CA1217469A - Crystalline aluminosilicate, process for the preparation thereof, and process for the conversion of organic materials using the same - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE:

The invention relates to a crystalline alumino-silicate, characterized by the fact that it has (1) a ratio of the silicon/alumunium atomic ratio of the external surface of the crystal to the average value of the silicon/aluminium atomic ratio in whole crystal equals to about 1 or more;(2) a chemical composition expressed in terms of oxyde molar ratios of: 0.8 ? 1.6 M2/no-A1203 -10 ? 100 SiO2 0 ? 40 H20, wherein " M" represents a cation and " n" represents the valence of M; and (3) a true monoclinic symmetry and a specific powder X-ray diffraction pattern. The invention also relates to a process for preparing the above mentioned crystal. This crystal shows good reaction selectivities in conversions of hydrocarbons when it is used as catalyst.

Description

~L2~7~

BACKGROUND OF THE INVENTION

1. Field of the Invention The present invention relates to a novel crystalline aluminosilicate, a process for the conversion of an organic material using said crystalline aluminosilicate, and a pro-cess for the preparation of a novel crystalline sodium aluminosilicate. More particularly, the present invention relates to a novel crystalline aluminosilicate having a characteristic distribution of Si and AQ, a process for the conversion of an organic material utilizing the molecular shape selectivity and catalytic ability of said crystalline aluminosilicate, and a process for the preparation of a novel crystalline sodium aluminosilicate.

2. Description of the Prior Art Crystalline aluminosilicates, generally kno~n as crystalline zeolites, are aluminosilicate hydrates. Their crystalline structure, whether they are natural or synthetic, are based on a three-dimensional framework of an SiO4 tetra-hedron, wherein four oxygen atoms centering around silicon (Si) are positioned at vertices, and of an AQO4 tetrahedron which is formed by replacing silicon atom of the Si O4 with aluminum (AQ).
It is known that these SiO4 and AQO4 tetrahedra form fun-damental units of 4, 5, 6, 8, or 12-membered rings formed by the interconnection of 4, 5, 6, 8, or 12 of them and double rings formed by superposing these 4, 5, 6, 8, and 12-membered rings on each other, and that the framework structure of a crystalline aluminosilicate is determined by the interconnec-tion of these units. There are specified cavities in the framework structure determined by the above interconnection.
An entrance of this cavity structure is an opening formed with 6, 8, 10, and 12-membered rings. Openings, described ,~

~2~

above, have a unified diameter so that only molecules smaller than a predetermined size can be adsorbed, and larger ones, which cannot enter through the openings are not adsorbed.
This action of the crystalline aluminosilicate is known as the amolecular sieve, which has been utilized as an adsor-bent, a catalyst, or a catalyst carrier for chemical reactions in various chemical processes.
In recent years, intensive studies have been made in various fields of chemical reactions for the combined use of crystalline aluminosilicates as the above-mentioned molecular sieve and as catalyst. This is the application as a so-called molecular shape selective reaction catalyst, as classified from the viewpoint of catalyst function by S.M.
Csicsery into the following three groups: (1) those charac-terized in that only specified reactants can approach to anactive site, (2) those characterized in that, after the reaction at the active site, only the substances of the specified shape can leave from the site of reaction; and

(3) those characterized in that, in a bimolecular reaction, each molecule can freely approach to or leave from the reac-tion site but they cannot react because the transition state is too large (Zeolite Chemistry and Catalysis ACS Monograph 171, ACS, Washington D.C., 1976, p. 680~.
The above classification is based on a consideration that the reaction occurs only in the cavity of crystalline aluminosilicate. The catalytic reaction on- or near the active site of the external surface of a crystal is low in reaction selectivity, unliXe the catalytic reaction described above, because all kinds of reaction are possible and reactions occur freely beginning with the reaction having small activation energy.
In order to suppress these non-selective reactions on or around l'the external surface of crystals'' (hereinafter referred to simply as ''the crystal surfacel', there has been

4~

suggested methods of burying ac-tive sites by covering the crystal surface with a compound, or controlling the solid acid acidity of the active sites by using alkaline substances or those with different solid acid acidity. Additions of silicon, phosphorus, or m~gnesium compounds have been suggested.
On the other hand, a method of controlling the size of the crystals is known, thereby controlling the ratio of the number Gf the active sites having molecular shape selec-tivity in the crystals and that of the active sites not hav-ing molecular shape selectivity on or around the crystalsurface. For example, when the crystals are large, the ratio of the number of the active sites in the crystals is relati-vely increased, thereby the molecular shape selectivity increases. However, this results in lower reactivity in general, because of the relative limitation in approach and/
or contact of the reactants to the active sites. On the other hand, when crystals are small, the reactivity is ele-vated because of relative increase in the opportunity of approach and/or contact of the reactants to the active sites, although the molecular shape selectivity is lowered as the result of relative increase of the number of the active sites on or around the crystal surface.
The electric charge of the tetrahedral crystalline sodium aluminosilicate, containing aluminum is balanced in an equilibrated state by incorporating sodium cation in the crystal. This cation is well known to act as solid acid catalyst when it is ion-exchanged into a hydrogen- or metal-lic ion-exchanged type in various methods.
It is understood therefore that the places where A~ atoms are present are intimately rela~ed, directly or indirectly, to those where active sites are present. It is also fully expected that the solid acid strength of an adjacent atom (silicon) bonded to the AQ atom with an interposed oxygen atom is strongly influenced by the neigh~

`i , ~2~6~

boring atom (silicon or another aluminum) to which it is bonded with another interposed oxygen atom.
It was elucidated by the so-called Loewenstein's rule (N. Loewenstein, Am. Miner. 39, 92 ~1954)) that the bond of an aluminum atom to another aluminum atom with interposed oxygen can not exist.
It is understood from the above that if the distri-bution of A~ atoms in a crystalline sodium aluminosilicate can be ~ontrolled, the solid acid strength itself or its distribution in the crystalline sodium aluminosilicate as catalyst can be controlled freely. Moreover, if the distri-bution of AQ atoms in crystals can be controlled, the active sites can be concentrated to the inside of crystals or contrarily concentrated on or around the external surface of crystals, whereby the same effect as that, attained when the solid acid acidity is controlled by the coverage with compounds, is expected. The amount of the compounds to be incorporated for modification is also expected to be reduced.
Although structures of crystalline aluminosilicates have been analyzed with X-ray, most of them only show a so-called framework structure, and there are few works in which exact positions of the silicon and aluminum atoms were determined. It is because the X-ray scattering ability of a silicon and an aluminum atoms are very similar, and because relatively large single crystals are hardly obtained.
However, since the surface elemental analysis of crystals in the order of micron has become possible by the recent development in surface analyzing technique, it has become possible to discuss about the elemental distribution in crystals.
As described above, the electric charge of the alu-minum-containing tetrahedral crystalline aluminosilicate is 74~

balanced in an equilibrated state by cations incorporated in the crystal. In natural crystalline aluminosilicates, they are cations belonging to Group I or II metal of the periodic table, preferably those of sodium, potassium, calcium, magnesium, or strontium. These metallic cations are also used in synthetic crystalline aluminosilicates, but recently the use of organic nitrogen cations, especlally those obtained from organic amine compounds for example, quaternary alkylammonium ions such as tetraalkylammonium ions, are suggestedD These nitrogen-containing organic compounds function as templates and were considered essential as an alkali source for the synthesis of crystalline alumino-silicates having a high silica/alumina ratio. Organic amine compounds which have been used include quaternary alkyl ammonium salts (e.g. tetramethylammonium hydroxide, tetraisopropylammoniumbromide), primary alkyl amines having 2 to 10 carbon atoms, polyalkylene polyamine and erithritols, such as pentaerithritol, dipentaerithritol, and tripenta-erithritol.
However, the use of nitrogen containing organic compounds is disadvantageous in high material cost, as well as complicated for the preparation, because they must be removed by firing at high temperatures when the obtained synthetic aluminosilicate is used as catalyst.
Moreover, -there have been problems in safety of operation in the conventional process wherein the above described tetraalkylammonium compounds or organic amine compounds such as C2 to C10 primary amines are used, because these organic compounds are dangerous themselves as well as decomposed products of them. Therefore they may bring out various dangers in steps of synthesis, drying, and firing.
The present inventors, as will be decribed briefly below, overcame these problems and provided a process for the preparation of a crystalline aluminosilicate from an ~7q~
5a -aqueous reaction mixture substantially consisting of only inorganic reaction materials (Japanese Patent Application n 143396/1981 published on March 16~ 1983).
The inventors also elucidated that the obtained crystalline aluminosilicate had a characteristic crystal-line structure as shown by th~ X-ray diffraction pattern.
The above application was related to.a crystal-line aluminosilicate having a chemical composition expressed in , terms of oxide molar ratios:
0-8 - 1-5 M2/n A Q~ O3 10 - 100 Sio2 ZH2' wherein M stands for a metallic cation, n for the valence of said metallic cation, and z for 0 to 40, and having a powder X-ray diffraction pattern showing at least the interplanar spacings, namely, shown in Table 1.

Table 1 10 interplanar spacing, d (A) relative intensity (I/Io) 11.2 + 0.2 S.
10.1 + 0.2 S.
7.5 + 0.15 W.
~.03 + 0.1 ~.
3.86 + 0.05 V.S.
3.~2 + 0.05 S.
3.76 + 0.05 S.
3.72 + 0.05 S.
3.64 + 0.05 S.

The aluminosilicate having the crystalline structure characterized by the above X-ray diffraction pattern, which has not been found in literature, was named TSZ.
The above values are obtained by the measurement with an X-ray aiffraction device manufactured by Rigaku Denki K.K. (Geigerflex R~D-rA) in the ordinary method. Irradiation was carried out with K- ~ doublet of copper. The relative intensity and the interplanar spacings (d) expressed in terms of angstrom (A~ corresponding to the recorded lines were determined from the height and position of the peak read from the chart as a function of 2 ~ (~ = Bragg angle) by using a scintillation counter provided with a strip chart pen recorder. The relative intensity in Table 1 is evaluated as very strong by V.S., strong by aS, medium by aM, weak by aW, and very weak by aV W As will be described below, the crystalline aluminosilicate of the above ~æ~

application is characterized by the X-ray diffraction pattern obtained by the ordinary powder X-ray diffraction method.
More particularly, the characteristics which distinguish the crystalline aluminosilicate of the above application most remarkably from the conventional crystalline zeolites in crystalline structure are that the diffraction line of 2 ~ = 14,7 (d = 6.03 ~) is singlet and those of 2 ~ = 23 (d = 3.86 A` and of 2 ~ = 23.3 (d = 3.82 ~) are clearly split.
The crystalline aluminosilicate of the above application was also subjected to powder X-ray diffraction analysis different from the ordinary method, by which 2 ~ (~ = Bragg angle) was measured with remarkably high accuracy. The analysis of the result showed that the crystalline aluminosilicate of the above application (TS~) belonged to a monoclinic system crystallographically.
For example, the TSZ having a composition of 1.02 Na2O -A12O3 - 26.2 SiO2 - 12.2 H2O, the product of Example 7 in the Japanese Patent Application n 143396/1981, shows the following monoclinic lattice constant : a = 20.159 (+0.004~ A, b = 19.982 (+0.006) A, c = 13.405 (+0.005~ A, and ~ -90.51 (+0.03). The observed and calculated values and Miller indices of the interplanar spacing of this typical TSZ are shown in Table 2. The interplanar spacing of this characteristic X-ray diffraction pattern was not much influenced by exchanging the substituting cations of the synthetic aluminosilicate, especially by exchangin~ to hydrogen ion, and also not influenced by change of the ratio SiO2/A12O3. Generally, it is well known that interplanar spacing d has Miller indices (h, k, 1) and can be represented by a set of lattice constants a, b, c and ~. Therefore, when lattice constants a, b, c and ~ have been determined, all interplanar spacings d can be calculated. But sometimes some of the caiculated interplanar spacings can not be observed. This phenomenon is called disappereance of diffraction lines. Even if both of two samples belong to the same monoclinic symmetry, their space groups differ from each other when their disappearance of diffraction lines are not the same.
The present inventors have arrived at the present invention as a result of further intensive studies based on the above described previous invention, finding that (1) a crystalline aluminosilicate having a novel crystal pos-sessing remarkable molecular shape se]ectivity and catalyticability, in which the distribution of aluminium atoms in the crystal is controlled and the solid acidity ~æ~7~

X

.
b _ ~ - 1~ ~ o o ~ 1~ 1-- t~
_ ~: ~ C~ ~ C~ o ~ U~ ~ ~ o ~ ~ U~
_ _ O ~ O ~ ~ C:~ ~ O C~
.r~ ~

o~
~ c~ C~ ~ O ~ ~ C~ C`~
V V
V

c~ ~ ~ ~ r~ ~ ~ o o .
~ c~ o o oo oo t~ ~ o c~
7 x - ~ l~
~ ~-~ ~
~ - ~
_ ~ ~ ~ I--' O _~ O ~ IN ~ I--~ IN I~ IN
~ O O c~ o ~ s~ o ~ ~--_, _ ~ c~ o ~ e~ ~ ~ o o c~ _~ O 1 ._ ~: ~
-o ~ ~ c~ o u~ ~r _ u~ o r- o ~3 oo ~o ~ ~r cn ~ ~ _ o c~ n ~ o ~-- c~ O
r~ ~ . . . . .~ . . . . . . .
In v _c,~ o P~ o o~ o ~r _ ca cn r-- o ~ o t~ o t-- Lt~ ~ D
~ o _ O c" c~

., ;; ' ~2~

distribution is approximately homogeneous can be provided, that (2) such crystalline aluminosilieate can be prepared from substantially inorganic reaction materials, and that (3~ such crystalline aluminosilicate brings about good re-sults in selective catalytic reactions of hydrocarbons.

SUMMARY OF THE INVENTION

The first object of the present invention is, there-fore to provide a crystalline aluminosilicate having a charac-teristic erystalline strueture in whieh the distribution of aluminum atoms in the crystal is controlled.
The seeond objeet of the present invention is to provide a erystalline aluminosilicate having a high siliea/
alumina ratio and excellent catalytie aetivity.
The third object of the present invention is to provide a crystalline aluminosilicate having a characteristic erystalline strueture exhibiting exeellent activities in seleetive eraeking of linear hydrocarbons and conversion of aromaties.
The fourth objeet of the present invention is to provide a process for the preparation of a crystalline sodium aluminosilicate having a characteristic crystalline structure, in the crystal of which the distribution of aluminum atoms is eontrolled, from an aqueous reaetion mixture substantially consisting of inorganie reaetion materials such as silicon, aluminum, alkali metal eompounds, and water.
The fifth objeet of the present invention is to pro-vide a proeess for the preparation of a erystalline sodium aluminosilieate, having sueh Na20-AQ203-SiO2-H20 composition, that enables the reduction in production cost based on an easy and simple proeess for the produetion, without any heat-treating proeess of the produet, whieh has been necessary in the conventional preparation of synthetic aluminosilicates.

~2~7~

Further, the sixth object of the present invention is to provide a conversion process for organic materials using as catalyst anovel crystalline aluminosilicate wherein the distribution of aluminium is controlled.
Thus, the present invention relates to a crystal-line aluminosilicate, characterized by the fact that it has:
(1) a ratio of the silicon/aluminium atomic ratio of the external surface of the crystaltothe average value of the silicon/aluminium atomic ratio in whole crystal equals to about 1 or more;
(2) a chemical composition in terms of oxide molar ratios of:
0.8 ~1.6 M2/nO - A12O3 - 10 ~100 SiO2 - 0 ~40 H20 wherein " M" represents a cation selected from the group consisting of one or more ions selected from the group consisting of H , Na , NH4 and cations of Group VIII in the periodic table,and 1I n" represents the valence of M; and (3~ a true monoclinic symmetry andapowder X-ray diffraction pattern showing at least the following inter-planar spacings:
Interplanar spacings d (A) relative intensity (I/Io~
11.2 + 0.2 strong 10.1 + 0.2 strong 7.5 + 0,15 weak 6.03 + 0.1 medium 3.86 + 0.05 very strong 3.82 + 0.05 strong 3.76 + 0.05 strong 3.72 + 0.05 strong 3.64 + 0.05 strong.
The present invention also relates to a process for the preparation of a novel crystalline sodium alumino-silicate.
The crystalline aluminosilicate of the present invention (TSZ-III) is of great value for its catalytic ~2~6~

- lOa -activity in a variety of organic reactions including hydrogenation-isomerization of normal paraffins, conver-sion of alcohols into hydrocarbons, alkylation of aromatics with alcohol and olefin, disproportionation or trans-alkylation between aromatic compounds and so on, especiallyshowing remarkable effects in the cracking of hydrocarbons.
Moreover, according to the present invention, such useful crystalline aluminosilicate (TSZ III) can be prepared extremely easily and economically.

~RIEF DESCRIPTION OF THE DRAWINGS

Figures 1 and 2 are graphical illustrations of the relationship between the amount of the desorbed pyridine and temperature.
In Figure 1, the solid line shows the results of the gas-chromatographic measurement of the sample of the present invention obtained in Example 4, and the broken line shows that of the sample obtained in Comparative Example 5.
In Figur~ 2, the solid line shows the results of the gas-chromatographic measurements of the sample of the pre sent .
.~

~7~

invention obtained in Example 1, and the broken line shows that of the sample obtained in Comparative Example 1.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the present invention the distribution of atoms on or around athe external surface of the crystal (abbreviat-ed as ~<the crystal surface>~) of the crystalline aluminosili-cate was measured by X-ray photoelectron spectroscopy.
It is necessary to reduce the number of the active sites having no molecular shape selectivity for the elevation of reaction selectivity in selective cracking of linear hydro-carbons, or in isomerization, alkylation and disproportiona-tion of aromatic hydrocarbons. It is important for this purpose to relatively decrease the number of aluminum atoms which tend to form framework on or around the crystal surface.
When the sample is irradiated with X-ray, photoelectron is released from the sample. Since the electron interact with substances strongly, its mean free path is small. Therefore the electrons released from the depths of the sample are scattered inside the sample and lose their energy, then they cannot go to the surface. In that case, the depths from which electrons can escape to the surface tescape depth) depends on the sort of element and the kinetic energy of the electron. Aluminum has an escape depth of 20 ~ in average (kinetic energy: 1,500 ev) and silicon has about 20 to 40 (kinetic energy: 554 ~ 1,178 ev).
On the other hand, the depths of the crystal is not recognized where the active sites, which have not high mole-cular shape selectivity, is able to exist. However, it isassumed that the active sites which are present at 20 ~
deep or more from the top surface are provided with suf-~icient molecular shape selectivity, because the size of the crystal is usually within the range of 1,000 ~ to several tens of thousand ~, and the size of the molecules taking part in the reaction is 10 ~ or less. In the present invention, therefore, X-ray photoelectron spectroscopy is the most suitable method of analysis. It is preferred for the measurement by X-ray photoelectron spectroscopy to use aluminum-K ~ ray as X-ray source with an X-ray output of 10 kv - 20 mA. The measured silicon/aluminum atomic ratio in this way is defined as ~silicon/aluminum atomic ratio on the external surface of a crystal.
On the other hand, the silicon/aluminum atomic ratio obtained by an ordinary chemical analysis such as atomic absorption is defined as average value of the silicon/aluminum atomic ratio in whole crystal (abbreviated as ~average silicon/
aluminum atomic ratio).
The aluminum distribution inside the crystal is able to be estimated by determining an adsorption/desorption curve of pyridine, from which the solid acid strength distribution of whole crystal is determined. Because, both of the silicon/
aluminum arrangement with an bridged oxygen atom inside the crystal and the arrangement of silicon/aluminum atoms on the crystal surface relate to the strength distribution of solid acid.
Moreover, it is generally known that pyridinium ions or coordinated pyridine are formed by adsorbing pyridine on the solid acid sites, but this pyridine is desorbed as temperature is raised, and the desorption temperature and solid acid strength is intimately interrelated.
In the present invention, pyridine is sufficiently adsorbed at 300C by H (hydrogen-type)-TSZ-III (TSZ-III will be defined later) obtained by the ion-exchange of crystalline aluminosilicate with ammonium chloride and/or mineral acid and successive ~iring at about 500C. Then H-TSZ-III is maintained in a nitrogen stream at 300C so that the physical-ly adsorbed pyridine is removed off. Thereafter the tempera-ture is raised at a predetermined rate to quantita-!J' 6g tively determine the desorbed pyridine by gas chromatography or other ordinary methods of measurement, whereby the amount and the strength distribution of the solid acid are deter-mined from the height, shape, or position of the peak obtained.
The process for the preparation of crystalline sodium aluminosilicate of the present invention will now be described.
The crystalline aluminosilicate of the present invention, having a characteristic distribution of silicon and aluminium atoms in its crystal (hereinafter referred to as TSZ-III), is usually prepared as follows:
An aqueous reaction mixture substantially consisting of inorganic reac~ion materials is prepared by using SiO2 as silicon source and A12O3 as aluminium source, ~ithin a certain range of ratio, and some appropriate alkali source and water. These components are mixed in predetermined range, then the reaction mixture is heated at a crystal-lization temperature until the crystals are formed. In the present invention seed cxystals are not added to the aqueous reaction mixture or to a subsequently formed aqueous reaction gel mixture, but are formed in situ.
The composition of the aqueous reaction mixture for the preparation of the crystalline sodium alumino-silicate of the present invention is as follows:
SiO2/A1203 10 ~ 100 Na2O/SiO2 0.03 ~0.5 H2O/SiO2 10 ~ 300 Cl /SiO2 0 . 1 ~ 10 still preferably:
SiO2/A12O3 20 ~ 80 Na2O/SiO2 0.05 ~0.3 H2O/SiO2 20 ~ 200 Cl /SiO2 0.1 ~5 .~

~æ~ 9 - 13a -The preparation of this aqueous reaction mixture, and of the subsequent aqueous reaction gel mixture, are especially important for the preparation of TSZ-III.
Generally, there are no essential differences S between the preparation of crystalline sodium alumino-silicate using in-~.2~7~6~

organic reaction materials as in the present invention andthe preparation of crystalline sodium aluminosilicate using organic nitrogen cations instead of cations of a Group l or II metal. In either case, an aqueous reaction gel mixture can be obtained at the same time when the acidic solution of silicon and the alkaline solution of aluminum are mixed together. In another method, the prepared homogeneous solu-tion of silicon and aluminum can be gelated with an acid or alkali. Further, the obtained gel can be converted into xerogel and then reconverted into aqueous reaction gel mixture.
Among these various methods of gelation, the most pre-ferred one for the preparation of TSZ-III (in which the distributions of silicon and aluminum in the crystal must be controlled) is a method of preparing a homogeneous solution of silicon and aluminum compounds firstly and then gelating the solution. ~ny combination of compounds can be used so long as a homogeneous solution of silicon and aluminum is obtained. For example, active alumina, y- alumina, alumina trihydrate, sodium aluminate, and chloride, nitrate, and sulfate of aluminum are used as aluminum source, and sodium silicate, silica gel, silicic acid, aqueous colloidal silica gel, dissolved silica, powdered silica, or amorphous silica as silica source. The most preferable sources are an aqueous sodium aluminate solution as aluminum compound source and aqueous solutions of various sodium silicates or colloidal silica as silica compound source, considering properties of the obtained crystals, economy, scale merit of industrializa-tion, and so on.
Thus, a homogeneous mixture of silicon and aluminum is obtained in the form of an alkaline solution, and an aqueous reaction gel mixture is obtained by neutralizing this alkaline solution with an acid solution. It is preferred to use a so-called mineral acid, more preEerably hydrochloric, sulfuric, or nitric acid for the neutralization. Hydrochloric acid is the most desirable because sodium chloride, formed by the 129~ ;i9 reaction with excess sodium hydroxide, serves as a mine-ralizer. The use of the mineralizer is desirable as will be described below for further improving the crystalliza-bility to suppress the formation of amorphous sodium aluminosilicate.
A solution of metal alkoxide can also be used to obtain a homogeneous solution of silicon and aluminium compounds.
The alkoxide compounds of silicon include, for example, methyl orthosilicate (tetramethyl orthosilicate), or ethyl orthosilicate (tetraethyl orthosilicate).
The typical alkoxide compounds of aluminium include aluminium isopropoxide.
A homogeneous solution of silicon and aluminium compounds can be prepared easily by mixing the metal alkoxide solution. A homogeneous gel can be obtained easily by the hydrolysis of the obtained solution in the presence of an acid or an alkali. An aqueous reaction gel mixture can be also obtained from a glassy compound formed by moderate hydrolysis of above obtained homogeneous solution of silicon and aluminium compounds. In this case also, a mineralizer such as sodium chloride is effective for improving the crystallizability of the obtained crystalline sodium aluminosilicate.
As discussed above, the aqueous reaction mixture and the aqueous reaction gel mixture consist essentially of inorganic reaction materials, and most preferably consist of inorganic reaction materials.
The following two mechanisms are assumed as a mechanism of forming crystalline aluminosilicate from an aqueous reaction gel mixture.
The first mechanism include the depolymerization and dissolution of gels in hydrothermal reaction so that separately formed crystalline nuclei grow gradually.

:~L2~
- 15a -Since the crystalline nuclei are formed centering around a cation, it is assumed that the organic cation establishes a circumstance in which crystalline nuclei are easily formed according to its action as " template" . Since the pH value of the solution is relatively higher in the presence of an organic cation that in the presence of an inorganic cation, the nuclei are considered to be formed with a cation serving as " template" immediately, after the formation of a hydrated silicate ion (H20) Si(OH)5 //

_ _ ................................. . .
,, ~

7~

by the action of the organic cation. The action of the hydro-xide ion is important in this depolymerization gels.
It is considered that, in this mechanism, the deposi-tion and subsequent crystallization of silicon compounds occur continuously around the nuclei ~which contain a rela-tively large amount of silicon) in the presence of the organic cation. If these nuclei are assumed to grow infinitely, it is not unreasonable that, as has been suggested, crystal-line silicic acid consisting of silicon alone exists. Actual-ly, it is known that the molar ratio of silica/alumina cannot be reduced to 20 or less, while it is possible to control freely the molar ratio of silica/alumina of the obtained crystalline aluminosilicate within the range from 20 to several thousands, when organic ion such as tetrapropyl ammonium salt is added in the reaction mixture.
The second mechanism include the formation of an alumino-silicate framework without dissolution of the gel. In this case, it is also considered that the nuclei grow in the gel phase and re-arrange from the gel phase into solid. In this case, of course, the silicon-aluminum arrangement in the aqueous reaction gel mixture is considered to affect greatly the silicon-aluminum arrangement of the obtained crystalline aluminosilicate. The assumption of the second formation mechanism is ad~antageously supported by the fact that, if the molar ratio of silica/alumina in the aqueous reaction gel mixture is increased to 100 or more with the purpose of elevating the molar ratio of silica/alumina in the obtained crystalline sodium aluminosilicate, the rearrangement be-comes difficult and silicon oxide crystals are formed.
According to the second formation mechanism, it is understood that the arrangementof silicon/alumina in the gel particles must be controlled in order to control that in the crystals.
Anyway, distribution of silicon and aluminum in the gel particles existing in a cJel mixture should be homogeneous because the aqueous reaction gel mixture is obtained from a homogeneous solution. This homogeneous distribution in the gel particles may influence also on crystallization, pre-sumably bringing about good results in the hvmogeneous dis-tribution of silicon and aluminum atoms in the formed crystal.
After the preparation of aqueous reaction gel mixture in this way, the reaction mixture is maintained under the following conditions: autogenous pressure, within the range of about 120 to about 230C for about 10 to about 50 hours.
In the crystallization process, the crystallizability can be further improved and the formation of amorphous aluminosilicate can be supressed by adding a mineralizer to the aqueous reaction gel mixture. Such mineralizers include neutral salts of alkali or alkaline earth metals, such as Na CQ, Na2C03, Na2S04, Na2Se O4, KCQ, KBr, KF, BaCQ or BaBr, among which Na CQ is preferable. The amount of Na C~
to be added is from about 0.1 to about 10, still preferably from about 0.1 to about 5 expressed by the molar ratio of CQ /SiO2.
The crystallinesodium aluminosilicate of the present invention (TSZ - III) is obtained by separàting the obtained crystalline aluminosilicate by filtration from the solution, washing it with water and drying it. The obtained crystals were confirmea to be a completely crystallized product by the examination of powder X-ray di~fraction.
The obtained X-ray diffraction pattern is remarkably characterized in that the diffraction line of 29= 14.7 (d=
6.03 A) is singlet and those of 2~= 23 (d= 3.86 A) and 2~=
23.3 (d= 3.32 A) are clearly split, which shows that the structure of crystalline aluminosilicate of the present invention is entirely different from that of known crys-talline zeolite. As mentioned before, the arrangement of silicon and aluminum atoms on the crystal surface of the crystallinealuminosilicate of the present invention is ~æ~7~

measured by X-ray photoelectron spectroscopy, while the distribution of silicon and aluminum atoms in whole crystal is determined by the adsorption/desorption curve of pyridine, basing on the information that the aluminum atom distribution influence on the solid acid strength distribution.
In the present invention, pyridine is sufficiently adsorbed at 300 DC by H (hydrogen-type)-T~Z-III obtained by the ion-exchange of crystalline aluminosilicate with ammonium chloride and/or mineral acid and subsequent firing at about 500C. Then the physically adsorbed pyridine is removed by maintaining it in a nitrogen stream at 300C, and the temperature is raised at a predetermined rate to quantita-tively determine the desorbed pyridine by gas chromatography or other ordinary methods of measurement. For example, when the quantitative determination was made with gas chromato-graph of flame ionization detector, the peak indicates exactly the amount and distribution of the solid acid as illustrated in the examples. In this case, a sharp peak suggests the presence of solid acid sites having the similar acid strength, which indicates that the combination of silicon and aluminum bridged by an oxygen atom is comparatively homogeneous. The presence of strong solid acid sites (for example, those in which pyridine can not desorb until at around 900C) indicate that the arrangement of aluminum atoms are coarse locally.
In order to use the crystalline sodium aluminosili-cate of the present invention as catalyst or catalyst compo-sition, the crystals are fired for dehydration at a temperature of about 200C or above in an atmosphere of air or an inert gas. The dehydrated product is useful as catalyst or catalyst carrier for chemical reactions, and the cations in the product is preferred to be removed or replaced at least partly by heat-treatment and/or ion-exchange. Particularly those exchanged by cations are excellent as catalyst for the conversion of hydrocarbons. Usually the ions to be exchanged can be selected according to the desired reaction. They can be exchanged with hydrogen ions by acid treatment, or by exchange with NH4 ~ followed by heat-treatment. Hydro gen ions and ions of Group VIII metals in periodical table are preferable for the decomposition, isomerization, alkylation, or other conversions of hydrocarbons.
In the present invention, the cation-exchange can be effected by contacting the crystal with a desired exchange-able cation or a cationic salt. A variety of neutral salts of Group VIII or alkaline earth metals can be used for this purpose, among which chlorides, nitrates~ sulfates, and acetates are preferable.
When the TSZ-III of the present invention is used as catalyst, it is preferred to introduce active metal compo-nents by ion-exchange or to introduce hydrogen ion by acid treatment, as described above, for the improvement in catalytic activity.
The TSZ-III of the present invention can ~e used as a mixture with a carrier such as silica-alumina or alumina as in an ordinary method. When such an active reforming com-ponent is incorporated in the TSZ-III, raw material can be catalytically reformed under the reaction conditions of about 380 to about 500C in temperature, about 5 to about 50 kg/cm2, preferably about lO to about 30 kg/cm2 in pressure, 25 and abo~t 0.5 to about 5.0 V/H/V, preferably from about l.0 to about 3.0 V/H/V in liquid space velocity.
Transition metals such as cobalt or nickel1 or noble metals such as platinum or palladium can be incorporated in the TSZ-III of the present invention by ion-exchange or other methods, for the use of the TSZ-III as catalyst for various catalytic reactions such as dewaxing of gas oil or lubricating oil fractions. For reactions such as catalytic dewaxing of gas oil or lubricating oil fractions, the reaction conditions are from about 250 to about 400C in temperature, about 5 to about 50 kg/cm2, preferably about lO to about 30 kg/cm2 in pressure, and about 0.25 to about 3 V/~/V/, preferably ~IL2~

about 1.0 to about 2.0 V/H/V in liquid space velocity.

EXAMPLES

The following examples are p~ovided to illustrate present invention, but are not to be construed as limiting present invention in any way.
Example 1 A solution of 12.5 g of sodium aluminate (NaAQ~2) in 29~.5 g of water was dropped under stirring into a solu-tion solved 269.1 g of water glass twater glass of Japanese Industrial Standard No. 3~ containing 9.5~ by weight of Na20 and 28.6% by weight of SiO2, hereinafter abbreviated as JIS No. 3) in 135.7 g of water. Independently, a diluted hydrochloric acid was prepared by mixing 77.7 g of 35~ concen-trated hydrochloric acid and 175.5 g of water. These two solutions were simultaneously dropped under stirring into a solution containing 48.6 g of sodium chloride in 403.7 g of water. The final pH value of the mixture into which all solutions had been added was 8Ø
The obtained solution was charged into a 2 Qit. auto-clave and maintained under stirring for 40 hours at 185C under autogenous pressure.
The pH value o~ the mother liquor after crystalli-zation was 11.6. The crystallized product was filtered andwashed after cooling, and dried overnight at 120C.
The powder X-ray diffraction of the obtained solid product showed that the product was completely crystallized and had the lattice surfaces consistent with those of zeolite-TSZ(TSZ-III).
As the result of chemical analysis, the following chemical composition was obtained:
87.1% by weight of SiO2; 5.33~ by weight of A~2 3; 2.88 by weight of Na20; and 4.44~ by weight of ignition loss (at 900C). The chemical composition expressed by oxide a69 molar ratios was 0.89 Na2O ~ AQ2O3 ~ 27.8 Si 2 4.7 H2O-The product was then molded into a disc of 12 mm in diameter with a tableting machine at a pressure of 10 ton/
cm2 for the analysis of silicon and aluminum on the crystal surface. The sample was irradiated with AQ-K~ ray as X-ray source at an output of 10 KV-20 mA and released X-ray photo-electrons were subjected to energy analysis to obtain an atomic ratio of silicon/aluminum of 14.5.
Consequently, the ratio of the silicon/aluminum atomic ratio on the crystal surface to the silicon/aluminum atomic ratio of the whole crystal was 1.04, from which it was con-cluded that the aluminum atoms were homogeneously distributed in the crystal.
Comparative Example 1 16.4 g of aluminum sulfate ~AQ2 (S 0~)3 ~ 17.8 H20) was dissolved in a solution of 8.6 g of 95~ sulfuric acid and 34.3 g of tetrapropylammonium bromide ((C3H7)4NBr) in 105 g of water (step ~).
Separately, a solution of 154.2 g of waterglass (JIS No. 3) in 76.5 g of water was prepared (step~
The two solutions were simulitaneously dropped under stirring into 300 g of water (step 0).
The obtained a~ueous reaction gel mixture was charged into 2 lit. autoclave and maintained under stirring for 20 hours at 160C under autogeneous pressure.
After the cooling of the autoclave, the crystallized product was filtered, washed, and dried overnight at 120C.
The product was further fired in an electric muffle furnace for 3 hours at 600C, and examined by powder X-ray diffrac-tion, showing excellent consistence in lattice spacings ofZSM-5. The product had high crystallinity and no uncrystal-lized parts were observed by electron microscopy.
The results of the chemical analysis were: 89.0% by weight of SiO2; 5.46% by weight of A~2O3; 1.78~ by ~2~7~g w~ight of Na2O; and 3.41~ by weight of ignition loss (at 900C). The chemical composition expressed by oxide molar ratios, on the assumption that the ignition loss at 900C
was due to the loss of H2O, was 0.54 Na2O AQ2 3 27.7 SiO2 3.5 H2O, The distribution of silicon and aluminum on the crys-tal surface was measured in the same manner as described in Example 1, obtaining the silicon/aluminum atomic ratio of lO.9. Consequently, the ratio of the silicon/aluminum atomic ratio on the crystal surface to the average silicon/aluminum atomic ratio in whole crystal was 0.79, which indicated that aluminum atoms were more distributed on the erystal surface.
Example 2 A solution of 7.5 g of sodium aluminate in 250 g of water was dropped under stirring into a solution oE 234 g of water-glass IJIS No. 3) in 116 g of water. Separately, a solution of 46.7 g of 35~ concentrated hydrochloric acid in 150 g of water was prepared. The two solutions were simulta-neously dropped under stirring into a solution of 41.5 g of sodium chloride in 345 g of water. The final pH value of the mixture into which all solutions had been added was 11.2.
The mixture was charged into a 2 Qit. autoclave and maintained under stirring for 24 hours at 185C under autogenous pressure.
The pH value of the mother liquor after erystalliza-tion was 12Ø The crystallized product was filtered andwashed after cooling, then dried overnight at 120C.
The powder X-ray diffraction of the obtained solid product showed that the product was completely crystallized and consistent with TSZ-zeolite in lattice spacing.
The results of the chemical analysis were:
88.3% by weight of SiO~; 3.82% by weight of AQ2 3; 2.52% by weight of Na20; and 7.34~ by weight of ignition loss. The chemical composition expressed in terms of oxide molar ratios 2 AQ203 39.3 SiO 10 9 H O

The atomic ratio of silicon to aluminum on the crys-tal surface determined by X-ray photoelectron spectroscopy in the same manner as described in Example 1 was 23.6.
Consequently, the xatio of the silicon/aluminum atomic ratio on the crystal surface to the average silicon/
aluminum atomic ratio in whole crystal was 1.20, which indi-cated that the aluminum atoms were more distributed inside than on the surface of the crystal.

Example 3 A solution of 5.4 g of sodium aluminate in 292.5 g of water was dropped under stirring into a solution of 201.2 g of colloidal silica (Ludox-40~*, containing 20~ by weight of Si 2' in 135.7 g of water. Separately, a solution of 58.1 g of 35% concentrated hydrochloric acid in 175.5 g of water was prepared.
The two solutions were simultaneously dropped under stirring into a solution of 48.8 g of sodium chloride in 403.7 g of water. The final pH value of the mixture into which all so~utions had been added was 10.4. The obtained aqueous reaction gel mixture was charged in a 2 Qit. auto-clave and maintained under stirring for 24 hours at 185C
under autogenous pressure.
The pH value of the mother liquor after crystalli-zation was 12 or more. The crystallized product was filteredand washed after cooling, then dried overnight at 120C.
The powder X-ray diffraction of the obtained solid product showed that the product was completely crystallized and consistent with TSZ-zeolite in lattice spacing.
The results of the chemical analysis were:
88.7% by weight of SiO2; 2.35% by weight of AQ203; 1.64~ by w~ight of Na20; and 6.40~ by weight of ignition loss. The chemical cornposition expressed by oxide molar ratio was 1.15 Na20 ~ AQ2 3 64,2 SiO2 15.4 H2O.

* Trade mark ~2~

The atomic ratio of silicon to aluminum on the crys tal surface determined by X-ray photoelectron spectroscopy in the same manner as described in Example 1 was 35Ø
Consequently, the ratio of the silicon/aluminum atomic ratio on the crystal surface to the average silicon/
aluminum atomic ratio in whole crystal was 1.09.
Example 4 A solution of 5.4 g of sodium aluminate in 293.0 g of water was dropped under stirring into a solution of 269.1 g of water-glass (JIS No. 3) in 135.7 g of water. Separately, a solution of 70.6 g of 35% concentrated hydrochloric acid in 175.5 g of water was prepared.
The two solutions were simultaneously dropped under stirring into a solution of 48.8 g of sodium chloride in 403.7 g of water. The final pH value of the mixture into which all solutions had been added was 8.8. The obtained aqueous reaction gel mixture was charged in a 2 Qit. auto-clave and maintained under stirring for 24 hours at 186C
under autogenous pressure.
The pH ~alue of the mother liquor after crystalliza-tion was 12Ø The crystallized product was filtered and washed after cooling, then dried overnight at 120C.
The powder X-ray diffraction of the obtained solid product showed that the product was completely crys~allized and consistent with TSZ-zeolite in lattice spacing.
The results of the chemical analysis were:
86.0% by weight of SiO2; 2.57% by weight of AQ2O3; 2.44~ by weight of Na20; and 6.40% by weight of ignition loss. The chemical composition expressed by oxide molar ratio was 1O56 Na20 A~2O3 56.9 SiO2 19.0 H20.
The silicon/aluminum ratio on the crystal surface of the obtained sample, measured in the same manner as described in Example 1, was the same as the silicon/aluminum ratio ~Z~7~69 calculated from the above chemical analysis values.
75 mQ of an aqueous solution of 5% by weight of ammonium chloride was added to 5 g of the obtained crystalline sodium aluminosilicate to effect ion-exchange at 80C for 1.5 hours. The ion-exchange treatments were carried out four times, and then the sample was washed with water, dried at 110C, and fired in air at 550C for 3 hours to form H (hydro-gen-type)-TSZ- III. The Na20 content in the H TS~-III was not more than 0.01~ by weight.
Comparative Examples 2, 3 and 4 Crystalline aluminosilicates having a variety of silicon/aluminum atomic ratios as shown in Table 3 were prepared in the same manner as described in Comparative Example 1.
These aqueous gel mixtures were maintained at 160C
for 20 hours and subjected to powder X-ray diffraction in the same manner as described in Comparative Example 1. All the samples showed the diffraction peaks of ZSM-5 with good crystallinity. The results of the chemical analysis of the samples after firing at 600C for 3 hours are summarized in Table 4.
Table 4 ComparativeComparative Comparative Example 2 Example 3 Example 4 Na2 0.68 0.81 0.98 Si 2 87.4 87.0 86.4 A~2 3 1.18 1.57 2.06 Ignition loss 11.5 10.1 9.98 SiO2/A~2O3125.4 93.8 71.2 Na2 O/A~2O3 0 95 0.85 0.78 The values in ~ab~e 4 are expressed by weight --except the ratios expressed by molar ratio.
The silicon and aluminum on the crystal surface of the obtained ZSM-5 was analyzed in the samemanner as described 7~

D ~ O r~_ Itl ~1 Lt~ O Lf~ I~ ~ O
~r ~o o o ~r ~ ._ __ ~ ._ '~ ~ Cr~ I_ ,1 ~ o Ln I~ ~ o o O o ..~._ -- __ _ ,_ _ o Lr~ r~ ~ o h ~ ~ ~ o o o S-a ~ ~ ~ ~ ~ ~ R
. ,~

X ~ ~ U~

O ~ ~, rd 8 ~ . 5_~ ~1 Ll ~::
o ~ ~ ~ ~ ~ ~ a u~~ 3 ~ 3 3 :~
a (3 --~' '7~69 ~ ~ ' .

~ ~ ~ ~ o ~ ~r ~

R~ ~

:

6~9 in Example 1, the results of which are summarized in Table 5.
Comparati~e Example 5 7.0 g of aluminum sulfate was dissolved in a solu-tion of 13.0 g of 95% sulfuric acid and 34.3 g of tetrapro-pylammonium bromide in 105 g of water.
Separately, a solution of 154.2 g of water-glass (JIS No. 3) in 76.5 g of water was prepared. These two solu-tions were dropped into 300 g of water to obtain an aqueous reaction mixture gel. ZSM-5 was obtained by crystalli~ing said gel in the same manner as described in Comparative Example 1. The obtained ZSM-5 was partly fired at 600C for 3 hours and subjected to chemical analysis, the result of which was: 94.5% by weight of SiO2; 2.57% by weight of AQ2O3; 1.22% by weight of Na2 ; and 1.76% by weight of ignition loss. The chemical composition expressed by oxide molar ratio was 0.78 Na20 AQ2O3 62.5 SiO~ 3.9 H2O.
The obtained ZSM-5, fired at 600~C for 3 hours, was ion-exchanged in the same manner as described in ~xample 4 to prepare H (hydrogen-type)-ZSM-5, the Na20 content of which was 0.01~ by weight of less.
Example 5 The hydrogen-type TSZ- III and the hydrogen-type ZSM-5 obtained in Example 4 and Comparative Example 5 were subjected to pyridine adsorption and heat desorption test.
In order to prevent the changes in pressure when pyridine is adsorbed or desorbed, the sample was made into granules of 30/10~ mesh be molding with an alumina binder was pr~pared as follows.
20.2 g of sodium aluminate was dissolved in 26.4 g of water, and 28.8 g of aluminum sulfate was dissolved in 50.7 g of water. These two solutions were simultaneously dropped into 480 g of hot water heated at 70 to 80C to prepare gel.

~2~746~

The obtained gel was aged at 70C for about 1 hour and filtered. The product was then washed with an aqueous solution of 1.5% by weight of ammonium carbonate until the Na20 content after firing at 600C reached 50ppm or less in terms of weight.
The obtained gel was kneaded and molded so that the binder (alumina) content was 30% by weight. The sample was prepared by drying the molded gel at 120C, firing it at 600C for 3 hours, and granulating it into 30/100 mesh granules 0.075 g of the sample, accurately weighed, was charged into anadso~rptiontube and dried at 600C for 1 hour in a dry nitrogen stream. Nitrogen was flown into the pyri-dine solution at a constant temperature of 15.5C at a flow velocity of 50 mQ/min.so that pyridine was adsorbed by the sample at 300C to saturation. Then only dry nitrogen was flown at a maintained temperature of 300C to remove the physically adsorbed pyridine.
The sample was then heated at a rate of 10Ctmin and the desorbed pyridine was quantitatively determined by flame ionization detecting gas chromatography. The temperature-pyridine desorption relationships of the samples of Example 4 and Comparative Example 5 are shown in Figure 1.
The samples obtained in Example 1 and Comparative Example 1 were then ion-exchanged in the same manner as described in Example 4 to prepare hydrogen-type TSZ- III and hydrogen-type ZSM-5. These products were made into 30~100 mesh granules in the same manner as described in Example 5 (the present example) and subjected to the same pyridine adsorption and desorption test. The results are shown in Figure 2.
It is confirmed from Figures 1 and 2 that the sample of the present invention (TSZ- III) shows more sharp distri-bution than ZSM-5, which indicates that TSZ- III has relatively larger amount active sites with the same acid strength than ~2~

ZSM-5 has. As the result of the comparison on the silica/
alumina ratio of the same level, the amount of adsorbed pyridine of TSZ-III is larger than that of ZSM-5.
The amounts of the adsorbed pyridine are as follows:

the present invention Z_M-5 Example 1 Example 4 Comp. Ex. 1 Comp. Ex. 5 0.346 0.192 0.188 0.146 (unit: m mole/g) Example 6 Toluene was alkylated with ethylene using the hydro-gen-type TSZ- III or the hydrogen-type ZSM-5, (which had bee prepared in Example 5 using TSZ- III obtained in Example 1 and ZSM-5 obtained in Comparative Example 1 respectively.), as catalyst, under the following conditions.
An atmospheric flow reactor was filled with 2.U mQ
of a 25/60 mesh granule catalyst, into which toluene, ethylene and hydrogen were introduced in a molar ratio of 5/1/5/ at a reaction temperature of 350C at a weight space velocity ~V/H/V) of 3.7/340/1,~80. The proportions of ethylene and hydrogen were determined based on the volumes of these gases at 20C. p-, m-, and o Ethyltoluenes were produced by the above reaction, among which p-ethyltoluene is of industrial value as material for synthetic resin because it can afford p-methylstyrene by the dehydrogenation of the ethyl group.
The results of the analysis of the products by gas chromatography were as follows:
Toluene p-Ethyltoluene 3~ conversion selectivity H-ZSM-5 19.74 27,9 ~Comp. Ex. 1) H-TSZ-III 18.82 33.1 (Ex. 1) ~ 7~

It was confirmed by the observation of the electron microscopy that the crystals of the hydrogen type TSZ- III
had almost the same size, approximately 0.5 X 1.0 ~m, as those of the hydrogen-type ZSM-5 before they were molded with a binder. Therefore, results of present example illustrate that the p~Ethyltoluene selectivity of TSZ- III is better than that of ZSM-5.
Example 7 The crystalline aluminosilicate obtained in Example 3 was converted into a hydrogen-type by the method described in Example 4, and kneaded with a binder by the method des-cribed in Example 5, to mold into a pellet of 1.5 mm in diameter. The ~SM-5 obtained in Comparative Example 4 was also converted into a hydrogen-type by the method of Example 4 and kneaded with a binder by the method of Example 5 to mold into a pellet of 1.5 mm in diameter. Both of the pellets were prepared so that the amount of the binder, after firing at 600C for 3 hours, was 30~ by weight.
Toluene was alkylated with methanol, using the obtained catalysts, and the resulting xylenes ~ere examined.
The reactions were effected using 2.0 mQ of the catalysts (25/60 mesh~ in an atmospheric flow reactor, and the products were analyzed by gas chromatography As understood from the results shown in Table 6, the superiority of the catalyst of the present invention in the toluene conversion, the yield of C8 aromatics, and the selectivity of p-xylene was proved.
Example 8 The crystalline aluminosilicate obtained in Example 2 was converted into a hydrogen-type by the method described in Example 4, and kneaded with a binder by the method described in Example 5 to mold into a pellet of 1.5 mm in diameter. The pellet was prepared so that the amount of the 12~4~9 ~- ~
~ ~ OIn ~ ~ ~1_1 ~ ~ ~1 ~
o ~ o ~ ~ ~ ~n ~ E E
o ~o _ _ _ _ _ _ _ _ ~0 '5 . C~
o ~ ~~ ~ ~ ~ o~ ~ C5~ ~ ~ ;r o Q. . . . . . . . . . . aJ~
~ ~ ~D O~ ~ Ln ~ O ~ U~ ~ ~ ~ a) 0 ~
Q X ~ o o~ ~1 ~ ~r ,1 ~
. ~ ._ __ _ _ _ . Q, ~
0 0 ~ S~ V
_ ~ ~, C

0 ~ E E ~ E ~ X
. _ ~ ~ V V V Oc~ ~: l l l ~ _ ~ ~ ~ C.)~ ~ o Q~ E~ O ..
~ ,~ ~ 0 ~ _ ~ _ _ t~
'01 U ~P _ ~

C O ~ o O C .~)~1 ~ o E 4 D ~ fl~ ~ o . . E- .¢ ~ ~ ~ _ ._ 7~

binder was 30% by ~eight after firing at 600C for 3 hoursO
The hydrogen-type Z~M-5 was prepared as follows for the comparison in the present example: 11.6 g of aluminum sul-fate was dissolved in a solution of 10.8 g of 95% sulfuric acid and 34.3 g of tetrapropylammonium bromide in 105 g of water. Separately, a solution of 154.2 g of water-glass (JIS No. 3) in 76.5 g of water was prepared. These two solu-tions were dropped into 300 g of water to obtain an aqueous reaction mixture gel. The gel was crystallized in the manner as described in Comparative Example 1 to obtain ZSM-5. The result of the chemical analysis of the product after firing at 600C for 3 hours was:
91.4~ by weight of SiO2~ by weight of AQ2 3; 1.77~ by weight of Na20; and 2.76~ by weight of ignition loss. The l_ chemical composition expxessed in oxide molar ratio was 0.71 Na20 AQ2 8 37.8 SiO2 3.8 H2O. The obtained ZSM-5 was converted into a hydrogen-type by the method described in Example 4, and kneaded with a binder by the method described in Example 5, to mold a pellet of 1.5 mm in diameter. The pe~let was prepared so that the amount of the binder was 30~ by weight after firing at 600C for 3 hours.
Toluene was disproportionated in the presence of the obtained catalysts and the resulting benzene and xylenes were examined. The reactions were effected with 1.0 m~ of the catalysts (25/60 mesh) in an atmospheric flow reactor, and the products were analyzed by gas chromatography.
As understood from the results shown in Table 7, the superiority of the catalyst of the present invention in the yield of C8 aromatics and the selectivity of p-xylene was proved.
Table 7 Crystalline aluminosilicate TSZ ZSM-_ Toluene conversion (%) 10.8 11.2 \ ~

Aromatic product yield ~%) 9g.0 98.7 (based on the amount of toluene, mol%~
Aromatic product distribution (mol%) C6 ~9.7 55.1 C8 48.7 ~3.~
C~ ~~ 1.6 1.5 C8 Aromatic isomer destribution (%) ethylbenzene less than less than 0.1 0.1 p-xylene 29.7 23.9 m-xylene 49.2 52.9 o-xylene 21.1 23.2 Reaction conditions:
Raw material: toluene Treatîng ~as: hy~rogen/toluene = 4/1 (molfmol) Reaction temperature: 420C
Reaction pressure: atmospheric Space velocity: 14.8 V/H/Y based on toluene :

Claims (15)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A crystalline aluminosilicate, characterized by the fact that it has:
(1) a ratio of the silicon/aluminium atomic ratio of the external surface of the crystal to the average value of the silicon/aluminium atomic ratio in whole crystal equals to about 1 or more, (2) a chemical composition expressed in terms of oxide molar ratios of:
0.8?1.6 M2/no - A1203 - 10 ? 100 SiO2 - 0?40 H2O, wherein " M" represents a cation selected from the group consisting of one or more ions selected from the group consisting of H+, Na+ , NH4+ and cations of Group VIII of the periodic table,and " n" represents the valence of "M";
and (3) a true monoclinic symmetry and a powder X-ray diffraction pattern showing at least the following interplanar spacings:

2. A Process for the preparation of a crystalline sodium aluminosilicate without adding seed crystals, com-prising: providing a homogeneous aqueous alkaline solution of silicon compounds and aluminium compounds,treating the homogeneous aqueous alkaline solution to obtain a reaction gel mixture, said aqueous reaction gel mixture consisting essentially of inorganic reaction materials having the following composition expressed in terms of oxide molar ratios:

Sio2/A1203 10?100 Na20/Sio2 0.03?0.5 H20/Sio2 10?300 C1-/Sio2 0.1?10 and then continuously heating and maintaining said aqueous reaction gel mixture at a crystallization temperature until crystals form.

3. A process for the preparation of a sodium aluminosilicate according to claim 2, wherein aqueous reaction gel mixture has the following composition expressed in term, of oxide molar ratios:
SiO2/A12O3 20 ? 80 Na2O/SiO2 0.05 ? 0.3 H2O/SiO2 20 ? 200 C1-/SiO2 0,3?5

4. A process for the preparation of a crystalline aluminosilicate, wherein a crystalline sodium alumino-silicate is brought into contact with a desired cation or cationic salt, the cationic ion being selected in the group consisting of H+, NH4+ and cations of group VIII of the Periodic Table,to replace at least a part of the sodium ions of said crystalline sodium aluminosilicate with saids other cations;said crystalline sodium aluminosilicate having:
(1) a ratio of the silicon/aluminiun atomic ratio of the external surface of the crystal to the average value of the silicon/aluminium atomic ratio in the whole crystal equals to about 1 or more;
(2) a chemical composition expressed in terms of oxide molar ratios of:
0.8?1.6 Na2O - A12O3 - 10?100 SiO2 - 0?40 H2O ; and (3) a true monoclinic symmetry and a powder X-ray diffraction pattern showing at least the following inter-planar spacings:

5. A process for the preparation of a hydrogen ion-exchanged crystalline aluminosilicate according to claim 4, wherein at least a part of the sodium ions of the crystalline sodium aluminosilicate are replaced with H by contacting said crystalline sodium aluminosilicate with an acid.

6. A process for the preparation of an ammonium ion-exchanged crystalline aluminosilicate according to claim 4, wherein at least a part of the sodium ions of the crystalline sodium aluminosilicate are replaced with NH4+.

7. Process for the preparation of a metallic ions-exchanged crystalline aluminosilicate according to claim 4, wherein at least a part of the sodium ions of the crystal-line sodium aluminosilicate are replaced with ions of Group VIII in the Periodic Table.

8. A process for the conversion of an organic material, characterized by using a fired crystalline aluminosilicate as a catalyst,under conversion conditions,of the organic material,the crystalline aluminosilicate catalyst being characterized by the fact that it has:
(1) a ratio of the silicon/aluminium atomic ratio of the external surface of the crystal to the average value of the silicon/aluminium atomic ratio in the whole crystal equals to about 1 or more, (2) a chemical composition expressed in terms of oxide molar ratios of:
0.8?1.6 M2/no - A1203 - 10?100 SiO2 - 0?40 H2O
wherein " M" represents a cation selected from the group consisting of one or more ions selected from the group consisting of H+, NH4+ and cations of Group VIII in the Periodic Table,and " n" represents the valence of " M" ; and (3) a true monoclinic symmetry and a powder X-ray diffraction pattern showing at least the following interplanar spacings:

9. A process according to claim 8, wherein the conversion of an organic material is the catalytic dewaxing of hydrocarbon oil fractions.

10. A process according to claim 8 or 9, wherein the reaction conditions for the conversion are from 250°C to 400°C in temperature, from 5 kg/cm2 to 50 kg/cm2 in pressure and 0.25 to 3 V/H/V in liquid space velocity.

11. A process according to claim 8 wherein the conversion is a catalytic reforming in which the conditions for conversion are from 380 to about 500°C
in temperature, about 5 to about 50 kg/cm2 in pressure, and about 0.5 to about 5.0 V/H/V in liquid space velocity.

12. A crystalline aluminosilicate according to claim 1, wherein it has the following X-ray-diffraction pattern:

13. A crystalline aluminosilicate according to claim 1, wherein the monoclinic lattice constants:
a = 20.159 (+0.004) .ANG., b = 19.982 (+0.006) .ANG.
c = 13.405 (+0.005) .ANG. and .alpha. = 90.51° (+0.03).

14. A process according to claim 2, wherein the treating comprises neutralizing the alkaline solution with an acid solution.

15. A process according to claim 2, wherein the aqueous reaction gel mixture does not contain any organic nitrogen containing compounds.