JPH0343209B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for selectively introducing ions into crystalline aluminosilicate zeolite and selectively introducing ions into crystalline aluminosilicate zeolite. More specifically, the present invention relates to a method for selectively introducing different types of ions into the surface layer and inner layer of crystallites during ion introduction into crystalline aluminosilicate zeolite, and a zeolite produced by the introduction. Conventionally, in order to use crystalline aluminosilicate zeolite synthesized from silica, alumina, alkali metals, water, and organic compounds for use as catalysts or adsorbents, the ions in the zeolite lattice have generally been replaced with other ions. It is being said. Usually, after the zeolite is calcined at a temperature of 350°C or higher, one or more types of ions are transferred to the ion exchange site of the zeolite by contacting the zeolite with a solution containing the desired cation once or multiple times. introduced, and the original ions are desorbed in their place. However, in conventional methods, desired ions are introduced almost uniformly throughout the entire layer of zeolite crystallites. The crystallite refers to a microcrystal that is a component of a polycrystal and can itself be considered a single crystal. When used as an adsorbent or as a catalyst, it is usually a favorable fact that the introduced ions are uniformly distributed over the entire layer of zeolite crystallites. However, for specific reactions, it may be preferable to use a zeolite catalyst designed and prepared so that the introduced ions are different between the surface layer and the inner layer of the zeolite crystallite. For example, when a primary reaction of raw materials occurs selectively at active points near the entrance of zeolite pores, and a secondary reaction occurs at active points with different characteristics deep inside the pores to increase the yield of the desired product. It is. Methods for selectively introducing the ions into the surface layer of zeolite crystallites include a method of spraying the ion-containing solution on the zeolite powder in a spray dryer and a method of rapidly performing ion exchange.
A considerable amount of the ions are introduced into the inner layer of the zeolite crystallites, and the initial purpose cannot be fully achieved. The present invention solves this problem. As a result of extensive research, the present inventors have found that instead of the iontophoresis method that has traditionally been preferably used for zeolite containing organic compounds, that is, the method of bringing the zeolite into contact with a solution of a predetermined ionic substance after calcination. Then, the zeolite is brought into contact with a solution of a predetermined ionic substance without being calcined, and after being calcined, the zeolite is brought into contact again with a solution of an ionic substance different from the ions, so that different species are formed in the surface layer and the inner layer of the zeolite crystallite. It has been found that it is possible to obtain a selectively ion-introduced crystalline aluminosilicate zeolite into which ions are selectively introduced. That is, in the present invention, an uncalcined crystalline aluminosilicate zeolite containing organic ions is brought into contact with a solution containing an ionic substance, and the ions are replaced with alkali metal ions, ammonium ions, and/or organic ions in the surface layer of the zeolite. The calcined zeolite is then heated and calcined at 300°C to 1000°C to remove organic ions, and then the calcined zeolite is further brought into contact with a solution containing the ionic substance and another type of ionic substance. A selective multi-species ion introduction method characterized in that the different ionic substances are exchange-supported in place of alkali metal ions, ammonium ions and/or organic ions in the inner layer of the organic ion-containing unsintered crystalline aluminosilicate. Zeolite is brought into contact with a solution containing an ionic substance, and the ions are exchange-supported in place of alkali metal ions, ammonium ions, and/or organic ions on the surface layer of the zeolite, and then heated and calcined at 300°C to 1000°C. After removing organic ions, the calcined zeolite is further contacted with a solution containing the ionic substance and another type of ionic substance to remove alkali metal ions, ammonium ions and/or organic ions in the inner layer of the calcined zeolite. The present invention provides a selective multi-species ion introduction crystalline aluminosilicate zeolite, which is characterized in that the different ionic substances are exchange-supported in place of the above. The organic ion-containing crystalline aluminosilicate zeolite used in the present invention generally has a methane-type structure.
SiO ₄ tetrahedrons and AlO ₄ tetrahedra share oxygen atoms at the vertices of each other, forming a three-dimensional mesh structure. Alkali metal cations, ammonium ions, and/or organic bases are bonded to AlO ₄ tetrahedra. It is a zeolite that is electrically neutralized and has a pore opening of about 5 to 15 Å. The zeolite can be produced, for example, as follows. The following composition expressed in molar ratio of oxides: Al ₂ O ₃ /SiO ₂ = 0 to 0.2 H ₂ O/SiO ₂ = 5 to 200 M/SiO ₂ = 0.01 to 3.0 (or NH ₄ ⁺ /SiO ₂ = 0.1 ~50) Silica, alumina, water, organic compound or alkali metal having R/SiO ₂ =0.02 to 0.5 (in the above formula, M is an alkali metal ion, NH ₄ ⁺ is an ammonium ion, and R is an organic compound). Alternatively, it can be obtained by hydrothermally synthesizing a reaction mixture containing ammonium ions. The alumina source and silica source mentioned above may be those commonly used in zeolite production, and examples thereof include aluminate, alumina, silicate, silica hydrosol, silica gel, silicic acid, hydroxide, and halogen salt. Examples of organic compounds include quaternary alkylammonium compounds, primary and secondary
and tertiary alkylamines, alcohol amines, alcohols, ethers, and amides, particularly tetra n-propylammonium compounds, tetra n-butylammonium compounds,
Organic basic compounds such as tetraethylammonium compounds or choline are preferably used. Also
Alkali metal cations such as Na ⁺ , K ⁺ , Li ⁺ or NH ₄ ⁺ can usually be used as crystal mineralizers to promote crystallization, but the addition of alkali metal cations can be omitted by increasing the amount of organic compounds added. It is also possible. The hydrothermal synthesis involves crystallizing the crystalline aluminosilicate zeolite by heating the reaction mixture at a temperature of 50-300°C, preferably 100-200°C for 1 hour to 60 days, preferably 6 to 24 hours. generate. Next, the organic cation-containing zeolite is filtered and washed from the mother liquor at a temperature of 50 to 200°C, preferably 100 to 100°C.
It is usually dried at 150°C for 0.5 to 50 hours, preferably 2 to 10 hours. Examples of ionic substances to be exchanged with zeolite in the present invention include metal ions, ammonium ions (NH ₄ ⁺ ), and hydrogen ions (H ⁺ ). The metal ion may be any of various metal ions from Groups to Groups of the periodic table. In particular, A and B groups (e.g. Li, Na, K, Rb, Cu, Ag,
Cs, Au, etc.), A, B genus (e.g. Be, Cd,
Ba, Hg, Mg, Ca, Sr, Zn, etc.), B genus (e.g. La, Ce, Pr, Nd, etc.), A, B genus (e.g. V, Bi, P, Sb, etc.), A, B genus (e.g. , Cr, Mo, W, Se, Te, etc.), A genus (e.g. Mn, Re, etc.) and genus (e.g. Fe, Co,
Various metal ions such as Ni, Ru, Rh, Pd, Os, Ir, Pt, etc. are preferably used. These ions are preferably chlorides, nitrates and sulfates. Among the metal ions mentioned above, the metal ions of Pt and Pd are preferably Pt(NH ₃ ) ₄ ⁺⁺ and Pd
Ammine complex ions such as (NH ₃ ) ₄ ⁺⁺ are used. Further, as the metal ions of Mo, W and P, anions such as ammonium molybdate, ammonium tungstate and ammonium phosphate are preferably used. The method of introducing ionic substances into zeolite in the present invention is usually carried out as follows. First, unfired organic ion-containing zeolite 5
×10 ^-5 -10 mol/liter, preferably 5 × 10 ^-4
- a solution of an ionic substance at a concentration of 2 mol/liter at 0-200°C, preferably 20-100°C for 10 minutes to 10 days;
Preferably, the contact is carried out for 0.5 to 5 hours to exchange and support the ionic substance in place of the alkali ions on the surface layer of the organic ion-containing zeolite crystallite. Note that the number of ionic substances that can be exchanged and supported in place of the alkali ions on the surface layer is not limited to one type, but it is possible to exchange and support multiple ionic substances at the same time by contacting with a solution containing multiple ionic substances. Alternatively, a plurality of ionic substances may be exchange-supported by contacting with a solution containing a single ionic substance multiple times. The organic ion-containing zeolite in which one or more types of ionic substances are selectively exchange-supported on the surface layer of the crystallites by the above method is then heated at 300°C to
30 minutes at a temperature of 1000℃, preferably 500℃~800℃
The zeolite is heated and calcined for 100 hours, preferably from 1 to 10 hours, in an inert gas or air, and the organic ions contained in the inner layer of the zeolite are decomposed (calcined) and removed. The zeolite is further made ionic by contacting with reducing gas such as H ₂ gas, CO gas, H ₂ S gas or various reducing solutions such as sulfite, thiosulfite, and hydrothionate. It is possible to stabilize substances. Next, an ionic substance different from the ionic substance exchanged into the surface layer is introduced into the inner layer of the calcined zeolite crystallite. That is, the calcined zeolite is added at 5×10 ⁻⁵ −10 mol/liter, preferably 5×
The inner layer of the zeolite crystallites is contacted with a solution of an ionic substance having a concentration of 10 ^-4 -2 mol/liter at 0 to 200°C, preferably 20 to 100°C, for 10 minutes to 10 days, preferably 0.5 to 5 hours. Exchanges and supports ionic substances. The number of ionic substances exchanged and supported in place of the alkali ions in the inner layer is not limited to one type, but multiple ionic substances can be exchanged and supported at the same time by contacting with a solution containing multiple ionic substances. Alternatively, a plurality of ionic substances may be exchange-supported by contacting with a solution containing a single ionic substance multiple times. In addition, if the amount of organic compound added instead of alkali metal ions is increased during the hydrothermal synthesis step of zeolite, or in the case of synthetic zeolite using ammonium ions (NH ₄ ⁺ ) instead of alkali metal ions,
Exchange of H ⁺ or NH ₄ ⁺ as ionic substances can be omitted. In other words, in these cases, by calcining at 300°C to 1000°C, preferably 450°C to 800°C, it can be directly converted into the H type and provided as a solid acid catalyst. Also, in cases other than the above, it is usually 300℃~
30 minutes at a temperature of 1000℃, preferably 450℃~800℃
Calcinate in inert gas or air for 100 hours, preferably 1 to 10 hours. The calcined zeolite is further ionized by contacting with a reducing gas such as H ₂ gas, CO gas, or H ₂ S gas at high temperature, or by contacting with various reducing solutions such as sulfite, thiosulfite, and hydrothionate. Stabilization of sexual substances can be achieved. A known method can be used to exchange and support an ionic substance in place of the alkali ions or the like on the zeolite. Examples include an impregnation method, an ion exchange method, a deposition method, and a kneading method. Particularly preferred are the impregnation method and the ion exchange method. The above-mentioned surface layer portion means a portion near the outer surface of the zeolite crystallite, and specifically refers to the outer surface of the zeolite crystallite and the pore entrance portion. The volume ratio of the surface layer to the entire crystallite is 0.1 to 30%. On the other hand, the inner layer portion refers to the portion of the zeolite crystallite excluding the surface layer portion, and specifically refers to the inside of the pore of the zeolite crystallite excluding the pore entrance portion. The volume ratio of the inner layer to the entire crystallite is 70 to 99.9%. The bulk concentration of the introduced ions is determined by a conventional analytical method, preferably by treating the supported zeolite with HF water and then dissolving it in HCl water, and quantifying it by atomic absorption spectrometry or colorimetric analysis. On the other hand, the concentration of supported ions in the surface layer of zeolite crystallites is usually measured by various solid surface analysis methods, but Auger electron spectroscopy or X-ray photoelectron spectroscopy is preferably used. Further, the supported ion concentration distribution in the inner layer of the zeolite crystallite can be quantified by measuring the above-mentioned Auger electron spectrum while scraping the surface of the zeolite crystallite with Ar ⁺ or the like. In many cases where the selectively ion-introduced zeolite prepared according to the present invention is used as a catalyst or adsorbent, it is desirable to use it by mixing it with a certain base material that has excellent heat resistance and durability. The zeolitic materials are often incorporated into natural clays such as bentonite and kaolin. These materials act as binders for the catalyst and provide a catalyst with high mechanical strength and good crush strength. Materials to be composited with the zeolites produced according to the invention include montmorillonite, kaolin, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryria, silica-titania and silica-alumina-thorium. , silica-alumina
Porous matrix materials include zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia. The proportion of the zeolite in these composite catalysts is usually 5 to 90 wt%. When the zeolite selectively introduced with ionic substances by the method of the present invention is used as a catalyst, the zeolite may be calcined in an inert gas or in air, and/or subjected to H ₂ reduction, and/or sulfurized prior to the reaction. . One example of the use of the selectively iontophorized zeolite obtained by the method of the present invention as a catalyst is in the synthesis gas-to-gasoline (STG) reaction for producing high octane gasoline in one step from synthesis gas. The method of the present invention can be applied to the surface layer of zeolite.
Metals such as Pd, Zu-Cu, or Ru that have methanol synthesis or Fischer-Tropsch reaction activity are introduced, and the inner layer contains H ⁺ or Ru.
High activity for STG reaction by introducing _NH4 ⁺ ,
Highly selective catalysts can be prepared. Other uses include hydrodewaxing to lower the pour point and viscosity of lubricating or fuel oils. Further examples include methylation and disproportionation of toluene, and isomerization of xylene. In this case, selectivity to paraxylene can be increased by poisoning only the acid sites in the surface layer with a basic substance such as Na or Mg. The organic cation-containing zeolite is coated in the surface layer according to the method of the present invention.
By introducing metals with hydrogenation ability such as Pt, Pd, Mo, and W, and introducing H ⁺ or NH ₄ ⁺ or divalent or trivalent metal cations into the inner layer, the activity and selectivity for the various reactions is increased. In particular, it is possible to create a hydrocracking catalyst with an excellent lifespan. In this case, ions of P, Mg, or B may be further introduced into the surface layer in order to increase selectivity. Furthermore, according to the method of the present invention, catalyst poisons for metals with hydrogenation ability, such as Sb, As, Bi, and Mn, are introduced into the surface layer of the organic cation-containing zeolite, and Pt, Pd, Rh, Ru, Fe, and other catalyst poisons are introduced into the inner layer. , Ni, Cs, Mo, W
By introducing a metal capable of hydrogenating, such as, it is possible to create a catalyst with excellent molecular shape selectivity, such as selective hydrogenolysis of n-paraffin in a naphtha fraction. Example 1 Al ₂ (SO ₄ ) ₃・18H ₂ O 6.48gr, concentrated sulfuric acid 18.6gr, water
180 c.c. and an aqueous solution consisting of 22.6 gr of tetrapropylammonium bromide ((n-Pr) ₄ NBr), 207 gr of water glass No. 3 (SiO ₂ /NaOH/H ₂ O = 29/9/62 weight ratio) and water. An aqueous solution consisting of 133c.c. was prepared separately. These were added dropwise to an aqueous solution consisting of 78.8 gr of NaCl and 313 c.c. of water while stirring well so that the pH of the mixture was within the range of 9.5 to 10.0, to obtain a heterogeneous gel-like mixture. This gel-like mixture has an internal volume of 1
After filling and sealing the stainless steel autoclave.
The mixture was heated and stirred at 150°C for 16 hours. The reaction product was washed separately and dried at 120° C. for 5 hours to obtain approximately 60 gr of a crude white powdery solid material. As a result of X-ray diffraction analysis, it was found that the solid material was a zeolite (1) equivalent to ZSM-5. (Comparative manufacturing method-1) Weigh out 20g of the above zeolite (1) and heat it at 500℃ for 50g.
Baked in air for an hour. Then 1Mol/
The operation of introducing NH ₄ ⁺ was performed three times at 70° C. using 200 c.c. of NH ₄ NO ₃ aqueous solution. After over-washing, suspend in 200 c.c. of distilled water and keep at 70°C while stirring well, and add about 1 ml of 0.01Mol/Pt(NH ₃ ) ₄ Cl ₂ aqueous solution 50 c.c.
Added drop by drop over time. After aging for 30 minutes, it was washed and baked in air at 500°C for 5 hours. As a result of colorimetric analysis, approximately 0.5 wt% of Pt, which is almost the entire amount of Pt added, was supported on the zeolite.
Also, according to Auger electron spectroscopy, it was confirmed that it was supported uniformly on the surface and inner layers of the zeolite. (Production method-2) 20g of the above zeolite (1) was weighed out and suspended in 200c.c. of distilled water. 0.01Mol/Pt(NH ₃ ) ₄ Cl ₂ aqueous solution 50 while keeping it at 70℃ by heating and stirring.
cc was added dropwise over about 1 hr. After aging for 30 minutes, it was washed and baked in air at 500°C for 5 hours.
As a result of colorimetric analysis and Auger electron spectroscopy analysis, only 0.01 wt% of Pt was supported on the surface layer of the zeolite, and the organic compounds in the inner layer were burned out. Next, after _H2 reduction at 500℃ for 3 hours, 1Mol/
Ion exchange operation with NH ₄ ⁺ was performed three times at 70° C. using 200 c.c. of NH ₄ NO ₃ aqueous solution. After over-cleaning, 500
It was baked in air at ℃ for 5 hours. As a result, 0.01 wt% of Pt was supported on the surface layer of the zeolite, unchanged from before the NH ₄ ⁺ ion exchange, and in the inner layer, sodium ions were exchanged with H ⁺ ions. (Production method-3) Weigh out 20gr of the zeolite (1) above, and add 0.01Mol/
The sample was immersed in 50 c.c. of an aqueous Pt(NH ₃ ) ₄ Cl ₂ solution and allowed to stand for about 1 hour, and then water was removed at 100° C. under reduced pressure using an evaporator. Then, it was fired in air at 500°C for 5 hours. As a result of colorimetric analysis and Augier electron spectroscopy, it was found that 0.5wt% of Pt was supported on the surface layer of the zeolite, and that the entire amount of Pt added was supported on the surface layer of the zeolite. 500℃
After 3hrH ₂ reduction in 1Mol/NH ₄ NO ₃ aqueous solution 200c.c.
Ion exchange operation with NH ₄ ⁺ was performed three times at 70°C using After excessive washing, the product was baked in air at 500°C for 5 hours. As a result of the analysis, the surface layer of zeolite contains
0.5wt% of Pt is supported as before NH ₄ ⁺ ion exchange, and almost all of the sodium ions are in the inner layer.
It was being exchanged with H ⁺ ions. Using the three types of Pt-H-zeolites obtained in Production Methods 1 to 3 as catalysts, n-C ₄ H ₉ CHO/tert-
A hydrogenation reaction of C ₄ H ₉ CHO=1/1 (mol/mol) was performed. Note that prior to the reaction, H ₂ reduction was performed at 500° C. for 3 hours. The reaction was carried out under normal pressure at 70℃ and H ₂ /
The reaction was carried out using C ₄ H ₉ CHO=5/1 (mol/mol). The main product was the reacting alcohol. Table 1 shows comparative examples and examples.

[Table] As is clear from the table, the product obtained by manufacturing method-1
In 0.5wt% Pt uniformly supported zeolite, n-
The hydrogenation activity toward C ₄ H ₉ CHO is much larger than that toward tert-C ₄ H ₉ OH, which has a bulky molecular structure, and molecular shape selectivity is observed. On the other hand, the 0.01wt% or 0.5wt% Pt surface- _supported zeolite obtained by Production Methods 2 and 3 converts tert- _C4H9CHO to _the same level or more than n- _C4H9CHO , Molecular shape selectivity (*1) as in Production Method-1 is not observed. It is known that when active sites (Pt sites in this case) are present in the zeolite pores, that is, in the inner layer, molecular shape selectivity usually appears. This model reaction demonstrated that in the catalyst, Pt is unevenly distributed outside the pores, that is, in the surface layer of the zeolite crystal. (*1) If the pore size of the catalyst is appropriate, there will be both molecules that are too large to enter the pores and molecules that can enter the pores, and the molecules that cannot enter have a much greater chance of reacting than the molecules that can. becomes less. on the other hand,
Regarding products, not only are molecules larger than the pore not produced within a narrow pore, but even among molecules smaller than the pore, smaller molecules are more likely to be produced. When the selectivity of a catalyst is determined by the relationship between the pore structure and the shape of the molecule in this way, this catalyst is called a molecular shape-selective catalyst. Example 2 Al ₂ (SO ₄ ) ₃・18H ₂ O 17.8gr, concentrated sulfuric acid 18.6gr, water
139 c.c. and 16.1 gr of tetrapropylammonium bromide ((n-Pr) ₄ NBr) and 207 gr of water glass No. 3 (SiO ₂ /NaOH/H ₂ O = 29/9/62 weight ratio) were mixed with water. A separate aqueous solution consisting of 103c.c. Add these to 242c.c. water until the pH of the mixture is 9.5~
It was added dropwise while stirring well so that the mixture was within the range of 10.0 to obtain a heterogeneous gel-like mixture. This gel-like mixture was filled into a stainless steel autoclave having an internal volume of 1, and after being sealed, the autoclave was heated and stirred at 175° C. for 16 hours. The reaction product was washed separately and dried at 120°C for 5 hours to obtain about 60g of a crude white powdery solid material. As a result of X-ray diffraction analysis, this solid material was found to be zeolite (2) equivalent to synthetic mordenite. (Comparative manufacturing method-1) Instead of 0.01Mol/Pt(NH ₃ ) ₄ Cl ₂
Example 1 using 0.02Mol/Pd( _{NH3 ) 4Cl2} ,
It was carried out in the same manner as Production Method-1. As a result of atomic absorption and Auger electron spectroscopy analysis, it was found that 0.6 wt% Pd was distributed and supported on the surface and inner layers of zeolite (2). (Production method-2) Instead of 0.01Mol/Pt(NH ₃ ) ₄ Cl ₂
Example 1 using 0.02Mol/Pd( _{NH3 ) 4Cl2} ,
It was carried out in the same manner as Production Method-2. As a result of atomic absorption and Auger electron spectroscopy analysis, it was found that the surface layer of zeolite (2) supported 0.05 wt% Pd, and the inner layer had sodium ions exchanged with H ⁺ ions. (Production method-3) Instead of 0.01Mol/Pt(NH ₃ ) ₄ Cl ₂
Example 1 using 0.02Mol/Pd( _{NH3 ) 4Cl2} ,
It was carried out in the same manner as Production Method-3. Zeolite (2) as a result of atomic absorption and Augier electron spectroscopy
It was found that 0.6 wt% Pd was supported on the surface layer, and sodium ions were exchanged with H ⁺ ions in the inner layer. Using the three types of Pd-H-zeolites obtained in Production Methods 1 to 3 as catalysts, n-
A hydrogenation _reaction of _C4H9CHO /tert- _C4H9CHO =5/1 (mol _/ mol) was performed. The main product was the corresponding butanol. The results are shown in Table-2.

[Table] As is clear from the table, the product obtained by manufacturing method-1
In 0.5wt% Pd uniformly supported zeolite, n-
It can be seen that the hydrogenation activity for C ₄ H ₉ CHO is much higher than that for tert-C ₄ H ₉ CHO, which has a bulky molecular structure, and has molecular shape selectivity. On the other hand, the 0.05wt% or 0.6wt% Pd surface-supported zeolites obtained by production methods 2 and 3 are n-
C ₄ H ₉ tert− equal to or greater than CHO
Since C ₄ H ₉ CHO is converted, the molecular shape selectivity as in Production Method-1 is not observed. It is known that when active sites (Pd sites in this case) are scattered within the pores of zeolite, molecular shape selectivity usually appears, and production methods 2 and 3 prepared according to the method of the present invention This model reaction proved that in the catalyst, Pd is unevenly distributed outside the pores, that is, in the surface layer of the zeolite crystal. Example 3 _An aqueous solution consisting of 100 g of water and 15.98 g of Al ₂ (SO ₄ ) 3.18H ₂ O was added to an aqueous solution consisting of 4.4 g of KOH, 38 g of choline chloride, 135.4 g of water glass, and 40 g of water to form a heterogeneous gel-like mixture. I got it. This gel-like mixture was filled into a stainless steel autoclave having an internal volume of 1, and after being sealed, the autoclave was heated and stirred at 100° C. for 95 days. The reaction product was overwashed and dried at 120° C. for 5 hours to obtain about 40 g of a crude white powder solid material. As a result of X-ray diffraction analysis, this solid material is a zeolite equivalent to ZSM-34 (3)
It turns out that it is. (Comparative production method _{-1) Example 1, production method using 2.0Mol/Ni(NO3)2 aqueous solution 50c.c. instead of 0.01Mol/Pt(NH3)4Cl2 aqueous solution} 50c.c. I did it in exactly the same way as 1. Atomic absorption and Augier electron spectroscopy results,
It was found that 0.8wt% Ni was supported on the surface and inner layers of zeolite (3). (Production method- _{2) Example 1, Production method 2 using 2.0Mol/Ni(NO3)2 aqueous solution} 50c.c. instead of 0.01Mol/Pt( _NH3 ) _4Cl2 aqueous solution and 50c.c. I did it in exactly the same way. Atomic absorption and Augier electron spectroscopy results,
It was found that 0.03wt% Ni was supported on the surface layer of zeolite (3), and potassium ions were exchanged with H ⁺ ions in the inner layer. (Production method-3) Example 1, Production method- _{3 using 0.06Mol/Ni(NO3)2 aqueous solution} 50c.c. instead of 0.01Mol/Pt( _NH3 ) _4Cl2 aqueous solution 50c.c. I did it in exactly the same way. As a result of atomic absorption and Auger electron spectroscopy, it was found that 0.8 wt% Ni was supported on the surface layer of zeolite (3), and potassium ions were exchanged to H ⁺ in the inner layer. Using the three types of Ni-H-zeolites obtained in Production Methods 1 to 3 as catalysts, n-
A hydrogenation _reaction of _C4H9CHO /tert- _C4H9CHO =5/1 (mol _/ mol) was performed. The main product was the corresponding butanol. The results are shown in Table-3.

[Table] As is clear from the table, the product obtained by manufacturing method-1
In 0.8wt%Ni uniformly supported zeolite, n-
It can be seen that the hydrogenation activity for C ₄ H ₉ CHO is much higher than that for tert-C ₄ H ₉ CHO, which has a bulky molecular structure, indicating molecular shape selectivity. On the other hand, 0.03wt% or
0.8wt% Ni surface supported zeolite is n-C ₄ H ₉ CHO
tert-C ₄ H ₉ CHO is converted to the same level or more, and the molecular shape selectivity as in Production Method-1 is not observed. It is known that when active sites (Ni sites in this case) are scattered within the zeolite pores, molecular shape selectivity usually appears. This model reaction proved that Ni is unevenly distributed outside the pores, that is, in the surface layer of the zeolite crystal. Example 4 An aqueous solution consisting of 100 g of water and 1.56 g of Al ₂ (SO ₄ ) _{3.18H 2} O was mixed with 80.2 g of NH ₄ OH, 27.2 g of TPABr, 300 g of colloidal silica (SiO ₂ /H ₂ O=20/80 weight) and In addition to an aqueous solution consisting of 170 c.c. of water, a heterogeneous gel-like mixture was obtained. This gel-like mixture has an internal volume of 1
After filling and sealing the stainless steel autoclave.
The mixture was heated and stirred at 160°C for 3 days. The reaction product was overwashed and dried at 120° C. for 5 hours to obtain about 60 g of a crude white powder solid material. As a result of X-ray diffraction analysis, this solid material was found to be a zeolite (4) equivalent to ZSM-5. Furthermore, compositional analysis revealed that the Na content of this zeolite was less than 0.01wt%, which was only a trace amount. (Comparative manufacturing method-1) Weighed out 20g of the zeolite (4) and heated it at 500℃ for 5
Baked in air for an hour. Then 23g Mg
(OAc) It was suspended in an aqueous solution consisting of 2.4H ₂ O and 50 g of water and left at _a temperature of 60° C. for 18 hours. Next, water was evaporated to dryness on an evaporating dish at 110°C, dried at 200°C for 2 hours, and then baked at 500°C for 5 hours. Results of atomic absorption and Augier electron spectroscopy Zeolite (4) Table
It was found that 11.4wt% Mg was supported throughout the inner layer. (Production method-2) Weigh out 20g of the zeolite (4) above, and add 23g of Mg
(OAc) It was suspended in an aqueous solution consisting of 2.4H ₂ O and 50 g of water and left at _a temperature of 60° C. for 18 hours. Next, water was evaporated to dryness on an evaporating dish at 110°C, dried at 200°C for 2 hours, and then baked at 500°C for 5 hours. Results of atomic absorption and Augier electron spectroscopy, zeolite
In (4), 10.5 wt% Mg was supported on the surface layer, and the inner layer was exchanged with H ⁺ ions. The two types of Mg-H-zeolites obtained in Production Methods 1 and 2 were used as catalysts at 550℃ under normal pressure, WHSV = 3.5 (g
The disproportionation reaction of toluene was carried out under the following reaction conditions: -toluene/g-catalyst hr ^-1 ). The results are shown in Table 4.

[Table] From the table above, the 10.5wt% Mg surface supported zeolite obtained by production method-2 is 11.4wt% obtained by production method-1.
The disproportionation activity of toluene is much higher than that of Mg homogeneously supported zeolite, making it a superior catalyst. In production method-2, the zeolite crystallite surface layer is
By selectively introducing Mg cations, only the acid sites in the surface layer are selectively poisoned while leaving the acid sites inside the pores, that is, in the inner layer, intact, resulting in a highly active and highly selective catalyst as shown in the table above. It is thought that the Example 5 Approximately 60 g of zeolite (5) (crude white powdery solid substance) was obtained in the same manner as in Example 1. (Comparative Production Method-1) 20 g of the zeolite (5) was weighed out and calcined in air at 500°C for 5 hours. Then 1Mol/
The operation of introducing NH ₄ ⁺ was performed three times at 70° C. using 200 c.c. of NH ₄ NO ₃ aqueous solution. After over-cleaning, 0.2Mol/
The mixture was suspended in 200 c.c. of SbCl ₃ aqueous solution and stirred at 70°C for 3 hours. After excessive washing, the product was baked in air at 500°C for 5 hours. Atomic absorption and electron spectroscopy analysis revealed that 0.6wt% of Sb and H ⁺ ions were supported on the surface and inner layers of the zeolite. Next, this Sb-supported zeolite was suspended in 200 c.c. of distilled water, and 0.01 Mol/Pt(NH ₃ ) ₄ Cl ₂ aqueous solution 50 was added while stirring at 70°C.
cc was added dropwise over about an hour. After aging for 30 minutes, it was washed and baked in air at 500°C for 5 hours. As a result of atomic absorption and Augier electron spectroscopy, 0.56wt% of the surface and inner layers of zeolite were found.
Sb and 0.5wt% of Pt and H ⁺ ions are supported, and almost all of the added Pt is on the surface of zeolite (1).
It was found that Sb was supported on the inner layer and that the previously supported Sb was hardly lost in this ion exchange process. (Production method-2) Weigh out 20g of the zeolite (5) and add 0.2Mol/
The mixture was suspended in 200 c.c. of SbCl ₃ aqueous solution and stirred at 70°C for 3 hours. After excessive washing, the product was baked in air at 500°C for 5 hours. As a result of analysis such as atomic absorption and Augier electron spectra, the surface layer of zeolite (1)
Only 0.01wt% of Sb was supported, and the organic ions in the inner layer were burned away. Next, 1Mol/
The ion exchange operation with NH ₄ ⁺ was repeated three times at 70° C. using 200 c.c. of NH ₄ NO ₃ aqueous solution. After filtration and cleaning
50 c.c. of 0.01Mol/Pt(NH ₃ ) ₄ Cl ₂ aqueous solution was suspended in 200 c.c. of distilled water at 70°C while stirring well.
Added dropwise over time. After aging for 30 minutes, it was washed and baked in air at 500°C for 5 hours. Atomic absorption and Augier electron spectroscopy results,
The surface layer of zeolite contains 0.01wt% Sb and 0.01wt
% of Pt was supported, and H ⁺ ions and 0.49 wt% of Pt were supported in the inner layer of the zeolite.
From the above, it was found that almost all of the Pt added was supported on the zeolite (1), and that the previously supported Sb was not lost during these ion exchange steps. (Manufacturing method-3) Weigh out 20g of the zeolite (5) and add 0.018Mol/
After being immersed in 50 c.c. of an aqueous SbCl ₃ solution and left for about 1 hour, water was removed under reduced pressure at 100°C using an evaporator. Then, it was fired in air at 500°C for 5 hours.
As a result of analysis such as atomic absorption and Augier electron spectra, 0.55wt% of Sb was found in the surface layer of zeolite (5).
The organic ions in the inner layer of the zeolite supported on it had been burnt out. Next, 1Mol/NH ₄ NO ₃ aqueous solution
The ion exchange operation with NH ₄ ⁺ was repeated three times at 70° C. using 200 c.c. After filtering and washing, suspend in 200c.c. distilled water and add 0.01Mol/Pt while stirring well at 70℃.
50 c.c. of (NH ₃ )Cl ₂ aqueous solution was added dropwise over about 1 hour. After aging for 30 minutes, rinse and heat at 500℃.
It was baked in air for 5 hours. As a result of analysis such as atomic absorption and Augier electron spectra, zeolite
The surface layer of (5) carries 0.5wt% Sb and 0.01wt% Pt, and the inner layer of the zeolite carries 0.49wt%.
Pt and H ⁺ were supported. Pt added from above
It was found that almost all of the Sb was supported on the zeolite (5), and that the previously supported Sb remained supported on the surface layer of the zeolite without disappearing during these ion exchange steps. Using the three types of Sb-Pt-H-zeolites obtained in Production Methods 1 to 3 as catalysts, n-C ₄ H ₉ CHO/tert-
A hydrogenation reaction of C ₄ H ₉ CHO=1/1 (mol/mol) was performed. Prior to the reaction, heat at 500℃ for 3 hours.
_H2 reduction was performed. The reaction was carried out at 70℃ under normal pressure, H ₂ /
The reaction was carried out using C ₄ H ₉ CHO=5/1 (mol/mol). The main product was the corresponding butanol.

[Table] As is clear from the table, the product obtained by manufacturing method-1
Although the 0.56 wt% Sb uniformly/0.50 wt% Pt uniformly supported zeolite contains 0.5 wt% Pt, it does not have any C ₄ H ₉ CHO hydrogenation activity. On the other hand, 0.01wt%Sb surface layer/0.50wt by manufacturing method 2
% Pt uniformly supported zeolite and 0.50wt% Sb surface layer/0.50wt% Pt uniformly supported zeolite produced by production method-3, n-C ₄ H ₉ CHO is selectively hydrogenated and excellent molecular shape selectivity appears. . This is particularly noticeable in Production Method 3, which has a large amount of Sb supported. Unlike Production Method-1, in Production Methods 2 and 3, Sb is supported only on the surface layer of zeolite crystallites, and acts as a catalyst poison to inactivate Pt near the surface layer. In particular, in production method 3, the amount of Sb supported was large, and the Pt in the surface layer was completely poisoned, resulting in it being supported inside the zeolite crystal pores.
It is thought that only Pt acted as an effective active site and exhibited excellent molecular shape selectivity. Example 6 An aqueous solution consisting of 100 g of water and 1.56 g of Al ₂ (SO ₄ ) _{3.18H 2} O was mixed with 81 g of tetrapropylammonium hydroxide (TPAOH), 300 g of colloidal silica (SiO ₂ /H ₂ O=20/80 weight) and Water 170c.c.
In addition to the aqueous solution, a heterogeneous gel-like mixture was obtained. This gel-like mixture was filled into a stainless steel autoclave having an internal volume of 1, and after being sealed, the autoclave was heated and stirred at 160° C. for 3 days. The reaction product was overwashed and dried at 120° C. for 5 hours to obtain about 60 g of a crude white powder solid material. As a result of X-ray diffraction analysis, this solid material was found to be ZSM-
It was found that the zeolite (6) is equivalent to 5.
Furthermore, as a result of compositional analysis using atomic absorption spectroscopy, it was found that the Na content of this zeolite (6) was less than 0.01 wt%, which was only a trace amount. (Comparative Production Method-1) 20 g of the above zeolite (6) was weighed out and calcined in air at 500°C for 5 hours. Results of atomic absorption spectrometry, etc.
It was found that tetrapropylammonium disappeared and H-zeolite was obtained in which H ⁺ was uniformly distributed in the surface and inner layers. (Comparative Production Method-2) 20 g of the above zeolite (6) was weighed out and calcined in air at 500°C for 5 hours. Next, it was suspended in 200 c.c. of an aqueous NaCl solution with a concentration of 2 mol/mole, and stirred for 3 hours while maintaining the temperature of the aqueous solution at 60°C. It was then overwashed, dried at 200°C for 2 hours, and calcined at 500°C for 5 hours. As a result of atomic absorption and Auger electron spectroscopy, a 0.5wt% Na-supported zeolite was obtained in which Na ⁺ was uniformly distributed in the surface and inner layers. (Production method-3) Weigh out 20g of the zeolite (6) above, and add 2mol/
The solution was suspended in 200 c.c. of NaCl aqueous solution with a concentration of 200 c.c., and stirred for 3 hours while maintaining the temperature of the aqueous solution at 60°C. next,
Excess washing was performed, followed by drying at 200°C for 2 hours and baking at 500°C for 5 hours. As a result of atomic absorption and Auger electron spectroscopy, a zeolite with 0.05 wt% Na supported only on the surface layer was obtained. Three types of zeolites obtained in Production Methods 1, 2, and 3 were used as catalysts at 500°C under normal pressure, WHSV = 6.0 (g-raw material/g-catalyst hr ^-1 ), raw material toluene/methanol ratio = 2/1 (mol/ The alkylation reaction of toluene was carried out under reaction conditions of (mol). The results are shown in Table-6.

【table】

[Table] From the above table, the H-zeolite obtained by Production Method-1 showed high activity, but had poor selectivity to para-xylene. ZSM-5 uniformly supported with 0.5 wt% Na obtained by Production Method-2 showed no activity at all.
The 0.05 wt% Na surface-supported zeolite produced by Production Method 3 showed significantly superior performance in selectivity to para-xylene. Na ⁺
This high selectivity is thought to be due to selective poisoning by

Claims (1)

[Claims] 1. An unfired crystalline aluminosilicate zeolite containing organic ions is brought into contact with a solution containing an ionic substance to replace the alkali metal ions, ammonium ions and/or organic ions in the surface layer of the zeolite. The ions are exchange supported and then
After heating and calcining at 300°C to 1000°C to remove organic ions, the calcined zeolite is further brought into contact with a solution containing the ionic substance and another type of ionic substance to remove the alkali metal in the inner layer of the calcined zeolite. 1. A selective multi-species ion introduction method characterized by carrying the different ionic substance in place of ions, ammonium ions and/or organic ions. 2. Bringing an unfired crystalline aluminosilicate zeolite containing organic ions into contact with a solution containing an ionic substance to exchange and support the ions in place of the alkali metal ions, ammonium ions, and/or organic ions in the surface layer of the zeolite. , then
After heating and calcining at 300°C to 1000°C to remove organic ions, the calcined zeolite is further brought into contact with a solution containing the ionic substance and another type of ionic substance to remove alkali metal ions in the inner layer of the calcined zeolite. , a selective multi-species ion introduction crystalline aluminosilicate zeolite, characterized in that said different type of ionic substance is exchange-supported in place of ammonium ions and/or organic ions.