JPS59174518A - Manufacture of crystalline alumino silicate - Google Patents

Abstract

PURPOSE:To manufacture TSZ-crystalline alumino silicate whose crystalline grain size is controlled by setting up the composition ratio of a silica source, alumina source and alkaline source in an aqueous reaction mixture consisting of inorg. reaction materials in a prescribed range. CONSTITUTION:An aqueous reaction mixture obtd. by mixing a silica source (e.g. sodium silicate), an alumina source (e.g. sodium aluminate), an alkaline source (e.g. sodium hydroxide), water and if necessary, a precipitation auxiliary, a mineralizer or the like is allowed to react at about 120-230 deg.C for 5hr-10 days for manufacturing crystalline alumino silicate (TSZ) which shows a specified powder X-ray diffraction pattern (refer to the table). In above-mentioned method, by setting up respectively the molar ratios of SiO2/Al2O3, M2/nO/SiO2, M2/nO/ Al2O3 (M is metallic cation, n is its atomic valence) to in the range of 10-130, 0.01-0.5, >=1; alumino silicate having about 0.1-2mu crystalline grain size is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing crystalline aluminosilicates from an aqueous reaction mixture consisting essentially of inorganic reactants, and in particular to a process for producing crystalline aluminosilicates from aqueous reaction mixtures consisting essentially of inorganic reactants, and in particular to The present invention relates to a method for producing a crystalline aluminosilicate having a structure. More specifically, the present invention provides a method in which the crystal grain size is controlled by setting the composition ratio of a silica source, an alumina source, and an alkali source within a specific range in an aqueous reaction mixture consisting of substantially inorganic reaction materials. A method for producing crystalline aluminosilicate is provided.

Crystalline aluminosilicate is generally known as crystalline zeolite, and its crystal structure in both natural and synthetic products is StO, which is formed around silicon (Sl) and has four oxygen atoms coordinated at the apex.

It is an aluminosilicate hydrate having a structure based on a three-dimensional skeleton of tetrahedrons and AlO2 tetrahedra in which aluminum (At) is substituted for silicon.

8104 tetrahedron and AtO4 tetrahedron are 4, 5, 6, 8 or 12 members connected to form a 4-membered ring, 5-membered ring, 8-membered ring or 12-membered ring, and these 4.6.8 and 12-membered rings. It is known that a double ring consisting of overlapping 12-membered rings serves as a basic unit, and that these are connected to determine the skeleton structure of a crystalline aluminosilicate. A specific cavity exists inside the skeletal structure determined by these connection methods, and the entrance of the cavity structure is
It forms a cavity consisting of 6, 8, 10, and 12-membered rings. The formed cavity has a uniform diameter, and only molecules below a certain size are adsorbed, and large molecules are not adsorbed because they cannot enter the cavity. Such crystalline aluminosilicates are known as "single-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-mentioned molecular sieving action and catalytic action have been actively researched in various fields of chemical reactions. This is what is called a molecular shape selective reaction catalyst, and S.

As classified by M.C.S.I.C.S.R.Y. 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 leave the reaction field, but the transition state is too large and the reaction occurs. There are five types of things that cannot be
Try and Cat a Iysi
s l+A CS M o nograph 17
Volume 1, page 680 AC8.

Waghingto, n D, C, (1976) This classification was made considering only the catalytic reactions inside the cavities of the crystalline aluminosilicate. In other words, unlike the above-mentioned catalytic action, the catalytic reaction on the outer surface of the crystal or on the active sites near the outer surface is free from reactions with small activation energy (because non-reactions occur freely), which reduces the selectivity of the reaction. become.

Therefore, in order to suppress such non-selective reactions on or near the outer surface of the crystal, there are methods of burying the active sites by coating the crystal surface with a compound, or methods of burying the active points by coating the crystal surface with a compound, or using a method that shows solid acidity or alkalinity. Methods of controlling the solid acidity of active sites have been considered, and the addition of silicon compounds, phosphorus compounds, magnesium compounds, etc. has been proposed.

On the other hand, a method is also known to control the ratio of the number of active sites with molecular shape selectivity within the crystal to the number of active sites without shape selectivity on or near the crystal surface by controlling the size of crystal particles. It is being For example, when crystal particles are made larger, the proportion of active sites within the crystal increases relatively, and shape selectivity increases. 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 particles are made smaller, the proportion of active sites on or near the crystal surface will increase relatively, resulting in a decrease in shape selectivity, but the opportunities for reactants to approach and/or contact the active sites will be relatively increased. , the reaction activity becomes higher.

The electron valence of the aluminum-containing tetrahedra of the crystalline aluminosilicate is balanced by retaining metal cations within the crystal. 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.

In natural crystalline aluminosilicates, the cations are metals of group 1 or group H of the Periodic Table of the Elements, in particular sodium, potassium, lithium, calcium, magne/rum 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. For the synthesis of crystalline aluminosilicate with a high silica-alumina molar ratio,
The use of nitrogen-containing organic compounds as mentioned above was essential and famous as an alkali source.

However, when using nitrogen-containing organic compounds,
In addition to the disadvantage of high raw material costs, 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 temperatures. This had the disadvantage of complicating the manufacturing process.

Furthermore, in the conventional manufacturing method using an amine-based organic compound such as a tetraalkylammonium compound or a C2-CIO primary azun as described above, the organic compound is The potential toxicity of organic compounds and the decomposition of these organic compounds pose various physiological risks, which pose problems in terms of operational safety. Further, the use of oxygen-containing organic compounds, sulfur-containing organic compounds, etc. has also been proposed, but these cases do not solve the problems encountered when using nitrogen-containing organic compounds.

As a result of various studies and experiments, the present inventors solved these difficulties and completed a method for producing crystalline aluminosilicate from an aqueous reaction mixture consisting essentially of inorganic reaction materials, and filed a patent application in Showa. It was proposed in No. 56-143396.

It has also been revealed that the crystalline aluminosilicate obtained by the production method described in Japanese Patent Application No. 56-143396 has a unique crystal structure characterized by an X-ray diffraction pattern.

It is expressed as the molar ratio of oxide, 08~1゜5M2
lnO jar At203 ・10~100Si02 ・Z
(2) has a chemical composition of 20 (where M is a metal cation, n is the valence of the metal cation, and 2 is 0 to 40; the same applies hereinafter), and The present invention relates to a crystalline aluminosilicate having a powder X-ray diffraction pattern exhibiting at least the lattice spacings, ie d-distances, shown in Table 1.

First surface lattice spacing d(A) Relative strength (111°) 11
．． 2 ±0.2, S.

10.1 ±02 8゜A
5 ±0.15W.

603±01 M.

686±0.05V, S
.

382±0.05 8゜37610, [
]5S.

3.72FD, 05 S.

3.64+0.05 8゜As above,
The aluminosilicate, which has a crystal structure characterized by an X-ray diffraction pattern, has not been described in the literature and was named TSZ.

However, as mentioned above, controlling the crystal particle size is extremely important for shape selectivity and catalytic performance, and in general, the amount of M2/no (alkali amount) produced under hydrothermal synthesis conditions is It is known that it affects the size, shape, growth rate, etc. of crystal grains, but high S A02 such as the crystalline aluminosilicate in the present invention
/AA20s molar ratio and a unique crystal structure can be achieved when producing silicates from an aqueous reaction mixture consisting essentially of inorganic reaction materials. Of the composition ratio, S
i O2/ A t2 03 molar ratio and M2/nQ/5
We discovered that the crystal grain size of the crystalline aluminosilicate produced by changing the molar ratio of i02 changes, and as a result of various studies, we found that the S A02 /A12 of the aqueous reaction mixture
03 M2/n depending on the molar ratio.

/sto□ By changing the molar ratio, M2/ n O/Al2
It has been found that crystalline aluminosilicate with a narrow particle size distribution can be produced for a wide range of S A02 /A/:203 molar ratios by specifying the O3 molar ratio based on the concept of equality. Furthermore, the M2/no/5i02 molar ratio was set to 0.
By setting in the range of 01 to 0.5, approximately 01μ to
It has been found that a crystalline aluminosilicate is produced having a grain size in the range of about 10 microns, in particular from about 01 microns to about 2 microns.

Therefore, the main object of the present invention is to prepare an aqueous reaction mixture consisting of essentially inorganic reaction materials of silicon source, aluminum source, alkali source, water and precipitation aids, mineralizing agents.
The object of the present invention is to provide a method for producing a crystalline aluminosilicate having a controlled crystal grain size by setting the A t203 mo/l/ratio and the Mz/no/SiO□ molar ratio within specific ranges.

Another object of the present invention is to provide a method for producing crystalline aluminosilicates having a small grain size and a unique crystal structure using an aqueous reaction mixture consisting essentially of inorganic reactants. It is to be.

Still another object of the present invention is to provide a method for producing a crystalline aluminosilicate having a unique crystal structure with controlled grain size and useful as a highly active catalyst for chemical reactions and an adsorbent for chemical processes. That's true.

The present invention was completed based on the above-mentioned knowledge, and can effectively achieve the above-mentioned object. That is, at least the following first surface lattice spacing d(λ) Relative intensity (■/r0) 11.2
±02 8゜10.1±02
8゜7.5±0.15
W.

6.03±0.1 M.

3.86fO, 05V, S.

3.82 0.05' S.

6.76±0.05 8°3.72
Shi o, os s.

It has a powder X-ray diffraction pattern with a lattice spacing of 5.64±o, os, and 3°, and is expressed as an oxide molar ratio of 0.8"-1,5M2/no・A2203. 10~
1005i02 ・For producing crystalline aluminosilicates having a chemical composition of 0 to 40H20 from an aqueous reaction mixture consisting essentially of inorganic reaction materials, 5A of the mixture
When the 02/A7zO3 molar ratio is in the range of 10 to 130, the M2/'n'0/S i 02'%le ratio is 0.01 to 130.
0.5, and 1 mole of M2 /no/Aj203
By making the above settings, we were able to achieve the above objective.

The values of the X-ray diffraction patterns given in the table above are based on the X-ray diffraction device manufactured by Rigaku Denki Co., Ltd.
-rA type) by a conventional method. The irradiation beam is one alpha doublet on the copper and is 20 mm (θ is the Bragg angle) from the chart using a non-tilt counter equipped with a strip chart pen recorder.
The peak height and its position are read as a function of , and from these the relative intensity corresponding to the recorded line and the interplanar spacing (d), expressed in Angstroms, are determined. In the relative intensities of Table 1 [v.

S, J are strongest, "S," is strong, "M," is medium strong, "W,"
” indicates weak, and [V, W, j indicates very weak.

The TSZ crystalline alkinosilicate according to the present invention is characterized by an X-ray diffraction pattern obtained by conventional powder X-ray diffraction. That is, 2θ-14°7' (d=6.o3
The diffraction line of a person) is a single line,
and 2θ-23° (d-3, 86 people) and 2θ=2
The two diffraction lines at 3.3° (d=3.82) are clearly separated, which is a remarkable feature that differs from the crystal structure of the crystalline zeolite that has been previously proposed.

Furthermore, apart from the conventional method, powder X-ray diffraction analysis was performed to measure 2θ (θ is Bragg angle) with particularly high accuracy, and the results were analyzed.
SZ ) was crystallographically found to belong to the monoclinic system. For example, 102Na20.At2 which is the product of Example 7 described in Japanese Patent Application No. 56-143396'
03 ・262S10□ -12,2H2O TSZ has a = 20.459 (±o, o O4) people, b = 19°982 (+0.006') people, c =
13, 405 (+005) people, +1-90.51°
(+003°) shows 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 cation of the synthetic aluminosilicate, especially a change to the hydrogen ion type, S +02 /'At2Q
] The lattice spacing was not significantly affected by changes in the ratio.

The preferable composition of the TSZ crystalline aluminosilicate of the present invention in the as-synthesized form is as follows: 0.8 to 1.5 N a20 ' A 7203 '2 when expressed in molar ratio of oxides
5 to 80 SiO2.o to 4oH2°, in which case at least one of the metal cations present during synthesis is
Parts can be replaced by ion exchange or the like. Ion exchange can be carried out using hydrogen ions such as metals or acids from Groups I to II of the Periodic Table of the Elements, or using ammonium ions. In this way, hydrogen,
Catalytic activity, especially activity as a hydrocarbon conversion catalyst, can be imparted by replacing with ammonium, noble metals, rare earth metals, etc., and if the SiO2/At, 03 ratio is in the range of 25 to 8o, The crystal structure remains unchanged, and the hydrogen form of TSZ is also monoclinic.

The shape and size of crystalline particles of crystalline aluminosilicate zeolite can be determined by microscopic observation. Separating the crystalline aluminosilicate of the present invention in the as-produced state, that is, the product obtained by crystallization of the aqueous reaction mixture,
After washing with water, the dried powder was subjected to microscopic observation so that the morphology of at least 100, usually 200-300, crystal grains could be determined. According to Part 1, the shape of the crystal grains of the present invention is close to columnar, circular and spherical. Moreover, the crystalline aluminosilicate obtained by the production method of the present invention is shown in the short axis of each shape from the micrograph. The size range of the crystal grains of the present invention, the so-called crystal grain size distribution, can be controlled by using the techniques detailed in this specification, and as exemplified in the embodiments, the relative It is also possible to have a relatively large size distribution or a relatively small size distribution.

Next, the method for producing crystalline sodium aluminosilicate of the present invention will be explained.

According to the present invention, the crystalline aluminosilicate is generally prepared by using 5i02 as a silicon source and At203 as an aluminum source in a certain range of ratios, and adding an appropriate alkali source and water to each in a certain range of ratios. They can be prepared by preparing an aqueous reaction mixture consisting essentially of inorganic reactant materials and maintaining the aqueous reaction mixture heated at a crystallization temperature until crystals form. These manufacturing conditions are
For example, under self-pressure, about 01μ to about 230℃ for about 5 hours
Includes maintenance for 10 days.

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

5i02 /A403: 10-130M2/
no 7s to2: 0.01~0.5H20/S
iO: 150-130 It is a positive ion.

n is the valence of the metal cation. M2/no is free M2/n.

It is generally in the form of salts such as aluminates, silicates, etc., which are effective in hydroxide and zeolite synthesis. X- is the anion of the salt of the precipitating agent and l or the mineralizing agent.

However, according to the present invention, in order to produce a crystalline aluminosilicate having a grain size of about 01μ to about 10μ, in particular about 0.1μ to about 2μ, 51o21At203 mo/l/
In addition to the ratio and M2 /no/S i02-v-le ratio, M
It is necessary to set the molar ratio of 2/no/At203 within a certain range, and therefore the aqueous reaction mixture used in the present invention is required to have the following composition expressed in terms of the molar ratio of oxides.

M2/ no/At203 1 or more S'02
/A40g 10~130M2/nO
/ S i OH0,01~0.1H210/5i02
5~130f/S i'02
0.01 to 20 (here, M is the first element in the periodic table of elements)
It is at least one metal cation selected from the group consisting of metals and metals in Group 1 of the same table, and n is the valence of the metal cation. A particularly preferred metal cation is sodium ion. Also, X- is an anion of a precipitation aid and a salt of l or a mineralizing agent. ) For example, when M is a sodium atom, Na20
/At2031 or above S i 02 / At203 15-100
Na20/Si02 0.01~0.0
9H20/SiO□ 10~12ONO□O/
At203 1.3 or more 5i02/A! r203
20~100Na207s i
020.01~0.5t (20/SiO□
10-120x-7sio2 0.05-15, more preferably Na2O/At203:, 1.5 or more 5i
02 7A120g: 20~8ON I
L20/S+02: 0.02~
0.2H20/SiO□. 10-100
X-7s to2 ” 0.1 to 10.

Here, Na2'O is free Na2O, and as mentioned above, it is generally in the form of a right acid salt, such as an aluminate or a silicate, which is effective in the synthesis of hydroxides and zeolites. In addition, the above [free Na 20 J is
It can be adjusted by adding aluminum sulfate, sulfuric acid, hydrochloric acid, nitric acid, etc.

In preparing the aqueous reaction mixture, the source of the oxidic reactant of the composition used is one commonly used in the production of synthetic zeolites.

Examples of silica sources include water glass, sodium silicate,
Examples include silica gel, silicic acid, aqueous colloidal silica gel-dissolved silica, powdered silica, and amorphous silica. Among these, sodium silicate, water glass, colloidal silica, and the like are particularly preferred.

As the alumina source, for example, activated alumina, r-alumina, alumina trihydrate, sodium aluminate, and various aluminum salts such as aluminum chloride, nitrate, and sulfate can be used, but among these, Particularly preferred are sodium aluminate and aluminum sulfate.

Na2O as a source of sodium cations is added in the form of sodium hydroxide, sodium aluminate or sodium silicate.

When preparing an aqueous reaction mixture by mixing the above-mentioned silica source, alumina source, alkali source, and water, in addition to controlling the amount of alkali, adding a precipitation aid and a mineralizing agent can improve the aqueous reaction mixture. The fluidity is improved, and during crystallization, the crystallinity of the product can be further improved, and the formation of amorphous aluminosilicate can be suppressed.

As precipitation aids and mineralizing agents, NaC4, Na2 CO
3, Na2 so4, Na2 S C04, KC4
Neutral salts of alkali metals or alkaline earth metals such as XKB rXKF, BaC42, or BaBr2 can be used. In this case, the amount added is
An amount that increases the fluidity of the aqueous reaction mixture and improves the crystallinity of the crystalline product is preferred, and the anion of the salt as a precipitation aid and mineralizing agent is equivalent.), preferred X /5i02
The molar ratio ranges from about 0.01 to about 20. A more preferred amount is in the range of about 0.05 to about 15, and an optimal amount is in the range of about 0.1 to about 10.

Different precipitation aids and mineralizers may be used, but
Preference is given to using the same one that acts effectively as precipitation aid and mineralizing agent. In producing the preferred TSZ crystalline aluminosilicate of the present invention, among the composition ratios of the aqueous reaction mixture, particularly the M2/ n O/ A t203 molar ratio, the S i 02 / A403 molar ratio, and the M2
/no/S+O□ molar ratio is an important factor. As mentioned above, the aqueous reaction mixture is SI 02/A
t203 Mo/L/ratio 10-130. Particularly preferably in the range of 25 to 8o, the M2/no/At203 molar ratio is 1 or more, particularly preferably about 1.5 or more, M2
/no/S+02 molar ratio must be set in the range 0.01-05, particularly preferably 002-02. M2 In0IAt203 molar ratio, S +02 /
The At203 molar ratio and the M2/n07sio□ molar ratio are set within the above ranges, that is, M2/ n o / A z4
Under the concept of equalizing the 03 molar ratio, S +02 /
By combining the A12 03 molar ratio and the M2/nO/5102 molar ratio, it is possible to produce a crystalline aluminosilicate having a crystal grain size equivalent to that of . Also, M2
/n O/S i 02 molar ratio 001~05
The crystal grain size of the crystalline aluminosilicate produced can be controlled within the range of about 01p to about 10μ.

For example, S l 02 / AA203 = 50, N
From the aqueous reaction mixture with a20/S i O2 = 0.12, crystals of relatively large particles of 5-10μ or
Also SiO21AL203-50, Na207s'1
Relatively small particle crystals of less than 1 micron can be produced from an aqueous reaction mixture of o2-0.04.

If the S +02 1Atz 03 molar ratio is greater or less than the above range, undesired crystalline phases will form. On the other hand, if the M2/no/5i02 molar ratio is smaller than the above range, it will take a very long time to crystallize or form an amorphous substance, and if the M21no/5i02 molar ratio is large, undesired crystals will form. phase is generated.

The M2/n O/A t203 molar ratio is the same as the above 5
+02/A/! 403 molar ratio and M2/nO/S
+02 molar ratio defined in combination with M2/n
If the o/At203 molar ratio is smaller than the above range, crystallization will take a very long time or an amorphous state will result. Also, the upper limit is S +02 / A tl)3
The molar ratio is limited to the range of M2/no/5i02 molar ratio.

This molar ratio of M2/no and 5i02 and M2/nO
The molar ratio of and At203 depends on the amount of alkali, and this is one important factor because in the hydrothermal synthesis of crystalline aluminosilicate, alkali (hydroxide ion) is added to the aqueous reaction mixture of aluminosilicate gel. involved in the depolymerization of This can be understood to be due to the successive bond 2 rearrangement of silicon and aluminum compounds that is involved in crystal growth and its speed.

When mixing the reaction reagents and after mixing, it is preferred that the aqueous reaction mixture be made into a slurry as uniform as possible. Therefore, the order of addition depends on the raw materials used,
It is necessary to pay sufficient attention to time, stirring, etc. In particular, the order of addition is preferably such that a uniform alkaline solution of silica alumina is prepared without stirring, and this is added together with a mineral acid solution to an aqueous solution of a precipitation aid and a mineralizing agent to form an aluminosilicate gel.

The aqueous reaction mixture is preferably stirred at or below the crystallization temperature, for example at room temperature, for several minutes to several hours prior to crystallization. Conditions for crystallization are a temperature of about 120°C to about 230°C.
The time is about 5 hours to about 10 days. Optimal crystallization conditions depend on the reaction materials used or the composition ratio of the aqueous reaction mixture, but generally the higher the temperature, the shorter the time, and the lower the temperature, the longer the time. However, excessively low or excessively high temperatures are undesirable because they may convert to amorphous state or form other undesirable crystals. Similarly, if the crystallization time is too short,
Alternatively, if it is made too long, it may become amorphous or convert into other undesirable crystals, which is not preferable.

The reaction mixture is introduced into a closed container, for example an autoclave made of iron, stainless steel or lined with Teflon, and crystallized under autogenous pressure.

The reaction mixture is preferably continuously stirred and kept homogeneous during crystallization. Stirring is particularly important for slurry-like reaction mixtures.

Therefore, it is difficult to uniformly stir a slurry with a device such as an anchor-shaped rotary blade that has a relatively small contact area with the liquid, so in order to stir the reaction mixture as uniformly as possible, it is necessary to It is preferable to use a stirring blade with a large contact surface or one that can forcibly stir most of the reaction mixture.

As mentioned above, the uniformity of the aqueous reaction mixture, stirring below the crystallization temperature, so-called ripening, the temperature and time of crystallization (synthesis), and the method of stirring are important from the viewpoint of formation of crystal nuclei, crystal growth rate, etc. I can understand that it is a requirement.

The produced crystalline aluminosilicate is separated from the solution by filtration, then washed with water and dried. After drying, the product is dehydrated by calcining in air or an inert gas atmosphere at a temperature of about 200° C. or higher. The dehydrated product is useful as a catalyst or catalyst support for chemical reactions. Furthermore, at least a portion of the cations in the product are removed by heat treatment and! Alternatively, it is preferable to remove or replace by ion exchange.

In this case, those that have undergone cation exchange are particularly useful as catalysts for hydrocarbon conversion. Substitution ions can be selected depending on the desired reaction, but include 11a, 11la, 1VaXI Jnb, mb of the Periodic Table of the Elements,
It is preferable to select the metal from Group 2b and Group 2 metals.

Further, substitution with hydrogen ions can be performed by acid treatment or heat treatment after substitution with NH4+. Preferred substituent ions for conversion reactions such as hydrocarbon decomposition, isomerization, and alkylation are hydrogen ions and Group I metal ions.

Cation exchange can be carried out by contacting the crystallized product with the desired exchange cation or salt of the cations. In this case, various neutral salts of alkali metals or alkaline earth metals can be used, with chlorides, nitrates, sulfates, acetates and the like being particularly suitable.

When the crystalline aluminosilicate according to the method of the present invention is utilized as a catalyst or support for chemical reactions by ion exchange methods such as those described above or by other methods, controlled grain size is important for improving activity, ability to maintain activity, and It has an effect on selectivity, and is particularly effective in molecular shape-selective catalytic reactions. In general, when a catalytic reaction is carried out using a crystalline aluminosilicate zeolite catalyst, the relative amount of active sites (e.g. solid acidic sites) on and near the outer surface of crystal particles and those present in cavities or pores inside the crystal particles is important.

In other words, at the active points on and near the outer surface, various reactions occur freely starting from those with a low activation energy level without being affected by the molecular shape selectivity derived from the zeolite skeleton structure, resulting in so-called selectivity. decreases. On the other hand, on the active sites inside the crystal grains, reactions that can occur due to the effect of molecular shape selectivity based on the skeletal structure of the zeolite are restricted, so that the so-called selectivity is increased. As the crystal particles become larger, the proportion of active sites inside the crystal increases relatively, resulting in higher shape selectivity. However, the approach and contact of the reactants with the active sites is relatively limited, and the amount of effective active sites is apparently small.
Activity and ability to maintain activity become lower.

Conversely, as the crystal grains become smaller, the proportion of active sites on and near the outer surface increases relatively, resulting in lower shape selectivity. However, the approach and contact of the reactant with the active site is generally increased, thereby increasing the activity and the ability to maintain the activity.

The crystalline aluminosilicate obtained by the present invention exhibits a remarkable effect in catalytic dewaxing of wax-containing hydrocarbon oil. That is, a silicate having a crystal grain size of 01 μm to 2 μm is suitable. The catalytic dewaxing treatment is carried out at a temperature of 26oC to 400C and a temperature of 0. IV/
H/V ~5V/H/V liquid hourly velocity, 10 to 91. c.
rtl~60 to 9/'cr! pressure and 35~9o
The reaction can be carried out under reaction conditions of 0 (z-gas 1 is one feedstock oil).

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

Example 1゜Water glass (Japanese Industrial Standard No. 3 water glass: S i 02
294% by weight, N A2 09.36% by weight) 23
Add 116 g of pure water to 4.9 and stir well, then add sodium aluminate (At20335.7 weight ratio, Na2O
29.1 weight ratio) was added to an aqueous solution of 2509 dissolved in pure water.

This solution, a hydrochloric acid aqueous solution prepared with 60°5 g of concentrated hydrochloric acid (HC155 weight ratio) and 150 g of pure water are chlorinated)
Jum aqueous solution (NaCt41.5,9.Pure water345.9
) was added to prepare a slurry aqueous reaction mixture. After stirring this for about 30 minutes, it was poured into a 1 L autoclave, heated, and maintained at 185° C. under autogenous pressure for 24 hours.

After the reaction is complete, the product is removed from the autoclave and
It was over-separated, washed with pure water, and then dried at 110°C.

The obtained product was a TSZ crystalline aluminosilicate exhibiting the powder X-ray diffraction pattern shown in Table 1.1) The experimental results showed a particle size of 05μ to 1.5μ as shown in Table 3. It was possible to obtain crystals with a remarkable effect on grain size control.

Example 2 An experiment was conducted in the same manner as in Example 1, except that the composition ratio of the aqueous reaction mixture and the crystallization conditions were changed.

The obtained TSZ zeolite is powder X listed in Table 1.
The pattern was basically the same as the line diffraction pattern. The result is the third
Shown in the table. When Na2O/5i02 was lowered,
The crystal grain size was reduced to 01 μ to 05 μ°, demonstrating that the manufacturing method of the present invention is excellent.

Comparative Example 1 An experiment was conducted in the same manner as in Example 1, except that the composition ratio of the aqueous reaction mixture and the crystallization conditions were different.

When the crystallization conditions were 185° C. for 200 hours, the product was amorphous and the objective of particle size control could not be achieved.

Examples 6 to 8 Experiments were carried out in the same manner as in Example 1, except that the composition ratio of the aqueous reaction mixture and the crystallization conditions were different. The results are shown in Table 3.

The obtained TSZ crystalline aluminosilicate was
The powder X-ray diffraction pattern was basically the same as the powder X-ray diffraction pattern listed in the table. It has been found that decreasing Na2O/s+02 reduces the crystal grain size, and increasing Na2olsi02 increases the crystal grain size.

Examples 9 to 16 An experiment was conducted in the same manner as in Example 1, except that the composition ratio of the aqueous reaction mixture and the agglutination conditions were different. The results are shown in Table 4.

The obtained TSZ crystalline aluminosilicate was
The powder X-ray diffraction pattern was basically the same as the powder X-ray diffraction pattern listed in the table.

Comparative Example 2° An experiment was conducted in the same manner as in Example 1, except that the composition ratio of the aqueous reaction mixture and the crystallization conditions were different.

The results are shown in Table 4.S i 02 / AA
Since the molar ratio of 203 exceeded the set range, pure crystals could not be obtained and a mixture of TSZ and crystalline silica was obtained.

Example 17 The crystalline alumina silicate obtained according to the present invention was used as a catalyst for catalytic dewaxing to produce a low pour point hydrocarbon oil.

The raw material oil used had the following properties.

Specific gravity [1514℃] 0.8753 Sulfur, weight%
1.56 Nitrogen, weight%゛ 0.06 Carbon/Hydrogen, weight ratio 669 Pour point, °C 15 Distillation properties, °C0) Initial boiling point 161 5% 273 10% 302 60% 345 50% 670 70% 392 90% 422 95% 435 97chi 444 (1) ASTMD-2887 method The above raw material oil was produced using the catalyst production example. Crystal grain size 05μ to 1.5
When catalytic dewaxing was carried out using μ H-TSZ catalyst (A), the results shown in Table 5 were obtained.

The processing conditions are also shown in the same table.

Comparative Example 3 Same catalyst production example as Example 17 except that catalyst (B) was used Catalyst (A) 5w of TSZ crystalline aluminosilicate produced in Example 1
t% ammonium chloride solution per 1 g of silicate acid.
The ion exchange treatment was carried out at 80° C. for a total of 4 times (each treatment time was 1.5 hours).

The ion exchange product was then washed with water and dried at 110°C.
H (hydrogen type)-TSZ was obtained by firing in air at 550°C for 3 hours. The Na2O content of this H-TSZ was less than 001% by weight.
- Obtained by molding TSZ using an alumina binder.

Preparation of alumina binder consists of sodium aluminate 1
41 was dissolved in 1852 of water, and separately 2 of aluminum sulfate was added.
Dissolve 022 in water 5552. Add these two liquids to 70-80%
Gels were prepared by simultaneously dropping them into hot water heated to 3.560 °C. After aging at 70°C for about 1 hour, it is thoroughly washed. For cleaning, use a 1.5 wt% ammonium carbonate aqueous solution to ensure that the Na2O content after firing at 600°C is 50 wppm.
Do this until the following. The thus obtained gel was kneaded with 1(-TSZ) so that the binder (alumina) content was 30 wt% and extruded to a diameter of about 1.5 mm.

After molding, it was dried at 110°C and further baked in air at 600°C for 3 hours.

Catalyst (B) Catalyst (A) except that TSZ produced in Example 7 was used
It was manufactured in the same manner.

9 Table 5 Example 17 Catalyst (A) Catalytic dewaxing condition temperature (°C) 340 Liquid hourly space velocity (V/H/V) 2
．． 0 pressure (Y/cJ 4'0 Processing gas velocity (t-gas lt-stock oil) 450
Produced oil* Yield (wt% vs. feedstock oil) 75 Pour point -250* Comparative example 3 of produced oil fraction with boiling point of 221°C or higher Catalyst (B) 40 0 0 50 8 200

Claims (1)

[Scope of Claims] (]) A crystalline aluminosilicate exhibiting a powder X-ray diffraction pattern having at least the lattice spacings shown in Table 1 below, in an aqueous reaction mixture consisting essentially of inorganic reaction materials. 5102, expressed by molar ratio, is produced by heating and maintaining at a crystallization temperature until crystals form.
In the range of 1At203 from 10 to 130, M2/
no/5i02 to 001 to 0.5, and M21
of grain size by using an aqueous reaction mixture that sets no/A/403 to 1 or more (where M is the metal cation and is the valence of the metal cation). A method for producing controlled crystalline aluminosilicates. First surface lattice spacing d(λ) Relative intensity (1/Io)11.
2 +n, 2 S. 101 ± 02 8°Z5 ± 0.15 W. 6.05±01M. 5.86-1: 0.05 V, S. 382± 0.05 3°3.76± 0.05 8°5.72±
0.05 8゜5.64± 0.05
8. (2) The method for producing a crystalline aluminosilicate according to claim 1, wherein the crystal grain size is in the range of about 01 microns to about 10 microns. (3) The method for producing a crystalline aminosilicate according to claim 2, wherein the crystal grain size is in the range of about 0.1 μ to about 2 μ. (4) The aqueous reaction mixture consists essentially of inorganic reactants and has the following composition expressed in molar ratio: M21nO/At2
0315 or more SiO□/At20325~8゜M2/no/S i02 0.02~
0.2H20/5i02 10~100x-
7sio□0.1-10 (where M is a metal cation, n is the valence of the metal cation, and X- is the anion of the salt of the precipitation aid and l or mineralizer) ) A method for producing a crystalline aluminosilicate according to claim 1, 2 or 3. (5) In the aqueous reaction mixture, M is at least one selected from the group of alkali metal cations and alkaline earth metal cations of Group 1 of the Periodic Table of the Elements and Group 4 of the Table 4. 4. The method for producing a crystalline aluminosilicate according to item 4. (6) The method for producing a crystalline aluminosilicate according to claim 5, wherein one selected from the group of alkali metal cations and alkaline earth metal cations is IJium.