JPS6174647A - Catalyst for isomerizing aromatic hydrocarbon of carbon number eight and its manufacture - Google Patents

Abstract

PURPOSE:To obtain a catalyst excellent in the isomerizing action of aromatic hydrocarbons of carbon number 8 by subjecting a pellet-type, an odd-type or a hollow-type molded body which consists of crystalline aluminosilicate and a binder to the hydrothermal reaction treatment. CONSTITUTION:A pellet-type, an odd-type or a hollow-type molded body which consists of crystalline aluminosilicate and a binder is subjected to the hydrothermal reaction treatment and the binder is crystallized into the crystal of crystalline aluminosilicate to obtain the binderless zeolite. The binderless zeolite is treated with a treatment soln. contg. ammonium ion to introduce ammonium ion thereinto. Thereafter the cation of metal excepting alkali metal is introduced byusing the treatment soln. contg. cation of metallic compd. excepting alkali metal.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides a catalyst for the isomerization of aromatic hydrocarbons and its use!
! Regarding the method of J-building. More specifically, the present invention relates to a binderless zeolite catalyst suitable for isomerizing aromatic hydrocarbons having 8 carbon atoms and a method for producing the same.

(Prior Art) Crystalline aluminosilicate is generally known as crystalline zeolite, and its crystal structure, both naturally occurring and synthetic, consists of four oxygen atoms formed around silicon (Si) arranged at the apex. It is an aluminosilicate hydrate having a structure based on a three-dimensional skeleton of A#0.4 tetrahedron in which silicon is substituted with 5i04 tetrahedron and aluminum (Al) is substituted in place of silicon.

5104 tetrahedron and AβOA tetrahedron are 4.5.6.8.
4-membered ring, 5-membered ring, 6-membered ring formed by connecting 10 or 12 members
membered ring, 8-membered ring, 10-membered ring or 12-membered ring, and these 4.
5.6.8. It is known that the basic unit is a double ring in which 10- and 12-membered rings are overlapped, and that these are connected to determine the skeletal structure of crystalline aluminosilicate.

Inside the fI case structure determined by these connection methods, there is a cavity with 'F constant, and the entrance of the cavity structure is 6.8
．． An aperture consisting of a 10- and 12-membered ring is formed.

The pores formed in the openings have a uniform diameter, and molecules of a certain size or less are adsorbed, and large particles are not adsorbed because they cannot enter the cavities. Such crystalline aluminosilicates are known as molecular sieves 1 due to their action;
In various chemical processes, it is used as an adsorbent, a catalyst for chemical reactions, or a carrier.

In recent years, the combined use of molecular sieve action and catalytic action has been intensively researched in various fields of chemical reactions. This is the so-called molecular shape selective reaction iQ+1+HaI, and S, M
.

As Cs1csery classifies from the aspect of sin, 0
) Only specific reactants can approach the active site; (2) After reacting at the active site, only specific reactants can leave the reaction site; (3) 2.
In molecular reactions, individual molecules can freely move in and out of the reaction field, but there are three types of molecules that cannot react because the transition state is too large (
”Zeolite Chemistry and
Catalysis ″ 8CS Monograp
h 171+ 8C5, Washington
D.C., 1976, p. 680).

This classification was made considering only the catalytic reactions inside the cavities of the crystalline aluminosilicate.

In other words, catalytic reactions on the outer surface of the crystal or on active sites near the outer surface are different from the above-mentioned catalytic action, and since all reactions occur freely, including reactions with small activation energy, the selectivity of the reaction is reduced. .

Therefore, in order to suppress such non-selective reactions on or near the outer surface of the crystal, there is a method of burying the active points by coating the outer surface of the crystal with a compound, or a method of burying the active points by coating the outer surface of the crystal with a compound, or using another method of solid acidity or alkalinity. A method of controlling the solid acidity of the active site has been considered, and the addition of silicone compounds, phosphorus compounds, magnesium compounds, etc. has been proposed.

On the other hand, by controlling the size of the crystal, we can control the ratio between the number of active sites with molecular shape selectivity within the crystal and the number of active sites with shape selectivity on or near the outer surface of the crystal. There are also known methods. For example, when the crystal is made larger, the proportion of active 1PI points within the crystal increases relatively, and the shape selectivity becomes higher. However, according to this method, the approach and/or contact of the reactants with the active site is relatively restricted, resulting in a lower overall reaction activity. On the other hand, if the crystal is made smaller, the proportion of active sites on or near the outer surface of the crystal increases, resulting in a decrease in shape selectivity, but this also increases the chances of the reactants approaching and coming into contact with the active sites. The reaction activity becomes higher because of the relative increase in .

To the crystalline aluminosilicate 7! The charge on the OA tetrahedron is balanced by retaining cations within the crystal. These cations are then ion-exchanged by various methods to become hydrogen type or metal ion exchange type,
It is well known that it functions as a solid acid catalyst.

In natural crystalline aluminosilicate, the cation is a metal cation of Group 1 or Group Ⅰ of the Periodic Table of Elements, but in recent years, organic cations such as tetraargylammonium ions have been used. Synthetic crystalline aluminosilicates containing ions are also known.

Furthermore, in recent years, a method has been disclosed for producing crystalline aluminosilicate from an aqueous reaction mixture consisting essentially of inorganic reaction materials (Japanese Patent Laid-Open No. 15111/1982).

It is expressed as a molar ratio of oxides, 0.8 to 1.5M7
/n0-Ai! 2031.0~100Si02・ZH2
0 (where M is a metal cation, n is the valence of the metal cation, and Z is 0 to 40), and at least as shown in the following table. The present invention relates to a crystalline aluminosilicate having a powder X-ray diffraction pattern exhibiting a lattice spacing, ie, d-distance.

- Kakuichiko Ayouka d (A) [Tato strong 1 work] 7 (Tsuchyu D-11,200.2 3゜10, 1 ±0.2 3゜7, 5
10.1.5 W.

6, 03±0.1 M.

4, 26±0.07 M.

3,86±0. 05 v, s.

3,82±0.05 3゜3,76±0.
05 3゜3, 72±0.05
3°3.642 to 0.055° above! A] An aluminosilicate having a crystal structure characterized by an X-ray diffraction pattern is named TSZ.

” - rV, S, J are the strongest in the relative intensities in the table, “S,
" is strong, "M," is medium fine, "W," is weak, rV, W, J
indicates that it is very weak.

In addition, from the analysis of the measurement results of 2θ (θ is Bragg angle), which has a high shear viscosity, by powder If it belongs to the monoclinic system, the crystalline structure is six-pointed. TSZ from an aqueous reaction mixture consisting essentially only of inorganic reaction materials.
5i02/A7! in the aqueous reaction mixture when preparing 5i02/A7!
It is also possible to control the crystal particle size by controlling the 203 ratio and the Na2O/5i02 ratio (Japanese patent application No. 5
No. 8-30797, No. 5B-46684).

On the other hand, when zeolite catalysts are used industrially, for example in fixed bed or fluidized bed operations such as catalytic solutions of gaseous and liquid feedstocks, particles with a certain shape, e.g. Supplied in pellet type particles and small spherical particles. Generally, the strength of shaped particles varies depending on the size of the constituent particles, the packing structure, the coordination number of the particles, the shape of the particles, etc., and further varies depending on the volume of the pores formed and the radius of the 2+11 pores. In particular, shaped zeolite catalysts are aggregates of crystal particles with various shapes, and the pore structure is a so-called binary pore structure, consisting of micropores possessed by the crystal particles themselves and macropores formed between the crystal particles. Ru. However, such crystal grains usually have little bonding force, and are molded using some kind of binder to give the pellet strength. In this case, the gas phase reaction is generally carried out at a large space velocity, and in the liquid phase reaction of heavy oil, diffusion from the catalyst surface is limited, so almost only the outer surface of the catalyst particles is used ( In U.S. Patent No. 3.966.644 this expansion & limit is approximately 1
/1.20 inch), it is desirable to increase the area of the active zeolite catalyst surface as much as possible. These traditional requirements are
This problem can be solved by using a binderless zeolite (Japanese Patent Application No. 39721/1983) consisting essentially of crystalline aluminosilicate.

In addition, although the isomerization reaction of aromatics using a catalyst has been widely known, due to the high industrial importance of p- or 0-xylene, the isomerization reaction of Cδ aromatics has not been studied in particular. , many improved methods have been developed.

(Problem that the invention attempts to solve) Generally, ethylbenzene contained in raw materials has a small difference in boiling point from p- and m-xylene, and it is difficult to separate and recover ethylbenzene by strawberry distillation. Since a large amount of energy is required, it is preferable to convert ethylbenzene to other easily separated hydrocarbons, and it is desirable to suppress the loss of xylene during this conversion reaction.
The milder the operating conditions for the isomerization step, the more convenient it is from the viewpoint of operating costs and the like. For this purpose, zeolites such as so-called ZSM-5 and mordenite have conventionally been used as catalysts. However, when these catalysts are used, (1) increasing the amount of ethylbenzene converted significantly increases the amount of xylene loss; (2) increasing the amount of ethylbenzene converted requires a high reaction temperature; ■ The amount of p-xylene produced is not sufficient, and ■ The crystal size of the zeolite catalyst is only effective within a specific range, and the production of the catalyst is complicated because it requires the inclusion of multi-component metals. This has many drawbacks, such as the high cost of the catalyst.

The inventors of the present invention, as a result of intensive studies to solve the above two drawbacks, have discovered that a certain range of binderless zeolites are particularly effective in the conversion reaction of C8 aromatics, and have arrived at the present invention.

Therefore, the first object of the present invention is to provide an excellent catalyst for the isomerization of aromatic hydrocarbons having 8 carbon atoms.

A second object of the present invention is to provide a binderless zeolite that is excellent as a catalyst for the isomerization of aromatic hydrocarbons having 8 carbon atoms.

A third object of the present invention is to provide a method for treating binderless zeolite to produce an excellent binderless zeolite catalyst for the isomerization of C8 aromatic hydrocarbons.

(Means for Solving the Problems) The above-mentioned aspects of the present invention are such that the binder is crystallized by subjecting a pellet-shaped, irregular-shaped or hollow-shaped molded body comprising a crystalline aluminosilicate and a binder to a hydrothermal reaction treatment. A binderless zeolite formed by crystallizing aluminosilicate crystals, wherein the secondary pores of the binderless zeolite have a pore radius in the range of 75 to 75,000 as determined by mercury pressure method. , the average pore radius is in the range of 1000 to 15,000, 25% or more of the pore volume is included in the range of 120% of the average pore radius, and the pore volume is 0.2 to 15,000. 1.0cc/g,
and (2) a binderless zeolite in which at least a part of the exchangeable cations of the crystalline aluminosilicate of the binderless zeolite is replaced by a cation other than an alkali metal, and a method for producing the same.

The aromatic hydrocarbon having 8 carbon atoms in the present invention is one that is subjected to isomerization, and specifically means ethylbenzene and xylene.

In the present invention, binderless zeolite is used as a catalyst for isomerizing aromatic hydrocarbons having 8 carbon atoms.

This binderless zeolite is different from conventional catalyst molded products that are formed by kneading catalyst particles and a binder.The binder not only crystallizes and acts as a catalyst, but also controls the secondary pores of the binderless zeolite. Therefore, it acts extremely effectively as a catalyst for the isomerization of aromatic hydrocarbons S having 8 carbon atoms. As the crystalline aluminosilicate forming the binderless zeolite used in this case, the above-mentioned TSZ and mordenite are particularly preferred.

In the present invention, it has not been theoretically elucidated what kind of secondary pores are particularly effective for the isomerization of aromatic hydrocarbons having 8 carbon atoms, but if the pore radius is 75 to 75,
000 people, the average pore radius is 1,000-
15,000, and 25% or more of the pore volume is preferably within 120% of the average pore radius.

In addition, the pore size is 0.2 gg/g to 1. occ7g is preferred.

The TSZ crystalline aluminosilicate is characterized by an X-ray diffraction pattern obtained by conventional powder X-ray diffraction. That is, the diffraction line at 2θ-14,7° (d-6,03 people) is a single line, and the 2θ
-23° (d=3.86 people) and 2θ-23,3°
(d=3.82) The two diffraction lines are clearly separated, which greatly differs from the crystal structure of the conventionally proposed crystalline zeolite. Such a specific X-ray diffraction pattern is caused by the fact that the lattice spacing of the synthetic aluminosilicate undergoes significant changes due to changes in the substituted cations, especially changes to the hydrogen ion type, changes in the 5i02/A7!203 ratio, etc. It's not a thing.

Such a method of synthesizing TSZ is described in JP-A-58-45111.

The outline of the manufacturing process of the binderless zeolite catalyst according to the present invention is as follows.

■Process of manufacturing raw material powder ■Process of manufacturing aluminosilicate gel for binder.

■Process of kneading and molding raw material powder and binder.

■The process of drying or firing the molded product.

■Process of hydrothermally treating molded products.

■Process of ion-exchanging the exchangeable cations of the synthesized binderless zeolite.

■ If necessary, the step of ion exchange and/or the step of performing calcination after ion exchange.

The raw material powder used in the present invention means a pre-synthesized crystalline aluminosilicate. As the pre-synthesized crystalline aluminosilicate used as such raw material powder, it is preferable to use one selected from TSZ crystalline aluminosilicate and mordenite, or a mixture thereof; Crystalline aluminosilicates such as ZSM
You can also add -5.

The above-mentioned mordenite used in the present invention is distinguished from naturally occurring mordenite and is classified as synthetic mordenite or large boat resin, and its crystals have lattice constants of a-18 and 13. It belongs to the orthorhombic system, b = 20.49 people, c = 7.52 people, and its pores are composed of 12 oxygen rings with a pore radius of 6.1'11.0 people, and an 8-membered channel. It has a pore radius of 2.9 x 5.7 channels consisting of oxygen rings.

As for the pre-synthesized crystalline aluminosilicate used in the present invention, it is sufficient to use the unfired as-synthesized one, and furthermore, it does not need to be in a completely crystalline form, but may be simply a pre-crystallized IJ. , an aluminosilicate exhibiting an X-ray diffraction pattern close to amorphous can also be used. In particular, it is preferable to use a crystalline aluminosilicate with a small particle size as the raw material powder, since it is possible to obtain a binderless zeolite with excellent activity and strength. Furthermore, in the production of raw material powder, a mineralizing agent such as NaCQ may be added for the purpose of improving the fluidity of the gel.

TSZ crystalline aluminosilicate is a silica source, an alumina source,
containing an alkali source, water and a neutral salt of an alkali metal,
The aqueous reaction mixture is prepared from an aqueous reaction mixture consisting essentially of inorganic reactants, and the composition of the aqueous reaction mixture, expressed in molar ratios of oxides, is as follows:

5i02/AI! 203” 10~13ONa20/
5i02 0.01~0.5(Na20+M2/n
o)/S 1020.03~0.3 H20/ (Na20+M2/n0) 150~800 is a metal cation selected from lithium, sodium, barium, calcium and strontium, and n
is the valence of the metal cation and X- is the ion of the salt of the precipitation aid and/or mineralizer. M2/nO
and Na2O are free M7/nO and Na2O, respectively.
and is generally in the form of interpolate salts, such as aluminates, silicates, etc., which are effective in hydroxide and zeolite synthesis. Moreover, the above-mentioned "free Na2O" can be adjusted by adding aluminum sulfate, sulfuric acid, hydrochloric acid, nitric acid, or the like.

A TSZ crystallizing aluminosilicate can be produced by heating and maintaining the aqueous reaction mixture prepared as described above at the crystallization temperature until crystals form. The manufacturing conditions are, for example, about 10° C. at about 20° C. to about 230° C. under self-pressure.
This is achieved by maintaining it for hours to 10 days.

In addition, the TSZ crystalline aluminosilicate has a particularly high concentration of 5i02/A7!203 molar ratio and N in the composition of the aqueous reaction mixture.
By changing the a2O/5i02 molar ratio, the crystal grain size of the produced crystalline aluminosilicate changes. That is, 5i02/AI! of the aqueous reaction mixture! , by changing the Na20/Si○2 molar ratio according to the 203 molar ratio.
After making sure that the 2O/5i203 molar ratio is the same,
When changing the molar ratio of 5i02/A#203,
A crystalline aluminosilicate having approximately the same grain size is produced. On the other hand, the Na2O/5i203 molar ratio is 1~
By varying the diameter within a range of 15, it is possible to produce a crystalline aluminosilicate having a desired crystal grain size within a range of about 0°1 to about 10μ.

Next, a method for producing mordenite as the raw material powder used in the present invention will be explained.

Mordenite that can be used in the present invention can be produced by the above-mentioned known method, but preferably contains a silica source, an alumina source, an alkali source, water, and if necessary a neutral salt of an alkali metal. It is prepared from an aqueous reaction mixture consisting of various inorganic reactive materials. Its composition expressed in molar ratio of oxides is as follows.

5i0z/8n203 16~35Na20/5
i02 0.05~0.5(Na20+M2/nO
)/5i02 0.05-0.5 H20/ (Na20+M77nO) 150-800 In the Ichihi formula, M is from Groups 1 and 2 of the Periodic Table of Elements, preferably from lithium, sodium, barium, calcium and strontium. is the metal cation selected, and n is the valence of the metal cation. M2/n
o and Na2O are free M2/no and Na2, respectively.
O, generally in the form of interpolate salts, such as aluminates, silicates, etc., which are effective in hydroxide and zeolite synthesis. In addition, the above [M separation NazOJ is
It can be adjusted by adding aluminum sulfate, sulfuric acid, hydrochloric acid, nitric acid, etc.

Therefore, high silica mordenite can be produced by heating and maintaining the above aqueous reaction mixture at the crystallization temperature until crystals form. Such manufacturing conditions include, for example, autogenous pressure at about 20°C to about 230°C for about 10 hours to
This is achieved by maintaining it for 10 days.

The aluminosilicate gel as a binder used in the present invention can be obtained by aging the aqueous reaction mixture, which is a precursor of the raw material powder, for a certain period of time, and then filtering it to crystallize the aluminosilicate gel or molded product. After washing until the composition is within a range that does not cause excessive crystallization, drain thoroughly to reduce the moisture content (dry basis) to approximately 65.
It is preferable to adjust the amount from 25% by weight to about 95% by weight so as not to require the addition of water during kneading.

The preferred composition of the aqueous reaction mixture for producing the aluminosilicate gel described in Section 2, expressed in molar ratio of oxides, is Na20/A12203 ≧ 1.2.
Si02/Al2O310~100 Na20/5i02 o, o1~o, 20H20
/5i02 5 to 150, preferably Na2O/A7!203 ≧ 1.5s i02/
A7!203 15~8ONa 20/S i 02
0. 02~0. 15820/5i02
10 to 130, but especially when mordenite is used as the raw material powder, Si
o2. /A7!203 molar ratio is 10-60, preferably 15-40. Here, Na2O is the same as in the above case.

The amount of alkali in the binder is an important factor for producing binderless zeolite.

In other words, if the amount of alkali is low, crystallization may take a long time or may remain amorphous, and if the amount of alkali is large, large crystals may be formed due to excessive crystal growth. It is preferable to keep the composition within a specific range since this may cause the formation of other undesirable crystal phases or powdering.

Another important factor for a binder is to impart strength to the molded pellets, but this is strongly influenced by the adhesiveness, moldability, and drying shrinkage force of the aluminosilicate gel. When preparing, it is preferable to form colloidal particles with good dispersibility.

In the present invention, a small amount of a neutral salt of an alkali metal can be added as a precipitation aid if necessary, but it is preferable not to add it if there are no problems in handling the gel such as stirring or post-treatment. There is also.

In the present invention, when the raw material powder and aluminosilicate gel produced as described above are kneaded and molded into pellets, the raw material powder prepared in advance is mixed with 20 to 80% by weight, and the aluminosilicate gel 80 is prepared to a rough composition. By kneading and molding ~20% by weight,
Strong pellets are obtained, and by hydrothermal treatment, a substantially crystalline aluminosilicate with unique secondary pores formed between crystal grains and with sufficient strength for practical use. A binderless zeolite consisting of

If the mixing ratio of the above raw material powder is less than about 20% by weight, the strength of the pellets tends to increase, but it is difficult to obtain stable physical properties such as shrinkage of the pellets and the occurrence of cracks due to drying or firing. Sometimes,
Furthermore, if the mixing ratio of the raw material powder is more than about 80% by weight, sufficient pellet strength may not be obtained, so in order to produce with good reproducibility, it is preferable to use the above mixing ratio.

Further, when the particle size of the raw material powder is relatively small, pellets with high strength tend to be obtained, and the strength is often maintained even after hydrothermal treatment, which is preferable. On the other hand, when the particle size of the raw material powder is relatively large, the strength of the pellet itself is not much different from that described above, but by performing hydrothermal treatment, the strength decreases (in the φ direction, which is not preferable).

Note that the compositions of the pre-prepared raw material powder and the aluminosilicate gel used as the binder may be different, but it is best to make them approximately the same, especially for binderless materials with good catalytic performance. It is preferable because zeolite can be obtained.

When molding the above-mentioned kneaded product, a molding aid can be used. The molding aid is preferably an organic type that is known and used in ordinary extrusion molding and is burnt out during post-treatment. However, when considering the final strength of the pellets, it is preferable to add the molding aid to the minimum necessary level, or to not add it at all.

In addition, if there is an excess or deficiency in the amount of alkali in the aluminosilicate gel, it is preferable to adjust it to a predetermined value before or during kneading.

The molded beret 1 is coated with a strip (!1, for example, after sufficient air drying,
Heating at 50-200'C2, preferably 1'00-150°C. If the strength of the pellets is sufficient after drying, there is no need for calcination, but if the strength is not sufficient or if a molding aid is used, the temperature is 400-700°C2, preferably 400°C.
It is preferable to bake at 50 to 600°C. Binderless zeolite can be produced by hydrothermal treatment even in a dry state and after calcination.

The alkaline form of the molded body is an important element for producing the binderless zeolite in the present invention. That is,
If the amount of alkali is small, crystallization may take a long time,
It may remain amorphous. In addition, alkaline deficiency can be added externally to cause crystallization, but in this case, crystallization tends to occur from the surface of the molded product, and crystallization of the molded product does not proceed uniformly, causing powdering. This is not preferable because it may lead to a decrease in the strength of the molded product.

On the other hand, if the amount of alkali is excessively large, the time required for crystallization will be shortened, but it may grow into large crystal particles, weakening the strength of the molded product, or causing other crystal phases to form. I don't like it.

Furthermore, an important factor for producing the binderless zeolite in the present invention is the ratio (weight ratio) between the solution and the molded body during hydrothermal treatment.

As the hydrothermal reaction progresses, the composition of the molded body or binder becomes closer to that of zeolite, and Na2O/A7
! 203 molar ratio approaches 1.

Therefore, as the hydrothermal reaction progresses, the remaining Na2O equivalent comes into the solution at 111. Therefore, when the composition of the molded body is constant, if the amount of solution is small, the alkaline concentration of the solution will be high, and if the amount of solution is large, the alkaline concentration of the solution will be relatively low.

Therefore, the composition of the molded body should be within the above range, and H20
/ By setting the weight M of the molded product to 10 or less, preferably in the range of 1 to 9, binderless zeolite 1- can be easily synthesized without adding a mineralizing agent, especially sodium salt, during hydrothermal treatment. can do.

When synthesizing a binderless zeolite catalyst, the shape of the solid used in the hydrothermal reaction is not particularly limited, but pellets are particularly preferred due to ease of molding or lack of efficiency when used as a catalyst. type, irregular type (
PolylObal), hollow cylindrical type (ho ] I o
The diameter of the tube is preferably about 1 to 5 mm.

The hydrothermal reaction of the present invention can be carried out by the method disclosed in JP-A-58-45111.

Conditions for crystallization are not particularly defined, such as maintaining heating at a crystallization temperature until crystals are formed, but for example,
The temperature is about 120°C to 230°C, and the time is about 10 hours to about 10 days.

Preferred crystallization conditions are dry or calcined Bereso J.
Generally speaking, the higher the temperature, the shorter the time, and the lower the temperature, the longer the time, although it depends on the composition ratio of water/8 liquid and the weight ratio of the pellets.

However, excessively low or excessively high temperatures are undesirable because they may become amorphous or form undesirable crystals. When hydrothermally treating the pellets, stirring is not particularly necessary, but it is preferable to stir at least in order to achieve homogeneous heat transfer throughout the system.

In addition, the aqueous solution used may be water alone if the composition ratio of the pellets themselves has been adjusted in advance to allow crystallization, but mineralizing agents may be used to speed up the crystallization rate or shorten the time. You may do so.

In particular, this selection is preferably determined based on the degree of growth of crystal particles, the physical properties thereof, or the catalytic performance.

The pellets are placed in a closed container, such as an autoclave made of iron, stainless steel, or lined with Teflon, together with water or an aqueous solution and allowed to crystallize under autogenous pressure.

The thus obtained binderless zeolite consisting essentially of crystalline aluminosilicate can be washed with water and subjected to post-treatment while dry, but may be calcined if necessary.

Drying is carried out at 50-250°C, preferably 100-200°C.
This is carried out for 10 minutes or more, preferably 30 minutes to 48 hours.

Firing is performed at 300 to 700°C for 10 minutes or more, preferably at 400°C.
It is carried out at ~600°C for 30 minutes to 24 hours.

The binderless zeolite obtained in this way, consisting essentially only of crystalline aluminosilicate, has a sharp distribution of macropores formed between crystal grains in the thousands. Has strength.

In the binderless zeolite catalyst of the present invention, which is substantially made of crystalline aluminosilicate, its pore size and pore volume can be adjusted by adjusting its manufacturing method. The total pore volume measured by the injection method was 0.2 cc/g/l, 0,007 g, and the average pore radius was 1°000 to 15,000 in the range of 75 to 75,000. Preferably, 25% or more of the pore volume is within a range of ±20% of the average pore radius. Further, the crystal particles are preferably composed of relatively small crystal particles from the viewpoint of strength as a catalyst.

Although a method for measuring the radius of secondary pores in binderless zeolite is not necessarily established, the average radius can be estimated by the so-called mercury intrusion method. In the present invention, the radius indicating the cumulative value of 172 pore volumes of the total pore volume obtained by this mercury intrusion method is
Defined as the average pore radius, the size of the pore radius is not only related to the actual catalyst surface area, but also affects the diffusion rate of reacting molecules and generated molecules, from the viewpoint of catalytic activity. It is important because

The shape and size of the raw material powder particles used in the present invention and the shape and size of the constituent particles of the binderless zeolite produced according to the present invention are measured by microscopic observation.

In the present invention, the size of raw material powder or crystal grains is expressed as (length of short axis) x (length of long axis).

For the short axis of the raw material powder and crystal particles, if the cross section of the short axis is circular or elliptical, measure the long axis, or if the cross section is angular, measure the long axis. The parts corresponding to the sides were measured.

The long axis of the raw material powder and crystal particles was determined by measuring the longest diameter or longest side of the cross section of the portion corresponding to the long axis.

As mentioned above, in order to judge the morphology of the raw material powder and crystal particles, at least 100 particles, usually 200 to 300 particles per ffl, are
Microscopic observation of UfXI can be performed.

In the present invention, the binderless zeolite thus obtained is further subjected to ion exchange treatment in order to be used as a catalyst for isomerization of aromatic hydrocarbons having 8 carbon atoms. The exchange ions in this case include ammonium ions, hydrogen ions, and divalent and trivalent metal cations, such as transition metal ions and rare earth metal ions, with ammonium ions being particularly preferred. By exchanging the cations of the crystalline aluminosilicate forming the binderless zeolite with these ions, solid acidity can be imparted to the binderless zeolite of the present invention.

This is carried out by treating unexchanged binderless zeolite with an aqueous solution containing the ions to be introduced, as is known in the art. In this case, particularly good results can be obtained when cations of metals other than alkali metals are introduced simultaneously with ammonium ions. In this way, as a method for simultaneous introduction of ammonium ions and other ions, it is possible to carry out multiple treatments separately with an aqueous solution containing the ions to be introduced, It is also possible to treat with an aqueous solution containing . As such a treatment liquid, a treatment liquid in which an ammine complex made of a metal other than an alkali metal is dissolved can be particularly preferably used.

In particular, when treated with ammine complex ions of palladium and/or platinum, the isomerism (1
? It shows extremely good performance as a catalyst for commercial use.

In the present invention, after the above-mentioned ion exchange, or between ion exchanges when ion exchange is performed multiple times, calcination treatment can be performed following water washing and drying. This calcination treatment eliminates organic substances and other unnecessary substances that may be mixed in during processing, improving the performance as a catalyst, and at the same time improving the reproducibility of the catalytic performance of the synthesized binderless zeolite. be able to.

The above calcination can be performed by a known method, but although the reason is not necessarily clear, it is also effective as a catalyst for isomerization of aromatic hydrocarbons having 8 carbon atoms, especially when it is obtained in the presence of steam. fl binderless zeolite
I can do that.

In the present invention, in addition to ion exchange, components such as iron, cobalt, nickel, chromium, manganese, molybdenum, tungsten, vanadium, rhenium, platinum, rhodium, ruthenium, and palladium can also be supported by impregnation.

The conversion conditions for the isomerization reaction of the present invention are temperature = 250°C to 5°C.
00℃, atmospheric pressure ~60kg/cn+, flow rate expressed in weight hourly space velocity (WHS V) 0.5~50W/H/
W, hydrogen/raw material hydrocarbon ratio: 0 to 10 mol 1 mol, more preferably temperature: 300°C to 430°C, pressure crab atmospheric pressure to 30kg/-1 flow rate is weight hourly space velocity (WH8
M) is 2 to 30 W/H/W, and the hydrogen/raw material hydrocarbon ratio is 20.5 to 5 mol/mol.

When using a raw material containing ethylbenzene as a C8 aromatic hydrocarbon, not only can ethylbenzene be isomerized to xylene with higher efficiency than ever before, but also the p-xylene equilibrium attainment rate is high. It is possible to achieve an isomerization process that is particularly advantageous for the production of baraxylene. Moreover, compared to conventional catalysts, the loss rate of xylene can be suppressed to a low level even under conditions where ethylbenzene can be sufficiently removed.

The isomerization method of the present invention having the above-mentioned characteristics can be achieved under relatively mild conditions, and in particular, the reaction temperature can be lowered than in the conventional case, so the energy cost required for equipment and operation can be reduced. It can also be reduced.

(Effects of the Invention) The binder jnos zeolite obtained by the present invention has good overall crystallinity, and the part where the binder is crystallized is so integrated that it cannot be distinguished from the crystals of the raw material powder in a micrograph. It is a zeolite structure. In addition, since the secondary pores are controlled to meet certain conditions, it has sufficient strength for practical use, and can be used to convert ethylhenzene into industrially useful xylene and other compounds with high efficiency. Xylene is selected from among hydrocarbon raw materials containing ethylhenzene and xylene because it can be converted into hydrocarbons, isomerized at the same time, and the loss rate of xylene can be suppressed. It is extremely effective when recovering materials.

The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Margin below (Example) Example 1 12.5g of sodium aluminate (AA203; 35.7% by weight, Na 20i29 in 292.5g of pure water)
．． This was dissolved in 273°8 g of Japanese Industrial Standards No. 3 water glass (Na20; 9.83 wt%, 5
i02: 28.6% by weight (hereinafter abbreviated as No. 3 water glass) and 135.7 g of pure water (liquid A) to be added to a water glass solution to make a homogeneous solution.

Next, add 83.7 g of concentrated hydrochloric acid (35%) and 175°5 g of pure water.
An aqueous hydrochloric acid solution (solution B) was prepared.

Furthermore, sodium chloride solution (48.6 g of sodium chloride,
Prepare 607.4 g of pure water and add liquid A and B while stirring.
liquid was added to obtain an aqueous reaction mixture.

The prepared aqueous reaction mixture was charged into a SUSM autoclave, heated and maintained at 185° C. for 48 hours under autogenous pressure. Stirring was performed at 300 rpm.

The crystallized solid product was separated by filtration and after washing with water 110
Dry at °C for 16 hours. Powder X-ray diffraction analysis of this product revealed that it was a TSZ crystalline aluminosilicate. Further, when the size of the crystal grains was measured by electron microscopy, the short axis was about 0°4 μm and the long axis was about 1.7 μm.

(Preparation of aluminosilicate gel) Aluminum sulfate (A7!203; 15.4%)
An aqueous solution of aluminum sulfate containing 65.9 g, 3.8 g of 95% sulfuric acid, 420 g of pure water, 606 g of No. The resulting aluminosilicate gel was filtered and washed with approximately 71% pure water, drained, and the water content was measured to be 86.4% by weight (dry basis). )Met.

(Preparation of pellets) 75 g of TSZ powder obtained by the above operation, 551 g of aluminosilicate gel and 0.73 g of sodium hydroxide
g was kneaded with a kneader while drying until the moisture content reached a moldable level, and molded into pellets with an outer diameter of 1.5 mm using an extruder.

After drying the pellet at about 110°C for 16 hours, a portion was taken out and chemically analyzed, and it was found that 5i02 was 85.1% by weight.
Aff203 was 5.62% by weight, Na2O was 4.74% by weight, and loss on ignition at 900°C was 3.95% by weight. Expressed in terms of oxide composition ratio (molar ratio), Na2O/Aj! 203=1.39 Si02/Aj! 203=25.7.

(Crystallization of the pellet) After further calcining the pellet at 600°C for about 3 hours, 87.5
g was taken out and put into 11 SUS autoclaves together with 613 g of pure water, and crystallized at 181° C. for 64 hours. Stirring was performed at a rotational speed of 15 rpm.

After the temperature was lowered, the pellet was taken out from the autoclave, washed, dried, and subjected to powder X-ray diffraction analysis to obtain a diffraction pattern of a highly purified substantially TSZ crystalline aluminosilicate.

Further, it was also clear from electron microscopic observation that most of the material was a crystalline substance and that the aluminosilicate gel was crystallized.

Furthermore, when the pore distribution was measured by mercury intrusion method, the average pore radius was 2200, and the total pore volume was 0. 495 cc
/g, and it was found that 31% of the total pore volume was contained within 120% of the average pore radius.

The breaking strength of this pellet after drying is] 8 kg/3
mm, and showed sufficient strength for practical use.

Examples 2 and 3 Preparation of crystalline aluminosilicate (TSZ) powder using concentrated hydrochloric acid of 75.5 g (for Example 2) and 89.1 g
It was prepared in the same manner as in Example 1, except that g (in the case of Example 3) was used.

Powder X-ray diffraction analysis of the obtained solid product revealed that
In both Examples 2 and 3, TSZ crystalline aluminosilicate was used. In addition, when the size of the crystal was measured by microscopic observation, the short axis of Example 2 was approximately 0.7 μm.
, the long axis was about 1.9 μm, and in the case of Example 3, the short axis was 0.2 μm and the long axis was about 0.6 μm.

In this case, the aluminosilicate gel and pellets were prepared in a similar manner to Example 1. Chemical analysis of the pellets yielded the following results.

Example 2 (wt%) Si02 8ff203 Na2O scorching w1. Amount 8
4.8 5.74 4.46 4.02Na20/A
#203=1.28 si02/Aβ203=25.1 Example 3 (wt%) sio2 A7!203 Na2O ignition loss 85.
4. 5.59 4.53 3.97Na20/Aj
! 203=1.33 Si02/Aj! 203=26.0 The pellets were crystallized in the same manner as in Example 1. Powder X-ray diffraction analysis of the product after crystallization was performed to obtain a substantially TSZ diffraction pattern of high purity. Furthermore, electron microscopy also revealed that most of the material was crystalline, and it was clear that the aluminosilicate gel had crystallized.

Furthermore, the pore distribution and fracture strength were measured by mercury porosimetry, and the results were as follows.

Example 2 Example 3 Total pore volume (cc/g) 0.652 0.346
Pore volume (%”) within 120% of the average pore radius 25.2.34.0 Average pore radius (people), 7510 124-0
Breaking strength (kg/3mm) 1.1 3.1 Example 4 29.6g of aluminum sulfate (A1203; 15.4% by weight) was dissolved in 194.8g of pure water, and 2
2.5 g of concentrated sulfuric acid (95% by weight) was added to cleave the aluminum sulfate aqueous solution (liquid A). On the other hand, 280; 8g
142 g of pure water was added to No. 3 water glass and stirred to obtain a water glass solution (Liquid B). Next, liquid A and liquid B were added to a sodium chloride aqueous solution (NaC7!; 86.2 g, H2O;
56°Ig) to prepare an aqueous reaction mixture.

The prepared aqueous reaction mixture was charged into a SUS autoclave, heated, and maintained at 180°C under autogenous pressure for 40 hours. After crystallization, the solid product is separated by filtration,
After washing with water, it was dried at 110°C for 16 hours. Powder X-ray diffraction analysis of this product revealed that it was a TSZ crystalline aluminosilicate.

In addition, the composition ratio (molar ratio) determined from chemical analysis is Na2O
/Aj2203=0.91 S10:z/A6:zo3=27.8, and the size of the crystal grains measured by electron microscopy is that the short axis is about 0.
The diameter was 3 μm, and the major axis was approximately 1.5 μm.

50 g of TSZ powder and 362.3 g of aluminosilicate gel (water content: 86.2% by weight) obtained by the above operations.
) was kneaded with a kneader while drying until the water content reached a moldable level, and molded into pellets with an outer diameter of about 1.5 fl using an extruder.

The aluminosilicate gel used here was 59.8 g of aluminum sulfate and 36.8 g of 95% sulfuric acid.

An aqueous solution of aluminum sulfate containing 389.6 g of pure water, 1.6 g of No. 3 water glass 5G, and a water glass aqueous solution containing 284.0 g of pure water were mixed with an aqueous solution of sodium chloride (32.
4 and 1112 g of pure water> and mixed with stirring for about 30 minutes, the resulting aluminosilicate gel was filtered, washed with about 742 g of pure water, and thoroughly drained. The composition ratio (molar ratio) determined from chemical analysis of this aluminosilicate gel is: Na2O/AA203=2.2 Si02/Aj! 203=27.3 Na20/5i02=0.08.

The molded pellet was dried at about 110°C for 16 hours, and then further calcined at 600°C for about 3 hours. Next, 50g of pellets after calcining were taken out, put into an autoclave with 690g of pure water and 25g of sodium chloride, and heated to 180℃ for 4 hours.
Crystallization was carried out for 0 hours. After the crystallization operation was completed, the pellets were filtered, washed with pure water, and dried at 110°C. When a portion was taken and powder X-ray diffraction analysis was performed, it was found that TS was essentially
It was a binderless zeolite consisting of Z crystalline aluminosilicate.

Furthermore, when the pore distribution was measured by mercury intrusion method, the total pore volume was 0.550 cc/g, which was 120% of the average pore radius.
It was found that 28.7% of the total pore volume was included in the % range and that the average pore radius was 1.7'50.

Further, from the observation results of electron micrographs, it was found that it was composed of relatively small crystal grains. The breaking strength of the obtained binderless zeolite is 2.5 kg/3
mm, and had sufficient strength for industrial use.

Below is a margin Example 5゜9.3g of sodium aluminate (in 292.5g of pure water)
A7! :zo3; 35.7% by weight, Na2O; 29.
1% by weight) was dissolved and added to a water glass solution containing 273.8 g of No. 3 water glass and 135.7 g of pure water to form a homogeneous solution. Next, the obtained /8 solution was combined with a hydrochloric acid solution (80.6 g of 35% hydrochloric acid, 175.5 g of pure water) and a sodium chloride solution (48.6 g of sodium chloride, 4.03.7 g of pure water).
g) to obtain an aqueous reaction mixture.

The prepared aqueous reaction mixture was placed in an autoclave, heated, and maintained at 180° C. for 28 hours at autogenous pressure.

The crystallized solid product was separated by filtration and washed with water.
It was dried at ℃ for 16 hours. Powder X-ray diffraction analysis of this product revealed that it was a TSZ coagulable aluminosilicate.

The composition ratio (molar ratio) determined from chemical analysis is Na2O/A#203=0.94 Si02/A#203=37.1.

In addition, the size of the crystal particles measured by electron microscopy was approximately 0.6 m in the minor axis and approximately 1.8 μm in the major axis. 50 g of TSZ powder and aluminosilicate gel obtained by the above procedure 312.5g (moisture content 84.0% by weight)
The mixture was kneaded with a kneader while drying until the water content reached a moldable level, and molded into pellets with an outer diameter of about 1.5 nm using an extruder.

The aluminosilicate gel used here was 38.6 g of aluminum sulfate, 32.0 g of 95% sulfuric acid, and 330 g of pure water.
aluminum sulfate aqueous solution and No. 3 water glass 476.2
g, 240.8 g of pure water in a water glass aqueous solution was added to a sodium chloride aqueous solution (27.2 g of sodium chloride, 942 g of pure water).
8 g) and mixed with stirring for about 30 minutes, the aluminosilicate gel formed was filtered.
After washing with pure water, the water was thoroughly drained. The composition ratio (molar ratio) determined from chemical analysis of this aluminosilicate gel is: Na2O/Al203=2.3 Si02/A7!203=33. 5 Na20/S 1o2=o, 07.

After drying the molded pellets at approximately 110°C,
It was calcined at 00°C for about 3 hours. Next, pellet 5 after calcination
0 [! The sample was collected, placed in an autoclave with 300 g of pure water, and crystallized at 180° C. for 40 hours. After the crystallization operation was completed, the pellets were filtered and washed with pure water.
It was dried at 10°C.

When one portion was taken and subjected to powder X-ray diffraction analysis, it was found to be essentially binderless zeolite 1-, which is TSZ crystalline myrminosilicate.

Furthermore, when the pore distribution was measured by mercury intrusion method, the total pore volume was 0.570 cc/g, which was 120% of the average pore radius.
% range includes 27.5% of the total pore volume and that the average pore radius is 4.500 pores.

Also, electronic microscope fi! / From the results of mirror observation, it was confirmed that it was composed of relatively small crystal grains. The breaking strength of the obtained binderless zeolite is 1.6 kg
/3 mm, which was strong enough to withstand industrial use.

Comparative Example 1 17.7g of aluminum sulfate (Ai1!203; 15.4% by weight) was dissolved in 194.8g of pure water, and 16.9g of concentrated sulfuric acid (95% by weight) was added thereto. An aluminum aqueous solution was prepared (liquid A). On the other hand, 280.8
142 g of pure water was added to No. 3 water glass and stirred to obtain a water glass solution (Liquid B). Next, solutions A and B were mixed with an aqueous sodium chloride solution (NaCj!; 86.2 g, H2O;
556°Ig) to prepare an aqueous reaction mixture.

The prepared aqueous reaction mixture was charged into a SUS autoclave, heated, and maintained at 180° C. for 16 hours under autogenous pressure. After the crystallization was completed, the solid product was separated by filtration, washed with pure water, and dried at 110° C. for 16 hours. Powder X-ray diffraction analysis of this product revealed that it was a TSZ crystalline aluminosilicate. Also, the composition ratio (molar ratio) determined from chemical analysis is Na2O/AI! , 203=1.30 Si○2/A#, 203=44.2, and the size of the crystal grains measured by electron microscopy is about 3.5 in the minor axis.
μm, and the long axis was approximately 10 μm.

50 g of TSZ powder and 373.1 g of aluminosilicate gel (water content 86.6% by weight) obtained by the above operations
The mixture was kneaded with a kneader while drying until the water content reached a moldable level, and molded into pellets with an outer diameter of about 1.5 fl using an extruder.

The aluminosilicate gel used here was prepared in the same manner as in Example 5. The composition ratio (molar ratio) determined from chemical analysis of this aluminosilicate gel is Na2O/AI! , 203=3.1 Si02/Al2O:5=34.5 Na20/5i02-0.09.

After drying the molded beret 1- at about 110℃,
It was calcined at 00°C for about 3 hours. Next, Peley I after calcination
-50g was collected, 690g of pure water, 24g of sodium chloride.
The mixture was placed in an autoclave with g and crystallized at 180°C for 20 hours. After the crystallization operation was completed, the pellets were filtered, washed with pure water, and dried at 110°C. When a portion was taken and powder X-ray diffraction analysis was performed, it was found that it was essentially TSZ.
It was a binderless zeolite made of crystalline aluminosilicate.

Furthermore, when the pore distribution was determined by mercury porosimetry, the total pore volume was 0.555 cc/g, which was within ± of the average pore radius.
It was found that the 20% range contained 24.1% of the total pore volume and that the average pore radius was 17.000 pores.

Further, from the observation results of electron micrographs, it was found that it was composed of relatively large crystal grains. The fracture strength of the obtained binderless zeolite was very low.

Example 6゜1.62.3g in pure water 24. ．． 9g of aluminum sulfate (A#203; 15.4% by weight) was melted and 18.9g of concentrated sulfuric acid (95% by weight) was added thereto to prepare an aluminum sulfate aqueous solution (Liquid A). On the other hand, 236.6
3 g of 118° pure water was added to a No. 3 water glass of 3 g, and stirred to obtain a water glass solution (liquid B). Next, liquid A and liquid B were added to a sodium chloride aqueous solution (NaCp; 71.8 g, H2O
;463°4g) to prepare an aqueous reaction mixture.

The prepared aqueous reaction mixture was placed in an autoclave, heated at 180°C for 40 hours under autoclave, and then heated to 180°C for 40 hours.
It's VL. After the crystallization is completed, the solid product is filtered into a11 portion,
After washing with water, it was dried at 110°C for 16 hours. Powder X-ray diffraction analysis of this product revealed that it was a TSZ crystalline aluminosilicate. Moreover, the composition ratio (molar ratio) determined from chemical analysis is Na2O/An203=1. ．． 01 S j 02 / A e 203 = 28,3.

50g of TSZ powder and 380g of aluminosolichye 1-gel (moisture content: 86°8% by weight) obtained by the above procedure
The mixture was kneaded while drying with a Ni-Goo until the moisture content reached a moldable level, and the pellets were molded into pellets with an outer diameter of about 1.51 mm using an extrusion molding machine.

The aluminosilicate gel used here was an aluminum sulfate aqueous solution containing 24.9 g of aluminum sulfate, 15.4 g of 95% sulfuric acid, and 162.3 g of O pure water, and a water glass aqueous solution containing 236.6 g of No. 3 water glass and 118.3 g of pure water. was added to 463.4 g of pure water and mixed with stirring for about 30 minutes, and the resulting aluminosilicate gel was filtered, washed with pure water, and then thoroughly drained.

After drying the molded pellets at about 110°C for 16 hours,
As a result of separating one portion and chemically analyzing it, the composition ratio of the pellet (
The molar ratio) was Na2O/Aj2203=2.34 Si02/A7!203=29.2.

This was further calcined at 600°C for about 3 hours. Next, 80 g of pellets after calcining were collected and added to 990 g of pure water.

Place in an autocrepe with 69 catties of sodium chloride,
Crystallization was carried out at 180°C for 40 hours. After the crystallization operation was completed, the pellets were filtered, washed with pure water, and dried at 110°C. One portion was taken and subjected to powder X-ray diffraction analysis.
It was a binderless zeolite consisting essentially of TSZ crystalline aluminosilicate.

Furthermore, when the pore distribution was measured by mercury intrusion method, the total pore volume was 0. It was found that 43% of the total zero pore volume was contained within ±20% of the average pore radius, and that the average pore radius was 1,900.

Further, from the observation results of electron micrographs, it was found that it was composed of relatively small crystal grains. The breaking strength of the obtained binderless zeolite is 2.8 kg73
mm, and had sufficient strength for industrial use.

Example 7゜194,. 14.1. 38.5 g of aluminum sulfate was dissolved in 8 g of pure water. H concentrated sulfuric acid (95% by weight)
was added to prepare an aqueous aluminum sulfate solution. This was mixed with 280.8 g of No. 3 water glass, 698.1 g of pure water, and 54.5 g of sodium chloride. g was added to the dissolved water glass solution to prepare an aqueous reaction mixture.

Pour the prepared aqueous reaction mixture into an autoclave,
The temperature was raised at about 0.7°C/min, and the heating was maintained at 182°C for 20 hours under autogenous pressure.

The product was filtered off, washed with water and dried at 1&1]0'c. Powder X-ray diffraction analysis of this product revealed that it was a crystalline aluminosilicate exhibiting diffraction patterns of TSZ and mordenite. In addition, the composition ratio determined from chemical analysis (
The molar ratio) was: Na2O/A7!203=0.95 Si02/A7!203=19.8.

Further, the size of the crystal grains measured by electron microscopy was approximately 0.8 μm in the minor axis and approximately 2 μm in the major axis.

50 g of the raw material powder obtained as described above and 324.7 g of aluminosilicate gel were kneaded in a kneader while drying until the moisture content reached a moldable level, and molded into pellets with an outer diameter of approximately 1.5N using an extruder. did.

The aluminosilicate gel used here was prepared in the same manner as in Example 5, except that 61.8 g of aluminum sulfate and 21.8 g of 95% sulfuric acid were used. Silk f2 (molar ratio) determined from chemical analysis of this aluminosilicate gel is Na20/A (1203=2,3S
i O2/Aρ2C)v=23.2Na? O/5i0
2=0.10.

After drying the molded Pereno 1- at about 110°C, it was further calcined at 600°C for about 3 hours. Next, 50 g of the calcined Pereso) was taken out and placed in an autoclave with 690 g of pure water and 48 g of thorium chloride, and heated to 180°C for 40 minutes.
Time crystallization was performed.

After the crystallization process was completed, Peresol was filtered off, washed with pure water, and dried at 110°C. One portion was collected and subjected to powder X-ray diffraction analysis, and it was found that it was essentially crystalline aluminosilicon 1%l.
It was a binderless zeolite consisting of iu.

Furthermore, when the pore distribution was measured using the water TP injection method, the total pore volume was 0.482 cc/g, which was ±2 of the average pore radius.
It was found that the 0% range contained 33.8% of the total i11 pore volume and that the average pore radius was 2,300.

Furthermore, the results of electron microscopy revealed that it was composed of relatively small crystal grains.

The fracture strength of the obtained binderless zeolite was 1.6
kg/3 mm, and its strength was industrially sufficient.

Example 8゜40g each of the sodium type binderless TSZ crystalline aluminosilicate pellets obtained in Examples 1 and 4
, 5 wt% ammonium chloride solution was added to TSZ Pereso 1
A total of 4 ion exchange treatments were carried out at 80° C. using 15 m 4 per gram (each treatment time was 1.5 hours). Next, the ion-exchange product is washed with water and dried at 110°C to obtain an ammonium (NH4) type binder-less TSZ crystal/aluminosilicate material A' (
using TSZ of Example 1) and B' (T of Example 4)
(using SZ) was prepared. Next, the obtained ammonium type TSZ, A' and Bo were each separated by tog and calcined in air at 600°C for 3 hours to form hydrogen (H) type TSZ.
was prepared. These are shown below as catalyst A (TSZ of Example 1).
(Using TSZ of Example 4) and Catalyst B (Using TSZ of Example 4).

The content of Na2O in all of these catalysts was 0.01% by weight or less.

Example 9 Catalyst B obtained in Example 8 was fractionated with
(No. 5) 2 solutions were treated at 80°C for 1 hour, washed with water, dried, and fired in air at 600°C for 3 hours to form a binderless TSZ bond containing 0.82% Ni. A high quality aluminosilicate catalyst was obtained (hereinafter referred to as catalyst C).

Example 10 10g of each of the catalysts A and Bo prepared on the day of the example were collected and platinum ammine complex ions (e.g. Pt (NH3)
, r2+) for about 20 hours at about 70°C, and then the pellets were separated, washed with water, dried at 110°C, and calcined in air at 600°C for 3 hours to obtain platinum-hydrogen type. A TSZ catalyst was prepared. Hereinafter, this will be referred to as catalyst D (
TSZ of Example 1) and Catalyst E (Using the catalyst of Example 4).

The platinum contents of Catalyst and E were 0.54% and 0.51% by weight, respectively.

Example 11゜40g of each of the binderless TSZ crystalline aluminosilicate pellets of the sl/lium type obtained in Examples 2.3 and 5 and Comparative Example 1 were subjected to ion exchange treatment in the same manner as in Example 8, Ammonium type TSZ was prepared. Next, 10 g of each of these was taken out and a platinum (Pt)-hydrogen (■) type TSZ catalyst was prepared in the same manner as in Example 10. These will be described below as Catalyst F (using TSZ from Example 2), Catalyst G (using TSZ from Example 3), Catalyst H (using TsZ from Example 5), and Catalyst I (using TSZ from Comparative Example 1). The platinum contents of the obtained catalysts F, G, H and I were 0.61.0.55.0.49 and 0.58% by weight, respectively.

Example 12゜ Sodium type binderless TS obtained in Example 6
Example 8 40 g of Z crystalline aluminosilicate Pereso I
Ammonium J2 type TS was treated with ion exchange in the same manner as
Z was mW. A platinum-hydrogen type TSZ catalyst was prepared in the same manner as in Example 10 by fractionating this ]Og.

210g of Oni Uno type TS is 60g in the air.
After baking at 0'C for 3 hours to form a hydrogen type, a platinum-containing TSZ catalyst was prepared in the same manner as in Example 10 (hereinafter abbreviated as catalyst-2).

Ammonium type TSZIOI in this example? at atmospheric pressure, 10
After treatment with 0% steam at 500°C for about 16 hours, a platinum-containing TSZ catalyst was prepared in the same manner as in Example 10.

In the preparation of catalyst-1, an aqueous solution of platinum ammine complex ions was added around d:l, and instead of being calcined in air at 600°C for 3 hours, 50% was added using 100% steam under atmospheric pressure.
One batch of catalyst was prepared in the same manner as in the case of catalyst-1 except that it was treated at 0°C for about 16 hours, and 7 pieces were prepared.

Example 13゜ j Sodium type binderless TS obtained in Example 6
Z crystalline aluminosilicate pellet] Og was treated in the same manner as in Example 10 using an aqueous solution containing platinum ammine complex ions. Then, after treatment using an aqueous ammonium chloride solution in the same manner as in Example 8, the
A TSZ catalyst was prepared by calcining at <RTIgt;C</RTI> for 3 hours (hereinafter abbreviated as catalyst-5).

Example 14゜ Sodium type binderless TS obtained in Example 6
Z crystalline aluminosilicate pellet) Log of 100 m of an aqueous solution containing ammonium ions and platinum ammine complex ions
j! (4.0g as ammonium chloride, 0 as platinum
．． The catalysts were prepared by immersing the pellets in water containing 1 g each for about 24 hours at room temperature, then separating the pellets, washing them with water, drying them at 110°C, and calcining them in air at 600°C for 3 hours (hereinafter referred to as This is abbreviated as catalyst-6).

Example 15 A palladium-containing catalyst was prepared in the same manner as in Example 14, except that a palladium (Pd) complex ion (e.g., Pd (N11)42+) was used instead of the platinum ammine complex ion. (Hereinafter, this will be abbreviated as catalyst-7).

Example 16 Using binderless crystalline aluminosilicate pellets of l-lium type obtained in Example 7, Example 11t
A platinum-hydrogen type catalyst was prepared in a manner similar to that described. Hereinafter, this will be abbreviated as catalyst, J.

Examples] 7゜ Catalysts A, B, C1D of the present invention prepared in the above examples,
For catalysts E, F, G, H, J and comparative examples, a fixed-bed flow reactor was used to supply a liquid containing ethylhenzene and xylene having the 11 components listed in Table 1 below. , the reaction activity was tested. The reaction conditions for the test were a temperature of 320
°C1 pressure kg/c♂ instrument pressure, weight space velocity (WH3
V) 6.5W/H/W, ratio of hydrogen to raw material liquid (H2
/IC) was 3.3 mol/mol. The results of each test are shown in Tables 1, 2 and 3 below.

(Weight%) NA 1.24B
2.57T O,
795,11 EB 18.46 10.40p-X
10.66 18.02m-X56.82
41.92 o -X 13. 27 15. 75ET
1.67TMB
O,84DEB
1.09EX 1
．． 47AIO+ Q p-X equilibrium attainment rate (%') 99.3 Xylene loss rate (%) 6.16 EB conversion rate (%
) 43.7 Aromatic yield (%)
99.6B C Yufu first edition '4) ('-14>1, 41
0. 872.70 1.1
1 5, 25 1. 26 9, 46 15. 10 1B, 40 19. 7641, 49
43. 7815, 91 1
6. 521, 76 0. 29 1, 01 0. 20 1, 30 0.61 1, 40 0. 54 103, 7 107. 36, 13
0. 85 48.7 18.3 99, 4 99. 4 Second Catalyst D (Prepared Zeolite) Example 10D - Product Composition - Raw Material 22 (wt%) NA 4.82B
3.14T O,
793,71 E8 1B, 46 9.73p -X
10.66 18.50m-X 56.
82 42.24o-X 13.27
15.93ET O,85
TMB O,77DEB
0. 52EX
0. 24A10+
0 p-X equilibrium attainment rate (%) 1.02.3 Xylene loss rate (silo) 5.05 EB conversion rate (%) 47.3 Aromatic yield (%)
96.8 Table E F Huff U lock and 1 -Ω line connection B 14, 07
4. 65 4, 27 2. 05 3, 57 3. 07 8, 53 10. 78 18, 52 18. 4042, 36
43. 6816, 14 15
．． 270, 94 0. 96 0, 80 0. 76 0, 35 0. 52 0.51 0.17 101, 7 99. 34.62
4.21 53, 8 41. 6 97, 5 96. 6 (wt%) NA 5.30 4.5
5B 3.71 2'
,40T O,793,423,39EB
1B, 46 8.49 10.21p-
X 10.66 19.16 18.44m-
X 56.82 40.57 43.63o-
X 13.27 16.92 15.34ET
O,571,01TMB
1.22 0.70DEB
0.48 0.56EX
O,640,14AID”
Q O aromatic yield (%) 96.4 96.8I
J "Le comparison side '1) mu ox 3.34 3.10 1.51 2.71 2.46 3.92 12.80 10.66 17.82 18.73 45.89 41.88 14.88 15 .89 0.5B 0.97 0.45 0.89 0.40 0.73 0.11 0.59 88.8 105.7 2.67 5.27 30.7 42,3 97.7 97.4 The various abbreviations and ratios used in the table have the following meanings.

NA: Non-aromatic hydrocarbon B having 1 to 9 carbon atoms
: Benzene T: Toluene EB : Ethylbenzene T)-X : Paraxylene m-X: Meta-xylene ox : Ortho-xylene ET : Ethyltoluene TMB: l-limethylbenzene DE13 Nidiethylbenzene EX : Ethylxylene AlO+: DEB and EX 10 or more carbon atoms excluding: Aromatic hydrocarbons of the above, F (X) -(X) X concentration (p-X): p-X concentration in the xylene 3 isomer in the product (p-X): p-X equilibrium concentration in the xylene 3 isomer at reaction temperature: xylene 3 isomer in the raw material liquid Concentration [X]: Concentration of xylene 3 isomer in the product (EB)
: Concentration of EB in the raw material liquid (+?, n): Concentration of I'l'3 in the product (A +?
:l: Total number of moles (moles) of aromatic hydrocarbons in 19I concentrated solution [total number of moles (moles) of aromatic hydrocarbons in R11:41-parabolic solution. However, all concentrations are weight %.

From these results, in Examples 1 to 5 and Example 7,
i+l It was demonstrated that each of the catalysts made of the binderless crystalline aluminosilicate had excellent xylene isomerization activity and ethylbenzene conversion activity.

Example 18 The reaction activities of the catalysts -1 to -7 prepared in Examples 12 to 15 were tested using a fixed bed flow reactor. The composition of the raw material liquid used was: toluene Q, 94% by weight;
Ethylbenzene 15.0fif%, paraxylene 11
．． 49% by weight, meta-xylene 59.36% by weight and ortho-xylene 13.15% by weight. The reaction conditions were as follows: pressure crab 7 kg/c JG
) Tests were conducted by varying the reaction temperature so that the conversion rate was around 50%.

The results when the EB conversion rate is about 50% are shown in Tables 4 and 5, and from these results, it can be seen that the catalysts prepared by any of the preparation methods of the present invention have a relatively low reaction temperature. It was demonstrated that in addition to converting ethylbenzene, it is possible to sufficiently achieve xylene isomerization with little xylene loss.

Claims (1)

[Scope of Claims] 1) A pellet-type, irregular-shaped, or hollow-type molded body consisting of a crystalline aluminosilicate and a binder is subjected to a hydrothermal reaction treatment to crystallize the binder into crystalline aluminosilicate crystals. (1) The secondary pores of the binderless zeolite have a pore radius of 75 to 75 as determined by mercury intrusion method.
,000 Å, and the average pore radius is 1000~
15,000 Å, 25% or more of the pore volume is within ±20% of the average pore radius, the pore volume is 0.2 to 1.0 cc/g, and (2 ) A catalyst for the isomerization of aromatic hydrocarbons having 8 carbon atoms, characterized in that at least a part of the exchangeable cations of the crystalline aluminosilicate of binderless zeolite are replaced by cations other than alkali metals. . 2) The carbon according to claim 1, which has an average pore radius in the range of 1,100 to 10,000 Å and a pore volume of 0.25 to 0.9 cc/g. number 8
Catalyst for isomerization of aromatic hydrocarbons. 3) The carbon according to claim 1, which has an average pore radius in the range of 1,200 to 8,000 Å and a pore volume of 0.3 to 0.8 cc/g. Catalyst for isomerization of number 8 aromatic hydrocarbons. 4) C8 aromatic hydrocarbon according to claim 1, wherein the crystalline aluminosilicate exhibits a powder X-ray diffraction pattern having at least the following lattice spacing d (Å): Catalysts for isomerization of types. ￥Lattice spacing d(Å)￥￥Relative intensity (I/I_o)
¥11.2±0.2 Strong 10.1±0.2 Strong 7.5±0.15 Weak 6.03±0.1 Medium-high 4.26±0.07 Medium-high 3.86±0.05 Strongest 3.82±0.05 Strongest 3.76±0.05 Strongest 3.72±0.05 Strongest 3.64±0.05 Strongest 5) Crystalline aluminosilicate exhibits a powder X-ray diffraction pattern of mordenite A catalyst for isomerizing C8 aromatic hydrocarbons according to claim 1. 6) The carbon according to claims 1 to 5, wherein the cation other than the alkali metal is at least one selected from hydrogen and Group VIII metals of the Periodic Table of the Elements. Catalyst for isomerization of number 8 aromatic hydrocarbons. 7) For the isomerization of C8 aromatic hydrocarbons as set forth in claim 6, wherein the Group VIII metal of the Periodic Table of Elements is any of nickel, palladium, and platinum. catalyst. 8) A binder-less zeolite obtained by subjecting a pellet-type, irregular-shaped or hollow-type molded body consisting of a crystalline aluminosilicate and a binder to a hydrothermal reaction treatment to crystallize the binder into crystalline aluminosilicate crystals. at least one of the exchangeable cations of the crystalline aluminosilicate of
An ion exchange method for exchanging a part of
) introducing ammonium ions using a treatment solution containing ammonium ions; and (2) introducing cations of metals other than alkali metals by using a treatment solution containing cations of metal compounds other than alkali metals. A method for exchanging cations of a crystalline aluminosilicate to form a binderless zeolite, comprising the step of: introducing a binderless zeolite. 9) The binderless product according to claim 8, wherein the ion exchange treatment is performed to introduce cations of metals other than alkali metals after the treatment to introduce ammonium ions. A method of exchanging cations in crystalline aluminosilicates to form zeolites. 10) Claim 8, characterized in that the ion exchange treatment is performed to exchange with cations of metals other than alkali metals, and then ion exchange treatment is performed to introduce ammonium ions. A method for exchanging cations of a crystalline aluminosilicate to form a binderless zeolite as described in Section 1. 11) The method according to claim 8, characterized in that ammonium ions and cations of metals other than alkali metals are simultaneously ion-exchanged using a solution in which ammonium ions and metal compounds other than alkali metals coexist. A method for exchanging cations of crystalline aluminosilicates to form binderless zeolites. 12) Claims 8 to 11, characterized in that the treatment liquid containing cations of metal compounds other than alkali metals contains at least one of ammine complex ions of palladium and platinum. A method for exchanging cations of a crystalline aluminosilicate to form a binderless zeolite as described in . 13) A binderless zeolite obtained by subjecting a pellet-type, irregular-shaped, or hollow-type molded body consisting of a crystalline aluminosilicate and a binder to a hydrothermal reaction treatment to crystallize the binder into crystalline aluminosilicate crystals. A method for producing a binderless zeolite in which at least a part of the exchangeable cations of a crystalline aluminosilicate is exchanged with cations other than ammonium ions and alkali metals, A method for producing binderless zeolite ion-exchanged with ammonium ions and cations of metals other than alkali metals, which comprises performing ion exchange with ions and then calcining the zeolite. 14) The method for producing binderless zeolite ion-exchanged with ammonium ions and cations of metals other than alkali metals according to claim 13, wherein the calcination is carried out in the presence of steam.