JPH0455974B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel crystalline aluminosilicate, a method for converting organic raw materials using the same, and a novel method for producing crystalline sodium aluminosilicate.
More specifically, the present invention focuses on unique Si within the crystal,
Novel crystalline aluminosilicate with Al distribution,
The present invention also relates to a method for converting an organic raw material using its molecular shape selectivity and catalytic ability, and a method for producing a novel crystalline sodium aluminosilicate. Crystalline aluminosilicate is generally known as crystalline zeolite, and the crystal structure of both naturally occurring and synthetic products is formed around silicon (Si).
SiO ₄ tetrahedron with oxygen atoms coordinated at the vertices,
Aluminum (Al) replaced silicon
It is an aluminosilicate hydrate with a structure based on a three-dimensional framework of AlO ₄ tetrahedra. SiO ₄ tetrahedron and AlO ₄ tetrahedron are 4, 5, 6, 8
or a 4-membered ring, a 5-membered ring, an 8-membered ring formed by connecting 12
A basic unit is a double ring in which a membered ring or 12-membered ring and each of these 4-, 6-, 8-, and 12-membered rings overlap, and these are linked to determine the skeletal structure of the crystalline aluminosilicate. is known. A specific cavity exists inside the skeleton structure determined by these connection methods, and the entrances of the cavity structure are 6, 8,
It forms a cavity consisting of 10- and 12-membered rings. The formed cavities have a uniform diameter, and only molecules below a certain size are adsorbed, and large molecules are not adsorbed because they cannot enter the cavities. Such crystalline aluminosilicates are known as "molecular sieves" due to their properties, and are used as adsorbents, catalysts for chemical reactions, or catalyst supports in various chemical processes. In recent years, methods that combine the above molecular sieve action and catalytic action have been intensively researched in various fields of chemical reactions. This is what is called a molecular shape selective reaction catalyst, and SM
As Csicsery categorizes them from a functional perspective, (1) only specific reactants can approach the active site, (2) after reacting at the active site,
(3) In a bimolecular reaction, individual molecules can freely enter and exit the reaction field, but the transition state is too large and the reaction occurs. There are three types of things that cannot be done (“Zeolite Chemistry”).
and Catalysis”ACS Monograph 171, ACS,
Washington DC 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 (hereinafter simply referred to as the crystal surface), there are methods of burying the active sites by coating the crystal surface with a compound, and methods of burying the active sites by coating the crystal surface with a compound. A method of controlling the solid acidity of the active site using substances exhibiting acidity or alkalinity has been proposed, and the addition of silicon compounds, phosphorus compounds, magnesium compounds, etc. has been proposed. On the other hand, it is also known that by controlling the size of the crystal, the ratio of the number of active points with molecular shape selectivity within the crystal to the number of active points without shape selectivity on or near the crystal surface is also known. ing. For example, when a crystal is made larger, the proportion of active sites within the crystal increases relatively, and 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 crystal surface increases, resulting in a decrease in shape selectivity, but the chances of the reactants approaching and/or contacting the active sites decreases. , the reaction activity increases. The electron valence of the aluminum-containing tetrahedra of crystalline sodium aluminosilicate is balanced by retaining sodium cations within the crystal. It is a well-known theory that these cations are ion-exchanged by various methods to become a hydrogen type or a metal ion exchange type and function as a solid acid catalyst. Therefore, it is understood that the location where the Al atom is present is directly or indirectly strongly related to the location where the active site is present. The solid acid strength is determined by the influence of the adjacent atom (silicon) bonded to an Al atom via an oxygen atom, and the next atom (silicon or another aluminum) bonded via another oxygen atom. It is quite expected that the country will be strongly influenced by the The state in which aluminum atoms are bonded to each other through oxygen is the so-called Loewenstein's law (W.
Loewenstein, Am. Miner. 39 92 (1954)) has shown that it does not exist. From the above, if the distribution of Al atoms in crystalline sodium aluminosilicate can be controlled,
It can be seen that the solid acid strength or solid acid strength distribution when catalyzed can be freely controlled. Furthermore, if the distribution within the crystal could be controlled, it would be possible to concentrate the active points on the inner surface of the crystal, or conversely, on or near the outer surface, resulting in compound coating. The same effect as solid acid control can be expected. Furthermore, even in the case of modification by addition of a compound, it is expected that the amount added can be reduced. On the other hand, crystalline aluminosilicates have been structurally analyzed using X-rays, but in most cases only the so-called skeletal structure has been shown, and the exact positions of both silicon and aluminum atoms have not been determined. There are few. This is because the X-ray scattering abilities of silicon and aluminum atoms are almost the same,
This is due to the difficulty in obtaining relatively large single crystals. However, in recent years, with the development of surface analysis techniques, it has become possible to perform surface elemental analysis of crystals on the micron scale, and it has become possible to discuss elemental analysis within crystals. As described above, the electron valence of the aluminum-containing tetrahedron of the crystalline aluminosilicate is maintained in equilibrium by containing cations in the crystal. In natural crystalline aluminosilicates, the cation is a group I of the Periodic Table of the Elements or a metal of group I of the same table, especially sodium, potassium, calcium,
Magnesium and strontium. The above-mentioned metal cations are also used in synthetic crystalline aluminosilicates, but in addition to metal cations, organic nitrogen cations, such as quaternary alkylammonium ions such as tetraalkylammonium ions, have recently been proposed. There is. And silica/
For the synthesis of crystalline aluminosilicate with a high alumina ratio, it has been considered essential to use the above-mentioned nitrogen-containing organic compounds as an alkali source. However, when using nitrogen-containing organic compounds, in addition to the disadvantage of high raw material prices,
In order to use the produced synthetic aluminosilicate as a catalyst, it is necessary to remove the nitrogen-containing organic compounds present in the compound by calcination at high temperature, which has the disadvantage of complicating the production process. It was hot. Furthermore, in the conventional manufacturing method using an amine-based organic compound such as a tetraalkylammonium compound or a C ₂ -C ₁₀ primary amine, etc., as described above, the above-mentioned Various risks have arisen due to the potential toxicity of organic compounds or the decomposition of the organic compounds, posing problems in terms of work safety. The inventors of the present invention have filed a patent application filed in 1983, as outlined below.
No. 143396 (filed on September 11, 1982) solved these problems and provided a method for producing crystalline aluminosilicate from an aqueous reaction mixture consisting essentially only of inorganic reactants. It was also revealed that the crystalline aluminosilicate thus obtained has a unique crystal structure characterized by an X-ray diffraction pattern. It is expressed as the molar ratio of oxide, and is 0.8~
1.5M _2/o O・Al ₂ O ₃・10~100SiO ₂・ZH ₂ O (where M is a metal cation, n is the valence of the metal cation, and Z is 0~ The present invention relates to a crystalline aluminosilicate having a chemical composition of 40) and a powder X-ray diffraction pattern showing at least the lattice spacing, ie, d-distance, shown in Table 1.

[Table] The aluminosilicate having a crystal structure characterized by an X-ray diffraction pattern as described above has not been described in any literature and is named TSZ. These values are the results of measurement using a conventional method using an X-ray diffraction apparatus (Geigerflex RAD-rA model) manufactured by Rigaku Denki Co., Ltd. The radiation was a copper K-α doublet, and the peak height and its peak height were measured from the chart as a function of 2θ (θ is the Bragg angle) using a scintillation counter with a strip chart pen recorder. The positions are read and from these the relative intensity corresponding to the recorded line and the lattice spacing (d) expressed in Angstroms.
Å was measured. In terms of relative strength in Table 1, "VS" is the strongest, "S." is strong, "M." is medium strong,
"W." indicates weak, and "VW" indicates very weak.
The crystalline aluminosilicate according to the present invention can be obtained by the conventional method of powder X-ray diffraction, as described below.
Characterized by a line diffraction pattern. That is, 2θ=
The diffraction line at 14.7° (d=6.03Å) is a single line.
and 2θ=23° (d=3.86Å) and 2θ=
The clear separation of the two diffraction lines at 23.3° (d=3.82 Å) is the most distinctive feature that can be distinguished from the crystal structure of crystalline zeolite that has been proposed so far. Furthermore, apart from the conventional method, powder X-ray diffraction analysis was performed to measure 2θ (θ is Bragg angle) with particularly high precision, and the results were analyzed. Scientifically, it was found to belong to the monoclinic system. For example, the patent application 1983-
143396, the product of Example 7
TSZ with the composition of 1.02Na ₂ O・Al ₂ O ₃・26.2SiO ₂・12.2H ₂ O is a=20.159 (±0.004) Å, b=19.982 (±0.006)
Å, c=13.405 (±0.005) Å, α=90.51゜(±
0.03°) is the monoclinic lattice constant. The measured values and calculated values of the lattice spacing of this representative TSZ and the Miller index are listed in Table 2. Such a specific X-ray diffraction pattern is due to a change in the substituted cations of the synthetic aluminosilicate, especially to a hydrogen ion type,
The lattice spacing was not significantly affected by changes in the SiO ₂ /Al ₂ O ₃ ratio.

【table】

[Table] As a result of further intensive research based on this invention, the present inventors have discovered a substantially uniform solid acidity that has remarkable shape selectivity and catalytic ability, and has a controlled distribution of aluminum atoms within the crystal. The present invention provides a crystalline aluminosilicate having a novel crystalline distribution, such a crystalline aluminosilicate can be prepared from substantially inorganic reactive materials; The present invention was achieved by discovering that salts can bring good results to selective catalytic reactions of hydrocarbons. Accordingly, a first object of the present invention is to provide a crystalline aluminosilicate having a unique crystal structure in which the distribution of aluminum atoms within the crystal is controlled. A second object of the present invention is to provide a crystalline aluminosilicate with a high silica/alumina ratio and excellent catalytic activity. A third object of the present invention is to provide a crystalline aluminosilicate having a unique crystal structure and excellent in selective decomposition reaction of chain hydrocarbons and aromatic conversion reaction activity. A fourth object of the present invention is to obtain from an aqueous reactive compound consisting essentially of inorganic reactive materials of a silicon compound, an aluminum compound, an alkali metal compound and water.
An object of the present invention is to provide a method for producing crystalline sodium aluminosilicate in which the distribution of aluminum atoms within the crystal is controlled and has a unique crystal structure. A fifth object of the present invention is to eliminate the heat treatment step of the composite, which was conventionally required in the synthesis technology of synthetic aluminosilicate, and to make it possible to reduce the manufacturing cost through an easy and simple manufacturing _process . −
An object of the present invention is to provide a method for producing crystalline sodium aluminosilicate having a composition of _{Al2O3 - SiO2} - _H2O . Furthermore, a sixth object of the present invention is to provide a novel crystalline aluminosilicate-catalyzed method for converting organic raw materials in which the distribution of aluminum is controlled. That is, the present invention is characterized in that the silicon/aluminum atomic ratio on the outer surface of the crystal and the average silicon/aluminum atomic ratio of the entire crystal are substantially the same, or the ratio on the outer surface of the crystal is larger. A novel crystalline aluminosilicate, a method for converting organic raw materials using the same, and a novel method for producing crystalline sodium aluminosilicate. The atomic distribution on the outer crystal surface (simply abbreviated as crystal surface) of the crystalline aluminosilicate of the present invention and its vicinity was measured by X-ray photoelectron spectroscopy. In order to increase reaction selectivity in selective decomposition reactions of chain hydrocarbons, isomerization reactions of aromatic hydrocarbons, alkylation or disproportionation reactions, etc., the number of active sites that do not have molecular shape selectivity is reduced. For this purpose, it is important to relatively reduce aluminum atoms, which tend to form a skeletal structure at or near the crystal surface. When a sample is irradiated with X-rays, photoelectrons are emitted from the sample, but because the electrons have a strong interaction with matter, their mean free path is small, so the electrons emitted from deep within the sample are It is scattered internally, loses energy, and cannot reach the surface. In this case, the depth at which electrons can escape (escape depth) varies depending on the type of element and the kinetic energy of the electrons, and in the case of aluminum, the average
20 Å (kinetic energy 1500 eV), and in the case of silicon it is approximately 20 to 40 Å (kinetic energy 554 to
1178eV). On the other hand, there is no established theory as to how deep the active sites exist near the surface of the crystal and do not have much molecular shape selectivity below the outermost surface, but the crystal size is usually 1000 Å ~ The range is tens of thousands of Å, and the size of the molecules involved in the reaction is less than 10 Å, so active sites existing at a depth of 20 Å or less from the outermost surface already have sufficient molecular shape selectivity. Therefore, X-ray photoelectron spectroscopy is the most suitable analytical means. In this case, aluminum-Kα rays are used as the X-ray source, and the X-ray output is 10Kv.
It is convenient to measure by X-ray photoelectron spectroscopy at −20 mA. The silicon/aluminum atomic ratio determined in this manner is defined as the "silicon/aluminum atomic ratio on the outer surface of the crystal." On the other hand, the silicon/aluminum atomic ratio obtained by ordinary chemical analysis such as atomic absorption spectroscopy is
It is defined as "the average silicon/aluminum atomic ratio for the entire crystal." Aligned with the arrangement of silicon/aluminum atoms on the crystal surface, silicon/aluminum atoms are arranged inside the crystal via oxygen atoms.
Since the combination of aluminum arrangements is involved in the strength distribution of the solid acid, it is possible to know the distribution of aluminum inside the crystal by determining the adsorption/desorption curve of pyridine from the strength distribution of the solid acid throughout the crystal. . That is, by adsorbing pyridine onto a solid acid site, pyridinium ions and coordinate bond pyridine are formed, but when the temperature is increased, pyridine is desorbed, and there is a good relationship between this desorption temperature and the solid acid strength. It is well known that there is a correlation. In the present invention, H (hydrogen form) obtained by ion-exchanging crystalline aluminosilicate with ammonium chloride or the like and then calcining it at about 500°C is used.
After fully adsorbing pyridine on TSZ- at 300°C, and then removing the physically adsorbed pyridine by holding it in a nitrogen stream at 300°C,
The temperature is raised at a constant rate, and the desorbed pyridine is quantified using commonly used measurement techniques such as gas chromatography. In this case, the amount of solid acid, solid acid strength distribution, etc. can be determined from the size, shape, peak position, etc. of the obtained peak. Next, the method for producing crystalline sodium aluminosilicate of the present invention will be explained. The crystalline aluminosilicate of the present invention (hereinafter referred to as TSZ-), which has a unique distribution of silicon and aluminum atoms in the crystal, generally contains SiO ₂ as a silicon source and Al ₂ O ₃ as an aluminum source within a certain range. an aqueous reaction mixture consisting essentially of inorganic reactants is prepared by adding a suitable alkali source and water in a range of ratios, and the reaction mixture is crystallized until crystals form. It can be manufactured by heating and maintaining the temperature. When producing the crystalline sodium aluminosilicate of the present invention, the composition of the aqueous reaction mixture is as follows: _SiO2 / _{Al2O3 10-100 Na2O} / _SiO2 0.03-0.5 _H2O /SiO ₂ 10-300 Cl ^- /SiO ₂ 0.1-10 Among this composition, especially SiO ₂ /Al ₂ O ₃ 20-80 Na ₂ O/SiO ₂ 0.05-0.3 H ₂ O/SiO ₂ 20-200 Cl ^- /SiO ₂ The range of 0.1 to 5 is preferable. The preparation of such an aqueous reaction mixture, as well as the subsequent aqueous reaction gel mixture, is of particular importance in the production of TSZ-. In general, even when producing crystalline sodium aluminosilicate from inorganic reactive materials as in the case of the present invention, organic nitrogen cations are used in place of Group I or Group metal cations. There is basically no difference in the manufacturing process; in either case, an aqueous reaction gel mixture can be obtained simultaneously by mixing acidic and alkaline solutions of silicon and aluminum compounds, or a homogeneous solution of silicon and aluminum can be mixed. After preparation, it is also possible to subsequently gel it with an acid or alkali, and furthermore, the gel thus obtained can be converted into a xerogel and then returned to the aqueous reaction gel mixture. Among these various gelation methods, the method in which a homogeneous solution of silicon and aluminum compounds is prepared and then gelled is particularly suitable for the crystalline aluminium of the present invention, which requires controlling the distribution of silicon and aluminum within the crystal. Most preferred for the production of sodium silicate. In this case, any combination of compounds may be used as long as a homogeneous solution of silicon and aluminum can be obtained. For example, aluminum sources include activated alumina, γ-alumina, alumina trihydrate, sodium aluminate, and aluminum chlorides, nitrates, and sulfates, and silica sources include, for example, sodium silicate, Silica gel, silicic acid, aqueous colloidal silica gel-dissolved silica, powdered silica, amorphous silica, etc. can be mentioned, but from the viewpoint of the performance of the crystals obtained, economic efficiency, scale merit during industrialization, etc., as an aluminum compound source, Particularly preferred is a sodium aluminate aqueous solution, and various sodium silicate aqueous solutions or colloidal silica aqueous solutions are preferred as the silicon compound source. Thus, a homogeneous silicon-aluminum mixture is obtained with an alkaline solution, and an aqueous reaction gel mixture is obtained by neutralizing this with an acidic solution. The acid used in this case is preferably a so-called mineral acid, and among these, hydrochloric acid, sulfuric acid and nitric acid are preferred, and hydrochloric acid is particularly preferred since sodium chloride produced by reacting with excess sodium hydroxide also acts as a mineralizing agent. The use of a mineralizing agent is preferred in order to further improve the crystallinity of the crystallized product and suppress the formation of amorphous sodium aluminosilicate, as described below. Another method for obtaining a homogeneous solution of silicon and aluminum compounds is to use a metal alkoxide solution. Examples of silicon alkoxide compounds include methyl orthosilicate (tetramethylorthosilicate) and ethyl orthosilicate (tetraethyl orthosilicate). On the other hand, a typical alkoxide compound of aluminum is aluminum isopropoxide. By mixing these metal alkoxide solutions, a homogeneous solution of silicon and aluminum compounds can be easily obtained. By hydrolyzing the solution thus obtained in the presence of an acid or alkali, a homogeneous gel can be easily prepared, and a vitreous compound can be prepared by gentle hydrolysis, and then This can also be used as a raw material to form an aqueous reaction gel mixture. In this case as well, a curing agent such as sodium chloride can effectively act to improve the crystallinity of the crystalline sodium aluminosilicate produced. The following two mechanisms can be considered as the formation mechanism of such a crystalline aluminosilicate from an aqueous reaction gel mixture. The first mechanism is that the gel depolymerizes and dissolves under a hydrothermal reaction, and separate crystal nuclei are successively grown. Since crystal nuclei are generated mainly from cations, the presence of organic cations is thought to act as a "template" and create an environment in which crystal nuclei are extremely likely to form.
When organic cations are present, the pH value under hydrothermal reaction conditions is relatively higher than that of inorganic cations, so hydrated silicate ions (H ₂ O), Si(OH) ₅ ^- It is thought that a nucleus is formed using the cation as a "template" immediately after it is generated by the action of organic cations, and in this case, hydroxyl ions play an important role in the depolymerization of the gel. According to this mechanism, it is thought that due to the presence of organic cations, a relatively large number of silicon nuclei becomes the center, and successive precipitation/crystal growth of silicon compounds occurs, and if this nucleus grows infinitely,
The presence of silicon-only crystalline silicates, which have already been proposed, cannot be said to be inconvenient. In practice, the presence of organic ions such as tetrapropylammonium salts can increase the silica/alumina molar ratio of the crystalline aluminosilicate by more than 20.
While it is possible to freely control the silica/alumina molar ratio up to 1,000, it is already known that the silica/alumina molar ratio cannot be lower than 20. The second generation mechanism is that the gel phase forms an aluminosilicate skeleton structure as it is without dissolving, but even in this case, nuclei are generated in the gel phase and rearrangement occurs in the solid-gel phase. is thought to be occurring. In this case, of course,
It is believed that the silicon-aluminum alignment within the aqueous reaction gel mixture greatly influences the silicon-aluminum alignment of the resulting crystalline aluminosilicate. In order to improve the silica/alumina molar ratio of the crystalline sodium aluminosilicate produced, if the silica/alumina molar ratio of the aqueous reaction gel mixture is increased to 100 or more, the rearrangement will be forced and the silicon oxide crystals will form. The fact that it is generated suggests that the second generation mechanism is effective. According to the second generation mechanism, it can be seen that in order to control the silicon/aluminum arrangement within the crystal, it is sufficient to control the arrangement of the gel particles. In any case, obtaining an aqueous reaction gel mixture from a homogeneous solution suggests that the gel mixture also has a uniform distribution of silicon and aluminum within the gel particles, and this uniform distribution is due to the crystallization. It is presumed that this also affects the crystallization process, resulting in a uniform distribution of silicon and aluminum atoms in the crystallized product. After preparing the aqueous reaction gel mixture as described above,
The reaction mixture is maintained under autogenous pressure at a temperature ranging from about 120°C to about 230°C for about 10 hours to about 50 hours. During crystallization, by adding a mineralizing agent to the aqueous reaction gel mixture, the crystallinity of the crystallized product can be further improved and the formation of amorphous aluminosilicate can be controlled. Such mineralizers include, for example, NaCl, Na ₂ CO ₃ ,
Neutral salts of alkali metals or alkaline earth metals such as Na ₂ SO ₄ , Na ₂ SeO ₄ , KCl, KBr, KF, BaCl ₂ or BaBr ₂ can be used. The preferred mineralizing agent is NaCl, and the amount added ranges from about 0.1 to about 10, more preferably from about 0.1 to about 5, expressed as a molar ratio of Cl ^- _-SiO2 . The crystalline sodium aluminosilicate of the present invention can be obtained by separating the produced crystalline aluminosilicate from the solution by filtration, washing with water, and drying. The obtained crystals were examined by powder X-ray diffraction and were confirmed to be 100% crystallized. The obtained X-ray diffraction pattern is 2θ=14.7° (d=
6.03A) is a single diffraction line (Singlet), and 2θ
= 23° (d = 3.86 Å) and 2θ = 23.3° (d = 3.82 Å)
The crystalline aluminosilicate according to the present invention has a very significant feature in that the two diffraction lines are clearly separated, indicating that the crystalline structure of the crystalline aluminosilicate according to the present invention is completely different from that of the crystalline gelalite that has been proposed in the past. The arrangement of silicon and aluminum atoms on the crystal surface of the crystalline aluminosilicate of the present invention is measured by X-ray photoelectron spectroscopy as described above, but the distribution of silicon and aluminum atoms in the entire crystal is As mentioned above, it can be determined from the adsorption and desorption curve of pyridine by utilizing the fact that the distribution of is related to the solid acid strength distribution. In the present invention, H (hydrogen form) obtained by ion-exchanging crystalline aluminosilicate with ammonium chloride or the like and then calcining it at about 500°C is used.
Pyridine is sufficiently adsorbed on TSZ- at 300℃. Next, the physically adsorbed pyridine is removed by holding it in a nitrogen stream at 300°C, and then the temperature is raised at a constant rate to remove the desorbed pyridine, which is normally used in gas chromatographs, etc. Quantitate using different measurement techniques. For example, when quantitative determination is made using a flame-ionization-detector type gas chromatograph, it can be seen that the peaks clearly indicate the amount of solid acid and the solid acid strength distribution, as shown in the examples. In this case, a sharp peak indicates that there are many solid acid sites with similar acid strengths. This means that the combination of silicon and aluminum mediated by oxygen atoms is relatively uniform, and that the strong solid acid site that finally desorbs pyridine at around 900°C has a local arrangement of aluminum atoms. This indicates that the texture has become coarser. In order to use the crystalline sodium aluminosilicate of the present invention as a catalyst or catalyst composition, the crystals are calcined at a temperature of about 200° C. or higher in an atmosphere of air or an inert gas and dehydrated. The product after dehydration is useful as a catalyst or catalyst support for chemical reactions, and therefore it is preferred to remove or replace at least a portion of the cations in the product by heat treatment and/or ion exchange. In this case, catalysts that undergo cation exchange in particular have excellent performance as hydrocarbon conversion catalysts, but in general, the substituent ions can be selected depending on the type of desired reaction. , substitution with hydrogen ions can also be performed by acid treatment or substitution with NH ₄₊ and heat treatment. Particularly preferred are hydrogen ions and group metal ions for conversion reactions such as hydrocarbon decomposition, isomerization, and alkylation. In the present invention, cation exchange can be performed by contacting the crystallized product with the desired exchange cation or salt of cations. In this case, neutral salts such as various group metals and alkaline earth metals can be used, but chlorides, nitrates, sulfates and acetates are particularly preferred. That is, in order to use the TSZ- of the present invention as a catalyst, it is desirable to improve the catalytic activity by introducing an active metal component by ion exchange or by introducing hydrogen ions by acid treatment as described above. The TSZ- of the present invention can also be, as is commonly done,
It can also be used in combination with a carrier such as silica/alumina or alumina. In this way, when TSZ- contains a modifying active ingredient, the temperature at about 380°C
About 0.5 to about 5.0 V/cm ² at a temperature of about 500°C and a pressure of about 5 to about 50 Kg/cm 2 , preferably about 10 to about 30 Kg/cm ²
The reforming feedstock can be catalytically reformed under reaction conditions of a liquid hourly space velocity of H/V, preferably about 1.0 to about 3.0 V/H/V. In addition, when transition metals such as Co and Ni or noble metal components such as platinum and palladium are contained by ion exchange or other methods, the TSZ- of the present invention can be used by catalytic desorption of light oil fractions and lubricating oil fractions. It can be used as a wax catalyst. Contact dewaxing is approximately 250℃ to approximately 400℃
about 5Kg/cm ² to about 50Kg/cm ² , preferably about 5Kg/cm 2 at a temperature of
Pressure of 10Kg/ ^cm2 to approx. 30Kg/ ^cm2 , approx. 0.25V/H/V
~about 3V/H/V, preferably about 1.0V/H/V
Reaction conditions of ~2.0 V/H/V can be employed. TSZ- of the present invention has a specific distribution of silicon and aluminum within the crystal,
In addition, since it has a specific composition and a specific lattice spacing, it can be used for hydroisomerization of normal paraffins, hydrodehydrogenation, conversion of alcohols to hydrocarbons, and alkylation of aromatics with alcohols and olefins. It has catalytic activity for various organic reactions such as disproportionation and transalkylation among aromatic compounds, and is extremely useful because it has a remarkable effect particularly in hydrocarbon decomposition reactions. Furthermore,
According to the present invention, such useful TSZ- can be produced extremely easily and economically, and the present invention has great significance. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 12.5g of sodium aluminate (NaAlO ₂ ) was added to water.
Dissolved in 292.5g water glass (Na ₂ O; 9.5% by weight,
It was dropped into a mixed solution of 269.1 g of SiO ₂ (28.6% by weight Japanese Industrial Standard No. 3 water glass (hereinafter abbreviated as "JIS No. 3")) and 135.7 g of water with stirring. Separately 35
A solution was prepared by mixing 77.7 g of concentrated hydrochloric acid and 175.5 g of water. Next, add these two liquids to sodium chloride.
48.6g was simultaneously added dropwise to a solution of 403.7g of water with stirring. PH after mixing all solutions
The value was 8.0. Next, this was placed in an autoclave with a capacity of 2 and maintained at 185° C. under autogenous pressure for 40 hours while stirring. The pH value of the mother liquor after crystallization was 11.6. After cooling, the crystallized product was filtered and washed, and dried at 120°C overnight. Examination of the obtained solid product by powder X-ray diffraction revealed that the product was 100% crystallized and had a lattice plane that matched that of TSZ zeolite. As a result of chemical analysis, SiO ₂ is 87.1% by weight, Al ₂ O ₃
is 5.33% by weight, Na ₂ O is 2.88% by weight, and 900℃
A chemical structure with ignition loss of 4.44% by weight was obtained. This was expressed as the molar ratio of oxides as follows. 0.89Na ₂ O・Al ₂ O ₃・ 27.8SiO ₂・4.7H ₂ O Next, in order to analyze the silicon and aluminum on the crystal surface, this product was compressed into a tablet with a diameter of 12 mm.
It was molded into a mm disk at a pressure of 10Ton/cm ² .
The sample was irradiated with an Al-Kα X-ray source at an output of 10 KV-20 mA, and the emitted X-ray photoelectrons were analyzed for energy, and the atomic ratio of silicon to aluminum was 14.5.
I got it. Therefore, the ratio of the silicon/aluminum atomic ratio on the crystal surface to the crystal average silicon/aluminum atomic ratio is 1.04, and from both values it was concluded that aluminum atoms are uniformly distributed within the crystal. . Comparative example 1 Aluminum sulfate (Al ₂ (SO ₄ ) ₃・17.8H ₂ O)
16.4 g of water, 105 g of 95% sulfuric acid and tetrapropylammonium bromide ((C ₃ H ₇ ) ₄ NBr)
34.3g was dissolved in the mixed solution. Separately, a solution was prepared by mixing 154.2 g of water glass (JIS No. 3) and 76.5 g of water. The above two solutions were simultaneously added dropwise into 300 g of water while stirring. The resulting aqueous reaction gel mixture was placed in an autoclave with a capacity of 2 and maintained at 160° C. for 20 hours under autogenous pressure while stirring. After cooling the autoclave, the crystallized product was filtered and washed, and dried at 120°C overnight. After further firing at 600℃ for 3 hours in an electric Matsufuru furnace, powder
As a result of examining by line diffraction, the lattice spacing was in good agreement with ZSM-5. Observation using a secondary electron beam image revealed that there was no amorphous portion and the material was extremely highly crystalline. As a result of chemical analysis, SiO ₂ is 89.0% by weight, Al ₂ O ₃
is 5.46 wt%, _Na2O is 1.78 wt%, ignition loss 3.41
It was in weight%. Assuming that the loss on ignition at 900°C was due to the disappearance of H ₂ O, it was expressed as the molar ratio of oxides as follows. 0.54Na ₂ O.Al ₂ O ₃ .27.7SiO ₂ .3.5H ₂ O The distribution of silicon and aluminum on the surface was measured in the same manner as in Example 1, and the atomic ratio of silicon/aluminum was 10.9. Therefore, the surface silicon/aluminum atomic ratio and the crystal average silicon/aluminum ratio
The aluminum atomic ratio was 0.79, demonstrating that more aluminum was distributed on the crystal surface. Example 2 7.5g of sodium aluminate was dissolved in 250g of water,
It was dropped into a solution of 234 g of water glass (JIS No. 3) and 116 g of water with stirring. Separately 35% concentrated hydrochloric acid
A solution was prepared by mixing 46.7g and 150g of water. The above two liquids were simultaneously added dropwise to a solution of 41.5 g of sodium chloride mixed in 345 g of water with stirring. The pH value after mixing all solutions was 11.2. Place this in an autoclave with a capacity of 2, and while stirring,
It was kept at 185°C for 24 hours under autogenous pressure. The pH value of the mother liquor after crystallization was 12.0. After cooling, the crystallized product was filtered and washed, and dried at 120°C overnight. When this solid product was examined by powder X-ray diffraction, it was found to be 100% crystallized and the lattice spacing matched that of TSZ zeolite. As a result of chemical analysis, SiO ₂ is 88.3% by weight, Al ₂ O ₃
was 3.82% by weight, Na ₂ O was 2.52% by weight, and the loss on ignition was 7.34% by weight. This was expressed as the molar ratio of oxides as follows. 1.1Na ₂ O.Al ₂ O 3 .39.3SiO ₂ .10.9H ₂ O In the same manner as in Example 1, _the atomic ratio of silicon to aluminum on the surface was determined by X-ray photoelectron spectroscopy and was found to be 23.6. Therefore, the ratio of the silicon/aluminum atomic ratio on the crystal surface to the crystal average silicon/aluminum atomic ratio is 1.20, and this value indicates that aluminum atoms are more distributed inside than on the surface. Example 3 5.4 g of sodium aluminate was dissolved in 292.5 g of water, and the solution was dropped into a mixed solution of 201.2 g of colloidal silica (Ludox-40) with a SiO ₂ content of 40% by weight and 135.7 g of water with stirring. Separately 35% concentrated hydrochloric acid
A solution was prepared by mixing 58.1 g and 175.5 g of water. The above two liquids were simultaneously added dropwise to a solution of 48.8 g of sodium chloride and 403.7 g of water with stirring. The PH value after mixing all solutions was 10.4.
The aqueous reaction gel mixture thus obtained was placed in an autoclave (volume 2) and kept at 185° C. for 24 hours under autogenous pressure with stirring. The pH value of the mother liquor after crystallization was 12 or higher.
After cooling, the crystallized product was filtered and washed, and dried at 120°C overnight. When this solid product was examined by X-ray powder diffraction, it was found to be 100% crystallized and the lattice spacing matched that of TSZ zeolite. As a result of chemical analysis, SiO ₂ is 88.7% by weight, Al ₂ O ₃
It had a composition of 2.35% by weight of Na ₂ O, 1.64% by weight of Na 2 O, and a loss on ignition of 6.40% by weight, which was expressed as the following molar ratio of oxides. 1.15Na ₂ O.Al ₂ O ₃ .64.2SiO ₂ .15.4H ₂ O In the same manner as in Example 1, the atomic ratio of silicon to aluminum on the surface was determined by X-ray photoelectron spectroscopy and was found to be 35.0. Therefore, the ratio between the silicon/aluminum atomic ratio on the crystal surface and the crystal average silicon/aluminum atomic ratio was 1.09. Example 4 5.4g of sodium aluminate was dissolved in 293g of water,
It was added dropwise to a mixed solution of 269.1 g of water glass (JIS No. 3) and 135.7 g of water while stirring. Separately, a solution was prepared by mixing 70.6 g of 35% concentrated hydrochloric acid and 175.5 g of water. The above two liquids were simultaneously added dropwise to a solution of 48.8 g of sodium chloride mixed in 403.7 g of water with stirring. The PH value after mixing all solutions was 8.8.
The aqueous reaction gel mixture thus obtained was placed in an autoclave (volume 2) and kept at 186° C. under autogenous pressure for 24 hours with stirring. The pH value of the mother liquor after crystallization was 12.0. After cooling, the crystallized product was filtered and washed, and dried at 120°C overnight. As a result of examining this solid product by X-ray powder diffraction, it was found to be 100% crystallized product and the lattice spacing matched that of TSZ zeolite. The chemical analysis results showed that SiO ₂ was 86.0% by weight.
The composition was 2.57% by weight of Al ₂ O ₃ , 2.44% by weight of Na ₂ O, and 6.40% by weight of loss on ignition, which was expressed as the following molar ratio of oxides. 1.56Na ₂ O・Al ₂ O ₃・ 56.9SiO ₂・19.0H ₂ O Using this sample in the same manner as in Example 1, the silicon/aluminum ratio on the crystal surface was measured. The silicon/aluminum ratio was the same. To 5 g of crystalline sodium aluminosilicate thus obtained, 75 ml of a 5% by weight ammonium chloride aqueous solution was added, and ion exchange was performed at 80° C. for 1.5 hours. After performing this ion exchange treatment four times, it was washed with water, dried at 110°C, and then calcined in air at 550°C for 3 hours to prepare H (hydrogen type) -TSZ-. In this case, the content of Na ₂ O was 0.01% by weight or less. Comparative Examples 2, 3, 4, and Comparative Example 1 Crystalline aluminosilicates having different silicon/aluminum atomic ratios as shown in Table 3 were produced using the same preparation method as in Comparative Example 1.

[Table] However, the values in the table are in grams. After holding these aqueous gel mixtures at 160°C for 20 hours, powder X-ray diffraction was measured in the same manner as in Comparative Example 1.
It showed a diffraction peak of The chemical analysis values after firing at 600°C for 3 hours were as shown in Table 4.

[Table] However, in Table 4, except where "ratio" is expressed as a molar ratio, all values are expressed in weight %. Analysis of silicon and aluminum on the crystal surface of ZSM-5 obtained in this way was carried out in Example 1.
The results shown in Table 5 were obtained.

[Table] Comparative Example 5 7.0g of aluminum sulfate was mixed with 105g of water and 95% sulfuric acid.
13.0g, tetrapropylammonium bromide
34.3g was dissolved in the mixed solution. Separately, a solution was prepared in which 154.2 g of water glass (JIS No. 3) was dissolved in 76.5 g of water. These two liquids were dropped into 300 g of water to obtain an aqueous reaction mixture gel. Crystallization was performed in the same manner as in Comparative Example 1 to obtain ZSM-5. One part of this was fired at 600°C for 3 hours and then chemically analyzed. As a result, SiO ₂ was 94.5% by weight, Al ₂ O ₃ was 2.57% by weight, Na ₂ O was 1.22% by weight, and the loss on ignition was 1.76% by weight. Obtained. This was expressed as the molar ratio of oxides as follows. 0.78Na ₂ O・Al ₂ O ₃・62.5SiO ₂・3.9H ₂ O After firing at 600°C for 3 hours, ion exchange treatment was performed in the same manner as in Example 4 to prepare H (hydrogen type)-ZSM-5. did. In this case, the content of Na ₂ O was 0.01% by weight or less. Example 5 Using hydrogen type TSZ- and hydrogen type ZSM-5 obtained in Example 4 and Comparative Example 5, pyridine adsorption and temperature-programmed desorption experiments were conducted. In order to prevent pressure fluctuations during adsorption and desorption of pyridine, the sample was made into 30/100 mesh granules.
The method involved molding using an alumina binder and pulverizing it into granules. The alumina binder was prepared as follows. 20.2 g of sodium aluminate was dissolved in 26.4 g of water, and 28.8 g of aluminum sulfate was separately dissolved in 50.7 g of water. Warm water heated to 70-80℃ of both these liquids
A gel was prepared by simultaneously dropping the mixture into 480 g. 1
After aging at 70°C for about an hour, the mixture was filtered and washed. For cleaning, use a 1.5% by weight aqueous ammonium carbonate solution.
The Na ₂ O content after firing at 600℃ is calculated by weight.
I kept going until it was below 50ppm. The thus obtained gel was kneaded and molded so that the binder (alumina) content was 30% by weight, then dried at 120°C and heated to 600°C.
Baked for an hour. This was made into 30/100 mesh granules and used as a sample. After accurately weighing 0.075 g of the sample, it was placed in an adsorption tube and dried at 600° C. for 1 hour in a stream of dry nitrogen. Nitrogen was flowed through the pyridine solution at a constant temperature of 15.5°C at a flow rate of 50 ml/min, and pyridine was saturated and adsorbed onto the sample at 300°C. Thereafter, only dry nitrogen was flowed and the temperature was maintained at 300°C to remove the physically adsorbed content. Thereafter, the temperature was raised at a rate of 10°C/min, and the desorbed pyridine was quantified using a gas chromatograph using a flame ionization detection method. FIG. 1 shows Example 4.
The relationship between temperature and amount of pyridine desorption is shown for the samples of Comparative Example 5 and Comparative Example 5. Next, the sample obtained in Example 1 and the sample obtained in Comparative Example 1 were ion-exchanged in the same manner as described in Example 4 to obtain hydrogen-type TSZ- and hydrogen-type ZSM-5. Prepared. 30/100 using the same method as described in Example 5 (this example).
After granulating into mesh, pyridine adsorption and desorption experiments were conducted in the same manner, and the results shown in FIG. 2 were obtained. In both Figures 1 and 2, the sample according to the present invention is ZSM
-5, it was demonstrated that it shows a sharper distribution. This means that in the sample according to the present invention, there are relatively more active sites with the same acid strength. In addition, when comparing the silica/alumina ratio at the same level, it was found that the TSZ of the present invention
− indicates that the relative amount of adsorption is also larger. The amount of pyridine adsorbed is shown in the table below. Application example ZSM-5 Example 1 Example 4 Comparative example 1
Comparative example 5 0.346 0.192 0.188
0.146 Unit: mmoleq/g Example 6 Hydrogen form of Example 1 produced in Example 5
An alkylation reaction of toluene was carried out under the following conditions using TSZ- and hydrogen type ZSM-5 of Comparative Example 1 as catalysts and ethylene. A normal-pressure flow reaction tube was filled with 2.0 ml of granular catalyst of 25/60 mesh, the reaction temperature was 350°C, and toluene/ethylene/hydrogen was mixed at a molar ratio of 5/1/5 to increase the weight hourly space velocity (V/H /V) was introduced at a ratio of 3.7/340/1680. The values for ethylene and hydrogen in this case are calculated from the volume of gas converted to 20°C. Through this reaction, p-, m-, and o-ethyltoluenes are synthesized. In particular, p-ethyltoluene can be used as a raw material for synthetic resins because the ethyl group can be dehydrogenated to form p-methylstyrene. Useful. The results of gas chromatograph analysis of the product were as follows. Conversion rate of toluene p-ethyl Toluene selectivity H-ZSM-5 19.74 27.9 (Comparative example 1) H-TSZ- (Example 1) 18.82 33.1 Furthermore, according to observation using a secondary electron beam image, Hydrogen type TSZ− before molding,
It has been confirmed that the crystal of hydrogen type ZSM-5 has a similar size, approximately 0.5×1.0 μm. Example 7 The crystalline aluminosilicate obtained in Example 3 was converted into a hydrogen form by the method of Example 4, kneaded with a binder by the method of Example 5, and formed into pellets with a diameter of 1.5 mm. Further, ZSM-5 obtained in Comparative Example 4 was also converted into a hydrogen form by the method of Example 4, kneaded with a binder by the method of Example 5, and formed into pellets with a diameter of 1.5 mm. In either case, the amount of binder is
The content was adjusted to 30% by weight after firing at 600°C for 3 hours. Using these catalysts, we investigated the alkylation of toluene with methanol and the production of xylenes. Reaction: 2.0ml (25/60 mesh)
The reaction was carried out using a normal pressure flow reaction tube using a catalyst, and the product was analyzed by gas chromatography.

[Table] As shown in Table 6, the toluene conversion rate and
It was demonstrated that the catalyst of the present invention is excellent in the production rate of _C8 aromatics and p-xylene selectivity. Example 8 The crystalline aluminosilicate obtained in Example 2 was converted into a hydrogen form by the method of Example 4, kneaded with a binder by the method of Example 5, and formed into pellets with a diameter of 1.5 mm. The amount of binder was adjusted to be 30% by weight after firing at 600°C for 3 hours. For comparison in this example, hydrogen form ZSM-5 was prepared as follows. 11.6 g of aluminum sulfate was dissolved in a mixed solution of 105 g of water, 10.8 g of 95% sulfuric acid, and 34.3 g of tetrapropylammonium bromide. Separately, add 154.2g of water glass (JIS No. 3) to 76.5g of water.
A solution was prepared by dissolving the Add these two liquids to 300g of water.
to obtain an aqueous reaction mixed gel. Comparative example 1
ZSM-5 was obtained by crystallization in the same manner as above. this
Chemical analysis after firing at 600℃ for 3 hours revealed that
91.4 wt% _SiO2 , 4.11 _wt % _Al2O3 , _Na2O
Values of 1.77% by weight and loss on ignition of 2.76% by weight were obtained. Expressing this in terms of the molar ratio of oxides,
0.71Na ₂ O・Al ₂ O ₃・37.8SiO ₂・3.8H ₂ O.
This ZSM-5 was converted into a hydrogen form using the method of Example 4, and kneaded with a binder using the method of Example 5.
It was molded into 1.5 mm pellets. In this case as well, the amount of binder was adjusted to 30% by weight after firing at 600°C for 3 hours. Using these catalysts, we carried out the disproportionation reaction of toluene and investigated the production of benzene and xylenes. The reaction was carried out using a normal pressure flow reaction tube using 1.1 ml (25/60 mesh) of catalyst.
The product was analyzed by gas chromatography. As shown in Table 7, the results demonstrate that the catalyst of the present invention is excellent in _C8 aromatic production rate and p-xylene selectivity.

【table】

[Table] However, the reaction conditions are: Raw material: Toluene Processing gas: Hydrogen/toluene = 4/1 (mol/mol) Reaction temperature: 420°C Reaction pressure: Atmospheric pressure Space velocity: 14.8 V/H/V relative to toluene Ta.

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 are both graphs showing the relationship between the amount of pyridine desorbed and the temperature. In FIG. 1, the solid line represents the results of gas chromatograph measurement of the sample of the present invention obtained in Example 4, and the dotted line represents the sample obtained in Comparative Example 5. In FIG. 2, the solid line represents the results of gas chromatograph measurement of the sample of the present invention obtained in Example 1, and the dotted line represents the sample obtained in Comparative Example 1.

Claims (1)

[Claims] 1. Has a chemical composition of 0.8 to 1.5M _2/o O・Al ₂ O ₃・10 to 100SiO ₂・ZH ₂ O expressed in molar ratio of oxides, and has at least the following: A crystalline aluminosilicate having a powder X-ray diffraction pattern showing the lattice spacing shown in FIG. A novel crystalline aluminosilicate characterized by being the same as or having a larger atomic ratio on the crystal surface; provided that M is a metal cation and n is the valence of the cation and Z is 0 to 40. Lattice spacing d (Å) Relative strength (I/I ₀ ) 11.2±0.2 Strong 10.1±0.2 Strong 3.86±0.05 Very strong 3.72±0.05 Strong 3.64±0.05 Strong 2 Crystalline aluminosilicate is H ⁺ , Na ⁺ , 1 or 2 selected from NH ₄ or group metal cations
The novel crystalline aluminosilicate according to claim 1, which is a salt with any of the above ions. 3. The novel crystalline aluminosilicate according to claim 1, wherein the crystalline aluminosilicate is a sodium salt. 4 consisting essentially of inorganic reactive materials, expressed in molar ratios, having the following composition: SiO ₂ /Al ₂ O ₃ 10-100 Na ₂ O/SiO ₂ 0.03-0.5 H ₂ O/SiO ₂ 10-300 Cl ^- A novel method for producing crystalline sodium aluminosilicate, characterized in that an aqueous reaction mixture having 0.1 to 10 /SiO ₂ is prepared and the reaction mixture is kept heated at a crystallization temperature until crystals form. 5 The aqueous reaction mixture has the following composition expressed in molar ratios: SiO ₂ /Al ₂ O ₃ 20-80 Na ₂ O/SiO ₂ 0.05-0.3 H ₂ O/SiO ₂ 20-200 Cl ^- /SiO ₂ 0.1- 5. The novel method for producing sodium aluminosilicate according to claim 4, characterized in that: 6. Production of novel crystalline sodium aluminosilicate according to claim 4, characterized in that the aqueous reaction mixture is an aqueous reaction mixture obtained from a homogeneous mixed solution of a silicon compound and an aluminum compound. Method. 7. Crystalline sodium aluminosilicate whose silicon/aluminum atomic ratio on the crystal surface is substantially the same as the average silicon/aluminum atomic ratio of the entire crystal, or where the atomic ratio on the crystal surface exhibits a larger value. 0.8～ _1.5Na2O・_Al2O3・₁₀ ～ _100SiO2・0～
40H ₂ O chemical composition, and at least the following lattice spacing d (Å) Relative intensity (I/I ₀ ) 11.2±0.2 Strong 10.1±0.2 Strong 3.86±0.05 Very strong 3.72±0.05 Strong 3.64±0.05 By contacting a crystalline sodium aluminosilicate with a powder X-ray diffraction pattern exhibiting a strongly lattice spacing with a desired cation or salt of cations, the sodium ions in the crystalline sodium aluminosilicate can be isolated. A method for producing a crystalline aluminosilicate, which comprises replacing at least a portion of it with another cation. 8. The method for producing a hydrogen ion exchange type crystalline aluminosilicate according to claim 7, which comprises bringing the crystalline sodium aluminosilicate into contact with an acid. 9. The method for producing an ammonium ion exchange type crystalline aluminosilicate according to claim 7, characterized in that at least a part of the sodium ions in the crystalline sodium aluminosilicate are replaced with NH ₄ ⁺ . . 10. The metal ion-exchanged crystalline aluminosilicate according to claim 7, characterized in that at least a part of the sodium ions in the crystalline sodium aluminosilicate are exchanged with metal ions of group 3 of the periodic table of the atoms. Method for producing silicates. 11 Conversion conditions in the conversion reaction of organic raw materials,
A salt with one or more ions selected from H ⁺ , Na ⁺ , NH ₄ ⁺ and group metal cations, and expressed in molar ratio of oxides, 0.8 to 1.5 M _2/o A crystalline aluminosilicate having a chemical composition of O.Al ₂ O _3.10 to 100SiO _{2.ZH 2} O and a powder X-ray diffraction pattern showing at least the lattice spacing shown below, A crystalline aluminosilicate in which the silicon/aluminum atomic ratio on the crystal surface is substantially the same as the average silicon/aluminum atomic ratio in the entire crystal, or the atomic ratio on the crystal surface is larger. A method for converting an organic raw material, characterized in that M is a metal cation, n is the valence of the cation, and Z is 0 to 40. Lattice spacing d (Å) Relative intensity (I/I ₀ ) 11.2±0.2 Strong 10.1±0.2 Strong 3.86±0.05 Very strong 3.72±0.05 Strong 3.64±0.05 Strong