a tetraalkylammonium component having 1 to 5 carbon atoms in the alkyl group, an alkali metal component, and at least one component selected from the group consisting of iron, boron, chromium, cobalt, nickel, zinc and gallium A zeolite precursor formed by supporting a substance on a silica molded body has the following formula (1):
Si ₁ (SDA) _x M ¹ _y M ² _z (1)
(In the formula, SDA is a tetraalkylammonium whose alkyl group has 1 to 5 carbon atoms, M ¹ is an alkali metal, M ² is at least one selected from the group consisting of iron, boron, chromium, cobalt, nickel, zinc and gallium. And x represents 0.001-1, y represents 0.0001-1, z represents a range of more than 0 and 0.5 or less.)
By contacting the zeolite precursor with saturated water vapor, the silica molded body is converted into zeolite while maintaining its shape, and selected from the group consisting of iron, boron, chromium, cobalt, nickel, zinc and gallium. A method for producing a ZSM5 type binderless zeolite molding, wherein at least one component is incorporated into the framework.   A method for producing a binderless zeolite molding, wherein the zeolite has a ZSM5 type crystal structure, and the metal component constituting the crystal skeleton is composed of silicon, iron, boron, chromium, cobalt, nickel, zinc and gallium. The composition ratio (atomic ratio) of the metal element with respect to silicon is at least in the range of 0.0001 to 0.5. The manufacturing method as described. The method according to claim 2 wherein the specific surface area of binderless zeolite molded body obtained from the nitrogen adsorption measured by the BET method is 300m ² / g~550m ² / g. The binderless zeolite molded body, pore size fine determined by mercury intrusion porosimetry has pores of more than 6 nm, the surface area of the pores is a ^{2m 2} / ^g~150m 2 / g, and before KiHoso hole The production method according to claim 2 or 3, wherein the pore volume of the solution is 0.15 ml / g to 1.5 ml / g.

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