JPH10194730A - Microsphere compact containing crystalline aluminosilicate, its production and catalyst for fluidized bed reaction therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suitably utilize microsphere compact containing crystalline aluminosilicate as a catalyst for fluidized bed reaction by forming the microsphere-like compact containing crystalline aluminosilicate having crystalline particles of TSZ crystalline aluminosilicate in a highly dispersed state. SOLUTION: This microsphere-like compact containing crystalline aluminosilicate includes crystalline aluminosilicate comprising TSZ crystalline aluminosilicate showing X-ray diffraction diagram of the formula, having an average particle diameter within a range of 10-200μm and includes the crystalline particles in a highly dispersed state in the compact. The content of the TSZ crystalline aluminosilicate is preferably <=90% based on the total weight of the microsphere-like compact containing the crystalline aluminosilicate. The production method of the microsphere-like compact containing the crystalline aluminosilicate comprises (1) a step for preparing microsphere-like compact of a mixture containing a silica source, an alumina source, an alkali cation source and water, and (2) a step for performing a hydrothermal treatment of an aqueous reaction mixture obtained by mixing the microsphere-like compact with an aqueous solution of a neutral salt or the water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystalline aluminosilicate-containing microspherical molded article and a method for producing the same, and more particularly, to a microspherical molded article containing TSZ crystalline aluminosilicate as a main component and a method for producing the same. The present invention relates to the manufacturing method. Further, the present invention provides a fluidized bed reaction catalyst comprising a crystalline aluminosilicate-containing microspherical compact,
In particular, the present invention provides a catalyst for adding a fluid catalytic cracking catalyst.

[0002]

2. Description of the Related Art Crystalline aluminosilicates are generally known as crystalline zeolites, and the crystal structure of both naturally occurring and synthetic products is such that four oxygen atoms formed around silicon (Si) are located at the top. Aluminosilicate hydrate having a structure based on a three-dimensional skeleton of a positioned SiO ₄ tetrahedron and an AlO ₄ tetrahedron substituted with aluminum (Al) instead of silicon.

[0003] SiO ₄ tetrahedron and AlO ₄ tetrahedron are 4,
A 4, 6, 8, 10 or 12-membered ring formed by linking 5, 6, 8, 10 or 12 rings, and each of these 4, 6, 8, and 12-membered rings is The overlapping double rings serve as the basic units, which are linked to determine the skeleton structure of the crystalline aluminosilicate. There are specific cavities in the skeletal structure determined by these connection schemes, and the entrance of the cavities forms cavities consisting of 6, 8, 10 and 12-membered rings. The formed cavity has a uniform diameter, and molecules smaller than a certain size are adsorbed, but large molecules cannot enter the cavity. Such a crystalline aluminosilicate is known as a “molecular sieve” from its action, and is used as an adsorbent for various chemical processes, a catalyst for a chemical reaction, and a catalyst carrier by utilizing the above-mentioned properties. Molecular shape selective reaction catalysts that combine molecular sieve action and catalytic action have been developed.

[0004] The electron valency of such a crystalline aluminosilicate tetrahedron containing aluminum is maintained in equilibrium by including cations in the crystal. In natural crystalline aluminosilicates, the cations are metals of Group I or II of the Periodic Table of the Elements, especially sodium,
Potassium, calcium, magnesium and strontium. The above-mentioned metal cations are also used in synthetic crystalline aluminosilicates. In addition to metal cations, organic nitrogen cations, for example, quaternary alkyl ammonium ions such as tetraalkyl ammonium ions have been proposed. It has been considered that the use of the above organic nitrogen-containing compound as an alkali source is inevitable for the synthesis of a crystalline aluminosilicate having a high silica / alumina ratio.

[0005] However, when an organic nitrogen-containing compound is used, in addition to the disadvantage that the raw material price is high, the organic nitrogen compound present in the synthesized product is used because the produced synthetic aluminosilicate is used as a catalyst. Need to be removed by firing at a high temperature, which disadvantageously complicates the manufacturing process.

Accordingly, the present inventors have already prepared a method for producing a crystalline aluminosilicate from substantially only an inorganic reaction material (Japanese Patent Publication No. 3-45010 and Japanese Patent Publication No. 4-566).
See No. 67 publication. ) To solve the above problem.

When a zeolite catalyst is used industrially, for example, when it is used as a catalyst for a fluidized bed reaction such as a catalyst for fluid catalytic cracking, it is necessary to supply a zeolite catalyst in a fine particle size. However, when the diameter of the catalyst particles is reduced, the strength is reduced and the catalyst particles are destroyed, so that conventionally, when a zeolite catalyst is used industrially, powder zeolite is formed into a bellet type using an appropriate binder. doing. However, according to this method, the zeolite component to be used is diluted, and its utilization rate is reduced, so that it is necessary to reduce the space velocity of the reactants.
Not only is the productivity inevitable, but the alkali or alkaline earth metal contained in the binder migrates into the zeolite, so that the zeolite is easily poisoned.

Further, such binders are of the type that they are thermally unstable and must be able to create a path to the zeolite crystals for the reactant gases or liquids. However, the microspheres used as a fluidized bed reaction catalyst had disadvantages in terms of the content and strength of the effective zeolite component.

Therefore, for example, a silica / alumina ratio of 12
As described above, a zeolite seed having a control index of 1 to 12 and a silica source,
The mixture obtained by mixing the alumina source and water is formed into discrete particles, and the discrete particles are heat-treated into wear-resistant particles,
There has been proposed a method in which zeolites are mixed with a zeolite seed and an alkali cation source and crystallized under hydrothermal reaction conditions (see JP-A-60-210518).

However, according to this method, it is essential to use seed crystals of zeolite and to prepare an aqueous reaction mixture by mixing the molded body with an alkali cation source, which still has problems in raw materials and operation. In addition, since the crystallization rate is low, the development of a crystalline aluminosilicate-containing microspherical compact that does not require complicated operations such as the use of zeolite seed crystals has been strongly desired.

[0011]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a crystalline aluminosilicate-containing microspherical compact in which crystal grains are present in a highly dispersed state.

Another object of the present invention is to provide a production method which does not require the use of crystalline alumina silicate seed crystals in producing a few micro-spherical shaped bodies containing crystalline aluminosilicate by hydrothermal reaction. Is to do.

Still another object of the present invention is to provide a catalyst for a fluidized bed reaction which has high activity and excellent strength and abrasion resistance.

[0014]

Means for Solving the Problems Accordingly, the present inventors have:
After diligent studies to solve the above problems, crystalline aluminosilicate is a TSZ crystalline aluminosilicate component, the average particle size of which is in the range of 10 μm to 200 μm, and the crystal particles are Thus, a crystalline aluminosilicate-containing microspherical compact having a specific particle size distribution, which is present in a highly dispersed state, was created. Focusing on the fact that this microspherical compact exhibits high performance as a catalyst for a fluidized bed reaction, furthermore, in the production method, the composition of the microspherical compact before crystallization is specified and hydrothermal treatment for crystallization is performed. It has been found that the above-mentioned object of the present invention can be achieved by specifying the reaction treatment conditions, and the present invention has been completed based on these findings.

That is, a first aspect of the present invention is a microspherical compact containing a crystalline aluminosilicate, wherein the crystalline aluminosilicate has a TSZ having an X-ray diffraction pattern shown in Table 1.
The present invention relates to a crystalline aluminosilicate-containing microspherical silicate having an average particle diameter of 10 μm to 200 μm, which is a crystalline aluminosilicate.

Table 1 Lattice spacing d (Å) Relative intensity (I / Io) 11.2 ± 0.2 S 10.1 ± 0.2 S 7.5 ± 0.15 W 6.03 ± 0.1 M 4.26 ± 0.07 M 3.86 ± 0.05 VS 3.82 ± 0.05 S 3.76 ± 0.05 S 3.72 ± 0.05 S 3.64 ± 0.05 S or The second aspect of the present invention is a microspherical compact containing a crystalline aluminosilicate, wherein the crystalline aluminosilicate is a TSZ crystalline aluminosilicate having an X-ray diffraction pattern shown in Table 1. (1) A method for producing a microspherical compact containing a conductive aluminosilicate, comprising: (1) a silica source, an alumina source, an alkali cation source and water, and the following composition represented by the following oxide molar ratio: Na ₂ O / _{Al 2 O 3 0.8~3 SiO 2 /} Al 2 O 3 10~100 Na 2 O / SiO 2 0.0 Or a mixture comprising the mixture and a refractory inorganic material, and (2) mixing the microsphere with an aqueous neutral salt solution or water to form an aqueous reaction mixture. (3) heating and maintaining the aqueous reaction mixture under hydrothermal reaction conditions until a TSZ crystalline aluminosilicate-containing microspherical compact is formed;
TECHNICAL FIELD The present invention relates to a method for producing a crystalline aluminosilicate-containing microspherical molded body, comprising the steps of recovering a crystalline aluminosilicate-containing microspherical molded body.

Further, the third aspect of the present invention is a microspherical compact containing a crystalline aluminosilicate, wherein the crystalline aluminosilicate is a TSZ crystalline aluminosilicate having an X-ray diffraction pattern shown in Table 1. A salt having an average particle diameter of 50 μm to 80 μm, and a particle diameter of 15 μm to 13 μm.
The present invention relates to a catalyst for a fluidized bed reaction comprising a crystalline aluminosilicate-containing microspherical molded product in which the microspherical molded product present in the range of 0 μm accounts for 90% or more of the whole molded product.

Hereinafter, the present invention will be described in detail. Crystalline aluminosilicate-containing microspherical compact The crystalline aluminosilicate of the crystalline aluminosilicate-containing microspherical compact of the present invention is represented by a molar ratio of oxide, 0.8 to 1.5 M _{2 / n} O.Al ₂ O ₃ .10-100
SiO ₂ .ZH ₂ O (where M is a metal cation, n is the valency of the metal cation and Z is from 0 to 40), and at least Table 1 2 shows a powder X-ray diffraction pattern having a lattice spacing represented by, that is, a d-distance.

Table 1 Lattice spacing d (Å) Relative intensity (I / Io) 11.2 ± 0.2 S 10.1 ± 0.2 S 7.5 ± 0.15 W 6.03 ± 0.1 M 4.26 ± 0.07 M 3.86 ± 0.05 VS 3.82 ± 0.05 S 3.76 ± 0.05 S 3.72 ± 0.05 S 3.64 ± 0.05 S TSZ The crystalline aluminosilicate has a crystal structure characterized by the X-ray diffraction pattern as described above.

In the relative intensities shown in Table 1, "VS" is the strongest, "S." is strong, "M." is medium strong, "W."
"VW" indicates that it is very weak.

In the above-mentioned X-ray diffraction pattern, the diffraction lines having a lattice spacing of 3.86 ° and 3.82 ° are separated and 6.03 °.
Is a single line, which indicates one feature of the crystal structure of the TSZ crystalline aluminosilicate.

In addition, powder X-ray diffraction analysis was carried out separately from the usual method, and particularly high precision 2θ (θ is the Bragg angle) was measured and the result was analyzed. As a result, TSZ crystalline aluminosilicate was found to have crystallographic properties. It has also been found that it belongs to the monoclinic system.

Further, TSZ crystalline aluminosilicate crystalline aluminosilicate-containing microspheres molded product of the present invention, the absorption band in the infrared absorption spectrum of the fired 3700cm ^-1 ~3550cm ^-1 at 600 ° C. in air Existence is a large singularity together with the crystal features shown by the X-ray diffraction pattern. The results of the infrared analysis indicate the characteristics of a zeolite having a high silica / alumina ratio substantially produced from an inorganic material, but as a crystalline aluminosilicate-containing microspherical compact, an acid based on hydroxyl groups on the crystal surface is used. It indicates that it has properties and ion-exchange ability, and has an effect such as a catalyst or an exchanger.

The content of the TSZ crystalline aluminosilicate is not particularly limited, but is preferably not more than 90% by weight, preferably 3% by weight, based on the total weight of the crystalline aluminosilicate-containing microspherical compact. % Is more preferred. Since the crystalline aluminosilicate-containing microspherical molded article of the present invention is prepared through a zeolite crystallization operation in the molded article, the crystal particles are present in a highly dispersed state in the molded article, and the dispersed state is It can be shown by electron microscopy techniques.

In the case of preparing from a conventional mixture of a zeolite crystal powder and a matrix component, there have been problems such as difficulty in dispersing the crystal particles at a high level or necessitating a pre-dispersion treatment such as mixing / kneading. This has been overcome.

When the content of TSZ crystalline aluminosilicate is 9
If the amount exceeds 0% by weight, the breaking strength and abrasion resistance of the molded body decrease, and the performance as a catalyst for a fluidized bed reaction may decrease. On the other hand, if the content is 3% by weight, it can be used as a catalyst component for a desired purpose.

The crystalline aluminosilicate-containing microspherical compact of the present invention is an aggregate having an average particle size in the range of 10 μm to 200 μm, and can be provided as arbitrarily controlled when used as a catalyst component. In the specification of the present application, the minute spherical molded body includes a spherical shape, an elliptical spherical shape, and other deformation products, and is not particularly limited. Crystalline Al
Method for Producing Minosilicate-Containing Microspheres Next, the T
A method for producing the SZ crystalline aluminosilicate-containing microspherical compact will be described.

The process for producing a crystalline aluminosilicate-containing microspherical molded product of the present invention is basically a process for producing a microspherical molded product containing an aluminosilicate having a specific composition and a hydrothermal reaction of the microspherical molded product. It consists of a crystallization operation by processing.

With respect to the production of the microspherical compact, it is necessary to prepare an aqueous mixture comprising a reaction material having a specific composition in order to generate a TSZ crystalline aluminosilicate by a hydrothermal reaction treatment.

First, the composition contains a silica source, an aluminum source, an alkali source and water and is represented by the following molar ratio of oxides: Na ₂ O / Al ₂ O ₃ 0.8-3 Na ₂ O / SiO the mixture having a _{2 0.03~0.12 SiO 2 / Al 2 O} 3 10~100 prepared, or to prepare a mixture consisting of the mixture and the refractory inorganic material.

Next, a method for producing a TSZ crystalline aluminosilicate-containing microspherical molded body, comprising forming the aqueous mixture into a microspherical molded body and subjecting the microspherical molded body to a hydrothermal reaction treatment to crystallize the same. To provide.

Examples of the silica source include sodium silicate, water glass, silica sol, silica gel, powdered silica, silicic acid, alkoxysilane, etc., with water glass being preferred.

Examples of the alumina source include sodium aluminate, aluminum sulfate, and alumina trihydrate, and any of them can be used without any particular limitation. As the alkali cation source, alkali hydroxide,
In particular, sodium hydroxide is used.

The aluminosilicate gel contained in the microspherical compact before crystallization by the hydrothermal reaction treatment has a preferred composition expressed by a molar ratio of oxides, Na ₂ O / Al ₂ O ₃ 0.8 to ₃ Na ₂ O / SiO ₂ 0.03 to 0.12 SiO ₂ / Al ₂ O ₃ 10 to 100, and more preferable composition is Na ₂ O / Al ₂ O ₃ 1.5 to ₃ Na ₂ O / SiO ₂ 0.04 to 0.1 SiO ₂ / Al ₂ O ₃ 20 to 80. If the molar ratio of Na ₂ O / Al ₂ O ₃ does not reach 0.8, it becomes difficult to incorporate aluminum into the crystal skeleton, while if it exceeds 3, there arises a problem of generation of an undesired crystal phase. Similarly, the Na ₂ O / SiO ₂ molar ratio is 0.03
If it is less than 0.1, the crystal formation rate of TSZ becomes extremely slow, and
If it exceeds 12, there is a problem that crystalline silica is produced as a by-product.

The refractory inorganic material used as a component of the crystalline aluminosilicate-containing microspherical compact of the present invention is the remaining component of the partially crystallized component of the aluminosilicate, and is obtained by a hydrothermal treatment. Mention may be made of mainly amorphous inorganic oxides and inorganic oxide-containing substances which cannot participate in crystallization, such as clay, chemically treated clay, α-alumina, zirconia, mullite, calcined silica alumina , Silica and the like can be used. Particularly preferred refractory inorganic materials include kaolin clay, metakaolin, calcined silica alumina and the like.

These refractory inorganic materials serve as a base material for dispersing the crystalline aluminosilicate particles in the microspherical compact, and provide a catalytic activity or control the catalytic activity of the crystalline aluminosilicate. Also fulfills. Further, it is effective for maintaining the breaking strength and wear resistance of the microspherical compact. The aluminosilicate gel (A) and the refractory inorganic material (B) are (A) :( B) = 90 parts by weight on a dry basis.
Parts by weight: 10 to 97 parts by weight can be mixed. The aluminosilicate gel can be particularly used in an amount of 60 parts by weight to 10 parts by weight from the viewpoint of the effect as a catalyst and the imparting of particle strength. On the other hand, if the amount of the refractory inorganic material exceeds 97 parts by weight, problems such as a decrease in the amount of TSZ crystalline aluminosilicate produced arise. The production of the microspherical compact is performed by molding the aluminosilicate gel prepared as described above or a mixture of the aluminosilicate gel and the refractory inorganic material into a microspherical compact. The microsphere molded body can be produced, for example, by spray drying. Specifically, it can be manufactured by drying using a spray drier having a nozzle for spraying centrifugally. The drying conditions greatly depend on the type of the dryer. For example, the inlet temperature in the tower is 150 ° C. to 300 ° C., the outlet temperature in the tower is 100 ° C. to 270 ° C., and the number of revolutions of the nozzle is 3,000.
Conditions such as rpm to 30,000 rpm can be adopted. By this spray drying, the average particle size is 10 μm to 20 μm.
It is possible to produce a microsphere having a diameter of 0 μm.

The thus obtained microsphere-containing aluminosilicate gel-containing compact before crystallization is subjected to firing. 400 to 900 ° C. in the baking treatment, preferably 5 to
A processing temperature of 00 ° C to 700 ° C and a processing time of 1 hour to 20 hours can be employed. If the processing temperature exceeds 900 ° C., the formation of TSZ will be adversely affected by the start of conversion from an amorphous state to crystalline state.

The shape and particle size of the fired microspherical compact can be analyzed by SEM (scanning electron microscope).

Next, the hydrothermal treatment of the microspherical compact containing the aluminosilicate gel prepared as described above will be described.

In the hydrothermal reaction treatment, a neutral salt aqueous solution or water can be used as a medium for crystallizing the aluminosilicate gel-containing microspherical compact before crystallization by the hydrothermal reaction treatment. A neutral salt aqueous solution is particularly preferred from the viewpoint of the crystallization ratio. In the crystallization operation, the crystalline aluminosilicate-containing microsphere-shaped compact is mixed with a neutral aqueous solution or water, and the resulting mixture is heated and maintained until TSZ crystalline aluminosilicate is formed in the microsphere-shaped compact. This is done by:

Examples of the aqueous neutral salt solution used for the crystallization operation of the microspherical compact of the present invention include aqueous neutral salt solutions such as alkali metals and alkaline earth metals. ,sodium carbonate,
An aqueous solution of sodium sulfate, barium chloride, or the like can be used. A particularly preferred neutral salt is sodium chloride or the like, which can be used as a 0.1% to 30% by weight aqueous solution.

Although an aqueous alkali hydroxide solution can be used, it alone contributes little to the crystallization of the TSZ crystalline aluminosilicate, and when used together with a neutral salt aqueous solution, the crystallization ratio is improved. Results can be obtained. As the aqueous alkali hydroxide solution, an aqueous solution of sodium or potassium hydroxide, particularly an aqueous solution of sodium hydroxide can be used.

The hydrothermal reaction treatment is carried out by employing a temperature of 100 ° C. to 200 ° C., preferably 140 ° C. to 180 ° C., and heating under reflux or self-pressure conditions for 10 hours to 120 hours.

As a result of the hydrothermal reaction treatment, the aluminosilicate gel portion in the microspherical compact was crystallized, and TSZ crystalline aluminosilicate having the lattice spacing shown in Table 1 was used in other refractory inorganic materials. In this case, it is possible to obtain a microsphere molded article which is highly dispersed and integrated and has a homogeneous distribution state. In the hydrothermal reaction treatment, it is preferable to gently stir the contents of the reactor or to circulate only the aqueous solution of the neutral salt or only the water.

The content of the crystalline aluminosilicate of the present invention is determined by the amount of the refractory inorganic material added. By controlling the partial crystallization of the aluminosilicate, the remaining component (matrix) is equivalent to the refractory inorganic material. An amount can be included.

In the crystallization operation of the present invention, the mixture is derived from a mixture of a silica source, an alumina source, an alkali cation source and water, and Na ₂ O / Al ₂ O ₃ = 0.8-3, N
a ₂ O / SiO ₂ = 0.03 to 0.12, SiO ₂ / A
By using an aluminosilicate gel adjusted to a controlled composition of l ₂ O ₃ = 10 to 100, the hydrothermal reaction can be performed in the presence of only water or a neutral salt aqueous solution, and the crystalline aluminosilicate Since no salt seed crystal is required, it is extremely advantageous in the production process.

After the completion of the hydrothermal reaction, the formed microspherical compact is recovered by removing the aqueous solution by filtration and washing. After being recovered, it is fired to complete a TSZ crystalline aluminosilicate-containing microspherical compact. By the hydrothermal reaction treatment of the present invention, a TSZ crystalline aluminosilicate-containing microspherical compact can be obtained, and the shape and particle shape thereof can be substantially the same as those before crystallization. The formation of the crystalline aluminosilicate “TSZ” can be measured by X-RD analysis, and the shape and particle shape can be measured by SEM analysis. Use of the Crystalline Aluminosilicate-Containing Micro-Spherical Molded Product The catalyst for a fluidized bed reaction of the present invention comprises a microspherical molded product containing a crystalline aluminosilicate, and the crystalline aluminosilicate contains TS showing the X-ray diffraction pattern represented by
Z microcrystalline aluminosilicate, wherein the average particle size of the micro-spheres is in the range of 50 μm to 80 μm, and the particle size is 15 μm.
The micro-spherical molded product present in the range of μm to 130 μm is composed of a crystalline aluminosilicate-containing micro-spherical molded product that accounts for 90% or more of the entire molded product.

The T used in the catalyst for a fluidized bed reaction of the present invention
The SZ crystalline aluminosilicate ion exchanges an alkali metal cation with a rare earth metal cation to form a rare earth, and by contacting with an acid, exchanges it for a hydrogen form. Can be used as a catalyst component.

The TSZ crystalline aluminosilicate-containing microspherical compact of the present invention is easy to handle in the exchange to hydrogen form, ion exchange operation of active metal species, etc., and has excellent activity and activity maintaining ability. Since the breaking strength and abrasion resistance of the micro spherical molded body are excellent, the catalyst for fluidized bed reaction,
In particular, it can be used as a catalyst for a fluid catalytic cracking process, and more specifically, as a catalyst for addition to a main catalyst containing a fluid catalytic cracking catalyst such as X-type zeolite, Y-type zeolite or ZSM-5. it can. The use as a catalyst for addition has a remarkable effect in obtaining a high octane naphtha and olefin (C _{2 to} C ₄ ) in a high yield.

The catalyst for addition of the fluid catalytic cracking catalyst can be used at a ratio of 1% to 10% with respect to the fluid catalytic cracking main catalyst. The catalyst for addition can be used by adding it to the main catalyst for fluid catalytic cracking or by introducing a predetermined amount to the catalyst regeneration section of the fluid catalytic cracking process.

The fluidized bed reaction catalyst of the present invention is effective in a wide range of reaction conditions in a fluidized catalytic cracking process,
For example, temperature: 400 ° C. to 550 ° C., weight hourly space velocity (WHSV): 10 to 40, catalyst / oil ratio (c / o ratio):
High activity can be achieved under normal reaction conditions such as 1 to 7.

Further, the catalyst for fluidized bed reaction comprising the TSZ crystalline aluminosilicate-containing microspherical compact of the present invention is as follows:
It has excellent performance as a catalyst for selective decomposition of n-paraffinic hydrocarbons, a catalyst for an aromatic alkylation reaction with an alkylating agent such as alcohols and olefins, and a catalyst for an isomerization reaction of aromatics. It can be widely used for catalytic reactions.

[0053]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a crystalline aluminosilicate-containing microspherical compact comprising a crystalline aluminosilicate and a refractory inorganic material, wherein the crystalline aluminosilicate is T-shaped.
SZ crystalline aluminosilicate; refractory inorganic material is kaolin; kaolin content is 20% by weight; average particle size is in the range of 60 μm to 70 μm;
T where most of the microspherical compact exists in the range of 10 μm
An SZ crystalline aluminosilicate-containing microspherical compact is provided, containing water glass, aluminum sulfate, sodium hydroxide and water, and expressed by the molar ratio of oxides as Na ₂ O / Al ₂ O ₃ kaolin blended into the mixture with _{1.5~3 SiO 2 / Al 2 O 3} 0.04~0.1 SiO 2 / Al 2 O 3 20~80, molding the microspheres by spray drying, it The present invention provides a method for producing a TSZ crystalline aluminosilicate-containing microspherical molded body, which is subjected to a hydrothermal reaction treatment in an aqueous sodium chloride solution and crystallized.

Further, as a catalyst for addition of a catalyst for fluid catalytic cracking, TSZ crystallinity obtained by controlling the required cation exchange of crystalline aluminosilicate and controlling the particle size and particle size distribution of the microspherical compact. A catalyst for a fluidized bed reaction comprising an aluminosilicate-containing microspherical compact is provided.

[0055]

The present invention will be described below in more detail with reference to examples and comparative examples. The crystal structure and the like of the crystalline aluminosilicate and the shape and particle size of the microspherical compact were measured by the following methods.

X-RD (X-ray diffraction) analysis: Measured by a powder X-ray diffraction method using a lint model 1400 manufactured by Rigaku Corporation. The measurement conditions were as follows: X-ray source; Cu-kα (copper copper alpha); output: 40 kv, 50 mA; scanning speed: 2 degrees / minute.

SEM (Scanning Electron Microscope) Analysis: A small amount of the microspherical compact was placed on a metal sample table, subjected to a conductive treatment, and measured by a conventional method. Using S-2460N manufactured by Hitachi, Ltd., an acceleration voltage of 30 kv and a magnification of 50 to 1000 times were employed.

IR (infrared absorption) analysis: A fine spherical molded product was pulverized into a powder, and calcined at 600 ° C. for 3 hours in the atmosphere.
An R measurement sample was used. After setting this sample in a diffuse reflection measurement cell, the sample was subjected to vacuum deaeration at 300 ° C. for 2 hours, and then returned to room temperature for measurement. Mattson as an IR device
n) GL-3020E FT-IR (Fourier exchange infrared spectrophotometer) manufactured by Spectratech as a sample measurement chamber
(Spectratech) Model 0030-072 high-temperature heating pressure control measuring cell was used.

Example 1 (Preparation of aqueous silica-alumina mixture) 150 g of aluminum sulfate hydrate (Al ₂
(SO ₄ ) ₃ = 53.7% by weight).
An aluminum sulfate solution was prepared by adding 5 g of concentrated sulfuric acid (95% by weight). Next, 1409.5 g of water glass (Na ₂ O = 8.7% by weight, SiO ₂ = 28.0% by weight) was dissolved in 657.5 g of ion-exchanged water to prepare a water glass solution.

The aluminum sulfate solution and the water glass solution were added simultaneously while stirring a sodium chloride solution in which 96.0 g of sodium chloride was dissolved in 500 g of ion-exchanged water. After completion of the addition, the solution was aged at room temperature for 1 hour. Expressed in terms of the molar ratio of oxides, Na ₂ O / Al ₂ O ₃ = 1.56 Na ₂ O / SiO ₂ = 0.052 SiO ₂ / Al ₂ O ₃ = 30 H ₂ O / SiO ₂ = 20.6 An aqueous silica-alumina mixture (slurry) having the following composition was obtained. (Preparation of microspherical compact) Using a spray drier (FOC-16 manufactured by Okawara Kakoki Co., Ltd.) having a nozzle for centrifugally spraying the aqueous silica-alumina mixture (slurry), the inlet temperature in the tower was 250. ° C, tower outlet temperature 150
° C, nozzle rotation speed 12,000 rpm, liquid sending speed 100
Drying was performed under the condition of ml / min to obtain a fine spherical molded body. (Heat treatment of microspherical compact before crystallization) This microspherical compact was fired in air at 600 ° C. for 3 hours. When the molded body after firing was analyzed by SEM (scanning electron microscope), the shape was spherical, the particle diameter range was 30 μm to 130 μm, and the center diameter was 7 μm.
It was 0 μm. (Hydrothermal reaction treatment of micro-spherical molded body) 50 g of the fired micro-spherical molded body was added to a 5.7% by weight aqueous sodium chloride solution 70.
0 g together with a stainless steel autoclave, and 65 ° C. at 180 ° C. with gentle stirring under self pressure.
Heating was maintained for hours.

The solid product after the hydrothermal treatment was recovered by filtration, washing and drying at 110 ° C. 600 dried products
When the product was calcined at ℃, and X-RD analysis of the calcined product was carried out, TSZ crystalline aluminosilicate was produced, and the crystallization (generation) rate was 90%. As a result of SEM analysis, the shape and particle shape of the molded body were substantially the same as those before the hydrothermal reaction treatment. As a result of composition analysis, Na ₂ O / Al ₂ O ₃ = 1.0 expressed as a molar ratio of oxides.
4 was _{SiO 2 / Al 2 O 3 =} 29.7. Further, after firing in air at 600 ° C., 3700 cm ^{−1 to} 3550
An absorption band appeared in the infrared absorption spectrum at cm ^-1 .

Example 2 A stainless steel autoclave was charged with 50 g of the heat-treated microspherical compact obtained before crystallization and obtained in the same manner as in Example 1 together with 700 g of ion-exchanged water. Heated and maintained at 80 ° C for 80 hours.

The solid product obtained after the hydrothermal treatment was collected by filtration, washed and dried at 110 ° C.

After calcining the dried product at 600 ° C., powder X-ray diffraction analysis was performed to confirm the formation of TSZ crystalline aluminosilicate. The crystallization (generation) rate was 35% or more. In the infrared absorption spectrum at 3700 cm ^{-1 to} 3550 cm ^-1 , it was confirmed that an absorption band was present as in the product of Example 1. As a result of SEM analysis, the shape and shape of the product were substantially the same as those before crystallization.

Example 3 50 g of the heat-treated molded body before crystallization obtained in the same manner as in Example 1 was replaced with 700 g of a 5.7% by weight aqueous sodium chloride solution.
Was added to a stainless steel autoclave together with a solution obtained by adding and dissolving 1.75 g of sodium hydroxide thereto, and heated and maintained at 180 ° C. for 65 hours under gentle pressure with gentle stirring.

The isomorphous product obtained after the hydrothermal reaction was collected by filtration, washing and washing. Dry the product at 110 ° C. to 600
After firing at ℃, powder X-ray diffraction was performed to confirm the formation of TSZ crystalline aluminosilicate. Crystal (generation) rate of 9
It was 0%. In addition, 3700 cm ^{-1 to} 3550 cm ^-1
It was confirmed that the infrared absorption spectrum of the sample had an absorption band as in the product of Example 1. As a result of SEM analysis, the shape and particle shape of the product were substantially the same as those before crystallization.

Example 4 An aqueous silica-alumina mixture (slurry) was prepared in the same manner as in Example 1, and the aqueous mixture contained 13% by weight of SiO ₂ and Al ₂ O ₃ as oxides. Was to do.

2 parts of kaolin was added to 100 parts by weight of the above silica-alumina aqueous mixture, and kneaded to prepare a mixed aqueous mixture of silica-alumina and kaolin.

The obtained aqueous mixture of silica alumina and kaolin was dried in a spray dryer having a nozzle for centrifugally spraying to obtain a fine spherical molded body. The drying conditions were the same as in Example 1, except that FOC- manufactured by Okawara Kakoki Co., Ltd. was used.
16 using a tower inlet temperature of 250 ° C; a tower outlet temperature of 15
0 ° C .; nozzle rotation speed 12,000 rpm;
The condition of 0 ml / min was adopted.

The microspherical compact obtained by the above-mentioned spray drying was fired at 600 ° C. in the atmosphere for 3 hours. When the molded body after firing was analyzed by SEM, the particle size range was 20 μm to 150 μm.
μm, and the center diameter was 75 μm.

A stainless steel autoclave was charged with 50 g of the above-mentioned microspherical compact together with 700 g of an aqueous sodium chloride solution (7.5% by weight).
C. and maintained for 65 hours with gentle stirring.

After the hydrothermal reaction, the solid product was filtered and washed to recover the product. The recovered product was dried at 110 ° C.

After calcining the dried product at 600 ° C.,
By RD analysis, it was found that a crystalline aluminosilicate “TSZ” was produced and the crystallization ratio was about 80%. 370
Absorption bands were present in the infrared absorption spectrum of 0cm ^-1 ~3550cm ^-1. As a result of SEM analysis, the product shape and particle shape were substantially the same as those before the crystal ratio.

Example 5 The microsphere-shaped compact of Example 4 was treated with an aqueous ammonium chloride solution, dried, and calcined at 600 ° C. to prepare a hydrogen ion exchange type TSZ-containing catalyst. The hydrogen ion-exchange molded body is sieved to have an average particle size of 65 μm,
A catalyst having a small spherical shape was obtained in which 96% of the whole particles were contained between 20 μm and 110 μm. After the catalyst was subjected to pseudo-equilibrium by steaming treatment, the catalytic activity in the catalytic cracking reaction was evaluated using a vacuum distillate (VGO) as a feed oil. Only a commercially available Y type zeolite-containing catalyst for fluid catalytic cracking was treated under the same conditions as described below and used in Reaction Experimental Example 1. Commercially available Y-zeolite-containing fluid catalytic cracking catalyst 100
The mixed catalyst obtained by adding 2 parts by weight of the above-mentioned TSZ-containing catalyst to the parts by weight was added at 800 ° C. to about 10 parts in the presence of steam.
After a time treatment, it was used in Reaction Experimental Example 2.

The catalytic cracking reaction conditions were the same in Reaction Experimental Example 1 and Reaction Experimental Example 2, and the following conditions were employed.

Reaction temperature: 520 ° C. Weight hourly space velocity (WHSV): 26 Catalyst / oil ratio (C / O ratio): 3.0 The results of the experiment are shown in Table 2.

Table 2 Reaction Experiment Example 1 Reaction Experiment Example 2 Δ (Difference from Experiment Example 1) Conversion (volume%) 61.8 61.1 -0.7 C ₅ ⁺ Naphtha yield (volume%) 53.6 53.1 -0.5 C ₅ ⁺ naphtha Octane number (RON) of ^* 86.1 89.6 +3.5 * Calculated by analyzing the component equivalent to C ₅ ⁺ naphtha by gas chromatography. From the above results, when the TSZ crystalline aluminosilicate-containing microspheres of the present invention are used as a catalyst for the addition of a catalytic cracking catalyst, naphtha having a high octane number can be obtained without a large decrease in yield. I understand.

Also, in gas chromatography analysis of light products of C ₄ or less, the olefin fraction in the C ₃ and C ₄ products was higher in Reaction Experiment Example 2 than in Reaction Experiment Example 1. Was.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the molar ratio of Na ₂ O / Al ₂ O ₃ of the aqueous silica-alumina mixture was changed to 1.0, and the molar ratio of Na ₂ O / SiO ₂ was changed to 0.15. When a microspherical molded product was prepared and subjected to a hydrothermal reaction treatment, the content of TSZ in the microspherical molded product was less than 1%. A large amount of crystalline silica was present in the product.

Comparative Example 2 (Preparation of Aqueous Silica-Alumina Mixture) In the same manner as in Example 1, 13% by weight as SiO ₂ and Al ₂ O ₃
An aqueous silica-alumina mixture (slurry) containing One part by weight of a crystalline aluminosilicate TSZ powder previously synthesized as a seed crystal was added to 100 parts by weight of a silica-alumina slurry and mixed to prepare a silica-alumina / zeolite mixed slurry. (Preparation of micro-spherical shaped body) A micro-spherical shaped body was prepared from a silica-alumina / zeolite mixed slurry in the same manner as in the production of the micro-spherical shaped body of Example 1, and the micro-sized spherical body before crystallization was obtained under the same conditions as in Example 1. The spherical molded body was fired. When the molded body after firing was analyzed by SEM (scanning electron microscope), it was found that the particle size range was 20 μm to 130 μm and the center diameter was 70 μm. (Hydrothermal reaction treatment of microspherical molded product) The fired microspherical molded product was subjected to hydrothermal reaction treatment under the same conditions as in Example 1, and the solid product after hydrothermal treatment was recovered in the same manner. 110 ° C
After drying, the dried product was calcined at 600 ° C., and as a result of X-RD analysis of the calcinable product, TSZ crystalline aluminosilicate was formed, and the crystallization rate was almost 100%. Also, SE
As a result of M analysis, as a result of a reduction in particle strength due to excessive crystallization, a considerable amount of a product other than a crushed spherical shape was recognized in the product, which was different from the shape before the hydrothermal reaction treatment (before crystallization).

[0081]

According to the present invention, there is provided a TSZ crystalline aluminosilicate-containing microspherical compact having a spherical or elliptical spherical shape, an average particle diameter of 10 μm to 200 μm, and in which crystal grains are highly and uniformly dispersed. can do.

The TSZ crystalline aluminosilicate-containing microspherical compact is useful as a catalyst for fluidized bed reaction, for example, a catalyst for fluid catalytic cracking of petroleum hydrocarbon oil. In particular, by using it as a catalyst for addition of a fluid catalytic cracking catalyst, a high octane naphtha is produced without a decrease in yield, and
Olefin can be produced with good yield.

Further, a preformed spherical shaped body composed of silica, alumina, alkali and water can be crystallized by a hydrothermal reaction treatment to produce a high content TSZ crystalline aluminosilicate. In this case, since a seed crystal is not required, an extremely efficient production method can be provided in terms of work.

Claims (6)

[Claims] 1. A microspherical compact containing a crystalline aluminosilicate, wherein the crystalline aluminosilicate is a TSZ crystalline aluminosilicate having an X-ray diffraction pattern shown in Table 1. The average particle size of the spherical molded body is from 10 μm to 200 μm
m, a crystalline spherical aluminosilicate-containing microspherical compact. Table 1 Lattice spacing d (Å) Relative intensity (I / Io) 11.2 ± 0.2 S 10.1 ± 0.2 S 7.5 ± 0.15 W 6.03 ± 0.1 M 26 ± 0.07 M 3.86 ± 0.05 VS 3.82 ± 0.05 S 3.76 ± 0.05 S 3.72 ± 0.05 S 3.64 ± 0.05 S 2. The method according to claim 1, wherein the content of the crystalline aluminosilicate is 90% by weight or less based on the total weight of the crystalline aluminosilicate-containing microspherical compact, and the remainder is a refractory inorganic material. A microspherical compact containing a crystalline aluminosilicate. 3. The crystalline aluminosilicate-containing microspherical compact according to claim 1, wherein the crystal particles of the TSZ crystalline aluminosilicate are in a highly dispersed state in the compact. 4. The infrared absorption spectrum of the TSZ crystalline aluminosilicate has an absorption band of 3700 after firing at 600 ° C. in air.
The crystalline aluminosilicate-containing microspherical compact according to claim ^1, which is present at a size of from cm ^{-1 to} 3100 cm ^-1 . 5. A crystalline spherical aluminosilicate containing a crystalline aluminosilicate, wherein the crystalline aluminosilicate is a TSZ crystalline aluminosilicate having an X-ray diffraction pattern shown in Table 1. In the method for producing a salt-containing microspherical molded product, (1) a silica source, an alumina source, an alkali cation source and water are contained, and the following composition is represented by the following oxide molar ratio Na ₂ O / Al ₂ O ₃ 0.8-3 SiO ₂ / Al ₂ O ₃ 10-100 Na ₂ O / SiO ₂ A mixture having 0.03-0.12 or a mixture of the mixture and a refractory inorganic material is used to form a microspherical compact. (2) preparing an aqueous reaction mixture by mixing the microspherical compact with a neutral salt aqueous solution or water; and (3) subjecting the aqueous reaction mixture to TSZ crystalline alumino under hydrothermal reaction conditions. Including silicate Heating maintained until microspheres molded body is produced,
(4) A method for producing a crystalline aluminosilicate-containing microspherical compact comprising the steps of collecting the TSZ crystalline aluminosilicate-containing microspherical compact. 6. A crystalline aluminosilicate-containing microspherical compact comprising a crystalline aluminosilicate and a refractory inorganic material, wherein the crystalline aluminosilicate has a TSZ having an X-ray diffraction pattern shown in Table 1. A crystalline aluminosilicate, the TS
The content of the Z crystalline aluminosilicate is 90% by weight or less based on the total weight of the crystalline aluminosilicate-containing microspherical compact, and the average particle size of the microspherical compact is 50 μm to 80 μm.
A catalyst for a fluidized bed reaction comprising a crystalline aluminosilicate-containing microspherical molded product in which the microspherical molded product having a particle size in the range of 15 μm to 130 μm is 90% or more of the whole molded product.